JPH04142975A - 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 an acidic substance, a color forming dye forming a color upon the contact with the acidic substance, a specific diamine derivative and a specific quinoid type electron acceptive compound. CONSTITUTION:A diamine derivative is represented by formula I (wherein A, B and X are respectively independently an aryl group and R<1> and R<2> are respectively independently hydrogen, a lower alkyl group, an aryl group or an aralkyl group). A quinoid type electron acceptive compound is represented by formula (II) [wherein P and Q are respectively independently an oxygen atom or =CZ2=N-R<3> (wherein Z is a cyano group or a 1-5C alkoxycarbonyl group and R<3> is an aryl group) and Y is a quinone ring conjugated with P and Q to form a quinoid structure]. As an acidic substance, both of org. and inorg. compounds can be used. As a dye forming a color upon the contact with the acidic substance, any one known heretofore is appropriately used. The mol ratio of diamine derivative/quinoid type electron acceptive compound is pref. 0.05-20.

Description

DETAILED DESCRIPTION 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 to near infrared rays and is thus useful for reading information by equipment. Regarding materials.

Previously, color-forming recording materials composed of dyes that are colorless per se and acidic substances have been widely used as heat-sensitive recording materials.

However, in recent years, with the development of electronic technology and information management systems, record 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. The color-forming recording material used, which uses a phthalide compound 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 region have been proposed.

For example, JP-A-64-49679 proposes a color-developing recording material containing a halogen-substituted benzoquinone compound together with a fluoran compound.

Furthermore, a color-forming recording material that does not contain a leuco dye such as the above-mentioned fluoran compound and has absorption in a long wavelength region has also 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 has been made to solve the above-mentioned problems with conventional color-forming recording materials. The object of the present invention is to provide a color-forming recording material that has strong absorption in the long wavelength region from the visible light region to the near-infrared region.

The color-forming recording material according to the present invention for reducing the amount of 2 comprises (a) an acidic substance, (b) a color-forming dye that develops color upon contact with it, and (c)
General formula (I) 8-NR'-X-NR"-B (wherein A, B and X each independently represent an aryl group, and R1 and R2 each independently represent hydrogen, a lower alkyl group, an aryl group) or an aralkyl group), (d) general formula (If) p=4'=Q (wherein P and Q each independently represent (1) an oxygen atom or (ii) general formula (wherein, Z represents a cyano group or an alkoxycarbonyl group having 1 to 5 carbon atoms) or (iii) a group represented by the general formula % (wherein, R3 represents an aryl group) The compound is characterized in that it contains a quinoid-type electron-accepting compound represented by the following formula.

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

In the present invention, the diamine derivative has the general formula (
I), where A, B and X each independently represent an aryl group, R1 and R2 each independently represent hydrogen, a lower alkyl group, an aryl group or an aralkyl group, and these aryl groups each 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,
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, It may have at least one substituent selected from the group consisting of an aryl-substituted amino group, a pyrrolidino group, a piperidino group, and a carbamoyl group.

Therefore, examples of such diamine derivatives include Eva,
N, N”-diphenyl-p-phenylenediamine, N
-(4-hydroxyphenyl) -N'--yenyl-p-phenylenediamine, N-(4-methoxyphenyl) -N'-phenyl-p-phenylenediamine, N-
(4-Ethoxyphenyl)-N゛phenyl p-phenylenediamine, N-(3hydroxyphenyl)-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)phenylN'-phenyl p-phenylenediamine, N-(1-methyl-4-hydroxyphenyl)
-N'-phenyl-p-phenylenediamine, N-(2
,3dimethyl-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-phenylenediamine, N-(3-methoxyphenyl)-N-methyl-N-phenyl-p-phenylenediamine, N-(3-methoxyphenyl) )-N”=methyl-N゛phenyl-p-phenylenediamine, N-(4t
-butylcarboxylphenyl)-N-ethyl-N'-
Phenyl-p-phenylenediamine, N(4-t-butylcarboxylphenyl)-N'ethyl-N'-phenyl-p-phenylenediamine, N-(3-oxyphenyl)-N-methylN'-methyl-N゛-phenyl-P
-phenylenediamine, N-(3-oxyphenyl)-
N-benzyl-N'-benzyl-N'-phenyl-p-
Examples include, but are not limited to, phenylenediamine.

The quinoid electron-accepting compound used in the present invention is
It is represented by the above general formula (n), where P and Q are each independently (i) an oxygen atom or (ii) a general formula (wherein Z is a cyano group or an alkoxycarbonyl group having 1 to 5 carbon atoms). ) or (iii) a group represented by the general formula (wherein R3 represents an aryl group). ), and Y represents a quinone ring that is conjugated with P and Q to form a quinoid structure.

As described above, the aryl group R3 is a halogen atom,
cyano group, hydroxyl group, alkyl group, aryl group, alkoxy group, aryloxy group, aralkyloxy group, alkylcarbonyloxy group, carbonyloxy 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.

The quinoid-type electron-accepting compound represented by the general formula (II) indicates a quinone compound when both P and Q are oxygen atoms, and indicates a quinodimethane compound when both P and Q are =CZ2 groups, and one is oxygen, When the other is .CZ2 group, it represents a quinomethane compound, and furthermore, both are -N-R3
When it is a group, it represents a quinone diimine compound.

Therefore, among such quinoid-type 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 L4-benzoquinone (chloranil), 2,3,5.6 tetracyano 1,4-
Benzoquinone, 2,3-dichloro-5,6-dicyath-L4-benzoquinone, 3゜4.5.6-tetracyano-
1,2-benzoquinone, 2゜3-dichloro-1,4-naphthoquinone, 3,6-dipromo-2,5-jethoxycarbonyl-1,4-benzoquinone, 3,6-cyphenylsulfonyl-2,5-jethoxy Carbonyl-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-tetracyano9.10-anthraquinodimethane, 11.11.12.12-tetracyano-2,
6-anthraquinodimethane, 10 (dicyanomethylene)
Examples include anthrone, 1o-bis(ethoxycarbonyl)methylene anthrone, 11.11dicyano-12,12-bis(ethoxycarbonyl)-9,10-anthraquinodimethane, and the like.

Furthermore, examples of the quinone diimine include those corresponding to diamine derivatives in which R1 and R2 are both hydrogen among the diamine derivatives described above.

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-quinonediimine, N(3-methoxyphenyl)-N'-phenyl-p-quinonediimine, N-(4-t-butylcarbonyloxyphenyl)-N'-phenyl-p -quinonediimine, 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-(2,3dimethyl-4-hydroxy phenyl)
-N'-phenyl-p-quinonediimine, N-(2-
methyl 4-methoxyphenyl) -N'-phenyl-p
Examples include, but are not limited to, quinone diimine.

Furthermore, in the present invention, both organic compounds and inorganic compounds can be used as the acidic substance. Examples of organic compounds include bisphenol A, 4.4
'-se c-butylidene bisphenol, 4.4
Phenol derivatives such as '-cyclohexylidene bisphenol, 2,2'-dihydroxydiphenyl, pentamethylene bis(4-hydroxybenzoate), aromatic carboxylic acids such as benzoic acid and naphthoic acid, hydroxybenzoic acid, hydroxynaphthoic acid, etc. Examples include, but are not limited to, aromatic hydroxycarboxylic acids and organic sulfonic acids such as p-toluenesulfonic acid.

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

In the present invention, conventionally known dyes that develop color upon contact with such acidic substances are appropriately used. As a specific example, for example, 3,3-bis(p-
dimethylaminophenyl) phthalide, 3,3-bis(p
-dimethylaminophthalide) 6-dimethylaminophthalide (crystal violet lactone aminophthalide) -6-ethylaminophthalide, 3,
3-bis(p-dimethylaminophenyl)-6 chlorphthalide, 3,3-bis(p-dibutylaminophenyl)
Phthalide, 3-cyclohexylamino-6-chlorofluoran, 3-dimethylamino-5.7-=dimethylfluoran, 3-diedylamino-7-chlorofluoran,
3-diethylamino-7-methylfluorane, 3-diethylamino 7,8-benzfluorane, 3-diethylamino-8-methyl-7-chlorofluorane, 3-(Np
-tolyl-N-ethylamino)-6-methyl 7-anilinofluorane, 3-pyrrolidino-6methyl-7-anilinofluorane, 2-(N(3=I-lylfluoromethylphenyl)amino)6 -dinitylfluorane, 3-diethylamino-6-methyl-7-(m-I-lylchloromethylanilino)fluorane, 3-diethylamino-7(0
-Chloranilino)fluoran, 3-dibutylamino-
7-(o-chloroanilino)fluorane, 3-N-methyl-N-amylamino-6-methyl-7-anilinofluorane, 3-N-methylN-cyclohexylamino-6
-Methyl-7anilinofluorane, 3-diethylamino-6methyl-7-anilinofluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3- (N-methyl-N-isopropyl)amino-6-methyl-7anilinofluorane,
3-pyrrolidino-7-(dyl-chlorophenyl)methylaminofluorane, 3-diethylamino-5-chloro-
7-(o-phenylethylamino)fluoran, 3-(
N-ethyl-p-)luidino)-7-(o-phenylethylamino)fluoran, 3-diethylamino-5-methyl-7-(o-phenylethylamino)fluoran,
3-diethylamino-7-piperidinofluorane, 3-
dibutylamino-6-methyl 7-anilinofluorane,
3-diethylamino6-chloro-7-anilinofluorane, 3-N■ Methyl-N-isopropyl-6-methyl-7anilinofluorane, 3-N-ethyl-N-amyl-6-methyl-
7-anilinofluorane, 3-diethylamino-6-methyl-7-<2'. Examples include 4'-dimethylanilino)fluoran.

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 A, 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 color-forming dye, diamine derivative, quinoid type electron-accepting compound, 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 diamine derivative and the quinoid electron-accepting compound have a diamine derivative/quinoid electron-accepting compound molar ratio of 0.01 to 1.
00, preferably in the range of 0.05 to 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 titane dioxide, clay, talc, calcium carbonate, aluminum hydroxide, silica, polystyrene resin, and formalin resin.

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, thioacetanilide, dimethyl phthalate, dibenzyl terephthalate,
Examples include dibenzyl isophthalate and 4,4'-dimethoxydiphenyl sulfone. Furthermore, anti-blocking agents such as stearic acid, zinc stearate, calcium stearate, carnauba wax, and paraffin wax can also be contained.

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, and gives a color with sufficient intensity for practical use immediately after the color-forming operation.
Moreover, it has strong absorption in the long wavelength range from visible light to near-infrared light, making it useful for reading information with equipment. Additionally, an overcoat layer can be provided.

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

3-diethylamino-6-methyl-7-anilinofluorane O,OO88g, diamine derivative 0.0088g
, quinoid electron-accepting compound o, o o s8g,
Stearamide 0.0264 g, 10% by weight polyvinyl alcohol aqueous solution 0.066 g and water 0.14
Dispersion A was obtained by processing 5 g in a ball mill for 20 hours.

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

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 the thermal head of a printer (PC-PRl 02TL).

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 addition, the diamine derivative, quinoid type electron-accepting compound, and acidic substance used in the above are as follows.

Diamine derivative (1) N,N'-diphenyl-p-phenylenediamine (2) N-(4-methoxyphenyl)-N'-phenyl-p-phenylenediamine (3) N-(2-methyl-4-methoxy phenyl)N'
Quinoid-type electron-accepting compound (a) without -phenyl-p-phenylenediamine (4) N,N''-diphenyl-p-quinonediimine (
b) N-(4-methoxyphenyl)-N゛-phenyl-
p-quinonediimine (c) N-(2-methyl-4-methoxyphenyl)N”
-Phenyl-p-quinone diimine (d) None Acidic substance (a) L-hydroxy-2-naphthoic acid (0) Clay (c) None Among the above, (1) -(a) -(a), ( 1)-
The reflection spectra of (d)-(a) and (4)-(a)-(a) before and after coloring are shown in FIGS. 1, 2, and 3, respectively.

[Brief explanation of the drawing]

FIG. 1 shows the foul spectrum of the color-forming recording material according to the present invention, in which (A) shows before color development and (B) shows after color development. FIGS. 2 and 3 show the reflection spectra of color-forming recording materials as comparative examples, with (A) showing before color development and (B) showing after color development. (0/,) Φ Hiroshi Y ('/,') Gekisho!

Claims (1)

[Claims] (1) (a) acidic substance, (b) chromogenic dye that develops color when in contact with it, (c) general formula (I) A-NR^1-X-NR^2-B (in the formula, A, B and X each independently represent an aryl group, and R^1 and R^2 each independently represent hydrogen, a lower alkyl group, an aryl group, or an aralkyl group. ) P=Y=Q (wherein P and Q are each independently (i) an oxygen atom or (ii) general formula=CZ_2 (wherein, Z represents a cyano group or an alkoxycarbonyl group having 1 to 5 carbon atoms) ) or (iii) a group represented by the general formula =N-R^3 (wherein R^3 represents an aryl group), and Y is conjugated with P and Q. shows a quinone ring forming a quinoid structure. ) A color-forming recording material characterized by containing a quinoid-type electron-accepting compound represented by: