JPH04364982A - Thermosensitive magnetic composite recording material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a heat-sensitive magnetic composite recording material. More specifically, the present invention is applicable to coupon tickets, gift certificate cards, highway cards, and other cards for various automatic systems. The present invention relates to a heat-sensitive magnetic composite recording material that can visualize a part of magnetically recorded information by thermal printing.

0002

BACKGROUND OF THE INVENTION With the rapid spread of telephone cards and orange cards, prepaid cards are suddenly attracting attention, and their practical use in various distribution service industries, including transportation, is rapidly becoming widespread. The spread of such heat-sensitive magnetic recording materials is due to the large information storage capacity of the magnetic recording layer, the ease and accuracy of reading written information, and the ease with which it can be processed by automatic ticket gates or vending machines. This seems to be due to the advantages such as being able to do a lot of things, being able to process fractional amounts, and being effective in saving labor.

[0003] As a balance display method for prepaid cards,
Conventionally, a punch hole method has been used, but this method has drawbacks such as the fact that the exact balance cannot be determined with the card alone, the usage history is not clear, and punch waste accumulates inside the reader/writer. be. Therefore, thermal recording methods have been adopted to enable accurate balance display.

Conventionally, a magnetic recording layer is provided on one side of a base paper,
Heat-sensitive magnetic composite recording paper with a heat-sensitive recording layer on the opposite side is used for train tickets, commuter passes, etc.
It has also come to be used for various cards.

However, the magnetic recording layer of such conventional recording materials is colored by magnetic powder used as its main component, and no consideration has been given to printing or printing on it. It was something. Therefore, as a method to solve such problems, there is a method of adding a coloring pigment to the magnetic coating material to give the magnetic recording layer a desired color when forming the magnetic recording layer, and a method of applying a desired color to the magnetic recording layer.
It has been proposed to apply a white pigment paint onto the magnetic recording layer, as disclosed in US Patent No. 204,991. With these methods, it is possible to print visible information on the magnetic recording layer, but it is not possible to print the usage status, such as displaying the balance, on the magnetic recording layer by thermosensitive recording and make it visible.

[0006] In order to visualize this remaining amount,
-310096, a magnetic recording layer is formed on one side of a support, a heat-sensitive recording layer is provided on this magnetic recording layer, and a protective layer cured by ultraviolet rays is further provided on this heat-sensitive recording layer. Thermosensitive magnetic composite recording materials have been proposed. In this recording material, even if printing is performed on the heat-sensitive coloring layer by heat-sensitive recording, the colored image is colored brown or dark black due to the magnetic powder in the magnetic recording layer below.
It has the disadvantage that it is difficult to read, is unclear, and detracts from its aesthetic appearance.

On the other hand, heat-sensitive recording materials generally include a substantially colorless color-forming dye precursor, such as an electron-donating leuco dye, and an electron-containing dye precursor, such as an electron-donating leuco dye, on one side of a support such as paper, synthetic paper, or plastic film. A heat-sensitive coloring layer containing as main components an organic acidic color developer such as a receptive phenolic compound and a binder is provided. A colored recorded image can be obtained by reaction. Such heat-sensitive recording materials have the advantage that the recording device is compact, inexpensive, and easy to maintain. It is widely used in applications such as CRT printers and CRT medical measurement printers.

However, conventional heat-sensitive recording materials in which a heat-sensitive coloring layer containing a dye precursor, a color developer, and a binder as active ingredients are coated on a support are It is unstable to plasticizers, oils, etc., and for this reason, changes in quality over time during storage have always been a problem.

[0009] In order to improve the storage stability as described above,
It has been proposed to provide a surface protective layer on the heat-sensitive coloring layer and cover it. For example, JP-A-56-146794
JP-A-58-199189 discloses forming a surface protective layer using a hydrophobic polymer compound emulsion, etc., and JP-A-58-199189 discloses that a water-soluble polymer compound or a water-soluble polymer compound or It is disclosed that a hydrophobic polymer compound emulsion is provided as an intermediate layer, and a surface protective layer is provided thereon using an oil-based paint containing a hydrophobic polymer compound as a resin component.

However, even when the above-mentioned surface protective layer is provided, an emulsion of a water-soluble polymeric substance or a hydrophobic polymeric compound is usually used as a binder in the heat-sensitive coloring layer. Conventional heat-sensitive coloring layers formed using such water-based paints have a problem in that their water resistance is unsatisfactory. Particularly when used in cards that will be 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, it is necessary to design the quality and structure of the heat-sensitive recording material so as to sufficiently prevent sticking to the thermal head.

[0011]

[Problems to be Solved by the Invention] The present invention solves the above-mentioned problems of conventional heat-sensitive magnetic composite recording materials, and records information such as the number of uses and remaining amount on the magnetic layer side in a clear and easily readable manner. In addition, the colored image has excellent water resistance, plasticizer resistance, oil resistance, etc., has long-term storage stability, and does not cause sticking to the thermal head during thermal recording operations. The aim is to provide a prepaid card with excellent recordability.

The present invention provides a heat-sensitive magnetic composite recording material in which a hiding layer is provided between the magnetic recording layer and the heat-sensitive coloring layer,
A protective layer and an overcoat layer are provided on the thermosensitive coloring layer, and a compound exhibiting low or insolubility in toluene is used as at least one of the dye precursor and the color developer in the thermosensitive coloring layer, and the binding thereof is performed. The above problem was successfully solved by using a toluene-soluble polymer substance as the agent.

That is, the thermosensitive magnetic composite recording material according to the present invention comprises a support, a magnetic recording layer formed on at least one surface of the support and containing magnetic powder and a binder as main components, A hiding layer formed on the magnetic recording layer and containing aluminum powder and a binder as main components; a substantially colorless dye precursor formed on the hiding layer; a thermosensitive coloring layer containing as a main component a mixture of a color developer that develops color by reacting with the color and a binder;
A protective layer formed on this heat-sensitive coloring layer and containing as main components at least one selected from a water-soluble polymeric substance and a hydrophobic polymeric substance, a pigment, and a crosslinking agent, and a protective layer formed on this protective layer. and an overcoat layer containing an ultraviolet curable resin as a main component, and in the thermosensitive color forming layer, (a) at least one of the dye precursor and the color developer has a solubility in toluene of 1% by weight or less at room temperature. and (b) the binder contains at least one polymeric substance that is soluble in toluene at room temperature.

[0014]

[Function] The thermosensitive magnetic composite recording material of the present invention is provided with excellent water resistance by forming the thermosensitive coloring layer using a solvent-based paint (solvent: toluene) containing a solvent-soluble binder. can do. Furthermore, when using a solvent-based paint, in order to maintain excellent whiteness, it is important to use a compound in which the solubility of the dye precursor and color developer in the solvent is 1% by weight or less.

Furthermore, in the thermosensitive magnetic composite recording material of the present invention, the brownish-brown and dark-black tones due to the magnetic powder of the magnetic recording layer formed on at least one surface of the support are hidden by coating with aluminum powder as a concealing layer. be able to. Further, by providing a protective layer on the heat-sensitive coloring layer formed using the above-mentioned solvent-based paint, the long-term storage stability of the colored image is maintained, and furthermore, an overcoat layer made of an ultraviolet curable resin is provided thereon. This makes it possible to prevent sticking in the thermal head and improve heat-sensitive recording suitability, without causing any problems in magnetic recording characteristics.

As illustrated in FIG. 1, the thermosensitive magnetic composite recording material 1 of the present invention comprises a support 2, a magnetic recording layer 3, a hiding layer 4, a thermosensitive coloring layer 5,
It is composed of a protective layer 6 and an overcoat layer 7.

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 films made of polyester resin materials such as polyethylene terephthalate and polybutylene terephthalate, films made of cellulose derivative materials such as cellulose triacetate film, polypropylene films, and polyolefin resins such as polyethylene. a film that becomes, and
These composite laminated films can be used. Furthermore, as the base paper for the support, high quality paper, processed base paper, synthetic paper, etc. can be used, but there is no particular limitation on the type thereof. Generally, it is preferable to use a support having a thickness of 50 to 200 μm.

The magnetic recording layer contains magnetic powder and adhesive as main components. As the magnetic powder, gamma iron monoxide, cobalt-modified gamma iron monoxide, barium ferrite, chromium oxide, etc. can be used. Adhesives include water-soluble polymers such as polyvinyl alcohol and casein, latexes or emulsions of water-insoluble resins such as styrene-butadiene copolymers, acrylic resins, and vinyl acetate resins, or polyurethane resins. Water-insoluble resins such as vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, and polyester resin can be used. Magnetic powder paints containing these magnetic powders and adhesives as main components are prepared using either an aqueous solvent or an organic solvent. Toluene, xylene, methyl ethyl ketone, etc. can be used as the organic solvent. The magnetic paint prepared can be prepared using an air knife coater, a roll coater,
A magnetic recording layer is provided by coating the base paper with a bar coater or the like. Generally, the weight of the magnetic recording layer is preferably 25 to 35 g/m2.

The concealing layer disposed on the magnetic recording layer contains aluminum powder and an adhesive as main components, and is formed from a water-based or organic solvent-based paint containing these. The aluminum powder contained in the hiding layer is easily oxidized and therefore loses its metallic luster.
An aluminum paste pigment is used which has been previously processed into paste form. The coating for forming a hiding layer is prepared by containing such an aluminum paste pigment and an adhesive as main components, and further adding additives or a coating conditioner as required, and the adhesive and solvent include those mentioned above. Adhesives and solvents similar to those used for magnetic recording layers can be used. The above-described coating material for forming a hiding layer is applied onto the magnetic recording layer using a roll coater, a blade coater, a gravure coater, or the like and dried, thereby forming a hiding layer. The coating amount of the concealing layer is 1 to 5 g.
/m2, and almost no deterioration in magnetic properties is observed due to the provision of the hiding layer.

A thermosensitive coloring layer containing a dye precursor, a color developer and a binder is formed on the hiding layer by a conventionally known coating method. The weight of this thermosensitive coloring layer is generally preferably 3 to 10 g/m<2>.

The dye precursor used in the present invention is a substantially colorless electron-donating compound that can develop a color by reacting with a color developer under heating. Among such color-forming dye precursors, as mentioned above, those having a solubility in toluene of 1% by weight or less at room temperature include, for example:
2,2-bis{4-[6'-(N-cyclohexyl-N
-methylamino)-3'-methylspiro[phthalide-3
,9'-xanthene]-2'-ylamino]phenyl}
Propane, 2-(2-fluorophenylamino)-6-
A compound consisting of at least one member selected from fluoran compounds such as diethylaminofluorane can be used. These dye precursors are prepared using a dispersing machine such as a sand grinder or an attritor to obtain particles with an average particle size of 1 μm.
It is preferable to miniaturize the particle size to less than m.

The color developer used in the present invention is composed of an electron-accepting organic acidic substance that can react with the color-forming paint under heating to cause it to develop color. Such a color developer can liquefy or vaporize at room temperature or higher, preferably 70° C. or higher, and react with the color-forming dye to develop color. As mentioned above, the color developer used in the present invention is one having a solubility in toluene of 1% by weight or less at room temperature, such as 3,4-dihydroxyphenyl-p-tolylsulfone, bis-(3 −
Allyl-4-hydroxyphenyl)-sulfone, stearyl gallate, methyl-bis(4-hydroxyphenyl) acetate, n-butyl-bis(4-hydroxyphenyl) acetate, 4-hydroxy-4-isopropoxydiphenyl sulfone, and 1,1-bis-(4
-Hydroxy-phenyl)-cyclohexane and the like can be used.

In the present invention, the color developer is usually used in an amount of 1 to 5 parts by weight, preferably 1.5 to 5 parts by weight, per 1 part by weight of the dye precursor.
It is mixed and used at a ratio of 3 parts by weight.

In the present invention, as the binder contained in the heat-sensitive coloring layer, a polymeric substance which is soluble in toluene at room temperature is used as described above. However, it is preferable that the mixed liquid does not develop color, aggregate, or become highly viscous when mixed with the respective dispersions of the dye precursor and the color developer. It is preferable that the heat-sensitive recording layer film satisfies requirements such as being tough, having no desensitizing effect, and not causing sticking to the thermal head.

Therefore, in the present invention, it is preferable to use a methyl methacrylate copolymer resin as the binder, which satisfies the above requirements. Such methyl methacrylate copolymer resin has a glass transition point (TG
) is preferably in the range of 75 DEG C. to 105 DEG C., such as copolymers of methyl methacrylate and acrylic esters and/or methacrylic esters (such as butyl methacrylate) or styrene. The binder is generally preferably used in an amount of 15 to 30% by weight based on the total dry weight of the heat-sensitive coloring layer.

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

[0027] The heat-sensitive coloring layer may also contain, if necessary, auxiliary additive components commonly used in conventional heat-sensitive recording materials, such as
Fillers, surfactants, thermofusible substances (or lubricants), etc. may be added in small amounts (10% or less based on the weight of the thermosensitive coloring layer).

Examples of thermofusible substances include stearic acid amide, stearic acid ethylene bisamide, oleic acid amide, palmitylic 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, paraffin wax, and ester wax; dimethyl terephthalate, dibutyl terephthalate, dibenzyl terephthalate, dibutyl isophthalate, phenyl 1-hydroxynaphthoate, 1,2-di(3-methyl phenoxy)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
Hindered phenols such as -butylphenol); and 2-(2'-hydroxy-5'-methylphenyl)
Sensitizers such as -benzotriazole and 2-hydroxy-4-benzyloxybenzophenone, lubricants, antioxidants, ultraviolet inhibitors, and the like can be used.

[0029] These additives are all used in the amounts conventionally used, but the thermofusible substance is generally
It is preferable that the heat-sensitive coloring layer contains 4 parts by weight or less based on the weight part.

[0030] To form the heat-sensitive coloring layer, a coating solution containing the above components and a solvent (for example, toluene) is prepared, and this is applied onto a support by a known coating method such as a roller coating method, a gravure coating method, or a coating solution. may be applied by a wire coating method or the like 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 polymeric substance or a hydrophobic polymeric substance as a main component, to which a pigment and a crosslinking agent are added. 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 coloring layer. By improving the above properties with the protective layer, it is possible to reliably avoid the adverse effects of water, plasticizers, oils, etc. on the colored image, such as fading of the colored image.

The water-soluble polymer used in the protective layer is preferably one having a barrier effect, such as polyvinyl alcohol resin and casein. As the polyvinyl alcohol resin, polyvinyl alcohol having any degree of polymerization and saponification can be used. Furthermore, unsaturated carboxylic acids or partial or complete esters, salts, anhydrides, nitriles, amides, unsaturated sulfonic acids or salts thereof, carbon atoms 2 to 30 as water-soluble polymeric substances.
Polyvinyl alcohol that has been copolymerized and modified with α-olefins, vinyl ethers, saturated branched fatty acid vinyl, etc.; polyvinyl alcohol that has been subjected to urethanization, acetalization, etherification, grafting, phosphoric acid esterification, sulfuric acid esterification, or acetoacetic acid esterification, etc. 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, and particularly preferably 500 to 1,000 from the viewpoint of paint viscosity and coatability.

Hydrophobic polymeric substances used in the protective layer include copolymers of acrylic esters and/or methacrylic esters, styrene, butadiene, copolymers of acrylic esters and/or methacrylic esters, and the like. These are used as aqueous emulsions or latexes. In the composition of the protective layer, the amount of the water-soluble polymeric substance or the total amount of the water-soluble polymeric substance and the hydrophobic polymeric substance is preferably 50% by weight or more based on the total weight of the protective layer. If it is less than this, the resulting heat-sensitive recording material may have insufficient plasticizer resistance, oil resistance, and solvent resistance.

Water-soluble crosslinking agents used in the protective layer include dialdehyde compounds such as glyoxal and polyaldehyde, polyamine compounds such as polyethyleneimine, epoxy polyamide resins, diglycidyl compounds such as glycerin diglycidyl ether, Examples include dimethylol urea, metal salts such as ammonium persulfate, ferric chloride, and magnesium chloride, and inorganic compounds such as chitosan, ammonium chloride, and boric acid. There is no particular limitation on the amount of the crosslinking agent added, but it is generally preferably 3 to 30% based on the weight of the water-soluble polymer substance.

The pigment added to the protective layer is effective for increasing the printability and whiteness of the resulting recording material, as well as 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, urea-formalin resin fine particles, etc. At least one type can be used. The pigment content 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 to an amount that does not impede the heat conduction properties from the thermal head to the coloring layer and the magnetic properties, but it is usually preferably 1 to 5 g/m2, and 1 to 5 g/m2. More preferably, it is 3 g/m2. In this way, the desired effect can be obtained without reducing the thermal sensitivity and magnetic properties of the thermosensitive coloring layer.

After forming the protective layer by coating, it is desirable to subject it to surface smoothing treatment using a supercalender or the like. If the Bekk smoothness of the protective layer is 1,000 seconds or less, even if an overcoat layer of ultraviolet curable resin is provided on the protective layer, a good glossy surface may not be obtained. It is preferable to adjust the Bekk smoothness 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. This overcoat layer is formed using a solvent-free ultraviolet curable resin, and not only has excellent water and solvent resistance, but since it is cured with ultraviolet light, it has no adverse effect on the thermosensitive coloring layer or magnetic recording layer. I won't give anything. In addition, since the recording material of the present invention can be sufficiently crosslinked and cured, when used as a magnetic card, it has sufficient film strength and a good gloss on the surface.

In the overcoat layer of the present invention, for compatibility with the thermal head, especially to prevent sticking,
A pigment and/or a lubricant (mold release agent) can be included. The coating amount of the overcoat layer is 1 to 5 g/m2
It is preferable that it is, and it is more preferable that it is 1-3 g/m2.

In the thermosensitive magnetic composite recording material of the present invention,
A photograph, a design, etc. may be printed on the back surface of the support opposite to the surface coated with the magnetic recording layer, depending on the purpose of use. Further, on the back side of the support, a thermosensitive coloring layer of the present invention,
It is also possible to laminate a protective layer and an ultraviolet curing resin overcoat layer so that both sides can be thermally recorded. The design and precautions for card use are printed on a protective layer, and a UV-curable resin overcoat layer is provided on top of the protective layer to create a heat-sensitive magnetic composite recording material (heat-sensitive magnetic card) suitable for various uses. can get.

[0041]

EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the scope of the present invention is of course not limited by these. In each example, "parts" indicate "parts 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 coating liquid for magnetic recording layer having the following composition was prepared. Barium ferrite (coercive force: 3000O
e, 10
0 parts
Average particle size: 0.6 μm) PVC-vinyl acetate copolymer
15 parts polyurethane

25 parts lecithin


Part 2 Toluene/MEK (1:1)

330 parts of this coating solution was then applied to a thickness of 188 μm.
milky white polyethylene terephthalate film (PE
T) with a dry weight of 30 g/m
2 and dried to form a magnetic recording layer.

(2) Formation of Hiding Layer A coating solution for hiding layer having the following composition was prepared. aluminum paste

25 parts polyurethane

10 parts
Toluene/ethanol (1:1)
100
This coating solution was applied onto the magnetic recording layer at a dry weight of 2 g/m.
2, and dried to form a concealing layer.

(3) Formation of thermosensitive coloring layer A coating solution for thermosensitive coloring layer having the following composition was prepared. 2-(2-fluorophenylamino)-6
-diethyl 20 parts
Toluene dispersion of aminofluorane (solid content 20
%) 4-hydroxy-4-isopropoxydiphenyl 60 parts
Toluene dispersion of sulfone (solid content 2
0%) 22 parts of a copolymer mainly composed of 30% methyl methacrylate
Toluene solution (trademark: BR-83, manufactured by Mitsubishi Rayon) Toluene

Five parts of this coating solution was coated on the above-mentioned hiding layer so that the dry weight was 4.5 g/m<2 >and dried to form a heat-sensitive coloring layer.

(4) Formation of protective layer A coating solution for a 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
Part 13 Water

20 parts of this coating solution was coated on the heat-sensitive coloring layer to a dry weight of 1.5 g/m<2>, and dried to form a protective layer.

(5) Formation of an ultraviolet curable resin overcoat layer Further, on the above protective layer, an ultraviolet curable vehicle (manufactured by Dainichiseika Kagyo Co., Ltd., trademark: Seikabeam PPC-D-9 (revised)) is applied.
) was coated with an offset printing machine at a dry coating weight of 2 g/m to a thickness of 2 μm, and then on this coated layer,
An overcoat layer was formed by irradiating ultraviolet rays at a distance from the lamp of 10 cm and a conveyance speed of 15 m/min using an ultraviolet curing device equipped with one 1.2 kW mercury lamp.

By the above operations, a heat-sensitive magnetic composite recording material was obtained in which five layers, ie, a magnetic recording layer, a hiding layer, a heat-sensitive coloring layer, a protective layer, and an ultraviolet curing resin layer, were successively formed on the support.

The above heat-sensitive magnetic composite recording material was cut into a card shape of a predetermined size, and a card printer tester having a line-dot type thick film head was used (0.66 mJ/dot).
, 14V, 1msec ON) to make a solid black record, evaluate the sticking suitability of this record during operation, and measure the obtained color density using a Macbeth reflection densitometer (RD
-914 type).

Separately, specified test pieces were prepared from the above thermosensitive magnetic recording material, and their water resistance, plasticizer resistance, chemical resistance and running durability were measured by the following test methods.

(1) Water resistance test: The specimen was washed once in a washing machine using a standard cycle, and the condition of scratches on the recording surface, the state of elution of the coating film, and the residual concentration after drying were observed and measured. ,evaluated.

(2) Plasticizer resistance: Place a plastic eraser (tonbow) on the recording side of the test piece.
Mono) was pressed at a pressure of 200 g/cm2 for 48 hours, and then the residual density of the colored image was measured and evaluated.

(3) Drop a 70% alcohol solution onto the recording surface side of the chemical resistance test piece,
After standing for 2 minutes, the solution was wiped off, and the remaining density of the colored image was measured and evaluated.

(4) Temperature and Humidity Resistance After the specimen was left in an atmosphere of 55° C. and 90% RH for 24 hours, the residual density of the colored image was measured, and the reflection density of the non-recorded portion was also measured and evaluated.

(5) Running durability The recording surface side of the specimen was subjected to a rubbing test (500 times at a load of 500 g) using an abrasion tester, and the degree of damage to the recording surface and the residual density of the colored image were determined. Measured and evaluated. The results of each test are shown in Table 1.

Example 2 The same operation as in Example 1 was carried out. However, 2,2-bis{4-[6'
-(N-cyclohexyl-N-methylamino)-3'-
Methylspiro[phthalide-3,9'-xanthene]-2
'-ylamino]phenyl}propane was used. The test results are shown in Table 1.

Example 3 The same operation as in Example 1 was carried out. However, bis(3allyl-4-hydroxyphenyl)-sulfone was used instead of 4-hydroxy-4-isopropoxydiphenylsulfone in the heat-sensitive coloring layer coating solution. The test results are shown in Table 1.

Comparative Example 1 The same operation as in Example 1 was carried out. However, instead of 2(2-fluorophenylamino)-6-diethylaminofluorane in the heat-sensitive coloring layer coating solution, 6-(n-ethyl- n-isopentyl)amino-3methyl-2-anilino-fluoran was used. The test results are shown in Table 1.

Comparative Example 2 The same operation as in Example 1 was carried out. However, when dispersing the dye precursor and color developer in the preparation of the heat-sensitive coloring layer coating solution, water was used instead of toluene, and water-based polyester was used instead of the copolymer mainly composed of methyl methacrylate.
Urethane resin (toluene insoluble) was used as a binder. The test results are shown in Table 1.

[Table 1]

(Notes for Table 1) *1 ◎: No sticking to the thermal head at all,
Furthermore, there was no sticking sound at all. ○: There was no sticking to the thermal head, but some sticking noise occurred. Δ: Slight adhesion to the thermal head was observed, and the image was distorted. x: The recording material often stuck to the thermal head, causing poor running of the recording material. *2 ◎ - Extremely excellent ○ - Good △ - Yaゝ Poor × - Extremely poor *3 Value expressed as a percentage of the reading output of the reference ticket of the cybernetic standard

As is clear from Table 1, the thermosensitive magnetic composite recording materials of each Example according to the present invention obtained satisfactory results, but the recording materials of each Comparative Example were unsatisfactory in some property. Met.

The thermosensitive magnetic composite recording material of the present invention also has excellent whiteness on the magnetic recording layer side, and there is no decrease in whiteness despite the use of a thermosensitive coloring layer formed from a solvent-based paint. Moreover, it is possible to improve water resistance and temperature and humidity resistance, and there is no deterioration in magnetic properties. Therefore, both magnetic and visible information can be recorded on one side of the card, and an extremely large amount of information can be recorded. It is possible to record, the long-term preservation of the record is sufficient, and it has extremely high practicality.

[Brief explanation of the drawing]

FIG. 1 is an explanatory cross-sectional view showing the structure of a thermosensitive magnetic composite recording material of the present invention.

[Explanation of symbols] 1...Thermosensitive magnetic composite recording material 2...Support 3...Magnetic recording layer 4...Hidden layer 5...Thermosensitive coloring layer 6...Protective layer 7...Overcoat layer

Claims (1)

[Claims] 1. A support, a magnetic recording layer formed on at least one surface of the support and containing magnetic powder and a binder as main components, and a magnetic recording layer formed on the magnetic recording layer and comprising aluminum powder. and a binder as main components; a substantially colorless dye precursor formed on the hiding layer;
A thermosensitive coloring layer containing a mixture of a color developer and a binder that reacts with this dye precursor under heating to develop color, and a binder as a main component, and a water-soluble polymer substance and At least one kind selected from hydrophobic polymer substances,
The thermosensitive coloring layer includes a protective layer containing a pigment and a crosslinking agent as main components, and an overcoat layer formed on the protective layer and containing an ultraviolet curable resin as a main component, and in the heat-sensitive coloring layer, (a) the dye precursor (b) at least one of the binder and the color developer contains at least one compound having a solubility in toluene of 1% by weight or less at room temperature; and (b) the binder contains at least one compound that is soluble in toluene at room temperature.
1. A thermosensitive magnetic composite recording material comprising a polymeric substance.