JPH0664342A - Heat-sensitive magnetic composite recording material - Google Patents

Abstract

(57) [Abstract] [Purpose] A thermosensitive magnetic composite recording material capable of stably recording magnetic information and visible information for a long period of time. [Structure] In the thermosensitive magnetic composite recording material, one of the supports
A colorless dye precursor, a thermosensitive coloring layer containing a color developer and a binder, a protective layer containing a polymeric substance, a pigment and a cross-linking agent, and an overcoat consisting of an ultraviolet curable resin are sequentially arranged on the surface, and a support is formed. A magnetic recording layer containing a magnetic powder and a binder and an aluminum coating layer containing an aluminum powder and a binder are arranged on the opposite surface of, and as a binder for the thermosensitive coloring layer, a hydrophobic polymer substance is used as a main component. The soap press emulsion containing is used. [Effect] A thermosensitive magnetic composite recording material having excellent water resistance, good adhesion between a support and a thermosensitive coloring layer, and capable of stably recording magnetic information and visible information over a long period of time is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosensitive magnetic composite recording material. More specifically, the present invention is a coupon ticket,
The present invention relates to a heat-sensitive magnetic composite recording material which is used for a gift certificate card, a highway card, and other cards for various automatic systems and which can visualize a part of magnetic recording information by thermal printing.

[0002]

2. Description of the Related Art With the rapid spread of telephone cards and orange cards, prepaid cards have been attracting a great deal of attention, and their practical use is rapidly spreading in the fields of various distribution service industries including transportation. The popularization of such heat-sensitive magnetic recording materials is that the information storage capacity of the magnetic recording layer is large, that the written information can be read easily and accurately, and it can be easily processed by an automatic ticket gate or a vending machine. It is believed that this is due to the fact that it is possible to process fractional amounts and is effective for labor saving. The punch hole method has been conventionally used as the balance display method for prepaid cards. However, in this method, the accurate balance cannot be grasped only by the card, so the usage history is not clear, and punches are made in the reader / writer. It has the drawback of collecting debris. Therefore, a thermal recording method has been adopted to enable accurate balance display.

Conventionally, a magnetic recording layer is provided on one side of a base paper,
The heat-sensitive magnetic composite recording paper provided with a heat-sensitive recording layer on the opposite surface is used for boarding tickets, boarding passes, etc.
It has also come to be used in various cards. However, in such a conventional recording material, the magnetic recording layer is colored by the magnetic powder used as its main component, and for printing or printing on it,
It was not considered at all. Therefore, as a method for solving such a problem, when a magnetic recording layer is formed, a coloring pigment is added to a magnetic coating material to give a desired coloring to the magnetic recording layer, or the method of JP-A-62-62 204991
It has been proposed to apply a white pigment paint on the magnetic recording layer as disclosed in U.S. Pat.

On the other hand, the heat-sensitive recording material is generally one of the supports made of paper, synthetic paper, plastic film or the like.
On the surface, a substantially colorless chromogenic dye precursor such as an electron-donating leuco dye, an organic acidic developer such as an electron-accepting phenolic compound, and a binder are main components. A heat-sensitive color-forming layer containing the color-forming dye is provided, and a color-recorded image can be obtained by reacting these color-forming dyes and a color developer with heat energy. Such a heat-sensitive recording material has the advantages that the recording apparatus is compact, inexpensive, and easy to maintain. Therefore, the output of a computer, a facsimile, an automatic ticket vending machine, a scientific measuring instrument, etc. It is widely used for printers, printers for CRT medical measurement, and the like.

However, a conventional thermosensitive recording material in which a thermosensitive coloring layer containing a dye precursor, a color-developing substance and a binder as an active ingredient is coated on a support is a water-, plasticizer and It is unstable with respect to oil and the like, so that the change with time in quality during storage has always been a problem. In order to improve the storage stability as described above, it has been proposed to provide a surface protective layer on the thermosensitive coloring layer and coat the surface protective layer. For example, JP-A-56-146794 discloses that a surface protective layer is formed using a hydrophobic polymer compound emulsion, and JP-A-58-19.
In Japanese Patent No. 9189, a water-soluble polymer compound or a hydrophobic polymer compound emulsion is provided as an intermediate layer on a thermosensitive coloring layer, and a surface protective layer is provided thereon by using an oil-based paint with the hydrophobic polymer compound as a resin component. It is disclosed.

However, even when the surface protective layer as described above is provided, a water-soluble polymer substance is usually used as a binder in the thermosensitive coloring layer. The formed conventional thermosensitive coloring layer has a problem that it is not satisfactory in water resistance. In particular, when it is used for a card that is used for a long period of time as described above, it is important to design the structure of the recording material so as to impart practically sufficient water resistance to the recording material. Furthermore, the adhesion between the synthetic resin film used for the support and the thermosensitive coloring layer is often insufficient. Further, as the heat-sensitive recording material, it is necessary to design its quality and configuration so that sticking prevention to the thermal head is sufficient.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the conventional heat-sensitive magnetic composite recording material, and is excellent in water-immersion resistance, water resistance of coloring portion, plasticizer resistance, oil resistance and the like. Provided is a thermosensitive magnetic composite recording material which has excellent long-term storage stability, does not cause sticking phenomenon to a thermal head during thermal recording operation, has excellent thermal recording suitability and magnetic recording suitability, and has long-term storage stability. Is what you are trying to do.

[0008]

According to the present invention, in a thermosensitive magnetic composite recording material, an aluminum coating layer is provided on a magnetic recording layer formed on one surface of a support, and is formed on the other surface of the support. A protective layer and an overcoat layer are provided on the heat-sensitive layer, and as a binder in the heat-sensitive color forming layer, by using a soapless emulsion containing a hydrophobic polymer as a main component, the above problems can be solved. It was successful.

That is, the thermosensitive magnetic composite recording material according to the present invention comprises a support, a dye precursor which is formed on one surface of the support and is substantially colorless, and the dye precursor reacts with heating. A thermosensitive coloring layer containing a mixture of a color developer and a binder as a main component, and a water-soluble polymeric substance or a hydrophobic polymeric substance formed on the thermosensitive coloring layer. A protective layer containing at least one of the above, a pigment, and a crosslinking agent as main components, an overcoat layer formed on the protective layer and containing an ultraviolet curable resin as a main component, and on the other surface of the support. A magnetic recording layer which is formed and contains magnetic powder and a binder as main components, and a concealment layer which is formed on the magnetic recording layer and contains aluminum powder and a binder as main components, The thermosensitive coloring layer is a binder. It is using a soapless emulsion of a hydrophobic polymeric substance Te is characterized in.

In the thermosensitive magnetic composite recording material of the present invention,
The dark brown and dark black tones of the magnetic powder of the magnetic recording layer formed on at least one surface of the support can be covered with the coating layer containing the aluminum powder. Further, by providing a protective layer on the thermosensitive coloring layer formed by using the above-mentioned adhesive of soapless emulsion of hydrophobic polymer substance, long-term storage stability of the colored image is maintained, and further ultraviolet curing By providing an overcoat layer made of a resin, it is possible to prevent adhesion of dust and sticking when printing with a thermal head, and improve thermal recording suitability. Moreover, these do not cause any trouble in the magnetic recording characteristics.

The support used in the present invention is composed of a synthetic resin film or base paper. Examples of the synthetic resin film used for the support include a film made of a polyester resin material such as polyethylene terephthalate and polybutylene terephthalate, a film made of a cellulose derivative material such as a cellulose triacetate film, a polypropylene film and a polyolefin resin such as polyethylene. Film, and
These composite laminated films and the like can be used. Further, as the base paper for the support, high-quality paper, processed base paper, synthetic paper and the like can be used, but the type is not particularly limited. Generally, a support having a thickness of 50 to 200 μm is preferable.

A thermosensitive coloring layer containing a dye precursor, a developer and a binder is formed on one surface of a support by a conventionally known coating method. In general, the coating amount of the thermosensitive coloring layer is preferably ^{3 to} 10 g / m ² in terms of dry weight.

The dye precursor used in the present invention is a substantially colorless electron-donating compound capable of reacting with a color developer under heating to develop a color. As such a color forming dye precursor, for example, 2,2-bis {4- [6'-
(N-Cyclohexyl-N-methylamino) -3'-methylspiro (phthalide-3,9'-xanthene) -2 '
-Ylamido] phenyl} propane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3- (N
-Methyl-N-cyclohexylamino) -6-methyl-
7-anilinofluorane, 3-diethylamino-7-chloroanilinofluorane, 3- [N-ethyl-N- (p
-Methylphenyl) amino] -6-methyl-7-anilinofluorane, 3-diethylamino-7- (metatrifluoromethyl) anilinofluorane, 3- [N-ethyl-N-tetrahydrofurfuryl] amino- 6-methyl-
7-anilinofluorane, 3- [N-ethyl-isopentyl] amino-6-methyl-7-anilinofluorane,
A compound having at least one member selected from fluorane compounds such as 3- [N, N-dibutyl] amino-6-methyl-7-anilinofluorane can be used. These dye precursors are preferably finely divided into particles having an average particle diameter of 1 μm or less by using a disperser such as a sand grinder or an attritor.

The color developer used in the present invention is composed of an electron-accepting organic acidic substance capable of reacting with a color-forming dye under heating to develop a color thereof.
4'-isopropylidene diphenol [bisphenol A], 4,4'-isopropylidene bis (2-chlorophenol), 4,4'-isopropylidene bis (2-methylphenol), 4,4'-isopropylidene bis (2,1-tert-butylphenol), 4,4′-
sec-butylidene diphenol, 4,4′-cyclohexylidene diphenol, 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, naphthol, β-naphthol, methyl-4-
Hydroxybenzoate, 4-hydroxy-acetophenone, anilide salicylate, novolac type phenol resin, halogenated novolac type phenol resin, 4,4 ′
-Thiobis (3-methyl-6-tert-butylphenol), isopropyl p-hydroxybenzoate, p-
Butyl hydroxybenzoate, benzyl p-hydroxybenzoate, methylbenzyl p-hydroxybenzoate, aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, stearic acid, benzoic acid, p
-Tert-butylbenzoic acid, phthalic acid, gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3,5-di-
α-Methylbenzylsalicylic acid, bis (4-hydroxyoxyphenyl) sulfide, 1,7-di (4-hydroxyphenylthio) -3,5-dioxaheptane, p-nitrobenzoic acid, these organic developers And salts of polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin and nickel, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone, 3,3'-dihydroxy. Diphenyl sulfone, 3,3'-diamino-4,4'-dihydroxy-diphenyl sulfone, 3,3'-diallyl-
4,4'-dihydroxydiphenyl sulfone, 3,3 '
-Dichloro-4,4'-dihydroxydiphenyl sulfone, 4-hydroxy-diphenyl sulfone, 4-hydroxy-4'-isopropyldiphenyl sulfone, 4-hydroxy-4'-isopropyloxydiphenyl sulfone, 4-hydroxy-4'-benzyl Examples thereof include oxydiphenyl sulfone, 2,4-dihydroxy-diphenyl sulfone, 2,4-dihydroxy-4′-methyldiphenyl sulfone, and 3,4-dihydroshikiphenyl-p-trisulfone.

Such a developer is preferably finely divided by the same dispersion treatment as that for the dye precursor so that the average particle diameter becomes 0.7 μm or less. In the present invention,
The developer is usually mixed and used in an amount of 1 to 5 parts by weight, preferably 1.5 to 3 parts by weight, based on 1 part by weight of the dye precursor.

The soapless emulsion used as the binder of the thermosensitive coloring layer in the present invention is an emulsifier (surfactant).
It is not made into an aqueous emulsion using an organic solvent or an organic solvent, but is made up of a hydrophobic polymer compound in which a part of the copolymer is made hydrophilic and dispersed in water, and the hydrophobic polymer compound is methyl or ethyl. Copolymers of acrylic acid or methacrylic acid esters having alkyl having 10 or less carbon atoms such as propyl, butyl, and 2-ethylhexyl, and copolymers of styrene-butadiene, styrene-butadiene-acrylic acid, or methacrylic acid esters. In addition, it is a copolymer of acrylamide, vinyl acetate, acrylonitrile and the like with acrylic acid or acrylate.

It is further desirable that the hydrophobic polymer compound used in these soapless emulsions has a reactive group and has reactivity with a crosslinking agent. Due to the synergistic effect of the soappressing effect and the crosslinking effect. Shows excellent water resistance after film formation. Examples of the crosslinking agent for this purpose include epoxy compounds, polyamides, polyhydric alcohols, aldehydes and polyvalent metal compounds.

In the thermosensitive magnetic composite recording material of the present invention,
The thermosensitive coloring layer may contain a pigment, especially a white pigment, if necessary. Examples of such pigments include calcium carbonate, magnesium carbonate, kaolin, clay,
Talc, calcined clay, silica, diatomaceous earth, synthetic aluminum silicate, zinc oxide, titanium oxide, aluminum hydroxide, barium sulfate, inorganic fine powder such as surface-treated calcium carbonate and silica, and urea-formalin resin, Organic resin fine powder such as styrene / methacrylic acid copolymer and polystyrene resin can be used.

In the thermosensitive coloring layer, if necessary, an auxiliary additive component conventionally used in conventional thermosensitive recording materials, for example,
A small amount (10% or less based on the weight of the thermosensitive color developing layer) of a filler, a surfactant, a heat-fusible substance (or a lubricant) and the like may be added.

Examples of the heat-fusible substance include stearic acid amide, stearic acid ethylenebisamide, oleic acid amide, valmitic acid amide, coconut fatty acid amide,
Fatty acid amides such as behenic acid amide; zinc stearate, calcium stearate, polyethylene wax,
Waxes such as carnauba wax, harafin wax, ester wax; terephthalic acid dimethyl ester, terephthalic acid dibutyl ester, terephthalic acid dibenzyl ester, isophthalic acid dibutyl ester, 1-hydroxynaphthoic acid phenyl ester, 1,2-di (3- Methylphenoxy) ethane, 1,2-diphenoxyethane,
1-phenoxy-2- (4-methylphenoxy) ethane, diphenyl carbonate, p-benzylbiphenyl, 2,
2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (6-t-butyl-3-methylphenol), 1,1,3-tris (2-
Methyl-4-hydroxy-5-t-butylphenyl) butane, 2,2'-methylenebis (4-ethyl-6-t-)
Butylphenol), 2,4-di-t-butyl-3-methylphenol, 4,4'-thiobis (3-methyl-6)
-T-butylphenol) and the like; and 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, and 2-hydroxy-
Sensitizers such as 4-benzyloxybenzophenone, lubricants,
Antioxidants, UV inhibitors and the like can be used.

Each of these additives is used in a conventionally customary amount, but the heat-fusible substance is generally the developer 1.
It is preferable that the thermosensitive coloring layer contains 4 parts by weight or less with respect to parts by weight. To form the thermosensitive coloring layer,
A coating solution containing the above components may be prepared, coated on a support by a known coating method such as a roller coating method, a gravure coating method, or a wire coating method, and dried.

In the thermosensitive magnetic composite recording material of the present invention, a protective layer is formed on the thermosensitive coloring layer. This protective layer usually contains a water-soluble polymer substance or a hydrophobic polymer substance as a main component, and a pigment and a cross-linking agent are added thereto. In the present invention, the protective layer is effective for improving the water resistance, plasticizer resistance and oil resistance of the heat-sensitive recording material, especially the heat-sensitive color developing layer. By providing the protective layer and improving the above-mentioned properties, it is possible to surely avoid the adverse effects of water, plasticizer, oil and the like on the color image, such as fading of the color image.

As the water-soluble polymer substance used for the protective layer, those having a barrier effect such as polyvinyl alcohol resin and casein are preferable. As the polyvinyl alcohol resin, polyvinyl alcohol having any degree of polymerization and saponification can be used. Further, as the water-soluble polymer substance, unsaturated carboxylic acid or its partial or complete ester, salt, anhydride, nitrile, amide, unsaturated sulfonic acid or its salt, carbon number 2 to 30
Polyvinyl alcohol copolymerized and modified with α-olefin, vinyl ether, saturated branched fatty acid vinyl, etc., subjected to urethanization, acetalization, etherification, grafting, phosphoric acid esterification, nitric acid esterification, or acetoacetic acid esterification. Modified polyvinyl alcohol and the like can also be used. The degree of polymerization of such a polymer substance is preferably in the range of 300 to 1,700,
In particular, those of 500 to 1,000 are desirable from the viewpoint of coating viscosity and coatability.

The hydrophobic polymer used in the protective layer may be a copolymer of acrylic acid ester and / or methacrylic acid ester, styrene-butadiene, styrene-butadiene-acrylic acid ester and / or methacrylic acid ester. Copolymers and the like, which are used as an aqueous emulsion or latex. The amount of the water-soluble polymer substance or the total amount of the water-soluble polymer substance and the hydrophobic polymer substance in the protective layer composition is preferably 50% by weight or more based on the total weight of the protective layer. If it is less than this range, the resulting thermal recording material may have insufficient plasticizer resistance, oil resistance, and solvent resistance.

Examples of the water-soluble crosslinking agent used in the protective layer include dialdehyde compounds such as glyoxal and polyaldehyde, polyamine compounds such as polyethyleneimine, epoxy polyamide resin, diglycidyl compounds such as glycerin diglycidyl ether, Dimethylol urea, and metal salts such as ammonium persulfate, ferric chloride, magnesium chloride, chitosan, ammonium chloride,
Examples thereof include inorganic compounds such as boric acid. The amount of the crosslinking agent added is not particularly limited, but is generally preferably 3 to 30% with respect to the weight of the water-soluble polymer substance.

The pigment added to the protective layer is effective for enhancing the printability and whiteness of the resulting recording material and improving its smoothness. Examples of such pigments include kaolin, clay, talc, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, silica, synthetic aluminum silicate, synthetic magnesium silicate, aluminum oxide, polystyrene fine particles, and urea-formalin resin fine particles. The thing which consists of at least 1 type can be used. The content of the pigment in the protective layer is preferably 50% or less based on the total weight of the protective layer.

The coating amount of the protective layer is appropriately adjusted so as not to impair the heat conduction property and magnetic property from the thermal head to the color forming layer, but it is usually 1 to 5 g / m 2 by dry weight.
² is preferable, and 1 to 3 g / m ² is more preferable. This makes it possible to obtain the desired effect without deteriorating the thermal sensitivity and magnetic properties of the thermosensitive coloring layer.

After forming the protective layer by coating, it is desirable to apply a surface smoothing treatment to it with a super calendar or the like. When the Bekk smoothness of the protective layer is 1,000 seconds or less, a glossy good surface may not be obtained even if an overcoat layer of an ultraviolet curable resin is provided on the protective layer. The Beck smoothness is preferably adjusted to 1,000 to 10,000 seconds, preferably 3,000 to 5,000 seconds.

In the heat-sensitive composite recording material of the present invention, an overcoat layer made of a resin material cured by ultraviolet rays is formed on the protective layer. Since this overcoat layer is formed using a solventless type UV curable resin, it not only has excellent water resistance and solvent resistance, but it is also cured by UV light, so it has no adverse effect on the thermosensitive coloring layer or magnetic recording layer. Never give. Further, since the recording material of the present invention can be sufficiently crosslinked and cured, it has a sufficient film strength when used as a magnetic card and has a good gloss on the surface.

In the overcoat layer of the present invention, for compatibility with the thermal head, especially for preventing sticking,
A pigment and / or a lubricant (release agent) can be contained. The coating amount of the overcoat layer is 1 to dry weight.
It is preferably 5 g / m ² , and more preferably 1 to 3 g / m ² .

In the thermosensitive magnetic composite recording material of the present invention,
A magnetic recording layer is formed on the opposite surface of the support. This magnetic recording layer contains magnetic powder and an adhesive as main components. As magnetic powder, γ-iron oxide, cobalt modified γ
-Iron oxide, barium ferrite, chrome oxide, etc. can be used. As the adhesive, polyvinyl alcohol, water-soluble polymer such as casein, styrene-butadiene copolymer, acrylic resin, latex of water-insoluble resin such as vinyl acetate resin, or emulsion, or polyurethane resin, Water-insoluble resins such as vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, and polyester resin can be used. The magnetic powder coating material containing these magnetic powder and adhesive as main components is prepared using either an aqueous solvent or an organic solvent. As the organic solvent, toluene, xylene, methyl ethyl ketone or the like can be used. The prepared magnetic coating material is coated on the base paper with an air knife coater, roll coater, bar coater or the like to provide a magnetic recording layer. Generally, the coating amount of the magnetic recording layer is preferably 25 to 35 g / m ² in terms of dry weight.

The aluminum coating layer disposed on the magnetic recording layer contains aluminum powder and an adhesive as main components, and is formed by an aqueous or organic solvent-based coating containing them. Since the aluminum powder contained in this aluminum coating layer is easily oxidized and therefore loses its metallic luster, an aluminum paste pigment processed into a pre-formed paste is used. The coating material for forming an aluminum coating layer is prepared by including such an aluminum paste pigment and an adhesive as main components, and further adding an additive, a paint adjusting agent or the like, if desired. As the solvent, the same adhesive and solvent as those used for the magnetic recording layer can be used.

The coating material for forming an aluminum coating layer as described above is coated on the magnetic recording layer by using a roll coater, a blade coater, a gravure coater or the like, and dried to form an aluminum coating layer. The coating amount of the aluminum coating layer is 1 to 5 g / m on a dry basis.
^{A value of 2} is preferable, and almost no deterioration in magnetic properties due to the provision of this layer is recognized. The aluminum coating layer hides the dark brown or black brown magnetic recording layer and enables desired printing and recording.

In the thermosensitive magnetic composite recording material of the present invention,
On the surface of the support on which the thermosensitive coloring layer is coated,
You may print a photograph or a design. Furthermore, since an aluminum coating layer (concealing layer) is provided on the magnetic recording layer of the support, it does not impair the aesthetics due to the unclearness of the magnetic recording layer of the conventional product. Can be printed, and the amount of recorded information can be increased accordingly.

[0035]

In the above-described thermosensitive magnetic composite recording material of the present invention, since the binder of the thermosensitive coloring layer is a hydrophobic polymer substance, the formed thermosensitive coloring layer is a normal water-soluble polymer substance. Shows more water resistance than the above, and since it is a soapless emulsion and does not use an emulsifier (surfactant), it has the function of imparting excellent water resistance. The adhesiveness between the heat-sensitive color forming layer and the heat-sensitive color forming layer is more suitable than the case of using a usual water-soluble polymer substance.

[0036]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto. In the examples, "part" means "part by weight" unless otherwise specified.

Example 1 A thermosensitive magnetic composite recording sheet was manufactured by the following steps. (1) Formation of magnetic recording layer First, a magnetic recording layer coating liquid having the following composition was prepared. Barium ferrite (coercive force: 3000 Oe, average particle size: 0.6 μm) 100 parts Vinyl chloride-vinyl acetate copolymer 15 parts Polyurethane 25 parts Lecithin 2 parts Toluene / MEK (1: 1) 330 parts Next, this coating solution A magnetic recording layer was formed by coating one surface of a support of a milk-white polyethylene terephthalate film (PET) having a thickness of 188 μm so that the dry weight was 30 g / m ² , and drying.

(2) Formation of Aluminum Coating Layer A coating liquid for aluminum coating layer having the following composition was prepared. Aluminum paste 25 parts Polyurethane 10 parts Toluene / ethanol (1: 1) 100 parts This coating solution is dried on the magnetic recording layer in a dry weight of 2 g / m ^2.
Was coated and dried to form a concealing layer made of an aluminum coating layer.

(3) Thermosensitive Coloring Layer A coating solution for thermosensitive coloring layer having the following composition was prepared. 1) Preparation of solution A 3- (N-ethyl-N-cyclohexylamino) -6-methyl-7-anilinofluorane 5 parts 10% methyl vinyl ether-maleic anhydride copolymer aqueous solution 5 parts water 8 parts 2) Preparation of solution B 2,4-dihydroxy-diphenyl sulfone 30 parts 10% methyl vinyl ether-maleic anhydride copolymer aqueous solution 30 parts water 22 parts The above solution A and solution B are separately sand grinders and have an average particle size of 1 μm or less. Disperse and crush until

3) Formation of thermosensitive coloring layer Liquid A 12 parts Liquid B 46 parts 60% Calcium carbonate 40 parts 40% Acrylic ester copolymer soappress emulsion (Jurimer FC-30, Nippon Pure Chemical Co., Ltd.) 45 parts Water 125 Parts are mixed in the above proportions to prepare a coating liquid. This coating solution was applied on the opposite surface of the support so that the dry weight was 6.0 g / m ² , and dried to form a thermosensitive color developing layer.

(4) Formation of Protective Layer A coating liquid for protective layer having the following composition was prepared. 10% carboxy-modified polyvinyl alcohol aqueous solution 100 parts 30% polyamide resin 3 parts 60% kaolin aqueous dispersion 13 parts water 20 parts This coating solution has a dry weight of 1.5 g /
It was coated so as to be m ² , and dried to form a protective layer.

(5) UV curable resin overcoat layer
Formation Further, an ultraviolet curable vehicle (trade name: Seika Beam PPC-D-9, manufactured by Dainichiseika Kogyo Co., Ltd.) is formed on the protective layer.
(Modified)) with an offset printing machine at a dry coating amount of ² g / m ² to a thickness of 2 μm, and then an ultraviolet curing device having one 1.2 kW mercury lamp is used for this coating layer. , Distance from the lamp 10cm, transport speed 15m /
The overcoat layer was formed by irradiating with ultraviolet rays under the condition of minutes.

By the above operation, the magnetic recording layer and the aluminum coating layer are sequentially formed on one surface of the support,
A thermosensitive magnetic composite recording material in which a thermosensitive coloring layer, a protective layer and an ultraviolet curable resin overcoat layer were sequentially formed on the other surface of the support was obtained. A card printer tester having a line dot type thick film type head, which is obtained by cutting the above thermosensitive magnetic composite recording material into a card shape having a predetermined size (0.66).
mJ / dot, 14V, 1msec ON), solid black recording was performed, and sticking suitability in the operation was evaluated on this recording, and the obtained color density was measured by a Macbeth reflection densitometer (RD-9).
14 type).

Separately, predetermined test pieces were prepared from the above thermosensitive magnetic composite recording materials, and their water resistance, plasticizer resistance, chemical resistance and running durability were measured by the following test methods. (1) Water resistance test The test piece was washed once in a washing machine in a standard cycle, and the state of scratches on the recording surface, the elution state of the coating film, and the residual concentration after drying were observed, measured, and evaluated. (2) Plasticizer resistance After a plastic eraser (dragonfly mono) was pressure bonded to the recording surface side of the test piece at a pressure of 200 g / m ² for 48 hours,
The residual density of the color image was measured and evaluated.

(3) Chemical resistance 70% alcohol solution was dropped on the recording surface side of the test piece,
After standing for 2 minutes, the solution was wiped off, and the residual density of the color image was measured and evaluated. (4) Resistance to temperature and humidity After the test piece was left in an atmosphere of 55 ° C. and 90% RH for 24 hours, the residual density of the color image was measured and the reflection density of the non-recorded portion was measured and evaluated. (5) Running durability The recording surface side of the test piece was subjected to a rubbing test (500 times with a load of 500 g) using an abrasion tester, and the degree of damage on this recording surface and the residual density of the color image were measured and evaluated. . The results of each test are shown in Table 1.

Example 2 The same operation as in Example 1 was performed. However, 3- (N-ethyl-N-cyclohexylamino) -in the thermosensitive color developing layer coating solution
3-Diethylamino-7- (metatrifluoromethyl) anilinofluorane was used in place of 6-methyl-7-anilinofluorane. The test results are shown in Table 1.

Example 3 The same operation as in Example 1 was performed. However, instead of 2,4-dihydroxy-diphenyl sulfone in the thermosensitive color developing layer coating solution, bis- (3-allyl-4-hydroxyphenyl)-
Sulfone was used. The test results are shown in Table 1.

Example 4 The same operation as in Example 1 was performed. However, instead of soapless acrylic emulsion, Julimer FC-30 in the thermosensitive color developing layer coating liquid, soapless acrylic emulsion, ET-L126 (acrylic ester copolymer),
A product manufactured by Chuo Rika Kogyo was used. The test results are shown in Table 1.

Example 5 The same operation as in Example 1 was performed. However, instead of the soapless acrylic emulsion and Julimer FC-30 in the thermosensitive color developing layer coating solution, soapless acrylic emulsion, SC-3295 (acrylic acid ester copolymer), manufactured by Nippon Shokubai was used. The test results are shown in Table 1.

Comparative Example 1 The same operation as in Example 1 was performed. However, instead of the soapless emulsion and the Julimer FC-30 in the thermosensitive color developing layer coating solution, an acrylic ester copolymer emulsion containing an emulsifier, EX-15, manufactured by Nippon Shokubai was used. The test results are shown in Table 1.

Comparative Example 2 The same operation as in Example 1 was performed. However, the acrylic acid copolymer-based soapless emulsion containing the emulsifier instead of the acrylic acid copolymer-based soapless emulsion and the Julimer FC-30 in the thermosensitive coloring layer coating liquid, Ricabond ES-
20, manufactured by Chuo Rika Kogyo Co., Ltd. was used. The test results are shown in Table 1.

[0052]

[Table 1]

[Notes in Table 1] * 1 ⊚: No sticking to the thermal head, and no sticking sound was generated. ◯: There was no sticking to the thermal head, but some sticking sound was generated. Δ: Some sticking to the thermal head was recognized, and the image was distorted. X: The thermal head was often stuck to the recording material, causing poor running of the recording material. * 2 ◎: Very good ○: Good Δ: Slightly bad ×: Very bad * 3 Value in% of the read output of the standard cybernet standard ticket

As is clear from Table 1, the thermosensitive magnetic composite recording materials of the respective examples according to the present invention obtained satisfactory results, but the recording materials of the respective comparative examples were unsatisfactory in some properties. Met.

[0055]

The heat-sensitive magnetic composite recording material of the present invention has excellent whiteness even on the magnetic recording layer side, and uses a heat-sensitive color forming layer using a hydrophobic polymer compound emulsion as a binder. In spite of this, there is no decrease in whiteness, it is possible to improve water resistance and temperature and humidity resistance, and there is no deterioration in magnetic characteristics. Therefore, both magnetic information and visible information can be recorded on one side of the card. It is possible to record an extremely large amount of information, has sufficient long-term storage stability of the record, and has extremely high practicality.

Claims (1)

[Claims] 1. A support, a substantially colorless dye precursor formed on one surface of the support, a color developer which reacts with the dye precursor under heating to develop a color, and A thermosensitive coloring layer containing a mixture of a binder as a main component, at least one selected from a water-soluble polymeric substance and a hydrophobic polymeric substance formed on the thermosensitive coloring layer, a pigment and a crosslinking agent. A protective layer containing the main component, an overcoat layer formed on the protective layer and containing an ultraviolet curable resin as the main component, a magnetic powder and a binder formed on the other surface of the support. A magnetic recording layer containing as a main component,
Soapless formed on the magnetic recording layer and having a concealing layer containing aluminum powder and a binder as main components, and the thermosensitive coloring layer containing a hydrophobic polymer substance as a binder as a main component. A heat-sensitive magnetic composite recording material characterized by using an emulsion.