JP3045175B2 - Chromogenic recording material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chromogenic recording material, and more particularly, to a chromogenic recording material that is sensitive to visible light or near-infrared light and is thus useful for reading information by an apparatus. .

2. Description of the Related Art Hitherto, a color-forming recording material comprising a colorless dye itself and an acidic substance has been widely used as a heat-sensitive recording material.

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

In other words, conventionally, in order to shift the absorption wavelength of a known phthalide compound to a long wavelength region to the near infrared region, not only a substituent effect on the compound but also a method of extending a π electron conjugate system has been adopted. However, the compound has a high molecular weight and its production is not easy, and the absorption in the near infrared region is still insufficient. Further, the color image is unstable, fading easily, and light resistance is poor.

Therefore, in recent years, various color-forming dyes that form a dye that absorbs electromagnetic waves in a long wavelength range have been proposed. For example, JP-A-62-142681 and JP-A-62-181361 propose a coloring recording material containing a phenylenediamine derivative or a naphthylenediamine derivative and an acidic substance. Is remarkably changed with time.

Further, JP-A-63-256486 discloses 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 phenylenediamine derivative or a naphthylenediamine derivative is brought into contact with a quinoid-type electron-accepting compound, practical use is not easy because practically no color development occurs.

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the conventional color-forming recording material, and provides a color having practically sufficient intensity immediately after the color-forming operation, It is an object of the present invention to provide a color recording material having strong absorption in a long wavelength region from an optical region to a near infrared region.

Means for Solving the Problems The color-forming recording material according to the present invention comprises: (a) a general formula (I) where AN = Y = NB (wherein A and B each independently represent an aryl group;
Y represents a quinone ring conjugated with two imino nitrogens to form a quinoid structure. (B) a polyvalent hydroxyaromatic compound, and (c) an acidic substance selected from aromatic carboxylic acids, aromatic hydroxycarboxylic acids and organic sulfonic acids. And

That is, the chromogenic recording material according to the present invention comprises three elements, and by contacting these elements, a dye having extremely strong absorption intensity and fastness in the visible light region to the near infrared region can be obtained, Accordingly, the present invention provides a practical chromogenic recording material that is sensitive to a semiconductor laser.

The quinoid electron accepting compound used in the present invention is represented by the above general formula (I), wherein A and B
Represents an aryl group each independently, and Y represents a quinone ring which is conjugated to two imino nitrogens to form a quinoid structure. Examples of Y include a benzoquinone ring, a naphthoquinone ring, and an anthraquinone ring.

A, B and Y each independently represent a halogen atom, a cyano group, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, a carboxyl group, an alkoxy group. Carbonyl group, allyloxycarbonyl group, nitro group, alkylsulfonyl group,
Having at least one substituent selected from the group consisting of an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, an amino group, an alkyl-substituted amino group, an aryl-substituted amino group, a pyrrolidino group, a piperidino group and a carbamoyl group; Is also good.

Accordingly, examples of such quinoid type electron accepting compounds include N, N'-diphenyl-p-quinonediimine, N- (4-hydroxyphenyl) -N'-phenyl-p-quinonediimine, N- (4 -Methoxyphenyl)
-N'-phenyl-p-quinone diimine, N- (4-ethoxyphenyl) -N'-phenyl-p-quinone diimine, N- (3-hydroxyphenyl) -N'-phenyl-p-quinone diimine, N- (3 -Methoxyphenyl)
-N'-phenyl-p-quinonediimine, N- (4-t
-Butylcarbonyloxyphenyl) -N'-phenyl-p-quinonediimine, N- (4-aminophenyl)-
N'-phenyl-p-quinone diimine, N- (4-anilinophenyl) -N'-phenyl-p-quinone diimine, N- (4- (3-methoxyphenylamino) phenyl-N'-phenyl-p-quinone diimine , N- (1-
Methyl-4-hydroxyphenyl) -N'-phenyl-
p-quinonediimine, N- (2,3-dimethyl-4-hydroxyphenyl) -N'-phenyl-p-quinonediimine, N- (2-methyl-4-methoxyphenyl) -N '
-Phenyl-p-quinonediimine and the like, but are not limited thereto.

Examples of the polyvalent hydroxy aromatic compound include hydroquinone and derivatives thereof, for example, t-butylhydroquinone, 2,6-di-t-butylhydroquinone, trimethylhydroquinone, neopentylhydroquinone, and 2,5-
Dineopentyl hydroquinone, t-octyl hydroquinone, 2,5-di-t-octyl hydroquinone, cumyl hydroquinone, 2,5-dicumyl hydroquinone,
-Cyclohexylhydroquinone, catechol and its derivatives, biphenol and its derivatives, for example, 3,3 '
5,5'-tetramethylbiphenol, 3,3 ', 5,5'-tetraethylbiphenol, 3,3', 5,5'-tetra-t-butylbiphenol, 3,3'-dimethyl-5,5 ' -Di-t-
Butyl biphenol, 3,5-dimethyl-3 ', 5'-di-
t-butyl biphenol, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,2-dihydroxynaphthalene, dihydroxynaphthalenes such as 2,3-dihydroxynaphthalene, anthracenes such as dihydroxyanthracene, trihydroxybenzene, etc. Can be mentioned.

In the present invention, as the acidic substance, for example,
Benzoic acid, aromatic carboxylic acids such as naphthoic acid, for example,
Aromatic hydroxycarboxylic acids such as hydroxybenzoic acid and hydroxynaphthoic acid, and organic sulfonic acids such as p-toluenesulfonic acid are used.

As is well known, conventional ordinary heat-sensitive recording materials include a color-forming dye and a developer such as bisphenol A,
In addition, an aqueous dispersion containing a binder together with additives used as necessary is prepared, and this is applied to a base material such as paper and dried to prepare the aqueous dispersion. When the color-forming recording material according to the present invention is also used as a heat-sensitive recording material, as described above,
Prepare an aqueous dispersion containing a binder together with the quinoid-type electron-accepting compound, a polyvalent hydroxyaromatic compound, an acidic substance, and other additives used as necessary, and apply this to a base material such as paper. And then dry.

As the binder, those conventionally used in the preparation of heat-sensitive recording materials can be suitably used. Examples of such a binder include polyvinyl alcohol, hydroxyethyl cellulose, sodium polyacrylate, polyvinyl pyrrolidone, and polyvinyl acetate. , Polyurethane, polyacrylic acid, polyacrylate,
Various latexes and the like can be mentioned.

In the color-forming recording material according to the present invention, the quinoid-type electron-accepting compound and the polyvalent hydroxyaromatic compound have a quinoid-type electron-accepting compound / polyvalent hydroxyaromatic compound molar ratio of 0.01 to 100, preferably 0.05 to 100. Used in the range of 20.

The chromogenic recording material according to the present invention may contain a fluorescent dye or pigment. As fluorescent dyes, for example, diaminostilbene, benzimidazole, benzidine,
Examples include imidazolones. As the pigment, titanium dioxide, clay, talc, calcium carbonate, aluminum hydroxide, silica, polystyrene resin,
Formalin resin and the like can be mentioned.

Further, the color-forming recording material according to the present invention may contain a sensitizer. Examples of the sensitizer include higher fatty acid amides such as stearic acid amide, benzamide, stearic acid anilide, acetoacetic anilide, thioacetanilide, dimethyl phthalate, dibenzyl terephthalate, dibenzyl isophthalate, and 4,4'-dimethoxydiphenyl. Sulfone and the like can be mentioned. Also, stearic acid, zinc stearate, calcium stearate,
An anti-tackiness agent such as carnauba wax and paraffin wax can also be included. Further, an overcoat layer can be provided.

Effect of the Invention As described above, the chromogenic recording material according to the present invention is an acidic substance selected from a quinoid-type electron-accepting compound, a polyvalent hydroxyaromatic compound, an aromatic carboxylic acid, an aromatic hydroxycarboxylic acid and an organic sulfonic acid. It provides practically sufficient color development immediately after the color development operation, and has strong absorption in a long wavelength range from the visible light range to the near infrared range, so that it is useful for reading information by a device.

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Quinoid-type electron-accepting compound 0.0264 g, stearic acid amide 0.0264 g, 10% by weight aqueous solution of polyvinyl alcohol
Treat 0.066 g and water 0.145 g in a ball mill for 20 hours,
Dispersion A was obtained.

Separately, 0.5 g of acidic substance, polyhydroxyaromatic compound 0.
026 g, zinc stearate 0.3 g, a 10 wt% aqueous solution of polyvinyl alcohol 1.5 g and water 5.0 g were treated in a ball mill for 20 hours to obtain a dispersion B.

Next, 1.0 g of Dispersion B was added to Dispersion A, applied to wood free paper using a bar coater, air-dried, and then a bar code was printed using a thermal head of an NEC printer (PC-PR102TL). Use this barcode as Symbol Technologie
It was read using a semiconductor laser (780 nm) barcode reader manufactured by s, Inc. The results are shown in Table 1.

In Table 1, the molar ratio indicates a quinoid-type electron accepting compound / polyvalent hydroxy aromatic compound molar ratio,
The number of readings indicates that the number of readings is ten.

The quinoid-type electron-accepting compound, polyvalent hydroxyaromatic compound and acidic substance used 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) None Polyvalent hydroxyaromatic compound (1) Hydroquinone (2) 2,6-dihydroxynaphthalene (3) 2-Cyclohexylhydroquinone (4) Biphenol (5) 3,3'5 , 5'-Tetra-t-butylbiphenol acidic substance (a) 1-hydroxy-2-naphthoic acid (b) clay (c) None

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hisaya Miki 61-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-63-256486 (JP, A) JP-A-4-320883 (JP, A) JP-A-3-500395 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/28-5/34 B41M 5 / 132 C09K 9/02

Claims (1)

(57) [Claims] (A) General formula (I) AN = Y = NB (wherein A and B each independently represent an aryl group,
Y represents a quinone ring conjugated with two imino nitrogens to form a quinoid structure. (B) a polyvalent hydroxyaromatic compound, and (c) an acidic substance selected from aromatic carboxylic acids, aromatic hydroxycarboxylic acids and organic sulfonic acids. Coloring material.