JP3053141B2 - 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, etc., and more particularly, to a magnetic recording layer having good water resistance and high temperature and high humidity. The present invention relates to a thermosensitive recording type magnetic ticket sheet in which no blocking occurs and the desensitization of a thermosensitive layer is good.

[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 disadvantage that it desensitizes the heat-sensitive recording layer and causes the magnetic recording layer and the heat-sensitive recording layer to stick together at high temperature and high humidity, which is liable to cause so-called blocking. 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. Further, tickets such as a ticket may be wet with water such as rain, and water resistance is also required. For this reason, even if other properties were good, if the blocking property, desensitization and water resistance were poor, it was not used for a thermosensitive recording type magnetic ticket sheet.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a heat-sensitive recording type magnetic ticket sheet which has good water resistance, 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. The purpose is to provide.

[0005]

The present inventors have conducted intensive studies to solve these problems, and as a result, have found that styrene-acrylic acid in which the ester group is an alkyl having 3 to 12 carbon atoms as an aqueous binder for the magnetic recording layer. By using an ester copolymer, preferably a styrene-2-ethylhexyl acrylate copolymer, the weight average molecular weight is more preferably 10
The ferromagnetic powder contains 10,000 to 1.5 million polyethylene oxide in an amount of 1% to 15% by weight, and is dispersed with a polyvinyl alcohol-based dispersant. It has been found that a good thermosensitive recording type magnetic ticket sheet can be obtained by using a certain metal stearate.

It is not clear why the use of a specific styrene-acrylate copolymer improves the water resistance of the magnetic recording layer, the blocking property with the heat-sensitive recording layer, and the desensitization, but the hardness of polystyrene is low. It is presumed that this is a synergistic effect of the hygroscopic property and the property of high flexibility and wet strength due to a moderately low glass transition temperature of the polyacrylate having an ester group of alkyl having 3 to 12 carbon atoms. When the number of carbon atoms is 2 or less or 13 or more, the glass transition temperature increases and the effect is reduced. Metal stearates dispersed with a polyvinyl alcohol-based dispersant are effective in preventing blocking, and acrylate, acrylamide, cellulose, sulfonic, and aliphatic amine dispersants are effective. I can't. 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 1% by weight of the ferromagnetic powder.
If the content is less than 1% by weight, a sufficient blocking improving effect cannot be obtained. Although there is no particular upper limit, the improvement of the blocking-improving effect is small even when the content is 30% by weight or more of the ferromagnetic powder. 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 narrower particle size distribution range is better, but a ball mill, a sand mill, a dyno mill, an attritor, a colloid mill, or the like can be used as a disperser for obtaining a preferable particle size. Also, liquefaction of stearic acid metal salt at high temperature,
A method is also preferable in which the emulsion is emulsified and then the temperature is lowered to obtain a dispersion having an appropriate particle size. Examples of the metal of the metal stearate include zinc, calcium, magnesium and the like.
Polyethylene oxide improves the magnetic stability by improving the dispersion stability of the ferromagnetic powder, but has a weight average molecular weight of 1
If it is smaller than 100,000 or less than 1% by weight of the ferromagnetic powder, the effect of dispersion stability is small.
If the amount is more than 5% by weight, the suitability for coating on the support will be poor.

In the magnetic recording layer of the present invention, a ferromagnetic powder and a copolymer of a specific acrylate ester and styrene are used as main components. Polyurethane, vinyl acetate, vinyl chloride, polyacryl, styrene A water-soluble or water-dispersible aqueous binder such as butadiene may be used in combination. or,
In addition to the polyethylene oxide and the metal stearate of the present invention, a dispersant, a wax, an antifoaming agent, and other additives are appropriately used. The magnetic ticket sheet can be obtained by applying or printing a magnetic coating material in which these are uniformly dispersed on a support such as paper. As the polyvinyl alcohol-based dispersant for dispersing the metal stearate, polyvinyl alcohol derivatives having various degrees of saponification and polyvinyl alcohol derivatives such as cation-modified or anion-modified are used. As the ferromagnetic powder, γ ferrite, strontium ferrite, cobalt-containing ferrite and the like are used, but the coercive force is 1500 to 5 so that magnetic recording information cannot be erased by a normal magnet.
000 Oersted barium ferrite and strontium ferrite are often used. Incidentally, a polyacrylic acid-based salt or the like can be used for dispersing the magnetic powder. As the wax, paraffin wax, polyethylene wax, higher aliphatic alcohol and higher fatty acid amide 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-chlorofluoran, 3-diethylamino-7-cyclohexylamino Fluoran, 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) aminofluoran, 3-diethylamino- 7-dibenzylaminofluoran, 3-cyclohexylamino-
6-chlorofluorane, 3-diethylamino-6-methyl-7-xylidinofluoran, 2-anilino-3-methyl-6- (N-ethyl-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.

As the acidic substance, 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 acid 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 phenol resin, halogenated novolak phenol resin, α-naphthol, β
Naphthol, 3,5-di-t-butylsalicylic acid,
3,5-di-α-methylbenzylsalicylic acid, 3-methyl-5-t-butylsalicylic acid, monoanilide phthalate paraethoxybenzoate, bis (4-hydroxyphenyl) sulfone, 4-hydroxy-4′-isopropyloxy Diphenylsulfone, di- (3-allyl-4-
(Hydroxyphenyl) sulfone, parabenzyloxybenzoic acid, benzyl parahydroxybenzoate and the like 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-1,3,3
7-triisocyanate, biphenyl-2,4,4'-
Triisocyanate, 4,4 ', 4 "-triisocyanate-2,5-dimethoxytriphenylamine, p-dimethylaminophenyl isocyanate, etc. These isocyanate groups may be phenols, lactams, oximes as required. The compound may be used in the form of a blocked isocyanate or a diisocyanate, which is an addition compound with, etc. However, when all the isocyanate groups are blocked, the effect may not be exhibited.

The imino compounds include 3-iminoindoline-1-one, 3-imino-4,5,6,7-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 -Isoindolin-1-one, 1-ethoxy-3-iminoisoindoline, 1,3-diiminoisoindoline, 1,3-diimino-4,5,6,7-
Tetrachloroindoline, 1,3-diimino-6-methoxyisoindoline, 1,3-diimino-6-cyanoisoindoline, 1,3-diimino-4,7-dithia-
5,5,6,6-tetrahydroisoindoline, 1-
Iminonaphthalimide, 1-iminodiphenimide, 1- (5 ′, 6′-dichlorobenzothiazolyl-
2′-imino) -3-iminoisoindoline, 1-
(6'-methylbenzothiazolyl-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
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 can be 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 mainly used. Synthetic paper, metal foil, laminated paper of polyethylene or the like, film of polyethylene terephthalate or the like, alone or in combination Sheet can also be used. The equipment used for coating the magnetic recording layer, thermal recording layer, and protective layer is an air knife coater, gravure coater, roll coater,
Rod coaters, curtain coaters, die coaters, lip coaters, blade coaters, 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 or the like can be 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 Co., Ltd.) (solid) 100 parts Acrylic dispersant (Aron T40, manufactured by Mitsui Toatsu Co., Ltd.) (solid) 1 part Styrene-2-ethylhexyl acrylate copolymer (solid) 30 parts polyethylene Oxide (manufactured by Sumitomo Seika Co., Ltd., weight average molecular weight 200,000) (solid) 5 parts Zinc stearate (polyvinyl alcohol dispersion, volume average particle diameter 0.9μ) (solid) 10 parts Water (solid) 200 parts

Preparation of Thermal Sensitive Recording Layer Coating Solution (A) Liquid 3-Dibutylamino-6-methyl-7-anilinofluoran (solid) 12 parts 10% aqueous solution of polyvinyl alcohol (NM11, manufactured by Nippon Synthetic Chemical Company) (solid 1.8 parts) 18 parts water 30 parts (B) liquid 4,4'-isopropylidene diphenol (solid) 40 parts p-benzylbiphenyl (solid) 40 parts zinc stearate (solid) 20 parts 10% aqueous polyvinyl alcohol solution (NM11) (solid 5 parts) 50 parts water 100 parts (A) liquid and (B) liquid are separately dispersed by a sand grinder until the average particle diameter becomes about 2 μm, and the heat-sensitive layer coating liquid is mixed with the following composition. It was adjusted. Calcium carbonate (Shiroishi Kogyo Brt15) (solid) 8 parts (B) liquid 30 parts 10% polyvinyl alcohol aqueous solution (NM11) (solid 4 parts) 40 parts (A) liquid 12 parts water 100 parts

[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 The procedure of Example 1 was repeated except that the styrene-n-propyl acrylate copolymer was used instead of the styrene-2-ethylhexyl acrylate copolymer in the preparation of the coating solution for the magnetic recording layer. A recordable magnetic ticket sheet was obtained.

Example 3 Thermal recording was carried out in the same manner as in Example 1 except that a styrene-2-ethyldecyl acrylate copolymer was used in place of the styrene-2-ethylhexyl acrylate copolymer. A type magnetic ticket sheet was obtained.

Example 4 A thermosensitive recording type magnetic sheet was obtained in the same manner as in Example 1 except that the amount of polyethylene oxide was changed to 2 parts in the preparation of the coating solution for the magnetic recording layer.

Example 5 A thermosensitive magnetic sheet was obtained in the same manner as in Example 1 except that the amount of polyethylene oxide was changed to 12 parts in the preparation of the coating solution for the magnetic recording layer.

Example 6 A thermosensitive recording-type magnetic ticket sheet was obtained in the same manner as in Example 1, except that the polyethylene oxide was changed to have a weight average molecular weight of 1.2 million in preparing the coating solution for the magnetic recording layer.

Example 7 In the preparation of the coating solution for the magnetic recording layer of Example 1, the heat sensitivity was the same except that the polyvinyl alcohol-dispersed zinc stearate having a volume average particle diameter of 2.0 μm was used instead of 0.9 μm. A recordable magnetic ticket sheet was obtained.

Example 8 A heat-sensitive recording type magnetic ticket sheet was obtained in the same manner as in Example 1 except that polyethylene oxide was removed and the amount of water was changed to 160 parts in preparing the magnetic recording layer coating solution.

Example 9 In preparing the coating solution for the magnetic recording layer of Example 1, polyethylene oxide and zinc stearate were removed, and the amount of water was adjusted to 160.
In the same manner except for the above, a thermosensitive recording type magnetic ticket sheet was obtained.

Example 10 After the heat-sensitive recording layer of Example 1 was applied, an aqueous solution of polyvinyl alcohol (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 11 A thermosensitive recording-type magnetic ticket sheet was obtained in the same manner as in Example 1, except that the following composition was adjusted instead of the heat-sensitive recording layer coating solution of Example 1, and the heat-sensitive recording layer was coated. . 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 heat-sensitive recording type magnetic ticket sheet was obtained in the same manner as in Example 1, except that an aqueous polyurethane resin was used instead of the styrene-2-ethylhexyl acrylate copolymer in preparing the coating solution for the magnetic recording layer. Was.

Comparative Example 2 A thermosensitive recording type was prepared in the same manner as in Example 1 except that a styrene-ethyl acrylate copolymer was used instead of the styrene-2-ethylhexyl acrylate copolymer in preparing the coating solution for the magnetic recording layer. A magnetic ticket sheet was obtained.

Comparative Example 3 A heat-sensitive material was prepared in the same manner as in Example 1 except that a styrene-n-tetradecyl acrylate copolymer was used in place of the styrene-2-ethylhexyl acrylate copolymer. A recordable magnetic ticket sheet was obtained.

As described above, Examples 1 to 11 and Comparative Examples 1 to 3
Was evaluated by the following method. Table 1 shows the evaluation results. (Squareness 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 superimposed under the conditions of 50 ° C. and 90% RH, and a pressure of 1 kg / cm ² is applied 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 were superposed under the conditions of 50 ° C. and 90% RH.
g / cm ² and left overnight. The heat-sensitive layer of the sheet before and after the treatment is colored by heating, and a comparison is made to evaluate a decrease in the coloring density. ○: no difference before and after treatment, Δ: slight difference before and after treatment,
X: The difference between before and after the treatment was large. (Water resistance) The sample was immersed in water at 20 ° C., taken out one minute later, and the magnetic recording layer was rubbed with gauze to evaluate the degree of contamination. ：: Almost no dirt, Δ: Stained but usable, ×: Excessive dirt. The volume average particle diameter was measured by Microtrac (manufactured by Nikkiso, laser diffraction method measuring instrument).

[0035]

[Table 1]

[0036]

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

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G11B 5/80 B41M 5/18 Z // G06K 19/06 G06K 19/00 BC (56) References JP-A-6-215352 (JP, A) JP-A-5-24388 (JP, A) JP-A-4-2711009 (JP, A) JP-A-52-155506 (JP, A) JP-A-53-4506 (JP, A) Kaisho 53-4509 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G11B 5/702 G11B 5/708 G11B 5/80 B41M 5/26 B42D 15/10 541 C09D 133 / 08

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 a copolymer of acrylate and styrene, wherein the ester residue is alkyl having 3 to 12 carbon atoms, is used as an aqueous binder of the magnetic recording layer. 2. The thermosensitive recording type magnetic ticket sheet according to claim 1, wherein a copolymer of 2-ethylhexyl acrylate and styrene is used as an aqueous binder of the magnetic recording layer. 3. The ferromagnetic powder according to claim 1, wherein the magnetic recording layer contains polyethylene oxide having a weight-average molecular weight in the range of 100,000 to 1,500,000 based on 1% to 15% by weight of the ferromagnetic powder. The thermosensitive recording type magnetic ticket sheet described in the above. 4. A method for dispersing a metal stearate having a volume average particle diameter in a range of 0.5 μm to 2.5 μm by a laser diffraction method, dispersed in a magnetic recording layer with a polyvinyl alcohol-based dispersant, to obtain a ferromagnetic powder. 4. The thermosensitive recording type magnetic ticket sheet according to claim 1, wherein the content is 1% by weight or more.