JPH04169276A - Heat sensitive recording type magnetic card sheet - Google Patents

Abstract

PURPOSE:To prevent output variation, wave form strain or drop-out, etc., caused by unevenness in thickness of a magnetic recording layer form happening by providing an under coat layer of which the major component is a water-base emulsion resin, on a supporting body. CONSTITUTION:An under coat layer 2 of which the major component is a water base emulsion is provided in one direction on a supporting body 1 made of paper, and a magnetic recording layer 3 of a water-base magnetic paint is provided on the top of the under coat layer 2, and a heat sensitive recording layer 4 is provided on the other surface. As a particularly preferable water-base emulsion resin, one with a favorable film formability of which the glass transition temperature is not higher than 100 deg.C is used, and the adhered quantity of the under coat layer is made not less than 2g/m<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-sensitive recording magnetic ticket sheet having a magnetic recording layer and a heat-sensitive recording layer.

(Prior art) Conventionally, a heat-sensitive recording type magnetic ticket sheet is made by forming a heat-sensitive recording layer mainly composed of leuco dye and acidic substance on one side of a plastic sheet or paper, and forming a heat-sensitive recording layer mainly composed of leuco dye and acidic substance on the other side. It is made by forming a magnetic recording layer whose main component is a binder.

Although this method of applying heat-sensitive recording magnetic ticket sheets is effective, it has many drawbacks.

In other words, when a plastic sheet is normally used as a support, it is often manufactured using an organic solvent-based material in order to obtain adhesive strength and durability to the support, which tends to cause safety and hygiene problems, and increases cost. The disadvantage is that it is also expensive.

Furthermore, if a fibrous material such as paper is used as the support, the above-mentioned problems will not occur, but unevenness will occur at the interface with the support due to penetration of the magnetic paint and its non-uniformity. The magnetic recording layer tends to have uneven thickness, and this uneven thickness increases output fluctuations and causes waveform distortion and dropouts.

(Problems to be Solved by the Invention) The present invention uses paper, cloth, etc. as the support and uses water-based magnetic paint, thereby eliminating safety and hygiene problems.
The present invention aims to provide a heat-sensitive recording type magnetic ticket sheet that is inexpensive and free from problems such as output fluctuations, waveform distortion, and dropouts caused by uneven thickness of the magnetic recording layer.

(Means for Solving the Problems) As a result of intensive research in order to solve the above problems, the present inventors have developed an aqueous emulsion mainly composed of an aqueous emulsion in the direction of the paper support 1, as shown in FIG. providing an undercoat layer 2;
It has been found that the above problems can be solved by forming a layer structure in which a magnetic recording layer 3 of a water-based magnetic paint is provided on top of the magnetic recording layer 3 and a heat-sensitive recording layer 4 is provided on the other surface.

That is, according to the studies of the present inventors, the uneven thickness of the magnetic recording layer is caused by the penetration of the magnetic paint into the support, and an undercoat layer mainly composed of an aqueous emulsion resin is formed on the support. It has been found that by providing this, it is possible to prevent the magnetic paint from penetrating and prevent the above-mentioned unevenness of the magnetic recording layer.

That is, according to the present invention, a magnetic recording layer mainly composed of a ferromagnetic material and a binder is provided on one side of a support made of fibrous material such as paper or cloth, and A heat-sensitive recording magnetic ticket sheet having a heat-sensitive recording layer on its surface containing a normally colorless or light-colored leuco dye and an acidic substance as color-forming components, wherein the main component is an aqueous emulsion resin between the support and the magnetic recording layer. A heat-sensitive recording magnetic ticket sheet is provided which is characterized by being provided with an undercoat layer.

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

Various conventional aqueous emulsion resins can be used as appropriate for the undercoat layer of the present invention, and specific examples include polyvinyl butyral, polyvinyl acetate, polyvinyl propionate, polyvinyl butyrate, and polymethyl acrylate. , polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, polyhebutyl acrylate, polyethylhexyl acrylate, styrene-butadiene rubber, nitrile rubber, natural rubber, polyisobutylene rubber, polybutadiene, polyacrylonitrile, polyacrylonitrile, polyvinylidene chloride, poly Dichlorostyrene, polystyrene, polyvinyl chloride, polymethacrylic acid, polymethyl methacrylate,
Examples include aqueous emulsion resins such as polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polyethylhexyl methacrylate, polyvinyl alcohol, and polyvinyl stearate, but the present invention is not limited thereto. Particularly preferred aqueous emulsion resins include those having a good film-forming ability and a glass transition temperature of 00'T.

The amount of adhesion of the undercoat layer is 2 g/d or more, preferably 4 g/d or more.

In addition, the undercoat layer contains fillers such as aluminum hydroxide, clay, talc, calcium carbonate, silica, and zinc oxide, and thermofusible fillers such as stearic acid amide, β-naphthyl benzyl ether, P-benzylbiphenyl, and behenic acid amide. A sexual substance (or lubricant) may also be added.

As the magnetic paint used in the magnetic recording layer of the present invention, it is preferable to use a water-based magnetic paint. In conventional organic solvent-based paints, the undercoat layer is easily swollen or dissolved by the organic solvent, and a magnetic layer with unevenness is formed at the interface with the undercoat layer. The paint may seep into the support, causing the same problem as described above.

The magnetic recording layer of the present invention includes barium ferrite, strontium ferrite, Co-γ-Fe2O3, γ-Feg
A coating material in which ferromagnetic powder such as os is uniformly dispersed in an aqueous binder such as the above-mentioned aqueous emulsion resin is coated on a support and dried to form a magnetic recording layer.

The leuco dyes used in the present invention may be applied singly or in a mixture of two or more types. As such leuco dyes, those applied to this type of recording material can be arbitrarily applied. For example, triphenyl Methane type, fluoran type, phenothiazine type, auramine type, spiropyran type,
Leuco compounds of dyes such as indolinophthalide are preferably used. Specific examples of such leuco dyes include those shown below.

3.3-bis(P-dimethylaminophenyl)-phthalide, 3.3-bis(P-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violin raftone), 3.3-bis(p -dimethylaminophenyl)-6-diethylaminophenyl, 3.3-bis(p-dimethylaminophenyl)-6-chlorophthalide, 3.3-bis(P-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlor Fluoran, 3-dimethylamino-5,7-dimethylfluoran, 3
-(N-Methyl-N-isobutylamino)-6-methyl-7=anilinofluorane, 3-(N-ethyl-N-ynamylamino)-6-methyl-7-anilinofluorane, 3- Diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7,8-benzfluorane, 3-diethylamino-
6-Methyl-7-chlorofluorane.

3-(N-P-tolyl-N-ethylamino)-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2-(N-(3'- trifluoromethylphenyl)
amino)-6-dinithylaminofluorane, 2-(3
, 6-bis(diethylamino)-9-(o-chloroanilino)xantylbenzoic acid lactam), 3-diethylamine-6-methyl-7-(m-)lichloromethylanilino)fluoran, 3-diethylamino-7-( o-chloroanilino)fluoran, 3-dibutylamino-7-(o-chloroanilino)fluoran, 3-N-methyl-N-amylamino-6-methyl-7-
Anilinofluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl -7-(2', 4'-
dimethylanilino)fluorane, 3-(N,N-diethylamino)-5-methyl-7~(
N,N-dibenzylamino) fluorane, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolino-bilillos biran, 6'-bromo-3'-methoxy-benzoindolino-bilillos biran, 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-fumethylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino- 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)fluoran.

3-(N-ethyl-P-toluidino)-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-(o-methoxycarbonylphenylamino)fluoran, 3-diethylamino-5-methyl-7-( α-phenylethylamino)fluorane, 3-diethylamino-7-piperidinofluorane, 2-
Chloro-3-(N-methyltoluidino)-7-(p-D
-butylanilino)fluorane, 3-(N-methyl-N-isopropylamino)-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3.6-bis (dimethylamino)fluorene spiro(9
,3')-6'-dimethylaminophthalide, 3-(N-
benzyl-N-cyclohexylamino) = 5.6-penzo-7-〇-naphthylamino-4--promofluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-N-ethyl-N -(2-ethoxypropyl)amino-6-methyl-7-anilinofluorane, 3-N-ethyl-N-tetrahydrofurfurylamino-
6-Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-mesitidino 4-15-benzofluorane, 3-(p-dimethylaminophenyl)-3-(1,1-
Bis(p-dimethylaminophenyl)ethylene-2-yl)phthalide, 3-(P-dimethylaminophenyl)-3-fl, l-
Bis(p-dimethylaminophenyl)ethylene-2-yl)-6-dimethylaminophthalide, 3-(p-dimethylaminophenyl)-3-(+-P-
Dimethylaminophenylethylene-2-yl)phthalide, 3-(p-dimethylaminophenyl) ~3-(]-]
p-dimethylaminophenyl-1P-chlorophenylethylene-2-yl)-6-dimethylaminophthalide, 3
-(4'-dimethylamino-2'-methoxy) -3-
(]''-]P-dimethylaminophenyl]'/, -chlorophenyl-111,31L-butadien-4''-yl)benzophthalide.

3-(4'-dimethylamino-2'-benzyloxy)
-3-(1''-p-dimethylaminophenyl-1''-phenyl-1''.

3″-butadien-4″-yl)benzophthalide, 3-
Dimethylamino-6-dimethylamino-fluorene-9
-spiro-3'-(6'-dimethylamino)phthalide,
3.3-bis(2-(P-dimethylaminophenyl)-
2-(P-methoxyphenyl)ethynyl)-4,5,6
,7-titrachlorophthalide, 3-bis(l,1-bis(4-pyrrolidinophenyl)ethylene-2-yl)-5,6-dichloro-4,7-dibromophthalide, bis(P-dimethyl aminostyryl)-tonaphthalenesulfonylmethane, etc.

Further, as the color developer used in the present invention, various electron-accepting compounds such as phenolic compounds, thiophenolic compounds, thiourea derivatives, organic acids and their metal salts, etc. can be used. Specific examples include those shown below.

4.4'-isopropylidene bisphenol, 4.4
′ -isopropylidene bis(0-methylphenol)
, 4.4'-Secondary-butylidenebisphenol, 4.4'-Isopropylidenebis(2-tertiary-
butylphenol), 4.4'-cyclohexylidene diphenol, 4.4
′ -isopropylidene bis(2-chlorophenol)
, 2.2'-methylenebis(4-methyl-6-tert-butylphenol), 2.2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butylphenol) -2-methylphenol), Ij, 3-tris(2-methyl-4-hydroxy-5-
tertiary-butylphenyl)butane, 1.1.3-
) Lis(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, 4,4′-thiobis(6-tert-butyl-2-
methylphenol), 4.47-diphenolsulfone, 4-impropoxy-4'-hydroxydiphenylsulfone, 4-benzyloxy-41-hydroxydiphenylsulfone, 4.4'-diphenolsulfoxide, isopropyl P-hydroxybenzoate, Benzyl P-hydroxybenzoate, Benzyl protocatechuate, 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-41-methyldiphenylsulfone, zinc 1-acetyloxy-2-naphthoate, 2-acetyloxy-1 -Zinc naphthoate, 2-acetyloxy-
Zinc 3-naphthoate, α,α-bis(4-hydroxyphenyl)-α-methyltoluene, antipyrine complex of zinc thiocyanate, tetrabromobisphenol A, tetrabromobisphenol S, etc.

In the present invention, various conventional binders can be used as appropriate in order to bind and support the leuco dye and color developer on the support. Specific examples include the following.

Polyvinyl alcohol, starch and its derivatives, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide/acrylic acid ester copolymer, acturamide/acrylic acid ester/methacrylic In addition to water-soluble polymers such as acid ternary copolymers, styrene/maleic anhydride copolymer alkali salts, inbutylene/maleic anhydride copolymer alkali salts, polyacrylamide, sodium alginate, gelatin, and casein, polyacetic acid Emulsions such as vinyl, polyurethane, polyacrylic ester, polymethacrylic ester, vinyl chloride/vinyl acetate copolymer, ethylene/vinyl acetate copolymer, styrene/butadiene copolymer, styrene/butadiene/acrylic copolymer etc. latex etc.

In the present invention, in addition to the leuco dye, color developer, and auxiliary components, if necessary, auxiliary additive components commonly used in this type of heat-sensitive recording material, such as fillers, surfactants, thermofusible A sexual substance (or lubricant), etc. can be used in combination. In this case, fillers include, for example, calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, and surface-treated inorganic fine powders such as calcium and silica. ,
Examples include organic fine powders such as urea-formalin resin, styrene/methacrylic acid copolymer, and polystyrene resin. Examples of thermofusible substances include higher fatty acids or their esters, amides, or metal salts, various waxes, condensates of aromatic carboxylic acids and amines,
Benzoic acid phenyl ester, higher linear glycol, 3,
50-200 of 4-epoxy-dialkyl xahydrophthalate, higher ketones, other thermofusible organic compounds, etc.
Examples include those having a melting point on the order of °C.

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 connection with the heat-sensitive recording layer. Further, the water-soluble polymer can be used together with a conventional water-resistant agent to make it water-resistant. Specific examples of this water-resistant agent include formaldehyde, glyoxal, chloralum, melamine, melamine-formaldehyde resin, and polyamide. Examples include resins, polyamide-epichlorohydrin resins, and the like. Furthermore, the overcoat layer can also contain conventional auxiliary additive components, such as fillers, thermofusible substances (lubricants), surfactants, etc., as necessary. Specific examples of fillers and thermofusible substances include: The examples include those exemplified in relation to the heat-sensitive recording layer.

(Effects) The heat-sensitive recording magnetic ticket sheet of the present invention has the above-described structure and is excellent in that there are no problems with output fluctuations, waveform distortion, dropouts, etc. caused by uneven thickness of the magnetic recording layer. be.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. still,
All parts and percentages shown below are by weight.

Example 1 Styrene/
Butadiene copolymer emulsion resin has a dry weight of 4
．． , Og/rd to form an undercoat layer, and on top of this, the magnetic paint shown below was coated and dried to a dry weight of 32 g/rd to form a magnetic recording layer.

Sodium polyacrylate (20% aqueous solution) 25.0
Part polyvinylidene chloride (49% dispersion) +00
．． 0 parts carbon blank (38% dispersion)
15.0 parts water
160.0 parts Next, in order to provide a heat-sensitive recording layer on the other side of the support, a mixture consisting of the following formulation was dispersed in a sand grinder for 3 to 5 hours to prepare solutions [^] and CB).

cA solution] Polyvinyl alcohol 10% aqueous e, 25.0 parts water
50.
1 [Liquid B] 3.3'-5,5'-tetrap amobisphenol S2
5.0 parts Calcium carbonate 100.0 parts Polyvinyl alcohol 10% aqueous solution 200.0 parts Water 40
0.0 parts 40 parts of solution [A] above, 320 parts of solution CB), 6 parts of water
A heat-sensitive recording layer coating solution is prepared by mixing 0 parts of the heat-sensitive recording layer coating solution, and the coating solution is applied onto the other side of the support having the magnetic recording layer so that the dry weight becomes 6 g1rd, and is dried to form the heat-sensitive recording layer. Obtained.

Next, in order to provide a protective layer on the heat-sensitive recording layer, a mixture consisting of the following formulation was dispersed in a sand grinder for 2 to 3 hours to prepare liquid C1 and liquid [D].

[C] Liquid zinc stearate 20.0 parts Methyl cellulose 5% aqueous solution 20.0 parts Water
60.0
Part [D] Liquid silica 1.5 parts Water
15.0
0.7 parts of liquid (C) above, 45.0 parts of liquid [D], 1 part of water
A coating solution for a protective layer is prepared by mixing 1.3 parts of the heat-sensitive recording layer, and the coating solution is applied onto the heat-sensitive recording layer to a dry weight of 3 g/rrr and dried to form a protective layer. A recordable magnetic ticket sheet was obtained.

Example 2 In Example I, the undercoat component was changed from the styrene/butadiene copolymer emulsion resin to a polyvinyl acetate emulsion resin, and its dry weight was reduced to 6. O3/
rr? A heat-sensitive recording type magnetic ticket sheet of the present invention was obtained in the same manner as in Example I except that .

Example 3 In Example 1, the undercoat component was changed from the styrene/butadiene copolymer emulsion resin to a polyvinyl chloride emulsion resin, and the dry weight was changed to 9.0 g/
n? A heat-sensitive recording type magnetic ticket sheet of the present invention was obtained in the same manner as in Example 1 except that .

Comparative Example 1 A heat-sensitive recording type magnetic ticket sheet for comparison was obtained in the same manner as in Example 1 except that the undercoat layer was omitted.

A quality performance test was conducted on the heat-sensitive recording type magnetic ticket sheet obtained above, and the results are shown in Table 1.

Table 1 <Test conditions, method> Output fluctuation: Recording is performed on the magnetic recording layer at a constant writing tfR, and then reproduction is performed to measure the fluctuation in the output voltage at that time.

Waveform distortion: Recording was performed on the magnetic recording layer with a constant write current, and the distortion state of the output waveform was visually determined when the data was reproduced.

◎...No distortion is observed.

O: A little distortion is seen, but there is no problem in practical use.

△...Distortion is observed and there is a problem in practical use.

×...Distortion is very visible and there is a problem.

Coercive force: Vibrating sample magnetometer (VSM-P manufactured by Toei Kogyo Co., Ltd.)
7 type).

Residual magnetic flux density...Same as above Squareness ratio: Obtained by measuring hysteresis loop.

Color density: Thermal head temperature 110℃ to 1506℃ using thermal gradient tester (manufactured by Toyo Seiki Co., Ltd.), pressure bonding pressure 1kg/c
d. Macbeth Densitometer Model RD-914, Filter! -106. The skin density is also measured in the same way.

As shown in Table 1, the present invention has excellent magnetic recording properties compared to the comparative example, and all other properties are satisfactory.

[Brief explanation of the drawing]

FIGS. 1 and 2 are schematic cross-sectional views of a typical heat-sensitive recording type magnetic ticket sheet of the present invention. l; support, 2; undercoat layer, 3; magnetic recording layer,
4: Heat-sensitive recording layer, 5: Protective layer.

Claims (5)

[Claims] (1) A magnetic recording layer mainly composed of a ferromagnetic material and a binder is provided on one side of a support made of fibrous material such as paper or cloth, and the other side of the support is usually colorless or In a heat-sensitive recording magnetic ticket sheet provided with a heat-sensitive recording layer containing a light-colored leuco dye and an acidic substance as coloring components, an undercoat layer mainly composed of an aqueous emulsion resin is provided between the support and the magnetic recording layer. A heat-sensitive recording magnetic ticket sheet. (2) The heat-sensitive recording type magnetic ticket sheet according to claim 1, wherein the undercoat layer is made of an aqueous emulsion resin having a glass transition temperature of 100° C. or lower. (3) The heat-sensitive recording magnetic ticket sheet according to claim 1, wherein the undercoat layer has a weight of 2.0 g/m^2 or more. (4) The heat-sensitive recording type magnetic ticket sheet according to claim 1, wherein a water-based magnetic paint is used for the magnetic recording layer. (5) The heat-sensitive recording type magnetic ticket sheet according to claim 1, characterized in that a protective layer is provided on the heat-sensitive recording layer.