JPH1148607A - Color developing recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color developing recording material such as a pressure-sensitive recording material and a heat-sensitive recording material, which is excellent in concentration, color tone and the preservation-stability of a recorded image, and wherein a misreading rate of an optical character reading device is low even after a long period of storage by jointly using a specified fluoran compound and other fluoran compound which is different from the first fluoran compound. SOLUTION: As electron donative coloring agents, at least one kind of fluoran compound represented by formula I and at least one kind of fluoran compound represented by formula II are contained. In this case, in formula I, R<1> , R<2> respectively indicate alkyl groups with the number of carbon atoms of 1-5, and in formula II, R<3> , R<4> respectively indicate an alkyl group, a cycloalkyl group, an alkoxyalkyl group or an aryl group, and also, R<3> and R<4> may form a nitrogen-containing heterocycle by connecting. R<5> indicates a hydrogen atom or an alkyl group. By this method, a color developing recording material such as a pressure-sensitive recording material, and a heat-sensitive recording material, which are excellent in concentration, color tone and the preservation-stability of a recorded image, and wherein a misreading rate of an optical character reading device is low even after a long period of storage can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color-forming recording material utilizing a color-forming reaction between a color-forming agent and a color-developing agent. The present invention relates to a color-forming recording material such as a pressure-sensitive recording material and a heat-sensitive recording material that can be read by a reading device and has a low erroneous reading rate even after a long period of time.

[0002]

2. Description of the Related Art Hitherto, a color-forming recording utilizing a color-forming reaction between a colorless or pale-colored electron-donating color-forming agent (hereinafter referred to as a color-forming agent) and an organic or inorganic electron-accepting color-developing agent (hereinafter referred to as a color-developing agent). The materials are already well known as pressure-sensitive recording materials, thermosensitive recording materials, reversible thermochromic materials, and the like. The pressure-sensitive recording material is disclosed, for example, in Japanese Patent Publication No. 42-20144, and is used in the field of copying paper such as slips and computer paper.

A heat-sensitive recording material is disclosed in, for example, Japanese Patent Publication No. Sho 45
Facsimile, printer and word processing paper, vending machines for tickets,
It is used in a wide range of fields such as barcode labels and rewritable cards.

More recently, information such as characters and barcodes recorded on these chromogenic recording materials has been mechanically read using LED (light emitting diode) light or laser light, that is, an optical character reading device. (Hereinafter abbreviated as OCR) has been widely used.

[0005] The characteristics of the chromogenic recording material suitable for reading by OCR include the whiteness of the background before recording and its storage stability, the density and color tone of the recorded image after color recording, its storage stability. In addition to the above, the accuracy of the OCR reading of the recorded image is important. Furthermore, it is necessary that information can be read accurately even after the recorded image has been left for a long period of time, especially in a pressure-sensitive recording material that uses a relatively small amount of a coloring agent or in a heat-sensitive label that is used under severe environmental conditions. It is important that the visibility of the recorded image after long-term storage and the OCR reading rate are high.

Further, as a chromogenic recording material capable of obtaining a recorded image suitable for reading by OCR, Japanese Patent Publication No. 58-5
The techniques disclosed in Japanese Patent Application Laid-Open No. 940, No. 62-243653, Japanese Patent Application Laid-Open No. 2-138368, Japanese Patent Application Laid-Open No. 4-251785, Japanese Patent Application Laid-Open No. 5-212957, and the like are known.

However, these color-forming recording materials are:
There is background fogging, the density and storage stability of the recorded image are insufficient, or the color tone of the recorded image is blue to green with insufficient visibility, and the OCR reading characteristics after long-term storage are poor. However, there has not yet been obtained a material having the above-mentioned drawbacks and satisfying the above-mentioned characteristics.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a pressure-sensitive recording material which is excellent in the above-mentioned properties, particularly, the density, color tone and storage stability of a recorded image, and has a low OCR misreading rate even after long-term storage.
An object of the present invention is to provide a color recording material such as a thermal recording material.

[0009]

Means for Solving the Problems The present inventors have studied to solve such problems, and as a result, a specific fluoran compound and another specific fluoran compound different therefrom have been developed. It has been found that the above-mentioned problems can be solved by using the compound as a color-forming agent, and the present invention has been completed.

That is, the present invention relates to a color-forming recording material utilizing a color-forming reaction between an electron-donating color-forming agent and an electron-accepting color developing agent.
And at least one of the fluoran compounds represented by the following general formulas (II) to (VI).

[0011]

Embedded image (In the formula (I), R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms.)

[0012]

Embedded image (In the formula (II), R ³ and R ⁴ each represent an alkyl group, a cycloalkyl group, an alkoxyalkyl group or an aryl group, and R ³ and R ⁴ may be linked to form a nitrogen-containing heterocyclic ring. .R ⁵ represents a hydrogen atom or an alkyl group.)

[0013]

Embedded image (In the formula (III), R ⁶ and R ⁷ each represent an alkyl group or an alkoxyalkyl group, and R ⁶ and R ⁷ may be linked to form a nitrogen-containing heterocycle. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom or an alkyl group.)

[0014]

Embedded image (In the formula (IV), R ¹² and R ¹³ each represent an alkyl group, a cycloalkyl group, an alkoxyalkyl group, an aralkyl group or an aryl group, and R ¹² and R ¹³ are linked to form a nitrogen-containing heterocyclic ring. be good .R ¹⁴ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, R ^15,
R ¹⁶ and R ¹⁷ each represent a hydrogen atom or an alkyl group. )

[0015]

Embedded image (In the formula (V), R ^{18 to} R ²¹ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an aralkyl group, and n represents an integer of 1 or 2.)

[0016]

Embedded image (In the formula (VI), R ²² represents an alkyl group, an alkoxyalkyl group or an aryl group, and R ²³ represents a hydrogen atom,
Indicates a halogen atom, an alkyl group or an alkoxy group.
R ²⁴ represents a hydrogen atom, a halogen atom or an alkyl group, R ²⁵ represents a halogen atom or an alkyl group, and m represents 0 or an integer of 1-2. )

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the fluoran compound represented by the general formula (I), R ¹ and R ² are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl. Group, isobutyl group, n-pentyl group and isopentyl group, and among them, those having 2 to 5 carbon atoms are particularly preferable.

Specific examples of the fluoran compound represented by the general formula (I) include 2- (3-methylanilino) -3-
Methyl-6-dimethylaminofluoran, 2- (3-methylanilino) -3-methyl-6-diethylaminofluoran, 2- (3-methylanilino) -3-methyl-6
-Di-n-propylaminofluoran, 2- (3-methylanilino) -3-methyl-6-diisopropylaminofluoran, 2- (3-methylanilino) -3-methyl-6-di-n-butylaminofluoran Oran, 2- (3-methylanilino) -3-methyl-6-diisobutylaminofluoran, 2- (3-methylanilino) -3-methyl-6- (N-methyl-N-isobutylamino) fluoran, 2- ( 3-methylanilino) -3-methyl-6-
(N-ethyl-N-propylamino) 2- (3-methylanilino) -3-methyl-6- (N-ethyl-N-isopentylamino) fluoran, 2- (3-methylanilino) -3-methyl-6 -Di-n-pentylaminofluoran and the like.

In particular, 2- (3-methylanilino) -3-methyl-6-diethylaminofluoran and 2- (3-methylanilino) -3-methyl-6-di-n-butylfluoran are preferred. Powder X by Kα ray
Diffraction angle (2θ ± 0.2 °) 7.6 ° in X-ray diffraction method,
12.2 °, 14.9 °, 15.9 °, 17.6 °, 2
2- (3-methylanilino) -3-methyl-characterized by an X-ray diffractogram showing a characteristic peak at 2.8 °
Preferred is the β-form modification of 6-diethylaminofluoran.

The fluoran compound represented by the general formula (I) can be produced, for example, by the following method.

General formula (1)

Embedded image (In the formula (1), R ¹ and R ² are the same as those in the general formula I.) and a benzophenone compound represented by the general formula (2)

[0022]

Embedded image (In the formula (2), Ra represents ^a hydrogen atom or a lower alkyl group.) A diphenylamine compound represented by the following formula: at a temperature of 0 to 50 ° C for several hours in the presence of a dehydrating condensing agent such as concentrated sulfuric acid. The reaction is carried out for several tens of hours, and the resulting reaction product is treated with an aqueous alkali solution such as sodium hydroxide, and then purified and recrystallized using an appropriate organic solvent, if necessary. ) Can be obtained in the form of a white to slightly colored powder.

In particular, 2- (3-methylanilino)-
The β-type crystal modification of 3-methyl-6-diethylaminofluoran can be obtained according to the method disclosed in JP-A-6-25249. For example, a benzophenone compound of the general formula (1) is reacted with a diphenylamine compound of the general formula (2) in the presence of a dehydrating condensing agent, and then impurities in an organic solvent extract of the treated product after alkali treatment are extracted. It can be produced by precipitating from an organic solvent extract that is 10% or less of the components.

In the fluoran compound represented by the general formula (II), R ³ and R ⁴ are an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a total of 3 to 8 carbon atoms.
And a phenyl group which may have a substituent are preferable, and an alkyl group having 1 to 4 carbon atoms or a phenyl group is particularly preferable. Examples of the nitrogen-containing heterocyclic ring formed by linking R ³ and R ⁴ include a piperidino group, a piperazino group, a pyrrolidino group, a morpholino group and the like, and a piperidino group or a pyrrolidino group is preferred.

R ⁵ is a hydrogen atom or a group having 1 to 1 carbon atoms.
An alkyl group of 2 is preferable, and an alkyl group having 1 to 8 carbon atoms is particularly preferable.

Specific examples of the fluoran compound represented by the general formula (II) are shown in Table 1 below.

[0027]

[Table 1]

The fluoran compound represented by the general formula (II) can be produced, for example, according to the following method.

General formula (3)

Embedded image (In the formula (3), R ³ and R ⁴ are the same as those in the formula (II).) A benzophenone compound represented by the general formula (4)

[0030]

Embedded image (In the formula (4), R ⁵ is the same as those in the formula (II), and R ^b is a lower alkyl group.) A phenothiazine-based compound represented by the following formula: The reaction is carried out at a temperature of 0 to 50 ° C. for several hours to several tens hours in the presence. The fluoran compound represented by the general formula (II) can be easily obtained by treating the reaction product with an alkali and, if necessary, further purifying the reaction product using an appropriate organic solvent.

In the fluoran compound represented by the general formula (III), R ⁶ and R ⁷ are preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Examples of the nitrogen-containing heterocyclic ring formed by linking R ⁶ and R ⁷ include a piperidino group, a piperazino group, a pyrrolidino group, a morpholino group, and the like, with a piperidino group or a pyrrolidino group being preferred.

As R ^{8 to} R ¹¹ , a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferable, and a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms is particularly preferable.

Specific examples of the fluoran compound represented by the general formula (III) are shown in Table 2 below.

[0034]

[Table 2]

The fluoran compound represented by the general formula (III) can be produced, for example, according to the following method.

General formula (5)

Embedded image (In the formula (5), R ^{8 to} R ¹¹ are the same as those in the formula (III).) And a benzophenone compound represented by the general formula (6):

[0037]

Embedded image (In the formula (6), R ⁶ and R ⁷ are the same as those in the formula (III), and R ^C is a lower alkyl group.) A diphenylamine compound represented by the following formula: Is reacted at 0 to 50 ° C. for several hours to tens of hours in the presence of, and the reaction product is treated with an alkali, and if necessary, purified using an appropriate organic solvent to obtain a compound represented by the general formula (III):
Can easily be obtained.

In the fluoran compound represented by the general formula (IV), R ¹² and R ¹³ are an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a total of 3 to 8 carbon atoms.
8 alkoxyalkyl groups, benzyl groups or phenyl groups which may have a substituent are preferable, and alkyl groups having 1 to 5 carbon atoms, cyclohexyl groups, alkoxyalkyl groups having 3 to 7 carbon atoms, benzyl groups, and phenyl groups are preferable. Or a tolyl group is particularly preferred.

The heterocyclic ring formed by linking R ¹² and R ¹³ includes a piperidino group, a piperazino group, a pyrrolidino group,
Examples include a morpholino group, and a piperidino group or a pyrrolidino group are preferred.

R ¹⁴ is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group, a benzyl group or a phenyl group which may have a substituent.
An alkyl, allyl, benzyl or phenyl group of 8 is particularly preferred.

As R ¹⁵ , R ¹⁶ and R ¹⁷ , a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

Specific examples of the fluoran compound represented by the general formula (IV) are shown in Table 3 below.

[0043]

[Table 3]

The fluoran compound represented by the general formula (IV) can be produced, for example, according to the following method.

General formula (7)

Embedded image (In the formula (7), R ¹² and R ¹³ are the same as those in the formula (IV).) And a benzophenone compound represented by the general formula (8):

[0046]

Embedded image (In the formula (8), R ^{14 to} R ¹⁷ represent the same as those in the formula (IV), and R ^d represents a lower alkyl group.) A quinoline-based compound represented by the following formula: Is reacted at 0 to 50 ° C. for several hours to several tens of hours in the presence of, and the reaction product is treated with an alkali and, if necessary, purified using a suitable organic solvent, whereby the compound represented by the general formula (IV) is obtained. Fluoran compounds can be easily obtained.

In the fluoran compound represented by the general formula (V), R ^{18 to} R ²¹ represent a hydrogen atom, a chlorine atom,
An alkyl group having 1 to 4 carbon atoms or a benzyl group is preferred.

Specific examples of the fluoran compound represented by the general formula (V) are shown in Table 4 below.

[0049]

[Table 4]

The fluoran compound represented by the general formula (V) can be produced, for example, according to the following method.

General formula (9)

Embedded image (In the formula (8), n is the same as in formula (V), R ^e is a lower alkyl group.) And phenylenediamine compound represented by the general formula (10)

[0052]

Embedded image (In the formula (9), R ^{18 to} R ²¹ are the same as those in the formula (V).) The benzophenone compound represented by the formula (1) is added at 0 to 50 ° C in the presence of a dehydrating condensing agent such as sulfuric acid. By reacting the resulting reaction product with an aqueous alkali solution such as sodium hydroxide, and purifying and recrystallizing using an appropriate organic solvent if necessary. The fluoran compound represented by the formula (V) can be easily obtained.

In the fluoran compound represented by the formula (VI), R ²² is preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms.
R ²³ is preferably a hydrogen atom, a chlorine atom or an alkyl group having 1 to 8 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ²⁴ has 1 to 4 carbon atoms
Is preferred, and a methyl group is particularly preferred. R
²⁵ is preferably a chlorine atom or an alkyl group having 1 to 4 carbon atoms.

Specific examples of the fluoran compound represented by the general formula (VI) are shown in Table 5 below.

[0055]

[Table 5]

The fluoran compound represented by the general formula (VI) can be produced, for example, according to the following method.

General formula (11)

Embedded image (In the formula (11), R ²² and R ²³ are the same as those in the formula (VI).) And a benzophenone compound represented by the general formula (12):

[0058]

Embedded image (In the formula (12), R ²⁴ , R ²⁵ , and m represent the same as those in the formula (VI), and R ^f represents a lower alkyl group.) In the presence of a dehydration condensing agent, the reaction is carried out at a temperature of 0 to 50 ° C. for several hours to several tens of hours, and the resulting reactant is treated with an aqueous alkali solution such as sodium hydroxide, and if necessary, an appropriate organic solvent is used. By performing purification, recrystallization and the like, the fluoran compound represented by the general formula (VI) can be easily obtained.

In the color-forming recording material of the present invention, the fluoran compound of the general formula (I) and the general formulas (II) to (VI)
The use ratio of the fluoran compound of formula (I): [fluorane compound of general formula (I): general formula (II) to (VI)
Fluoran compound = 2: 8 to 8: 2]. If the amount of the fluoran compound of the general formula (I) is less than 20% of the total amount of the color former, the visibility of the color image may be deteriorated, and the light fastness of the color image may be lowered. If the amount of the fluoran compound represented by any of the general formulas (II) to (VI) is less than 20% of the total amount of the color former, the reading rate by OCR may decrease.

In the color-forming recording material of the present invention, other color-forming agents can be used in combination as long as the effect is not impaired.

Further, as the color former which can be used in combination, those applied to this type of recording material can be arbitrarily applied.

Examples of these fluoran compounds include 3,6-dimethoxyfluoran and 2-fluorinated fluoran compounds.
Chloro-6-cyclohexylaminofluoran, 3-chloro-6-cyclohexylaminofluoran, 2-methyl-6-cyclohexylaminofluoran, 3-methyl-6-cyclohexylaminofluoran, 1,3-dimethyl-6 Diethylaminofluoran, 2-tert-
Butyl-6-diethylaminofluoran, 2-chloro-
6-diethylaminofluoran, 2-chloro-3-methyl-6-diethylaminofluoran, 2-methyl-6
(N-ethyl-4-methylanilino) fluoran, 8-
Diethylaminobenzo [a] fluoran, 2-dibenzylamino-6-diethylaminofluoran, 2-dibenzylamino-4-methyl-6-diethylaminofluoran, 2-n-octylamino-6-diethylaminofluoran, 2- Anilino-6- (N-ethyl-NNn-hexylamino) fluoran, 2- (N-methylanilino) -6- (N-ethyl-4-methylanilino) fluoran, 2-anilino-3-methyl-6-dimethyl Aminofluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-di-n-propylaminofluoran,

2-anilino-3-methyl-6-di-n-
Butylaminofluoran, 2-anilino-3-methyl-
6-di-n-pentylaminofluoran, 2-anilino-3-methyl-6- (N-methyl-N-ethylamino)
Fluoran, 2-anilino-3-methyl-6- (N-methyl-NN-propylamino) fluoran, 2-anilino-3-methyl-6- (N-methyl-N-n-butylamino) fluoran, 2-anilino-3-methyl-6
(N-methyl-N-isobutylamino) fluoran, 2
-Anilino-3-methyl-6- (N-methyl-Nn-
(Pentylamino) fluoran, 2-anilino-3-methyl-6- (N-methyl-N-cyclohexylamino) fluoran, 2-anilino-3-methyl-6- (N-ethyl-N-n-propylamino) fluoran , 2-anilino-3-methyl-6- (N-ethyl-NN-butylamino) fluoran, 2-anilino-3-methyl-6
(N-ethyl-N-isobutylamino) fluoran, 2
-Anilino-3-methyl-6- (N-ethyl-N-n-
(Pentylamino) fluoran, 2-anilino-3-methyl-6- (N-ethyl-N-isopentylamino) fluoran, 2-anilino-3-methyl-6- (N-ethyl-Nn-octylamino) Fluoran, 2-anilino-3-methyl-6- [N-ethyl-N- (3-ethoxypropyl) amino] fluoran, 2-anilino-3-chloro-6-diethylaminofluoran, 2-anilino-
3-chloro-6-di-n-butylaminofluoran,

2- (2-chloroanilino) -6-diethylaminofluoran, 2- (2-chloroanilino) -6
-Di-n-butylaminofluoran, 2- (2-fluoroanilino) -6-diethylaminofluoran, 2-
(2-fluoroanilino) -6-di-n-butylaminofluoran, 2- (3-trifluoromethylanilino)
-6-dimethylaminofluoran, 2- (3-trifluoromethylanilino) -6-diethylaminofluoran, 2- (3-trifluoromethylanilino) -6-di-n-butylaminofluoran, 2 -(4-methylanilino) -3-methyl-6-diethylaminofluoran,
2- (4-t-amylanilino) -3-methyl-6-diethylaminofluoran, 2- (3-chloro-4-methylanilino) -3-methyl-6-diethylaminofluoran, 2- (2,4-dimethyl Anilino) -3-methyl-6-diethylaminofluoran, 2- (2,4-dimethylanilino) -3-methyl-6-di-n-butylaminofluoran, 2- (2,6-dimethylani Reno) -3
-Methyl-6-di-n-butylaminofluoran, 2-
(2,6-diethylanilino) -3-methyl-6-diethylaminofluoran, 2- (2,6-diethylanilino) -3-methyl-6-di-n-butylaminofluoran, 2-anilino -3-methoxy-6-diethylaminofluoran, 2,2-bis {4- [6- (N-cyclohexyl-N-methylamino) -3-methylfluoran-
2-ylamino] phenyl} propane and the like,

As the diarylphthalide compound,
3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide (general name: CVL), 3- (4-dimethylaminophenyl) -3- (4-diethylamino-
2-methylphenyl) -6-dimethylaminophthalide,
3,3-bis (9-ethylcarbazol-3-yl)-
6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3- (1-methylpyrrol-3-yl)
-6-dimethylaminophthalide and the like, as an indolylphthalide compound, 3- (4-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl)
Phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-
Bis (1-ethyl-2-methylindol-3-yl)
Phthalide, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (1-
n-octyl-2-methylindol-3-yl) phthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindole-3-
Yl) phthalide, 3- (2-ethoxy-4-dibutylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3- (2-ethoxy-4-
Diethylaminophenyl) -3- (1-octyl-2-
Methylindol-3-yl) phthalide and the like,

As the azaphthalide compound, 3- (4
-Diethylamino-2-ethoxyphenyl) -3- (1
-Ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-n-octyl-2-methylindol-3-yl) -4 Azaphthalide and the like; diarylmethane compounds such as 4,4'-bis (dimethylamino) benzhydryl benzyl ether and N-halophenylleucouramine; and rhodamine lactam compounds such as rhodamine B anilinolactam. , Rhodamine B (4-nitroanilino) lactam, rhodamine B (4-chloroanilino) lactam and the like, as thiazine compounds, benzoylleucomethylene blue, p-
Nitrobenzoyl leucomethylene blue and the like,

Examples of spiropyran compounds include 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3-phenylspirodinaphthopyran, 3-benzylspirodinaphthopyran, and 3-propylspirodinaphthopyran. As the fluorene-based compound, 3,6-bis (dimethylamino) fluorenespiro [9,3 ′]-
6'-dimethylaminophthalide, 3-diethylamino-
6- (N-allyl-N-methylamino) fluorenespiro [9,3 ′]-6′-dimethylaminophthalide, 3,
6-bis (dimethylamino) spiro [fluorene-9,
6′-6′H-chromeno (4,3-b) indole],
3,6-bis (dimethylamino) -3′-methylspiro [fluorene-9,6′-6′H-chromeno (4,3-
b) Indole], 3,6-bis (diethylamino)-
3'-methylspiro [fluorene-9,6'-6'H-
Chromeno (4,3-b) indole] and the like.

These can be used alone or in combination of two or more.

When the color-forming recording material of the present invention is a pressure-sensitive recording material, various known methods disclosed, for example, in JP-B-42-20144 can be applied. As a specific example, after a color former solution obtained by dissolving a color former in a microencapsulation solvent is microencapsulated with a polymer compound as a film agent, it is applied to the back surface of a high-quality paper, synthetic paper, plastic film, or other support. Apply to make upper paper. On the other hand, a developer is applied to the surface of another support to prepare a lower sheet. When the upper paper and the lower paper are overlapped so that the coating surfaces are in contact with each other and a pressure such as a pen pressure or a pressing pressure is applied, the microcapsules in the pressurized portions are broken, and the color forming agent in the microcapsules is developed. Reaction with the agent forms a recorded image on the surface of the lower sheet. In addition, a plurality of copy records can be obtained by inserting several sheets of middle paper coated with a developer on the front surface of the support and microcapsules on the back surface between the upper paper and the lower paper.

Also, a so-called self-contained paper type containing a developer and microcapsules on the same surface of a support, a form in which a developer is contained in microcapsules and a color former is applied, Alternatively, both can be applied to those contained in microcapsules.

Further, an ink for a pressure-sensitive recording material can be prepared and printed on an arbitrary portion on a support for use.

As a developer used in the pressure-sensitive recording material,
Inorganic acidic substance, aliphatic carboxylic acid, aromatic carboxylic acid or polyvalent metal salt thereof, phenolic compound, phenolic resin or modified polyvalent metal thereof, mixture of phenolic resin and metal salt of aromatic carboxylic acid, terpene A phenol resin or a polyvalent metal modified product thereof may, for example, be mentioned.

Examples of these inorganic acids include acidic clay, activated clay, attapulgite, zeolite, bentonite, kaolin, colloidal silica, and the like.
Aluminum silicate, magnesium silicate, zinc silicate, etc.
As aliphatic carboxylic acids, oxalic acid, maleic acid, tartaric acid, succinic acid, stearic acid and the like, and as aromatic carboxylic acids or polyvalent metal salts thereof, benzoic acid, p-ter
t-butylbenzoic acid, gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid,
3-phenyl-5- (2,2-dimethylbenzyl) salicylic acid, 3,5-di- (2-methylbenzyl) salicylic acid, 2-hydroxy-1-benzyl-3-naphthoic acid,
These zinc, magnesium, metal salts such as aluminum,

As a phenolic compound, 6,6′-methylenebis (4-chloro-m-cresol) or the like is used as a phenolic resin or a polyvalent metal-modified product thereof.
Examples include octylphenol resin, p-tert-butylphenol-acetylene resin, and zinc-modified products thereof.

In particular, a zinc salt of a salicylic acid derivative, a phenolic resin or a zinc-modified product thereof is preferably used.

The pressure-sensitive recording material of the present invention may contain known additives such as an ultraviolet absorber and an antioxidant.

Examples of these additives include salicylic acid ultraviolet absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy Benzophenone, 2
-Hydroxy-4-benzyloxybenzophenone, 2
-Hydroxy-4-octyloxybenzophenone, 2
Benzophenone-based ultraviolet absorbers such as -hydroxy-4-methoxy-5-sulfobenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole,
-(2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2-
(2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- [2-hydroxy-4-
(2-ethylhexyl) oxyphenyl] benzotriazole, methyl-3- [3-tert-butyl-5-
(2H-benzotriazol-2-yl) -4-hydroxyphenyl] benzotriazole-based ultraviolet absorber such as a condensate of propionate and polyethylene glycol,
Cyanoacrylate-based ultraviolet absorbers such as 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate and ethyl-2-cyano-3,3-diphenylacrylate; bis (2,2,6,6-tetramethyl -4-piperidyl) sebacate,

Succinic acid-bis (2,2,6,6-tetramethyl-4-piperidyl) ester, 2- (3,5-
Bis (1,2-, 2-di-tert-butyl) malonic acid
Hindered amine antioxidants such as 6,6, -pentamethyl-4-piperidyl) ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-ethylenebis (4-methyl- 6-te
rt-butylphenol), 2,2′-methylenebis (4,6-di-tert-butylphenol), 4,
4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (2-chloro-6-t
hindered phenolic antioxidants such as tert-butylphenol) and other N-methyl-N-phenyl-N ′
-Methyl-N'-isopropyl-p-phenylenediamine, N-methyl-N-phenyl-N'-methyl-N'-
P-phenylenediamines such as (1-methylheptyl) -p-phenylenediamine, 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1-ethyl- Quinolines such as 2,2,4-trimethyl-1,2-dihydroquinoline and 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2-dihydroquinoline; 6-ethoxy-1-phenyl-
2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, 6-ethoxy-1-octyl-2,2,4
-Tetrahydroquinolines such as trimethyl-1,2,3,4-tetrahydroquinoline, 4-methoxy-di-n-
Examples include anilines such as butylaniline.

When the color-forming recording material of the present invention is a heat-sensitive recording material, various known methods disclosed in, for example, JP-B-45-14039 can be applied. Specifically, in the presence of water, a color developing agent, a developing agent, and, if necessary, a sensitizer together with a water-soluble binder using an attritor, a sand mill or the like, the particle size of the drug is several microns. Crush and disperse as follows. The sensitizer is
In addition to one or both of the color former and the developer, they may be ground and dispersed at the same time, and in some cases, may be prepared in advance by forming a eutectic with the color former or the developer and then ground and dispersed. Is also good.

These dispersions are mixed, and if necessary, a pigment, a water-insoluble binder, an anti-sticking agent, an anti-adhesion agent, an antioxidant, an ultraviolet absorber, a dispersant, and the like are added thereto. And After applying the obtained heat-sensitive coating liquid on a support, if necessary, smoothness is imparted by calendering to obtain a heat-sensitive recording material. Further, the heat-sensitive coating liquid may be applied to a support having an undercoat layer of a heat insulating agent such as a plastic pigment or silica in order to improve the coloring property, if necessary. Further, if necessary, in order to impart water resistance and chemical resistance, an overcoat layer may be provided on the heat-sensitive recording layer with a water-soluble polymer aqueous solution or the like.

As the developer used in the heat-sensitive recording material,
Examples include phenol derivatives, organic acids or metal salts / complexes, and urea derivatives.

To illustrate some of these, as phenol derivatives, 4-tert-butylphenol, 4-octylphenol, 4-phenylphenol, 1-naphthol, 2-naphthol, hydroquinone, resorcinol, 4-tert-octylcatechol, 2,2'-
Dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 2,2-bis (4-hydroxyphenyl) propane [generic name bisphenol A], tetrabromobisphenol A, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2, 2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (2
-Methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,4-bis (4-hydroxycumyl) benzene, 1,3 , 5-Tris (4-hydroxycumyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl)
Butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,

4,4 '-(m-phenylenediisopropylidene) bisphenol, 4,4'-(p-phenylenediisopropylidene) bisphenol, bis (4-hydroxyphenyl) acetic acid ethyl ester, 4,4-bis ( 4-hydroxyphenyl) valeric acid-n-butyl ester, 4-hydroxybenzoic acid benzyl ester,
4-hydroxybenzoic acid phenethyl ester, 2,4-
Dihydroxybenzoic acid-2-phenoxyethyl ester, 4-hydroxyphthalic acid dimethyl ester, gallic acid-n-propyl ester, gallic acid-n-octyl ester, gallic acid-n-dodecyl ester, gallic acid-
n-octadecyl ester, hydroquinone monobenzyl ether, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (2-methyl-4-hydroxyphenyl) sulfide, bis (3-phenyl-4-hydroxyphenyl) sulfide, bis (3-cyclohexyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone [generic name bisphenol S],

Tetrabromobisphenol S, bis (3
-Allyl-4-hydroxyphenyl) sulfone, 2,
4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-methyldiphenylsulfone, 4-hydroxy-4'-chlorodiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, 4
-Hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-butoxydiphenylsulfone, 3,4-dihydroxy-4'-methyldiphenylsulfone, 2,4-dihydroxydiphenylsulfone, 2-methoxy-4 '-Hydroxydiphenylsulfone, 2-ethoxy-4'-hydroxydiphenylsulfone, bis (2-hydroxy-5-tert-
Butylphenyl) sulfone, bis (2-hydroxy-
5-chlorophenyl) sulfone, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone,
1,7-bis (4-hydroxyphenylthio) -3,5
-Dioxaheptane, 1,5-bis (4-hydroxyphenylthio) -3-oxapentane and the like,

As the organic carboxylic acid or its metal salt / complex, salicylic acid, 3-isopropylsalicylic acid,
-Tert-butylsalicylic acid, 3-benzylsalicylic acid,
3-chloro-5- (α-methylbenzyl) salicylic acid,
3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, 3,5-bis- (α-methylbenzyl) salicylic acid, 4- (3-p-toluenesulfonylpropyloxy) salicylic acid, 5- {4- [ 2- (4-methoxyphenoxy) ethoxy] cumyl salicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-methyl-5-α-methylbenzylsalicylic acid, 4- [2- (4- Methoxyphenoxy) ethoxy]
Salicylic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, monobenzyl phthalate, monophenyl phthalate, 4-nitrobenzoic acid, 3-nitrobenzoic acid, 2-nitrobenzoic acid, 4-
Organic acids such as chlorobenzoic acid or metal salts thereof (for example, metal salts such as nickel, zinc, aluminum and calcium), zinc thiocyanate antipyrine complex,
Molybdate acetylacetone complex and the like are used as urea derivatives as phenylthiouric acid, N, N'-diphenylthiourea, N, N'-bis (3-trifluoromethylphenyl) thiourea, 1,4-bis (3-chlorophenyl) Thiosemicarbazide, 4,4′-bis (4 ″ -methylphenylsulfonylcarbonylamino) diphenylmethane and the like.

These can be used alone or in combination of two or more.

As the sensitizer, various heat-fusible substances can be used. Examples of these acid amide compounds include, as acid amide compounds, caproic amide, capric amide, stearic amide, palmitic amide, oleic amide, stearyl uric acid, stearic anilide, etc., as fatty acids or metal salts thereof. stearic acid,
Fatty acids such as behenic acid and palmitic acid and zinc, aluminum and calcium salts thereof are used as ester compounds as benzyl 4-benzyloxybenzoate, 2-naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid phenyl ester, Oxalic acid dibenzyl ester, oxalic acid bis (4-methylbenzyl) ester, oxalic acid bis (4-chlorobenzyl) ester, glutaric acid diphenacyl ester, bis (4-methylphenyl)
Carbonate, dibenzyl terephthalate, etc.

Examples of the hydrocarbon compound include 4-benzylbiphenyl, m-terphenyl, fluorene, fluoranthene, 2,6-diisopropylnaphthalene, and 3-benzylacenaphthene, and ether compounds such as 2-benzyloxynaphthalene and 2- ( 4-methylbenzyloxy) naphthalene, 1,4-diethoxynaphthalene, 1,
4-dibenzyloxynaphthalene, 1,2-diphenoxyethane, 1,2-bis (3-methylphenoxy) ethane, 1-phenoxy-2- (4-ethylphenoxy) ethane, 1- (4-methoxyphenoxy) -2-phenoxyethane, 1- (4-methoxyphenoxy) -2- (3
-Methylphenoxy) ethane, 1- (4-methoxyphenoxy) -2- (2-methylphenoxy) ethane, 4-
(4-methylphenoxy) biphenyl, 1,4-bis (2-chlorobenzyloxy) benzene, 4,4′-di-n-butoxydiphenylsulfone, 1,2-diphenoxybenzene, 1,4-bis (2 -Chlorophenoxy) benzene, 1,4-bis (4-methylphenoxy)
Benzene, 1,4-bis (3-methylphenoxymethyl) benzene, 1- (4-chlorobenzyloxy) -4
-Ethoxybenzene, 4,4'-diphenoxydiphenyl ether, 1,4-bis (4-benzylphenoxy)
Benzene and 1,4-bis (4-methylphenoxymethoxymethyl) benzene are exemplified. These alone,
Alternatively, two or more kinds can be used in combination.

As the support, paper, coated paper, synthetic paper,
A plastic film or the like is used.

Examples of the water-soluble binder include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, starches, styrene-maleic anhydride copolymer hydrolyzate, ethylene-maleic anhydride copolymer hydrolyzate, isobutylene-maleic anhydride copolymer. Polymer hydrolyzate, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyacrylamide and the like are used.

As the pigment, organic and inorganic pigments can be used. Preferred specific examples include calcium carbonate,
Examples include barium sulfate, titanium oxide, aluminum hydroxide, amorphous silica, urea formalin resin powder, polyethylene resin powder, and the like.

As the water-insoluble binder, styrene-
Butadiene rubber latex, acrylonitrile-butadiene rubber latex, vinyl acetate emulsion and the like are used as needed.

As the anti-sticking agent, stearic acid, carnauba wax, paraffin wax, carboxy-modified wax, polyethylene wax, zinc stearate, calcium stearate, aluminum stearate and the like are used.

Examples of the anti-adhesion agent include inorganic pigments such as kaolin, clay, talc, calcium carbonate, titanium oxide, and silica; and organic pigments such as styrene microballs, nylon powder, polyethylene powder, urea, formalin resin filler, and starch. Used.

Examples of the ultraviolet absorber include benzophenone and its derivatives, benzotriazole and its derivatives, benzoin and its derivatives, 2-chloroanthraquinone,
Benzyl peroxide, salicylates such as pt-butylphenyl salicylate, and cyanoacrylates such as ethyl diphenylacrylate can be used.

As antioxidants, 2,6-di-t-butyl-4-methylphenol, di (3-t-butyl-4)
-Hydroxy-5-methylphenyl) thioether,
1,1-bis (2-methyl-4-hydroxy-5-t-
Hindered phenols such as butylphenyl) butane; di (2,2,6,6-tetramethyl-4 sebacate)
Hindered amines such as (piperidine).

Examples of pigments include talc, clay, silica,
Titanium oxide, aluminum hydroxide, calcium carbonate can be used.

[0098]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples. Example 1 Preparation of Pressure-Sensitive Recording Material 1.5 g of β-type crystal of 2- (3-methylanilino) -3-methyl-6-diethylaminofluoran and the compound of Specific Example (II) -5 in Table 1 above 1.5 g with solvent KMC
It was dissolved in 47 g of -113 (trade name, manufactured by Kureha Chemical Co., Ltd.) under heating to prepare a color former solution.

On the other hand, 100 g of water was added to the system modifier SM-10.
After adding 5 g of 0 (trade name, manufactured by Mitsui Toatsu Chemicals), the pH was adjusted to 4 with an aqueous sodium hydroxide solution, and 50 g of the above color former solution and 10 g of prepolymer UMC-300 (trade name, manufactured by Mitsui Toatsu Chemicals) were added. And emulsified using a homogenizer until the oil droplet diameter was about 4 microns. Then, the mixture was heated to 60 ° C. with stirring and stirred at the same temperature for 1 hour. After cooling to room temperature, the pH was adjusted to 7.5 with 25% aqueous ammonia to prepare a capsule dispersion of the color former.

After 10 g of the capsule dispersion liquid of the coloring agent thus prepared, 2 g of flour starch and 1 g of latex were thoroughly mixed, the mixture was coated on a high-quality paper so as to have a solid content of 5 g / m ² , dried, and dried. Paper (upper paper) was produced.

(Example 2) Preparation of pressure-sensitive recording material In Example 1, instead of 1.5 g of the compound of Specific Example (II) -5 of Table 1, specific example (III) of Table 2 was used.
CB paper was produced in the same manner as in Example 1, except that 1.5 g of Compound 1 was used.

(Example 3) Preparation of pressure-sensitive recording material In Example 1, instead of 1.5 g of the compound of Specific Example (II) -5 of Table 1, specific example (IV) -1 of Table 3 above
CB paper was produced in the same manner as in Example 1, except that 1.5 g of Compound 1 was used.

(Example 4) Preparation of pressure-sensitive recording material In Example 1, instead of 1.5 g of the compound of Example (II) -5 in Table 1, the compound of Example (V) -7 in Table 4 was used. CB paper was prepared by performing the same operation as in Example 1 except that 1.5 g of the compound was used.

Comparative Example 1 In Example 1, 2- (3
Instead of 1.5 g of the β-form crystal modification of -methylanilino) -3-methyl-6-diethylaminofluoran and 1.5 g of the compound of the specific example (II) -5 in Table 1, 2- (3-
CB paper was produced in the same manner as in Example 1, except that only 3.0 g of the β-form modification of (methylanilino) -3-methyl-6-diethylaminofluoran was used.

Comparative Example 2 In Example 1, 2- (3
Instead of 1.5 g of the β-form crystal modification of -methylanilino) -3-methyl-6-diethylaminofluoran and 1.5 g of the compound of Specific Example (II) -5 of Table 1, specific examples (II CB paper was produced in the same manner as in Example 1 except that only 3.0 g of the compound of () -5) was used.

(Comparative Example 3) In Example 2, 2- (3
1.5 g of 2-anilino-3-methyl-6- (N-ethyl-N-isopentylamino) fluorane instead of 1.5 g of the β-form modification of -methylanilino) -3-methyl-6-diethylaminofluoran Example 2 except used
The same operation as described above was performed to produce CB paper.

(Comparative Example 4) In Example 3, 2- (3
In place of 1.5 g of the β-form modification of -methylanilino) -3-methyl-6-diethylaminofluoran and 1.5 g of the compound of Specific Example (IV) -11 in Table 3, Table 3
CB paper was produced in the same manner as in Example 3, except that 3.0 g of the compound of Specific Example (IV) -11 was used.

(Comparative Example 5) In Example 4, 2- (3
Instead of 1.5 g of the β-form crystal modification of -methylanilino) -3-methyl-6-diethylaminofluoran and 1.5 g of the compound of Specific Example (V) -7 of Table 4, specific examples (V CB-7 paper was produced in the same manner as in Example 4, except that only 3.0 g of the compound of () -7) was used.

(Example 5) Preparation of heat-sensitive recording material 2.5 g of β-type crystals of a color former dispersion liquid 2- (3-methylanilino) -3-methyl-6-diethylaminofluoran and specific examples shown in Table 1 above ( 2.5 g of the compound of II) -5 was added to 45 g of a 2.5% aqueous solution of polyvinyl alcohol, and the mixture was ground by a sand mill so that the average particle diameter became 1 μm, to obtain a colorant dispersion.

A developer dispersion liquid 10 g of bisphenol A and 10 g of p-benzylbiphenyl (sensitizer) are added to 80 g of a 2.5% aqueous solution of polyvinyl alcohol, and ground by a sand mill so that the average particle diameter becomes 3 μm. Thus, a developer dispersion was obtained.

[0111] After mixing the total amount of the heat-sensitive coating liquid coloring agent dispersion and the developer dispersion liquid, calcium carbonate 50% dispersion 30g of paraffin wax 30
% Dispersion was added and mixed well to obtain a heat-sensitive coating liquid.

The heat-sensitive coating solution obtained above was coated on a high-quality paper at a solid content of 4.5 g / m ² and dried.
The recording layer was calendered to a Beck smoothness of 400 to 500 seconds to obtain a heat-sensitive recording material.

(Example 6) Preparation of heat-sensitive recording material In Example 5, instead of 2.5 g of the compound of Specific Example (II) -5 of Table 1, specific Example (III) of Table 2 was used.
The same operation as in Example 5 was carried out except that 2.5 g of compound 1 was used to obtain a thermosensitive recording material.

(Example 7) Preparation of heat-sensitive recording material In Example 5, instead of 2.5 g of the compound of Specific Example (II) -5 of Table 1, specific example (IV) -5 of Table 3 above was used.
A thermosensitive recording material was obtained by performing the same operation as in Example 5 except that 2.5 g of the compound was used.

(Example 8) Preparation of heat-sensitive recording material In Example 5, the compound of Specific Example (V) -7 of Table 4 was replaced by 2.5 g of the compound of Specific Example (II) -5 of Table 1 Except that 2.5 g was used, the same operation as in Example 5 was performed to obtain a thermosensitive recording material.

(Example 9) Preparation of heat-sensitive recording material In Example 5, instead of 2.5 g of the compound of Specific Example (II) -5 in Table 1, specific example (VI) -1 in Table 5 above
A thermosensitive recording material was obtained by performing the same operation as in Example 5 except that 2.5 g of the compound 6 was used.

(Performance Evaluation Test of Pressure-Sensitive Recording Material) Example 1
And CB paper prepared in Comparative Examples 1 to 5 are superimposed on CF paper containing a zinc salt of a salicylic acid derivative as a color developer, and a color is formed at 300 kg / cm ² using a mini roll. It was left still for one day.

Next, the reflectance of the CF surface using light of 680 nm was measured using a spectrophotometer U-3500 (manufactured by Hitachi, Ltd.). PCS (Print Contrast)
(Signal) value was calculated by the following equation. Table 6 shows the results
Shown in

[0119] Next, after exposing this colored CF paper to sunlight for 7 hours, the reflectance using 680 nm light was measured in the same manner, and P
The CS value was calculated. Table 6 shows the results.

[0120]

[Table 6]

As shown in Table 6, the pressure-sensitive recording material of the present invention had a black color tone and high visibility, and had a high PCS value at 680 nm, and thus had excellent OCR reading characteristics. High robustness against

(Performance Evaluation Test of Thermosensitive Recording Material) Example 5
The thermal recording material prepared in any one of Examples 1 to 9 was used in a printing apparatus TH-PMD.
(Okura Electric Co., Ltd.) was used to develop a solid black color, and the reflectance using light of 680 nm was measured with a spectrophotometer U-3500. The PCS value was calculated by the following equation. Table 7 shows the results.

[0123]

[0124]

[Table 7] As shown in Table 7, the heat-sensitive recording material of the present invention has a black color tone and high visibility, and has a high PCS value at 680 nm, and thus has excellent OCR reading characteristics.

[0125]

The color-forming recording material of the present invention has a black color tone, high visibility, excellent OCR reading characteristics, and a high light fastness of the color image.
Suitable for use in various fields that require reading.

Claims (5)

[Claims] 1. A color-forming recording material utilizing a color-forming reaction between an electron-donating color-forming agent and an electron-accepting color-developing agent, wherein at least one of a fluoran compound represented by the following general formula (I) is used as the electron-donating color-forming agent. One kind, and the following general formulas (II) to
A color recording material comprising at least one fluoran compound represented by the formula (VI). Embedded image (In the formula (I), R ¹ and R ² each represent an alkyl group having 1 to 5 carbon atoms.) (In the formula (II), R ³ and R ⁴ each represent an alkyl group, a cycloalkyl group, an alkoxyalkyl group or an aryl group, and R ³ and R ⁴ may be linked to form a nitrogen-containing heterocyclic ring. R ⁵ represents a hydrogen atom or an alkyl group.) (In the formula (III), R ⁶ and R ⁷ each represent an alkyl group or an alkoxyalkyl group, and R ⁶ and R ⁷ may be linked to form a nitrogen-containing heterocycle. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom or an alkyl group.) (In the formula (IV), R ¹² and R ¹³ each represent an alkyl group, a cycloalkyl group, an alkoxyalkyl group, an aralkyl group or an aryl group, and R ¹² and R ¹³ are linked to form a nitrogen-containing heterocyclic ring. be good .R ¹⁴ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, R ^15,
R ¹⁶ and R ¹⁷ each represent a hydrogen atom or an alkyl group. ) (In the formula (V), R ^{18 to} R ²¹ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an aralkyl group, and n represents an integer of 1 or 2.) (In the formula (VI), R ²² represents an alkyl group, an alkoxyalkyl group or an aryl group, R ²³ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R ²⁴ represents a hydrogen atom, a halogen atom or an alkyl group. And R ²⁵
Represents a halogen atom or an alkyl group, and m represents an integer of 0 to 2. ) 2. The fluoran compound represented by the general formula (I) is 2- (3-methylanilino) -3-methyl-6-
The color-forming recording material according to claim 1, which is diethylaminofluoran or 2- (3-methylanilino) -3-methyl-6-di-n-butylaminofluoran. 3. 2- (3-methylanilino) -3-methyl-6-diethylaminofluoran has a diffraction angle (2θ ± 0.2 °) in powder X-ray diffraction using Cu-Kα ray.
7.6 °, 12.2 °, 14.9 °, 15.9 °, 1
The β-form modification characterized by an X-ray diffraction pattern showing characteristic peaks at 7.6 ° and 22.8 °.
Chromogenic recording material. 4. The color-forming recording material according to claim 1, which is a pressure-sensitive recording material. 5. The color-forming recording material according to claim 1, which is a heat-sensitive recording material.