JPH04173388A - Fluorane compound and recording material using the same - Google Patents

Abstract

PURPOSE:To obtain a pressure-sensitive and thermal recording material imparting high background whiteness and a developed color image having high stability, especially, high NOx resistance by using a specific fluorane compound as the color former of the recording material. CONSTITUTION:A fluorane compound represented by general formula (I) is used as a color former. This fluorane compound is a white solid stable in the atmosphere and reacted with a developer to immediately develop a color to form a blackish brown-reddish black dye. This dye shows excellent storage stability. Further, the color image of a recording material using this fluorane compound has extremely high NOx resistance. As an embodiment of the fluorane compound represented by the general formula (I), 2-(N-methyl-3,4- dichloroanilino)-6-N,N-di-n-propyl aminofluorane is designated. It is necessary that the fluorane compound occupies 50% or more by wt. of the color former in the recording material and, if necessary, other color former can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a fluoran compound and a recording material using the compound. More specifically, the present invention relates to a novel fluoran compound that develops a color from a black edge color to a reddish-black color by reacting with an electron-accepting color developer, and to recording materials such as pressure-sensitive recording materials and heat-sensitive recording materials that use the compound.

<Prior art> Recording materials that utilize a color-forming reaction between an electron-donating color former (hereinafter referred to as a color former) and an electron-accepting color developer (hereinafter referred to as a color developer) are used as pressure-sensitive recording materials and heat-sensitive recording materials. already well known.

For example, pressure-sensitive recording materials are disclosed in Japanese Patent Publication No. 42-20144, etc., and are used in the field of printers such as computers.

Further, heat-sensitive recording materials are disclosed in Japanese Patent Publication No. 14039/1983 and are used in a wide range of fields such as measurement recorders, facsimile machines, printers, and ticket vending machines.

In recent years, there has been an increasing demand for recording materials with high background whiteness and high stability of colored images, especially recording materials with high NOx resistance. In order to meet these demands, research on improving recording materials is active.

For example, 2-
A recording material using (3-trifluoromethylanilino)-6-dinithylaminofluorane has high background whiteness and fairly high NOx resistance. However, when producing color former capsules for pressure-sensitive recording materials, the fluoran compound has a low solubility in a solvent, so there is a problem in producing capsules with a high color former concentration. Furthermore, the NOx resistance is not always fully satisfactory.

In addition, Japanese Patent Publication No. 52-29650 discloses similar compounds in which the amino group at the 6-position is cyclohexylamino, but these compounds have low solubility in solvents because the amino group at the 6-position is a secondary amino. , both the NOx resistance of the colored image is poor.

<Problems to be Solved by the Invention> The present invention provides a novel fluoran compound useful as a coloring agent for recording materials, and a method using the fluoran compound that has high background whiteness, high stability of colored images, and particularly NOx resistance. An object of the present invention is to provide a high pressure-sensitive recording material and a heat-sensitive recording material.

<Means for Solving the Problems> The objects of the present invention have been achieved by using a fluoran compound represented by -maximum (I) as a coloring agent.

(In the formula, R1 and R2 represent a straight chain or branched alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, a tetrahydrofurfuryl group, or a phenyl group which may have a substituent. , R+ and R2 may be combined with each other to form a 5-membered or 6-membered heterocycle, R3 represents an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom, provided that When R+ and Ri simultaneously represent a methyl group or an ethyl group, R1 does not represent a methyl group or an ethyl group, and R
+ When R2 and R2 simultaneously represent an n-butyl group and R5 represents a methyl group, each X is not at the 3,4-position of the anilino group. ) The fluoran compound of the present invention is a new substance synthesized for the first time by the inventors, and is a white solid that is stable in the atmosphere, and when it reacts with a color developer, it immediately develops a color, forming a black-red to black-red pigment. However, this dye exhibits excellent storage stability.The fluoran compound of the present invention was disclosed in
2, which is a known fluoran compound disclosed in No. 75.
In comparison with -(3-trifluoromethylanilino)-6-diethylaminofluorane, pressure-sensitive recording solvents KMC-113 (manufactured by Kureha) and 5A
Because of its high solubility in S-296 (manufactured by Nihon Joyu Co., Ltd.), it is suitable for producing capsules with a high color former concentration, and the colored image of the recording material using the fluoran compound of the present invention has very high NOx resistance.

Therefore, the fluoran compound of the present invention is extremely useful as a coloring agent in recording materials such as pressure-sensitive recording materials and heat-sensitive recording materials.

The fluoran compound of the present invention can be synthesized by a known fluoran compound synthesis method.

For example, 2-(2-hydroxy-,4-N,N-di-n-
Propylaminobenzoyl)benzoic acid and N-methyl-3
', 4°-dichloro-4-methoxydiphenylamine in concentrated sulfuric acid, the reaction product is treated with an alkaline aqueous solution such as caustic soda, and then purified with a solvent such as toluene to form 2-(N-methyl -3,4-dichloroanilino)-6-di-n-propylaminofluorane is obtained as white crystals.

Specific examples of the fluoran compound represented by the general formula (1) thus obtained include 2-(N-methyl-3,4-dichloroanilino)-6-N, N-di-n-propylaminofluoran, 2-(N-methyl-3,4-dichloroanilino)-6-N-ethyl-N=isopropylaminofluorane, 2-(N-methyl-3,4-dichloroanilino)-6-'N- Ethyl-N-see, -butylaminofluorane, 2-(N-methyl-3,4-dichloroanilino)-6-N,N-diisobutylaminofluorane, 2
-(N-methyl-3,4-dichloroanilino)-6-N
-ethyl-N-tetrahydrofurfurylaminofluorane, 2-(N-methyl-3,4-dichloroanilino)-
6-,N-ethyl-N-phenylaminofluorane, 2
-(N-methyl-3,4-dichloroanilino)-6-N
-cyclohexyl-N-methylaminofluorane, 2-
(N-methyl-3,4-dichloroanilino)-6-N-
Cyclohexyl-N-butylaminofluorane, 2-(
N-methyl=3,4-dichloroanilino)-6-N-cyclobenti-N-methylaminofluorane, 2-(N
-Methyl-3,4-dichloroanilino)-6-N-cyclohebutyl-N-methylaminofluorane, 2-(N-
Ethyl-3,4-dichloroanilino)-6-N, N-di-n-propylaminofluorane, 2-(N-ethyl-
3,4-dichloroanilino)-6-N-cyclohexyl-N-methylaminofluorane, 2-(N-ethyl-3
, 4-dichloroanilino)-6-pyrrolidinofluorane, 2-(N-ethyl-3,4-dichloroanilino)-6
- and loridinofluorane, 2- (N-ethyl-3,4
-dichloroanilino)-6-N,N-di-n-butylaminofluorane, 2-(N-n-propyl-3,4-dichloroanilino)-6-N,N-dimethylaminofluorane, 2-(N-n-propyl-3,4-dichloroanilino)-6-N,N-diethylaminofluorane, 2-
(N-n-propyl-3,4-dichloroanilino)-6
-N,N-di-n-propylaminofluorane, 2-(
N-n-propyl-3,4-dichloroanilino)-6-
N,N-di-n-butylaminofluorane, 2-(N-
n-butyl-3,4-dichloroanilino)-6-N,N
-dimethylaminofluorane, 2-(N-n-butyl-
3,4-dichloroanilino)-6-N,N-diethylaminofluorane, 2-(N-n-butyl-3,4-dichloroanilino)-6-N,N-di-n-propylaminofluorane Orane, 2-(N-n-butyl-3,4-dichloroanilino)-6-N, N-di-n-butylaminofluorane, 2-(N-methyl-2,3-dichloroanilino) -6-N,N-di-n-butylaminofluorane, 2
-(N-methyl-2,4-dichloroanilino)-6-N
, N-di-n-butylaminofluorane, 2-(N-methyl-2,5-dichloroanilino)-6-N,N-di-
n-butylaminofluorane, 2-(N-methyl-2,
6-dichloroanilino)-6-N,N-di-n-butylaminofluorane, 2-(N-methyl-3,5-dichloroanilino)-6-N,N-di-n-butylamino Fluorane, 2-(N-methyl-2,3-dichloroanilino)-6-N-cyclohexyl-N-methylaminofluorane, 2-(N-methyl-2,3-dichloroanilino)
-6-N-di-n-butylaminofluorane, 2-(N
-ethyl-3,4-difluoroanilino)-6-N,N
-di-n-butylaminofluorane, 2-(N-ethyl-3,4-difluoroanilino)-6-N,N-di-1
-butylaminofluorane and the like.

The fluoran compound of the present invention is one of the color formers in the recording material.
It is necessary that the content be 0% by weight or more.

Further, other color formers may be used in combination, if necessary.

As the coloring agent that can be used in combination, any coloring agent that is used in this type of recording material can be used, and coloring agents such as triphenylmethane phthalide, fluoran, fluorene, and vinylophthalide are preferably used. .

Some examples of these include 3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide;
2-anilino-3-methyl-6-dimethylaminofluorane, 2-anilino-3-methyl-6-dinithylaminofluorane, 2-anilino-3-methyl-6-dipropylaminofluorane, 2- Anilino-3-methyl-6-
Sibutylaminofluorane, 2-anilino-3-methyl-6-diamylaminofluorane, 2-anilino-3-
Methyl-6-N-methyl-N-propylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-
Butylaminofluorane, 2-anilino-3-methyl-
6-N-ethyl-N-amylaminofluorane, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluorane, 2-anilino-3-methyl-6
-N-ethyl-N-tetrahydrofurfurylaminofluorane, 3,6-bis(dimethylamino)fluorenespiro[9,3']-6°-dimethylaminophthalide, 3
．． 3-bis(2,2-bis(p-dimethylaminophenyl)ethynyl-4,5,6,7-titrachlorophthalide, 3,3-bis(2,2-bis(1-ethyl-2- Methylindol-3-yl)ethynyl i4.5,6.7
-Titrachlorophthalide and the like. These can be used alone or in combination of two or more.

In order to apply the fluoran compound of the present invention to a pressure-sensitive recording material, various known methods can be used, such as those disclosed in Japanese Patent Publication No. 42-20144. Generally, top paper is created by encapsulating a coloring agent solution in which a coloring agent is dissolved in an encapsulating solvent and then applying it to the back side of a support such as high-quality paper, synthetic paper, or plastic film. do. On the other hand, a color developer is applied to the surface of another support to prepare a base paper. When you stack the top paper and the bottom paper so that their coated surfaces are in contact and apply pressure such as pen pressure or hammer pressure, the capsule in the area that is pressurized is destroyed, and the color forming agent in the capsule becomes a color developer. In response, a recorded image is formed on the surface of the lower paper. Furthermore, by inserting several inner sheets coated with a color developer on the surface of the support and capsules on the back side between the upper and lower sheets, a plurality of copies can be recorded.

Examples of the color developer used in the pressure-sensitive recording material include acid clay, salicylic acid derivative zinc salt, p-octylphenol resin zinc salt, and p-phenylphenol resin. In particular, salicylic acid derivative zinc salts and p-octylphenol resin zinc salts are preferably used.

In order to apply the fluoran compound of the present invention to a heat-sensitive recording material, various known methods can be used, such as those disclosed in Japanese Patent Publication No. 14039/1983. In general, color formers,
A color developer and a sensitizer are each dispersed with an aqueous solution of a water-soluble polymer such as polyvinyl alcohol using an attritor, a sand mill, etc. so that the particle size of the drug becomes several microns or less. The sensitizer may be dispersed simultaneously with either or both of the color former and color developer, or in some cases, it may be dispersed by preparing a eutectic with the color former or color developer in advance. You can. These dispersions are mixed and, if necessary, pigments, binders, waxes, metal soaps, antioxidants, ultraviolet absorbers, etc. are added to prepare a heat-sensitive coating liquid. A heat-sensitive recording material is obtained by applying the obtained heat-sensitive coating liquid to a support such as high-quality paper, synthetic paper, or plastic film, and then imparting smoothness by calendering. In addition, heat-sensitive coating liquid is
If necessary, in order to improve color development, it may be applied to a support that has an undercoat layer of plastic pigment or heat insulating agent such as silica. Furthermore, if necessary, water resistance and chemical resistance can be imparted. In order to do this, an overcoat layer may be provided on the heat-sensitive recording layer using a water-soluble polymer aqueous solution or the like.

Various phenolic compounds can be used as color developers for heat-sensitive recording materials. As a specific example, 2.2-
Bis(p-hydroxyphenyl)propane (bisphenol A), 2,2-bis(p-hydroxyphenyl)-
4-Methylpentane, 1,1-bis(p-hydroxyphenyl)cyclohexane, bis(p-hydroxyphenyl)sulfone (bisphael S), bisphenol S monoisopropyl ether, 3,3°-diallylbisphenol S, 1.5 -bis(p-hydroxyphenylmercapto)-3-oxapentane, benzyl p-hydroxybenzoate, tetrabromobisphenol A, tetrabromobisphenol S, and the like. In particular, bisphenol A is preferably used.

As a sensitizer, p-benzylbiphenyl, m-terphenyl, 2-benzyloxynaphthalene, 1,4-dibenzyloxynaphthalene, dibenzyl oxalate, di-p-methylbenzyl oxalate, 1,2-diphenoxy Ethane, 1,2-di-m-toluoxyethane, 1,2-di-
p-Toluoxyethane, 1,4-diphenoxybutane,
Benzyl p-benzyloxybenzoate, phenyl 2-naphthoate, phenyl 1-hydroxy-2-naphthoate,
Examples include dibenzyl terephthalate. In particular, p-benzylbiphenyl, m-terphenyl, 2-benzyloxynaphthalene, di-p-methylbenzyl oxalate, 1
, 2-di-m-toluoxyethane is preferably used.

Organic and inorganic fillers can be used as fillers. Preferred specific examples include calcium carbonate, barium sulfate, titanium oxide, aluminum hydroxide, amorphous silica, urea-formalin resin powder, polyethylene resin powder, and the like.

As the binder, water-soluble polymers and water-insoluble polymers can be used. Preferred specific examples include methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, starch pulp, styrene-maleic anhydride copolymer hydrolyzate, ethylene-
Maleic anhydride copolymer hydrolyzate, isobutylene-maleic anhydride copolymer hydrolyzate, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyacrylamide, etc., and as water-insoluble polymers, styrene-butadiene rubber latex, acrylonitrile. -Butadiene rubber latex, vinyl acetate emulsion and the like.

Preferred specific examples of wax include paraffin wax, carboxy-modified paraffin wax, polyethylene wax, and the like.

As the metal soap, higher fatty acid metal salts are used. Preferred specific examples include zinc stearate, calcium stearate, aluminum stearate, and the like.

Hindered phenols are used as antioxidants. In addition, as ultraviolet absorbers, benzophenone type,
Ultraviolet absorbers such as benzotriazole are used.

<Example> An example is shown below, but the present invention is not limited to this example.

Example 1 Synthesis of 2-(N-methyl-3,4-dichloroanilino)-6-N,N-di-n-propylaminofluorane 50 g no. 2
-(2-hydroxy-1-N,N-di-n-propylaminobenzoyl)benzoic acid was added and dissolved. Next, 8.5 g of N-methyl-3°,4'-dichloro-4-methoxydiphenylamine was added while cooling with water, and the mixture was stirred at room temperature for 20 hours. The reaction mixture was poured into 500 IIl of water, and a lot of the precipitate was collected and washed with water. Next, the r powder was stirred and refluxed for 1 hour with 200 liters of toluene and 50 sl of a 20% caustic soda aqueous solution. The toluene layer was collected, washed with hot water, and then collected. The P solution was concentrated, the precipitate was collected and dried, and 12.5 g (yield 73%) of 2-(
N-methyl-3,4-dichloroanilino)-6-N,N
-di-n-propylaminofluorane with a melting point of 197-1
Obtained as a white powder at 98°C. It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound. The infrared absorption spectrum of this compound is shown in FIG.

CIN Calculated value (C,, H3, Cl2N20.) 69.1 (H
5,28$ 4.89$actual value 69.
12$ 5.33g 4.83$rice/e 5 7
2 (M”) Example 2 2-(N-methyl-3,4
-dichloroanilino)-6-N=ethyl-N-isopropylaminofluorane synthesis 50y concentration! 9.8 g of 2-(2-hydroxy-4-N-ethyl-N-isopropylaminobenzoyl)benzoic acid was added and dissolved in the acid with stirring.

Next, 8.5 g of N-methyl-3',4'- was cooled with water.
After adding dichloro-4-methoxydiphenylamine, the mixture was stirred at room temperature for 20 hours. After treatment in the same manner as in Example 1, 9.3 g (yield 55.51) of 2-(N-methyl-3,4-dichloroanilino)-6-N-ethyl-N-
Isopropylaminofluorane with a melting point of 177-179℃
It was obtained as a white powder. It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound. The infrared absorption spectrum of this compound is shown in FIG.

CHN Calculated value (C3□H21ItJ2N20.> 68.69
$ 5.05 $ 5.011 Actual value 6
8.56$ 5.08$ 4.97Ks/e 558
(M”) Example 3 Synthesis of 2-(N-methyl-3,4-dichloroanilino)-6-N-ethyl-N-see,-butylaminofluorane. Then, 2-(2-hydroxy-4-N-ethyl-N-See,-butylaminobenzoyl)benzoic acid of 3. was added and dissolved.
8.5 g of N-methyl-3° under water cooling.

After adding 4'-dichloro-4-methoxydiphenylamine, the mixture was stirred at room temperature for 20 hours. After treatment in the same manner as in Example 1, 7.5 g (yield 43.3 $) of 2-(N-methyl-3,4-dichloroanilino)-6-N-ethyl-
N-see,-butylaminofluorane with a melting point of 158~
Obtained as a white powder at 161°C.

FIG. 3 shows the infrared absorption spectrum of this compound, which was confirmed to be the desired compound based on elemental analysis values and mass spectrometry values.

CIN Calculated value (C33H, Cl2N20.) 69.10$
5.28$ 4.89$ Actual value 69
．． 50$ 5.26$ 4.95Ks/e 572(
Example 4 Synthesis of 2-(N-methyl-3,4-dichloroanilino)-6-N,N-diisobutylaminofluorane 10.8 g in concentrated vifa at 50 y below pH f'f 2 (2-Hydroxy-4-N,N-diisobutylaminobenzoyl)benzoic acid was added and dissolved in 0. Then, under water cooling, the N-methyl-3',4'-dichloro-4-methoxy of 8.5. After adding diphenylamine, it was stirred at room temperature for 20 hours. Post-treatment was carried out in the same manner as in Example 1, and 9
．． 2. (Yield 50.9$) No2-(N-methyl-3°4-dichloroanilino)-6-N,N-diisobutylaminofluorane was obtained as a white powder with a melting point of 197-198°C. It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound. The infrared absorption spectrum of this compound is shown in FIG.

CIN Calculated value (CssH3<CLLOa) 69.87$ 5
．． 71$ 4.66g Actual value 70.0
3$ 5.67$ 4.60Ks/e 600 (M
) Example 5 Synthesis of 2-(N-ethyl-3,4-dichloroanilino)-6-piperidinofluorane 9.8 g of 2-(2-hydroxy- 4-Piperidinobenzoyl) benzoic acid was added and dissolved, and then 8.9 g of N-ethyl-3',4'-dichloro-4-methoxydiphenylamine was added under water cooling.
Stirred at room temperature for 20 hours. After treatment in the same manner as in Example 1, 7.4# (yield 43.0g) No2-(N-x chill-3
, 4-dichloroanilino)-6-piperidinofluorane was obtained as a white powder with a melting point of 153 to 156°C, and it was confirmed to be the desired compound based on the nine element analysis values and mass spectrometry values.

CHN Calculated value (C33H2, Cl2N20.) 69.35$
4.95$ 4.901 Actual value 69
．． 53$ 4.91$ 4.84π import/e 570
(M”) Example 6 Synthesis of 2-(N-ethyl-3,4-dichloroanilino)-6-pyrrolidinofluorane 9.4 g of 2-(2-hydroxy -4-pyrrolidinobenzoyl)benzoic acid was added and dissolved. Then, 8.9 g of N-ethyl-3',4'-dichloro-4-methoxydiphenylamine was added under water cooling.
Stirred at room temperature for 20 hours. After treatment in the same manner as in Example 1, 11.1 FI (yield 65.9 g) of 2-(N-ethyl-3,4-dichloroanilino)-6-pyrrolidinofluorane was obtained with a melting point of 210 to 212°C. It was confirmed that it was the desired compound from the 0 elemental analysis value and mass spectrometry value obtained as a white powder.

CIIN Calculated value (C1JziC12N2oz) 68.94$
4.71$ 5.032 Actual value 68.
91$ 4.79$ 5.03$m/e 5 5
6 (M”) Example 7 2-(N-methyl-3,4
Synthesis of -dichloroanilino)-6-N-ethyl-N-tetrahydrofurfurylaminofluorane 50g concentrated! Stir in M TNm10.5yno2 (2
-Hydroxy-4-N-ethyl-N-tetrahydrofurfurylaminobenzoyl)benzoic acid was added and dissolved. Then, 8.5 fI of N-methyl-3°, 4 was added under water cooling.
After adding '-dichloro-4-methoxydiphenylamine, the mixture was stirred at room temperature for 20 hours.

After post-processing in the same manner as in Example 1, the result was 2.51? (Yield 18.
0 element analysis value obtained from 2-(N-methyl-3,4-dichloroanilino)-6-N-ethyl-N-tetrahydrofurfurylaminofluoran ($1) as a white powder with a melting point of 148-151°C The compound was confirmed to be the desired compound based on mass spectrometry and mass spectrometry values.

CHN Calculated value (C, J, Cl2N, 0.) 67.88$
5.04$ 4.66g Actual value 67.
9715.0!14.64$vh/e 6 0 0
(M”) Example 8 2-(N-methyl-3,4-
Synthesis of (dichloroanilino)-6-N-ethyl-N-phenylaminofluorane in 50 g of concentrated sulfuric acid with stirring 10.8. Then, 8.5 g of N-methyl-3',4'-dichloro- After adding 4-methoxydiphenylamine, - stirred at room temperature for 20 hours. After post-treatment in the same manner as in Example 1, 8.1 g (
Yield 45.7K) 2-(N-methyl-3,4-dichloroanilino)-6-N-ethyl-N-phenylaminofluoran was obtained as a white powder with a melting point of 161-162.5°C. It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound. The infrared absorption spectrum of this compound is shown in FIG.

CIN calculated value (CssH*sC1'zN20s) 70.82
$ 4.42 $ 4.72g Actual value 7
0.56$ 4.38$ 4.71gm/e 5
9 2 (M”) Example 9 2-(N-methyl-2
,3-dichloroanilino)-6-N,N-di-n-butylaminofluorane 11.1. 2-(2-
Hydroxy-4-N,N-di-n-butylaminobenzoyl)benzoic acid was added and dissolved. Next, 8.52 of N-methyl-2',3''-dichloro-4-methoxydiphenylamine was added under water cooling, and the mixture was stirred at room temperature for 20 hours. Post-treatment was carried out in the same manner as in Example 1, and 2. 3g (yield 12.7$) of 2-(N-methyl-2,3-dichloroanilino)-6-N,N-di-1-butylaminofluoran as a white powder with a melting point of 145-147°C. Obtained.

It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound.

CHN il [value (C, 5H,, Cl2N203) 69.87
$ 5.7114.661 Actual value 69
．． 73$ 5.67$ 4.63$ Export/e 6 0
0 (M”) Example 10 2-(N-methyl-2
,4-dichloroanilino)-6+-N,N-di-n-butylaminofluorane synthesis 50! ? 11. in concentrated vX acid under stirring. 2-(2-
Hydroxy-4-N,N-di-n-butylaminobenzoyl)benzoic acid was added and dissolved. Next, 8.59 N-methyl-2°,4"-dichloro-4-methoxydiphenylamine was added under water cooling, and the mixture was stirred at room temperature for 20 hours. Similarly to Example 1, 8.7 g of post-treated shite was added. (Yield 48.1$) No2-(N-methyl-2,4-dichloroanilino)-6-N,N-di-n-butylaminofluorane was obtained as a white powder with a melting point of 150-152°C. Ta0
It was confirmed that it was the desired monster based on the elemental analysis and mass spectrometry values.

CIN Calculated value (C3sH,, (12N, O,) 69.87$
5.71$ 4.66$Actual value 69
．． 44$ 5.65$ 4.75$m/e 600
(M”) Example 11 Synthesis of 2-(N-methyl-2,5-dichloroanilino)-6-N,N-di-n-butylaminofluorane 11. 1 & 2-(2-hydroxy-1-N, N-di-n-butylaminobenzoyl)benzoic acid was added and dissolved. Then, 8
．． After adding 59 N-methyl-2',5'-dichloro-4-methoxydiphenylamine, the mixture was stirred at room temperature for 20 hours. After treatment in the same manner as in Example 1, 1.9 g (yield 15.8 g) of 2-(N-y< thyl-2,5-dichloroanilino)-6-N,N-di-n- Butylaminofluoran was obtained as a white powder with a melting point of 141-143°C. It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound.

CHN Calculated value (C35H34CI!2N2M 69.87$
5.71$ 4.66$ Actual value 69.
9'H5,7114,59$ import/e 600(M”
) Example 12 Synthesis of 2-(N-methyl-2,6-dichloroanilino)-6-N,N-di-n-butylaminofluorane. (2-Hydroxy-4-N,N-di-n-butylaminobenzoyl)benzoic acid was added and dissolved.
．． After adding 5 g of N-methyl-2",6"-dichloro-4-methoxydiphenylamine, the mixture was stirred at room temperature for 20 hours. After treatment in the same manner as in Example 1, 2.5 g (yield 13.8 $) of 2-(N-methyl-2,6-dichloroanilino)-6-N,N-di-n-butyl Aminofluorane was obtained as a white powder with a melting point of 145.5-146.5°C. It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound. The infrared absorption spectrum of this compound is shown in FIG.

CIN Calculated value (C3J, 4 (J2N203) 69.8715
．． 71g 4.66g Actual value 69.8
8$ 5.75$ 4.55$wb/e 6 0
0 (M”) Example 13 2-(N-methyl-3,
Synthesis of (5-dichloroanilino)-6-N,N-di-n-butylaminofluorane 11. in 50 g of concentrated sulfuric acid with stirring. 2-(2-Hydroxy-4-N,N-di-n-butylaminobenzoyl)benzoic acid was added and dissolved in 8.h and then cooled with water.
After adding 5 g of N-methyl-3',5'-dichloro-4-methoxydiphenylamine, the mixture was stirred at room temperature for 20 hours. After treatment in the same manner as in Example 1, 8.6 g (yield: 4
7.6 g) of 2-(N-methyl-3,5-dichloroanilino)-6-N,N-di-n-butylaminofluoran was obtained as a white powder with a melting point of 171-172°C. It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound. The infrared absorption spectrum of this compound is shown in FIG.

CIN Calculated value (C, S) I, 4C/2N20. ) 69.87
$ 5.71 $ 4.66 Actual value 6
9.95$ 5.81$ 4.45$-/e 6
0 0 (M”) Example 14 1-(N-methyl-
Synthesis of 2,3-dichloroanilino)-6-N-cyclohexyl-N-methylaminofluorane 501? 10.6. under stirring in concentrated sulfuric acid. 2-(2-
Hydroxy-1-N-cyclohexyl-N-methylaminobenzoyl)benzoic acid was added and dissolved. Then,
8.5 g of N-methyl-2' under water cooling.

After adding 3'-dichloro-4-methoxydiphenylamine, the mixture was stirred at room temperature for 20 hours. After treatment in the same manner as in Example 1, 9.6 g (yield 54.7 g) of 2-(N-methyl-2,3-dichloroanilino)-6-N-cyclohexyl-N-methylamino Fluorane has a melting point of 240~2
Obtained as a white powder at 42°C.

It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound.

CIN Total 3E value (C3, HffO (J2N20.) 69.7
3$ 5.17$ 4.79g Actual value
69.88$ 5.1814.66X theory/e 58
4(M”) Example 15 Synthesis of 2-(N-butyl-3,4-dichloroanilino)-6-N,N-di-n-butylaminofluorane. 2-(2-Hydroxy-4-N, N-di-n-butylaminobenzoyl)benzoic acid was added and dissolved in 9. Then, under water cooling.
After adding 72% of N-butyl-3",4"-dichloro-4-methoxydiphenylamine, the mixture was stirred at room temperature for 20 hours. After-ripening FI was performed in the same manner as in Example 1 to give 15.1y (yield: 46.5y). 9$) No2-(N-butyl-3,4-dichloroanilino)-6-N,N-di-lobylaminofluoran was obtained as a white powder with a melting point of 181-182°C.

It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound. The infrared absorption spectrum of this compound is shown in FIG.

CHN Calculated value (C3, H,, C/2N203) 70.90$
6.28$ 4.35$ Actual value 71
．． 01$ 6.30$ 4.41gm/e 642
(M'') Example 16 Synthesis of 2-(N-ethyl-3,4-dichloroanilino)-6-N,N-di-1-butylaminofluorane in 50 g of concentrated sulfuric acid with stirring for 11.h. 2-(2-hydroxy-4-N,N-di-n-butylaminobenzoyl)benzoic acid was added and dissolved in 8.
After adding 9 g of N-ethyl-3',4°-dichloro-4-methoxydiphenylamine, the mixture was stirred at room temperature for 20 hours. Post-process in the same manner as in Example 1, 11. h (yield 5
9.5 g) 2-(N-x thyl-3,4-dichloroanilino)-6-N,N-di-n-butylaminofluoran was obtained as a white powder with a melting point of 156-157°C.

It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound.

CIN Calculated value (C,,H,,CZ2N20.) 70.23$
5.85g 4.55$ Actual value 69
．． 81$ 5.83$ 4.511m/e 6 1
4-(M”) Example 17 2-(N-methyl-3
, 4-Difluoroanilino L-6-N, Synthesis of N-di-n-butylaminofluorane 509 in concentrated sulfuric acid under stirring in 11.1. 2-(2-hydroxy-1-N,N-dilobylaminobenzoyl)benzoic acid was added and dissolved. Then, under water cooling,
．． After adding 93 N-ethyl-3',4°-difluoro-4-methoxydiphenylamine, the mixture was stirred at room temperature for 20 hours. After treatment in the same manner as in Example 1, 7.4g<yield 43.3f)-2-(N-methyl-3,4-difluoroanilino)-6-N,N-di-n-butylamino Fluoran was obtained as a white powder with a melting point of 160.0-161.0°C. It was confirmed from the elemental analysis values and mass spectrometry values that it was the desired compound. The infrared absorption spectrum of this compound is shown in FIG.

CHN Calculated value (C, J3.F2N203) 73.91$ 6
．． 04$ 4.93g Actual value 73.82
$ 6.03π4.98gm/e 568 (M”
) Example 18 Production of pressure-sensitive recording material 3 g of 2-(N-methyl-3,4-dichloroanilino)-6-N,N-di-n-propylaminofluorane, which is a coloring agent, was added to KMC-113. (manufactured by Kureha) 479 under heating to prepare a coloring agent solution.

On the other hand, add 5 g of a system modifier to 100 g of water, make 9H4 with an aqueous solution of caustic soda, add the above coloring agent solution and 10 g of melamine-formaldehyde initial polymer,
Emulsified with a homomixer until the oil droplets are 4 microns.
Then, the mixture was heated to 60° C. with stirring and stirred 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.

Capsule dispersion of color former prepared in this way 10y
After thoroughly mixing 2 g of wheat flour starch and 1 g of latex, the solid content coating amount of 510 g 7 m' high-quality paper was 5 f.
A white top paper was prepared by applying the solution at a ratio of I/m2.

When the upper paper created in this way is stacked on the lower paper coated with p-octylphenol resin zinc salt containing a color developer so that the coated side is in contact with it and type printed, a clear black record is recorded on the lower paper. The image formed.

Example 19 Production of heat-sensitive recording material 5 g of 2-(N-, methyl-3,4-dichloroanilino)-6-N-ethyl-N-phenylaminofluorane, which is a coloring agent, was mixed with 45 y of a 2.5 z polyvinyl alcohol aqueous solution.
The mixture was also ground using a sand mill so that the average particle size was 1 micron to obtain a dispersion.

On the other hand, 10 g of bisphenol A as a color developer and 10 y of p-benzylbiphenyl as a sensitizer were ground together with 80 ft of 2.5z bilibinyl alcohol aqueous solution using a sand mill so that the average particle size was 1 micron, and a dispersion was prepared. I got it.

After mixing the above two dispersions, 50% calcium carbonate
30g of dispersion and 15I of 30% paraffin wax dispersion
? was added and mixed well to obtain a heat-sensitive coating liquid.

The heat-sensitive coating liquid prepared in this way has a basis weight of 50 fI/M.
2, coated on high-quality paper with a solid content coating amount of 4.5 fI/+", dried, and then calendered so that the Bekk smoothness of the surface of the heat-sensitive recording layer was 400 to 500 seconds. A material was prepared. This heat-sensitive recording material instantly developed color when heated, and a stable black recorded image was formed.

Example 20 Production of heat-sensitive recording material 2-(N-methyl-3, the coloring agent in Example 19)
,4-dichloroanilino)-6-N-ethyl-N-phenylaminofluorane instead of 2-(N-methyl-3
,4-dichloroanilino)-6-N-ethyl-N-isopropylaminofluorane and p-
A heat-sensitive recording material was prepared in the same manner as in Example 19 except that cocoon-terphenyl was used instead of benzylbiphenyl.

Example 21 Production of heat-sensitive recording material 2-(N-methyl-3, the coloring agent in Example 19)
,4-dichloroanilino)-6-N-ethyl-N-phenylaminofluorane instead of 2-(N-methyl-3
,4-dichloroanilino)=6-N-ethyl-NS
A heat-sensitive recording material was prepared in the same manner as in Example 19, except that ee,-butylaminofluorane was used and 2-benzyloxynaphthalene was used instead of p-benzylbiphenyl as the sensitizer.

Example 22 Production of heat-sensitive recording material 2-(N-methyl-3
,4-dichloroanilino)-6-N-ethyl-N-phenylaminofluorane instead of 2-(N-methyl-3
,4-dichloroanilino)-6-N,N-diisobutylaminofluorane and p-methylbenzyl oxalate instead of p-benzylbiphenyl as the sensitizer. A heat-sensitive recording material was prepared.

Example 23 Production of heat-sensitive recording material 2-(N-methyl-3, the coloring agent in Example 19)
,4-dichloroanilino)-6-N-ethyl-N-phenylaminofluorane instead of 2-(N-methyl-3
, 4-dichloroanilino)-6-piperidinofluorane and 1,2-di-1-toluoxyethane as the sensitizer instead of p-benzylbiphenyl. A heat-sensitive recording material was prepared in the same manner.

Comparative Examples 1 and 2 2-(N-methyl-3, the coloring agent in Example 18)
,4-dichloroanilino)-6-N,N-di-n-propylaminofluorane, 2-(3-)lifluoromethylanilino)-6-dinithylaminofluorane (Comparative Example 1 ) and 2-(2,4-dimethylanilino)
A top paper was obtained by processing in the same manner as in Example 18, except that -3-methyl-6-dinithylaminofluorane (Comparative Example 2) was used.

Comparative Examples 3 and 4 2-(N-methyl-3
, 4-dichloroanilino)-6-N-ethyl-N-phenylaminofluorane (Comparative Example 3) and 2-anilino-3- Except for using methyl-6-di-n-butylaminofluorane (Comparative Example 4),
A heat-sensitive recording material was prepared in the same manner as in Example 19.

Evaluation 1 Pressure-sensitive recording solvent KMC-1 of the fluoran compound of the present invention
13 (dialkylnaphthalene solvent manufactured by Krem) and 5
The solubility in AS-296 (diphenylethane solvent manufactured by Nippon Oil) was measured together with 2-(3-)lifluoromethylanilino)-6-dinithylaminofluorane, which is a comparative substance.

The solubility was measured according to the following method.

About 10 w/w% of a fluoran compound/'solvent warm solution was heated and dissolved on a hot plate at 110°C±2.5°C. This solution was transferred to an Erlenmeyer flask with a stopper and stirred at a temperature of 20°C±0.1°C for 48 hours. After removing the precipitated fluoran compound, approximately IFI of the r liquid was accurately weighed and placed in a 100+s1 volumetric flask, and 95% acetic acid was added to bring the total volume to 100ml.
And so. This solution 2al was placed in a 100@1 volumetric flask, and 95% acetic acid was added to bring the total volume to 100mf.

The absorbance of this coloring solution at the maximum absorption wavelength in the visible region is 95%.
Measurement was carried out using a spectrophotometer using acetic acid as a control solution, and the amount of dissolved fluoran compound was determined from the previously prepared calibration curve. These results are shown in Table 1.

Table 1 Evaluation 2 The three types of upper papers obtained in Example 18 and Comparative Examples 1 and 2 were stacked on the lower paper coated with salicylic acid derivative zinc salt as a color developer so that the coated surfaces were in contact with each other, and a mini A color development test was performed using a roll, and the color density was determined by Macbeth RD-9.
It was measured using a 14-inch reflection densitometer. Then, a NOx fastness test was performed using J I 5LO855, which exposed the colored image to NOx.
This was done using the method described in . However, the NOx exposure time was 30 minutes. The strength of fastness to NOx can be determined by measuring the hue change before and after NOx@dew using a color difference meter (Tokyo Denshoku TC-
Determination was made by measuring with PI [[). These results are shown in Table 2.

Table 2 Evaluation 3 Example 19.20.21.22.23 and Comparative Example 3.
A color development test was performed on the seven types of heat-sensitive recording materials obtained in 4 using Toshiba facsimile C0PIX TF370 and Fax Test Chart No. 1 (Imaging Electronics Institute of Japan).
Background density and color density were measured using a Macbeth RD-914 reflection densitometer.

Next, a NOx fastness test was conducted in the same manner as Evaluation 1 except that the NOx exposure time was changed to 90 minutes.

These results are shown in Table 3.

Description of Judgment Values In the above measurements, Δa represents the degree of redness, and in determining the NOx fastness, the larger Δa is, the lower the fastness to NOx;
The smaller a is, the higher the fastness to NOx is.

Effect> As is clear from the above explanation, by using the fluoran compound of the present invention as a coloring agent, extremely practical pressure-sensitive recording materials and heat-sensitive recording materials were obtained.

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum of the fluoran compound produced in Example 1, Figure 2 shows the infrared absorption spectrum of the fluoran compound produced in Example 2, and Figure 3 shows the infrared absorption spectrum of the fluoran compound produced in Example 3. Fig. 4 shows the infrared absorption spectrum of the fluoran compound produced in Example 4, Fig. 5 shows the infrared absorption spectrum of the fluoran compound produced in Example 8, and Fig. 6 shows the infrared absorption spectrum of the fluoran compound produced in Example 12. Infrared absorption spectrum of the fluoran compound, FIG. 7 shows the infrared absorption spectrum of the fluoran compound produced in Example 13, FIG. 8 shows the absorption spectrum of the fluoran compound produced in Example 15, and FIG. 9 shows the absorption spectrum of the fluoran compound produced in Example 17. The infrared absorption spectrum of the produced fluoran compound is shown. Patent Applicant Yamamoto Kasei Co., Ltd. (3 others) Date of 1991/8/1991 Director General of the Patent Office Toshi Uematsu 1, Indication of the case 1990 Patent Application No. 303402 2, Name of the invention Fluoran compound and said compound Recording material using 3, Relationship with the case of the person making the amendment Address and name of patent applicant Yamamoto Kasei Co., Ltd. 4, Agent 6, The statement in the statement of contents of the amendment is corrected as follows. Page Line Before correction After correction 9 Bottom 4
Pyrrolidino Piperinoa 11 11 N-Ethyl N-Methyl 35 5 Solution and Solution sog and 3610 Bilibinyl Polyvinyl 43 9 Rating 1 Rating 2 or higher

Claims (5)

[Claims] (1) Fluoran compound represented by general formula (I), ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1 and R_2 are linear or branched alkyl groups with 1 to 4 carbon atoms, cycloalkyl groups with 5 to 7 carbon atoms, tetrahydrofurfuryl group, or It represents a phenyl group which may have a substituent, and R_1 and R_2 may be combined with each other to form a 5- or 6-membered heterocycle. R_3 is an alkyl group having 1 to 4 carbon atoms. and X represents a halogen atom.However, when R_1 and R_2 simultaneously represent a methyl group or an ethyl group, R_3 does not represent a methyl group or an ethyl group, R_1 and R_2 simultaneously represent an n-butyl group, and R_3 represents a methyl group or an ethyl group. When representing a methyl group, each X represents an anilino group of 3,
Not 4th place. ). (2) In a recording material that utilizes a color-forming reaction between an electron-donating color former and an electron-accepting color developer, at least one of the electron-donating color formers is a fluoran compound represented by general formula (I). Recording materials characterized by: ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 are linear or branched alkyl groups having 1 to 4 carbon atoms, and 5 to 7 carbon atoms. R_1 and R_2 may be bonded to each other to form a 5- or 6-membered heterocycle. R_3 represents an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom.However, when R_1 and R_2 simultaneously represent a methyl group or an ethyl group, R_3 does not represent a methyl group or an ethyl group, and R_1 and R_2 At the same time, it represents an n-butyl group, and when R_3 represents a methyl group, each X represents 3,
(not 4th place). (3) The recording material according to claim 2, wherein the recording material is a pressure-sensitive recording material. (4) The recording material according to claim 2, wherein the recording material is a heat-sensitive recording material. (5) The electron-accepting color developer is bisphenol A, and at least one of the sensitizers is p-benzylbiphenyl, m-
Claim 4 selected from terphenyl, 2-benzyloxynaphthalene, di-p-methylbenzyl oxalate and 1,2-di-m-toluoxyethane.
Heat-sensitive recording material.