JPH046935Y2 - - Google Patents

Description

[Detailed explanation of the idea]

The present invention relates to a heat-sensitive recording type magnetic ticket paper used for train tickets and the like. Conventional thermosensitive magnetic tickets have a magnetic recording layer on one side of a support, and a thermosensitive coloring layer on the other side containing a coloring component consisting of a usually colorless or light-colored leuco dye and an acidic substance that causes the leuco dye to develop color when heated. There are also those with improved storage stability by providing a protective layer containing a water-soluble resin as a main component on the heat-sensitive coloring layer. However, the former is limited to plasticizers and other chemicals (e.g. alcohol,
It is not used for coupon tickets, commuter passes, cash vouchers, etc. that require long-term shelf life, as the printed area may fade or the non-printed area may develop color due to water, oil). In addition, in order to improve shelf life, the latter has a protective layer to prevent penetration of chemicals, so the absorption of stamp ink, etc. is extremely poor, and therefore stamp ink used for in-vehicle inspection tickets does not dry out. They tend to stain passengers' hands and clothes, or get stuck on ticket gates, causing trouble. This invention improves the imprintability, which is the drawback mentioned above, and
Furthermore, by containing a coloring component in the ink absorbing layer, a decrease in print density due to concealment is prevented, and the present invention relates to a heat-sensitive recording ticket paper that has both preservability and imprintability. That is, the present invention provides a magnetic recording layer mainly composed of a ferromagnetic material and a binder on one side of a support, and a normally colorless or light-colored leuco dye on the other side and an acidic substance that causes the leuco dye to develop color when heated. a heat-sensitive color-forming layer having a color-forming component consisting of; a protective layer comprising a water-soluble polymer and a water-resistant agent for the water-soluble polymer as main components; and at least one type of inorganic pigment or organic pigment and a binder. A heat-sensitive recording type magnetic ticket paper characterized by sequentially providing absorbent layers. The heat-sensitive recording magnetic ticket paper according to claim 1, wherein the ink absorbing layer contains a normally colorless or light-colored leuco dye and an acidic substance that causes the leuco dye to develop color when heated. be. The cross-sectional structure of the heat-sensitive recording type magnetic ticket paper of the present invention is shown in the figure. As the support 1, for example, ordinary paper such as high-quality paper or medium-quality paper is used. A magnetic layer 2 is provided on the back side of this support. The magnetic layer is formed in the same manner as known magnetic ticket paper, for example γ-
A ferromagnetic powder such as Fe ₂ O ₃ and a vinyl chloride resin may be uniformly dispersed in a solvent such as toluene or methyl isobutyl ketone, and this may be applied onto a support and dried. A thermosensitive coloring layer 3 and a protective layer 4 are provided on the surface of the support 1, and an ink absorbing layer 5 is further provided thereon. The thermosensitive coloring layer is mainly composed of a colorless or light-colored leuco dye, a color developer that causes the dye to develop color when heated, and a binder such as a water-soluble resin. The leuco dyes used here include conventional triphenylmethane-based, fluoran-based,
Phenothiazine-based, auramine-based, and spiropyran-based ones are preferably applied. Specific examples of these leuco dyes are shown below. 3.3-bis(p-dimethylaminophenyl)-6-
Dimethylaminophthalide, 3-diethylamino-
6-Methyl-7-anilinofluorane, 3-(N
-ethyl-N-paratolylamino)-6-methyl-7-anilinofluorane, 3-pyrrolidino-
6-Methyl-7-anilinofluorane, 3-(N
-Methyl-N-cyclohexylamino)-6-methyl-7-anilinofluorane, 3-piperidino-7-pyrrolidinofluorane, 3-dibutylamino-7-o-chloroanilinofluorane, 3-diethylamino- 7-(N-metatrifluoroanilino)-fluorane, 3-diethylamino-7-
o-chloroanilinofluorane, 3-(N-methyl-N-isoamylamino)-6-methyl-7-
Anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane. As the color developer, various electron-accepting substances that react with the leuco dye to develop color when heated are used. Specific examples thereof include 4,4'-isopropylidene diphenol (bisphenol A), 4.4'-cyclohexylidene diphenol,
4.4'-sec-butylidene diphenol, 4.4'-isopropylidene bis(2-tert-butylphenol), 4-phenylphenol, 4.4'-thiobis(1-methyl-4-t-butylphenol),
2.2'-methylenebis(4-ethyl-6-t-butylphenol), 4-hydroxyacetophenone,
Examples include benzoic acid, p-hydroxybenzoic acid benzyl ester, 2-hydroxy-p-toluic acid, and the like. Pigments, thermofusible substances, etc. can be added to the heat-sensitive coloring layer as necessary. Examples of pigments include calcium carbonate, magnesium carbonate, talc, silica, titanium oxide, zinc oxide, barium sulfate, and water. aluminum oxide, magnesium hydroxide,
Examples include inorganic pigments such as aluminum silicate, and organic pigments such as fluororesins and urea-formalin resins. Examples of thermofusible substances include waxes such as carnauba wax, beeswax, montan wax, and paraffin wax, polyhydric alcohol esters of higher fatty acids, higher fatty acid amides, aromatic amides, higher straight chain alcohols, and higher fatty acids. metal salts and the like. In the heat-sensitive coloring layer, a binder is used as necessary to bind components such as leuco dyes and color developers to the support. Examples include binders. Starch and its modified products, casein, gelatin, cellulose, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, polyvinylpyrrolidone,
Polyacrylamide, polyacrylic acid, alkali salts of styrene-maleic anhydride copolymers, alkali salts of isobutylene-maleic anhydride copolymers.
Further, if necessary, a water-dispersible polymer resin can be used in combination with the water-soluble resin. Typical water-dispersed polymer resins include polyvinyl acetate, vinyl chloride/vinyl acetate copolymer, polyurethane, polyacrylic ester, styrene/butadiene/acrylic copolymer, polyester, etc. . In the present invention, a protective layer containing a water-soluble resin as a main component is formed on the heat-sensitive coloring layer, and the water-soluble resin described above can be used as the water-soluble resin in this case. In addition, generally known water resistant agents can be added to improve water resistance. The pigments and thermofusible substances described above can be added to the protective layer on the heat-sensitive coloring layer, if necessary. Furthermore, in the present invention, an ink absorbing layer made of a pigment and a binder is provided on the protective layer, and the above-mentioned pigment is used as the pigment, and the above-mentioned water-soluble resin is used as the binder. Further, a thermosensitive color forming component can be added to the ink absorbing layer for the purpose of increasing print density. In this case, a coloring component consisting of the above-mentioned colorless or light-colored leuco dye and the above-mentioned color developer is used. Next, the present invention will be specifically explained using Examples and Comparative Examples. Example 1 The following ingredients were dispersed with a paint conditioner for 1 hour to form a magnetic layer coating solution, and the dry coating amount was 40g/
A magnetic layer was provided by coating and drying the magnetic layer on a base paper (basis weight: 157 g/m ² ) so as to form ^a magnetic layer. Magnetic layer coating liquid Magnetic powder (γ-Fe ₂ O ₃ ) 100 parts by weight PVC-vinyl acetate copolymer resin 30 Toluene 120 Methyl ethyl ketone 100 Ethyl acetate 10 Next, mix each of the following compositions with a paint conditioner. Time dispersed, A liquid, B liquid, C
A liquid was prepared. A Liquid Bisphenol A 10 parts by weight Calcium carbonate 5 10% polyvinyl alcohol aqueous solution 15 Water 30 B Liquid 3-(N-ethyl-N-isoamyl)amino-
6-Methyl-7-anilinofluorane 5 parts by weight Methylolamide 5 〃 10% polyvinyl alcohol aqueous solution 5 〃 Water 5 〃 C Liquid calcium carbonate 50 parts by weight Dispersant 25% aqueous solution 1 〃 Water 70 〃 25 parts by weight of the above liquid A, 3 parts by weight of liquid B, 9 parts by weight of liquid C, 4 parts by weight of 20% polyvinyl alcohol aqueous solution,
A heat-sensitive coloring layer coating solution was prepared by mixing and stirring 4 parts by weight of 40% styrene-butadiene latex. This coating liquid was applied to the other side of the base paper using a wire doctor so that the dry coating amount was 7 g/m ² and dried to form a heat-sensitive coloring layer, and then a 10% polyvinyl alcohol aqueous solution A protective layer was formed by applying and drying using a wire doctor so that the dry coating amount was 2 g/m ² . Further, on top of the protective layer, apply an ink absorbing layer coating solution prepared by mixing and stirring 10 parts by weight of a 20% polyvinyl alcohol aqueous solution and 19 parts by weight of the above-mentioned liquid C using a wire doctor so that the coating amount when dried is 3 g/ ^m2 . It was dried to form an ink absorbing layer. Next, surface treatment was performed using a super calender to produce a heat-sensitive recording type magnetic ticket paper according to the present invention. Example 2 A heat-sensitive recording type magnetic ticket paper of the present invention was produced in the same manner as in Example 1 except that the composition of the ink absorbing layer coating liquid was changed as follows. 50 parts by weight of liquid A 10 parts of liquid C 100 20% polyvinyl alcohol aqueous solution 100 Comparative Example 1 A thermosensitive recording magnetic ticket was prepared in the same manner as in Example 1 except that the protective layer and ink absorption layer were not provided. A paper was made. Comparative Example 2 A heat-sensitive recording magnetic ticket paper was produced in the same manner as in Example 1 except that the ink absorption layer was not provided. A plasticizer resistance test and a stampability test were conducted on the four types of heat-sensitive recording type magnetic ticket papers obtained as described above. Plasticizer resistance test
Press each seed paper onto a hot plate at a temperature of 130°C.
200g/cm ² of contact for 5 seconds to develop color, measure the color density at this time, and then apply a plastic eraser (PE-01 manufactured by Tombow Pencil Co., Ltd.) to 200g/cm ² of pressure.
The samples were left in contact with each other for 48 hours at 20°C and 65%RH, and changes in concentration were measured. The stampability test is
A seal was stamped with Shachihata Name (manufactured by Shachihata Industries), and rubbed with a finger after 30 seconds to compare the extent to which the letters remained. The test results are shown in the table.

[Table] As is clear from the table, in the ticket paper of the present invention, the decrease in color density due to the plasticizer is small, which is at a level that poses no problem in practical use, and the stamp ink absorbability is also good. As described above, since the present invention has a protective layer provided on the heat-sensitive coloring layer, it has much better preservability in terms of plasticizer resistance, oil resistance, alcohol resistance, etc. than ordinary heat-sensitive tickets. Therefore, it is suitable for use in coupon tickets, commuter passes, etc. that require long-term shelf life. In addition, since there is an ink absorbing layer on the top, it is highly absorbent for stamp ink used for in-vehicle inspection and validation, which prevents problems such as ink staining passengers' clothes or adhering to ticket gates. do not have. That is, it is possible to compensate for the drawbacks of both conventional thermal tickets and thermal tickets with improved shelf life (coupon ticket type). Furthermore, by adding a coloring component to the ink absorbing layer, it is possible to prevent a decrease in density due to the ink absorbing layer hiding the print. In this case, even if the print on the ink absorption layer is erased by a plasticizer etc., there is still print on the thermosensitive coloring layer protected by the protective layer.
Print density does not drop below a certain level. This idea can of course be applied to thermal tickets that do not have a magnetic recording layer. In addition, if applied to general heat-sensitive recording paper for facsimiles and printers, the printing performance of the recording paper will be improved, and the stamped characters will be easily erased and become unreadable by rubbing with fingers or clothes. Problems will disappear.

[Brief explanation of the drawing]

The drawing is a sectional view showing the structure of the heat-sensitive recording type magnetic ticket paper of the present invention. DESCRIPTION OF SYMBOLS 1...Support, 2...Magnetic layer, 3...Thermosensitive coloring layer, 4...Protective layer, 5...Ink absorption layer.

Claims (1)

[Claims for Utility Model Registration] (1) A magnetic recording layer mainly composed of a ferromagnetic material and a binder is provided on one side of the support, and the leuco dye, which is usually colorless or light-colored, is coated on the other side by heating. A thermosensitive coloring layer having a coloring component made of an acidic substance that causes the dye to develop color; a protective layer containing a water-soluble polymer and a water-resistant agent for the water-soluble polymer as main components; and at least one kind of inorganic pigment or organic pigment. 1. A heat-sensitive recording magnetic ticket paper, characterized in that an ink-absorbing layer consisting of a binder and a binder is sequentially provided. (2) The heat-sensitive recording magnet according to claim 1, wherein the ink absorbing layer contains a normally colorless or light-colored leuco dye and an acidic substance that causes the leuco dye to develop color when heated. ticket paper.