JPS63156790A - Novel fluorane derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> and R<2> are 1-9C alkyl, cyclohexyl, benzyl or form pyrrolidine, piperidine or morpholine ring together with linking N atom; benzene ring A may be have halogen or lower alkyl as a substituent; ring B is benzene or naphthalene which may have halogen, 1-9C alkyl or phenyl as a substituent). EXAMPLE:3-p-Dimethylaminophenylamino-6-methyl-7-chlorofluorane expressed by formula II. USE:A coloring component for recording material capable of forming a pigment of dark green - dark blue absorbing electromagnetic wave over a visible region from near infrared region by action of a developer. PREPARATION:A diphenylamine derivative expressed by formula III (R<3> is H or lower alkyl) is reacted with a benzoic acid derivative expressed by formula IV at an equimolar ratio in concentrated sulfuric acid at ordinary temperature or below for several hr or more.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a fluoran derivative that produces a dark green, dark blue or black pigment that absorbs electromagnetic waves ranging from the near-infrared region to the visible region by the action of a color developer, and its use. The present invention relates to a recording material containing a fluoran derivative as a color-forming component.

[Conventional technology]

Various proposals have been made for color-forming dyes that are colorless in themselves, but which absorb electromagnetic waves in the wavelength range from the long wavelength portion of visible light to near-infrared light upon contact with acidic substances.

That is, as compounds having such properties, phthalide compounds are disclosed in JP-A-51-121,035 and JP-A-51.
-121,037, JP-A-51-121,038,
JP-A-55-115,448, JP-A-55-115,
No. 449, JP-A-55-115,450, JP-A-55
-115,451, JP-A-55-115,452,
JP-A-55-115,456, JP-A-57-167.
No. 979, JP-A-58-157.779, JP-A-60
In addition, thiofluorane-based compounds are disclosed in JP-A No. 59-148.
695, a fluorene-based compound was disclosed in Japanese Patent Application Laid-open No. 1983-
199.7 s No. 7, European Patent Application Publication No. 12
Although proposed in Japanese Patent No. 4377, most of these color-forming dyes have a gray-blue or gray-green color tone.

[Problem that the invention seeks to solve]

However, in the industry, there is a demand for a color-forming dye that has absorption in the near-infrared region and whose color is black or close to black in terms of clarity.

[Means to solve the problem]

Therefore, the present inventors searched for color-forming dyes that met the above requirements, and as a result discovered a certain type of fluoran compound, which they proposed earlier (Japanese Patent Application Nos. 126, 149, 1980, 18/1982).
No. 1,224 and invention filed on December 8, 1986).

However, the present inventors further discovered the following general formula (in which R1
and R2 each independently represent an alkyl group having 1 to 9 carbon atoms, a cyclohexyl group, or a benzyl group, and R1 and R2 together with the nitrogen atom to which they are bonded form a pyrrolidine ring, piperidine ring, or morpholine ring. The benzene ring A may have a rogen atom or/and a lower alkyl group as a substituent.
fiB represents a benzene ring or a non-containing Natsuta ring, which may have a rogen atom, an alkyl group having 1 to 9 carbon atoms, or/and a phenyl group as a substituent); It was discovered that by the action of a color developer, a dye having absorption ranging from the near-infrared to the visible region and exhibiting a dark green, dark blue, or black color was formed.

Therefore, an object of the present invention is to provide a novel fluoran derivative represented by the general formula (1).

A second object of the present invention is to provide a recording material containing a fluoran derivative represented by the general formula (I) as a color-forming component.

Recently, the use of barcodes has become popular as a means of managing the distribution of products. As for reading the markings, there is a tendency for reading devices that utilize semiconductor lasers to be frequently used because the devices are inexpensive. Since semiconductor lasers emit visible light and near-infrared rays with a wavelength of 650 nm or more, markings read by this device must absorb visible light or near-infrared rays in this wavelength range.

At the same time, in in-situ armoring, in order to confirm that the coloring has been completed, it is desirable that the coloring be black or a tone close to black so that the coloring can be most clearly recognized.

However, many fluoran compounds that develop a blackish color are already known, but although none of them have absorption in the near-infrared wavelength range, the fluoran derivative represented by the general formula (1) above is relatively Although it has a simple structure, it is usually colorless or pale in color, but when used with a color developer, it develops a black-rimmed color, black-blue, or black color, and it absorbs not only the visible region but also the near-infrared region of electromagnetic waves. That is surprising.

Some examples of the fluoran derivatives represented by the general formula (I) are listed below, but the fluoran derivatives of the present invention are not limited to these.

3-p-dimethylaminophenylamino-6-chlorofluoran, 3-p-dimethylaminophenylamino-6-methylfluoran, 6-p-dimethylaminophenylamine-7-methylfluoran, 3-p-dimethyl Aminophenylamine-6-methyl-
7-chlorofluoran, 6-p-dimethylaminophenylamine-7-nonylfluoran, 3-p-dimethylaminophenylamine-7-phenylfluoran, 3-p-diethylaminophenylamine-6-chlorofluoran, 3-p-diethylaminophenylamine-5,7-dichlorofluorane, 3-p-diethylaminophenylamine-6-methylfluoran, 3-p-diethylaminophenylamine-7-methylfluorane, 3-p-diethylaminophenyl Amino-6-methyl-
7-chlorofluoran, 3-p-diethylaminophenylamino-7-nonylfluoran, 3-p-dibutylaminophenylamino-6-chlorofluoran, 3-p-dibutylaminophenylamino-6-methylfluoran, 3-p-dibutylaminophenylamino-6,7-dimethylfluorane, 3-p-dibutylaminophenylamine-6-)fk-
7-chlorofluorane, 3-p-dibutylaminophenylamine-7-octylaminofluorane, 3-p-dibutylaminophenylamino-7-phenylfluoran, 3-p-(N-propylmethylamino)phenylamino -6-chlorofluorane, 5-p-(N-propylmethylamine)phenylamino-7-methylfluorane, 3-p-(N-propylmethylamine)phenylamino-6-methyl-7-chlorofluorane , 3-p-(N-butylethylamino)phenylamino-
6-Methyl-7-chlorofluorane, 3-p-dioctylaminophenylamino-6-methyl-7-chlorofluorane, 3-p-(n-cyclohexylmethylamino)phenylamino-6-methyl-7-chloro Fluoran, 3-p-(N-cyclohexylmethylamino)phenylamino-7-octylfluorozine, 3++ p-,)
Benzylaminophenylamino-6-meth-7-chlorofluorane, 3-p-pyrrolidinophenylamine-6-chlorofluoran, 3-p-pyrrolidinophenylamino-7-methylfluorane, 3-p- Pyrrolidinophenylamine-6-methyl-7-
Chlorofluorane, 3-p-piperidinophenylamino-6-methylfluoran, 3-p-piverizinone enylamino-7-octylfur tertinaryne, 3-p-morpholinophenylamino-6-chlorofluoran Orane, 3-p-morpholinophenylamino-7-phenylfluorane.

3-p-dimethylaminophenylamino-5,6-benzofluorane, 3-p-dimethylaminophenylamine-7,8-benzofluorane, 5-promo 8-dimethylaminophenylaminobenz[α]fluorane.

To produce a fluoran derivative represented by the general formula (T), a diphenylamine derivative represented by the formula (in which R4, R2 and benzene mA are the same as above, and R5 represents a hydrogen atom or a lower alkyl group) and a formula An equimolar amount of #Y is reacted with a benzoic acid derivative represented by the formula (in which ring B is the same as above).

This reaction is preferably carried out in concentrated sulfuric acid at a temperature below room temperature. The reaction time requires several hours or more.

The diphenylamine derivative represented by formula (II) used in this reaction can be produced by the reaction of =13- or or.

In the reactions (4) and (B), the respective raw materials are heated together with a Lewis acid such as anhydrous zinc chloride or phosphoric acid in an inert solvent or without using a solvent.

In the reactions (A) and (B), the respective raw materials may also be reacted in the presence of titanium alcohol-1. (0
) The reaction involves mixing and heating one of the raw materials as a hydrochloride.

The fluoran derivative represented by the general formula (I) has the formula (wherein R1, R2 and benzene ring A are the same as above,
Haλ represents a halogen atom. can be manufactured.

Typical examples of color developers used to color the fluoran derivative represented by general formula (1) are listed below, but the invention is not limited to these examples.

Typical color developers include acid clay, activated clay,
attapulgite, bentonite, colloidal silica,
Inorganic acidic substances such as aluminum silicate, magnesium silicate, zinc silicate, tin silicate, calcined kaolin, talc, aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, stearic acid, benzoic acid sp. -te
rt-butylbenzoic acid, 4-hydroxybenzoic acid, phthalic acid, phthalamic acid, 2,3,4.5-tetrachloro-N,N-U butylphthalamic acid, gallic acid, salicylic acid, 6-isoprobylsalicylic acid% 3-7 Kt IJ thylic acid, 3-cyclohexylsalicylic acid,
3,5-di-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5-(2,
2-:)methylbenzyl) salicylic acid, 3,5-di(
2-methylbenzyl)salicylic acid, 2-hydroxy-1
- aromatic carboxylic acids such as benzyl-3-naphthoic acid,
These aromatic carboxylic acids and zinc, tin, magnesium,
Salts with metals such as calcium, aluminum, and titanium, p-phenylphenol-formalin resin% p
- Phenol resin color developers such as butylphenol-acetylene resin, mixtures of these phenol resin color developers and the metal salts of aromatic carboxylic acids, and bisphenol A, 4.4'-Secondary Butylidene bisphene/- bisphenol compounds such as 1,7-di(4-hydroxyphenylthio)- Sulfur-containing bisphenol compounds such as 3,5-dioxahebutane, Hensyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, Isobutyl 4-hydroxybenzoate, Chlorobenzyl 4-hydroxybenzoate, Methylbenzyl 4-hydroxybenzoate, 4-
4-hydroxybenzoic acid esters such as diphenylmethyl hydroxybenzoate, 4-hydroxy-47-methyldiphenylsulfone, 4-hydroxy-4'-1sopropoxydiphenylsulfone, 4-hydroxy-4'-
Hydroxysulfones such as butoxydiphenylsulfone, dimethyl 4-hydroxyphthalate, dicyclohexyl 4-hydroxyphthalate, 4-hydroxyphthalic acid diesters of diphenylcad 4-hydroxyphthalate,
For example, esters of hydroxynaphthoic acid such as 2-hydroxy-6-carboxynaphthalene, or hydroxyacetophenone, p-phenylphenol, 4-
benzyl hydroxyphenylacetate, p-benzylphenol, p-quinone monobenzyl ether, and nitrobenzoic acid derivatives such as 4-nitrobenzoic acid, 2-op-4-nitrobenzoic acid, and 3-nitrobenzene. Sulfonic acid, nitrobenzenesulfonic acid derivatives such as 2-methyl-5-nitrobenzenesulfonic acid, aromatic acids having these nitro groups as a substituent, and metals such as zinc, tin, magnesium, calcium, aluminum, titanium, etc. complexes of zinc thiocyanate with salts, antipyrine or pyridine, and also halogen 2 by heat or light, such as tribromomethylphenylsulfone, trichloromethylphenylsulfone, tribromomethyl-p-chlorophenylsulfone, etc.
:) Examples include organic halogen compounds that generate Cal.

Further, as other color developers, substances capable of forming a charge transfer complex can also be used, such as tetracyanobenzoquinone, tetracyanobenzoquinone, tetracyanoethylene, 9-dicyanomethylene-2,4,7
-) Linitrofluorenone, or various quinodimethane derivatives, such as tetracyanoquinodimethane, tetracyanonaphthoquinodimethane, tetracyanoanthoquinodimethane, or anthrone derivatives, and the fluoran derivatives of the present invention are suitable for this type of quinodimethane derivatives. It exhibits a color that extremely strongly absorbs near-infrared electromagnetic waves using a coloring agent.

The fluoran compound represented by the general formula (1) can be used in color-forming recording materials in exactly the same manner as known fluoran compounds. In addition to heat-sensitive recording sheets or pressure-sensitive copying sheets, color-forming recording materials include, for example, heat-sensitive transfer recording, electrification heat-sensitive recording, electrophotography using toner containing an acidic substance as a developer, ultrasonic recording, photosensitive recording, and electron beam recording. It can be used as a recording material such as a recording material, a stamp ink, a typewriter ribbon, etc.

In this case, the fluoran compound represented by the general formula (1) can of course be used alone or in combination of several types in the color-forming recording material, and it can also be used in combination with 1) or other types of color-forming dyes. May be used for sex recording materials.

Other types of color-forming dyes may be used in combination with compounds that form dyes that absorb electromagnetic waves ranging from the visible region to the near-infrared region, such as the above-mentioned fluorene-based, phthalide-based, or thiofluorane-based dyes; Known chromogenic dyes such as crystal violet lactone, benzoyl leucomethylene blue, 2,3-dimethyl-7-(1
-octyl-2-methyl-indol-3-yl) -
7-(4-N,N-diphenylaminophenyl)-5,
Blue color-forming dyes such as 7-cyhydrofuro[3,4-E:]]pyrazine-5-o, 3-diethylamine-5-methyl-7-dibenzylaminofluorane, 3-N-inbutyl-ethelamino-7-phenyl Green coloring dyes such as aminofluorane, 5-diethylamino-6-methyl-7-chlorofluorane, 5-7chlorohexylamino-
6-chlorofluorane or 6.6-bis-(1″-
a red color-forming dye such as octyl-2'-methylindol-3'-yl)-phthalide, or 6-:)ethylamino-6-methyl-7-phenylaminofluorane;
3-N-methyl-cyclohexylamino-6-methyl-
7-phenylaminofluorane, 3-N-methyl-n-
Propylamino-6-methyl-7-phenylaminofluorane, 3-N-isopentyl-ethylamino-6-
Methyl-7-phenylaminofluorane, 6-ethylamino-7-m-trifluoromethylphenylaminofluorane, 3-di-n-butylamino-7-chlorophenylaminofluorane, 3-N-ethyltoluidino-6
It can also be used in combination with a black coloring dye such as -methyl-7-phenylaminofluorane.

The method for producing thermal recording paper using the fluoran derivative represented by the general formula (I) is the same as that for known color-forming dyes, for example, Japanese Patent Publication No. 39-27579 and Japanese Patent Publication No. 43-4160. , Japanese Patent Publication No. 45-14039 or Japanese Unexamined Patent Publication No. 59-7087.

That is, for example, a suspension in which fine particles of a fluoran derivative represented by the general formula (1) or a mixture thereof with other color-forming dyes and fine particles of an acidic color developer are dispersed in an aqueous solution of a water-soluble binder is prepared on paper. By coating and drying, heat-sensitive recording paper with excellent color development can be obtained. When a sensitizer is added to the above suspension, a heat-sensitive recording paper with extremely high sensitivity can be obtained. The suspension may further contain fillers, dispersants, color image stabilizers, antioxidants, desensitizers, antiblocking agents, antifoaming agents, light stabilizers, fluorescent brighteners, etc. .

U.S. Pat. No. 2,548,365, U.S. Pat. No. 2,548,366, U.S. Pat. No. 2,800,457 for using fluoran derivatives represented by formula (I) in pressure-sensitive copying paper;
Specification No. 2,800,458, JP-A-58-112
Pressure-sensitive copying paper can be manufactured according to the method described in No. 041 or Japanese Patent Application Laid-open No. 169758/1983.

Pressure-sensitive copying paper is divided into two types: upper paper, which has microcapsules containing a color-forming dye in an organic solvent applied to its lower surface, and lower paper, which has a color developer (acidic substance) applied to its upper surface. (furthermore, an inner sheet paper carrying a color developer on the upper surface and microcapsules on the lower surface may also be included in the unit), or in which the microcapsules and the color developer are coated on the same paper surface. The so-called self-continence) o-, ,2- may be used.

As the organic solvent, there may be used an inert, nonvolatile organic solvent that dissolves the color-forming dye well, such as diphenylmethane, alkylnaphthalene, or alkyltriphenyl.

The use of the fluorane derivative represented by the general formula (1) for thermal transfer is described in, for example, JP-A-58-212985, JP-A-59-33185, JP-A-59-42995, or JP-A-59-225986. It can be used according to the method described, and for use in electrically conductive recording paper, for example, JP-A-48-96157 and JP-A-48-10193 are used.
No. 5 or JP-A-49-11344, and for use in electrophotography, for example, JP-A-52-1999.
It can be used according to the method described in No. 24530 or JP-A-52-56952. Further, in order to use the fluoran compound of the present invention for photosensitive recording, for example, Japanese Patent Publication No. 38-24188, Japanese Patent Publication No. 10550-1987, Japanese Patent Publication No. 45978-1978, Japanese Patent Publication No. 80120-1988,
JP-A-50-126228, JP-A-52-14163
It can be used according to the method described in No. 3 or JP-A-54-147829. In this case, examples of acid precursors that generate protonic acids or Lewis acids by energy rays include organic compounds described in JP-A-55-13780 (which can also be sensitized with amine compounds); In addition to diazonium salts, iodonium salts, etc., dimethylphenacylsulfonium hexafluorophosphate or triphenylsulfonium hexafluoroantimonic acid sulfonium salts are used.

Also, for use in ultrasonic recording, French Patent No. 2.120
, No. 922, Belgian Patent No. 7 for use in electron beam recording.
．． No. 959.986, Special Publication No. 1973 for use in electrostatic recording
-5952, for use in photosensitive printing materials, JP-A-48-
It can be used according to the method described in No. 12104.

Recording paper produced according to these methods can be provided with a protective layer on its surface, if necessary, and an adhesive layer on its back surface to facilitate use as a label.

In addition, recording materials manufactured according to these methods are used not only for the barcodes mentioned above, but also for copying books, documents, computers, facsimile machines, ticket machines, cards, etc.
It is used in Ubarugado, and it can also be applied to information input at a higher density, for example, forgery prevention, copy prevention, unlocking devices, laser discs, etc., where recorded information cannot be seen with the naked eye, and its field of use is extremely wide.

As mentioned above, the most remarkable feature of the fluoran derivative represented by the general formula (1) is that its color has absorption in the near-infrared region and has a black or nearly black color tone, but this color has excellent fastness. Another major feature of these fluoran derivatives is that they have the following properties:

The present invention will be explained in more detail below with reference to Examples.

Example 1 (Production example) 2-(5-chloro-
2-Hydroxy-4-methyl)hendiylbenzoic acid 29
1 t (0,1 nobu) and 22.8 f (0,1 mo) of 6-hydroxy-4'-dimethylaminodiphenylamine
°C) was added, and stirring was continued for 24 hours while maintaining the temperature at 15 °C or lower. The reaction solution was dispersed in ice water, made weakly alkaline by adding caustic soda, and refluxed with 400% toluene.
Stirring was continued for an hour. Leave to cool and separate the layers. After washing the toluene layer with hot water, add activated clay 5y and filter. Concentrate the filtrate to remove precipitated crystals and wash with a small amount of toluene. It was dried to obtain 5-p-dimethylaminophenylamine-6-methyl-7-chlorofluorane □ crystals.

3-hydroxy-4'- used as raw material in this experiment
Dimethylaminodiphenylamine was synthesized as follows.

Resorcinol 44.51 (0,405mofi), N
, N-dimethyl-p-phenylenediamine 50.8f (
0,368non) and 3.7y of 80tisic acid to 1
After reacting for 5 hours with stirring at a temperature of 80-200 DEG C., the reactant was poured into a solution of 20% caustic soda dissolved in 200% water, and then neutralized to 70% using 50% sulfuric acid. The desired product precipitated as a viscous oil. The aqueous layer was removed, and the oil was distilled under reduced pressure of 3 mmHg to 180°-
Recrystallization was performed using a fraction in the temperature range of 225°C to obtain gray crystals with a melting point of 975-98.5°C. In this distillation, the main fraction was at 220°C/3 mmHg.

Example 2 (thermal recording paper) Various dispersions were prepared as follows.

Dye dispersion (with dispersion-1) Clay 11
．． 5215% PVA aqueous solution'
41.5f water
40. Of color developer dispersion (dispersion B-1) Bisphenol A 1
0. ! M clay
aOf15% PVA aqueous solution
41.5f water
4C1,Of color developer dispersion (Dispersion B
-2) 4-human 10xy-41-impropoxydiphenyl sulfone 10.
5f clay
aorl 5% PVA aqueous solution
41.5f water
4D, Of color developer dispersion (dispersion B-6
) Zinc 4-nitrobenzoate 10.5
F clay a
O215chi PVA aqueous solution 4
1.4M water
40. Of color developer dispersion (dispersion B-4) 2-methyl-5-nitrobenzene sulfo 4 1
0.5F clay
85215% PVA aqueous solution
41.5F water
40. Of color developer dispersion (dispersion B-5) Zinc salicylate 10.5
f clay a
5F15% PTA aqueous solution 4
1.5F water
40. Of color developer dispersion (dispersion B-6) Tetracyanoquinodimethane 10.
5f clay
a5F15% PTA aqueous solution
41.5 water
4 [LOf] Each of the mixtures with the above composition has a diameter of 1~
Put it in a polyethylene bottle with 1.5 m of glass beads 1501, seal it tightly, and grind it with paint conditioner for several hours to obtain dispersions A-1, B-1, B-2, B-3, and B-4.
, B-5 and B-6 were prepared.

Dispersions B-1 to B-6 to 11 parts by weight of Dispersion A-1
Six types of coating solutions were prepared by mixing 2 parts by weight of each coating solution, and each coating solution was coated on white base paper using a wire rod No. 18 and dried to produce heat-sensitive recording paper. These thermal recording papers are designated as thermal recording papers -■, -■, -■, -■, -■ and 1■ corresponding to the numbers of the dispersions used. (The coated surface of heat-sensitive recording paper -■ has a yellow color).

These thermosensitive recording papers were heated for 5 seconds from both sides using a dry heat tester to develop color. The heating temperature was 150°C for thermal recording paper -■ and -■, and 2 for the others.
It was 00℃. The color tones are described below.

Thermal recording paper ■ Blue-black thermal recording paper ■ Dark and dark blue thermal recording paper ■ Black color thermal recording paper ■ Dark and dark blue thermal recording paper ■ Black color thermal recording paper ■ Green-black Spectrophotometric analysis of these colored papers with an integrating sphere Reflection curves over a wavelength range of 400 nm to 1200 nm were measured using a meter. The results are shown in FIGS. 1 and 2.

Further, the color-forming surfaces of these color-forming papers and the reflectance of the 1-hour light fastness test conducted using a carbon Puke type fading tester were measured using a spectrophotometer. The results are shown in Table 1.

After the first reflected light test a8 1a1 31.7 64.3
96.0 ■ Before light test 1α2 20.6 35.
3 6 & 5 97.6 After light resistance test 12.8 27.
3 45.0 76.7 97.5 ■ Before light test
7.0 9.1 1 & 8 54.9 87.4 After the light test 7.1 9.5 14.656. B
8a4■ Before light test al 12.5 2α2
44.2 87.9 After light resistance test 7.712.0
19.8 43.9 87.9■ Before light emission test
7.1 9.6 14.8 36.8 87.2 After light resistance test a2 11.8 1&5 40.8 81
The measured values listed in Table 1 of 11L3 show that the color development of these thermosensitive recording papers has excellent light fastness.

Example 6 (Pressure sensitive copying paper) 3-p-dimethylaminophenylamine-6-methyl-
7-Chlorofluocine2. Of is alkyldiphenylmethane (Nisseki Chemical Co., Ltd. [Hisol 5AS296J
) 25. Of and diisopropylnaphthalene (Kureha Chemical Co., Ltd. JKMc-113J) 1aOf were mixed and heated to dissolve (Liquid A).

On the other hand, 10 of sulfonic acid-modified polyvinyl alcohol (Nippon Gosei Kagaku Kogyo Co., Ltd. "Gohsenol φKs-50")
15.0% aqueous solution of ethylene-maleic anhydride copolymer (Monsando “EMA-31”) 10% aqueous solution 7
．． 5f and water 34. o-, and then add 2.5 urea
After adding and dissolving 0.25 f and resorcin, 20
The pH was adjusted to 3.4 using a % caustic soda aqueous solution (B
liquid).

Add solution A to solution B to make an emulsion using a homomixer, then add 65q6 formalin aqueous solution7. Of was added and stirring continued for 1 hour at a temperature of 60-65°C. 40℃
After cooling, 28% ammonia water was added to adjust the temperature to 7.5 K to obtain a microcapsule dispersion.

This dispersion 27. Of, wheat starch 3.5F, 8 tons wheat starch aqueous solution, a5 liter and water 64. A coating liquid was prepared by mixing o-.

This coating liquid was applied to a white base paper using a wire bar N112 and dried to prepare an upper sheet of pressure-sensitive copying paper.

When I put the coated side of the upper sheet on the coated side of the lower sheet for pressure-sensitive copying paper made by applying phenol-formalin resin and drying it, and wrote letters on the upper surface of the upper sheet, Clear dark green letters appeared on the coated surface.

〔Effect of the invention〕

As is clear from the above description, the present invention provides a fluorane derivative that absorbs near-infrared electromagnetic waves, has a black or nearly black color tone, and exhibits extremely excellent light resistance. By using the fluorane derivatives of the present invention, it is possible to produce chromogenic recording materials for a very wide range of uses.

[Brief explanation of the drawing]

Figures 1 and 2 are reflection curves of the coloring surface of the thermal recording paper in Example 2, where a is the thermal recording paper I, b is the thermal recording paper ■, C is the thermal recording paper ■, and d is the thermal recording paper ■. Heat-sensitive recording paper
e is the reflection curve of the thermal recording paper V, and f is the reflection curve of the thermal recording paper ■. Patent Applicant Nisso Kako Co., Ltd. Procedural Amendment June 18, 1985 Commissioner of the Patent Office Kuro 1) Mr. Akio 1, Indication of the case 1985 Patent Application No. 301421 2, Name of the invention New fluoran derivative 3. Relationship with the case of the person making the amendment Patent Applicant Address: 3-1-60 Ukima, Kita-ku, Tokyo Name: Shin Nisso Kako Co., Ltd. 4. Agent: 5. Date of the amendment order (voluntary) 7. Contents of the amendment 1) "Invention filed on December 8, 1986" on page 5, lines 6-7 will be amended to "No. 6!-290379". 2) Next to the last line of page 8, add "3-p-dimethylaminophenylamino-6,7-dimethylfluoran". 3) Add "rl-p-dibutylaminophenylamino-7-methylfluorane" between the first and second lines of page 10. 4) Page 10, lines 10, 12, and 14 “
"Propylmethyl" are respectively corrected to "Propyl-N-methyl," and "Butylethyl" at the bottom of the same page is corrected to "Butyl-N-ethyl." 5) Correct "cyclohexylmethyl" in lines 4 and 7 of page 11 to "cyclohexyl-N-methyl." 6) Add the following statement between the first and second lines of page 12. "3-p-piperidinophenylamino-7-methylfluorane, 3-p-piperidinophenylamino-6-methyl-7-
7) Change “benz [α]” in line 13 of the same page to “benz [8]
” and correct it. 8) On page 16, line 9, r2,4- before “phthalic acid”
Add dichlorobenzoic acid. 9) On page 18, line 8, in front of “4-hydroxy”, insert “3”.
．． 4-dihydroxy-4'-methyldiphenylsulfone. 10) On page 24, correct "suspension" in lines 4, 6, and 8 to "dispersion." 11) Page 27, lines 9-10, “Electron beam...7,9
No. 59,986,” will be deleted. 12) Add the following statement between lines 4 and 5 on page 31. [Similarly, the following compounds were produced from the corresponding benzoyl derivatives and diphenylamine derivatives. 3-p-dimethylaminophenylamino-7-methylfluorane, m, p, 99-102°C, 189-192
°C, off-white crystals, 3-p-di-n-butylaminophenylamino-6-methyl-7-chlorofluoran, m, p, 103.7~
1.06.8°C, off-white crystals, 3-p-di-butylaminophenylamino-7-methylfluoran, m, p, 1
81.5-185°C1 Gray-white crystals, 3-p-pyrrolidinophenylamino-7-methylfluorane, m, l), 125-126.2°C9 Gray-white crystals 0. 3-1)-pyrrolidinophenylamino-6-methyl-7
-Chlorofluorane, m, p, 158.4-160°C,
Gray-white crystals, 3-p-piperidinophenylamino-7-methylfluorane, rn, T1.119.8-123°C1 white crystals, 3-p-piperidinophenylamino-6-methyl-7-
Chlorofluorane, m, p, 139.8-143.5°C
, yellow crystals, 3-p-diethylaminophenylamino-7-methylfluorane, m, p, 10.6-108°C1 grayish-white crystals, 3-p-diethylaminophenylamino-6-methyl-
7-Chlorofluorane, m, p. 188.9-189.5°C, grayish brown crystals. ”13) 3rd
Correct “sulfonic acid” in line 10 of page 2 to “zinc sulfonate”. 14) Add the following statement at the end of page 35. [Example 3 (Thermosensitive recording paper) Dispersion A-2 was prepared using 3-p-dimethylaminophenylamino-7-methylfluoran in the same manner as in Example 2, and 1 weight of dispersion A-2 was dispersion B-1,
A coating solution was prepared by mixing 2 parts by weight of each of B-2 and B-3, and heat-sensitive recording papers (1), (2) and (2) were produced and colored by heating. The color tone was a bluish black in all cases. After exposing a portion of this colored paper to sunlight for 10 hours, the reflectance of the uncolored surface and the colored surface before and after exposure was measured. The results are shown in Table 2. Example 4 (Thermosensitive recording paper) Similarly to Example 2, 3-p-di-n-butylaminophenylamino-6-methyl-7-chlorofluorane, 3-
p-di-n-butylaminophenylamino-7-methylfluorane and 3-p-pyrrolidinophenylamino-
Dispersions A-3, A-4 and A-5 were prepared using 7-methylfluorane. To 1 part by weight of each of these dispersions, double parts of dispersions B-1, B-2 and B-3 were added to prepare a coating solution, and heat-sensitive recording paper was produced. When heated, it develops a dark green to greenish-black color. When the reflectance of the coloring surface of these colored papers was measured before and after the light emission test, the results shown in Table 3 were obtained. In the table, thermal recording paper X, XI and ■ are suspension A-3.
, ■, ■ and W are suspension A-4, and XVI,
The thermal recording paper obtained from Suspension A-5. 15) Change “Example 3” in the first line of page 36 to “Example 5”
I will correct it. More than lO−

Claims (1)

[Claims] 1) General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R^1 and R^2 each independently represent an alkyl group having 1 to 9 carbon atoms, a cyclohexyl group, or a benzyl group. In addition, R^1 and R^2 may form a pyrrolidine ring, piperidine ring or morpholine ring together with the nitrogen atom to which they are bonded, and the benzene ring A has a halogen atom or/and a lower alkyl group as a substituent. Ring B represents a benzene ring or a naphthalene ring, which may have a halogen atom, an alkyl group having 1 to 9 carbon atoms, or/and a phenyl group as a substituent) Fluorane derivative. 2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 and R^2 each independently represent an alkyl group having 1 to 9 carbon atoms, a cyclohexyl group, or a benzyl group, and R^1 and R^2 may form a pyrrolidine ring, piperidine ring or morpholine ring together with the nitrogen atom to which they are bonded, and the benzene ring A may have a halogen atom or/and a lower alkyl group as a substituent. , Ring B represents a benzene ring or a naphthalene ring, which may have a halogen atom, an alkyl group having 1 to 9 carbon atoms, and/or a phenyl group as a substituent) as a color-forming component. Recording material held as.