JP3040527B2 - Chromogenic recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a color recording material. More specifically, the present invention relates to a color recording material which exhibits absorption in visible light to near infrared rays and is thus useful for reading information by an apparatus.

[0002]

2. Description of the Related Art Hitherto, a color 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 / reading devices that are sensitive to electromagnetic waves in a long wavelength range from a long wavelength range to a near infrared range of visible light have come into practical use. However, conventionally, a chromogenic recording material using a phthalide-based compound as a chromogenic dye does not have practical absorption in such a long wavelength region.

That is, in order to shift the absorption wavelength of a conventionally known phthalide compound to a longer wavelength side to the near-infrared region, not only use of the substituent effect on the compound but also extension of the π-electron conjugated system. However, according to this method, the compound has a high molecular weight, making it difficult to produce the compound, and the absorption in the near infrared region is still insufficient. Also,
The color image is unstable, is easily discolored, and has poor light fastness.

Therefore, in recent years, various color-forming dyes have been proposed which form a dye that absorbs electromagnetic waves in a long wavelength range. JP-A-62-142681 and JP-A-62-18
No. 1361 proposes a color-forming recording material containing two elements of a phenylenediamine derivative or a naphthylenediamine derivative and an acidic substance.

However, according to an experiment conducted by the present inventors, according to the additional test of the embodiment described in the above publication,
It was difficult to achieve sufficient color development in the near infrared and reading at 780 nm. Further, Japanese Unexamined Patent Publication No.
JP-A-3-256486 proposes a color-forming recording material containing two elements such as a phenylenediamine derivative or a naphthylenediamine derivative and a quinoid-type electron-accepting compound as an oxidizing agent. However, according to the experiments of the present inventors, the recording paper containing a phenylenediamine derivative or a naphthylenediamine derivative and a quinoid-type electron-accepting compound was prepared by a supplementary test of the example described in the publication. In some cases, sufficient color development could not be achieved even by heating.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color recording material. Another object of the present invention is to provide a chromogenic recording material which gives practically sufficient intensity of color immediately after the color forming operation and has an absorption in a long wavelength region from a visible light region to a near infrared region. .

[0008]

According to the present invention, the above objects and advantages of the present invention are as follows: (a) the general formula (I)

[0009]

Embedded image

[0010]

Embedded image And (b) aromatic carboxylic acid, aromatic hydroxy carboxylic acid
Selected from the group consisting of acids, organic sulfonic acids and acidic resins
This is achieved by a chromogenic recording material characterized by containing at least one acidic substance.

The color-forming recording material according to the present invention comprises the above two components (a) and (b). These two
By bringing the components into contact, a dye having extremely strong absorption intensity and fastness in the visible light region or near infrared region can be obtained. Accordingly, the present invention provides a practical color recording material that is sensitive to a semiconductor laser.

The quinone diimine derivative (a) used in the present invention is represented by the above general formula (I). However,
The fluoran compound represented by the above formula (a) is excluded.
You.

In the formula (I), A and B each independently represent an aryl group, an alkyl group or an aralkyl group.
The aryl group and the aryl group portion of the aralkyl group include 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, an amino group, and an alkyl group. It may have at least one substituent selected from the group consisting of a substituted amino group, an aryl-substituted amino group, an acylamino group, a pyrrolidino group, a piperidino group and a carbamoyl group.

In the formula (I), R ¹ , R ² , R ³
And R ⁴ are the same or different and are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxyl group or a halogen atom, or R ¹ and R ² or R ³ and R ⁴ are bonded to each other to form the following formula: —CR ^{5 = CR 6 -CR 7 = CR 8} - may represent a group represented by. R ⁵ , R ⁶ , R ⁷
And R ⁸ are the same or different and are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxyl group or a halogen atom.

When R ¹ , R ² , R ³ and R ⁴ are all hydrogen, alkyl, aryl, aralkyl, hydroxyl or halogen, the compounds of formula (I) are quinone diimines. One of R ¹ and R ² or R ³ and R ⁴ is a group —CR ⁵ ＣＲCR ⁶ —CR ⁷ ＣC
When R ⁸ — is represented, the compounds of formula (I) are naphthoquinone diimines. Also, when both sets of R ¹ and R ² and both sets of R ³ and R ⁴ represent the group —CR ⁵ ＣＲCR ⁶ —CR ⁷ ＣＲCR ⁸ —, the compounds of formula (I) are anthraquinone diimines. .

The quinone diimine derivative (a) of the formula (I) includes, for example, N, N'-diphenyl-p-quinone diimine, N- (4-hydroxyphenyl) -N'-phenyl-p-quinone diimine, N- ( 4-methoxyphenyl) -N′-phenyl-p-quinonediimine, N- (4
-Ethoxyphenyl) -N'-phenyl-p-quinone diimine, N- (3-hydroxyphenyl) -N'-phenyl-p-quinone diimine, N- (3-methoxyphenyl) -N'-phenyl-p-quinone diimine, N- (4
-T-butylcarbonyloxyphenyl) -N'-phenyl-p-quinonediimine, N- (4-aminophenyl) -N'-phenyl-p-quinonediimine, N- (4
-Alininophenyl) -N'-phenyl-p-quinonediimine, N- (4- (3-methoxyphenylamino) phenyl-N'-phenyl-p-quinonediimine, N-
(1-methyl-4-hydroxyphenyl) -N'-phenyl-p-quinonediimine, N- (2-methyl-4-methoxyphenyl) -N'-phenyl-p-quinonediimine, N- (2,3-dimethyl -4-hydroxyphenyl) -N'-phenyl-p-quinonediimine, N- (4
-T-butylcarboxyphenyl) -N'-ethyl-
N'-phenyl-p-quinonediimine, N- (4-fluorophenyl) -N'-phenyl-p-quinonediimine, N- (4-chlorophenyl) -N'-phenyl-p
-Quinone diimine, N- (4-bromophenyl) -N '
-Phenyl-p-quinonediimine, N- (4-nitrophenyl) -N'-phenyl-p-quinonediimine, N,
N′-diphenyl-1,4-naphthoquinone diimine, N,
N′-diphenyl-1,4-anthraquinone diimine,
N, N'-diphenyl-2,3,5,6-tetrachloro-p
-Benzoquinonediimine, N, N'-diphenyl-2,3
-Dichloro-p-benzoquinone, N, N'-diphenyl-2,5-dichloro-p-benzoquinone, N, N'-diphenyl-2,5-dichloro-5,6-dicyano-p-benzoquinone, N, N '-Diphenyl-2-chloro-p-benzoquinone, N, N'-diphenyl-2-methyl-p-
Benzoquinone, N, N'-diphenyl-2-ethyl-p
-Benzoquinone, N, N'-diphenyl-2,3-dimethyl-p-benzoquinone, N, N'-diphenyl-2,5-
Dimethyl-p-benzoquinone, N, N'-diphenyl-
2,3-diethyl-p-benzoquinone, N, N′-diphenyl-2,5-diethyl-p-benzoquinone, 2, N,
N'-triphenyl-p-benzoquinone, 2,5, N,
N'-tetraphenyl-p-benzoquinone, N, N'-
Diphenyl-2-benzyl-p-benzoquinone, N,
N'-diphenyl-2,3-benzyl-p-benzoquinone, N, N'-diphenyl-2,5-benzyl-p-benzoquinone, N, N'-diphenyl-2-hydroxy-p
-Benzoquinone, N, N'-diphenyl-2,5-dihydroxy-p-benzoquinone and the like.

In the present invention, the acidic substance (b) includes an aromatic carboxylic acid, an aromatic hydroxycarboxylic acid,
Organic sulfonic acids and organic compounds that are acidic resins are used
Can be Examples of these organic compounds include benzoic acid, aromatic carboxylic acids such as naphthoic acid, hydroxybenzoic acid, aromatic hydroxycarboxylic acids such as hydroquinaphthoic acid, organic sulfonic acids such as p-toluenesulfonic acid, and phenol resins. it can be mentioned acidic resins as preferred.

[0018]

As the acidic substance (b), the above compounds can be used alone or in combination of two or more.

Further, the color-forming recording material of the present invention comprises:
An oxidizing agent may be included. The oxidizing agent used may be either organic or inorganic. Examples of the organic oxidizing agent include quinoid-type electron accepting compounds, organic halogen compounds, phosphine oxides, sulfoxides, disulfides, N-oxides, radical compounds, and other organic oxides. Examples of suitable agents include oxygen, halogen, metal oxides, halides, and organic acid metal salts.

As is well known, a conventional ordinary heat-sensitive recording material is prepared by preparing an aqueous dispersion containing a binder together with a coloring dye and a developer such as bisphenol A and other additives used as required. This is applied to a substrate such as paper and dried. When the color forming recording material according to the present invention is used as a heat-sensitive recording material, an aqueous dispersion containing a binder together with the quinone diimine derivative, an oxidizing agent, an acidic substance, and other optional additives is prepared in the same manner as described above. This is applied to 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. As such a binder, for example, polyvinyl alcohol, hydroxyethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylate, polymethacrylic acid, polymethacrylic acid ester and the like are preferable. Can be mentioned.

In the color-forming recording material of the present invention, the quinone diimine derivative (a) and the acidic substance (b), that is, the color developer, preferably have a quinone diimine derivative / acidic substance molar ratio of 0.01 to 100, more preferably 0 to 100. .05-20
Used in the range.

The color-forming recording material of the present invention may further contain a fluorescent dye or pigment. As a fluorescent dye,
For example, diaminostilbene type, benzimidazole type, benzidine type, imidazolone type and the like can be mentioned. Examples of the pigment include titanium dioxide, clay, talc, calcium carbonate, aluminum hydroxide, silica, and polystyrene resin.

Further, the color-forming recording material of 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, cisetoacetic anilide, thioacetanilide, dimethyl phthalate, dibenzyl oxalate, dibenzyl terephthalate, dibenzyl isophthalate, and 4,4 ′. -Dimethoxyphenylsulfone and the like. Further, the recording material of the present invention may contain an anti-tackiness agent such as stearic acid, calcium stearate, zinc stearate, carcarnauba wax, paraffin wax, or may be overcoated.

As the pressure-sensitive recording paper, for example, based on a conventional method, for example, an upper leaf having a microcapsule containing a solution of a color-forming dye applied to and supported on a lower surface, and a developer is applied and supported on an upper surface. The unit may be a unit composed of a lower paper sheet, or a microcapsule and a developer may be applied on the same paper surface.

[0027]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

Example 1 0.10 g of N, N'-diphenyl-p-quinonediimine
0.2178 g of 1-hydroxy-2-naphthoic acid, 0.10 g of stearic acid amide, 0.10 g of zinc stearate
g, 10% aqueous polyvinyl alcohol solution (0.75 g) and water (1.75 g) were mixed with a planetary-type fine-mill (FRITSCH).
For 10 minutes to obtain a coating solution.

Next, the obtained liquid is applied to fine paper using a bar coater (Tester Sangyo, P11210).
After air-drying, thermal paper coloring tester (T, manufactured by Okura Electric Co., Ltd.)
H-PMD) was used to develop color by heating. The reflectance before and after coloring is measured by a UV measuring device (Shimadzu Corporation UV-310)
It measured at 300-1300 nm using 1).

FIG. 1 shows absorption curves before and after coloring.

An NEC printer (PC-PR1)
(02TL) using a thermal head. This barcode is transferred to a semiconductor laser (780n
m) Bar code reader (Symbol Technologies Inc.,
LS8200) and an LED barcode reader (Mechano Systems, M10).

[0032]

The coloring recording material of the present invention contains a quinone diimine derivative and an acidic substance, gives practically sufficient coloring after the coloring operation, and absorbs light in a long wavelength region from the visible light region to the near infrared region. This is useful for reading information by a device.

[Brief description of the drawings]

FIG. 1 is an absorption curve before and after color development of a color recording material of Example 1.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masatoshi Futadahara 6-1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Hisaya Miki, Waki-machi, Kuga-gun, Yamaguchi Prefecture 6-1-2 Ki, Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-63-256486 (JP, A) JP-A-4-115987 (JP, A) JP-A-4-142974 (JP, A A) Special Table 3-500395 (JP, A) (58) Fields surveyed (Int. Cl. ⁷ , DB name) B41M 5/28-5/34 B41M 5/132 C09K 9/02

Claims (1)

(57) [Claims] (A) General formula (I) And (b) an aromatic carboxylic acid, an aromatic hydroxycar
From the group consisting of boric acid, organic sulfonic acids and acidic resins
A color recording material comprising at least one selected acidic substance.