JPH08104690A - New fluorane compound, its production and recording medium using the compound - Google Patents

Abstract

PURPOSE: To obtain the new compound useful as a color coupler remarkably excellent in plasticizer resistance and oil resistance and giving pressure-sensitive or heat-sensitive recording media excellent in the storability of colored images. CONSTITUTION: This compound is represented by formula I [R1 is H, 1-20C linear or branched alkyl, etc.; (CH2 )n is methylene chain wherein n is 1-20; (CH2 )m is methylene chain wherein m is 1-20; R2 is H, halogen, etc.; R3 is H, acyl, etc.; R4 is H, nitro, etc.,], e.g. 2-anilino-3-methyl-6-(N-methyl-N-(3'-n-(4"-hydroxy) butoxycarbonyl) propylamino)fluorane. The compound is obtained by reacting an ester fluorane compound of formula II (R5 is 1-4C alkyl) with a diol compound of formula: HO(CH2 )n OH in the presence of an acid catalyst such as concentrated sulfuric acid preferably at 50-70 deg.C. The diol compound is preferably used in an amount of 1-30 times moles that of the formula II, and the acid catalyst is preferably used in an amount of 0.5-2pts. per pt. of the compound of formula II.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluoran compound, a method for producing the same, and a pressure-sensitive or heat-sensitive recording material characterized by using the compound.

[0002]

2. Description of the Related Art Conventionally, a recording material utilizing a color reaction of a colorless or light-colored electron-donating color former and an electron-accepting compound is well known and is used for pressure-sensitive recording and heat-sensitive recording.

The pressure-sensitive recording medium is prepared by using a support made of, for example, paper, in which microcapsules containing an electron-donating color-forming agent and a color-developing agent which is an electron-accepting compound are provided on separate sheets or on a single sheet. Apply on the same side, if they are different papers, oppose these, and if it is a single paper, apply the writing pressure or the pressure of a typewriter as it is to destroy the microcapsules, A color developer and a color developer are brought into contact with each other to develop a color. Since many pressure sensitive recording sheets can be copied, they are used for slips and the like.

On the other hand, the heat-sensitive recording material is one in which heat is applied to a heat-sensitive recording layer composed of an electron-donating color former, an electron-accepting compound and the like provided on a support made of paper, for example, to melt a color-forming component to develop a color. , Facsimiles, printers, bar code labels, tickets, etc.

With the recent increase in speed and diversification of recording systems, these recording materials are required to have excellent color developing sensitivity and color developing rate, high ground whiteness, and image storability of the color developing body. Various qualities are required, such as being sufficient.

Examples of electron-donating color formers used in these recording materials include various leuco dyes such as fluorane type, triphenylmethanephthalide type, phenothiazine type and spiropyran type. Of these, most of the fluoran-based leuco dyes are leuco dyes capable of producing black color alone, and are particularly useful color formers.

As the fluoran-based leuco dye, fluoran dyes having various substituents as described below, for example, 2-anilino-3-methyl-6- (N-cyclohexyl-N-methylamino) fluorane (Japanese Patent Publication No. 51-232).
No. 04), 2-anilino-3-methyl-6- (N-
Ethyl-N-isoamylamino) fluorane (Japanese Patent Publication 5)
6-52759), 2-anilino-3-methyl-
6- (N-ethyl-N-normalpropylamino) fluorane (JP-A-59-120654), 2-anilino-3-methyl-6- (N-ethyl-N-furfurylamino) fluorane (JP-A No. 60-184878), 2-anilino-3-methyl-6-dinormal butylaminofluorane (JP-A-60-202155), 2-anilino-3-chloro-6-diethylaminofluorane (special (Kaisho 58-7453), 2-o-
Chloranilino-6-diethylaminofluorane (JP-A-55-265), 2-p-acetylanilino-
6-Dinormalhexylaminofluorane (JP-A-59
-199759), 2-o-nitroanilino-6.
-Diethylaminofluorane (JP-A-58-17316)
No. 0) and the like. These fluoran compounds have advantages such as good color development sensitivity and low manufacturing cost. However, it has many drawbacks such as poor background color and color density when used as recording paper, and insufficient storability of a color image.

As a leuco dye for improving this drawback, JP-A-6-172362 discloses a fluoran-based leuco dye having an ester functional group on its side chain (hereinafter, this fluoran dye is referred to as ester fluoran. To). This ester fluoran has markedly superior ground color and color density compared with conventional fluoran compounds, and the light resistance, heat resistance, and water resistance of color images are also improved over conventional fluoran dyes. . However, for example, when storing a slip of pressure-sensitive recording paper in a commercially available file containing a plasticizer or when using the heat-sensitive recording paper for a bar code label of food etc., it may come into contact with wrap or edible oil. However, it has a defect that the color image becomes thin or the color is considerably erased. Therefore, as a further improvement of these image storability, it is possible to create a fluoran dye that does not easily decolorize when contacted with a plasticizer in pressure-sensitive recording paper, and to easily contact with a plasticizer or oil in heat-sensitive recording paper. It was desired to create a fluoran dye that does not fade.

[0009]

Therefore, the present invention is to improve the above-mentioned drawbacks of the existing fluorane dyes and ester fluorane dyes, that is, specifically, a plasticizer for the ester fluorane skeleton. It was an object of the present invention to provide a novel fluoran compound in which the above-mentioned drawbacks have been improved by newly introducing a strong functional group into oil and oil.

[0010]

[Means for Solving the Problems] To solve this problem, the present inventors have aimed to improve the drawbacks of conventional fluoran-based leuco dyes by introducing a structure resistant to plasticizers and oils to the above ester fluoran. , Continued to search for useful functional groups. As a result of earnest studies, they have found that the ester fluoran compound having a hydroxyl group represented by the following general formula (1) is a color former having remarkably excellent plasticizer resistance and oil resistance.

That is, the present invention relates to a novel fluorane compound represented by the following general formula (1).

[0012]

Embedded image [In the formula, R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and (CH ₂ ) n has n of 1 to 20. Represents an integer methylene chain of Further, (CH ₂ ) m represents a methylene chain in which m is an integer from 1 to 20, and R ² represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ³ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or an acyl group, and R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group, a nitro group, an amino group, a substituted amino group or an acyl group. ]

The following are specific examples of the compound, but the present invention is not limited thereto.

2-anilino-3-methyl-6- (N-methyl-N- (3'-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane 2-anilino-3-methyl-6- ( N-ethyl-N-
(3′-n- (4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane 2-anilino-3-methyl-6- (Nn-propyl-
N- (3'-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane 2-anilino-3-methyl-6- (N-methyl-N-
(8'-n- (4 "-hydroxy) butoxycarbonyl) octylamino) fluorane 2-anilino-3-methyl-6- (N-ethyl-N-
(8′-n- (4 ″ -hydroxy) butoxycarbonyl) octylamino) fluorane 2-anilino-3-methyl-6- (Nn-propyl-
N- (8'-n- (4 "-hydroxy) butoxycarbonyl) octylamino) fluorane 2-anilino-3-methyl-6- (N-methyl-N-
(3'-n- (8 "-hydroxy) octoxycarbonyl) propylamino) fluorane 2-anilino-3-methyl-6- (N-ethyl-N-
(3′-n- (8 ″ -hydroxy) octoxycarbonyl) propylamino) fluorane 2-anilino-3-methyl-6- (Nn-propyl-
N- (3'-n- (8 "-hydroxy) octoxycarbonyl) propylamino) fluorane 2-anilino-3-methyl-6- (Nn-hexyl-
N- (3'-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane 2-anilino-3-methyl-6- (N-i-butyl-N)
-(3'-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane 2-anilino-3-methyl-6- (N-cyclohexyl-N- (3'-n- (4" -hydroxy) butoxy Carbonyl) propylamino) fluorane 2-anilino-3-methyl-6- (Nn-decyl-N)
-(3'-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane 2-anilino-3-methyl-6- (Nn-pentadecyl-N- (3'-n- (4" -hydroxy ) Butoxycarbonyl) propylamino) fluorane 2-anilino-3-ethyl-6- (Nn-eicosyl-N- (3'-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane 2-anilino- 3-Methyl-6- (N-cyclohexyl-N- (5'-n- (4 "-hydroxy) butoxycarbonyl) pentylamino) fluorane 2-anilino-3-methyl-6- (N-i-butyl-N
-(5'-n- (4 "-hydroxy) butoxycarbonyl) pentylamino) fluorane 2-anilino-3-methyl-6- (Nn-hexyl-
N- (5'-n- (4 "-hydroxy) butoxycarbonyl) pentylamino) fluorane 2-anilino-3-methyl-6- (N-ethyl-N-
(10'-n- (4 "-hydroxy) butoxycarbonyl) decylamino) fluorane 2-p-chloroanilino-3-n-propyl-6- (N
-Methyl-N- (10'-n- (4 "-hydroxy) butoxycarbonyl) decylamino) fluorane 2- (o-acetyl-N-methyl) anilino-3-n-
Butyl-6- (N-methyl-N- (3'-n- (4 "-
(Hydroxy) butoxycarbonyl) propylamino) fluorane 2-N-ethylanilino-3-chloro-6- (N-benzyl-N- (3'-n- (10 "-hydroxy) decyloxycarbonyl) propylamino) fluorane 2- (N-Acetyl-p-chloro) anilino-3-methyl-6- (N-ethyl-N- (7'-n- (4 "-hydroxy) butoxycarbonyl) heptylamino) fluorane 2- (N-methyl- p-methyl) anilino-3-methyl-6- (N-ethyl-N- (10'-n- (4 "-hydroxy) butoxycarbonyl) decylamino) fluorane 2- (N-methyl-o-nitro) anilino- 3-chloro-6- (Nn-hexyl-N- (3'-n- (15 "
-Hydroxy) pentadecyloxycarbonyl) propylamino) fluorane 2- (N-methyl-p-dimethylamino) anilino-3
-N-butyl-6- (N-cyclohexyl-N- (3 '
-N- (20 "-hydroxy) eicosyloxycarbonyl) propylamino) fluorane 2- (N-methyl-o-acetyl) anilino-3-methyl-6- (Nn-decyl-N- (3'- n- (4 "-
Hydroxy) butoxycarbonyl) propylamino) fluorane 2-N-acetylanilino-3-chloro-6- (N-n
-Decyl-N- (8'-n- (4 "-hydroxy) butoxycarbonyl) octylamino) fluorane 2-N-methylanilino-3-methyl-6- (N-i-
Butyl-N- (15'-n- (8 "-hydroxy) octoxycarbonyl) pentadecylamino) fluorane 2-N-n-butylanilino-3-methyl-6- (N-
Phenyl-N- (20'-n- (4 "-hydroxy) butoxycarbonyl) eicosylamino) fluorane 2-anilino-6- (N-methyl-N- (3'-n-
(4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane 2-p-aminoanilino-6- (N-methyl-N- (3
′ -N- (4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane

The fluorane compound of the present invention is a novel compound, and is characterized by having a hydroxyl group at the side chain terminal of ester fluorane. These compounds are usually colorless or light-colored powders or amorphous substances, but they react with an electron-accepting compound to instantly develop a color, and give a color image with high storage stability. In particular, its plasticizer resistance and oil resistance are significantly higher than those of conventional fluoran and ester fluoran.

As the method for producing the fluoran compound of the present invention, an ester fluoran compound represented by the following general formula (2) and a diol compound represented by the following general formula (3) are reacted in the presence of an acid catalyst. It can be manufactured.

[0017]

[Chemical 4] [In the formula (2), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and (CH ₂ ) n represents n. 1
Represents an methylene chain of an integer of up to 20. R ² represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ³ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or an acyl group. R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group, a nitro group, an amino group, a substituted amino group or an acyl group, and R ₅ represents a lower alkyl group having 1 to 4 carbon atoms. Further, (CH ₂ ) m in the formula (3) represents a methylene chain in which m is an integer of 1 to 20. ]

The reaction is usually carried out by adding a mixture of the starting ester fluoran and diol to an inorganic acid such as concentrated sulfuric acid, concentrated nitric acid or polyphosphoric acid, or an organic acid such as paratoluenesulfonic acid or metanitrobenzenesulfonic acid.
0.1 part to 10 parts relative to 10 parts, reaction temperature 20 ° C to 1
It is carried out by stirring under conditions of 50 ° C. (preferably 50 ° C. to 70 ° C.) and a reaction time of 30 minutes to 10 hours. The acid catalyst may be any of the above, but if the addition amount is too small, the reaction hardly progresses, and if it is too large, the ester portion of the ester fluoran is hydrolyzed, and the yield is lowered, so that the ester 0.5-2 for 1 copy of Oran
It is preferable to add a part. Further, it is desirable to add the diol in an equimolar to 30-fold molar amount with respect to the ester fluorane, and the diol may also serve as the reaction solvent.

When the fluorane compound of the present invention is produced by using the above reaction, the starting ester fluorane and diol may have any structure represented by the general formulas (2) and (3). However, m and n of the side chain portion are preferably in the range of 1 to 10 in view of availability of raw materials and handling. In addition, the substituent R on the fluoran skeleton
Regarding ^{1 to} R ⁴ , those having a substituent that gives black coloration are most useful in terms of practicality. Therefore, as the fluoran compound of the present invention, compounds satisfying these conditions, for example, the compounds shown in Synthesis Examples are particularly useful.

The fluoran compound represented by the general formula (1) of the present invention can be used as a color former in a pressure-sensitive recording material or a heat-sensitive recording material, and a pressure-sensitive recording material or a pressure-sensitive recording material using the fluoran compound of the present invention can be used. The heat-sensitive recording material is extremely excellent in plasticizer resistance and oil resistance. When these recording materials are manufactured using the fluoran compound of the present invention, various conventionally known manufacturing methods can be used.

In the case of producing a pressure-sensitive recording material, the fluoran compound of the present invention is dissolved alone or together with other leuco dyes in a hydrophobic medium, and microcapsules having the core material as a core substance are treated with paper or a plastic sheet. It can be produced by applying it to a support such as a resin coated paper.
The amount of the color former used depends on the desired coating thickness, the form of the pressure-sensitive recording material,
It is determined by the capsule manufacturing method and other conditions.

The microcapsules used in the present invention are conventionally known by the coacervation method (see, for example, US Pat.
No. 00457, No. 2800458, etc.), interfacial polymerization method (for example, JP-A-57-140638).
No. 60-227828, etc.), i
n-situ polymerization method (for example, Japanese Examined Patent Publication No. 51-9079,
No. 53-84881, etc.).

Further, as the above-mentioned hydrophobic medium, a diarylalkane such as phenylxylylethane, phenylethylphenylethane or phenylbutylphenylmethane,
Alkylnaphthalene such as monoisopropylnaphthalene and diisopropylnaphthalene, isopropyl biphenyl
Examples thereof include, but are not limited to, butyl biphenyl, partially hydrogenated terphenyl, and materials containing these as main components. In addition, starch, latex, polyvinyl alcohol, etc. can be used in the preparation of the paint.

Examples of the color developing agent that can be used in the pressure-sensitive recording material of the present invention include, but are not limited to, the following compounds. Also, two or more of these may be mixed and used.

Aromatic carboxylic acids and their polyvalent metal salts include benzoic acid, p-hydroxybenzoic acid, chlorobenzoic acid, brombenzoic acid, nitrobenzoic acid, methoxybenzoic acid, ethoxybenzoic acid, toluic acid and ethyl. Benzoic acid, pn-propylbenzoic acid, p-isopropylbenzoic acid, 3-methyl-4-hydroxybenzoic acid, 3-ethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, p-tert. -Butylbenzoic acid, o
-Benzoylbenzoic acid, p-cyclohexylbenzoic acid,
Salicylic acid, 3-methyl-5-tert-butylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 5-
Nonylsalicylic acid, 5-cyclohexylsalicylic acid,
3-cyclohexylsalicylic acid, cresotinic acid, 3-cumylsalicylic acid, 3-phenylsalicylic acid, 3,5-di-sec-butylsalicylic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, gallic acid, naphthoic acid Acid, monobenzyl phthalate, monocyclohexyl phthalate, salicylosalicylic acid, 3-tert-butyl-5-α-methylbenzylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, phthalic acid, terephthalic acid, isophthalic acid Acid, diphenic acid, naphthalene dicarboxylic acid and magnesium, aluminum, cadmium, calcium, titanium, zinc of these compounds,
Nickel, cobalt, manganese, vanadium, iron, copper salts, etc.

Examples of the activated clays include inorganic materials such as activated clay, acid clay, attapulgite, bentonite, zeolite, montmorillonite, halloysite, kaolinite, silicic anhydride, anhydrous magnesium silicate and anhydrous aluminum silicate.

Examples of the phenol resin include p-phenylphenol-formaldehyde polymer, p-octylphenol-formaldehyde polymer, p-cumylphenol-formaldehyde polymer, p-tert-butylphenol-formaldehyde polymer, p-nonylphenol-formaldehyde. Polymer, p-cyclohexylphenol-formaldehyde polymer, p-ethylphenol-formaldehyde polymer, p-propylphenol-formaldehyde polymer, p-amylphenol-
Formaldehyde polymer, p-hexylphenol-formaldehyde polymer, p-heptylphenol-formaldehyde polymer, p-decylphenol-formaldehyde polymer, p-dodecylphenol-formaldehyde polymer, p-octylphenol-acetaldehyde polymer, p- Phenylphenol-acetaldehyde polymer, p-tert-butylphenol-acetaldehyde polymer and the like.

A polyvalent metal-modified phenol resin obtained by modifying the above-mentioned phenol resin with a polyvalent metal such as zinc or a polyvalent metal salt of a carboxylated terpene phenol resin can also be used.

When the heat-sensitive recording material of the present invention is manufactured, it can be manufactured by the following method. That is, the fluoran compound of the present invention alone or in combination,
Alternatively, in combination with another leuco dye, the electron-accepting developer and the sensitizer are atomized by a crusher such as a ball mill, an attritor, and a sand grinder, or an emulsifier,
Various fillers and various additives are added and dispersed in an aqueous solution of a water-soluble binder to obtain a coating, which is then air-knife-coated.
Various types of coaters, such as terrain, blade coaters, roll coaters, etc.
A heat-sensitive recording material can be obtained by coating it on an arbitrary support with a taper or the like.

Examples of the developer that can be used in the heat-sensitive recording material of the present invention include the following, but the invention is not limited thereto and two or more kinds of them may be used in combination.

4,4'-isopropylidenediphenol, 1,7-di (4-hydroxyphenylthio) -3,
Bisphenols such as 5-dioxaheptane, 4,4'-cyclohexylidene diphenol, 4,4 '-(1-methyl-normal hexylidene) diphenol and 2,2'-dihydroxydiphenol, 4-hydroxy 4-, such as benzyl benzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate and butyl 4-hydroxybenzoate.
Hydroxybenzoates, dimethyl 4-hydroxyphthalate, diisopropyl 4-hydroxyphthalate,
4-hydroxyphthalic acid diesters such as 4-hydroxyphthalic acid dibenzyl and 4-hydroxyphthalic acid dihexyl, phthalic acid such as phthalic acid monobenzyl ester, phthalic acid monocyclohexyl ester, phthalic acid monophenyl ester and phthalic acid monomethylphenyl ester Monoesters, bis- (4-hydroxy-3-te
bis- (hydroxy) such as rt-butyl-6-methylphenyl) sulfide, bis- (4-hydroxy-2,5-dimethylphenyl) sulfide, and bis- (4-hydroxy-2-methyl-5-ethylphenyl) sulfide. Phenyl) sulfides, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-4'-
Methyldiphenyl sulfone, 4-hydroxy-4'-n
4-hydroxyphenyl aryl sulfones such as propoxydiphenyl sulfone, 4-hydroxyphenylbenzenesulfonate, 4-hydroxyphenyl-p-
4-hydroxyphenyl aryl sulfonates such as tolyl sulfonate and 4-hydroxyphenyl-p-chlorobenzene sulfonate, 1,3-di [2- (4-hydroxyphenyl) -2-propyl] benzene, 1 , 3
-Di [2- (4-hydroxy-3-alkylphenyl)
1,3-di [2- (hydroxyphenyl) -2-propyl] benzenes such as 2-propyl] benzene, 4-
Benzyl hydroxybenzoyloxybenzoate, methyl 4-hydroxybenzoyloxybenzoate, ethyl 4-hydroxybenzoyloxybenzoate, propyl 4-hydroxybenzoyloxybenzoate, butyl 4-hydroxybenzoyloxybenzoate, 4-hydroxybenzoyloxybenzoic acid 4-Hydroxybenzoyloxybenzoic acid esters such as isopropyl, bis- (3-butyl-4-hydroxy-6-methylphenyl) sulfone, bis- (3-ethyl-4-hydroxyphenyl) sulfone, bis- (3- Propyl-4-hydroxyphenyl) sulfone, bis- (3-isopropyl-4-hydroxyphenyl) sulfone, bis- (3-ethyl-4-hydroxyphenyl) sulfone, bis- (4-hydroxyphenyl) sulfone 2-hydroxy-4'-
Hydroxyphenyl sulfone, bis- (3-chloro-4
-Hydroxyphenyl) sulfone, bis- (3-bromo-4-hydroxyphenyl) sulfone and other bisphenol sulfones, p-tert-butylphenol, p
-Phenylphenol, p-benzylphenol, 1-
Phenols such as naphthol and 2-naphthol, benzoic acid, p-tert-butylbenzoic acid, trichlorobenzoic acid, 3-sec-butyl-4-hydroxybenzoic acid,
3-cyclohexyl-4-hydroxybenzoic acid, 3,5
-Dimethyl-4-hydroxybenzoic acid, terephthalic acid,
Salicylic acid, 3-isopropylsalicylic acid, 3-ter
Examples thereof include aromatic carboxylic acid metal salts such as t-butyl salicylic acid.

In a heat-sensitive recording material containing a color-forming agent and a color-developing agent as color-forming components, a sensitizer is usually used to increase the color-developing sensitivity. Sensitizer is information paper (Paper Industry Times, 198
7 years), non-impact printing (CMC, 19
1986) and various patent publications can be used. The following compounds can be illustrated as specific examples, but the compounds are not limited thereto, and two or more kinds of these may be used.

Stearic acid, zinc stearate, aluminum stearate, calcium stearate, zinc palmitate, stearic acid amide, palmitic acid amide, oleic acid amide, behenic acid, zinc behenate, ethylenebisstearamide, coconut fatty acid amide, Montan wax, polyethylene wax, phenyl-α-naphthyl carbonate, di-p-tolyl carbonate, diphenyl carbonate, 4-biphenyl-p-tolyl ether, p-benzyl biphenyl, m-terphenyl,
Triphenylmethane, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 1,1,3
-Tris (2-methyl-4-hydroxy-5-tert)
-Butylphenyl) butane, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (phenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane,
1,4-bis (phenoxy) butane, 1,4-bis (phenoxy) butene, 2-naphthylbenzyl ether,
1,4-diethoxynaphthalene, 1,4-dimethoxynaphthalene, 1-hydroxy-2-naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid methyl ester, 2-naphthoic acid phenyl ester, p-benzyloxybenzoic acid Benzyl, dibenzyl terephthalate, dimethyl terephthalate, 1,1-diphenylethanol,
Examples thereof include 1,1-diphenylpropanol, 1,3-diphenoxy-2-propanol, p- (benzyloxy) benzyl alcohol, N-octadecylcarbamoyl-p-methoxycarbonylbenzene and N-octadecylcarbamoylbenzene.

As the binder that can be used in the heat-sensitive recording material of the present invention, fully saponified or partially saponified polyvinyl alcohol having various degrees of polymerization, modified polyvinyl alcohol such as carboxy-modified polyvinyl alcohol, or the like, Starch and various modified starches, hydroxyethyl cellulose, methyl cellulose, cellulose derivatives such as carboxymethyl cellulose, casein, gelatin, styrene-maleic anhydride copolymer, styrene-butadiene copolymer, styrene,
Polymers and copolymers of vinyl acetate, acrylamide, acrylic acid ester, etc., polyamide resins, silicone resins, petroleum resins, terpene resins, ketone resins, coumarone resins, and the like, but are not limited to these. Not a thing. These natural and synthetic polymer substances are used by dissolving them in water or an organic solvent such as alcohol.
It can be used in the state of being emulsified or dispersed in a medium such as water. Also, two or more of these may be used.

Fillers usable in the thermosensitive recording medium of the present invention include clay, calcined clay, diatomaceous earth, talc, kaolin, calcium carbonate, basic magnesium carbonate, barium sulfate, barium carbonate, aluminum hydroxide, zinc oxide. , Silica, magnesium hydroxide, titanium oxide, urea-
Formalin resin, polystyrene resin, phenol resin,
Other natural or synthetic inorganic or organic fillers can be included, but are not limited to. Two or more of these may be used.

As the additive, an ultraviolet absorber, a defoaming agent,
Examples thereof include fluorescent whitening agents, waterproofing agents, lubricants such as waxes, stay agents, etc., but are not limited thereto.

The amounts of the color-developing agent and the color-developing agent used in the thermosensitive recording medium of the present invention, and the types and amounts of the other main components are determined according to the required performance and recording suitability, and are not particularly limited. , Usually 1 color developer to 1 color developer
.About.8 parts and 1 to 20 parts of filler are used, and 10 to 25% of the total solid content of the binder is suitable.

Examples of the support used in the recording material of the present invention include papers such as high-quality paper, medium-quality paper, and coat paper, synthetic paper, plastic film, and the like, but are not limited thereto. Not something.

An overcoat layer of a polymeric substance or the like may be provided on the thermosensitive coloring layer for the purpose of further improving the storage stability. Further, an undercoat layer containing an organic filler or an inorganic filler may be provided between the color forming layer and the support for the purpose of enhancing the storage stability and sensitivity.

[0040]

The fluoran compound represented by the general formula (1) of the present invention is extremely useful as a color former for various recording materials such as pressure-sensitive recording materials and heat-sensitive recording materials. The reason is the high plasticizer resistance and oil resistance that conventional fluoran dyes do not have. In a pressure-sensitive or heat-sensitive recording material, the solubility of a color-forming material produced by a reaction between a color-developing agent and a color-developing agent in a plasticizer or oil has a great influence on these properties. That is, it is considered that if the solubility in the plasticizer or oil is high, the oil resistance of the image is poor, and if the solubility is low, the oil resistance is good. The fluoran compound of the present invention has a highly polar hydroxyl group at the terminal of the ester, and has a higher polarity than conventional fluoran compounds. Therefore, it is considered that the solubility in the plasticizer and the oil is lowered, and the plasticizer resistance and the oil resistance are dramatically improved. Therefore, the present compound is extremely useful as a color former for various recording materials, particularly in applications where the plasticizer resistance and oil resistance of images are required.

[0041]

EXAMPLES Synthesis examples and examples of the present invention are shown below, but the present invention is not limited to these.

(Synthesis Example 1) [Synthesis of 2-anilino-3-methyl-6- (N-ethyl-N- (3'-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane] 30 ml 3 g of 2-anilino-3-methyl-6- (N-ethyl-N- (3'-ethoxycarbonyl) propylamino) fluorane was dissolved in 1,4-butanediol, and 0.5 ml of concentrated sulfuric acid was added. The mixture was stirred at 70 ° C. for 6 hours, added to 400 ml of ice water and extracted with ethyl acetate, the extract was washed with water, dried over magnesium sulfate, the solvent was distilled off, and the concentrated residue was subjected to silica gel column chromatography. 2-anilino-
3-Methyl-6- (N-ethyl-N- (3'-n-
2.88 g (yield 89%) of (4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane was obtained. The molecular weight by mass spectrometry was 606. <Infrared spectrum (cm ⁻¹ )> 3464,3385,1752 , 1736,
1633,1618,1518,1412,1249 < ¹ H-nuclear magnetic resonance spectrum (δ ppm)> 1.15 (3H,
t, J = 7), 1.56-1.72 (4H, m), 1.92 (2H, qu, J = 7), 2.22 (3H, s),
2.35 (2H, t, J = 7), 3.32 (2H, t, J = 7), 3.37 (2H, t, J = 7), 4.09
(2H, t, J = 7), 5.26 (1H, s), 6.37 (1H, dd, J = 3,8), 6.46 (1H, d,
J = 3), 6.55-6.58 (4H, m), 6.72 (1H, t, J = 7), 7.06 (2H, t, J =
8), 7.13 (1H, s), 7.20 (1H, d, J = 8), 7.55 (1H, t, J = 7), 7.63 (1
H, t, J = 7), 7.93 (1H, d, J = 7) < ¹³ C-nuclear magnetic resonance spectrum (δ ppm)> 12.0,18.
0,22.5,25.0,29.0,31.3,45.0,49.3,62.1,64.4,84.1,97.
8,105.1,108.4,114.9,117.3,118.8,119.3,121.0,123.8,
124.8,126.9,128.8,129.1,129.4,134.7,134.9,135.9,14
4.7,147.8,149.6,152.9,153.0,169.5,173.1

(Synthesis Example 2) [Synthesis of 2-anilino-3-methyl-6- (N-ethyl-N- (3'-n- (8 "-hydroxy) octoxycarbonyl) propylamino) fluorane] 2 -Anilino-3-methyl-6- (N-ethyl-N-
2 g of (3'-ethoxycarbonyl) propylamino) fluorane was dissolved in 10 g of 1,4-octanediol and 0.1 ml of concentrated sulfuric acid was added. The mixture was stirred at 50 ° C. for 4 hours, added to 400 ml of ice water, and extracted with ethyl acetate. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, and the concentrated residue was separated and purified by silica gel column chromatography to give 2-anilino-
3-Methyl-6- (N-ethyl-N- (3'-n-
1.53 g (yield 65%) of (8 ″ -hydroxy) octoxycarbonyl) propylamino) fluorane was obtained.
The molecular weight by mass spectrometry was 662. <Infrared spectrum (cm ^-1 )> 3466,3377,1752,1733,
1618,1518,1495,1419 < ¹ H-nuclear magnetic resonance spectrum (δ ppm)> 1.16 (3H,
t, J = 7), 1.31 (8H, br), 1.51-1.64 (4H, m), 1.92 (2H, qu, J =
7), 2.23 (3H, s), 2.35 (2H, t, J = 7), 3.29-3.40 (4H, m), 3.60
(2H, t, J = 7), 4.07 (2H, t, J = 7), 5.25 (1H, s), 6.37 (1H, dd, J =
3,8), 6.46 (1H, d, J = 3), 6.55-6.58 (4H, m), 6.72 (1H, t, J =
7), 7.06 (2H, t, J = 8), 7.13 (1H, s), 7.20 (1H, d, J = 8), 7.55 (1
H, t, J = 7), 7.63 (1H, t, J = 7), 7.93 (1H, d, J = 7) < ¹³ C-nuclear magnetic resonance spectrum (δ ppm)> 12.1,18.
0,22.5,25.6,25.8,28.5,29.1,29.2,31.3,32.6,45.0,49.
4,62.8,64.7,84.0,97.8,105.1,108.3,114.9,117.4,118.
7,119.3,121.1,123.8,124.8,127.0,128.9,129.1,129.4,
134.6,134.9,135.8,144.7,147.8,149.6,152.9,153.1,16
9.5,173.2

(Synthesis Example 3) [2-anilino-3-methyl-6- (N-cyclohexyl-N- (5'-n- (4 "
-Hydroxy) butoxycarbonyl) pentylamino)
Synthesis of Fluoran] 2-anilino-3-methyl-6- (N-cyclohexyl-N- (5'-ethoxycarbonyl) pentylamino)
95 mg of fluoran was dissolved in 1 ml of 1,4-butanediol and 0.05 ml of concentrated sulfuric acid was added. The mixture was stirred at 60 ° C. for 30 minutes, added to 100 ml of ice water, and extracted with ethyl acetate. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, and the concentrated residue was separated and purified by silica gel column chromatography to obtain 2
-Anilino-3-methyl-6- (N-cyclohexyl-
N- (5'-n- (4 " - hydroxy) butoxycarbonyl).. Pentylamino) fluoran 58.7 mg (molecular weight according to obtain a 58% yield) mass spectrometry was 688 <Infrared spectrum (cm ^{- 1} )> 3445,3387,1758,1736,
1617,1511,1496,1412 < ¹ H-nuclear magnetic resonance spectrum (δ ppm)> 1.30-1.8
4 (20H, m), 2.23 (3H, s), 2.32 (2H, t, J = 7), 3.16 (2H, t, J = 7),
3.55 (1H, m), 3.64 (2H, t, J = 7), 4.10 (2H, t, J = 7), 5.27 (1H,
s), 6.37 (1H, dd, J = 3,8), 6.46 (1H, d, J = 3), 6.55-6.58 (4H,
m), 6.72 (1H, t, J = 7), 7.06 (2H, t, J = 8), 7.14 (1H, s), 7.21 (1
H, d, J = 8), 7.57 (1H, t, J = 7), 7.63 (1H, t, J = 7), 7.93 (1H, d, J
= 7) < ¹³ C-nuclear magnetic resonance spectrum (δ ppm)> 18.0,, 2
4.7,25.0,25.7,26.0,26.6,28.9,29.0,30.6,34.2,44.6,5
7.3,62.1,64.1,84.1,98.2,105.0,108.8,114.9,117.3,11
8.7,119.2,121.1,123.8,124.8,127.0,128.7,129.1,129.
3,134.6,134.9,135.8,144.7,147.8,150.3,152.9,153.0,
169.5,173.6

(Synthesis Example 4) [Synthesis of 2-anilino-3-methyl-6- (N-i-butyl-N- (5'-n- (4 "-hydroxy) butoxycarbonyl) pentylamino) fluorane] 2-anilino-3-methyl-6- (N-i-butyl-N
1 g of-(5'-ethoxycarbonyl) pentylamino) fluorane was dissolved in 10 ml of 1,4-butanediol and 0.5 ml of concentrated sulfuric acid was added. This mixture at 60 ° C
After stirring for 6 hours, the mixture was added to 100 ml of ice water and extracted with ethyl acetate. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, and the concentrated residue was separated and purified by silica gel column chromatography to give 2-anilino-3-methyl-6- (N-i-butyl-N- (5'-n).
464 mg (yield 47%) of-(4 "-hydroxy) butoxycarbonyl) pentylamino) fluorane was obtained.
The molecular weight by mass spectrometry was 662. <Infrared spectrum (cm ^-1 )> 3379,3389,1735,1618,
1516,1495,1413 < ¹ H-nuclear magnetic resonance spectrum (δ ppm)> 0.91 (6H,
d, J = 7), 1.54-1.71 (10H, m), 2.20 (1H, m), 2.21 (3H, s), 2.30
(2H, t, J = 7), 3.08 (2H, d, J = 7), 3.31 (2H, t, J = 7), 3.62 (2H,
t, J = 7), 4.07 (2H, t, J = 7), 5.26 (1H, s), 6.37 (1H, dd, J = 3,
8), 6.46 (1H, d, J = 3), 6.55-6.58 (4H, m), 6.70 (1H, t, J = 7),
7.04 (2H, t, J = 8), 7.13 (1H, s), 7.20 (1H, d, J = 8), 7.54 (1H,
t, J = 7), 7.63 (1H, t, J = 7), 7.92 (1H, d, J = 7) < ¹³ C-nuclear magnetic resonance spectrum (δ ppm)> 17.8,20.
3,24.6,24.8,26.0,26.3,26.7,28.8,34.0,51.5,58.7,61.
8,64.1,84.2,97.8,104.6,108.5,114.7,117.1,118.6,11
9.0,120.8,123.7,124.6,126.8,128.5,128.9,129.3,134.
6,134.8,135.8,144.7,147.6,149.9,152.7,152.8,169.5,
173.5

Synthesis Example 5 [2-anilino-3-methyl-6- (Nn-hexyl-N- (5'-n- (4 "-
Synthesis of (hydroxy) butoxycarbonyl) pentylamino) fluorane] 2-anilino-3-methyl-6- (Nn-hexyl-
880 mg of N- (5'-ethoxycarbonyl) pentylamino) fluorane was dissolved in 5 ml of 1,4-butanediol and 0.5 ml of concentrated sulfuric acid was added. The mixture was stirred at 65 ° C. for 10 hours, added to 100 ml of ice water, and extracted with ethyl acetate. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, and the concentrated residue was separated and purified by silica gel column chromatography to give 2-
Anilino-3-methyl-6- (Nn-hexyl-N-
600 mg of (5'-n- (4 "-hydroxy) butoxycarbonyl) pentylamino) fluorane (yield 64
%) Was obtained. The molecular weight by mass spectrometry was 690. <Infrared spectrum (cm ^-1 )> 3379,1731,1631,1516,
1495,1413 < ¹ H-nuclear magnetic resonance spectrum (δ ppm)> 0.90 (3H,
t, J = 7), 1.37-1.72 (18H, m), 2.21 (3H, s), 2.31 (2H, t, J = 7),
3.27 (4H, m), 3.62 (2H, t, J = 7), 4.08 (2H, t, J = 7), 5.39 (1H,
s), 6.37 (1H, dd, J = 3,8), 6.46 (1H, d, J = 3), 6.55-6.58 (4H,
m), 6.71 (1H, t, J = 7), 7.05 (2H, t, J = 8), 7.14 (1H, s), 7.20 (1
H, d, J = 8), 7.54 (1H, t, J = 7), 7.63 (1H, t, J = 7), 7.92 (1H, d, J
= 7) < ¹³ C-nuclear magnetic resonance spectrum (δ ppm)> 13.9,17.
8,22.5,24.6,24.9,26.4,26.5,26.7,26.9,28.8,31.5,34.
0,50.6,50.9,61.9,64.0,84.2,97.4,104.5,108.1,114.7,
117.2,118.6,119.0,120.8,123.7,124.6,126.8,128.6,12
8.9,129.3,134.6,134.8,135.8,144.7,147.6,149.7,152.
8,152.9,169.5,173.5

(Synthesis Example 6) [Synthesis of 2-anilino-3-methyl-6- (N-ethyl-N- (10'-n- (4 "-hydroxy) butoxycarbonyl) decylamino) fluorane] 2-anilino -3-Methyl-6- (N-ethyl-N-
1.8 g of (10'-ethoxycarbonyl) decylamino) fluorane was dissolved in 18 ml of 1,4-butanediol and 0.3 ml of concentrated sulfuric acid was added. 70 of this mixture
After stirring at 0 ° C for 6 hours, the mixture was added to 100 ml of ice water and extracted with ethyl acetate. The extract was washed with water and dried over magnesium sulfate. The solvent was distilled off, and the concentrated residue was separated and purified by silica gel column chromatography to give 2-anilino-3-methyl-6- (N-ethyl-N- (10'-n
1.51 g (yield 79%) of-(4 "-hydroxy) butoxycarbonyl) decylamino) fluorane was obtained. The molecular weight by mass spectrometry was 704. <Infrared spectrum (cm- ¹ )> 3480,3379,1756 , 1731,
1600,1517,1495,1413 < ¹ H-nuclear magnetic resonance spectrum (δ ppm)> 1.16 (3H,
t, J = 7), 1.31-1.73 (20H, m), 2.22 (3H, s), 2.30 (2H, t, J = 7),
3.26 (2H, t, J = 7), 3.36 (2H, q, J = 7), 3.63 (2H, t, J = 7), 4.09
(2H, t, J = 7), 5.45 (1H, s), 6.37 (1H, dd, J = 3,8), 6.46 (1H, d,
J = 3), 6.55-6.58 (4H, m), 6.71 (1H, t, J = 7), 7.05 (2H, t, J =
8), 7.13 (1H, s), 7.21 (1H, d, J = 8), 7.54 (1H, t, J = 7), 7.63 (1
H, t, J = 7), 7.93 (1H, d, J = 7) < ¹³ C-nuclear magnetic resonance spectrum (δ ppm)> 12.0,17.
7,24.7,24.8,26.8,27.2,28.8,28.8,28.9,29.1,29.2,29.
3,34.0,44.7,50.1,61.8,63.9,84.2,97.3,104.4,108.0,1
14.7,117.1,118.5,118.9,120.8,123.6,124.6,126.8,12
8.6,128.8,129.2,134.5,134.8,135.8,144.7,147.6,149.
5,152.8,152.9,169.7,173.7

<Production of Pressure Sensitive Recording Material> [Example 1] 70 parts of acrylic acid and 1 of styrenesulfonic acid
Copolymer consisting of 5 parts of methacrylic hydroxylethyl 15 parts, 30 parts of anionic water-soluble polymer, 1 part of deionized water
15 parts was added and diluted with stirring. 10 more urea
And 1.4 parts of resorcin are dispersed and dissolved, and 10% caustic soda is prepared.
The aqueous solution of Da was carefully added dropwise to adjust the pH to 3.4. On the other hand, a high-boiling solvent containing phenylxylylethane as a main component (Hisole SAS manufactured by Nisseki Chemical) and a high-boiling solvent containing diisopropylnaphthalene as a main component (KMC manufactured by Kureha Chemical)
-113) was mixed at a ratio of 1: 1 and 170 parts of this mixed solvent was mixed with 2-anilino-3-methyl-6- (N-
Ethyl-N- (3'-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane (6.7 parts) was mixed and dissolved, and this solution was used as an aqueous solution containing the copolymer anionic water-soluble mixture prepared above. The resulting mixture was mixed with a homomixer (manufactured by Tokushu Kiki Co., Ltd.) under strong stirring at 9000 rpm to give an emulsion dispersion having an average particle diameter of 3.9 μm.
26 parts of 7% aqueous formaldehyde solution was added and the temperature was raised to 55
The temperature was raised to 0 ° C. and the mixture was allowed to cool for 2 hours to obtain a color developer-containing microcapsule dispersion (concentration 47%). The particle size of the microcapsules was 4.0μ. This microcapsule dispersion, a copolymer latex, and a wheat starch (average particle size: 17 μ) that is a capsule protector were mixed in a ratio of 100: 38: 12 parts, thoroughly mixed with a lab mixer and mixed with water to give a solid. A 20% min paint was prepared. 40g / m of this paint
An upper sheet for pressure-sensitive recording was obtained by coating the upper sheet of No. ^{2 with} a Mayer bar to a coating amount of 4.0 g / m ² and drying.

[Example 2] 2-anilino-3-methyl-6- (N-ethyl-N- (3'-) as a fluorane dye
2-anilino-3-methyl-6- (N-ethyl-N- (3′-) obtained in Synthesis Example 2 instead of n- (4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane
An upper paper for pressure-sensitive recording was obtained in the same manner as in Example 1 except that n- (8 ″ -hydroxy) octoxycarbonyl) propylamino) fluorane was used.

[Example 3] 2-anilino-3-methyl-6- (N-ethyl-N- (3'- as a fluorane dye
2-anilino-3-methyl-6- (N-cyclohexyl-N-obtained in Synthesis Example 3 instead of n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane
An upper paper for pressure-sensitive recording was obtained in the same manner as in Example 1 except that (5′-n- (4 ″ -hydroxy) butoxycarbonyl) pentylamino) fluorane was used.

[Example 4] 2-anilino-3-methyl-6- (N-ethyl-N- (3'- as a fluorane dye
2-anilino-3-methyl-6- (Ni-butyl-N- (5) obtained in Synthesis Example 4 instead of n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane
An upper paper for pressure-sensitive recording was obtained in the same manner as in Example 1 except that'-n- (4 "-hydroxy) butoxycarbonyl) pentylamino) fluorane was used.

[Example 5] 2-anilino-3-methyl-6- (N-ethyl-N- (3'- as a fluorane dye
2-anilino-3-methyl-6- (N-ethyl-N- (3′-) obtained in Synthesis Example 5 instead of n- (4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane
An upper paper for pressure-sensitive recording was obtained in the same manner as in Example 1 except that n- (8 ″ -hydroxy) octoxycarbonyl) propylamino) fluorane was used.

[Example 6] 2-anilino-3-methyl-6- (N-ethyl-N- (3'- as a fluorane dye
2-anilino-3-methyl-6- (N-ethyl-N- (10 ′) obtained in Synthesis Example 6 instead of n- (4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane
An upper paper for pressure-sensitive recording was obtained in the same manner as in Example 1 except that -n- (4 "-hydroxy) butoxycarbonyl) decylamino) fluorane was used.

[Example 7] 2-anilino-3-methyl-6- (N-ethyl-N- (3'- as a fluorane dye
n- (4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane 3.3 parts and 2-anilino-3-methyl-6- (N-ethyl-N-isopentylamino) fluorane 3.3 parts were used. In the same manner as in Example 1, an upper sheet for pressure-sensitive recording was obtained.

[Comparative Example 1] 2-anilino-3-methyl-6- (N-ethyl-N- (3'- as a fluorane dye
Same as Example 1 except that 2-anilino-3-methyl-6- (N-ethyl-N-isopentylamino) fluorane was used instead of n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane. An upper sheet for pressure-sensitive recording was obtained by various methods.

[Comparative Example 2] 2-anilino-3-methyl-6- (N-ethyl-N- (3'-) as a fluorane dye
2-anilino-3-methyl-6- (N-ethyl-N- (3'-ethoxycarbonyl) propylamino) fluorane was used in place of n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane. In the same manner as in Example 1, a pressure-sensitive recording upper sheet was obtained.

<Production of Thermal Recording Material> [Example 8] Liquids A and B having the following compositions were prepared,
It was ground with a sand grinder until the average particle size became 1 micron. Liquid A (developer dispersion liquid) Bisphenol A 6.0 parts 10% aqueous polyvinyl alcohol solution 18.8 parts Water 11.2 parts Liquid B (dye dispersion liquid) 2-anilino-3-methyl obtained in Synthesis Example 1 -6- (N-ethyl-N- (3'-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluoran 2.0 parts 10% polyvinyl alcohol aqueous solution 4.6 parts water 2.6 parts The above dispersion and kaolin clay were blended in the following proportions to give a coating liquid: A liquid 36.0 parts B liquid 9.2 parts Kaolin clay (50% dispersion liquid) 12.0 parts This coating liquid 50 g / 6.0 g on one side of m ² base paper
/ M ² was applied and dried, and this sheet was treated with a super calender so as to have a smoothness of 500 to 600 seconds to obtain a heat-sensitive recording paper.

[Example 9] 2-anilino-3-methyl-6- (N-ethyl-N- (3'- as a fluoran dye
2-anilino-3-methyl-6- (N-ethyl-N- (3′-) obtained in Synthesis Example 2 instead of n- (4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane
A thermal recording paper was obtained in the same manner as in Example 8 except that n- (8 ″ -hydroxy) octoxycarbonyl) propylamino) fluorane was used.

[Example 10] 2-as a fluoran dye
Anilino-3-methyl-6- (N-ethyl-N- (3 '
2-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane was obtained in place of 2-
Anilino-3-methyl-6- (N-cyclohexyl-N
A thermal recording paper was obtained in the same manner as in Example 8 except that-(5'-n- (4 "-hydroxy) butoxycarbonyl) pentylamino) fluorane was used.

[Example 11] 2-as a fluoran dye
Anilino-3-methyl-6- (N-ethyl-N- (3 '
2-n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane was obtained in place of 2-
Anilino-3-methyl-6- (N-i-butyl-N-
A thermal recording paper was obtained in the same manner as in Example 8 except that (5′-n- (4 ″ -hydroxy) butoxycarbonyl) pentylamino) fluorane was used.

[Example 12] 2-as a fluoran dye
Anilino-3-methyl-6- (N-ethyl-N- (3 '
2-n- (4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane was obtained in place of 2-
Anilino-3-methyl-6- (N-ethyl-N- (3 '
A thermal recording paper was obtained in the same manner as in Example 8 except that -n- (8 "-hydroxy) octoxycarbonyl) propylamino) fluorane was used.

[Example 13] 2-as a fluoran dye
Anilino-3-methyl-6- (N-ethyl-N- (3 '
2-n- (4 ″ -hydroxy) butoxycarbonyl) propylamino) fluorane was obtained in place of 2-
Anilino-3-methyl-6- (N-ethyl-N- (10
A thermosensitive recording paper was obtained in the same manner as in Example 8 except that'-n- (4 "-hydroxy) butoxycarbonyl) decylamino) fluorane was used.

[Example 14] 2-as a fluoran dye
Anilino-3-methyl-6- (N-ethyl-N- (3 '
-N- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane 3.3 parts and 2-anilino-3-
Methyl-6- (N-ethyl-N-isopentylamino)
A thermosensitive recording paper was obtained in the same manner as in Example 8 except that 3.3 parts of fluoran was used.

[Comparative Example 3] 2-anilino-3-methyl-6- (N-ethyl-N- (3'- as a fluoran dye
Same as Example 7 except that 2-anilino-3-methyl-6- (N-ethyl-N-isopentylamino) fluorane was used instead of n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane. A thermal recording paper was obtained by various methods.

Comparative Example 4 2-anilino-3-methyl-6- (N-ethyl-N- (3'- as a fluorane dye
2-anilino-3-methyl-6- (N-ethyl-N- (3'-ethoxycarbonyl) propylamino) fluorane was used in place of n- (4 "-hydroxy) butoxycarbonyl) propylamino) fluorane. A thermal recording paper was obtained in the same manner as in Example 7.

The pressure-sensitive recording paper and the heat-sensitive recording paper produced in the above Examples 1 to 12 and Comparative Examples 1 to 4 were color-developed by the following methods, and the plasticizer resistance and oil resistance tests were conducted. The results are shown in Tables 1 and 2.

<Testing Method for Pressure Sensitive Recording Paper> Coloring Method: The prepared upper paper is the lower paper NW40 manufactured by Nippon Paper Industries.
In combination with B, the entire surface was colored with a calendar. Plasticizer resistance test method: Colored paper was sandwiched between vinyl chloride sheets containing a plasticizer, left for 24 hours at a temperature of 60 ° C. and a humidity of 90%, and the residual image density was measured with a Hunter whiteness meter (manufactured by Toyo Seiki). .

[0068]

[Table 1]

<Test Method for Thermal Recording Paper> Coloring Method: Facsimile Printer (KB-4800,
Full color was developed by Toshiba. Oil resistance test method: The coloring paper was immersed in salad oil for 1 hour, and the residual image density was measured with a Macbeth densitometer. Test method for plasticizer resistance: Colored paper is sandwiched between vinyl chloride sheets containing plasticizer (Hilap KMA manufactured by Mitsui Toatsu),
After leaving at a temperature of 40 ° C. for 24 hours, the residual image density was measured with a Macbeth densitometer.

[0070]

[Table 2]

From the above results, in the pressure-sensitive recording material and the heat-sensitive recording material using the fluorane compound of the present invention as the electron-donating color former, the plasticizer resistance and oil resistance of the color image are higher than those of the conventional fluoran compound. You can see that it has improved significantly.

[0072]

The fluorane compound of the present invention has a high polarity because it has an alcohol functional group at the end of the ester group of the side chain, and the compatibility of the chromophore with plasticizers and oils of conventional fluorane compounds and esters is high. It is much lower than that of Fluoran. Therefore, by using the fluorane compound of the present invention as a color former, it was possible to dramatically improve the plasticizer resistance and oil resistance of a color image in a pressure-sensitive recording material or a heat-sensitive recording material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B41M 5/145 5/30 C09B 11/28 // C07B 61/00 300 B41M 5/18 105 (72 ) Inventor Hiroaki Umeda No. 1 Kujoda Kujo, Nakoso-cho, Iwaki-shi, Fukushima Nihon Paper Co., Ltd. Nakoso Mill

Claims (4)

[Claims] 1. A novel fluorane compound represented by the following general formula (1): Embedded image [In the formula, R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and (CH ₂ ) n has n of 1 to 20. Represents an integer methylene chain of Further, (CH ₂ ) m represents a methylene chain in which m is an integer from 1 to 20, and R ² represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ³ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or an acyl group, and R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group, a nitro group, an amino group, a substituted amino group or an acyl group. ] 2. A novel fluoran represented by the general formula (1), which comprises reacting a compound represented by the following general formula (2) with a compound represented by the following general formula (3) in the presence of an acid catalyst. Method for producing compound. Embedded image [In the formula (2), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group, and (CH ₂ ) n represents n. 1
Represents an methylene chain of an integer of up to 20. R ² represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ³ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or an acyl group. R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group, a nitro group, an amino group, a substituted amino group or an acyl group, and R ₅ represents a lower alkyl group having 1 to 4 carbon atoms. Further, (CH ₂ ) m in the formula (3) represents a methylene chain in which m is an integer of 1 to 20. ] 3. A pressure-sensitive recording material comprising a color-forming reaction between the fluorane compound according to claim 1 and an electron-accepting compound. 4. A thermosensitive recording medium comprising a color-forming reaction between the fluorane compound according to claim 1 and an electron-accepting compound.