JPH06135155A - Thermal recording type magnetic ticket sheet - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a heat-sensitive recording type magnetic ticket sheet having good blocking resistance under high temperature and high humidity, and good storability, magnetic properties and heat-sensitive properties without desensitization of the heat-sensitive layer. [Structure] As a protective layer of a thermosensitive recording type magnetic ticket sheet having a magnetic recording layer on one surface of a support and a thermosensitive recording layer and a protective layer on the other side, the presence of a polymer latex having a glass transition temperature of 50 ° C. or lower. In addition, the main component is a water-dispersible polymer having a specific softening point obtained by polymerizing a hydrophobic vinyl-based monomer having a glass transition temperature of 55 ° C. or higher, and preferably the magnetic recording layer has a molecular weight within a specific range. Polyethylene oxide and a metal salt of stearic acid having a specific volume average particle diameter dispersed with a polyvinyl alcohol-based dispersant. More preferred is zinc stearate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive recording type magnetic ticket sheet which is effective for boarding tickets, coupon tickets, commuter tickets and the like. More specifically, it has good blocking resistance even under high temperature and high humidity environmental conditions, The present invention relates to a heat-sensitive recording type magnetic ticket sheet which is not desensitized and has good storability.

[0002]

2. Description of the Related Art Conventionally, automatic sales of tickets such as boarding tickets, coupon tickets and commuter tickets have been promoted. Tickets used at that time are magnetic recording layer on one side of the support, electrophotographic method, electrostatic recording method, diazo copying method on the other side,
A recording layer such as a chelate type 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 system using a dye precursor and an acidic substance as a coloring component has come to be used. However, in the heat-sensitive recording method, the white paper part of the heat-sensitive recording layer is colored with an organic solvent such as toluene or methyl ethyl ketone, and the color-developed part is colored by an eraser, a plasticizer such as dibutyl phthalate or dioctyl phthalate contained in vinyl chloride, etc. It may disappear, or the colored part that gets wet with water may disappear due to rubbing. In addition, when the colored area is discolored with magic ink or a fluorescent pen or the white paper area is colored, the sticking phenomenon that the thermal head and the thermal recording sheet stick to each other during the color development, or the defective coloring due to the accumulation of dust on the thermal head may occur. There is. In recent years, a protective layer has been provided on the heat-sensitive recording layer including improvement of storage stability against organic solvents, chemicals, etc., and a heat-sensitive recording system using a color-forming component of an aromatic isocyanate and an imino compound has also been used.

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, there is no thickener which satisfies all the properties such as the magnetic properties, the binder and the like agglomerating with those thickeners and the like, resulting in poor magnetic properties. For example, polyethylene oxide has good dispersion stability, but it desensitizes the heat-sensitive recording layer, and at the time of high temperature and high humidity, the magnetic recording layer sticks to the heat-sensitive recording layer or the protective layer on the heat-sensitive recording layer, so-called blocking. It has the drawback of causing it. In particular, since the aqueous binder does not contain an organic solvent, it is beneficial for the environment, fire protection and human health, but it is likely to cause blocking. Since the heat-sensitive recording type magnetic ticket sheet is handled as a roll until it is released, the magnetic layer and the heat-sensitive recording layer facing each other in the rolled-up state or the protective layer on the heat-sensitive recording layer easily cause blocking under high temperature and high humidity, The desensitizing substance of the magnetic recording layer is easily transferred to the heat sensitive layer. Therefore, even if the other properties are good, if the storage stability such as blocking property and desensitization is poor, it cannot be used for a heat-sensitive recording type magnetic ticket sheet.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a heat-sensitive recording magnetic ticket sheet which does not cause blocking under high temperature and high humidity conditions, does not desensitize the heat-sensitive layer, has excellent storage stability, and has good magnetic characteristics and heat-sensitive characteristics. The purpose is to provide.

[0005]

Means for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have found that in the presence of a polymer latex having a glass transition temperature of 50 ° C. or lower in a protective layer on a thermosensitive recording layer, A water-dispersible polymer having a softening point of 200 to 350 ° C., which is obtained by polymerizing at least one kind of hydrophobic vinyl-based monomer having a glass transition temperature of 55 ° C. or more as a main component, is preferably magnetic. The recording layer contains polyethylene oxide having a weight average molecular weight of 100,000 to 1,500,000 in an amount of 2 to 18% by weight of the ferromagnetic powder, and has a volume average particle diameter of 0.5 to 0.5 dispersed by a polyvinyl alcohol-based dispersant.
By containing 2.5 μm of stearic acid metal salt in an amount of 2% by weight or more of the ferromagnetic powder, more preferably by using zinc stearate, it is possible to obtain a heat-sensitive recording type magnetic ticket sheet having various properties. I found it.

The water-dispersible polymer used in the protective layer of the heat-sensitive recording layer of the present invention is a polymer latex in which a hydrophobic vinyl monomer is polymerized. Structurally has a core-shell structure, the core part uses a relatively soft latex,
The shell part is a relatively hard polymer, and the chemical resistance, plasticizer resistance, and water resistance of the heat-sensitive recording layer are improved in the core part by setting the softening point of the composition to a specific range. This is probably because it has an effect of improving the sticking resistance with the thermal head and the blocking resistance with the magnetic recording layer. When the glass transition temperature of the core portion is higher than 50 ° C, the thermal coloring property and printability are poor, and there is no lower limit, but the lower limit of the softening point of the water-dispersible polymer of the present invention limits the temperature, and about -30 ° C is the lower limit. Become. The glass transition temperature of the shell portion is roughly determined by the range of the softening point of the water-dispersible polymer of the present invention, but if the glass transition temperature is lower than 55 ° C., the sticking resistance and blocking resistance become poor. If the softening point of the polymer of the present invention is lower than 200 ° C, sufficient sticking resistance and blocking resistance cannot be obtained. If the temperature is higher than 350 ° C, sufficient surface strength and printability cannot be obtained. The protective layer on the heat-sensitive recording layer of the present invention may be two or more layers, in which case at least the protective layer containing the water-dispersible polymer of the present invention as the main component is provided on the uppermost layer.

The glass transition temperature of the present invention is a temperature at which a polymer changes from a glassy solid state to a rubber state, and is measured by a change in specific heat or specific volume. The specific heat and specific volume rapidly change at the transition temperature. Change. The measurement method is differential thermal analysis (DT
A method) and a differential scanning calorimetry method (DSC method) are used. The softening point is the temperature at which a material begins to deform and soften due to heating. Like the glass transition temperature, the DTA method, DS
The C method is used. When there are a plurality of peaks of the softening point measured by the DTA method and the DSC method, the highest temperature, which is the softening point of the shell portion of the polymer having a great influence on the sticking property and the blocking property, is adopted. An example of the glass transition temperature is described as a glass transition point in the "Handbook of Polymer Materials" (edited by The Polymer Society of Japan) and as a glass transition temperature in "Chemical Dictionary" (edited by the Chemistry Editorial Committee).

The polymer latex used during the polymerization of the water-dispersible polymer of the present invention is a styrene-butadiene copolymer,
Methyl Methacrylate-Butadiene Copolymer, Methyl Methacrylate-Styrene-Butadiene Copolymer, Acrylonitrile-Butadiene Copolymer, Styrene Polymer, Isoprene Polymer, Butadiene Polymer, Vinyl Acetate-Ethylene Copolymer, Vinyl Chloride Among polymers, vinylidene chloride polymers, etc., and their derivatives, the glass transition temperature is 50 ° C.
It is as follows. The hydrophobic vinyl-based monomer used at the time of polymerization of the water-dispersible polymer of the present invention is a polymer that produces a hydrophobic polymer having a glass transition temperature of 55 ° C. or higher, specifically, styrene. , Aromatic vinyl compounds such as methylstyrene, methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and isopropyl methacrylate, nitrile compounds such as acrylonitrile and methacrylonitrile, p-carbomethoxyphenyl acrylate,
Examples include acrylic compounds such as 2,4-dichlorophenyl acrylate and glycidyl methylol methacrylic acid acrylate, and vinyl chloride. Incidentally, the water-soluble vinyl-based monomer is preliminarily copolymerized with the polymer latex used in the polymerization of the water-dispersible polymer of the present invention, or is used in combination with the polymer latex and the hydrophobic vinyl monomer when polymerized. By doing so, it is possible to improve the water dispersibility of the polymer, the plasticizer resistance, and the like. Specific examples include acrylamide, methacrylamide, acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, and the like. The water-dispersible polymer of the present invention can be obtained by a conventionally known polymerization method. Examples thereof include radical polymerization using a peroxide such as ammonium persulfate and potassium persulfate, and a redox method performed by using a combination of a peroxide and a reducing agent such as sodium thiosulfate.

It is preferable to use polyethylene oxide having a specific weight average molecular weight in the content ratio within a specific range for the magnetic recording layer of the present invention because the molecular weight is less than 100,000 or the content ratio to the ferromagnetic powder. Is less than 2% by weight, the dispersion stability of the magnetic powder and the coating suitability of the magnetic recording layer coating solution are not sufficient, and the dispersion stability is achieved when the molecular weight exceeds 1.5 million or the content ratio exceeds 18% by weight. The coating property is good, but the coating suitability is poor. Although the reason is unknown, metal stearate dispersed with a polyvinyl alcohol-based dispersant is effective for blocking. Dispersion of acrylate, acrylamide, cellulose, sulfonic acid, and aliphatic amine The effect is difficult to obtain with the agent. It is supposed that the migration property of the metal stearate to the surface layer during the drying process after coating the magnetic recording layer is different. The content of the metal stearate is preferably 2% by weight or more of the ferromagnetic powder, and if it is less than 2% by weight, it is difficult to obtain a sufficient blocking improving effect in the case where the polyethylene oxide is added in a large amount. There is no upper limit, but if the weight ratio of the ferromagnetic powder in the magnetic recording layer is lower than 50%, the magnetic properties will be deteriorated, which is not preferable. The volume average particle diameter of the stearic acid metal salt is preferably 0.5 μm to 2.5 μm, which is considered to be due to the migration property. A ball mill, a sand mill, a dyno mill, an attritor, a colloid mill or the like can be used as a disperser for adjusting the metal stearate salt to a preferable particle size.

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. Γ-ferrite, strontium ferrite, cobalt-containing ferrite, etc. are used as the ferromagnetic powder, but barium ferrite and strontium ferrite with coercive force of 1500 to 5000 oersted are often used because magnetic recording information cannot be erased by a normal magnet. To be done. A polyacrylic acid salt or the like can be used to disperse the magnetic powder. Paraffin wax, polyethylene wax, higher fatty acid alcohol,
Higher fatty acid amides are used.

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.

Dye precursors include crystal violet lactone, 3-indolino-3-p-dimethylaminophenyl-6-dimethylaminophthalide, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-cyclohexylamino. Fluorane, 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-ethyl-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 is 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-tert-butyl-3-methylphenol), 4,4'-isopropylidene bis (2-methylphenol), 4,4'-
Ethylene bis (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-methylbenzylsalicylic acid, 3-methyl-5-t-butylsalicylic acid, monoanilide phthalate, paraethoxybenzoic acid, bis (4-hydroxyphenyl) sulfone, 4-hydroxy-4′-isopropyloxydiphenyl Sulfone, 2,4'-dihydroxydiphenyl sulfone, di- (3-allyl-4-hydroxyphenyl) sulfone, parabenzyloxybenzoic acid, parahydroxybenzoic acid benzyl ester are 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'-
There are triisocyanate, 4,4 ′, 4 ″ -triisocyanate-2,5-dimethoxytriphenylamine, p-dimethylaminophenylisocyanate, etc. These isocyanate groups may be phenols, lactams, oximes as necessary. The compound may be used in the form of a so-called blocked isocyanate or a diisocyanate which is an addition compound with, etc., but 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 -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-Diimino-6-cyanoisoindoline, 1,3-Diimino-4,7-dithio-
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 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
7-tetrachloroisoindoline-1-one and the like.

Examples of the binder include starches such as oxidized starch, phosphate 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, styrene-butadiene latexes, latexes such as polyacrylic latex are used.

A sensitizer can be used in the heat-sensitive recording layer to improve sensitivity. Aromatic ethers such as 2-benzyloxynaphthalene, oxalate esters such as di-p-methylbenzyl oxalate, and benzoic acid can be used. And terephthalic acid esters, naphthalene sulfonic acid esters, naphthyl ethers, aromatic compounds such as p-benzyl biphenyl, and phenanthrene. Pigments used in the thermosensitive coloring layer include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide,
Examples thereof include 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, hindered phenol etc. Agents, benzophenone-based and benzotriazole-based ultraviolet absorbers, surfactants, fluorescent dyes and the like are used.

The protective layer provided on the heat-sensitive color developing layer contains the specific water-dispersible polymer of the present invention as a main component, but other aqueous resins may be used in combination as long as the effects of the present invention are not impaired. Examples thereof include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic amide, carboxymethyl cellulose, hydroxyethyl cellulose, styrene-butadiene polymer, starches and their derivatives. Epoxy water resistance agents such as formalin, glyoxal, melamine, polyamide resin, epiclohydrin, etc., kaolin, calcined kaolin, clay, talc, inorganic pigments such as silica, titanium oxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, polystyrene. , Polyacrylic, organic pigments such as urea-formalin, higher fatty acid metal salts, lubricants such as paraffin and polyethylene, defoaming agents, surfactants and the like are appropriately added.

Paper is used as the support provided with the magnetic recording layer and the like used in the present invention. Synthetic paper, metal foil, laminated paper made of polyethylene or the like, film made of polyethylene terephthalate or the like is used 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.

[0020]

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, parts and% are parts by weight and% by weight,
The average particle diameter indicates a volume average particle diameter measured by a laser diffraction method.

Example 1 Preparation of Coating Liquid for Magnetic Recording Layer The following formulation was dispersed in a ball mill for one day to prepare a coating liquid for magnetic recording layer. Barium ferrite (manufactured by Toda Kogyo, MC127) (solid) 100 parts Urethane-acrylic resin (solid) 30 parts Polyethylene oxide (Sumitomo Seika Chemical Co., Ltd., weight average molecular weight 300,000) (solid) 5 parts Zinc stearate (polyvinyl) Alcohol dispersion, average particle size 0.9μ) (solid) 10 parts water 200 parts

Preparation of coating liquid for heat-sensitive recording layer (A) liquid 3-dibutylamino-6-methyl-7-anilinofluorane (solid) 12 parts 10% aqueous solution of polyvinyl alcohol (Nippon Gosei Kagaku KK, NM11) (solid) 1.8 parts) 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) are separately dispersed with a sand grinder until the average particle size becomes about 2μ, and the heat-sensitive layer coating liquid is prepared by the following formulation. It was adjusted. Calcium carbonate (Brt15 manufactured by Shiraishi Industry) (solid) 8 parts (B) liquid 30 parts 10% polyvinyl alcohol aqueous solution (NM11) 40 parts (A) liquid 12 parts water 100 parts

Preparation of Protective Layer Coating Liquid Methyl methacrylate, acrylonitrile and methacrylamide were polymerized in the presence of a polymer latex of styrene-butadiene-methyl methacrylate-acrylic acid (glass transition temperature, 5 ° C.) to disperse them in water. Polymer L was obtained. (Softening point, 235 ° C.) A protective layer coating liquid was prepared with the following formulation. 20% water-dispersible polymer aqueous dispersion 100 parts Calcium carbonate (solid) 2 parts 20% zinc stearate dispersion 2 parts Epoxy crosslinking agent (solid content 20%) 2 parts Water 50 parts

On one side of a paper having a basis weight of 160 g / m ² , the magnetic recording layer coating liquid was applied in a solid content of 30 g / m ^2, and the magnetic field was oriented and dried. Subsequently, the solid solution of the thermosensitive recording layer coating liquid was applied to the other surface at 6 g / m ²
After coating and drying, the protective layer was coated as a solid at 2 g / m ² and dried and subjected to supercalendering treatment to obtain a heat-sensitive 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 amount of the ferromagnetic powder) in the preparation of the magnetic recording layer coating liquid. Got

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

Example 4 A thermosensitive 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 μ) was used in place of zinc stearate in the preparation of the magnetic recording layer coating liquid. Got

Example 5 In the preparation of the magnetic recording layer coating solution of Example 1, polyvinyl alcohol-dispersed zinc stearate having an average particle size of 0.9 was used.
A thermal recording type 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 magnetic recording layer coating solution of Example 1, polyvinyl alcohol-dispersed zinc stearate having an average particle size of 0.9 was used.
A thermosensitive 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 magnetic recording layer coating solution of Example 1, polyvinyl alcohol-dispersed zinc stearate having an average particle size of 0.9 was used.
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 A thermosensitive recording type magnetic ticket sheet was obtained in the same manner as in Example 1 except that polyethylene oxide was used instead of polyethylene oxide having a weight average molecular weight of 300,000 in the preparation of the magnetic recording layer coating liquid. .

Example 9 A thermosensitive recording type magnetic ticket sheet was obtained in the same manner as in Example 1 except that polyethylene oxide was used in place of 300,000 instead of polyethylene oxide in the preparation of the magnetic recording layer coating liquid. .

Example 10 Water-dispersible polymer L used for preparing the coating liquid for protective layer of Example 1
Instead of acrylonitrile-acrylic acid-styrene-butadiene polymer latex (glass transition temperature, 41
C.) in the presence of a water-dispersible polymer obtained by polymerizing acrylonitrile and methacrylamide (softening point 325.degree. C.) to obtain a heat-sensitive recording magnetic ticket sheet 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 thermosensitive recording layer was coated in the following composition instead of the thermosensitive recording layer coating liquid of Example 1. . 1,3'-diimino-4,5,6,7-tetrachloroisoindolin 15 parts 4,4 ', 4 "-triisocyanate-2,5-dimethoxytriphenylamine 10 parts stearic acid amide 5 parts 2-methoxy -5-N, N-diethylsulfamoylaniline 0.5 part Polyvinyl alcohol 20 parts Calcium carbonate 30 parts Zinc stearate 10 parts

Example 12 The same procedure as in Example 1 was repeated except that zinc stearate (average particle size, 0.9 μm) dispersed in polyacrylic acid amide was used instead of polyvinyl alcohol in the preparation of the magnetic recording layer coating liquid. Thus, a heat-sensitive recording type magnetic ticket sheet was obtained.

Example 13 A thermosensitive recording type magnetic ticket sheet was obtained in the same manner as in Example 1 except that zinc stearate was removed in the preparation of the magnetic recording layer solution.

Example 14 A heat-sensitive recording type magnetic ticket sheet was obtained in the same manner as in Example 1 except that polyethylene oxide and zinc stearate were omitted in the preparation of the magnetic recording layer coating liquid.

Comparative Example 1 Water-dispersible polymer L used for preparing the coating liquid for protective layer of Example 1
Instead of, a water-dispersible polymer having a softening point of 245 ° C. obtained by polymerizing methyl methacrylate and acrylonitrile in the presence of a polymer latex of methyl methacrylate-styrene-acrylic acid (glass transition temperature 65 ° C.) A thermal recording type magnetic ticket sheet was obtained in the same manner except that was used.

Comparative Example 2 Water-dispersible polymer L in the preparation of the protective layer coating liquid of Example 1
Methyl methacrylate used in the polymerization of, methyl acrylate instead of acrylonitrile and methacrylamide,
A water-dispersible polymer having a softening point of 175 ° C. was similarly obtained except that methyl methacrylate and butadiene were used, and a thermosensitive recording magnetic ticket sheet was obtained in the same manner except that the water-dispersible polymer L was used instead. It was

Comparative Example 3 Water-dispersible polymer L in the preparation of the coating liquid for protective layer of Example 1
A thermosensitive recording magnetic ticket sheet was obtained in the same manner except that polyvinyl alcohol (softening point: 230 ° C.) was used instead of.

Comparative Example 4 A thermosensitive recording magnetic ticket sheet was obtained in the same manner as in Example 1 except that polyethylene glycol having a weight average molecular weight of 80,000 was used in place of polyethylene oxide in the preparation of the magnetic recording layer coating liquid.

As described above, Examples 1 to 14 and Comparative Examples 1 to 4
The heat-sensitive recording type magnetic ticket sheet obtained in 1. was evaluated by the following method. The evaluation results are shown in Table 1. (Sticking property) The sound was evaluated by a color-developing machine manufactured by Okura Electric Co., Ltd., and the evaluation was made based on the sound, white spots on the color-developed portion, and shrinkage of the color-developed portion. ○: No sticking, △: Some sticking is available, but ×: Sticking is too large to be used. (Blocking property) Under the conditions of 50 ° C. and 90% RH, the magnetic recording layer of the heat-sensitive recording type magnetic ticket sheet and the heat-sensitive recording layer are overlapped and a pressure of 1 kg / cm ² is applied and left overnight. After that, the degree of peeling of the magnetic recording layer and the heat-sensitive recording layer is peeled off and evaluated below. ○: No peeling, △: Some peeling, but usable. ×: Many peeling. (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. % In Table 1
It is represented by. (Desensitization) The magnetic recording layer and the heat-sensitive recording layer of the heat-sensitive recording type magnetic ticket sheet are superposed under the conditions of 50 ° C. and 90% RH 100
Apply a pressure of g / cm ^{2 and} let stand overnight. The heat-sensitive layers of the sheet before and after the treatment were subjected to color development by heating and compared to evaluate the decrease in color density. ◯: No difference before and after treatment, Δ: Some difference before and after treatment, ×: Large difference before and after treatment. (Water resistance) A heat-sensitive recording type magnetic ticket sheet in which a heat-sensitive recording layer is heated and colored is left in water at 20 ° C. for a whole day and night, and the decrease in color density is evaluated. ○: No change, △: There is a slight decrease in density,
X: Large decrease in density. (Plasticizer resistance) Three sheets of wrap film are stacked on a sheet on which the heat-sensitive recording layer is thermally colored, and a load is applied at 50 ° C, 90% R
Leave for 24 hours under the condition of H. Evaluated by the degree of density decrease in the color development area after processing. ◯: There is no difference between before and after the treatment, Δ: There is a slight decrease in the concentration after the treatment, ×: A large decrease in the concentration. (Printability) Printing was performed with an offset printing ink using an RI printing machine (manufactured by Akira Seisakusho), and peeling of the sheet surface was visually evaluated. ○: No peeling, △: Some peeling but usable level, ×: Large peeling.

[0043]

[Table 1]

[0044]

EFFECTS OF THE INVENTION 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, heat-sensitive properties and storability.

Claims (4)

[Claims] 1. A thermosensitive recording type 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 thermosensitive recording layer and a protective layer are sequentially provided on the other surface. In the magnetic ticket sheet, the protective layer is mainly composed of at least one hydrophobic vinyl monomer having a glass transition temperature of 55 ° C. or higher of a polymer in the presence of a polymer latex having a glass transition temperature of 50 ° C. or lower. Softening point 200-35 obtained by polymerization
A heat-sensitive recording-type magnetic ticket sheet, which comprises a water-dispersible polymer at 0 ° C. as a main component. 2. The heat-sensitive recording type magnetic material according to claim 1, wherein the magnetic recording layer contains 2 to 18% by weight of the ferromagnetic powder of polyethylene oxide having a weight average molecular weight of 100,000 to 1,500,000. Ticket sheet. 3. A stearic acid metal salt dispersed in a polyvinyl alcohol-based dispersant in a magnetic recording layer and having a volume average particle diameter of 0.5 to 2.5 μm measured by a laser diffraction method. 3. The heat-sensitive recording type magnetic ticket sheet according to claim 1 or 2, characterized by containing the above. 4. The heat-sensitive recording magnetic ticket sheet according to claim 3, wherein the metal stearate is zinc stearate.