JPH04142974A - Color forming recording material - Google Patents

Abstract

PURPOSE:To obtain a dye having extremely high absorbancy and fastness within a visible region-a near infrared region by adding a specific quinoide type electron acceptive compound, a polyhydric hydroxy aromatic compound and an acidic substance. CONSTITUTION:A quinoid type electron acceptive compound is represented by formula (I) wherein A and B are respectively independently an aryl group and Y is a quinone ring conjugated with two imino nitrogen atoms to form a quinoid structure, for example, a benzoquinone ring, a naphthoquinone ring or an anthraquinone ring). As a polyhydric hydroxy aromatic compound, hydroquinone and a derivative thereof, catechol and a derivative thereof and bisphenol and a derivative thereof are designated. As an acidic substance, both of org. and inorg. compounds can be used. As the org. compound, for example, benzoic acid or naphthoenic acid can be designated and, as the inorg. compound, activated clay, acid clay, kaolin, clay or an acidic resin such as a phenol resin can be designated. The mol ratio of quinoid type electron acceptive compound/ polyhydric hydroxy aromatic compound is pref. 0.05-20.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color-forming recording material, and more particularly to a color-forming recording material that is sensitive to visible light to near-infrared rays and is thus useful for reading information by equipment. Regarding materials.

Conventional ■ Limb Distortion Conventionally, color-forming recording materials made of dyes and acidic substances, which are colorless in themselves, have been widely put into practical use as heat-sensitive recording materials.

However, in recent years, with the development of electronic technology and information management systems, recording/reading devices that are sensitive to electromagnetic waves in the long wavelength range from the long wavelength range of visible light to the near infrared range have come into practical use. A color-forming recording material using a phthalide compound used in C as a color-forming dye does not have practical absorption in such a long wavelength region.

In other words, in order to shift the absorption wavelength of conventionally known phthalide compounds to the near-infrared region, not only the substituent effect on the compound but also a method of extending the π-electron conjugated system is adopted. However, the compound has a high molecular weight, making it difficult to manufacture, and absorption in the near-infrared region is still insufficient. In addition, the colored image is unstable, easily fades, and has poor light resistance.

Therefore, in recent years, various color-forming dyes that form pigments that absorb electromagnetic waves in the long wavelength range have been proposed.

For example, JP-A-62-142681 and JP-A-62
JP-A-181361 proposes a color-forming recording material containing a phenylene diamine derivative or a naphthylene diamine derivative and an acidic substance, but the color changes significantly over time after color development.

Further, JP-A-63-256486 proposes a color-forming recording material containing a phenylenediamine derivative or a naphthylenediamine derivative and a quinoid-type electron-accepting compound, but according to the present inventors, Even if a phenylene diamine derivative or a naphthylene diamine derivative is brought into contact with a quinoid type electron-accepting compound, no substantial color development occurs, so it is not easy to put it into practical use.

The present invention was made in order to solve the above-mentioned problems with conventional color-forming recording materials. It is an object of the present invention to provide a color-forming recording material that has strong absorption in the long wavelength range from 100 to 200 nm to the near infrared region.

The color-forming recording material according to the present invention for recording the tongue has the following formula: (a) General formula (I) 8-N=Y=N-B (wherein A and B each independently represent an aryl group;
Y represents a quinone ring that is conjugated with two imino nitrogens to form a quinoid structure. ) A quinoid-type electron-accepting compound represented by (b) a polyvalent hydroxy aromatic compound, and (c) an acidic substance.

That is, the color-forming recording material according to the present invention consists of three elements, and by bringing these into contact, it is possible to obtain a dye that has extremely strong absorption strength and fastness in the visible light region to near-infrared region. The present invention provides a practical color-forming recording material that is sensitive to semiconductor lasers.

The quinoid electron-accepting compound used in the present invention is
It is represented by the general formula (I), where A and B each independently represent an aryl group, and Y represents a quinone ring that is conjugated with two imino nitrogens to form a quinoid structure. Y
For example, benzoquinone ring, naphthoquinone ring,
Examples include an anthraquinone ring.

These A, B and Y are each independently a halogen atom,
Cyano group, hydroxyl group, alkyl group, aryl group, alkoxy group, aryloxy group, aralkyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group,
carboxyl group, alkoxycarbonyl group, allyloxycarbonyl group, nitro group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, amino group, alkyl-substituted amino group, aryl-substituted amino group, pyrrolidino group, piperidino group, and It may have at least one substituent selected from the group consisting of carbamoyl groups.

Therefore, such quinoid-type electron-accepting compounds include, for example, N,N'-diphenyl-p-quinonediimine, N-(4-hydroxyphenyl)No-phenyl-
p-quinonediimine, N-(4methoxyphenyl)-N
o-phenyl-p-quinonediimine, N-(4-ethoxyphenyl)-N'-phenyl-p-quinonediimine,
N-(3-hydroxyphenyl)-N“-phenyl-p
-Quinonediimine, N-(3-methoxyphenyl)-
N'phenyl-p-quinonediimine, N-(4-tbutylcarbonyloxyphenyl)-N''-phenyl-p-
Quinonediimine, N-(4-aminophenyl)-N'-
Phenyl-p-quinonediimine, N(4-anilinophenyl)-N''-phenyl-p-quinonediimine, N-(i
(3-methoxyphenylamino)phenyl-N'-phenyl-p-quinonediimine, N-(1-methyl-4-
hydroxyphenyl)-N'-phenyl-P-quinonediimine, N-(2,3-dimethyl-4-hydroxyphenyl)-N'-phenyl-p-quinonediimine, N-(
Examples include, but are not limited to, 2-methyl-4-methoxyphenyl)-N"-phenyl-p-quinone diimine.

Examples of polyvalent hydroxy aromatic compounds include hydroquinone and its derivatives, such as L-butylhydroquinone,
2,6-di-t-butylhydroquinone, trimethylhydroquinone, neopentylhydroquinone, 2,5-
dineobentylhydroquinone, t-octylhydroquinone, 2,5-di-t-octylhydroquinone, cumylhydroquinone, 2,5-dicumylhydroquinone,
2-cyclohexylhydroquinone, catechol and its derivatives, biphenol and its derivatives, such as 3.
3',5.5'-tetramethylbiphenol, 3,3"
, 5゜5''-tetraethylbiphenol, 3.3',
5.5''-tetra-t-butylbiphenol, 3,3'
-dimethyl5.5”-di-t-butylbiphenol, 3
, 5-dimethyl-3',5'-di-butylbiphenol, 2,6-dihydroxynaphthalene, ■, dihydroxynaphthalenes such as 4-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene; Examples include anthracenes such as dihydroxyanthracene, trihydroxybenzene, and the like.

In the present invention, both organic compounds and inorganic compounds can be used as the acidic substance. Examples of the organic compound include aromatic carboxylic acids such as benzoic acid and nara-1-engineic acid, aromatic hydroxycarboxylic acids such as hydroxybenzoic acid and hydroxynaphthoic acid, and organic sulfonic acids such as p-toluenesulfonic acid. However, it is not limited to these.

On the other hand, examples of inorganic compounds include activated clay, acid clay, kaolin, clay, and acidic resins such as phenol resins.

As is well known, conventional heat-sensitive recording materials are prepared by preparing an aqueous dispersion containing a binder together with a color-forming dye, a color developer such as bisphenol, and other additives used as necessary. It is prepared by coating it on a substrate such as paper and drying it. When the color-forming recording material according to the present invention is also used as a heat-sensitive recording material, the quinoid type electron-accepting compound, the polyvalent hydroxy aromatic compound, the acidic substance, and other additives used as necessary are used in the same manner as above. An aqueous dispersion containing a binder may be prepared, applied onto a substrate such as paper, and dried.

As the binder, those conventionally used in the preparation of heat-sensitive recording materials can be suitably used. Examples of such binders include polyvinyl alcohol, hydroxyethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone, polyvinyl acetate, etc. , polyurethane, polyacrylic acid, polyacrylic acid ester, various latexes, and the like.

In the color-forming recording material according to the present invention, the quinoid type electron-accepting compound and the polyvalent hydroxy aromatic compound are:
The molar ratio of quinoid electron-accepting compound/polyvalent hydroxy aromatic compound is 0.01 to 100, preferably 0.05 to 100.
Used in the range of 20.

The color-forming recording material according to the present invention may contain fluorescent dyes and pigments. Examples of fluorescent dyes include diaminostilbene-based, benzimidazole-based, benzidine-based, and imidasilone-based dyes. Examples of pigments include titanium dioxide, clay, talc, calcium carbonate, aluminum hydroxide, silica, polystyrene resin, formalin resin, and the like.

Furthermore, the color-forming recording material according to the invention may contain a sensitizer. Examples of the sensitizer include higher fatty acid amides such as stearamide, benzamide, stearanilide, acetoacetanilide, and thioacetate 1-
Examples include anilide, dimethyl phthalate, dibenzyl terephthalate, dibenzyl isophthalate, and 4,4'-dimethoxydiphenyl sulfone. In addition, stearic acid, zinc stearate, calcium stearate,
Anti-blocking agents such as carnauba wax and paraffin wax may also be included. Additionally, an overcoat layer can be provided.

As described above, the color-forming recording material according to the present invention contains a quinoid-type electron-accepting compound, a polyhydric hydroxy aromatic compound, and an acidic substance, and develops a color with sufficient intensity for practical use immediately after the color-forming operation. Furthermore, it has strong absorption in the long wavelength range from visible light to near-infrared light, making it useful for reading information with equipment.

Implementation (2) The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.

Dispersion A was obtained by processing 0.0264 g of a quinoid electron-accepting compound, 0.0264 g of stearamide, 0.066 g of a 10% by weight aqueous polyvinyl alcohol solution, and 06145 g of water in a ball mill for 20 hours.

Separately, 0.5 g of acidic substance, 0.026 g of polyvalent hydroxy aromatic compound, 0.3 g of zinc stearate, 10% by weight.
Dispersion B was obtained by processing 1.5 g of a polyvinyl alcohol aqueous solution and 5.0 g of water in a ball mill for 20 hours.

Next, dispersion liquid B is added to dispersion liquid A. 1. Add Og, apply it to high-quality paper using a bar coater, air dry, and then apply NEC
A barcode was printed using a printer (PC-PR102TL) using a square head.

Please send this barcode to Symbol Technology.
It was read using a semiconductor laser (780 nm) barcode reader manufactured by ES, Inc. The results are shown in Table 1.

In Table 1, the molar ratio indicates the quinoid electron-accepting compound/polyvalent hydroxy aromatic compound molar ratio, and the number of readings indicates the number of readings out of 10.

Further, the quinoid type electron-accepting compound, polyvalent hydroxy aromatic compound, and acidic substance used in the above are as follows.

Quinoid-type electron-accepting compound (a) N,N'-diphenyl-p-quinonediimine (
b) N-(4-methoxyphenyl)-N゛-phenyl-
p-quinonediimine (c) N-(2-methyl-4-methoxyphenyl)N-phenyl-p-quinonediimine (d) Polyhydric hydroxy aromatic compound (1) Hydroquinone (2) 2,6-hydroxynaphthalene (3) 2-cyclohexylhydroquinone (4) Biphenol (5) 3.3',5.5''-tetra-t-butylbiphenol acidic substance (a) 1-hydroxy-2-naphthoic acid (b) Clay (c) (without spaces below) Table 1 ■ Table (continued) Table (continued)

Claims (1)

[Claims] (1) (a) General formula (I) A-N=Y=N-B (wherein A and B each independently represent an aryl group,
Y represents a quinone ring that is conjugated with two imino nitrogens to form a quinoid structure. 1. A color-forming recording material characterized by containing a quinoid electron-accepting compound represented by (b) a polyvalent hydroxy aromatic compound, and (c) an acidic substance.