JP2907596B2 - Thermal recording type 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 thermosensitive recording type magnetic ticket sheet which is effective for a ticket, a coupon, a commuter pass and the like. More particularly, the present invention has a good blocking resistance and a reduced heat sensitive layer even under a high temperature and high humidity environment. The present invention relates to a heat-sensitive recording type magnetic ticket sheet having no feeling.

[0002]

2. Description of the Related Art Conventionally, automatic sales of tickets, such as tickets, coupons, and commuter passes, have been promoted. The tickets used at that time include a magnetic recording layer on one side of the support and an electrophotographic method, an electrostatic recording method, a diazo copying method on the other side,
A recording layer of a chelate type or the like is provided. However, these systems increase the complexity and size of the apparatus and increase the cost. In order to improve these drawbacks, a thermosensitive recording system using a dye precursor and an acidic substance as a coloring component has been used. In recent years, a coloring component of an aromatic isocyanate and an imino compound has been included, including improvement in storage stability against organic solvents, chemicals, and the like. A thermal recording method using a CRT has also been used.

[0003] Further, as the density of magnetic recording has increased, the size of ferromagnetic powder has been reduced. However, further stabilization of dispersion has been required, and a binder, a thickener, and the like have been used. ing. However, there is no thickener that satisfies all the properties, such as agglomeration of the thickener and the magnetic powder, the binder and the like, resulting in poor magnetic properties. For example, polyethylene oxide has good dispersion stability, but has the drawback of desensitizing the heat-sensitive recording layer and causing the magnetic recording layer and the heat-sensitive recording layer to stick together at high temperature and high humidity, so-called blocking occurs. I have. In particular, since the aqueous binder does not contain an organic solvent, it is beneficial for the environment, fire prevention, and human health, but tends to cause blocking. Until the heat-sensitive recording type magnetic ticket sheet is released, it is handled in a roll form, so that the magnetic layer and the heat-sensitive recording layer that face each other in the wrapped state are likely to cause blocking under high temperature and high humidity, and the desensitizing substance of the magnetic recording layer Easy to transfer to heat sensitive layer. Therefore, even if other properties were good, if the blocking property and the desensitization property were bad, it was not used for a thermosensitive recording type magnetic ticket sheet.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-sensitive recording type magnetic ticket sheet which does not cause blocking even under conditions of high temperature and high humidity, does not desensitize the heat-sensitive layer, and has good magnetic properties and heat-sensitive properties. And

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve these problems, and as a result, it is preferable that the magnetic recording layer contain a metal stearate dispersed with a polyvinyl alcohol-based dispersant. Can be obtained by adding 2% by weight or more of the ferromagnetic powder, more preferably by using zinc stearate having a volume average particle size of 0.5 μm to 2.5 μm to obtain a better thermosensitive recording type magnetic ticket sheet. I found something to be done.

[0006] Although the reason is unknown, the metal stearates dispersed in a polyvinyl alcohol-based dispersant are effective for blocking, and are useful for acrylates, acrylamides, celluloses, sulfonic acids, and aliphatic amines. No effect can be obtained with a dispersant. It is presumed that the migration of the metal stearate to the surface layer in the drying process after the magnetic recording layer is coated is different. The content of the metal stearate is preferably at least 2% by weight of the ferromagnetic powder, and if it is less than 2% by weight, a sufficient blocking improving effect cannot be obtained. Although there is no particular upper limit, it is not preferable that the weight ratio of the ferromagnetic powder in the magnetic recording layer be 50% or less, since the magnetic properties deteriorate. The volume average particle size of the metal stearic acid salt is preferably from 0.5 μm to 2.5 μm, which is preferable from the viewpoint of migration. A ball mill, a sand mill, a dyno mill, an attritor, a colloid mill and the like can be used as a dispersing machine for adjusting the metal stearate to a preferable particle size.

The magnetic recording layer of the present invention comprises a ferromagnetic powder formed of a water-soluble, water-dispersible aqueous binder such as polyurethane, vinyl acetate, vinyl chloride, polyacryl, styrene butadiene, polyethylene oxide, etc. It can be obtained by coating or printing a magnetic paint uniformly dispersed with carboxymethylcellulose, 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 degrees of saponification. As ferromagnetic powder, γ ferrite, strontium ferrite, cobalt-containing ferrite, etc. are used, but barium ferrite and strontium ferrite having a coercive force of 1500 to 5000 Oe are often used so that magnetic recording information cannot be erased by a normal magnet. Is done. Incidentally, a polyacrylic acid-based salt or the like can be used for dispersing the magnetic powder. As wax, paraffin wax, polyethylene wax, higher fatty acid alcohol,
Higher fatty acid amides are used.

Conventionally known colorless or pale color dye precursors, acidic substances, aromatic isocyanate compounds, imino compounds and binders used in the heat-sensitive recording layer of the present invention are used.

As the dye precursor, crystal violet lactone, 3-indolino 3-p-dimethylaminophenyl-6-dimethylaminophthalide, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-cyclohexylaminofluoran 3-diethylamino-5-methyl-7-t-butylfluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-p-butylanilinofluoran, 2- (N-phenyl-N -Ethyl) aminofluorane, 3-diethylamino-7-dibenzylaminofluoran, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6-methyl-7-xyridinofluoran, 2-anilinol-3-methyl-6- (N -Echi -P-toluidino) fluoran, 3-pyrrolidino 6-methyl-7-anilinofluoran, 3-pyrrolidino 7-cyclohexylaminofluoran, 3-piperidino 6-methyl-7-toluidinofluoran, 3-piperidino 6-methyl-7-anilinofluoran, 3 -(N-methylcyclohexylamino) -6-methyl-7-anilino) fluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3
Dibutylamino-6-methyl-7-anilinofluoran is used.

Examples of the acidic substance include 4,4′-isopropylidene diphenol, 4,4′-isopropylidenebis (2-chlorophenol), 4,4′-isopropylidenebis (2-tert-butylphenol), ,
4'-Secondary butylidene diphenol, 4,4 '
-(1-methyl-normal-hexylidene) diphenol, 4-phenylphenol, 4-hydroxydiphenol, methyl-4-hydroxybenzoate, phenyl-4-hydroxybenzoate, 4-hydroxyacetophenone, salicylic anilide, 4,4 '-Cyclohexylidenediphenol, 4,4'-cyclohexylidenebis (2-methylphenol), 4,4'-benzylidenediphenol, 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-isopropylidenebis (2-methylphenol), 4,4 '
-Ethylenebis (2-methylphenol), 4,4'-cyclohexylidenebis (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, novolak-type phenol resin, halogenated novolak-type phenol resin, α Naphthol, β
Naphthol, 3,5-di-tert-butylsalicylic acid,
3,5-di-α-methylbenzylsalicylic acid, 3-methyl-5-t-butylsalicylic acid, monoanilide phthalate paraethoxybenzoic acid, bis (4-hydroxyphenyl) sulfone, 4-hydroxy-4′-isopropyloxydiphenylsulfone, di (3 -Allyl-4-hydroxyphenyl) sulfone, parabenzyloxybenzoic acid, benzyl parahydroxybenzoate are used.

As the aromatic isocyanate compound,
2,6-dichlorophenyl isocyanate, p-chlorophenyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,
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, etc. These isocyanate groups If necessary, phenols, lactams, oximes and the like may be used in the form of so-called blocked isocyanate, which is an addition compound, or may be used in the form of diisocyanate, but if all isocyanate groups are blocked, The effect may not appear.

As the imino compound, 3-iminoindoline-1-one, 3-imino 4,5,6,7-tetrachloroisoindoline-1-one, 3-imino 4,
5,6,7-Tetrabromoindoline-1-one, 3-Iminnow 4,5,6,7-Tetrafluoroisoindoline-1-one, 3-Iminnow 5,6-dichloroisoindoline-1-one, 3-Iminnow 4,5 7-trichloro-6-methoxy-isoindoline-1-one, 1-ethoxy-3-iminoisoindoline, 1,3 diiminoisoindoline, 1,3 diimino 4,5,6,7-tetrachloroindoline, 1,3 diimino 6 -Methoxyisoindoline, 1,3-diiminor 6-cyanoisoindoline, 1,3-diiminor 4,7-dithiar 5,5,6,6-tetrahydroisoindoline, 1-iminonaphthalimide, 1-iminodiphenimide, 1- ( 5 ', 6'dichlorobenzothiazolyl 2'-imino) -3-imino Soindorin, 1 chromatography (6 'over-methyl benzothiazolinone Lu 2' Imino) -3
-Iminoisoindoline, 3-Imino 1-sulfobenzoic imide, 3-Imino 1-sulfo 6-chlorobenzoic imide, 3-Imino 1-sulfo 5-bromonaphthoic imide, 3-Imino 2-methyl-4,5,6,6
7-tetrachloroisoindoline-1-one and the like.

Examples of the binder include starches such as oxidized starch, phosphate esterified starch and etherified starch, hydroxyethylcellulose, methylenecellulose, polyvinyl alcohol, styrene-acryl, polyacrylamide, carboxymethylcellulose, gum arabic and casein. Latexes such as water-soluble binders and their derivatives and styrene butadiene latex are used.

Examples of the pigment 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, paraffin oxide, polyethylene and polyethylene oxide, wetting agents such as dioctyl sulfosuccinate, benzophenone-based, benzotriazole-based and the like. An ultraviolet absorber, a surfactant, a fluorescent dye and the like are used.

When a protective layer is provided on the heat-sensitive coloring layer of the present invention, an aqueous resin is preferred from the viewpoint of preventing coloring with the dye precursor. For example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, carboxymethylcellulose, hydroxyethylcellulose, styrene-butadiene-based polymer and the like, and derivatives thereof can be mentioned.

As the support on which the magnetic recording layer and the like used in the present invention are provided, paper is used. Synthetic paper, metal foil, laminated paper of polyethylene and the like, film of polyethylene terephthalate and the like are used alone or in combination. Sheets can also be used. 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 and the heat-sensitive recording layer, a size press device, a gate roll device, and the like used in a paper making process are also used. In addition, a printing method such as offset and silk screen is also used. Further, a machine calender, a super calender, a gloss calender, brushing and the like are used to improve the surface smoothness of the coated product.

[0017]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
In the examples, parts and% are parts by weight and% by weight,
The average particle diameter indicates a volume average particle diameter.

Example 1 Preparation of Coating Solution for Magnetic Recording Layer The following formulation was dispersed in a ball mill for 24 hours to prepare a coating solution for the magnetic recording layer. Barium ferrite (MC127 manufactured by Toda Kogyo KK) (solid) 100 parts Urethane-acrylic resin (solid) 30 parts Polyethylene oxide (manufactured by Sumitomo Seika) (solid) 5 parts Zinc stearate (polyvinyl alcohol dispersed average particle diameter 0. 9μ) (Solid) 10 parts Water 200 parts

Preparation of Coating Solution for Thermosensitive Recording Layer (A) Solution 12 parts of 3-dibutylamino-6-methyl-7-anilinofluoran (solid) 10% aqueous solution of polyvinyl alcohol (NM11, manufactured by Nippon Synthetic Chemical Industry) (solid 1.8) Part) 18 parts water 30 parts (B) solution 4,4'-isopropylidene diphenol (solid) 40 parts p-benzylbiphenyl (solid) 40 parts zinc stearate (solid) 20 parts 10% aqueous solution of polyvinyl alcohol (NM11) (Solid 5 parts) 50 parts water 100 parts The liquid (A) and the liquid (B) were separately dispersed by a sand grinder until the average particle diameter became about 2 μ, and the coating solution of the heat-sensitive layer was prepared by the following composition. 8 parts of calcium carbonate (Brt15 manufactured by Shiraishi Kogyo) (solid) (B) 30 parts of 10% aqueous solution of polyvinyl alcohol (NM11) 40 parts (A) 12 parts of water 100 parts of water

[0020] and then dried field orientation was 30 g / m ² coated with a solid basis weight 160 g / m ² of the magnetic recording layer coating solution on one side of the paper fraction. Subsequently, the heat-sensitive recording layer coating solution was solid-coated on the other surface at 6 g / m ^2.
Coating, drying and super calendering were performed to obtain a thermosensitive recording type magnetic ticket sheet of the present invention.

Example 2 A thermosensitive recording magnetic ticket sheet was prepared in the same manner as in Example 1 except that the amount of zinc stearate was changed to 2 parts (2% by weight of the ferromagnetic powder) in the preparation of the coating solution for the magnetic recording layer. I got

Example 3 A thermosensitive magnetic sheet was prepared in the same manner as in Example 1 except that the amount of zinc stearate was changed to 30 parts (30% by weight of the ferromagnetic powder) in the preparation of the magnetic recording coating solution. Obtained.

Example 4 A heat-sensitive recording magnetic ticket sheet was prepared in the same manner as in Example 1 except that calcium stearate (polyvinyl alcohol dispersion average particle size: 0.9 μm) was used instead of zinc stearate in preparing the coating solution for the magnetic recording layer. I got

Example 5 In the preparation of the coating solution for the magnetic recording layer of Example 1, zinc stearate dispersed in polyvinyl alcohol had an average particle diameter of 0.9.
A thermosensitive recording magnetic ticket sheet was obtained in the same manner except that 0.4 μ was used instead of μ.

Example 6 In the preparation of the coating solution for the magnetic recording layer of Example 1, zinc stearate dispersed in polyvinyl alcohol had an average particle diameter of 0.9.
A heat-sensitive recording type magnetic ticket sheet was obtained in the same manner except that 2.2 μ was used instead of μ.

Example 7 In the preparation of the coating solution for the magnetic recording layer of Example 1, zinc stearate dispersed in polyvinyl alcohol had an average particle diameter of 0.9.
A thermosensitive recording-type magnetic ticket sheet was obtained in the same manner except that 3.0 μ was used instead of μ.

Example 8 After the heat-sensitive recording layer of Example 1 was applied, an aqueous polyvinyl alcohol solution (NM11, manufactured by Nippon Synthetic Chemical Company) was applied on the layer.
Was overcoated with 2 g / m ² as a solid, and then subjected to surface treatment in the same manner.

Example 9 A heat-sensitive recording type magnetic ticket sheet was obtained in the same manner as in Example 1 except that the heat-sensitive recording layer was coated in the same manner as in Example 1 except that the heat-sensitive recording layer was coated in the following manner. . 1,3'-diimino 4,5,6,7-tetrachloroisoindoline 15 parts 4,4 ', 4 "-triisocyanate-2,5-dimethoxytriphenylamine 10 parts stearamide 5 parts 2-methoxy-5-N , N-diethylsulfamoylaniline 0.5 part Polyvinyl alcohol 20 parts Calcium carbonate 30 parts Zinc stearate 10 parts

Comparative Example 1 A thermosensitive recording type magnetic ticket sheet was obtained in the same manner as in Example 1 except that zinc stearate was omitted in preparing the coating solution for the magnetic recording layer.

Comparative Example 2 A heat-sensitive material was prepared in the same manner as in Example 1 except that zinc stearate (average particle diameter: 0.9 μm) dispersed in polyacrylamide was used in place of polyvinyl alcohol in preparing the coating solution for the magnetic recording layer. A recordable magnetic ticket sheet was obtained.

Comparative Example 3 A thermosensitive recording type magnetic material was prepared in the same manner as in Example 1 except that zinc stearate dispersed in methylcellulose (average particle size: 2.2 μm) was used instead of polyvinyl alcohol in preparing the coating solution for the magnetic recording layer. I got a ticket sheet.

The heat-sensitive recording magnetic ticket sheets obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated by the following methods. Table 1 shows the evaluation results. (Rectangular Ratio) Using a BH curve tracer, the saturation magnetic flux density Bm and the residual magnetic flux density Br in the orientation direction of the magnetic recording layer of the sheet 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) The magnetic recording layer and the thermosensitive recording layer of the thermosensitive recording type magnetic ticket sheet are overlapped under the conditions of 50 ° C. and 90% RH, and a pressure of 1 kg / cm ² is applied thereto and left overnight. Thereafter, the degree of peeling of the magnetic recording layer and the heat-sensitive recording layer is evaluated below. ：: No peeling, Δ: Slight peeling, but usable ×: Peeling, (Desensitization) The magnetic recording layer and the thermosensitive recording layer of the thermosensitive recording type magnetic ticket sheet are superposed under the conditions of 50 ° C. and 90% RH. 10
A pressure of 0 g / cm ² is applied and left overnight. The heat-sensitive layer of the sheet before and after the treatment was colored by heating, and a comparison was made to evaluate a decrease in the coloring density. ○: no difference before and after treatment, Δ: slight difference before and after treatment, ×: large difference before and after treatment. The volume average particle diameter is measured by Microtrac (manufactured by Nikkiso, laser diffraction method measuring instrument).

[0033]

[Table 1]

[0034]

The heat-sensitive recording type magnetic ticket sheet of the present invention has good blocking properties, no desensitization of the heat-sensitive layer, and excellent magnetic properties and heat-sensitive properties.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) B42D 15/10 541 B41M 5/26 G11B 5/80

Claims (4)

(57) [Claims] 1. A heat-sensitive recording type magnetic sheet having a magnetic recording layer comprising a ferromagnetic powder and an aqueous binder as main components on one surface of a support and a heat-sensitive recording layer on the other surface. A heat-sensitive recording magnetic ticket sheet, wherein the magnetic recording layer contains a metal stearate dispersed with a polyvinyl alcohol-based dispersant. 2. The thermosensitive recording type magnetic ticket sheet according to claim 1, wherein the content of the metal stearate is 2% by weight or more of the ferromagnetic powder. 3. The thermosensitive recording magnetic ticket sheet according to claim 2, wherein the volume average particle diameter of the metal stearic acid salt measured by a laser diffraction method is in the range of 0.5 μm to 2.5 μm. 4. The thermosensitive recording type magnetic ticket sheet according to claim 3, wherein the metal stearate is zinc stearate.