JPS60264289A - Thermal recording magnetic ticket paper - Google Patents

Abstract

PURPOSE:To obtain excellent thermal color developability, a sharp color image and excellent plasticizer resistance and a head matching property, by using specific dioxaheptane as a coupler and providing a specific coating layer onto a thermal color forming layer. CONSTITUTION:1,7-di(p-hydroxyphenylthio)-3,5-dioxaheptane is used as a coupler and a coating layer containing modified polyvinyl alcohol, glyoxal modified polyacrylic acid and an org. filler is provided onto a thermal color forming layer. The polymerization degree of polyacrylic acid is 1,000 or less and the amount to be used of glyoxal is generally 0.5-10pts.wt. of polyacrylic acid. As modified polyvinyl alcohol, carboxyl group modified polyvinyl alcohol is especially suitable. As the org. filler, a phenol resin, a urea-formalin resin, polycarbonate, a melamine resin, polystyrene or polypropylene are pref. adapted.

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.

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.

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 also becomes large. However, since printing methods use ink, half-dry ink sticks to hands and clothes become dirty. 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 shortened production time, and future improvements are expected. has been done.

In view of the current situation, the inventors have been conducting research on the recording method for these tickets, and as a result, they found that if a thermal recording method, which allows recording by simply heating the recording material, was adopted, it would be possible to replace the conventional method. This eliminates the complicated development and fixing processes required in , or the printing process that tends to get dirty, making the process a breeze! Furthermore, since the printing mechanism can be simplified and the machine body can be made compact because it is possible to record by simply installing a heat generating element that can generate heat inside the vending machine, it is possible to reduce the cost. Focusing on the fact that even in the case of revisions, it is possible to correct printing by simply changing the electrical signal, and there is no need to replace the printing machine or mechanical equipment, there are many advantages to be obtained, and we have developed a magnetic ticket paper for the tickets. We have conducted various studies on heat-sensitive recording magnetic ticket paper that uses heat-sensitive recording methods.

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.

Therefore, in the present invention, a heat-sensitive recording type magnetic ticket paper was prepared using a dye-based material consisting of a leuco body and an acidic substance that reacts with the leuco body under heat to develop a color, and the recording was clear at the beginning. However, when this was stored in a wallet, commuter pass, etc. normally used to store these tickets, and stored for 3 or 6 months, the records on the colored part faded and became unreadable. This is a plasticizer contained in the transparent resin film of a wallet or commuter pass that is in contact with the heat-sensitive coloring layer.
For example, this is due to the penetration of dioctyl phthalate (DOP) and dioctyl adipate (DOA) into the heat-sensitive coloring layer. As disclosed in the publication, an investigation was made by providing an organic resin coating layer soluble in an organic solvent that does not substantially dissolve the color-forming component on the heat-sensitive recording layer. I couldn't do it.

Therefore, the present inventors provided a coating layer of water-soluble resin in place of the above-mentioned organic solvent-soluble resin coating layer, and were able to obtain a considerable plasticizer resistance effect.3 However, this water-soluble resin By disposing the coating layer, sufficient plasticizer resistance effect can be obtained, but the resulting product has poor thermal coloring properties,
Further, the matching property with respect to the thermal head was not sufficient, and it was not practically satisfactory.

〔the purpose〕

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-sensitive recording magnetic ticket paper which has excellent thermochromic properties, provides clear colored images, is also excellent in plasticizer resistance, and has good head matching properties.

〔composition〕

As a result of extensive research to overcome the problems of the prior art described above, the present inventors have developed a specific color developer for leuco dyes to be contained in the heat-sensitive coloring layer of heat-sensitive recording magnetic ticket paper. The inventors have discovered that all of the above problems can be overcome by using a phenolic compound and providing a coating layer containing specific components on the heat-sensitive coloring layer, and have completed the present invention.

That is, according to the present invention, a magnetic recording layer containing a ferromagnetic material and a binder as main components is provided on one side of the support, and a heat-sensitive recording layer containing a leuco dye and a color developer as main components is provided on the other surface. In the heat-sensitive recording magnetic ticket paper provided with a coloring layer, as the color developer, ■, 7
- Di(P-hydroxyphenylthio)-3,5-dioxahebutane was used, and a coating layer containing modified polyvinyl alcohol, a glyoxal modified product of polyacrylic acid, and an organic filler was provided on the heat-sensitive coloring layer. A heat-sensitive recording type magnetic ticket paper is provided.

The color developer used in the present invention is represented by the following structural formula.

The present invention is characterized in that a coating layer containing modified polyvinyl alcohol and glyoxal modified polyacrylic acid is provided on the heat-sensitive coloring layer. In this case, although the molecular weight of polyacrylic acid is not particularly limited, The degree of polymerization is preferably 1000 or less, particularly preferably 100 or less. The glyoxal modified polyacrylic acid is a conventionally known substance, and commercially available products can be used. This product can be obtained by prepolymerizing acrylic acid in the presence of a catalyst, then adding glyoxal and performing a reaction treatment. In this case, the amount of glyoxal used is not particularly limited, but is generally 0.5 to 10 parts by weight per 1 part by weight of polyacrylic acid.

In the present invention, by using the color developer and coating layer as described above, it is possible to obtain a heat-sensitive recording material that is highly sensitive and has excellent preservability (solvent resistance, plasticizer resistance, oil resistance, etc.). However, in order to provide even better head matching properties, an organic filler is added.

The amount of glyoxal modified polyacrylic acid to be contained in the coating layer is preferably 10 to 30 parts by weight, preferably 20 to 25 parts by weight, based on 100 parts by weight of modified polyvinyl alcohol. When the amount decreases, storage stability such as solvent resistance becomes inferior. On the other hand, if the amount is too large, thermal sensitivity tends to deteriorate. Further, the amount of organic filler is preferably 1 to 20 parts by weight per 100 parts by weight of modified polyvinyl alcohol.

Although various types of modified polyvinyl alcohol can be used, carboxy group-modified polyvinyl alcohol is particularly suitable. As the organic filler, phenol resin, urea-formalin resin, polycarbonate, melamine resin, polystyrene, polypropylene, etc. are preferably used. The thickness of the coating layer is usually 1 to 10 μm, preferably 2 to 5 μm.

The leuco dyes used in the present invention can be applied singly or in combination of two or more types, but such leuco dyes include:
Those applied to this type of heat-sensitive material can be arbitrarily applied, such as triphenylmethane type, fluoran type, phenothiazine type, auramine type, etc.
Leuco compounds of spiropyran and indolinophthalide 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-dibutylaminophenyl, 3.3-bis(p-dimethylaminophenyl)-6-chlorphthalide, 3.3-bis(P-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlor Fluoran, 3-dimethylamino-5,7-dimethylfluoran, 8
- 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-ethylaminofluorane, 2-(3
, 6-bis(diethylamino)-9-(o-chloroanilino)xantylbenzoic acid lactam), 3-diethylamino-6-methyl-7-(+o-trichloromethylanilino)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-(N,N- diethylamino)-5-methyl-7-(
N.

N-dibenzylamino)fluoran, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolino-pyrillospirane, 6'-bromo-37-medoxybenzoindolino-pyrillospirane, 3-(2'- 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'
-methylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7-( N-benzyl-trifluoromethylanilino)fluoran, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluoran, 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-)Dylethylamino)fluoran, 11-3-diethylamino-7-piperidinofluorane.

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 color forming 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, isobutylene/maleic anhydride copolymer alkali In addition to water-soluble polymers such as salt, polyacrylamide, sodium alginate, gelatin, and casein, polyvinyl acetate, polyurethane, styrene/butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride/vinyl acetate copolymer , polybutyl methacrylate, 12-ethylene/vinyl acetate copolymer, styrene/butadiene/acrylic copolymer, and other latexes.

In addition, in the present invention, in addition to the leuco dye and color developer, if necessary, auxiliary additive components commonly used in this type of heat-sensitive recording material, such as fillers, surfactants, thermofusible substances ( 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. , urea-formalin resin, styrene-methacrylic acid copolymer, polystyrene resin, etc. Examples of thermofusible substances include higher fatty acids or their esters, amides, or metal salts. In addition, various waxes, condensates of aromatic carboxylic acids and amines, benzoic acid phenyl esters, higher linear glycols, dialkyl 3,4-epoxy-hexahydrophthalates, higher ketones, and other thermofusible organics. Examples include 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〕

In addition to using a specific phenol compound as a color developer,
By providing a specific coating layer on the thermosensitive coloring layer, it is possible to obtain a thermosensitive recording magnetic ticket paper particularly excellent in thermochromic properties, plasticizer resistance, and head matching properties.

〔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 The following ingredients were dispersed in a ball mill for 48 hours to form a magnetic recording layer, and coated on commercially available high quality paper (basis weight 157 g/rrl') to a dry coating weight of 40 g/rrl', dried to form a magnetic recording layer. Established.

Magnetic recording layer coating liquid Magnetic powder (γ-Fe2O3), 1.00 parts lecithin
2 parts Vinyl chloride resin 15 parts Polyurethane resin 10 parts Toluene 120 parts Methyl isobutyl ketone (M, 1.B, K) 100 parts Next, the mixtures consisting of the following formulations were pulverized and dispersed in a magnetic ball mill for 24 hours to obtain liquids A and B. A liquid was prepared.

[Liquid A]

3-(N-methyl-N-cyclohexylamino)-6-
Methyl-7-anirite fluorane 150 parts 5% polyvinyl alcohol aqueous solution, 150 parts water 200 parts 15- Next, 10 parts of solution A, 20 parts of solution B, and 20% aqueous ammonium salt solution of isobutylene/maleic anhydride copolymer.
This was coated on the back side of the support having the magnetic recording layer obtained as above at a dry weight of 5 g/rrr and dried to form a heat-sensitive coloring layer, and further, on this heat-sensitive coloring layer, 50 parts of carboxy group-modified polyvinyl alcohol, 1 part of urea-formalin resin, glyoxal modified polyacrylic acid (glyoxal 90%, polyacrylic acid 10%, trade name: J-003, manufactured by Showa Denko ■) 0.5
A composition containing 50 parts of water and 50 parts of water was pulverized and dispersed in a ball mill for 24 hours and used as a coating liquid, and the dry weight was 3 g/rr.
A protective coating was provided by coating and drying to give a heat-sensitive recording type magnetic ticket sample.

Comparative Example 1 A sample was obtained in the same manner as in Example 1, except that the following liquid B' was used instead of liquid B used for forming the heat-sensitive coloring layer.

[Liquid B'] Ethyl P-oxybenzoate 120 parts 16- 5% polyvinyl alcohol aqueous solution 120 parts Water 160
Comparative Example 2 A sample was obtained in the same manner as in Example 1 except that inorganic calcium carbonate was used instead of the urea-formalin resin organic filler in the protective coating provided on the thermosensitive coloring layer.

After the surface of the sample obtained above was treated with a super calender, printing was performed using a ticket vending machine with a built-in thermal head, and tests were performed on color development, decolorization with a plasticizer, and head matching. The results are shown in Table-1.

〔effect〕

Table-1 Color development: The color density when printed by a ticket vending machine was measured using a Macbeth densitometer.

Plasticizer color erasing property...The colored sample printed by the ticket vending machine,
Wrapped in food wrap film containing 5 to 10 times more plasticizer than a regular soft commuter pass, and exposed to pressure 10g/c+#, temperature 40℃, and contact time for 1 hour, the Macbeth densitometer Measured in.

Head matching property: Approximately 50% solid black color development rate, 3
1000 sheets were continuously printed at intervals of seconds, and the presence or absence of debris adhesion to the head was observed.

From the results in Table 1, it can be seen that the product of the present invention is a heat-sensitive recording type magnetic ticket paper with excellent color development, no discoloration due to plasticizer, and excellent head matching.

Patent Applicant Ricoh Co., Ltd. - Attorney Patent Attorney Toshiaki Ikeura 19- Proceeding Amendment Date of April 1980 Manabu Shiga Commissioner of the Patent Office 1982 Patent Application No. 122582 2 Name of Invention Thermal Recording Type magnetic ticket paper 3, relationship with the case of the person making the amendment Patent applicant address 1-3-6 Nakamagome, Ota-ku, Tokyo Name (
674) Ricoh Co., Ltd. - Representative Hama 1) Hiro 4, Agent Address: 1-58-10-8 Yoyogi, Shibuya-ku, Tokyo 1-58-10 Contents of Amendment The following amendments will be made to the specification of this application.

(1) Add the following sentence after the last line of page 16.

r (Liquid B) 1.7-di(p-hydroxyphenylthio) -3,5
-Dioxahebutane 1.20 parts 5% polyvinyl alcohol aqueous solution 120 parts Water 160
491

Claims (1)

[Claims] (1) A magnetic recording layer containing a ferromagnetic material and a binder as main components was provided on one side of the support, and a thermosensitive coloring layer containing a leuco dye and a color developer as main components was provided on the other surface. In the heat-sensitive recording magnetic ticket paper, L7 (p-hydroxyphenylthio)-3,5-dioxahebutane is used as the color developer, and modified polyvinyl alcohol and polyacrylic acid are added on the heat-sensitive coloring layer. 1. A heat-sensitive recording magnetic ticket paper comprising a coating layer containing a glyoxal modified substance and an organic filler.