JPH036552A - Utilization permit card and prepaid card - Google Patents

Abstract

PURPOSE:To improve repetitive stability by providing an optically recordable part by using a mixture or reaction product of a spiro compd. and the zinc salt of arom. hydroxycarboxylic acid in which a hydroxyl group and carboxyl group exist in the adjacent positions as a photochromic material. CONSTITUTION:The optically recordable part is provided by using the mixture or reaction product of the spiro compd, and the zinc salt of the arom. hydroxycarboxylic acid in which the hydroxyl group and carboxyl group exist in the adjacent positions as the photochromic material. The spiro compd. to be used is not particularly limited and, for example, a spirobenzopyrane compd. and spironaphthoxazine compd. are more preferable examples. The utilization permit and prepaid card which are wide in a color developing range and are excellent in heat resistance, light resistance, image stability, and repetitive stability are obtd. in this way.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is applicable to facility use permits such as commuter passes, coupon tickets, train tickets, admission tickets, membership cards, etc., which are used when using transportation facilities and facilities. This relates to prepaid cards such as identification cards and telephone cards.

[Conventional technology]

In urban transportation systems, mainly railways, and various facilities, managers of transportation facilities and facilities use membership cards and boarding information to manage users of these transportation systems and facilities (hereinafter simply referred to as users). Tickets, admission tickets, and facility use permits such as commuter passes and coupon tickets are widely used.

Conventionally, to determine whether these usage permits are being used properly, a so-called ticket check is conducted at the beginning and end of use, and the use of the license is determined by checking the use of the license, which is written in the form of text on the surface of the usage permit. This has been done by checking the possible scope, validity period, effective users, etc.

[Problem to be solved by the invention]

However, with current confirmation methods, it is difficult to confirm whether a user is using a certain amount of information by, for example, using multiple commuter passes for different ride sections, or by combining an admission ticket or a regular one-time use ticket with a commuter pass. Unauthorized use may occur, such as using a section without purchasing a valid license.

In order to prevent such unauthorized use, methods such as in-vehicle ticket inspection have been adopted to check the usage permit during the process of using the facility, but in cases where there are a large number of users such as in urban transportation. In some cases, complete verification is virtually impossible and requires significant costs. It is also possible to issue so-called numbered tickets that indicate the time and place at which the user starts using the facility, but this is difficult to implement in mass transportation systems.

On the other hand, with the aim of increasing the speed of ticket issuance and ticket gates, etc. for the convenience of users and streamlining operations, the use of magnetic cards such as commuter passes and train tickets is progressing. It is also possible to provide these tickets with information to prevent their use. However, the method using magnetic information requires a special device to confirm the recorded contents, and the recorded contents cannot be arbitrarily confirmed. In addition, since the user cannot confirm the contents when recording, there is a problem that problems may arise if unauthorized use is pointed out. Furthermore, since the recorded contents could not be visually confirmed, the effect of preventing unauthorized use was insufficient.

As a method for easily visually confirming the content of recorded information, it is also possible to use a photochromic material that causes a reversible hue change when exposed to light. However, spiro compounds such as spiropyran and spironaphthoxazine, which are conventionally known typical photochromic materials, have heat resistance,
In terms of usage characteristics such as light resistance, image stability, and repeated stability, it has not been possible to apply it to items that are used for long periods of time and under various usage conditions, such as commuter passes.

Fulgide compounds, another typical photochromic material, are limited in color development to reds, and although they are superior to spiro compounds in terms of heat resistance and reversibility, they are still insufficient.

[Means to solve the problem]

The inventors of the present invention have conducted intensive research on train tickets, commuter passes, coupon tickets, admission tickets, and other permits for use of various transportation facilities and various facilities that are sufficiently effective in suppressing unauthorized use. Optical recording media using photochromic materials as information recording carriers have excellent heat resistance, light resistance, image stability, and repetition stability, and can be used for long periods of time under various usage conditions. We discovered that when used for coupon tickets or admission tickets, etc., for permits for use of various transportation facilities and various facilities, it has a sufficient effect of suppressing fraudulent use, and that when used for prepaid cards, it is possible to repeatedly display balances, etc. The invention was completed.

That is, the present invention provides an optically recordable portion using a mixture or reaction product of a spiro-based compound and a zinc salt of an aromatic hydroxycarboxylic acid in which a hydroxyl group and a carboxyl group are present at adjacent positions, as a photochromic material. The present invention provides a usage permit and a prepaid card, which are characterized by having:

The use permit and prepaid card of the present invention make use of the wide coloring range of spiro-based photochromic dyes, and are also endowed with excellent heat resistance, light resistance, image stability, repeat stability, etc. ,commuter pass,
It is excellent as a prepaid card, such as a coupon ticket or admission ticket, or a permit to use various transportation facilities or various facilities.The card is colored by light, and the destination, available range of use, valid institutions, etc. are printed using a heat transfer method. It has a remarkable feature not found in conventional photochromic materials: it does not fade, and conversely, it does not develop color even when thermal transfer printing is performed on a colorless or light-colored state.

The spiro compound used in the present invention is not particularly limited, but preferable examples include spirobenzobilane compounds and spironaphthoxazine compounds,
Among these, spirobenzopyran compounds represented by the following general formula (I) and/or spironaphthoxazine compounds represented by the following general formula (n) are preferred.

General formula (I) Furthermore, the zinc salt of an aromatic hydroxycarboxylic acid in which a hydroxyl group and a carboxyl group are present in adjacent positions (hereinafter abbreviated as zinc aromatic hydroxycarboxylic acid) used in the present invention may be, for example, the following general formula ( Compounds represented by III) are preferred.

General Formula (n) Specific examples of the compounds represented by the above general formulas (I), (n), and (III) include the following compounds.

Examples of spirobenzopyran compounds represented by general formula (I) (I-6) H3 ... (I-7) CL ... (I-117 Spironaphtho represented by general formula (II) Examples of oxazine compounds: H3 Cz+1in3COO ... (n-11) ... (n-17) ... (II-19) Printing of the compound represented by the general formula (III); Examples of prepaid cards include transparent or translucent films or sheets containing a photochromic material, or cards in which a layer containing a photochromic material is formed on the entire surface or a portion of a support.

In the present invention, the layer containing the photochromic material is formed by dissolving or dispersing the photochromic material in a suitable solvent, or dissolving or dispersing it in a binder resin solution, suspension, or emulsion, and then coating or dispersing the photochromic material on a support. Formed by printing. Alternatively, it can be formed by adhering a film-like material containing a photochromic material onto a support.

In the present invention, a transparent or translucent film or sheet containing a photochromic material, a binder used in forming a layer containing a photochromic material on a support, and a photochromic material adhered onto a support are used. Examples of resins that can be used as the film material include polyethylene resin, polypropylene resin, chlorinated polypropylene resin, polyvinyl chloride resin, polyvinylidene resin, acrylic resin, methacrylic resin, polystyrene resin, polyamide resin, polyurethane resin, and polycarbonate. Resin, polyester resin, polyketone resin, polyether resin, epoxy resin, silicone resin, chloroprene resin, isoprene resin, polyvinyl butyral resin, polyacetal resin, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, styrene- Butadiene copolymer, styrene-
Maleic anhydride copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, cellulose resin, ABS resin,
Examples include nitrocellulose resin, melamine resin, melamine alkyd resin, acrylic melamine resin, phenolic resin, alkyd resin, and the like.

As the support, metal, glass, plastic plates, films, paper, etc. can be used singly or in combination.

Note that an antireflection layer or an adhesive layer can be provided between the support and the layer containing the photochromic material, if necessary.

Furthermore, it is also possible to perform printing on the support, or to form a magnetic recording layer or a heat-sensitive recording layer in addition to the layer containing the photochromic material, if necessary.

In the present invention, the ratio of the spiro-based compound to the zinc aromatic hydroxycarboxylate is preferably 0.5 to 10 mol per 1 mol of the spiro-based compound, particularly for heat resistance and image stability. The amount of 1.5 to 4 moles is particularly preferable because it has good repeatability, can be easily erased and the hue can be changed, and can be easily processed by an automatic ticket gate or the like.

The permits and prepaid cards of the present invention are capable of optical recording and erasure and conversion of optical recording to the photochromic material used as the record carrier. Optical recording involves projecting the information to be recorded onto licenses and prepaid cards as images using a light source containing a wavelength sensitive to the photochromic material used, or scanning the light source or optical system along the optical path, or This can be done by arranging multiple light sources and making them flicker. Furthermore, erasing or converting the recorded information can be performed in the same manner as during recording using a light source that is sensitive to the photochromic material that has changed color or developed color due to recording and that includes a wavelength different from that used during recording.

Recording can be easily confirmed visually because the recorded portion is colored or discolored. It is also possible to perform it mechanically using an optical scanner or the like.

A more specific description of how to use the license of the present invention is as follows. During the period of transportation or at the time when the user of the facility begins to use the transportation means or facility, only unrecorded usage permits, etc. can be validly used. Here, "not recorded" refers to a state in which the portion containing the photochromic material is colorless or exhibits a specific hue. At the stage when a user starts using the transportation facility or facility through a formal procedure through an entrance or ticket gate, arbitrary information such as location and time is optically recorded on a usage permit or the like. Recording is performed by converting colorless to colored, colored to colorless, or colored to colored with another hue. The information to be recorded may be not only character information but also symbols, figures, etc. Permits and the like are collected when the user of the transportation facility or facility finishes using them, or their records are erased so that they can be reused.

If a user's permit is not recorded, the user cannot finish using the transportation facility or facility.

In other words, according to the use permit etc. of the present invention, a user who has started using transportation facilities or facilities etc. through regular procedures,
They have a usage permit etc. recorded during their use, and are clearly distinguishable from those who started using them without going through the official procedures.

Furthermore, it is easy for the manager of the transportation facility or facility to check the information at any time as necessary, which is highly effective in preventing unauthorized use.

〔Example〕

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto. Furthermore, in the examples, parts represent parts by weight.

Example 1 Offset ink was prepared by kneading 160 parts of an offset ink face containing phenol resin as a main component, 10 parts of Exemplary Compound (■-1), and 30 parts of Exemplary Compound (III-5). On the other hand, a base layer was coated on a polyethylene terephthalate film having a thickness of 180 microns using an ink containing titanium white as a pigment to prepare a support. Using a test printing machine, a pattern was printed on the support using the offset ink described above to create a mock commuter pass and a mock prepaid card. When this simulated commuter pass and simulated prepaid card were irradiated with light from a mercury-xenon lamp through a filter (Toshiba UV-35), the printed part, which was mostly colorless, turned gray-blue. The ticket and mock prepaid card were stored in a dark place24
No fading was observed even after hours. This filters the light from the mercury-xenon lamp (Toshiba L-42).
When irradiated through the glass, the gray-blue color quickly disappeared.

Next, we investigated the repeated stability of color development and decolorization, and found that 7
It has been confirmed that it can be repeated more than 00 times, and it has been found that it can be used for a six-month commuter pass, which has the longest validity period among commuter passes. Furthermore, when characters were printed on colored simulated commuter passes and simulated prepaid cards using a thermal transfer method, the colored areas around the characters were not affected at all.

Example 2 40 parts of a face for gravure ink containing nitrocellulose and polyamide resin as main components, 50 parts of methyl ethyl ketone, 50 parts of toluene, 3 parts of exemplified compound (n-1) and 7 parts of exemplified compound (III-5) were kneaded. Then, gravure ink was prepared. Using a test printing machine, a pattern was printed on the same support as in Example 1 to create a mock commuter pass and a mock prepaid card. When the performance was evaluated in the same manner as in Example 1, it showed the same excellent image stability, repeatability, and heat resistance as the simulated commuter pass and simulated prepaid card obtained in Example 1.

Comparative Example 1 Example 1 except that exemplified compound (I[-5) was not used
A mock commuter pass and a mock prepaid card were created in the same manner. Mercury in this simulated commuter pass and simulated prepaid card
When the light from a xenon lamp was irradiated through a filter (Toshiba UV-35), the printed area, which was mostly colorless, turned gray-blue, but when the light irradiation was stopped, the color quickly disappeared and the colorless state remained. I returned to In addition, when repeating stability was investigated, photochromic properties were no longer exhibited after several dozen repetitions.

Example 3 Exemplified compound (■-6) was substituted for Exemplified compound (III-5)
) A simulated commuter pass and a simulated prepaid card were created in the same manner as in Example 1, except that a simulated prepaid card was used.

The obtained mock commuter pass and mock prepaid card are Example 1
It showed the same heat resistance, image stability, and repeatability characteristics as the simulated commuter pass and simulated prepaid card obtained in .

Examples 4 to 9 In place of exemplified compound (II-1), exemplified compounds (II-2), (II-3), (II-4), and (n-5) were used, respectively.
), (II-9), and (I[-12) were used, but a mock commuter pass and a mock prepaid card were created in the same manner as in Example 1. Both the obtained simulated commuter pass and simulated prepaid card exhibited heat resistance, image stability, and repeatability characteristics equivalent to those of the simulated commuter pass and simulated prepaid card obtained in Example 1.

Examples 10 to 17 Exemplified compound (I-1) in place of exemplary compound (n-1),
(I-2), (I-3), (I-4), (I-7), (
A mock commuter pass and a mock prepaid card were created in the same manner as in Example 1 except that I-9), (I-10), and (■-12) were used.

Both the obtained simulated commuter pass and simulated prepaid card exhibited heat resistance, image stability, and repeatability characteristics equivalent to those of the simulated commuter pass and simulated prepaid card obtained in Example 1.

Example 18 Exemplified compound (I-3) was used in place of Exemplified compound (n-1), and Exemplified compound (I[l-5) was used in place of Exemplified compound (I[l-5).
A mock commuter pass and a mock prepaid card were created in the same manner as in Example 1 except that III-1) was used. The obtained simulated commuter pass and simulated prepaid card exhibited heat resistance, image stability, and repeatability characteristics equivalent to those of the simulated commuter pass and simulated prepaid card obtained in Example 1.

Comparative Example 2 3-hydroxy-2 instead of exemplified compound (III-5)
- A mock commuter pass and a mock prepaid card were created in the same manner as in Example 1 except that nickel naphthoate was used. After developing the color, it was stored in a dark place, and the color density decreased to about one-fourth after one hour.

Comparative Example 3 A mock commuter pass and a mock prepaid card were produced in the same manner as in Example 1, except that zinc 2-hydroxyphenylacetate was used in place of Exemplary Compound (III-5). After developing the color, it was stored in a dark place, and the color density decreased to about one-fourth after one hour.

Example 19 In place of 10 parts of Exemplified Compound (I[-1), Exemplified Compound (I[-1)
A mock commuter pass and a mock prepaid card were prepared in the same manner as in Example 1, except that 4 parts of I-16) and 6 parts of Exemplified Compound (II-14) were used. The obtained simulated commuter pass and simulated prepaid card had the same heat resistance and image stability as the simulated commuter pass and simulated prepaid card obtained in Example 1.
It showed repeatability characteristics.

Example 20 Exemplary compound (■-8) 1 of 200 parts of methyl ethyl ketone
After dissolving 0 parts, it was irradiated with light from a mercury-xenon lamp through a filter (UV-35, manufactured by Toshiba) to convert it into merocyanine, which is a color former. Then, the exemplified compound (II
30 parts of I-8) were added, stirred, and reacted. Methyl ethyl ketone was distilled off under reduced pressure, and the exemplified compound (If-
8) and exemplified compound (III-8), 40 parts of a reaction product was obtained. Using this, a mock commuter pass and a mock prepaid card were created in the same manner as in Example 1. The obtained simulated commuter pass and simulated prepaid card exhibited heat resistance, image stability, and repeatability characteristics equivalent to those of the simulated commuter pass and simulated prepaid card obtained in Example 1.

〔Effect of the invention〕

Since the usage permit and prepaid card of the present invention use a spiro-based compound, they have a wide coloring range and are excellent in heat resistance, light resistance, image stability, and repetition stability.

Claims (1)

[Claims] 1) A spiro-based compound as a photochromic material;
1. A utilization permit characterized by having an optically recordable moiety made of a mixture or reaction product of an aromatic hydroxycarboxylic acid with a zinc salt in which a hydroxyl group and a carboxyl group are present in adjacent positions. 2) The utilization permit according to claim 1, wherein the spiro compound is a spirobenzopyran compound and/or a spironaphthoxazine compound. 3) The spiro-based compound has the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1: substituted or unsubstituted alkyl group, R_
2, R_3: lower alkyl group, R_4 to R_7: hydrogen atom, halogen atom, nitro group,
Alkyl group, aryl group, alkoxy group, alkoxycarbonyl group, or alkylsulfonyl group, R_8 to R_1_1: hydrogen atom, halogen atom, nitro group, alkyl group, alkoxy group, aryl group, alkoxycarbonyl group, acyloxy group, or hydroxyl group. ) Spirobenzopyran compounds and/or general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R_1 to R_7: Same as above, R_1_2 to R_1_7: Hydrogen 2. The utilization permit according to claim 1, which is a spironaphthoxazine-based compound represented by a spironaphthoxazine compound represented by a halogen atom, a nitro group, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, an acyloxy group, or a hydroxyl group. 4) As a photochromic material, a spiro compound,
1. A prepaid card having an optically recordable portion made of a mixture or reaction product of a zinc salt of an aromatic hydroxycarboxylic acid in which a hydroxyl group and a carboxyl group are present in adjacent positions. 5) The prepaid card according to claim 4, wherein the spiro compound is a spirobenzopyran compound and/or a spironaphthoxazine compound. 6) The spiro-based compound has the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1: substituted or unsubstituted alkyl group, R_
2, R_3: lower alkyl group, R_4 to R_7: hydrogen atom, halogen atom, nitro group,
Alkyl group, aryl group, alkoxy group, alkoxycarbonyl group, or alkylsulfonyl group, R_8 to R_1_1: hydrogen atom, halogen atom, nitro group, alkyl group, alkoxy group, aryl group, alkoxycarbonyl group, acyloxy group, or hydroxyl group. ) Spirobenzopyran compounds and/or general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R_1 to R_7: Same as above, R_1_2 to R_1_7: Hydrogen 5. The prepaid card according to claim 4, which is a spironaphthoxazine compound represented by an atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, an acyloxy group, or a hydroxyl group.