JPH0673204B2 - Thermosensitive magnetic recording material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermosensitive magnetic recording material in which a protective layer is provided on a magnetic recording layer.

2. Description of the Related Art Thermal recording materials are advantageous in their high-speed recording property or simple recording means, and are used as recording paper for various purposes. For example, it is used as output paper for computers, facsimile paper, ticket paper such as tickets, labels and the like.

In particular, a thermosensitive magnetic recording material having a magnetic recording layer provided on the back side is used for the ticket paper, and an automatic ticket gate or the like is performed by the information recorded on the magnetic recording layer. Therefore, if the magnetic recording layer of the heat-sensitive magnetic recording material is physically destroyed, it becomes impossible to write and read accurate information, which causes a problem in automatic ticket gates.

The conventional heat-sensitive magnetic recording materials have a problem that the magnetic recording layer may fall off due to chemicals such as water and organic solvents, or may block when the humidity is high, so that improvement in reliability is desired.

An object of the present invention is to provide a thermosensitive magnetic recording material in which a thermosensitive coloring layer and a magnetic recording layer are provided on a support, in which detachment or blocking of the magnetic recording layer is eliminated and reliability is improved. To do.

Structure The present invention is a thermosensitive magnetic recording material in which a thermosensitive recording layer and a magnetic recording layer are provided on a support, wherein a protective layer containing a water-soluble resin and a zirconium compound as essential components is provided on the magnetic recording layer. It is a thermosensitive magnetic recording material.

In the present invention, the surface of the protective layer provided on the magnetic recording layer is made water-repellent while a strong surface is formed by the bond of the water-soluble resin and the zirconium compound.
With such a protective layer, infiltration of water or an organic solvent into the magnetic recording layer is prevented, and the magnetic recording layer is prevented from falling off or blocking.

Although various known zirconium compounds can be used, the following compounds are preferable.

Na ₂ ZrSiO ₅ , ZrOcl ₂ , 8H ₂ O, ZrOSO ₄ , nH ₂ O, ZrO (NO ₃ )
_{2 · 4H 2 O, ZrO (} CO 3) 2 · nH 2 O, ZrO (OH) 2, ZrO (C 2
H ₃ O ₂ ) ₂ , (NH ₄ ) ₂ ZrO (CO ₃ ) ₂ , ZrO (C ₁₈ H
₃₅ O ₂ ) ₂ , ZrO (C ₈ H ₁₅ O ₂ ) ₂ , ZrSiO ₄ , ZrO _2, etc.

The zirconium compound is a water-soluble resin that is a protective layer forming resin, such as polyvinyl alcohol, starch and its derivatives, methoxycellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose,
Cellulose derivatives such as ethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylic acid amide /
Acrylic ester copolymer, acrylic acid amide / ethyl acrylate / methacrylic acid terpolymer, styrene /
It is added to at least one resin such as alkali salt of maleic anhydride copolymer, almari salt of isobutylene / maleic anhydride copolymer, polyacrylamide, sodium alginate, gelatin and casein.

The adhesion amount of the protective layer is 0.5 to 1 g / m ² as a dry solid content,
The amount of the zirconium compound added is 2 to the water-soluble resin.
30% by weight is preferable, and if it is out of this range, a sufficient effect cannot be exhibited.

That is, if the amount of the zirconium compound added is less than 2% by weight with respect to the water-soluble resin, sufficient water resistance and blocking resistance cannot be obtained, and if it exceeds 30% by weight, slipping properties when used as magnetic ticket paper, for example. Becomes too large, causing problems such as winding deviation.

As the leuco dye in the heat-sensitive color forming layer, any leuco dye used in this type of heat-sensitive recording material may be arbitrarily selected and used alone or in combination of two or more. For example, leuco dyes such as triphenylmethane type, fluorane type, phenothiazine type and auramine type spiropyran type are used. As a specific example,
The following may be mentioned.

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-chlorophthalide, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-7,8-benzfluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3- (N -P-tolyl-N-ethylamino) -6-methyl-7-anilinofluorane, 3-virolidino-6-methyl-anilinofluorane, 2- {3,6-bis (diethylamino) -9- ( o-Chloranilino) xanthylbenzoic acid lactam}, 3-diethylamino-6-methyl-7- (m-trichloromethylanilino) fluorane, 3-di Ethylamino-7- (o-chloroanilino) 0fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-N-methyl-N-amylamino-6-methyl-7-
Anilinofluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilifluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N
-Dibenzylamino) fluorane, benzoyl leuco methylene blue, 6'-chloro-8'-methoxy-benzoindolino-pyrrolispirane, 6'-bromo-3'-methoxy-benzoindolino-pyrrolispirane, 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'-ditylaminophenyl) -3- (2'-hydroxy-4'-chloro-5'-
Methylphenyl) phthalide, 3-morpholino-7- (N-propyl-trifluoromethylanilino) fluorane, 3-virolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7- (N- Benzyl-trifluoromethylanilino) fluorane, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluorane, 3-diethylamino-5-chloro-7- (α-phenylethylamino) fluorane, 3- (N-ethyl-p-toluidino) -7- (α-phenylethylamino) fluorane, 3-diethylamino-7- (o-methoxycarbonylphenylamino) fluorane, 3-diethylamino-5-methyl-7- ( α-phenylethylamino) fluorane, 3-diethylamino-7-piperidi Fluoran, 2-chloro-3-(N-Mechirutoruijino)-7-(p
-N-butylanilino) fluorane, 3- (N-benzyl-cyclohexylamino) -5,6-
Benzo-7-α-naphthylamino-4′-bromofluorane, 3-diethylamino-6-methyl-7-mesitidino-
4 ', 5'-benzofluorane and the like.

Known developers may be used as the color developer, but the following are preferable examples.

Benzoic acid, salicylic acid, 3,5-xylenol, thymol, p-tert-butylphenol, 4-hydroxyphenoxide, methyl-4-hydroxyacetophenone, α
-Naphthol, β-naphthol, catechol, resorcin, hydroquinone, 4-tert-octylcatechol, 4,
4'-sec-butylidenephenol, 2,2-dihydroxydiphenyl, 2,2-methylenebis (4-methyl-6-ter)
t-buorphenenol), 2,2'-bis (4'-hydroxyphenylpropane), 4,4'-isopropylidene-bis (2-tert-butylphenol), 4,4'-sec-butylidene diene Phenol, pyrogallol, phloroglucin, etc.

In the present invention, in order to fix the leuco dye and the color developer to the support, known binders used in heat-sensitive recording materials, for example, the water-soluble resin used in the above-mentioned protective layer,
Polyvinyl acetate, polyurethane, styrene / butadiene copolymer, polyacrylic acid, polyacrylic ester,
A latex such as vinyl chloride / vinyl acetate copolymer, polybutyl methacrylate, ethylene / vinyl acetate copolymer, styrene / butadiene / acrylic copolymer can be used.

The amounts of leuco dye, developer and binder used in the thermosensitive coloring layer are 5 to 30% by weight, 40 to 80% by weight and 2 to 20%, respectively.
A suitable weight% is a solid content of 1 to 10 g / m ² as an adhesion amount of the thermosensitive coloring layer.

The amounts of leuco dye, developer and binder used in the thermosensitive coloring layer are 5 to 30% by weight, 40 to 80% by weight and 2 to 20%, respectively.
A suitable amount is 10% by weight, and a solid content of 1 to 10 g / m ² is suitable for the amount of the thermosensitive color developing layer deposited.

Further, in the present invention, in addition to the leuco dye and the color developer, various auxiliary additive components can be optionally used in the thermosensitive color developing layer. These auxiliary additive components are known ones, for example, inorganic fine powders such as calcium carbonate and silica, organic fine powders such as urea-formalin resin, various heat fusible substances such as higher fatty acids or their esters and amides. Substances.

As the ferromagnetic material used for forming the magnetic recording layer in the present invention, various conventionally used materials can be applied. Generally, γ-ferric oxide or the like is used in the form of fine powder. Further, as the binder for binding the ferromagnetic material to the support, acrylic resin, epoxy resin, phenol resin, vinyl acetate, vinyl chloride / vinyl acetate copolymer, polybutadiene resin, polyester resin, polyacrylamide, polystyrene resin , Melamine resin, polyvinyl chloride, polyurethane and the like can be used.

The thermosensitive magnetic recording material of the present invention is prepared by coating a thermosensitive coloring layer-forming coating liquid containing the above-mentioned components on a support such as paper, synthetic paper, or a plastic film, and then drying it on the back surface of the support or the thermosensitive coloring layer. The magnetic recording layer-forming liquid containing the above-mentioned components is applied to the support region which is the support surface and does not impart the function of heat-sensitive color development, and then the zirconium compound and the water-soluble resin are contained as essential components on the layer. It can be produced by forming a protective layer. The thermosensitive coloring layer can have various layer structures such as laminating the leuco dye and the developer as separate layers.

Effect The thermosensitive magnetic recording material of the present invention has the above-mentioned constitution.
The loss and blocking of the magnetic recording layer are eliminated, and the reliability in magnetic recording is improved.

EXAMPLES The present invention will be described in more detail with reference to examples. The parts shown below are based on weight.

Example 1 [Liquid A] 3-N-methyl-N-cycloxylamino 20 parts-6-methyl-7-anilinofluorane hydroxyethyl cellulose (10% aqueous solution) 20 parts water 60 parts Dispersion was carried out for 24 hours to prepare dispersion A.

[Liquid B]

Bisphenol A 15 parts Carbonic acid carbonate 5 parts Polyvinyl alcohol (10% aqueous solution) 20 parts Water 60 parts The above composition was dispersed in a ball mill for 24 hours to prepare a dispersion B.

[C liquid]

Polyvinyl alcohol (10% aqueous solution) 20 parts Calcium carbonate 5 parts ZrSiO ⁴ (10% solution) 5 parts Water 60 parts The above composition was dispersed for 10 hours in an attritor to prepare a dispersion C.

[D liquid]

Magnetic powder (γ-Fe ₂ O ₃ ) 100 parts SBR resin 20 parts Monomethylterephthalic acid stearylamide 15 parts Water 100 parts The above composition was dispersed for 24 hours using a ball mill to prepare a dispersion D.

The above dispersions A and B are mixed to obtain a fine paper (157 g / m ² ) 2 g / m
^It was applied and dried so as to be ² (solid content). Further, the dispersion D was applied and dried on the back surface of the support so as to be 40 g / m ² (solid content), and then the dispersion C was applied and dried on the layer so as to be 1 g / m ² (solid content). The thermosensitive magnetic recording material of the present invention was obtained.

Example 2 A thermosensitive magnetic recording material of the present invention was obtained in the same manner as in Example 1 except that Na ₂ ZrSiO ₅ was used instead of ZrSiO ₄ used in the liquid C of Example 1.

Example 3 A thermosensitive magnetic recording material of the present invention was obtained in the same manner as in Example 1 except that ZrSiO ₄ used in the liquid C of Example 1 was replaced with ZrO ₄ .

Comparative Example 1 A thermosensitive magnetic recording material for comparison was obtained in the same manner as in Example 1 except that the liquid C in Example 1 was omitted.

Comparative Example 2 A thermosensitive magnetic recording material for comparison was obtained in the same manner as in Example 1 except that ZrSiO ₄ used in the liquid C of Example 1 was omitted.

Using the heat-sensitive magnetic recording materials of the present invention and comparative samples obtained as described above as samples, a chemical resistance and water resistance test and a blocking test for confirming the degree of detachment of the magnetic recording layer were performed. The test procedure and test results are shown below.

Chemical resistance 0.02cc of ethanol (first-grade reagent) on the magnetic recording layer of the sample
After dropping, the dropping portion is rubbed with a white paper to check the degree of detachment of the magnetic recording layer.

Water resistance 1 cc of water is dropped on the magnetic recording layer of the sample, and the dropping portion is rubbed with a white paper to check the degree of drop of the magnetic recording layer.

Blocking property 10 samples are piled up, a load of 300 g / m ² is applied under the conditions of 40 ° C. and 90% RH, and blocking of the magnetic recording layer after 10 days standing is confirmed.

The above test results are shown in Table 1.

Claims (1)

[Claims] 1. A thermosensitive magnetic recording material in which a thermosensitive recording layer and a magnetic recording layer are provided on a support, wherein a protective layer containing a water-soluble resin and a zirconium compound as essential components is provided on the magnetic recording layer. A heat-sensitive magnetic recording material.