JP3041833B2 - Thermal recording type magnetic ticket sheet - Google Patents

Description

The present invention relates to a thermosensitive recording type magnetic ticket sheet having a magnetic recording layer and a thermosensitive recording layer.

(Prior Art) Conventionally, a thermosensitive magnetic sheet has a thermosensitive recording layer mainly composed of a leuco dye and an acidic substance on one surface of a plastic sheet or paper, and a ferromagnetic material on the other surface. It is formed by forming a magnetic recording layer mainly containing a binder. Although such a method of applying a thermosensitive recording type magnetic ticket sheet is effective, it has many disadvantages.

That is, when a plastic sheet is used for the support, it is usually manufactured with an organic solvent-based material in order to obtain adhesive strength to the support, durability, etc., and safety and hygiene problems are likely to occur, and cost is reduced. Also has the disadvantage of being expensive.

When a fibrous material such as paper is used for the support, the problems described above do not occur, but irregularities occur at the interface with the support due to infiltration of the magnetic paint and its non-uniformity. The magnetic recording layer tends to be uneven in thickness, and this uneven thickness increases output fluctuations and causes waveform distortion and dropout.

(Problems to be Solved by the Invention) The present invention uses paper, cloth, and the like for a support, and has no safety and hygiene problems by using an aqueous magnetic paint, and is low in cost. Another object of the present invention is to provide a thermosensitive recording type magnetic ticket sheet having no problem in output fluctuation, waveform distortion, dropout, and the like due to uneven thickness of a magnetic recording layer.

(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have found that an aqueous emulsion is mainly contained on one side of a paper support 1 as shown in FIG. The above problem can be solved by providing a layer structure in which an undercoat layer 2 is provided, a magnetic recording layer 3 of an aqueous magnetic paint is provided thereon, and a thermosensitive recording layer 4 is provided on the other surface. I found it.

That is, according to the study of the present inventors, unevenness in the thickness of the magnetic recording layer is caused by infiltration of the magnetic paint into the support,
It has been found that by providing an undercoat layer containing an aqueous emulsion resin as a main component on a support, it is possible to prevent infiltration of a magnetic paint and to prevent unevenness of the magnetic recording layer as described above.

That is, according to the present invention, a magnetic recording layer containing a ferromagnetic material and a binder as main components is provided on one surface of a support made of paper, and the other surface of the support is usually colorless or light-colored. In a thermosensitive recording type magnetic ticket sheet provided with a thermosensitive recording layer containing a leuco dye and an acidic substance as coloring components, an aqueous magnetic paint is used as a magnetic paint when forming the magnetic recording layer, and the support and the magnetic recording medium are used. A heat-sensitive recording type magnetic ticket sheet is provided, wherein an undercoat layer containing an aqueous emulsion resin (excluding styrene-butadiene-based latex) as a main component is provided between the layers.

 Next, the materials constituting the present invention will be described in detail.

As the aqueous emulsion resin used in the undercoat layer of the present invention, various conventional ones can be appropriately used,
Specific examples thereof include polyvinyl butyral, polyvinyl acetate, polyvinyl polypropionate, polyvinyl butyrate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polyheptyl acrylate, polyethylhexyl acrylate, nitrile rubber, and natural rubber. Rubber, polyisobutylene rubber,
Polybutadiene, polyacrylonitrile, polymethacrylonitrile, polyvinylidene chloride, polydichlorostyrene, polystyrene, polyvinyl chloride, polymethacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polyethylhexyl methacrylate, polyvinyl stearate An aqueous emulsion resin such as a rate is exemplified, but the present invention is not limited to these. As a particularly preferred aqueous emulsion resin, those having a glass transition temperature of 100 ° C. or less, which has good film-forming ability, are preferably used.

Deposition amount of the undercoat layer is 2 g / m ₂ or more, preferably 4
g / m ₂ or more.

Also, aluminum hydroxide,
Fillers such as clay, talc, calcium carbonate, silica, and zinc oxide, and heat-fusible substances (or lubricants) such as stearamide, β-naphthylbenzyl ether, P-benzylbiphenyl, and behenic amide may be added. .

As the magnetic paint used in the magnetic recording layer of the present invention, an aqueous magnetic paint is preferably used. Organic solvent-based paints that have been widely used in the past tend to swell or dissolve the undercoat layer with an organic solvent, and a magnetic layer with irregularities is formed at the interface with the undercoat layer. As a result, the paint may soak into the support to cause the same problem as described above.

The magnetic recording layer of the present invention is such that barium ferrite, strontium ferrite, Co-γ-Fe ₂ O ₃ , and ferromagnetic powder such as γ-Fe ₂ O ₃ are uniformly dispersed in an aqueous binder such as the aqueous emulsion resin. The obtained coating material is applied on a support and dried to form a magnetic recording layer.

The leuco dyes used in the present invention are applied alone or as a mixture of two or more types. As such leuco dyes, those applied to this type of recording material are arbitrarily applied. Leuco compounds of dyes such as methane, fluoran, phenothiazine, auramine, spiropyran and indolinophthalide are preferably used. Specific examples of such leuco dyes include, for example, those shown below.

3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis (p-dimethyl Aminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3-cyclohexylamino-6-chlorofurf Oran, 3-dimethylamino-5,7-dimethylfluoran, 3- (N-methyl-N-isobutylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamylamino ) -6-Methyl-7-anilinofluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfluora 3-diethylamino-7,8-benzfluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3- (Np-tolyl-N-ethylamino) -6-methyl-7-aniline Linofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 2- {N- (3'-trifluoromethylphenyl) amino} -6-diethylaminofluoran, 2- {3,6-bis (Diethylamino) -9- (o-chloroanilino) xanthyl lactam benzoate, 3-diethylamino-6-methyl-7- (m-trichloromethylanilino) fluoran, 3-diethylamino-7- (o-chloroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-N-methyl-N-amylamino-6-methyl-7
-Anilinofluoran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl -7- (2 ', 4'-
Dimethylanilino) fluoran, 3- (N, N-diethylamino) -5-methyl-7-
(N, N-dibenzylamino) fluoran, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolino-
Pyrirospiran, 6'-bromo-3'-methoxy-benzoindolino-
Pyrirospiran, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl)- 3- (2'-methoxy-5'-nitrophenyl) phthalide, 3- (2'-hydroxy-4'-diethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl) phthalide, 3- ( 2'-methoxy-4'-dimethylaminophenyl) -3- (2'-hydroxy-4'-chloro-5'-
Methylphenyl) phthalide, 3-morpholino-7- (N-propyl-trifluoromethylanilino) fluoran, 3-pyrrolidino-7-trifluoromethylanilinofluoran, 3-diethylamino-5-chloro-7- (N -Benzyl-trifluoromethylanilino) fluoran, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluoran, 3-diethylamino-5-chloro-7- (α-phenylethylamino) fluoran, 3 -(N-ethyl-p-toluidino) -7- (α-phenylethylamino) fluoran, 3-diethylamino-7- (o-methoxycarbonylphenylamino) fluoran, 3-diethylamino-5-methyl-7- (α -Phenylethylamino) fluoran, 3-diethylamino-7-piperidi Fluoran, 2-chloro-3-(N-Mechirutoruijino) -7-
(Pn-butylanilino) fluoran, 3- (N-methyl-N-isopropylamino) -6
Methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluoran, 3,6-bis (dimethylamino) fluorenespiro (9,
3 ')-6'dimethylaminophthalide, 3- (N-benzyl-N-cyclohexylamino)-
5,6-benzo-7-α-naphthylamino-4′-bromofluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-N-ethyl-N- (2-ethoxypropyl) amino -6-methyl-7-anilinofluoran, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-mesitidino-
4 ', 5'-benzofluoran, 3- (p-dimethylaminophenyl) -3- {1,1-
Bis (p-dimethylaminophenyl) ethylene-2-yl} phthalide, 3- (p-dimethylaminophenyl) -3- {1,1-
Bis (p-dimethylaminophenyl) ethylene-2-yl} -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (1-p
-Dimethylaminophenylethylene-2-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (1-p
-Dimethylaminophenyl-1-p-chlorophenylethylene-2-yl) -6-dimethylaminophthalide, 3- (4'-dimethylamino-2'-methoxy) -3
-(1 "-p-dimethylaminophenyl-1" -p-chlorophenyl-1 ", 3" -butadiene-4 "-yl) benzophthalide, 3- (4'-dimethylamino-2'-hensyloxy) -3- (1 "-p-dimethylaminophenyl-1"
-Phenyl-1 ", 3" -butadiene-4 "-yl) benzophthalide, 3-dimethylamino-6-dimethylamino-fluorene-9-spiro 3 '-(6'-dimethylamino) phthalide, 3,3-bis {2- (p-dimethylaminophenyl)-
2- (p-methoxyphenyl) ethenyl} -4,5,6,7-
Tetrachlorophthalide, 3-bis {1,1-bis (4-pyrrolidinophenyl) ethylene-2-yl} -5,6-dichloro-4,7-dibromophthalide, bis (p-dimethylaminostyryl) -1-naphthalenesulfonylmethane and the like.

The developer used in the present invention includes various electron-accepting compounds, for example, phenolic compounds,
Thiophenolic compounds, thiourea derivatives, organic acids and metal salts thereof can be used, and specific examples thereof include the following.

4,4'-isopropylidenebisphenol, 4,4'-isopropylidenebis (o-methylphenol-
4,4'-secondarybutylidenebisphenol, 4,4'-isopropylidenebis (2-tert-butylphenol), 4,4'-cyclohexylidenediphenol, 4,4 '-Isopropylidenebis (2-chloropheno-
2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'- Butylidenebis (6-tert-butyl-
2-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-
Tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-
(Cyclohexylphenyl) butane, 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-diphenolsulfone, 4-isopropoxy-4'-hydroxydiphenylsulfone, 4-benzyloxy-4 '-Hydroxydiphenyl sulfone, 4,4'-diphenol sulfoxide, isopropyl P-hydroxybenzoate, benzyl P-hydroxybenzoate, benzyl protocatechuylate, stearyl gallate, lauryl gallate, octyl gallate, 1,3-bis (4-hydroxyphenylthio) -propane, 1,3-bis (4-hydroxyphenylthio) -2-hydroxypropane, N, N'-diphenylthiourea, N, N'-di (m-chlorophenyl) thiourea , Salicylanilide, 5-chloro-salicylanilide, bis- (4 (Hydroxyphenyl) acetic acid methyl ester, bis- (4-hydroxyphenyl) acetic acid benzyl ester, 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 2,4 '-Diphenolsulfone, 2,2'-diallyl-4,4'-diphenolsulfone, 3,4-dihydroxy-4'-methyldiphenylsulfone, zinc 1-acetyloxy-2-naphthoate, 2-acetyl Zinc oxy-1-naphthoate, zinc 2-acetyloxy-3-naphthoate, α, α-bis (4-hydroxyphenyl) -α-methyltoluene, antipyrine complex of zinc thiocyanate, tetrabromobisphenol A And tetrabromobisphenol S.

In the present invention, various conventional binders can be appropriately used for binding and supporting the leuco dye and the developer on the support. Specific examples thereof include the following.

Polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide / acrylate copolymer, acrylamide / acrylate /
Water-soluble polymers such as methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt, isobutylene / maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein, and polyacetic acid Vinyl, polyurethane, polyacrylate,
Emulsions such as polymethacrylic acid esters, vinyl chloride / vinyl acetate copolymers, ethylene / vinyl acetate copolymers, and latexes such as styrene / butadiene copolymers and styrene / butadiene / acrylic copolymers.

In the present invention, together with the leuco dye, the developer and the auxiliary component, if necessary, auxiliary auxiliary components commonly used in this type of heat-sensitive recording material, for example, fillers, surfactants, and heat-fusible materials. Substances (or lubricants) can be used in combination. In this case, as the filler, for example, other than inorganic fine powder such as calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, surface-treated calcium and silica, etc. Organic fine powder such as urea-formalin resin, styrene / methacrylic acid copolymer, and polystyrene resin. Examples of the heat-fusible substance include, in addition to higher fatty acids or their esters, amides or metal salts, various waxes, condensates of aromatic carboxylic acids and amines, benzoic acid phenyl esters, higher linear glycols, 3 , 4-epoxy-dialkylhexahydrophthalate, higher ketones, other heat-fusible organic compounds, etc.
Those having a melting point of about 200 ° C. are mentioned.

In the present invention, as shown in FIG. 2, a protective layer containing a water-soluble polymer as a main component can be provided on the heat-sensitive recording layer 4, if necessary. Specific examples of the water-soluble polymer in this case include those exemplified as the water-soluble polymer binder in relation to the heat-sensitive recording layer. The water-soluble polymer can be used together with a conventional water-proofing agent for making it water-resistant. Specific examples of the water-proofing agent include, for example, formaldehyde, glyoxal, chloroallum, melamine, melamine-formaldehyde resin,
Polyamide resin, polyamide-epichlorohydrin resin, and the like are included. Further, the overcoat layer may contain a conventional auxiliary additive component such as a filler, a heat-fusible substance (lubricant), a surfactant and the like, if necessary. Specific examples of the filler and the heat-fusible substance Examples thereof include those exemplified in relation to the heat-sensitive recording layer.

(Effect) The heat-sensitive recording type magnetic ticket sheet of the present invention, having the above-described configuration, is excellent in having no problem in output fluctuation, waveform distortion, dropout, etc. due to uneven thickness of the magnetic recording layer. Things.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
In addition, all the parts and% shown below are based on weight.

"Reference Example 1" basis weight 150 g / m ₂ of the one surface of woodfree paper of styrene / butadiene copolymer emulsion resin dry weight is 4.0 g / m ₂
Then, an undercoat layer was provided by applying and drying, and a magnetic recording layer shown below was also applied thereon by applying and drying the magnetic paint shown below so that the dry weight was 32 g / m ₂ .

Barium ferrite (coercivity 2800oe, average particle size 0.6μ)
m) 100.0 parts Sodium polyacrylate (20% aqueous solution) 25.0 parts Polyvinylidene chloride (49% dispersion) 100.0 parts Carbon black (38% dispersion) 15.0 parts Water 160.0 parts Next, heat is applied to the other surface of the support. To provide a recording layer,
Mix a mixture of the following formulas with a sand grinder
After dispersing for 5 hours, [A] and [B] solutions were prepared.

[A liquid]

3- (N-methyl-N-cyclohexyl) amino-6
-Methylanilinofluorane 25.0 parts Polyvinyl alcohol 10% aqueous solution 25.0 parts Water 50.0 parts 40 parts of [A] solution, 320 parts of [B] solution and 60 parts of water were mixed to prepare a thermosensitive recording layer coating solution, and the coating solution was dried on the other surface of the support having the magnetic recording layer. The coating was dried so that the hourly weight became 6 g / m ₂ to obtain a heat-sensitive recording layer.

Next, in order to provide a protective layer on the heat-sensitive recording layer, a mixture having the following formulation was dispersed with a sand grinder for 2 to 3 hours to prepare Solution [C] and Solution [D].

[C] Solution Zinc stearate 20.0 parts Methylcellulose 5% aqueous solution 20.0 parts Water 60.0 parts [D] Solution Carboxy-modified polyvinyl alcohol 10% aqueous solution 20.0 parts Silica 1.5 parts Polyamide epichlorohydrin 12.5% aqueous solution 6.5 parts Water 15.0 parts [C] solution above 0.7 parts of [D] was 45.0 parts water 11.3 parts were mixed coating solution of protective layer was prepared, the coating liquid dry weight coating and drying so as to be 3 g / m ₂ in the heat-sensitive recording layer Thus, a protective layer was provided to obtain a thermosensitive recording type magnetic ticket sheet of the present invention.

Example 1 In Reference Example 1, the undercoat component was changed from a styrene / butadiene copolymer emulsion resin to a polyvinyl acetate emulsion resin, and the dry weight was 6.0 g.
A thermosensitive recording magnetic ticket sheet of the present invention was obtained in the same manner as in "Reference Example 1" except that / m ₂ was changed.

Example 2 In Reference Example 1, the undercoat component was changed from a styrene / butadiene copolymer emulsion resin to a polyvinyl chloride emulsion resin, and the dry weight was 9.0 g.
A thermosensitive recording magnetic ticket sheet of the present invention was obtained in the same manner as in "Reference Example 1" except that / m ₂ was changed.

Comparative Example 1 A comparative thermosensitive magnetic sheet was obtained in the same manner as in "Reference Example 1" except that the undercoat layer was omitted.

A quality performance test was performed on the thermosensitive recording type magnetic ticket sheet obtained above, and the results are shown in Table 1.

<Test conditions and methods> Output fluctuation: recorded on the magnetic recording layer with a constant write current, and then reproduced to measure the fluctuation of the output voltage at that time.

Waveform distortion: When the magnetic recording layer was recorded with a constant write current and then reproduced, the distortion state of the output waveform was visually determined.

A: No distortion is observed.

…: Some distortion is observed, but there is no practical problem.

Δ: Distortion is observed and there is a practical problem.

×: Distortion was observed very much and there was a problem.

Coercive force, residual magnetic flux density, squareness ratio: Hysteresis loop was measured using a vibrating sample magnetometer (VSM-P7 manufactured by Toei Kogyo Co., Ltd.).

Color density: Thermal head temperature of 110 ° C to 150 ° C with a thermal gradient tester (manufactured by Toyo Seiki Co., Ltd.), compression pressure of 1 kg / cm ₂ , and compression time of 3
The maximum color density when printing in seconds is determined by Macbeth densitometer RD-
Measured with a Model 914, Filter W-106. The background density is measured in the same manner.

As shown in Table 1, the present invention is excellent in magnetic recording characteristics as compared with the comparative example, and has no problem in other characteristics.

[Brief description of the drawings]

1 and 2 are schematic sectional views of a typical thermosensitive recording type magnetic ticket sheet of the present invention. 1; support, 2; undercoat layer, 3; magnetic recording layer, 4; heat-sensitive recording layer, 5; protective layer.

Continuation of front page (56) References JP-A-56-156927 (JP, A) JP-A-3-274179 (JP, A) JP-A-4-43094 (JP, A) JP-A-61-172212 (JP) JP-A-56-31 (JP, A) JP-A-2-125794 (JP, A) JP-A-56-170534 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB Name) B41M 5/28-5/34 G11B 5/80 B42D 15/10

Claims (1)

(57) [Claims] 1. A colorless or light-colored leuco dye is provided on one side of a support made of paper and provided on one side with a magnetic recording layer containing a ferromagnetic material and a binder as main components. In a thermosensitive recording type magnetic ticket sheet provided with a thermosensitive recording layer containing an acidic substance as a coloring component, an aqueous magnetic paint is used as a magnetic paint in forming the magnetic recording layer, and between the support and the magnetic recording layer. Aqueous emulsion resin (however,
A thermosensitive recording type magnetic ticket sheet characterized by having an undercoat layer mainly composed of a styrene-butadiene-based latex).