JP3401723B2 - Magnetic ticket sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic ticket sheet which is effective for boarding tickets, coupon tickets, commuter tickets, prepaid cards, etc.
More specifically, the present invention relates to a magnetic ticket sheet that does not desensitize a thermal recording sheet that comes into contact even under high temperature and high humidity environmental conditions.

[0002]

2. Description of the Related Art Conventionally, automatic sales of tickets such as boarding tickets, coupon tickets, commuter tickets, and prepaid cards have been promoted. Tickets used at that time are often magnetic ticket sheets having a magnetic recording layer on one side of a support, but electrophotographic method, electrostatic recording method, diazo copying method, chelate on the other side. In many cases, a recording layer such as a system is provided. However, in these methods, the device is complicated and large, and the cost is high. In order to improve these drawbacks, a heat-sensitive recording method using a dye precursor and an acidic substance as a color-forming component is used, and in recent years, a color-forming component of an aromatic isocyanate and an imino compound including improvement of storage stability against organic solvents and chemicals. The heat-sensitive recording method using is also used.
These heat-sensitive recording systems are often used individually as a heat-sensitive recording sheet for labels, facsimiles, word processors, etc., and as a magnetic recording layer of a magnetic ticket sheet and a heat-sensitive recording layer of a heat-sensitive recording sheet. Have more opportunities to come into contact with each other.

Further, as the density of magnetic recording has been increased, the atomization of ferromagnetic powder has been promoted, but further dispersion stabilization is required accordingly, and it is dealt with by a binder, a thickener and the like. ing. However, these thickeners and the like, magnetic powders, binders and the like cause agglomeration, and sufficient dispersion stabilization cannot be obtained, so that the magnetic properties are inferior or the dispersion stability is good but in the thermosensitive recording layer. There is no thickener or binder that satisfies all the characteristics such as when adversely affecting. For example, polyethylene oxide has good dispersion stability,
In particular, it has a defect that the heat-sensitive recording layer is desensitized at high temperature and high humidity, and so-called blocking occurs, which causes the magnetic recording layer and the heat-sensitive recording layer to stick to each other. In particular, since a heat-sensitive recording type magnetic ticket sheet having a heat-sensitive recording layer provided on one side of a magnetic ticket sheet is handled in a roll form until it is released, the magnetic layer and the heat-sensitive recording layer facing each other in a wound state are closely attached to each other, Under high temperature and high humidity, the desensitizing substance of the magnetic recording layer is easily transferred to the heat sensitive recording layer. Therefore, even if the material having other good properties is used, the heat-sensitive recording layer cannot be used for the heat-sensitive recording type magnetic ticket sheet if the heat-sensitive recording layer is desensitized or colored, or if the blocking property is poor. As a countermeasure, for example, in order to prevent desensitization, the magnetic recording layer does not contain a plasticizer such as dioctyl phthalate or dioctyl adipate, and in order to prevent the thermal recording layer from being colored by an organic solvent that cannot be sufficiently removed by drying, A method using water as a medium has been proposed (Japanese Patent Publication No. 62-23366). In addition, a method of covering the surface of the magnetic recording layer or the surface of the heat-sensitive recording layer with a coating layer has been proposed and used. However, it is not possible to prevent sufficient desensitization of the heat-sensitive recording layer by removing the main material that is poor in desensitization or by not making direct contact with the magnetic recording layer and the heat-sensitive recording layer by these measures. Even if the desensitizing substance contained in the material is at least a magnetic ticket sheet, the desensitizing property becomes large due to migration due to drying, concentration, transformation, etc., and
Since the coating layers of the magnetic recording layer and the heat-sensitive recording layer have a limited thickness in order not to significantly reduce the magnetic characteristics and the heat-sensitive characteristics, it is considered that the desensitizing substance moves through the coating layers.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a magnetic ticket sheet having good magnetic properties and good heat-sensitive properties, which does not desensitize the heat-sensitive recording sheet even under high temperature and high humidity conditions.

[0005]

As a result of intensive studies to solve these problems, the present inventors have found that a magnetic recording layer containing a ferromagnetic powder and an aqueous binder as main components is formed on one surface of a support. In a magnetic ticket sheet provided with a thermosensitive recording layer on the other surface of the support, the nitrogen content of the compound eluted from the magnetic recording layer is 100 ml of ion-exchanged water, and the surface area of the support provided with the magnetic recording layer. Immerse a sheet of 200 cm ² for 40
When the amount of nitrogen was measured by a total nitrogen analyzer after removal of undissolved compounds from the aqueous solution that had been subjected to elution treatment by shaking with a constant temperature shaker at 10 ° C, the measured value was 1.6 ppm or less (per 1 m ^{2 of} sheet). The converted value of the amount is 80 ppm or less), more preferably 1.0 ppm or less (sheet 1 m ²
The converted value of the amount per unit is 50 ppm or less), and 10 g of water at 40 ° C. for 10 minutes from 1 g of the dry solid content of the aqueous binder.
The amount of nitrogen in the compound eluted in 0 ml is 10 ppm or less,
It is more preferably 2 ppm / m ² or less, the coating amount of the magnetic recording layer is 10 to 60 g / m ² , and even more preferably the aqueous binder is an acrylic resin, vinyl chloride-acrylic resin or vinyl chloride-vinyl acetate system. It was found that by using a resin, a magnetic ticket sheet without desensitization of the heat-sensitive recording layer can be obtained even in a hot and humid environment.

The nitrogen content of the compound eluted from the magnetic ticket sheet in water at 40 ° C. is measured as follows. 100 ml of ion-exchanged water was put into a 300 ml Erlenmeyer flask, and 200 cm ² of a sheet having a magnetic recording layer on a support was dipped into the Erlenmeyer flask.
The elution treatment is performed by shaking with a constant temperature shaker at 0 ° C. for 10 minutes. After removing the undissolved compound from the obtained aqueous solution, the nitrogen content is measured with a total nitrogen analyzer. Here, the amount of nitrogen eluted from the unit surface area of the magnetic recording layer is 80 ppm means that a sheet 1 m ² obtained by multiplying the measured value of nitrogen amount per sheet 200 cm ² by 1.6 ppm by 50
It means the value converted into the amount per hit. 100m of water at 40 ° C in 10 minutes from the magnetic ticket sheet defined as above.
The method of setting the nitrogen content of the eluted compound to l to 1.6 ppm or less (converted value per sheet 1 m ² is 80 ppm or less) can be confirmed only by actually combining various materials and measuring it as a magnetic ticket sheet. The amount of the water-eluting nitrogen compound can be reduced by a method of using a material having a small amount of water-eluting nitrogen compound by, for example, sufficiently washing the material of the support and the magnetic recording layer with water.

In the magnetic recording layer of the present invention, a ferromagnetic powder is used as a water-soluble or water-dispersible aqueous binder such as polyurethane type, vinyl acetate type, vinyl chloride type, polyacrylic type, styrene butadiene type, polyethylene oxide, It can be obtained by coating or printing a magnetic paint uniformly dispersed with carboxymethyl cellulose, metal stearate, wax and other additives on a support such as paper. As the polyvinyl alcohol-based dispersant for dispersing the metal stearate, cation-modified or anion-modified polyvinyl alcohol derivatives are used in addition to polyvinyl alcohol having various saponification degrees. As the ferromagnetic powder, γ-ferrite, barium ferrite, strontium ferrite, cobalt-containing ferrite and the like are used, but the coercive force is 1500 to 500 in order to prevent the magnetic recording information from being erased by a normal magnet.
Barium ferrite and strontium ferrite of 0 oersted are often used. A polyacrylic acid salt or the like can be used to disperse the magnetic powder. As the wax, paraffin wax, polyethylene wax, higher fatty acid alcohol, higher fatty acid amide, higher fatty acid metal salt and the like are used. The material used should be as small as possible in the amount of water-eluting nitrogen compounds. Preferably 100g of water at 40 ° C for 10 minutes from 1g of dry solids of each material
A compound having a nitrogen content of 10 ppm or less is selected, but the upper limit of the water-eluting compound nitrogen content of each material changes depending on the material composition and coating amount of the magnetic recording layer. The coating amount of the magnetic recording layer is in the range of 10 g / m ² to 60 g / m ² .

As the colorless or light-colored dye precursor, the acidic substance, the aromatic isocyanate compound, the imino compound and the binder used in the heat-sensitive recording layer of the present invention, conventionally known ones are used.

As the dye precursor, crystal violet lactone, 3-indolino 3-p-dimethylaminophenyl-6-dimethylaminophthalide, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-cyclohexylaminofluorane 3-diethylamino-5-methyl-7-t-butylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-p-butylanilinofluorane, 2- (N-phenyl-N -Ethyl) aminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6-methyl-7-xylidinofluorane, 2-anilino-3-methyl-6- (N -Echi -P-Toluidino) fluorane, 3-pyrrolidino 6-methyl-7-anilinofluorane, 3-pyrrolidino 7-cyclohexylaminofluorane, 3-piperidino 6-methyl-7-toluidinofluorane, 3-piperidino 6-methyl-7-anilinofluorane, 3 -(N-methylcyclohexylamino) -6-methyl-7-anilino) fluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3
Dibutylamino-6-methyl-7-anilinofluorane and the like are used.

As acidic substances, 4,4'-isopropylidenediphenol, 4,4'-isopropylidenebis (2-chlorophenol), 4,4'-isopropylidenebis (2-tert-butylphenol), 4 ，
4'-Secondary butylidene diphenol, 4,4 '
-(1-Methyl-normal-hexylidene) diphenol, 4-phenylphenol, 4-hydroxydiphenol, methyl-4-hydroxybenzoate, phenyl-4-hydroxybenzoate, 4-hydroxyacetophenone, salicylic acid anilide, 4,4 ' -Cyclohexylidene diphenol, 4,4'-cyclohexylidene bis (2-methylphenol), 4,4'-benzylidene diphenol, 4,4'-thiobis (6-t-butyl-3-methylphenol), 4, 4'-isopropylidene bis (2-methylphenol), 4,4'-ethylenebis (2-methylphenol), 4,4'-cyclohexylidene bis (2-isopropylphenol), 2,
2'-dihydroxydiphenyl, 2,2'-methylenebis (4-chlorophenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 1,1 '
-Bis (4-hydroxyphenol) -cyclohexane, 2,2'-bis (4'-hydroxyphenyl) propane, novolac type phenol resin, halogenated novolac type phenol resin, α-naphthol, β-naphthol, 3,5-di-t-butylsalicylic acid , 3,5-di α-methylbenzyl salicylic acid, 3-methyl-5-t-
Butyl salicylic acid, phthalic acid monoanilide paraethoxybenzoic acid, bis (4-hydroxyphenyl) sulfone, 4-hydroxy-4'-isopropyloxydiphenyl sulfone, di (3-allyl-4-hydroxyphenyl) sulfone, parabenzyloxybenzoic acid, parahydroxy Benzoic acid benzyl ester and the like can be used.

As the aromatic isocyanate compound,
2,6-dichlorophenyl isocyanate, p-chlorophenyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,
3-dimethylbenzene-4,6-diisocyanate,
1,4-Dimethylbenzene-2,5-diisocyanate, 1-methoxybenzene-2,4-diisocyanate, 1-methoxybenzene-2,5-diisocyanate, 1-ethoxybenzene-2,4-diisocyanate, diphenylether-4 4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-1,3
7-triisocyanate, biphenyl-2,4,4'-triisocyanate, 4,4 ', 4 "-triisocyanate-2,5-dimethoxytriphenylamine, p-dimethylaminophenylisocyanate and the like can be used.
These isocyanate groups may be used in the form of so-called blocked isocyanates or diisocyanates which are addition compounds with phenols, lactams, oximes, etc., if necessary, but the isocyanate groups are all blocked. If it does, the effect may not appear.

Examples of the imino compound are 3-iminoindoline-1-one, 3-imino4,5,6,7-tetrachloroisoindoline-1-one, 3-imino-4.
5,6,7-Tetrabromoindoline-1-one, 3-imino 4,5,6,7-tetrafluoroisoindoline-1-one, 3-imino 5,6-dichloroisoindoline-1-one, 3-imino 4,5 7-Trichloro-6-methoxy-isoindoline-1-one, 1-ethoxy-3-iminoisoindoline, 1,3-diiminoisoindoline, 1,3-diimino4,5,6,7-tetrachloroindoline, 1,3-diimino6 -Methoxyisoindoline, 1,3-diimino 6-cyanoisoindoline, 1,3-diimino 4,7-dithia 5,5,6,6-tetrahydroisoindoline, 1-iminonaphthalic acid imide, 1-iminodiphenic acid imide, 1- ( 5 ', 6'-dichlorobenzothiazolyl 2'-imino) -3-imino Soindorin, 1 over (6 'over-methyl benzothiazolinone Lu 2' Imino) -3
-Iminoisoindoline, 3-imino-1-sulfobenzoic acid imide, 3-imino-1-sulfo-6-chlorobenzoic acid imide, 3-imino-1-sulfo-5-bromonaphthoic acid imide, 3-imino-2-methyl-4,5,6,6
7-Tetrachloroisoindoline-1-one etc. can be used.

Examples of the binder include starches such as oxidized starch, phosphoric acid esterified starch, etherified starch, hydroxyethyl cellulose, methylene cellulose, polyvinyl alcohol, styrene-acryl, polyacrylamide, carboxymethyl cellulose, gum arabic and casein. Water-soluble binders and their derivatives, and latexes such as styrene-butadiene latex are used.

Examples of pigments used in the thermosensitive coloring layer include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide and urea-formalin resin. Other additives include higher fatty acid metal salts such as zinc stearate and calcium stearate, waxes such as paraffin, oxidized paraffin, polyethylene and polyethylene oxide, wetting agents such as dioctyl sulfosuccinate, benzophenone-based and benzotriazole-based additives. An ultraviolet absorber, a surfactant, a fluorescent dye, etc. are used.

When a protective layer is provided on the magnetic recording layer or the thermosensitive coloring layer of the present invention, a water-dispersible binder or a water-soluble binder is preferred in the sense of preventing color formation with the dye precursor. Examples thereof include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, carboxymethyl cellulose, hydroxyethyl cellulose, styrene-butadiene polymer, and the like, and derivatives thereof. A water resistant agent such as a crosslinking agent, an organic or inorganic pigment, etc. may be used in combination with the binder used.

Paper is used as the support on which the magnetic recording layer and the like used in the present invention are provided. Synthetic paper, metal foil, laminated paper of polyethylene or the like, film of polyethylene terephthalate or the like, alone or in combination. You can also use a sheet. As an apparatus used for coating the magnetic recording layer, the heat-sensitive recording layer and the protective layer, an air knife coater, a gravure coater, a roll coater, a rod coater, a curtain coater, a die coater, a lip coater, a blade coater and the like are used. In particular, when an undercoat is provided on the magnetic recording layer or the heat-sensitive recording layer, a size press device, a gate roll device or the like used in the paper making process of paper is also used. Also, printing methods such as offset and silk screen are used. Further, in order to improve the surface smoothness of the coated product, machine calender, super calender, gloss calender, brushing, etc. are used.

[0017]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the examples, “part” and “%” are “part by weight” and “% by weight”, and “average particle size” is “volume average particle size”. The water-eluting compound nitrogen content of the aqueous binders used in Examples 1 to 3 and Comparative Example 1 represents the nitrogen content of the compound eluting from 1 g of dry solid matter to 100 ml of water at 40 ° C. for 10 minutes.

Example 1 Preparation of Magnetic Recording Layer Coating Liquid The following composition was dispersed in a ball mill for one day to prepare a magnetic recording layer coating liquid. Barium ferrite (MC127 manufactured by Toda Kogyo Co., Ltd.) (solid) 100 parts Acrylic resin (water-eluting compound nitrogen content 0.5 ppm) (solid) 30 parts Carboxymethyl cellulose (solid) 5 parts Zinc stearate (solid) 10 parts Water 200 parts

Preparation of coating liquid for thermosensitive recording layer (A) Liquid 3-dibutylamino-6-methyl-7-anilinofluorane (solid) 12 parts 10% polyvinyl alcohol aqueous solution (NM11 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (solid 1.8) Part) 18 parts water 30 parts (B) liquid 4,4′-isopropylidenediphenol (solid) 40 parts p-benzylbiphenyl (solid) 40 parts zinc stearate (solid) 20 parts 10% polyvinyl alcohol aqueous solution (NM11) (Solid 5 parts) 50 parts Water 100 parts Liquid (A) and liquid (B) were separately dispersed by a sand grinder until the average particle size became about 2 μ, and the heat-sensitive layer coating liquid was prepared by the following formulation. Calcium carbonate (Brt15 manufactured by Shiraishi Kogyo) (solid) 8 parts (B) liquid 30 parts 10% polyvinyl alcohol aqueous solution (NM11) 40 parts (A) liquid 12 parts water 100 parts

A magnetic recording sheet coating was obtained by coating a magnetic recording layer coating liquid on one side of a high-quality paper having a basis weight of 160 g / m ^{2 in} a solid content of 30 g / m ² and aligning with a magnetic field and then drying. From the obtained magnetic ticket sheet, the amount of nitrogen due to the compound eluted in 100 ml of water at 40 ° C. in 10 minutes was 0.6 ppm (the converted value of the amount per 1 m ^{2 of} sheet was 30 ppm). Subsequently, a coating solution for the heat-sensitive recording layer is coated on the other surface of the magnetic recording layer in a solid amount of 6 g / m ² and dried,
Supercalendering was performed to obtain a magnetic ticket sheet provided with the heat-sensitive recording layer of the present invention.

Example 2 A magnetic ticket of the present invention was prepared in the same manner as in Example 1 except that a vinyl chloride-acrylic resin (water-eluting compound nitrogen content: 2 ppm) was used instead of the acrylic resin in the preparation of the magnetic recording layer coating liquid. Got the sheet. The amount of nitrogen in the obtained magnetic ticket sheet due to the compound eluted into 100 ml of water at 40 ° C. for 10 minutes was 0.84 ppm (the conversion value per sheet of 1 m ² was 4).
2 ppm).

Example 3 A magnetic ticket sheet of the present invention was prepared in the same manner as in Example 1 except that a vinyl chloride-vinyl acetate resin (water-eluting compound nitrogen content 8 ppm) was used in place of the acrylic resin in the preparation of the magnetic recording coating liquid. Got The amount of nitrogen by the eluted compound in 100 ml of water at 40 ° C. in the obtained magnetic ticket sheet for 10 minutes was 1.5 ppm (the conversion value of the amount per 1 m ^{2 of the} sheet was 75).
ppm).

Comparative Example 1 A thermal recording layer was provided in the same manner as in Example 1 except that a urethane-acrylic resin (water-eluting compound nitrogen amount: 13 ppm) was used in place of the acrylic resin in the preparation of the magnetic recording layer coating liquid. I got a magnetic ticket sheet. The amount of nitrogen due to the compound eluted into 100 ml of water at 40 ° C. for 10 minutes of the magnetic ticket sheet before providing the heat-sensitive recording layer was 2.2 ppm (sheet 1 m ²
The converted value per amount was 110 ppm).

The magnetic ticket sheets obtained in Examples 1 to 3 and Comparative Example 1 were evaluated by the following methods. The heat-sensitive recording sheet used for evaluation of desensitizing property and blocking property had a basis weight of 160.
The heat-sensitive recording layer coating liquid used in Example 1 was coated on one side of a high-quality paper of g / m ^{2 in} a solid amount of 6 g / m ² , dried, and supercalendered. The evaluation results are shown in Table 1. (Nitrogen amount) The nitrogen amount of the water-eluting compound of the magnetic ticket sheet was measured with a total nitrogen analyzer (TN-02) manufactured by Mitsubishi Kasei Co., Ltd.
It was converted to m / m ² units. (Desensitization) Under the conditions of 40 ° C. and 90% RH, the magnetic recording layer of the magnetic ticket sheet and the heat-sensitive recording layer of the heat-sensitive recording sheet are superposed on each other and a pressure of 100 g / cm ² is applied, and the mixture is left for three days and nights. The heat-sensitive recording layer of the sheet before and after the treatment was color-developed by heating at 120 ° C. for 5 seconds to evaluate the decrease in color density. In the case of a heat-sensitive recording type magnetic ticket sheet, the heat-sensitive recording layer was used. ◯: No difference before and after treatment, Δ: Some difference before and after treatment, ×: Large difference before and after treatment (squareness ratio) Using a BH curve tracer, saturation magnetic flux density Bm in the orientation direction of the magnetic recording layer of the magnetic ticket sheet And the residual magnetic flux density Br were measured, and the ratio Br / Bm between them was determined.
The larger the value, the better the dispersibility of the magnetic powder. (Blocking property) Under the conditions of 40 ° C. and 90% RH, the magnetic recording layer of the magnetic ticket sheet and the heat-sensitive recording layer of the heat-sensitive recording sheet are superposed, and a pressure of 1 kg / cm ² is applied and left for 3 days and nights. After that, the degree of peeling of the magnetic recording layer and the heat-sensitive recording layer is peeled off and evaluated below. In the case of a heat-sensitive recording type magnetic ticket sheet, the heat-sensitive recording layer was used. ○: No peeling, △: Peeling resistance, but usable, ×: Peeling

[0025]

[Table 1]

[0026]

INDUSTRIAL APPLICABILITY The magnetic ticket sheet of the present invention has almost no desensitization of the heat-sensitive recording layer, and has good blocking characteristics and magnetic characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI G11B 5/70 G06K 19/00 B (56) References JP-A-63-273213 (JP, A) JP-A-62-290576 ( JP, A) JP 61-172212 (JP, A) JP 56-156927 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B42D 15/10

Claims (3)

(57) [Claims] 1. A magnetic ticket sheet in which a magnetic recording layer containing a ferromagnetic powder and an aqueous binder as main components is provided on one surface of a support, and a heat-sensitive recording layer is provided on the other surface of the support. The nitrogen content of the compound eluted from the magnetic recording layer was 100 ml of ion-exchanged water, and the surface area was 2 when the magnetic recording layer was provided on the support.
When the amount of nitrogen was measured by a total nitrogen analyzer after removing the undissolved compound from the aqueous solution that had been subjected to the elution treatment by immersing the 00 cm ² sheet in a constant temperature shaker at 40 ° C. for 10 minutes, the measured value was 1 Water of not more than 6 ppm and water at 40 ° C. for 10 minutes from 1 g of the dry solid content of the aqueous binder.
A magnetic ticket sheet, wherein the amount of nitrogen of the compound eluted in ml is 10 ppm or less, and the coating amount of the magnetic recording layer is 10 to 60 g / m ² . ^2. A sheet having a surface area of 200 cm ² provided with a magnetic recording layer on a support is immersed in 40 ml of ion-exchanged water in which the amount of nitrogen of the compound eluted from the magnetic recording layer is 40,
When the amount of nitrogen was measured by a total nitrogen analyzer after removal of undissolved compounds from the aqueous solution which had been subjected to elution treatment by shaking with a constant temperature shaker at 10 ° C., the measured value was 1.0 ppm or less, and the aqueous binding The magnetic ticket sheet according to claim 1, wherein the amount of nitrogen of the compound eluted in 100 ml of water at 40 ° C from 1 g of the dry solid content of the agent is 2 ppm or less. 3. The magnetic ticket sheet according to claim 1, wherein the aqueous binder is an acrylic resin, a vinyl chloride-acrylic resin, or a vinyl chloride-vinyl acetate resin.