JPS6129586A - Thermal recording-type magnetic coupon paper - Google Patents

Abstract

PURPOSE:To obtain thermal recording-type magnetic coupon paper having high water-proofness and solvent-resistance by providing a coat of ultraviolet ray curing resin on the magnetic recording layer of thermal recording-type magnetic coupon paper. CONSTITUTION:A thermal recording layer consisting of leuco dye and a developer such as phenol material is formed on one surface of a support. And on the other surface, powerful magnetic powder of e.g. gamma-Fe2O3 is applied with an appropriate solvent and then is dried to form a magnetic recording layer. This magnetic recording layer is covered with a coat consisting of an ultraviolet ray curing resin. As ultraviolet ray curing resin, ester cinnamate derivatives such as polyvinyl cinnamate and ethylene vinyl alcohol copolymer are used. Ultraviolet ray absorbent, e.g. benzoin and benzophenone can be added.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a heat-sensitive recording magnetic ticket paper useful for train tickets, coupon tickets, commuter passes, and the like.

[Prior art]

In recent years, the number of users of train tickets, coupon tickets, commuter passes, etc. has been increasing for travel and commuting, especially in the Tokyo metropolitan area and Osaka area, where urban transportation networks such as national railways, private railways, and subways are well-developed. The increase is significant. For this reason, the number of people and time required to create tickets such as train tickets, coupon tickets, and commuter passes has increased dramatically. It has already been put into practical use in the department.

Conventional printing methods for tickets include an electrophotographic method, an electrostatic recording method, a diazo copying method using a chemical reaction between two components, a chelate method, and a printing method using ink. However, when these conventional recording methods are adopted for vending machines, "developing and fixing processes are required, which makes the printing mechanism of the vending machine complicated and large, and the machine body that houses it is also large." However, since printing methods use ink, half-dry ink sticks to hands and stains clothes. Furthermore, vending machines generally use high-quality paper as a support for the tickets, which has the disadvantage that if this support gets wet, it can bend or wrinkle, causing the machine to stop working. .

Although there are many unresolved issues, the automatic sale of tickets is being promoted due to the advantages of automation, such as increased efficiency of personnel and shorter production time, and future improvements are expected. It is expected.

In view of the current situation, the inventors have been conducting research on the recording method of these tickets for some time, and as a result, they found that if a thermal recording method, which allows recording by simply heating, is adopted as a recording material, it would be possible to surpass the conventional method. This method simplifies the process by eliminating the complicated development and fixing processes required by the vending machine, as well as the printing process that is prone to stains.Furthermore, the printing mechanism can be improved by simply installing a heating element that can generate heat inside the vending machine. Simplified and compact machine body,
Furthermore, costs can be reduced, and even in the case of price revisions, for example, corrected printing can be done by simply changing the electrical signal, and there are many advantages such as no need to replace the printing machine or other mechanical equipment. With this in mind, various studies have been conducted on heat-sensitive recording magnetic ticket paper, in which a heat-sensitive recording method is applied to the magnetic ticket paper for tickets.

Dye-based materials and metal chelate-based materials have been known as the thermosensitive color-forming components of thermal recording materials used in thermal recording methods, but dye-based materials, especially usually colorless or light-colored leuco bodies and acidic substances, are known. It is widely used because the color tone of the records obtained is clear and the storage stability is excellent.

On the other hand, the magnetic recording layer is provided, for example, by applying ferromagnetic powder to the back surface of the support using vinyl chloride or the like as a binder, or by bonding a ferromagnetic laminate. However, conventional magnetic recording layers have had problems such as detachment of the magnetic material or peeling of the magnetic recording layer from the support when it comes into contact with organic solvents such as water or alcohol.

〔the purpose〕

An object of the present invention is to provide a heat-sensitive recording magnetic ticket paper whose magnetic recording layer has excellent water resistance and solvent resistance.

〔composition〕

As a result of extensive research in order to overcome the problems of the prior art described above, the present inventors have solved the problems described above by providing a coating layer of an ultraviolet curable resin on the surface of the magnetic recording layer of a heat-sensitive recording type magnetic ticket paper. We have found that all of these points can be overcome and have completed the present invention.

That is, according to the present invention, in a heat-sensitive recording magnetic ticket paper in which a magnetic recording layer mainly composed of a ferromagnetic material is provided on one surface of a support and a heat-sensitive coloring layer is provided on the other surface, A heat-sensitive recording type magnetic ticket paper is provided, which is characterized in that a coating layer made of an ultraviolet curable resin is provided on the surface of the magnetic recording layer.

In the present invention, the magnetic recording layer is coated with an ultraviolet curable resin layer, and this coating layer is exposed to ultraviolet rays (usually 500nm).
(wavelength below m), it polymerizes to form a strong resin coating. Therefore, infiltration of water, organic solvents, etc. is prevented, and problems such as falling off of the magnetic recording layer and peeling of the support and the magnetic recording layer do not occur. Various conventionally known UV-curable resins can be used, but particularly important ones include cinnamic acid derivatives 1, such as polyvinyl cinnamate, cinnamic acid ester of ethylene-vinyl alcohol copolymer, and glyptal resin. cinnamic acid ester, cinnamoyl type polymer with styrene as a backbone, cinnamic acid ester of styrene-maleic anhydride copolymer, polyvinyl cinnamylidene acetate,
Examples include polyvinylbenzalacetophenone, polyvinylstilketone, and spiran resin. In addition, an ultraviolet absorber can be added to the ultraviolet curable resin layer together with the ultraviolet curable resin. Examples of such ultraviolet absorbers include benzoin, benzoin methyl ether, benzophenone and its derivatives, 2-chloroanthrinone, penzole peroxide, and the like.

In the present invention, any thermosensitive coloring layer can be used, but from the viewpoint of coloring properties, it is preferable to use a combination of a leuco dye and a color developer. Leuco dyes can be applied singly or in combination of two or more types, and as such leuco dyes, those applied to this type of heat-sensitive material can be arbitrarily applied,
For example, leuco compounds of triphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based, spiropyran-based, and indolinobutalide-based dyes 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 violet lactone).

3.3-bis(p-dimethylaminophenyl)-6-diethylaminophenyl, 3.3-bis(p-dimethylaminophenyl)-6-chlorophthalide, 3.3-bis(p-dibutylaminophenyl)phthalide, 3 -cyclohexylamino-6-chlorofluorane, 3-dimethylamino-5,7-dimethylfluorane 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)xaditylbenzoic acid lactam), 3-diethylamino-6-methyl-7-(m-trichloromethylanilino)fluoran, 3-diethylamino-7-(o-chloroanilino) ) fluoran, :(-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-(N,N-diethylamino)-5-methyl-74(
N.

N-dibenzylamino)fluorane.

Benzoylleucostyrene blue, 6'-chloro-8'-methoxy-benzoindolino-pyrylosvirane, 6'-bromo-37-medoxipenzoindolino-pyrylospirane, 3-(2'-hydroxy-4'-dimethyl aminophenyl)-3-(2'-methoxy-5'-chlorophenyl)phthalide, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5p-nitrophenyl) Phthalide, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenylene)
phthalide, 3-(2'-methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chloro-5'
-methylphenyl)phthalide.

3-morpholino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7-(N-benzyl-trifluoro methylanilino)fluorane, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluorane, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluorane, 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.

Further, as the color developer used in the present invention, various electron-accepting substances that react with the leuco dye and develop color when heated are used, and specific examples thereof include phenol as shown below. Examples include acidic substances, organic or inorganic acidic substances, or their esters and salts.

gallic acid, salicylic acid, 3-isopropylsalicylic acid,
3-Cyclohexylsalicylic acid, 3,5-ter
7-Butylsalicylbenzylsalicylic acid, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene bis(2-chlorophenol), 4,4'-isopropylidene bis(
2,6-dibromophenol), 4,4'-isopropylidene bis(2,6-dichlorophenol), 4.

4'-isopropylidene bis(2-methylphenol)
, 4,4'-isopropylidene bis(2,6-dimethylphenol), 4,4'-isopropylidene bis(2t
ert-butylphenol), 4.4' -see-
Butylidene diphenol, 4,4'-cyclohexylidene bisphenol, 4,4'-cyclohexylidene bis(2-methylphenol), 4-t. ert-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α-naphthol, β-naphthol,
3,5-xylenol, thymol, methyl-4-hydroxybenzoate, 4-hydroxyacetophenone, novolac type phenolic resin, 2,2'-thiobis(4,
6-dichlorophenol), catechol, resorcinol,
Hydroquinone, pyrogallol.

Phloroglycin, prologlycine carboxylic acid, 4-te
rt-octylcatechol, 2,2'-methylenebis(
4-chlorophenol), 2,2'-methylenebis(4
-methyl-6-te-butylphenol), 2.

2'-dihydroxydiphenyl, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, p-chlorobenzyl p-hydroxybenzoate, P
-Chlorbenzyl hydroxybenzoate, p-methylbenzyl p-hydroxybenzoate, n-octyl p-hydroxybenzoate.

Benzoic acid, zinc salicylate, ■-hydroxy-2-naphthoic acid, 2-hydroxy-6-naphthoic acid, zinc 2-hydroxy-6-naphthoic acid, 4-hydroxydiphenylsulfone, 4-hydroxy-4'-chlorodiphenylsulfone, bis( 4-hydroxyphenyl) sulfide,
2-Hydroxy-p-toluic acid, 3,5-diter
Zinc tert-butylsalicylate, tin 3,5-di-tert-butylsalicylate, tartaric acid, oxalic acid, maleic acid, citric acid, succinic acid, stearic acid, 4-hydroxyethylic acid, boric acid, etc.

In order to support the above-mentioned leuco dye and color developer on the support, various conventionally used binders can be included in the thermosensitive coloring layer. Specifically, the following can be cited.

Polyvinyl alcohol, starch and its derivatives, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, sodium polyacrylate,
Polyvinylpyrrolidone, acrylic amide/acrylic ester copolymer, acrylic amide/acrylic ester/methacrylic acid ternary copolymer, styrene/maleic anhydride copolymer alkali salt 2, isobutylene/maleic anhydride copolymer In addition to water-soluble polymers such as polymer alkali salts, polyacrylamide, sodium alginate, gelatin, and casein, polyvinyl acetate, polyurethane, styrene/butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride/vinyl acetate Latex such as copolymers, polybutyl methacrylate, ethylene/vinyl acetate copolymers, styrene/butadiene/acrylic copolymers, etc.

In addition, in the present invention, in addition to the leuco dye and color developer, if necessary, auxiliary additives commonly used in this type of heat-sensitive recording material, such as fillers, surfactants, thermofusible Substances (or lubricants) etc. can be used together. 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. , urea-formalin resin, styrene/methacrylic acid copolymer, polystyrene resin, and other organic fine powders. Examples of the thermofusible substance include higher fatty acids or their esters, amides, and kinobaba. In addition, various waxes, condensates of aromatic carboxylic acids and amines, benzoic acid phenyl esters, higher linear glycols, 3,4-epoxy-
Examples include dialkyl hexahydrophthalate, higher ketones, and other heat-fusible organic compounds having a melting point of about 50 to 200°C.

In the present invention, a magnetic recording layer is provided on the other surface of the support, that is, the surface not having a thermosensitive coloring layer, and this magnetic recording layer is formed in the same manner as known magnetic ticket paper. For example, ferromagnetic powder of γ-Fe2O3 and vinyl chloride resin or polyurethane resin are uniformly dispersed in a solvent such as toluene or methyl isobutyl ketone, and this is coated on a paper support and dried, or the ferromagnetic material is All you have to do is join the laminate.

〔effect〕

By providing an ultraviolet curable resin coating layer on the surface of the magnetic recording layer, it is possible to obtain a heat-sensitive recording magnetic ticket paper with excellent water resistance and solvent resistance of the magnetic recording layer.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples. Note that all parts shown below are based on weight.

Example 1 [Liquid A] 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane 20 parts N-octadecylgalbamoylbenzene 5 10% polyvinyl alcohol aqueous solution 20//water
55 Dispersion A was prepared by dispersing the above composition in a ball mill for 24 hours.

[Liquid B]

Bisphenol A 15 parts Calcium carbonate 5 Polyvinyl alcohol 10% aqueous solution 201/water
601/Dispersion B was prepared by dispersing the above composition in a ball mill for 24 hours.

[Liquid C]

Violet, external radiation curable resin (product name: Aronix 8030,
(manufactured by Toagosei Kagaku Kogyo ■) 90 parts Fine silica powder 10 Benzophenone 21 The above composition was dispersed with an attritor in the dark for 10 hours to prepare dispersion C.

[Liquid D]

Magnetic powder (γFe203) 100
Part styrene/butadiene rubber 20 Monomethyl terephthalic acid stearylamide water
100//
The above composition was dispersed in a ball mill for 24 hours to prepare a dispersion liquid.

Mix the A liquid and B liquid obtained as above, and mix it with high-quality paper (15
7g/rrI') surface with a dry coating amount of 2g/♂(
Next, Solution D was coated on the back side to a concentration of 40 g/ff1 (solid content upon drying) and dried. Furthermore, apply liquid C to 2g1rd (solid content when dry) on top of it, and immediately apply it at 100W/c.
The thermosensitive recording type magnetic ticket paper of the present invention was obtained by irradiating ultraviolet rays for 1 second using a high-pressure mercury lamp of 500 m and drying and curing the paper.

Comparative Example 1 A heat-sensitive recording type magnetic ticket paper for comparison was obtained in the same manner as in Example 1 except for the C liquid used in Example 1.

Comparative Example 2 10% polyvinyl alcohol instead of liquid C in Example 1
All examples except using an aqueous solution and omitting the ultraviolet irradiation step.
A heat-sensitive recording type magnetic ticket paper for comparison was obtained in the same manner as in Example 1.

The heat-sensitive recording type magnetic ticket paper obtained as described above was tested for water resistance and solvent resistance. Water resistance test to 20℃ water7
After immersion for a time, the magnetic layer was observed for shedding and peelability, and the solvent resistance test was conducted by immersing it in an 80% ethanol aqueous solution for 13 minutes, and then observing the magnetic layer for peeling and peelability.

The results are shown in Table-1.

Table 1 From the results in Table 1, it can be seen that the heat-sensitive magnetic ticket paper of the present invention has excellent water resistance and solvent resistance, and is highly reliable.

Claims (1)

[Claims] (1) In a heat-sensitive recording magnetic ticket paper in which a magnetic recording layer mainly composed of ferromagnetic material is provided on one side of a support and a heat-sensitive coloring layer is provided on the other side, the surface of the magnetic recording layer is A heat-sensitive recording type magnetic ticket paper characterized by being provided with a coating layer made of an ultraviolet curable resin.