JP2801733B2 - Thermal recording type magnetic ticket sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application The present invention relates to a thermosensitive recording type magnetic ticket sheet useful for a ticket, a coupon, a commuter pass, etc. The present invention relates to a thermosensitive recording type magnetic ticket sheet which does not curl even when humidity changes, has excellent dimensional stability, and has excellent magnetic characteristics and heat-sensitive characteristics.

(B) Conventional Art Conventionally, automatic sales and automatic ticket gates of tickets, such as tickets, coupons, and commuter passes, have been promoted. The tickets used at that time are provided with a magnetic recording layer on one side of a support and a recording layer of an electrophotographic type, an electrostatic recording type, a diazo copying type, a chelate type or the like on the other side. However, these systems increase the complexity and size of the apparatus and increase the cost. In order to improve these drawbacks, a thermal recording system using a dye precursor and an acidic substance has come to be used. However, in particular, coupons and commuter passes have a long validity period. During this period, they are stored in a wallet or a regular bag. However, the thermal recording method uses a plasticizer (dioctyl phthalate, dioctyl adipate, etc.) existing in the resin film to erase the colored portion. Color occurs.

In order to prevent discoloration by the plasticizer, a protective layer of a water-soluble polymer compound, an organic solvent-based organic resin, or the like is provided on the thermosensitive coloring layer. By performing this process, the difference in the thermal shrinkage between the heat-sensitive recording layer and the magnetic recording layer is further widened, and the curl of the heat-sensitive recording type magnetic ticket sheet after the coating step and the drying step is increased. This causes a problem in the running performance of the vehicle. Especially when the support of the magnetic ticket sheet is paper, it is widely used because it is inexpensive as compared with plastic sheets such as polyethylene terephthalate sheet and vinyl chloride sheet. Problems are likely to occur.
As a countermeasure, a method has been proposed in which a polyolefin resin layer is provided on both sides of a support, and then a magnetic recording layer is provided on one side and a heat-sensitive recording layer is provided on the other side. (Open Utility Model Showa 64-
50974). However, especially when paper is used as the support, if the polyolefin resin layer is provided on both sides, then the magnetic recording layer, the heat-sensitive recording layer, and the protective layer are applied and dried. As the moisture contained in the base paper evaporates, drying wrinkles are more likely to occur due to the internal pressure, and the coated surface becomes rougher.

(C) Problems to be Solved by the Invention The present invention suppresses the occurrence of curl during the manufacturing process of a thermosensitive recording type magnetic ticket sheet, and reduces the dimensional stability with respect to a change in humidity. It is intended to improve the magnetic properties and the heat sensitivity by smoothing the coated surface.

(D) Means for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have found that a styrene-butadiene-based latex layer having a gel content of 5 to 65% is provided on both sides of the base paper. After that, a magnetic recording layer is provided on one side and a heat-sensitive recording layer is provided on the other side, and in some cases, the above problem can be solved by providing a protective layer on each recording layer. The invention has been reached.

Gel content of styrene / butadiene latex is 65
If it is more than 5%, dry wrinkles and roughness of the coated surface are conspicuous and 5%
If the amount is less, the coating layer strength is weak and troubles in the production process are likely to occur.

A white pigment, for example, calcium carbonate, kaolin, talc, calcined kaolin, silica, urea resin, polystyrene resin and the like can be added to the styrene / butadiene latex layer of the present invention. In this case, the addition amount is preferably 30% or less by weight. However, the styrene / butadiene-based latex layer below the heat-sensitive recording layer may contain a highly oil-absorbing pigment up to about 70 to 80% of the latex layer in relation to heat-sensitive properties. In addition, starch, cellulose derivatives, water retention agents such as acrylic resins, inorganic peroxides, organic peroxides, phenolic resins, amino resins, aldehyde compounds, epoxy compounds, boric acid, phosphorus compounds, zirconium compounds, silane compounds, etc. A crosslinking agent or the like can be added as needed. The thickness of the styrene / butadiene latex layer is preferably 3 to 15 μm on one side.

In some cases, a layer containing a latex and a pigment as main components is further provided between the styrene / butadiene-based latex layer and the heat-sensitive recording layer. In such a case, the latex having the gel content of the present invention is preferable.

The magnetic recording layer of the present invention, the magnetic powder is a polyester resin,
It is formed by applying or printing a paint uniformly dispersed in a binder such as a vinyl chloride resin, a polyurethane resin, and a styrene / butadiene copolymer resin on the styrene / butadiene latex layer. As magnetic powder, γFe ₂ O ₃ ,
Ferromagnetic materials such as barium ferrite and strontium ferrite are used, but in order to prevent troubles in which magnetically recorded information is erased by ordinary permanent magnets, barium ferrite and strontium ferrite with a coercive force of 1500 to 5000 Oe are used. Is used. A protective layer such as a nitrocellulose or polyurethane resin layer can be further applied or printed on the magnetic recording layer.

As the colorless or pale color dye precursor, acidic substance and binder used in the heat-sensitive recording layer of the present invention, those conventionally known are used.

The dye precursor used in the heat-sensitive recording layer includes (1) crystal violet lactone (2) 3-indolino-3-p-dimethylaminophenyl-6-dimethylaminophthalide (3) 3-diethylamino-7-chlorofluoran (4) 3-diethylamino-7-cyclohexylaminofluoran (5) 3-diethylamino-5-methyl-7-t-butylfluoran (6) 3-diethylamino-6-methyl-7-anilinofluoran (7 ) 3-Diethylamino-6-methyl-7-p-butylanilinofluoran (8) 2- (N-phenyl-N-ethyl) aminofluoran (9) 3-Diethylamino-7-dibenzylaminofluoran ( 10) 3-cyclohexylamino-6-chlorofluoran (11) 3-diethylamino-6-methyl-7-xy Jinofuruoran (12) 2-anilino-3-methyl-6-(N-ethyl -
p-Toluidino) fluoran (13) 3-pyrrolidino-6-methyl-7-anilinofluoran (14) 3-pyrrolidino-7-cyclohexylaminofluoran (15) 3-piperidino-6-methyl-7-toluidine Nofluoran (16) 3-piperidino-6-methyl-7-anilinofluoran (17) 3- (N-methylcyclohexylamino) -6
Methyl-7-anilinofluoran (18) 3-diethylamino-7- (m-trifluoromethylanilino) fluoran (19) 3-diethylamino-6-methyl-7-chlorofluoran (20) 3-dibutylamino -6-Methyl-7-anilinofluoran Next, typical examples of the acidic substance used in the heat-sensitive recording layer will be described.

(1) 4,4'-isopropylidene diphenol (2) 4,4'-isopropylidenebis (2-chlorophenol) (3) 4,4'-isopropylidenebis (2-tert-butylphenol) (4) 4,4'-secondary-butylidene diphenol (5) 4,4 '-(1-methyl-normal-hexylidene) diphenol (6) 4-phenylphenol (7) 4-hydroxydiphenoxide (8) methyl-4 -Hydroxybenzoate (9) Phenyl-4-hydroxybenzoate (10) 4-Hydroxyacetophenone (11) Salicylic anilide (12) 4,4'-Cyclohexylidenediphenol (13) 4,4'-Cyclohexylidenebis (2 -Methylphenol) (14) 4,4'-benzylidenediphenol (15) 4,4'-thiobis (6-tert-butyl-3)
-Methylphenol) (16) 4,4'-isopropylidenebis (2-methylphenol) (17) 4,4'-ethylenebis (2-methylphenol) (18) 4,4'-cyclohexylidenebis ( 2-isopropylphenol) (19) 2,2'-dihydroxydiphenyl (20) 2,2'-methylenebis (4-chlorophenol) (21) 2,2'-methylenebis (4-methyl-6-t-butylphenol) (22) 1,1'-bis (4-hydroxyphenol) -cyclohexane (23) 2,2'-bis (4'-hydroxyphenyl) propane (24) novolak phenolic resin (25) halogenated novolak phenolic resin (26) α-naphthol (27) β-naphthol (28) 3,5-di-t-butylsalicylic acid (29) 3,5-di-α-methylbenzylsalicylic acid (30) 3-methyl-5-t- Butyl Lylic acid (31) phthalic acid monoanilide paraethoxybenzoic acid (32) bis (4-hydroxyphenyl) sulfone (33) 4-hydroxy-4'-isopropyloxydiphenylsulfone (34) di- (3-allyl-4- (Hydroxyphenyl) sulfone (35) parabenzyloxybenzoic acid (36) benzyl parahydroxybenzoate The coating solution for the heat-sensitive recording layer of the present invention can be obtained by the following method. That is, the acidic substance, the dye precursors that develop color with the acidic substance are separately or simultaneously pulverized and dispersed in fine particles by a pulverizer, mixed with a binder, a pigment, and the like, and by adding various additives as necessary. Adjust the coating liquid.

Examples of the binder include water-soluble binders such as starches, hydroxyethylcellulose, methylenecellulose, polyvinyl alcohol, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, polyacrylamide, carboxymethylcellulose, gum arabic, and casein. And latexes such as styrene-butadiene latex.

Examples of the pigment include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, and urea-formalin resin.

In addition, zinc stearate, higher fatty acid metal salts such as calcium stearate, paraffin, paraffin oxide,
Waxes such as polyethylene and polyethylene oxide, wetting agents such as dioctyl sulfosuccinate, ultraviolet absorbers such as benzophenone and benzotriazole, surfactants, fluorescent dyes and the like are used. When a protective layer is provided on the heat-sensitive recording layer of the present invention, an aqueous resin is preferable from the viewpoint of preventing coloring with the dye precursor. For example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, carboxymethyl cellulose, hydroxyethyl cellulose, and the like, and modified products thereof can be mentioned.

Paper is used as the support used in the present invention, but synthetic paper, plastic film, metal foil, etc. are used alone,
Alternatively, a combination sheet can be used.

As the apparatus used for coating the styrene-butadiene-based latex layer, the magnetic recording layer, the heat-sensitive recording layer, and the protective layer of the present invention, an air knife coater, a gravure coater, a roll coater, a rod coater, a curtain coater, a blade coater, or the like is used. In particular, in the case of a styrene / butadiene-based latex layer, a size press device and a gate roll device used in a paper making process are also used.
In addition, printing methods such as offset and silk screen are also used.

Further, in order to improve the surface smoothness of the coated product, a machine calender, a super calender, a gloss calender, brushing and the like can be used.

In addition, the following method was used for the measurement of the gel content of the present invention.

That is, a latex film is prepared by drying at room temperature, and the latex film is immersed in about 200-fold benzene, left to dissolve for 48 hours, filtered through a filter paper (# 2), and the filtrate is dried at 70 ° C. It was calculated from the sol content of the film.

(E) Action In the thermosensitive magnetic recording sheet, a styrene / butadiene latex layer having a gel content of 5 to 65% is provided on both sides of the base paper, and a magnetic recording layer is provided on one side and a thermosensitive recording layer is provided on the other side. Due to this, there are few troubles such as drying wrinkles in the manufacturing process, roughening of the coated surface, curls and troubles in dimensional stability, good running properties of recording and reproducing devices, and a magnetic recording layer and thermal recording with a latex layer. Since the layer can be prevented from penetrating into the base paper, a sheet having improved magnetic properties and heat-sensitive properties can be obtained.

(F) Example Next, the present invention will be described in detail with reference to specific examples, but the present invention is not limited thereto. In the examples, “parts” and “%” are “parts by weight” and “% by weight”, respectively.
Is shown.

Example 1 A styrene-butadiene-based latex (T202 manufactured by Nippon Synthetic Rubber Co., Ltd.) having a gel content of 28% was coated on both sides of a base paper having a basis weight of 160 g / m ^2.
8) was applied in a solid form at 5 g / m ² (per side) and dried.
This is designated as support A.

The above components were dispersed in a ball mill to prepare a magnetic recording layer coating solution.

 Subsequently, the heat-sensitive recording layer coating solution was prepared as follows.

Solution A and solution B were separately dispersed by a sand grinder until the average particle diameter became about 2 μm, and the coating solution of the heat-sensitive layer was prepared according to the following formulation.

A coating liquid for the magnetic recording layer was applied to one surface of the support A in a solid content at 30 g / m ² , and after orientation in a magnetic field, dried. Subsequently, the other surface was coated with a heat-sensitive recording layer coating solution in a solid form at 6 g / m ² , dried, and subjected to a super calendar treatment to obtain a heat-sensitive recording magnetic ticket sheet of the present invention.

Example 2 A 3 g / m ² aqueous solution of polyvinyl alcohol was applied in a solid form on the heat-sensitive recording layer of the heat-sensitive recording type magnetic ticket sheet before super-calendering in Example 1 and dried. I got a ticket sheet.

Example 3 The same procedure as in Example 1 was performed until the magnetic layer coating solution was applied and the magnetic field orientation was dried. Further, a polyurethane resin layer was applied in a solid form at 2 g / m ² and dried to provide a protective layer for the magnetic layer. Thereafter, on the other surface, a heat-sensitive recording layer was provided in the same manner as in Example 1, and a polyvinyl alcohol layer was provided on the heat-sensitive recording layer in the same manner as in Example 2.
Super calender processing was performed to obtain a thermosensitive recording type magnetic ticket sheet.

Example 4 Instead of the styrene / butadiene latex having a gel content of 28% in Example 1, styrene / gel having a gel content of 8% was used.
Butadiene latex (Sumitomo Nogatack, P-
8702) except that a heat-sensitive recording layer was provided in the same manner as in Example 1, and a polyvinyl alcohol layer was further provided on the heat-sensitive recording layer in the same manner as in Example 2; I got a sheet.

Example 5 Example 1 was repeated except that a styrene / butadiene latex having a gel content of 60% (L-1462, manufactured by Asahi Kasei Corporation) was used instead of the styrene / butadiene latex having a gel content of 28%. In the same manner as in Example 2, a heat-sensitive recording layer was provided, and a polyvinyl alcohol layer was further provided on the heat-sensitive recording layer in the same manner as in Example 2 to perform a super calendar treatment to obtain a heat-sensitive recording magnetic ticket sheet.

Comparative Example 1 A base paper having a basis weight of 160 g / m ² was directly applied without treating with a styrene / butadiene latex having a gel content of 28% in Example 1.
A magnetic recording layer and a heat-sensitive recording layer were provided in the same manner as in Example 1,
Super calender processing was performed to obtain a thermosensitive recording type magnetic ticket sheet.

Comparative Example 2 Same as Example 1 except that a styrene / butadiene-based latex having a gel content of 75% (L-1225 manufactured by Asahi Kasei Corporation) was used instead of the styrene-butadiene-based latex having a gel content of 28% in Example 1. Thus, a thermosensitive recording type magnetic ticket sheet was obtained.

Comparative Example 3 Same as Example 1 except that a styrene / butadiene latex having a gel content of 75% (L-1225 manufactured by Asahi Kasei Corporation) was used instead of the styrene / butadiene latex having a gel content of 28% in Example 1. to a coating to heat sensitive recording layer, dried, aqueous solution of polyvinyl alcohol in solid 3 g / m ² coating,
It was dried and subjected to a super calendar treatment to obtain a thermosensitive recording type magnetic ticket sheet.

The heat-sensitive recording magnetic ticket sheets obtained in the above Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 1.

(Squareness ratio) Using a BH curve tracer, the saturation magnetic flux density Bm and the residual magnetic flux density in the orientation direction of the magnetic recording layer of the sheet
Br was measured, and the ratio Br / Bm of both was determined. The larger the value, the better the dispersibility.

(Printing Density) Printing was performed on the heat-sensitive recording layer with a thermal inclinometer (manufactured by Toyo Seiki) at a temperature of 120 ° C., a pressure of 1 kg / cm ² , and a contact time of 3 sec, and the coloring density thereof was measured with a Macbeth densitometer.

(Curlability) The sheet was cut to the size of a card (54 mm x 86 mm), and the distance between the edge of the card and the lithographic plate when left on the lithographic plate for 3 hours in an environment of 20 ° C and 65% RH was measured. .

(Dimensional stability) Sheet size of card (54mm x 86mm)
After measuring the dimensions after standing at 20 ° C and 65% RH1 day and night, measuring the dimensions after leaving at 20 ° C and 85% RH1 day and night, and measuring at 20 ° C and 8%
The difference between the dimensions at 5% RH and the dimensions at 20 ° C and 65% RH is
It was divided by the size at% RH and multiplied by 100 to get the elongation (%).

(Roughness of the surface) Both sides of the heat-sensitive recording type magnetic ticket sheet sample before the super calendar were visually evaluated, and
The evaluation was made in three stages of Δ and X.

The recording sheets of Examples and Comparative Examples were prepared at the same application speed and the same drying speed.

(G) Effects of the Invention It is apparent that the thermosensitive recording type magnetic ticket sheet of the present invention has good curl properties and dimensional stability, and also has excellent print density of the square specific heat sensitive recording layer of the magnetic recording layer.

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Claims (2)

(57) [Claims] 1. A styrene / butadiene latex layer having a gel content of 5 to 65% is provided on both sides of a base paper, and a magnetic material mainly composed of a ferromagnetic powder and an aqueous binder is provided on one side of the base paper. A thermosensitive recording type magnetic sheet comprising a recording layer and a thermosensitive recording layer containing a colorless or pale color dye precursor and an acidic substance as a coloring component on the other side of the base paper. 2. The thermosensitive recording type magnetic ticket sheet according to claim 1, wherein a protective layer is provided on at least one of the magnetic recording layer and the thermosensitive recording layer.