JP3045176B2 - 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 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, its production is not used, 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-64-49679 proposes a color-forming recording material containing a fluoran compound and a halogen-substituted benzoquinone compound. Further, a coloring recording material which does not contain a leuco dye such as the above-mentioned fluoran compound and has absorption in a long wavelength region has been proposed.

For example, JP-A-62-142681 and JP-A-62-181361
In Japanese Patent Application Laid-Open Publication No. H11-157, a color-forming recording material containing a phenylenediamine derivative or a naphthylenediamine derivative and an acidic substance is proposed, but the change with time after coloring is remarkable.

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) an acidic substance composed of an organic compound; (b) a color-forming dye which forms a color by contacting it; (c) a general formula (I) A-NR ¹ -X-NR ² -B (wherein, a, B and X each independently represent an aryl group, R ¹ and R ² represents hydrogen, a lower alkyl group, an aryl group or an aralkyl group each independently (D) General formula (II) P = Y = Q (wherein P and Q are each independently (i) an oxygen atom or (ii) General formula: CCZ ₂ (wherein Z represents a cyano group or an alkoxycarbonyl group having 1 to 5 carbon atoms.) Or a group represented by (iii) a general formula ＮNR ³ (wherein R ³ represents an aryl group). Y represents a quinone conjugated with P and Q to form a quinoid structure. It is shown. ) Characterized by containing a quinoid electron accepting compound represented by the formula:

That is, the chromogenic recording material according to the present invention is composed of four elements, and by contacting them, it is possible to obtain a dye having extremely strong absorption intensity and fastness in the visible light region to the near infrared region, Accordingly, the present invention provides a practical chromogenic recording material that is sensitive to a semiconductor laser.

In the present invention, the diamine derivative is represented by the general formula (I), wherein A, B and X each independently represent an aryl group, R ¹ and R ² each independently represent hydrogen, A lower alkyl group, an aryl group or an aralkyl group, each of which independently represents 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, Arylcarbonyloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl 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, such diamine derivatives include, for example, N, N'-diphenyl-p-phenylenediamine, N
-(4-hydroxyphenyl) -N'-phenyl-p-
Phenylenediamine, N- (4-methoxyphenyl)-
N'-phenyl-p-phenylenediamine, N- (4-
(Ethoxyphenyl) -N'-phenyl-p-phenylenediamine, N- (3-hydroxyphenyl) -N'-phenyl-p-phenylenediamine, N- (3-methoxyphenyl) -N'-phenyl-p-phenylene Diamine, N- (4-t-butylcarbonyloxyphenyl)
-N'-phenyl-p-phenylenediamine, N- (4
-Aminophenyl) -N'-phenyl-p-phenylenediamine, N- (4-anilinophenyl) -N'-phenyl-p-phenylenediamine, N- (4- (3-methoxyphenylamino) phenyl-N '-Phenyl-p-
Phenylenediamine, N- (1-methyl-4-hydroxyphenyl) -N'-phenyl-p-phenylenediamine, N- (2,3-dimethyl-4-hydroxyphenyl)
-N'-phenyl-p-phenylenediamine, N- (2
-Methyl-4-methoxyphenyl) -N'-phenyl-
p-phenylenediamine, N- (4-methoxyphenyl) -N-methyl-N'-phenyl-p-phenylenediamine, N- (4-methoxyphenyl) -N'-methyl-N'-phenyl-p-phenylene Diamine, N- (3
-Methoxyphenyl) -N-methyl-N'-phenyl-
p-phenylenediamine, N- (3-methoxyphenyl) -N'-methyl-N'-phenyl-p-phenylenediamine, N- (4-t-butylcarboxylphenyl) -N-ethyl-N'-phenyl- p-phenylenediamine, N- (4-t-butylcarboxylphenyl)
-N'-ethyl-N'-phenyl-p-phenylenediamine, N- (3-oxyphenyl) -N-methyl-N '
-Methyl-N'-phenyl-p-phenylenediamine,
Examples thereof include, but are not limited to, N- (3-oxyphenyl) -N-benzyl-N'-benzyl-N'-phenyl-p-phenylenediamine.

The quinoid electron accepting compound used in the present invention is represented by the above general formula (II), wherein P and Q are each independently (i) an oxygen atom or (ii) a general formula: CCZ ₂ (wherein , Z represents a cyano group or an alkoxycarbonyl group having 1 to 5 carbon atoms.) Or (iii) a general formula: ＮR ³ (wherein R ³ represents an aryl group). Represents a group to be And Y represents a quinone ring conjugated with P and Q to form a quinoid structure.

The aryl group R ³ is 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, aryloxycarbonyl 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.

The quinoid-type electron-accepting compound represented by the general formula (II) represents a quinone compound when P and Q are both oxygen atoms, and represents a quinodimethane compound when both are = CZ ₂ groups. When the other is a = CZ ₂ group, it represents a quinomethane compound, and when both are a = NR ³ group, it represents a quinone diimine compound.

Accordingly, among such quinoid electron accepting compounds, quinone compounds, quinodimethane compounds and quinomethane compounds include, for example, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro-1,4- Benzoquinone, 2,3,5,6
-Tetrachloro-1,4-benzoquinone (chloranil),
2,3,5,6-tetracyano-1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 3,4,5,6
-Tetracyano-1,2-benzoquinone, 2,3-dichloro-
1,4-naphthoquinone, 3,6-dibromo-2,5-diethoxycarbonyl-1,4-benzoquinone, 3,6-diphenylsulfonyl-2,5-diethoxycarbonyl-1,4-benzoquinone, 7,7 , 8,8-Tetracyano-1,4-quinodimethane (tetracyanoquinodimethane), 7,7,8,8-tetrakis (methoxycarbonyl) -1,4-quinodimethane, 9,9,10,10-tetracyano- 1,4-naphthoquinodimethane, 9,9,10,10-tetracyano-2,6-naphthoquinodimethane, 11,11,12,12-
Tetracyano-9,10-anthraquinodimethane, 11,11,1
2,12-tetracyano-2,6-anthraquinodimethane, 10
-(Dicyanomethylene) anthrone, 10-bis (ethoxycarbonyl) methyleneanthrone, 11,11-dicyano-12,12-bis (ethoxycarbonyl) -9,10-anthraquinodimethane and the like.

Examples of the quinone diimine include those corresponding to the diamine derivatives in which R ¹ and R ² are both hydrogen. That is, N, N'-diphenyl-p-quinonediimine, N- (4-hydroxyphenyl) -N'-phenyl-p-quinonediimine, N-
(4-methoxyphenyl) -N'-phenyl-p-quinonediimine, N- (4-ethoxyphenyl) -N'-phenyl-p-quinonediimine, N- (3-hydroxyphenyl) -N'-phenyl-p- Quinone diimine, N-
(3-methoxyphenyl) -N'-phenyl-p-quinone diimine, N- (4-t-butylcarbonyloxyphenyl) -N'-phenyl-p-quinone diimine, N-
(4-aminophenyl) -N'-phenyl-p-quinonediimine, N- (4-anilinophenyl) -N'-phenyl-p-quinonediimine, N- (4- (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- (2-methyl-4-methoxyphenyl) -N'-phenyl-p-quinonediimine and the like can be mentioned. It is not limited.

In the present invention, as the acidic substance, a substance composed of an organic compound is used. Examples of such acidic substances include bisphenol A, 4,4'-sec-butylidenebisphenol, 4,4'-cyclohexylidenebisphenol, 2,2'-dihydroxydiphenyl, pentamethylenebis (4-hydroxybenzoate) ), Aromatic carboxylic acids such as benzoic acid and naphthoic acid, aromatic hydroxycarboxylic acids such as hydroxybenzoic acid and hydroxynaphthoic acid, and organic sulfonic acids such as p-toluenesulfonic acid. However, the present invention is not limited to these.

In the present invention, conventionally known dyes are appropriately used as the dye that develops color upon contact with such an acidic substance. As a specific example, for example, 3,3-bis (p-
Dimethylaminophenyl) phthalide, 3,3-bis (p-
Dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl)
-6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3-cyclohexylamino-6
-Chlorofluorane, 3-dimethylamino-5,7-dimethylfluoran, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluoran,
3-diethylamino-7,8-benzfluoran, 3-diethylamino-8-methyl-7-chlorofluoran, 3
-(Np-tolyl-N-ethylamino) -6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 2- (N- (3'-tolyl Fluoromethylphenyl) amino) -6-diethylfluoran, 3-diethylamino-6-methyl-7- (m
-Tolylchloromethylanilino) fluoran, 3-diethylamino-7- (o-chloroanilino) fluoran,
3-dibutylamino-7- (o-chloroanilino) fluoran, 3-N-methyl-N-amylamino-6-methyl-7-anilinofluoran, 3-N-methyl-N-cyclohexylamino-6-methyl- 7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3 −
(N-methyl-N-isopropyl) amino-6-methyl-7-anilinofluoran, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluoran, 3-
Diethylamino-5-chloro-7- (o-phenylethylamino) fluoran, 3- (N-ethyl-p-toluidino) -7- (o-phenylethylamino) fluoran, 3-diethylamino-5-methyl-7- (O-phenylethylamino) fluoran, 3-diethylamino-
7-piperidinofluoran, 3-dibutylamino-6-
Methyl-7-anilinofluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-N-methyl-N-isopropyl-6-methyl-7-anilinofluoran, 3-N-ethyl -N-amyl-6-methyl-7
-Anilinofluoran, 3-diethylamino-6-methyl-7- (2 ', 4'-dimethylanilino) fluoran and the like.

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 chromogenic dye, the diamine derivative, the quinoid-type electron-accepting compound, the 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 recording material according to the present invention, the diamine derivative and the quinoid electron accepting compound have a molar ratio of the diamine derivative / quinoid electron accepting compound of 0.01 to 10;
0, preferably used in the range of 0.05 to 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.

Effects of the Invention As described above, the color-forming recording material according to the present invention contains a diamine derivative, a quinoid-type electron-accepting compound, and an acidic substance composed of an organic compound, and gives a color with practically sufficient intensity immediately after the color-forming operation. Moreover, since it has strong absorption in a long wavelength region from the visible light region to the near infrared region, it is useful for reading information by a device. Further, an overcoat layer can be provided.

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

0.0088 g of 3-diethylamino-6-methyl-7-anilinofluoran, 0.0088 g of a diamine derivative, 0.0088 g of a quinoid-type electron-accepting compound, 0.0264 g of stearamide,
0.066 g of a 10% by weight aqueous solution of polyvinyl alcohol and 0.14 of water
5 g was treated with a ball mill for 20 hours to obtain Dispersion A.

Separately, 0.5 g of an acidic substance, 0.3 g of zinc stearate, 1.5 g of a 10% by weight aqueous solution of polyvinyl alcohol and 5.0 g of water 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.

The diamine derivatives, quinoid-type electron-accepting compounds and acidic substances used above are as follows.

Diamine derivatives (1) N, N'-diphenyl-p-phenylenediamine (2) N- (4-methoxyphenyl) -N'-phenyl-p-phenylenediamine (3) N- (2-methyl-4-methoxy) Phenyl)-
N'-phenyl-p-phenylenediamine (4) None Quinoid-type electron-accepting compound (a) N, N'-diphenyl-p-quinonediimine (b) N- (4-methoxyphenyl) -N'-phenyl-p -Quinone diimine (c) N- (2-methyl-4-methoxyphenyl)-
N'-phenyl-p-quinonediimine (d) None Acidic substances (A) 1-hydroxy-2-naphthoic acid (B) Clay (C) None Of the above, (1)-(a)-(a), (1)-
FIG. 1, FIG. 2, and FIG. 3 show reflection spectra before and after color development for (d)-(a) and (4)-(a)-(a), respectively.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the reflection spectrum of the chromogenic recording material according to the present invention, wherein (A) shows before coloring and (B) shows after coloring. 2 and 3 show the reflection spectra of the chromogenic recording material as a comparative example, wherein (A) shows before coloring and (B) shows after coloring.

Continuation of 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-63-256486 JP-A-62-181361 (JP, A) JP-A-63-173687 (JP, A) JP-A-63-256487 (JP, A) JP-A-1-113283 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) B41M 5/28-5/34 B41M 5/145 C09K 9/02

Claims (1)

(57) [Claims] (1) an acidic substance composed of an organic compound; (b) a color-forming dye which forms a color upon contact with it; (c) a general formula (I) A-NR ¹ -X-NR ² -B (wherein , A, B and X each independently represent an aryl group; R ¹ and R ² each independently represent hydrogen, a lower alkyl group,
It represents an aryl group or an aralkyl group. (D) a general formula (II) P = Y = Q (wherein P and Q are each independently (i) an oxygen atom or (ii) a general formula: CCZ ₂ , wherein Z is Represents a cyano group or an alkoxycarbonyl group having 1 to 5 carbon atoms.) Or a group represented by the formula (iii): NR ³ (wherein R ³ represents an aryl group). And Y represents a quinone ring conjugated with P and Q to form a quinoid structure. A chromogenic recording material comprising a quinoid electron accepting compound represented by the formula: