FI69859C - KROMOGEN FOERENING LAEMPLIG FOER KOPIERING OCH REGISTRERING - Google Patents

Description

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JgpTg '11> UTLÄGGNINGSSKRIFT 6985 9 ® c (45) Patent granted l Onlyn f e '11 -. '' R 1 - £ <-> '.- η ~ (51) KvikVintCi * C 09 B'57 / 00B *. 1 "m 5/12, (ol) Kv.lk. /Int.CI. C 07 D * 493/1 0 (21) Patent application - Patentansökning 782 * 420 (22) Application date Ansökningsdag 07.08.78 (23) Starting date - Giltighetsdag 07-08.78 (41) Become public— · Blivit offcntlig 09.02.79

National Board of Patents and Registration of Finland Date of display and moonshine. - 3112 85

Patents and registries' 'Ansökan utlagd och utl.skriften publicerad J' (32) (33) (31) Privilege requested — Begärd priority 08.08.77 Japan-Japan (JP) 95270/77 (71) Yamada Chemical Co., Ltd ., 1- * 4 Kami Toba-Kamichosh i cho, Minami-ku, Kyoto-shi, Kyoto-fu, Japan-Japan (JP) (72) Haj ime Kawai, Kyoto-fu, Katsuhiko Tsunemitsu, Kyoto-fu,

Yoshiharu Fujino, Kyoto-fu, Yoji Shimizu, Kyoto-fu,

Japan i-Japan (JP) (7 * 0 Berggren Oy Ab (5 * 0 Color-generating compound suitable for copying or storage - Chromogen-free lamps for copying and recording

The present invention relates to novel color-generating fluorane compounds and their use as color-forming agents in pressure- and heat-sensitive copying (or recording) sheets.

The novel color-generating compounds according to the invention have the following general formula: * 1 X. N * 1 \ I VV 111 ° \ "3„ C = 0 i O 7 "

V J

having an alkyl group of 5 to 8 carbon atoms; R 2 is an alkyl group of 1 to 8 carbon atoms, a benzyl group, a cyclohexyl group or a phenyl group having or lacking a lower alkyl group of 1 to 4 carbon atoms; R 1 is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms or a 2,6859 benzyl group; is a hydrogen atom; X 2 is a hydrogen atom or a lower alkyl group of 1 to 2 carbon atoms; is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms, a halogen atom or a trifluoromethyl group; and n is an integer 1; provided that R 1 is not an amyl group when R 2 is an alkyl group of 1 to 5 carbon atoms, X 1 and X 2 are both hydrogen atoms, X 1 is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms or a halogen atom.

As such, the fluorane compounds of general formula (I) are essentially colorless. However, they have the property that when they are in direct contact with electron-accepting substances such as organic acids, acid clay, activated clay, phenol formalin resin, metal salts of aromatic carboxylic acids and bis-phenol A, the lactone rings and produce dark or green colors. These compounds are therefore very suitable color-forming agents in pressure-sensitive and heat-sensitive copying sheets used in the electrophotographic production of copies.

Known color-generating compounds having a structure similar to that of formula (I) and capable of producing colors from black to dark green are those shown below: 3-diethylamino-6-methyl-7-anilinofluorane: t ° r '(Belgian patent publication n). No. 744 705) 3 69859 3- (N-ethyl-p-tolyl) -amino-6-methyl-7-anilinofluorane: Japanese Patent Application No. 29180/1976) 3- ( N-cyclohexyl-N-methyl) -amino-6-methyl-7-anilinofluorane: CH3 (Japanese Patent Publication No. 23204/1976).

It has now been found that the color-generating compounds of the invention are clearly superior to these known compounds in all or some of the following points a to d.

a. Spontaneous color formation in dilute acidic aqueous solutions.

b. Solubility in organic solvents.

c. Spontaneous color-forming ability that occurs after addition to heat-sensitive sheets.

d. Thermal sensitivity that occurs after addition to heat-sensitive sheets.

These characteristic features a to d are very significant and important properties of the color-generating compounds so that they can in practice act as color-forming agents in pressure-sensitive and heat-sensitive copying sheets.

4 69859

According to one embodiment of the invention, the most useful color-generating compounds of formula (I) according to the invention are those in which R 1 is selected from the group consisting of alkyl radicals having 5 to 3 carbon atoms, R 2 is selected from the group consisting of alkyl radicals having 1 to 8 carbon atoms, R 1 is a hydrogen atom, X 1 is a hydrogen atom, x 2 is a methyl or ethyl radical and X 1 is selected from the group consisting of a hydrogen atom and lower alkyl radicals having 1 to 4 carbon atoms, and which meet the above requirements, except that X2 is a hydrogen atom and X3 is a trifluoroethyl radical.

It has been found that the compounds belonging to these groups are capable of producing clear black colors and satisfactorily satisfy all the requirements of (a) to (d) above. Typical compounds in these classes are 3- (R-ethyl-N-isoamyl) -amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-hexyl) -amino-6-methyl-7-anilyl- nofluorane, 3- (N-di-n-octyl) amino-6-methyl-7-anilinofluorane and 3- (N-ethyl-Hn-amyl) amino-7- (1H-trifluoromethylphenyl) aminofluorane.

The compounds of formula (I) of the invention may be prepared synthetically by the general method described below.

First, the m-aminophenol derivative (II) and the phthalic anhydride (III) are condensed to prepare a 2- (4'-amino-2'-hydroxybenzoyl) -benzoic acid derivative (IV) as schematically shown below. / <“/ -Λ

/ - \ 0) + [OJ

K2 '----- / \ / R \ _ / ^ c0 “2 -'> - '

(H> (III) (IV) COOH

(wherein R 1 and R 2 are as defined above).

Thereafter, the 2- (4'-amino-2'-hydroxybenzoyl) -benzoic acid derivative (IV) is reacted with a diphenylamine derivative (V) having the following formula: XX 69859 λ1 χ2 RQ -Ν - (3) η (V) Κ3 (wherein Χ ^, Χ2, Χ3 and Rj are as defined above and R is selected from the group consisting of hydrogen, lower alkyl radicals having 1 to 4 carbon atoms) in the presence of a dehydration condensing agent such as sulfuric acid or polyphosphoric acid in the range of -10 to + 100 ° C with a reaction time of a few minutes to a few hours. The fluorane compound of formula (I) is obtained in the form of colorless crystals by pouring the reaction product into ice water, separating the precipitate from this ice water, treating the precipitate with alkali, separating the treated precipitate, filtering, drying it and recrystallizing it from an organic solvent.

Although the colors formed by the fluorane derivatives of formula (I) upon contact with the electron accepting agents are from black to dark green, the dark colors formed by the fluorane derivatives can be altered by mixing the fluorane derivatives with chromogens capable of forming other colors. Otherwise, other color shades formed by the use of certain color-generating compounds may be altered by mixing these color-generating compounds with the fluorane derivatives of formula (I). Furthermore, the light fastness of fluorane derivatives can be improved by mixing them with, for example, an ultraviolet absorbing agent.

The effective use of these color-generating compounds in pressure-sensitive copying sheets can be accomplished by following any of the methods described in U.S. Patent Nos. 2,548 3G6, 2,800,458, and 2,969,370. is described, for example, in Japanese Patent Publication Nos. 6040/1955, 4160-1968 and 14039/1970.

These color-generating agents are very suitable for use as weight-sensitive copying agents. These substances are used, for example, in sheets in the form of a double sheet and containing at least one color-forming compound of the formula (I) or a similar compound in microcapsules which break under pressure and dissolve in an organic solvent and an electron acceptor. When this color-forming compound is brought into contact with an electron-accepting substance under pressure, color is formed at the points to which the pressure is applied. Due to the isolation from the electron accepting substance, the color-forming compound contained in the pressure-sensitive substance does not become active. Generally, this isolation is accomplished by adding a color-forming compound to the structure in the form of a foam, sponge, or honeycomb. Most preferably, the color-forming compound is added in the form of microcapsules.

When the color-forming compound of formula (I) is dissolved in an organic solvent, it is microencapsulated and can be used immediately in the preparation of pressure-sensitive sheets. A colored pattern is obtained when these capsules are broken by compression, for example, with a pen, and thus a solution of the color-forming compound enters an adjacent sheet coated with a substrate capable of acting as an electron acceptor. Thus, a dye is formed which produces a color that is absorbed in the visible zone of the electromagnetic spectrum.

Several different methods for making microcapsules have been known in the art for a long time. Such known methods are described, for example, in U.S. Patent Nos. 2,183,053, 2,800,457, 2,800,458, 3,265,630, 2,964,331, 3,418,656, 3,418,250, 3,016 3C8, 3,424 to S27, 3,427. 250, 3,405,071, 3,171,878 and 2,797,201. Other methods are described in British Patent No. 989,264 and especially in British Patent No. 1,156,725. These and other available methods are very suitable for encapsulating the color-forming compounds of the invention.

The color-forming compounds of the invention are preferably dissolved in organic solvents upon encapsulation. It is preferred that these solvents be non-volatile. Examples are polyhalogenated diphenyls such as trichlorodiphenyl and mixtures thereof, liquid paraffins, tricresyl phosphate, di-n-butyl phthalate, dioctyl phthalate, trichlorobenzene, triphoxybenzene, nitrobenzene, carbonyl ether, n-ethylphosphate, such as ethyl phosphate; with chlorinated or hydrogenated condensed aromatic hydrocarbons. The walls of the capsules are preferably obtained as described in U.S. Patent No. 2,300,457 by uniformly adding an encapsulating agent formed by gelatin to the surface of the drops of the solution of the color-forming compound.

Alternatively, these capsules can be preferably obtained by polycondensing an aminoplast or a modified plastic as disclosed in British Patent Publication Nos. 989,254 and 1,156,725.

The preferred arrangement is such that the microencapsulated color-forming compound is applied to the reverse side of the transfer sheet and the electron acceptor to the front side of the sheet.

The microcapsules may be in the lower coating of the upper sheet and the pigment reactor or electron accepting agent and coupling agent may be in the upper coating of the lower sheet. These components can also be used in pulp. These methods are called "chemical transfer methods".

Another arrangement is composite papers. In this arrangement, the microcapsules containing the color-forming compound and the pigment reactor are inside or on the same sheet or as one or more separate coatings or among the pulp.

Such pressure sensitive copying agents are discussed, for example, in U.S. Patent Nos. 3,516,846, 2,730,457, 2,932,532, 3,427,180, 3,418,250 and 3,418,654. Other systems are disclosed in British Patent Nos. 1,042,597, 1,042. 598, 1,042,596, 1,042,599, 1,053,935 and 1,517,650. Microcapsules containing color-forming compounds of formula (I) are suitable for use in all of these systems.

These capsules are preferably attached to their carriers with suitable adhesives. Since paper is a preferred raw material for such carriers, any paper coating agent such as gum arabic, polyvinyl alcohol, hydroxymethylcellulose, casein, methylcellulose and dextrin can be used as suitable adhesives.

69859 These new fluorane compounds can also be used as color-forming compounds in heat-reactive amplifiers formed of at least the following ingredients: a support part, a binder, a color-forming compound and an electron-accepting agent. The heat-responsive copying system comprises a heat-sensitive recording medium, a copying medium and paper. Such a system is used to store data on computers, remote recorders or measuring devices. Recording can also be accomplished with a hand-heated pen. Another way to achieve recording is to use a laser beam. In another possible arrangement of the heat-reactive recording medium, the color-forming compound may be dissolved or dispersed in the binder layer, and the color-generating agent and the electron-accepting agent may be dissolved or dispersed in the binder in the second layer. Another possibility is that the color-forming compound and the color-developing agent are dispersed in the same layer. As a result of the heat, the binder softens in the form of a certain pattern in a certain area and the corresponding point becomes discolored. This is because the color-forming compound comes into contact with the electron acceptor at the points where heat has been added.

The color developing agent is the same electron accepting agent used in pressure sensitive paper. For practical reasons, the color developing agent must be solid at normal room temperature and must melt or soften at temperatures above 50 ° C. Examples of products that meet these requirements are phenolic resins or phenolic compounds such as 4-tert-butylphenol and 4-phenylphenol, 4-hydroxydiphenyl oxide, α-naphthol, 4-hydroxy-benzoic acid methyl ester, β-naphthol, 4-hydroxyacetophenone , 2,2'-dihydroxy-diphenyl, 4,4'-isopropylidene-diphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 4,4'-bis- (hydroxyphenyl.) -Valer ianic acid, hydroquinone, pyrogallol, fluoroglycine, p-, m- or o-hydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, boric acid and aliphatic dicarboxylic acids such as tartaric acid, oxalic acid and malic acid, maleic acid, maleic acid, maleic acid

Preferably, a binder that is soluble or capable of forming a film is used. This binder should be water soluble. This is because fluorane compounds and color-developing agents are insoluble in water. It must be possible to disperse this binder 69859 at ordinary room temperature so that the color-forming compound and the color developer are immobilized. Thus, both of these reactive components are present simultaneously in the uncombined state in the binder. As the heat is added, the binder softens or melts and brings the color-forming compound into contact with the color-developing agent to form the color. In this case, the color-developing agent may be any of the above-mentioned co-reactants, such as a clay, a phenolic resin or another phenolic compound.

A binder that is soluble in water or at least swells in water is a hydrophilic polymer. Examples of such hydrophilic polymers are polyvinyl alcohol, polyacrylic acid, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, polyacrylamide, polyvinylpyrrolidone, gelatin and starch.

Conventional heat-reactive recording materials in which the color-forming compounds of the invention can be used are described in German Patent 2,228,581, French Patent 1,524,826, Swiss Patent 407,185, German Patent Application No. 16,1104 and Swiss Patent Application No. 2,110,854. 444 196 and 444 197.

Examples of Synthetic Preparation Methods 1. 3- (N-Methyl-Nn-amyl) -amino-6-methyl-7-anilinofluorane: 34.1 g of 2- [2'-hydroxy-4 '- (are dissolved in 100 ml of concentrated sulfuric acid). N-methyl-Nn-amyl) aminobenzoyl / benzoic acid and 21.3 g of 2-methyl-4-methoxy-diphenylamine at 30 ° C and then stirred at room temperature for 48 hours. After completion of the reaction, the reaction product is poured into 1000 g of ice water, and the solid is then precipitated and filtered off. The solid is disintegrated in water, made alkaline with sodium hydroxide solution and filtered and dried. The dried product is then recrystallized from n-butyl alcohol to give 34.3 g of a white solid, m.p. 173.5-176.5 ° C, which was found to be 3- (N-methyl-N-n-amyl) -amino-6-methyl-7-anilinofluorane (structural formula shown below). The major residues of this compound in 95% acetic acid are 452 nm and 584 nm. The toluene solution of this compound is colorless and upon contact with the silica gel immediately forms a very dark purple color.

69859 10 CH3 \ n ° Y ^ Y CHs CHt-CHo-CH0-CHo-CH0 ^ O I O / \ 3 2 2 2 2 2. Synthesis of 3- (N-ethyl-N-n-amyl) -amino-6-methyl-7-anilinofluorane;

By repeating the synthetic preparation method of item 1 using 2- [2'-hydroxy-4 '- (N-ethyl-N-amyl) -aminobenzoyl] -benzoic acid, 2- [2'-hydroxy-4' - (N-methyl-Nn- instead of amyl) aminobenzoyl / benzoic acid 30.5 g of a white solid are obtained, m.p. 181 to 183.5 ° C. This compound was found to be 3- (N-ethyl-N-n-amyl) -amino-6-methyl-7-anilinofluorane (structural formula shown below). The λmax of this compound in 95% acetic acid was 454 nm and 587 nm. The toluene solution of this compound is colorless and on contact with the silica gel immediately forms a dark purple color.

CH3 ~ CH2 \ CH3

CH3-CH2-CH2-CH2-CH2 / O I O / -V

= o

(OJ

3. Synthesis of 3- (N-ethyl-N-n-amyl) -amino-6-methyl-7- (N-methyl-N-phenyl) -aminofluorane:

By repeating the synthetic treatment described in 1 using 2- [2'-hydroxy-4 '- (N-ethyl-Nn-amyl) -aminobenzoyl] -benzoic acid 2- [2'-hydroxy-4- (N-methyl-Nn-amyl) ) -aminobenzoyl / benzoic acid and 4-methoxy-N-methyl-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine, a white solid was obtained, m.p. 121-123 ° C, which was found to be 3- (N-ethyl-N-n-amyl) -amino-6-methyl-7- (N-methyl-N-phenylamino) -fluorane (structural formula shown below). A solution of this compound in 95% acetic acid is colorless and immediately forms a dark red color upon contact with silica gel.

1 1 69859 CH 3 -CH 2 wCH * = 0 CH 3

Oj 4. Synthesis of 3- (N-ethyl-N-n-amyl) amino-7- (N-m-trifluoromethylphenyl) aminofluorane:

Repeating the procedure of 1 using 2- [2'-hydroxy-4 '- (N-ethyl-Nn-amyl) -aminobenzoyl] -benzoic acid 2- / 2'-hydroxy-4' - (N-methyl-Nn-amyl) ) -aminobenzoyl-benzoic acid and 4-methoxy-3'-trifluoromethyl-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine, a white solid is obtained, m.p. 118-121 ° C. This compound was found to be 3- (N-ethyl-H-n-amyl) -amino-7- (N-m-trifluoromethyl) -aminofluorane (structural formula shown below). The λ qt n „max in D ° acetic acid of this compound was 437 nm and 504 nm. The toluene solution of this compound is colorless and immediately forms a dark purple color on contact with silica.

ch3-ch, -ch2-ch, -ch2 ^ (J U / - \ \ \

X = O XCF

(OJ 3 69859 12 6 * Synthetic preparation of 3- (N-ethyl-N-iso-amyl) -amino-6-methyl-7-anilinofluorane:

When repeating the synthesis described in 1 using 2- [2'-hydroxy-4- (N-ethyl-N-isoamyl) -aminobenzoyl] -benzoic acid, 2- [2'-hydroxy-4 '- (N-ethyl-Nn- amyl) -aminobenzoyl / benzoic acid to give a white solid, m.p. 164-166.5 ° C- This compound is 3- (N-ethyl-H-isoamyl) -amino-6-methyl-7-anilinofluorane (structural formula shown below). The λ in 95% acetic acid of this compound is 454 nm and 533 nm. The toluene solution of this compound is colorless and upon contact with the silica gel an immediate dark purple color forms.

CH3. CH3-α, 2 \ N C1'3 c "-c" 2-c "2 / \ Oj 1OJ // Λ / X Jc = o 7. 3- (N-isoamyl-Nn-hexyl) amino- Synthesis of 6-methyl-7-anilinofluorane;

When repeating the synthetic treatment according to 1 using 2- (2 * -hydroxy-4 '- [U-isoamyl-Nn-hexyl) aminobenzoyl] -benzoic acid, 2- [2'-hydroxy-4' - (N- instead of methyl-N (amyl) -aminobenzoyl) -benzoic acid, a white solid is obtained, m.p. 102-105 ° C. This compound is 3- (N-iso-amyl-N-n-hexyl) -amino-6-methyl-7-anilinofluorane (structural formula shown below). The λ 95 ° o acetic acid of this compound has 455 nm and 589 nm. The toluene solution of this compound is colorless and immediately forms a purple color upon contact with the silica gel.

13 C »69859

CH-CH, -CH, X 0___ CH

CH3 2 2ΧΝ-τ ^ Χ / 0νγ ^ Ν ^ 'CH3 ch2-ch2-ch ^ / ~ \ CH2-CH2-CH2 - (O) toi = ° Ö. Synthetic preparation of 3- (N-10-amyl-N-n-hexyl) -amino-7-anilinofluorane:

When repeating the synthesis described in step 1 using 2- [2'-hydroxy-4 '- (N-isoamyl-Nn-hexyl) aminobenzoyl] benzoic acid, 2- [2'-hydroxy-4' - (N-methyl- Instead of Nn-amyl) aminobenzoyl / benzoic acid and 4-hydroxy-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine, a white solid is obtained, m.p. 145-147 ° C.

This compound is 3- (N-iso-amyl-N-n-hexyl) -amino-7-anilinofluorane (structural formula shown below). 95% acetic acid in this compound has 446 nm and 604 nm. The toluene solution of this compound is colorless and a dark green color immediately forms on contact with the silica gel.

CH, 3 \ CH-CH2-CH2 ch2-ch2-ch '“ΊρΤ Ύθ) ^

Synthetic preparation of 3- (N-isoamyl-N-p-tolyl) -amino-6-methyl-7-anilinofluorane: Ih2-ch2-ch3 NH-yOy "oj 9.

Repeating the synthesis of 1 using 2- [2'-hydroxy-4 '- (N-isoamyl-Np-tolyl) aminobenzoyl) benzoic acid 2- [2'-hydroxy-4' - (H-methyl-Nn -amyl) -aminobenzoyl / benzoic acid gives a white solid, m.p. 226 to 227.5 ° C. This compound is 3- (N-iso-amyl-N-p-tolyl) -amino-6-methyl-7-anilinofluorane (structural formula shown below). The Amakg of this compound in 95% acetic acid is 461 nm and 597 nm. The toluene solution of this compound is colorless and immediately on contact with the silica gel forms a black color.

14 CH3 v 69859 nch-ch;? - ch9 (of 10. Synthetic preparation of 3- (N-isoamyl-N-cyclohexyl) -amino-6-methyl-7-anilino-fluorane:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-isoamyl-N-cyclohexyl) aminobenzoyl] -benzoic acid, 2- / 2'-hydroxy-4' - (N-methyl-Nn- instead of amyl) aminobenzoyl / benzoic acid a white solid is obtained, m.p. 183-135 ° C. This compound is 3- (N-iso-amyl-N-cyclohexyl) -amino-6-methyl-7-anilinofluorane (structural formula shown below). 95% acetic acid in this compound has 458 nm and 593 nm. The toluene solution of this compound is colorless and upon contact with the silica gel an immediate dark purple color forms.

CH0 3 \

CH-CH9-CH0 λ _ CH

Synthetic preparation of 3- [3 /] s / V 3 (Τ '° 11 · 3- (N-isoamyl-N-benzyl) -amino-6-methyl-7-anilinofluorane:

Repeating the synthesis of 1 using 2- [2'-hydroxy-4 '- (N-isoamyl-N-benzyl) aminobenzoyl) benzoic acid 2- [2'-hydroxy-4- (N-methyl-Nn-amyl) ) -aminobenzoyl / benzoic acid gives a light solid, m.p. 178-130 ° C. This compound is 3- (N-iso-amyl-N-benzyl) -amino-6-methyl-7-anilinofluorane (structural formula shown below). The λ of this compound in 95% acetic acid is 178 nm and 130 nm. The toluene solution of this compound is colorless and immediately on contact with the silica gel forms a black color.

15 ch3x 6985 9 "'cH-CHj-CH x _ n / CH, ch3 / νΤοΥΎοΤ (§r η $ ίτ · ® (of 12. 3- (N-isoamyl-N-cyclohexyl) -amino-7- Synthetic preparation of anilinofluorane:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-isoamyl-N-cyclohexyl) aminobenzoyl] -benzoic acid, 2- [2'-hydroxy-4' - (N-methyl-Nn -amyl) -aminobenzoyl / benzoic acid and 4-ethoxy-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine to give a white solid, m.p. 184 to 185.5 ° C. This compound is 3- (N-isoamyl-N-cyclohexyl) amino-7-anilinofluorane (structural formula shown below). 95% acetic acid in this compound has 450 nm and 607 nm. The toluene solution of this compound is colorless and a dark green color immediately forms on contact with the silica gel.

CH.

J X

CH-CH0-CH0 / 2 2 \ / O, CH, N- [Λγ ΥΙΟ O '= O' - '13. Preparation of 3-dl-isoamylamino-6-methyl-7-anylnofluorane:

Repeating the synthesis of 1 using 2- (2'-hydroxy-4'-diisoamylaminobenzoyl) benzoic acid 2- [2'-hydroxy-4 '- (N-methyl-Nn-amyl) aminobenzoyl] instead of benzoic acid a white solid is obtained, i.e. 168-170 ° C. This compound is 3-di-isoamylamino-6-methyl-7-anilinofluorane (structural formula shown below). The λ ^ 95% acetic acid of this compound has 456 nm and 593 nm. The toluene solution of this compound is colorless and immediately after contact with silica gel forms a dark purple color.

16 ch3x 69859 ΓΗ / 2 2 \ (X ^ CII3

CH3 N - / \ / Y ^ Y J

/ [0 jo] ch3-ch-ch2-ch2 XvAvA nh_ / q \ H3 ^ - \ / c = 0 ^ Θ 14. 3- (N-Methyl-Nn-hexyl) -amino-6-methyl-7-anilinofluorane synthetic manufacture:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-methyl-Nn-hexyl) -aminobenzoyl] -benzoic acid, 2- [2'-hydroxy-4' - (N-methyl-Nn- instead of amyl) aminobenzoyl / 7-benzoic acid a white solid is obtained, i.e. 154-156 ° C. This compound is 3- (N-methyl-N-n-hexyl) -amino-6-methyl-7-aninofluorofluorane (structural formula shown below). The λΓη3 ^ ς of this compound in 95% acetic acid has 453 nm and 587 nm. The toluene solution of this compound is colorless and on contact with the silica gel immediately forms a dark purple color.

CH2-CH "-CH9 ^ O I O ._, CH - CH - CH ,, S \ W /

= O N — V

(oj 15. Synthetic preparation of 3- (N-methyl-N-n-hexyl) -amino-7-anilinofluorane:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-methyl-Nn-hexyl) -aminobenzoyl] -benzoic acid 2- / 2'-hydroxy-4' - (N-methyl-Nn-amyl) ) -aminobenzoyl / benzoic acid and 4-methoxydiphenylamine instead of 2-methyl-4-methoxydiphenylamine to give a white solid, m.p. 134-137 ° C. This compound is 3- (N-methyl-N-n-hexyl) -amino-7-anilinofluorane (structural formula shown below). The λmax of this compound in 95% acetic acid is 444 nm and 602 nm. The toluene solution of this compound is colorless and immediately on contact with the silica gel forms a dark green color.

17 ch3 \ "69859 ch2-ch2-ch2 / 1X31 tC * / —v ch2-ch2-ch3 NH - (Q) &" 16. 3- (N-ethyl-Nn-hexyl) -amino-6-methyl-7 -Synthetic preparation of anilofluorane:

Repeating the synthesis of 1 using 2- [2'-hydroxy-4 '- (N-ethyl-Nn-hexyl) aminobenzoyl] benzoic acid 2- [2'-hydroxy-4' - (N-methyl-Nn-amyl) -aminobenzoyld.7-benzoic acid gives a white solid, m.p. 145-148 ° C. This compound is 3- (N-ethyl-N-n-hexyl) -amino-6-methyl-7-anilinofluorane (structural formula shown below). The lmax of this compound in 95% acetic acid is 453 nm and 587 nm. The toluene solution of this compound is colorless and immediately on contact with the silica gel forms a dark purple color.

Synthetic preparation of 3- (N-ethyl-Nn-hexyl) -amino-7-anilinofluorane CH-j-CH0 ph CH0-CHo-CH2- / 2 2 3 X'N -'- 'C * 0 17. ;

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-ethyl-Nn-hexyl) -aminobenzoyl] -benzoic acid 2- [3'-hydroxy-4' - (N-methyl-Nn-amyl) -aminobenzoyl-7-benzoic acid and 4-methoxy-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine to give a white solid, m.p. 170-172 ° C. This compound was found to be 3- (N-ethyl-N-n-hexyl) -amino-7-anilino-fluorane (structural formula shown below). 95% acetic acid in this compound has 446 nm and 601 nm. The toluene solution of this compound is colorless and a dark green color immediately forms on contact with the silica gel.

18 εΗ3 "εΗ2χΜγ ^ γ ° γ ^ 69859 frCHa-CH // q \ ch2-ch2-ch3 I vc, 0 \ - / (oj 13. 3- (N-ethyl-Nn-hexyl) -amino-7- ( Synthetic preparation of Nm-tolyl) aminofluorane:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4'- (N-ethyl-Nn-hexyl) -aminobenzoyl] -benzoic acid 2- [2'-hydroxy-4 '- (N-methyl-Nn-amyl) ) -aminobenzoyl-benzoic acid and 4-methoxy-3'-methyl-diphenylamine instead of 2-motyl-4-methoxy-diphenylamine give a white solid, m.p. 145-147 ° C. This compound is 3- (N-ethyl-N-n-hexyl) -amino-7- (N-m-tolyl) -amino-

fluorane (structural formula shown below). A of this compound

1 max in 95% acetic acid is 446 nm and 605 nm. The toluene solution of this compound is colorless and a dark green color immediately forms on contact with the silica gel.

CHT-CH0

N - S * —v I

CH0-CH-CH2 / CH2-CH2-CH3-O (Oj 19. 3- (N-ethyl-Nn-hexyl) -amino-7- (N-methyl Synthetic preparation of -N-phenyl) -aminofuran:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-ethyl-Nn-hexyl) -aminobenzoyl] -benzoic acid 2- [21-hydroxy-4' - (N-methyl-Nn-amyl) -aminobenzoyl / benzoic acid and 4-methoxy-N-methyl-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine to give a white solid, m.p. 127-130 ° C. This compound is 3- (N-ethyl-N-n-hexyl) -amino-7- (N-methyl-N-phenyl) -aminofluorane (structural formula shown below). 95% acetic acid in this compound has 442 nm and 600 nm. The toluene solution of this compound is colorless and a dark green color immediately forms on contact with the silica gel.

19 ch3-ch2 ^ 698 5 9 ch, -ch9-ch, L 1w 1 / - \ I Vv 'Η · Λ °) CH2-CH2-CH3 ^ 0j3 V_y ^ N ^ -c = 0

Co] 20. Synthetic preparation of 3- (M-ethyl-N-n-hexyl) -amino-7- (N-methyl-N-p-tolyl) -aminofluorane:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-ethyl-Nn-hexyl) -aminobenzoyl) -benzoic acid 2- [2'-hydroxy-4' - (N-methyl-Nn-amyl) ) -aminobenzoyl./-benzoic acid and 4-methoxy-4'-N-dimethyldiphenylamine instead of 2-methyl-4-methoxy-diphenylamine to give a white solid, m.p. 146-149 ° C. This compound is 3- (N-ethyl-N-n-hexyl) -amino-7- (N-methyl-N-p-tolyl) -aminofluorane (structural formula shown below). The Xmakg of this compound in 95% acetic acid is 444 nm and 605 nm. The toluene solution of this compound is colorless and a dark green color immediately forms on contact with the silica gel.

CHt-CH0 CHy-CH ^ -CH ^ I U I L ^ J / \ 2 2 2 ^^^ yC ^^ NH_ / OV-CH3

CH9-CH9-CH7 \ CH3 \ -J

c = O

(OJ

21. Synthetic preparation of 3- (N-ethyl-N-n-hexyl) -amino-7- (N-benzyl-N-phenyl) -aminofluorane:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4- (N-ethyl-Nn-hexyl) -aminobenzoyl-benzoic acid 2- [2'-hydroxy-4 '- (N-methyl-Nn-amyl) -aminobenzoyl] instead of benzoic acid and 4-methoxy-N-benzyl-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine to give a white solid, m.p. 146-149 ° C. This compound is 3- (N-ethyl-N-n-hexyl) -amino-7- (N-benzyl-N-phenyl) -aminofluorane (structural formula shown below).

95% acetic acid in this compound has 439 nm and 601 nm.

The toluene solution of this compound is colorless and a dark green color immediately forms on contact with the silica gel.

20 chj-ch 6985 9 ^ s \ o CK -CH -CH / "ΤδΤ Ί Ο / 7Λ j h2 CH2 CH2 - N-CH2- ^ (J) y ch ^ -ch ^ -ch-, \

s \ ^ c- ° lOJ

(OJ ^ 22. Synthetic preparation of 3- (N-ethyl-N-n-hexyl) -amino-6-methyl-7- (N-p-tolyl) -aminofluorane:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-ethyl-Nn-hexyl) -aminobenzoyl] -benzoic acid, 2- [2'-hydroxy-4' - (N-methyl-Nn- amyl) aminobenzoyl / benzoic acid and 2,4'-dimethyl-4-methoxy-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine to give a white solid, m.p. 150-152 ° C. This compound is 3- (N-ethyl-N-n-hexyl) -amino-6-methyl-7- (N-p-tolyl) -aminofluorane (structural formula shown below). 95% acetic acid in this compound has 452 nm and 597 nm. The toluene solution of this compound is colorless and a black color immediately forms on contact with the silica gel.

CH3-CH0 \ ° \ / ^ v "CH3 N-fO-Of | p CH0-CH0-Cllf X /" ΓΛ I NH— (O> - CK3 CH2-CH2-CII \ '- / 23. 3- ( Synthetic preparation of N-ethyl-N (hexyl) -amino-6-ethyl-7-anilinofluorane:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-ethyl-Nn-hexyl) -aminobenzoyl) -benzoic acid 2- [2'-hydroxy-4' - (N-methyl-Nn-amyl) ) -aminobenzoyl / benzoic acid and 2-ethyl-4-methoxy-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine, a white solid is obtained, m.p. 114-11G ° C.

This compound is 3- (N-ethyl-N-n-hexyl) -amino-6-ethyl-7-anilino-fluorane (structural formula shown below). 95% acetic acid in this compound has 455 nm and 589 nm. The toluene solution of this compound is colorless and upon contact with the silica gel an immediate dark purple color forms.

21 CH -en 69 85 9

3 2'-N

Synthetic preparation of 3- (N-ethyl-Nn-hexyl) -amino-6-ethyl-7- (Np-tolyl) -aroinofluorane ch2-cH2-ch2 / ch2-ch2-ch3 ^ \ \ ___ / <kr :

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4- (N-ethyl-Nn-hexyl) -aminobenzoyl] -benzoic acid 2- [2'-hydroxy-41- (N-methyl-Nn-amyl) -aminobenzoyl] instead of benzoic acid and 2-ethyl-4-methoxy-4'-methyl-diphenylamine in place of 2-methyl-4-methoxy-diphenylamine a white solid is obtained, m.p. 160.5 to 162 ° C. This compound is 3- (N-ethyl-N-n-hexyl) -amino-6-ethyl-7- (N-p-tolyl) -aminofluorane (structural formula shown below). The Amaks of this compound in 95% acetic acid are 455 nm and 596 nm. The toluene solution of this compound is colorless and a black color immediately forms on contact with the silica gel.

3 2 \ vvWc "! - £" 3

ch7-ch0-ceS 'I O J IO / -V

CH2-CH2-CH3 \ 1_ / = o 25. Synthetic preparation of 3- (N-ethyl-N-n-hexyl) -amino-7- (N-n-butyl-N-phenyl) -aminofluorane:

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-ethyl-Nn-hexyl) -aminobenzoyl] -benzoic acid 2- [2'-hydroxy-4' - (N-methyl-Nn-amyl) -aminobenzoyl./-benzoic acid and 4-methoxy-Nn-butyl-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine to give a white solid. This compound is 3- (N-ethyl-N-n-hexyl) -amino-7- (N-n-butyl-N-phenyl) -aminofluorane (structural formula shown below). The λ max of this compound in 95% acetic acid is 441 nm and 603 nm. The toluene solution of this compound is colorless and a dark green color immediately forms on contact with the silica gel.

22 CH3 ~ CH2xn 6 9 8 5 9 CH2-CH? -CH S 'ίθ 1 O ^ - N- / q \

I I

ch2-ch2-ch3 ', / C = O 2 -CH, -CH, -CH, 26 6. Synthetic 3- (N-methyl-Mg-ethylhexyl) -amino-6-methyl-7-aminofluorane manufacturing:

When repeating the synthetic preparation according to 1 using 2- [2'-hydroxy-4 '- (N-methyl-N-6-ethylhexyl) aminobenzoyl] -benzoic acid, 2- [2'-hydroxy-4' - (N-methyl- Instead of nn-amyl) -aninobenzyl-1-benzoic acid, a white solid is obtained, m.p. 91-93 ° C. This compound is 3- (N-methyl-N-tert-ethylhexyl) -amino-6-methyl-7-anilinofluorane (structural formula shown below). The max% ethanic acid of this compound has 456 nm and 589 nm. The toluene solution of this compound is colorless and upon contact with the silica gel an immediate dark purple color forms.

CH3 CH2-CH.-CH-Ch / [O Oi r-, ch2 ch2 ox CH, CH-, = ° (oj 27. 3- (N-ethyl-Ng-ethylhexyl) -amino-6-methyl-7- synthetic manufacture of anilofluorane:

When repeating the synthesis according to step 1 using 2- [2'-hydroxy-4 '- (n-ethyl-Ng-ethylhexyl) aminobenzoyl) benzoic acid 2- [2'-hydroxy-4' - (N-methyl-Nn-amyl) ) -aminobenzoyl // -benzoic acid gives a white solid, m.p. 136-139 ° C. This compound is 3- (N-ethyl-N-g-ethylhexyl) -amino-6-methyl-7-anilinofluorane (structural formula shown below). Λ, 95% of this compound:

IHciK S

acetic acid has 455 nm and 589 nm. The toluene solution of this compound is colorless and upon contact with the silica gel an immediate dark purple color forms.

23 ch3-ch2 69 85 9 2 \ _r ^ ° -Y ^ CH3 ch2-cH2-cb-c „2 / ^ Oj IO ^ nh 9h2 ch2 J ° \ v _ .. y I I = o

CH3 CII3 [O

2Ö. Synthetic preparation of 3- (N-ethyl-N-β-ethylhexyl) -amino-7-anilinofluorane;

When repeating the synthesis of step 1 using 2- [2'-hydroxy-4 '- (N-ethyl-N-3-ethylhexyl) aminobenzoyl] -benzoic acid, 2- [2'-hydroxy-4' - (N-methyl-Nn -amyl) -aminobenzoyl-7-benzoic acid and 4-methoxy-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine to give a white solid, m.p. 136-13S ° C. This compound is 3- (N-ethyl-N-3-ethylhexyl) -amino-7-anilinofluorane (structural formula shown below). In λ 95? Of this compound

ITlclKS

acetic acid has 447 nm and 605 nm. The toluene solution of this compound is colorless and a dark green color immediately forms on contact with the silica gel.

CH -.- CH- 3 2 \ N / 0 ch2-ch2-ch-ch2 / 1 O I I O J _

CK2 L2 NH

CHo CHo = °

L2J

29. Synthetic preparation of 3- (N-methyl-N-β-ethylhexyl) -amino-7-anilinofluorane;

Repeating the synthesis of 1 using 2- [2'-hydroxy-4- (N-methyl-NB-ethylhexyl) -aminobenzoyl] -benzoic acid 2- [21-hydroxy-4 '- (N-methyl-Nn-amyl) -aminobenzoyl] instead of benzoic acid and 4-methoxy-diphenylamine instead of 2-methyl-4-methoxy-diphenylamine, a white solid is obtained, m.p. is 135-138 ° C. This compound is 3- (N-methyl-N-β-ethylhexyl) -amino-7-anilinofluorane (structural formula shown below). 95% acetic acid in this compound has 446 nm and 602 nm. The toluene solution of this compound is colorless and a dark green color immediately forms on contact with the silica gel.

24 ch3 6 9 8 5 9 ch2-ch2-ch-ch2 ^ NTo] jO -, h2 i „2 I I λ NC = 0 V_y 3 c" 3 mj

As can be seen from the following tables, similar fluorane compounds are obtained using different raw materials 2- [2'-hydroxy-4 '- (N-methyl-Nn-amyl) aminobenzoyl) benzoic acid and 2-methyl-4-methoxy instead of diphenylamine. The toluene solutions of these compounds are colorless and, upon contact with silica, the indicated color tones are rapidly formed.

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34

Results of comparative experiments 69859

Comparative experiments were performed on the compounds of the invention and the corresponding known compounds in which the above-mentioned properties a to d were examined.

Known compounds used in the comparative experiments A. 3-Diethylamino-6-methyl-7-anilinofluorane B. 3-Diethylamino-6-ethyl-7-anilinofluorane C. 3-Diethylamino-6-methyl-7- (Np-tolyl) aminofluorane D 3-Diethylamino-6-ethyl-7- (Np-tolyl) -aminofluorane E. 3- (N-ethyl-N-benzyl) -amino-6-methyl-7-anilinofluorane F. 3-Diethylamino-7- ( Nm-Trifluoromethylphenyl) aminofluorane G. 3-Diethylamino-5-methyl-7- (Nm-trifluoromethylphenyl) aminofluorane H. 3- (H-ethyl-Np-tolyl) amino-6-methyl-7-anilinofluorane I 3- (N-Methyl-N-cyclohexyl) -amino-6-methyl-7-anilinofluorane J. 3-Diethylamino-7- (Nm-tolyl) -aminofluorane K. 3-Diethylamino-7-anilinofluorane L. 3- diethylamino-7- (N-methyl-N-phenyl) -aminofluorane M. 3-Diethylamino-7- (N-methyl-Np-tolyl) -aminofluorane N. 3- (N -methyl-N-cyclohexyl) -amino-7-anilinofluorane O. 3-Diethylamino-7- (N-benzyl-N-phenyl) -aminofluorane P. 3-Diethylamino-6-methyl-7- (N-methyl- n-phenyl) -aminofluora very.

Experiment a. Spontaneous color formation in dilute decomposed aqueous solutions; A 3% toluene solution containing various fluorane compounds (15 ml) and a 15% acetic acid solution (10.5 ml) were shaken vigorously for one minute and the resulting mixture was allowed to stand for some time. The stained aqueous solution of acetic acid was examined colorimetrically using a Shimadzu spectrophotometer. The results are shown in Table 1.

j 35

Table 1 6 9 8 5 9

Compound according to the invention

Obtained from the Pre-Absorption Absorption Signal Wavelength Absorption Wavelength Maximum Capacity of Absorption. . (ro »u) _ (m, u) _ / _ 1 535 0/180 A 570 1/11 2 535 0.188 6 540 0.140 7 570 0.100 13 575 0.115 14 564 0.131 16 550 0.139 26 553 0.152 27 550 0.060 60 550 0.130 53 553 0.090 23 550 0.060 B 550 1.570 22 550 0.030 C 543 0.585 61 540 0.163 62 540 0.100 24 550 0.025 D 550 0.400

The results show that the fluorane compounds of the invention have a very low degree of solubility in dilute acids compared to known fluorane compounds. This fact ensures that when coagulating an aqueous solution of gelatin with dilute acid in the preparation of microcapsules used in pressure-sensitive copying sheets, the fluorane compound according to the invention has only a very low possibility of staining the solution.

Experiment b. Solubility in organic solvent:

The solubility of the various compounds was tested at 25 ° C in "Hi-sol SAS" (a diarylethane-type solvent manufactured by Nihon Sekiyu K.K. and used in pressure-sensitive copying sheets) and toluene. The results are shown in Table 2.

36

Table 2 69 8 5 9

A compound of the invention

Pre-obtained Hi-sol SAS Toluene Known compound from (%) (S) Hi-sol-SAS Toluene No._%% 1 9.1 8.0 A 1.2 8.0 2 8.7 8.0 6 3.5 16.5 7 over 20 over 40 13 over 15 over 40 14 5 10 16 3.1 16.0 26 over 20 over 40 27 over 20 over 40 60 15.9 18.2 63 10.2 40.3 23 over 25 over 60 B over 25 over 60 22 16.5 8.2 C 2.4 2.7 61 3.2 6.1 62 15.0 25.0 24 10 11 D 8.6 9.1 1110 12 E 8.1 6.1 4 over 15 over 30 F 4.0 6.8 9 1, 3 4.0 H 0.9 2.3 10 7.5 18.0 I 5.5 4.5 18 13, 3 18.9 J 10.3 8.2 8 11.4 48.0 K 2.6 1.6 15 14.0 6.4 17 4.9 7.9 28 over 20 over 20 29 over 20 over 20 19 16.9 42.6 L 11.9 10.0 64 30 30 20 over 20 over 40 M 877 775 12 1 0 25.0 N 8.8 6.6 21 over 20 over 30 0 8.8 13.0 3 over 20 over 40 P over 20 over 20 69859 37

It is clear from the above table that according to the invention the compounds are more soluble in organic solvents. This ensures that these compounds do not have the ability to form crystals in microcapsules during the manufacture of pressure sensitive copy sheets and that they are economical in the microencapsulation process because they do not require the use of expensive aromatic solvents but relatively inexpensive petroleum solvents.

Koe c. Spontaneous color formation after addition on heat-sensitive sheets:

According to the method disclosed in Japanese Patent Publication No. 14039/1970, various fluorane compounds were finely divided into an aqueous solution of PVA and then mixed with, for example, bis-phenol A to prepare a coating material in order to obtain heat-sensitive copying sheets, see Experiment e below. at this stage, when known fluorine compounds were used in the coating materials, a green to black color formed and, as a result, heat-sensitive copy sheets coated with these materials were already pre-dyed. The surface properties of the sheets thus prepared were then tested using a "Macbeth Reflection Densitometer" and a filter "WRATTEN No. 106". The results are shown in Table 3.

38 φ,, 69859

Table 3

Compounds of the Invention Known compounds

Obtained from the example Color Density Color Density No. 1 0.09 A 0.18 2 0.08 7 0.09 13 0.12 26 0.1 3 27 0.11 60 0.11 53 0.06 23 0 .08 B 0.25 22 0.08 C 0.20 61 0.09 62 0.11 24 0.08 D 0.22

It can be seen from Table 3 that the heat-sensitive copy sheets prepared using the fluorane compounds of the invention cause less discoloration of the structure and are more useful than those prepared using previously known fluorane compounds.

Koe d. Thermal Sensitivity After Addition to Heat-Sensitive Sheets: Heat-sensitive copy sheets prepared as described in "C" were tested using color-forming concentrations and a "Macbeth Reflection Densitometer" and a "WRATTEN" filter No. 106, with varying experimental temperatures.

2 The heat addition time was 1 s and the pressure was 1.5 kg / cm. The results are shown in Table 4.

39

Table 4 69859 _ According to the invention: compounds_ Known compounds _

Obtained ..... o es ime r -__ Temperature (° C) _ _Temperature (C) _- No. 90 100 110 130 150 170 90 100 110 130 150 170 1 0.10 0.13 0.20 0, 72 1.15 1.20 Λ 0.15 0.18 0.20 0.54 1.04 1.14 2 0.03 0.10 0.15 0.58 1.10 1.19 7 0.13 0 .23 0.46 0.6c 1.05 1.10 13 0.13 0.15 0.25 0.76 1.21 1.22 26 0.15 0.23 0.55 0.95 1.14 1 , 14 27 0.11 0.14 0.33 0.88 1.18 1.20 60 0.11 0.15 0.27 0.80 1.18 1.18 53 0.15 0.33 C, 50 0.80 1.10 1.10 23 1.10 0.32 0.53 0.94 1.16 1.16 B 0.25 0.41 0.54 0.80 1.05 1.08 22 0, 08 0.11 0.28 0.84 1.08 1.15 CC, 18 0.22 0.28 0.72 1.05 1.15 61 0.10 0.11 0.20 0.84 1.18 1.18 62 0.12 0.25 0.48 0.96 1.20 1.20 24 0.08 0.09 0.15 0.80 1.10 1.16 D 0.22 0.33 0, 50 0.78 1.05 1.14 4 0.18 0.40 0.68 0.90 1.18 1.20 F 0.11 0.15 0.23 0.80 1.15 1.20 9 0 .07 0.08 0.09 0.22 0.30 0.98 H 0.07 0.06 0.06 0.14 0.99 1.23 10 0.10 0.14 0.22 0.76 1 .20 1.22 I 0.15 0.17 0.26 0.76 1.19 1.24 11 0.08 0.08 0.20 0.66 1.16 1.18 E 0.10 0.10 0.12 0.44 1.10 1.18 18 0.09 0.15 0.34 0.89 1.10 1.14 J 0.16 0.20 0.30 0.74 1.16 1.18

It is clear from Table 4 that the heat-sensitive copy sheets made using the fluorane compounds of the invention cause less coloration of the structure, but they stain more strongly than sheets made using previously known fluorane compounds, which invalidates the generally assumed theory that sheets with are less discolored, also cause poor discoloration when used. This shows that the preparation of heat-sensitive copy sheets using the fluorane compounds according to the invention is very advantageous.

69859 40

Koe e.

Lightfastness of Heat-Sensitive Recording Papers A mixture of 150 parts by weight of a 10% by weight aqueous solution of polyvinyl alcohol, 65 parts by weight of water and 30 parts by weight of 3- (N-ethyl-N-3-methylbutene) obtained from Experiment 6 of the present invention style) amino-6-methyl-7-anilinofluorane, an aqueous dispersion (henceforth component A) containing fluorine particles having a size of 1-3 μm was prepared with a des-integrator. Similarly, from a mixture of 35 parts by weight of bisphenol A, 150 parts by weight of a 10% by weight aqueous solution of polyvinyl alcohol and 65 parts by weight of water, a dispersion (henceforth component B) containing 1 part by weight was prepared by treatment with a disintegrant. -3 bisphenol A particles.

Then 3 parts by weight of component A and 67 parts by weight of component B were mixed together and the resulting mixture was applied in a thickness of 2 to 5 g / m 2 on a sheet of paper. The coated paper sheet was dried to obtain a heat-sensitive recording paper.

According to the above procedure, 3- (N-methyl-Nn-hexyl) amino-6-methyl-7-anilinofluorane from Experiment 14 and 3- (N-ethyl-Nn-hexyl) amino from Experiment 16 were prepared using heat-sensitive recording papers. -6-methyl-7-anilino-fluorane to replace 3- (N-ethyl-N-3-methylbutyl) amino-6-methyl-7-anilinofluorane as a chromogenic compound.

The prepared heat-sensitive recording papers showed no spontaneous staining and were substantially white in color.

The following series of tests were performed on heat-sensitive recording papers.

The light fastness of the heat-sensitive recording papers prepared by the above method was determined by comparing the reflectance densities of the sample surface before and after the surface of the sample was exposed to summer sunlight for a total of 20 hours at an ambient temperature of 10-20 ° C. The reflectance was determined on a MacBeath reflection densitometer, model RD 514 equipped with a Wratten # 47 blue filter. The results are shown in Table 5.

Table 5

Surface Reflection Sample Sample Before Exposure After Exposure

Sheet of paper containing 3- (N-ethyl-N-3-methylbutyl) amino-6-methyl-0.10 0.23 7-anilinofluorane

Sheet of paper containing 3- (N-methyl-N-n-hexyl) amino-6-methyl-7- 0.10 0.24 anilinofluorane

Sheet of paper containing 3- (N-ethyl-N-n-hexyl) amino-6-methyl-7-anilino-0.09 0.24 fluorane

Koe f.

Color that develops on heat-sensitive registration paper

It was found that each heat-sensitive recording paper of Experiment e reacted when the tip of the pen heated to 150 ° C touched its surface. As a result of the contact, the point of contact of the surface of each sample immediately turned black.

Koe g.

The color density of the heat-sensitive recording paper under practical conditions of use

The color developed on the surface of the sample was measured after each heat-sensitive recording paper of Experiment e was heated to 150 ° C and 170 ° C, respectively, for one second and then cooled to room temperature. The measurement was performed with the above-mentioned reflectance densitometer equipped with a Wratten j = f-106 type filter. The results are shown in Table 6.

69859 42

Table 6

Density of developed color Sample 150 ° C 170 ° C

Sheet of paper containing 3- (N-ethyl-N-3-methylbutyl) amino-6-methyl-7-anilinofluorane 1.18 1.20

Sheet of paper containing 3- (N-methyl-N-n-hexyl) amino-6-methyl-7-anilinofluorane 1.18 1.20

Sheet of paper containing 3- (N-ethyl-N-n-hexyl) amino-6-methyl-7-anilinofluorane 1.15 1.20

Experiment h. Comparative Test of Comparative Examples A-P Each heat-sensitive recording paper was prepared by the same methods as in Test e except that known chromogenic compounds were used.

The same tests e-g were performed on each sample thus prepared. The results are shown in Table 7 together with the results of tests c-g.

43

Table 7 69859

Chromogenic compounds and test results

Example Test result, no. / ---—-—— --—-__ f test e test f test g

/ Chromogenic compound '! ~ "~ ~: TT

/ lightfastness developing color density / before light-colored "/ after exposure to 10 * * -N-3-methylbutyl-6'-methyl-amino-6-methyl- 7-anilino-10 ° · 23 muS a 1 · 10 1 · 20-fluoro [3- (n) -methyl-Nn-hexyl) -n, n.

14 amino-6-methyl-7-anilino-V ° °; 24 m “s, ta 1] 13t l’20 fluorane __ <+> <+> <+> ifi 3- (N-etvv 1 iNn-hexyl) - 7-Z-, 37-7Ί,, -, amino-6-methyl-7-amino-° '° ^ ° '24 black 1.15 1.20 fluorane t +) 1 +) l *> <+> <-> 3-diethylamino- 6-methyl-o.13 0.34 black i.04 lu 7-anilinofluorane (-) (-) (+) (-) (-) 3-diethylamino-6-ethyl-7-io.s 0.32 black 1.05 l.os Anilofuran (-) (-) (+) (-) (-) "to give 1 amino-b-methyl o.to 0.35 greenish l.os 1.15 3 r (p-tolyl) aminofluores "1 (-} black (-) - M (-) 3_dietyy 1 iamίηο-6-ethyl> 1 i ~ 7- 0.22 o.3S greenish 1.05 1.14„ c (Np-tolyl) aminofluorane (-) {-) black ( _) <-) (_)> 1 - ------------------------------- - 3- (K-ethyl-N -benzyl) -10> 0-8-black 1-amino-6-methyl-7-anilino- (+, * fluoro-3'-3-diethylamino-7- (Nm-tri-o. 11 0.2S greenish 1.1s 1.20 ci (fluoromethylphenyl) -black (+) (+) E-aminofluorane 1-10 0 -----; -; -; -—------ 3-diethylamino-5-methyl - o.10.27 greenish 1.13 Ώ 7- (Nm-trifluorom ethyl (+) (-) black (-) (-) (1) phenyl) aminofluoran 4j 3- (N-ethyl-Np-tolyl) -0.07 0.23 greenish o 99 1 23 1 fT ^ g? älnTeCyy 1 i ~ 7 "Anilin ° M <+> mu5ta (~} <+> £ <3- (N-methyl-N-cyclohexyl) 15 0.35 black i24 amino-6-methyl-7-anil- \ 1+; (+ \ f +)

Inoi lorane _ v '_______v K' 3 "diethylamino-7- (Nm-. | 0> 1S o.31 green 1.1s 1.1a tolylanilofluorane (_} (+) (_ °! 3-diethylamino-7- anilino- | o.16 0.30 green l.is 1.17 fluorane | (-) <“) t“) i +> (-) 3-diethylamino-7 - (, Ν'-meth- q.17 0.35 green 1.13 i. ig

raaÄTN_phenyl ^ aminofluo- ~ (_) (_) (_) M M

3-diethylamino-7-NNmeth-0o. 36 green 1.12 1.15 yy 1 i) -Np-tolyl 1 i) amino- ,,,,, * f fluorine .__ 1) K 1 {'_ (' (~> 3- (Nymethyl 1 iN-cyclohex- Γ77 ö ~ 3'-phenyl (amino) -N-anilino-fluoro-1,11- (17,3-diethylamino-7-) - (N-benzyl -,. 15 ', green 1.10 1.15 I rane <-> <"> (-J (-) (-1 | 3-uietyy 1 iammo-ö-methyl l ιη 1 1 ~ —--. 7- (N-meyl- Nf enyy1i) - 0'1® 0-22 brown 1-15 1.18 aminofluorane ~ _ (-) 69859 44

The following are practical criteria for the results of tests e-g. Among the heat-sensitive recording paper samples, those with reflectance densities before and after illumination (test e), color formed (test f), and color densities at 150 ° C and 170 ° C (test g) met the criteria. practical applications.

Tested value Criterion reflection density (before exposure): not more than 0,10 reflection density (after exposure): not more than 0,24 color formed (test 2): black color density (at 150 ° C): not less than 1,15 color density ( At 170 ° C): not less than 1.20

It can be seen from Tables 5, 6 and 7 that only the heat-sensitive recording papers of this invention prepared using any of the chromogenic compounds of Examples 6, 14 and 16 of this application meet all of the selection criteria. Thus, the chromogenic compounds of Examples 6, 14 and 16 of this invention are best suited for practical applications. Samples prepared using any of the known chromogenic compounds were unable to meet all of the selection criteria (see Tables 5, 6, and 7), where (+) indicates suitability and (-) unsuitability).

Claims (6)

69859 45 A color-generating compound of the general formula I X 1 R 1 ^ N 0 1 R 1 ^ 0 | I Oi «3> n (οΓ ° -1 wherein R1 is an alkyl group of 5 to 8 carbon atoms; R2 is an alkyl group of 1 to 8 carbon atoms, a benzyl group, a cyclohexyl group or a phenyl group having or lacking a lower alkyl group of 1 to 4 carbon atoms; R , is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms or a benzyl group, X 1 is a hydrogen atom, is a hydrogen atom or a lower alkyl group of 1 to 2 carbon atoms, is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, a haloceniaton or a trifluoromethyl group, and n is an integer of 1; provided that there is no amyl group when R 2 is an alkyl group of 1 to 5 carbon atoms, and X 2 is both a hydrogen atom, X 1 is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms, or a halogen atom. selected from the group consisting of 3- (N-methyl-Nn-amyl) -amino-6-methyl-7-anilino-fluorane, 3- (N-ethyl-Nn-amyl) -amino-6-methyl-7-anilino - fluorane, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7-anilino-fluorane ', 3- (N-isoamyl-Nn-hexyl) li) -Amino-6-methyl-7-anilinofluorane, 3-diisoamylamino-6-methyl-7-anilino-fluorane, 3- (N-methyl-Nn-hexyl) -amino-6-methyl -7-anilino-fluorane, 3- (N-ethyl-Nn-hexyl) -amino-6-methyl-7-anilino-fluorane, 3- (N-ethyl-Nn-hexyl) -amino-6-methyl-7 - (Np-tolyl) aminofluorane, 3- (N-ethyl-Nn-hexyl) -amino-6-ethyl-7-anilinofluorane, 3- (N-ethyl-Nn-hexyl) -amino-6-ethyl-7 - (N-tolyl) -aminofluorane, 3- (N-methyl-N-β-ethyl-hexyl) -amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-8-ethylhexyl) -amino -6-methyl-7-anilinofluorane, 3- (N-di-n-46,6859 octyl) -amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-isoamyl) -amino-6 -methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamyl) -amino-6-methyl-7- (Np-tolyl) -aminofluorane, 3- (N-methyl-Nn-hexyl) -amino -6-methyl-7- (Np-tolyl) aminofluorane, 3- (N-isoamyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane and 3- (N-ethyl-Nn-amyl) amino-7- (Nm-tri-fluoro) methyl (phenyl) -aminofluor sound. 3. A color-forming mixture suitable for pressure- and heat-sensitive copying sheets, characterized in that it contains, as a color former, at least one color-generating compound of the general formula R1 X1 ^ NW ° WX2 ^ <v in which R1 is an alkyl group of 5-8 carbon atoms ; R 2 is an alkyl group of 1 to 8 carbon atoms, a benzyl group, a cyclohexyl group or a phenyl group having or lacking a lower alkyl group of 1 to 4 carbon atoms; R 1 is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms or a benzyl group; is a hydrogen atom; X 2 is a hydrogen atom or a lower alkyl group of 1 to 2 carbon atoms; X3 is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms, a halogen atom or a trifluoromethyl group; and n is an integer 1; provided that Ry is not an amyl group when R2 is an alkyl group of 1 to 5 carbon atoms, X1 and X2 are both hydrogen atoms, X3 is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms or a halogen atom, dissolved in an organic solvent and incorporated into microcapsules capable of decomposing and the effect of the flake, and an electron-accepting substance. 4. A color-forming composition suitable for use in a heat-sensitive copying material, characterized in that it contains, as a color-forming agent, at least one color-generating compound 47 of the general formula 6985 9 R, \ * 1 / N γ '-' γ, '0 r' ^ Y '* 2 *! i ° i .. - “Λ R 3 has an alkyl group of 5 to 8 carbon atoms; R 2 is an alkyl group of 1 to 8 carbon atoms, a benzyl group, a cyclohexyl group or a phenyl group having or lacking a lower alkyl group of 1 to 4 carbon atoms; R 1 is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms or a benzyl group, a hydrogen atom, X 2 is a hydrogen atom or a lower alkyl group of 1 to 2 carbon atoms, X 1 is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms, a halogen tern or a trifluoromethyl group, and n is an integer of 1; R 1 is an amyl group, when R 2 is an alkyl group of 1 to 5 carbon atoms, and X 2 is both hydrogen atoms, X 1 is a hydrogen atom, a lower alkyl group of 1 to 4 carbon atoms or a halogen tower, and an electron acceptor. Color-forming mixture according to Claim 3 or 4, characterized in that the color-generating compound is selected from the group consisting of 3- (N-methyl-Nn-amyl) -amino-6-methyl-7-anilinofluorane, 3- (N-ethyl -Nn-amyl) -amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamyl) -amino-6-methyl-7-anilinofluorane, 3- (N-isoamyl-Nn -hexyl) -amino-6-methyl-7-anilinofluorane, 3-diisoamylamino-6-methyl-7-anilinofluorane, 3- (N-methyl-Nn-hexyl) -amino-6-methyl- 7-Anilinofluorane, 3- (N-ethyl-Nn-hexyl) -amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-Nn-hexyl) -amino-6-methyl-7- (Np-tolyl ) -aminofluorane, 3- (N-ethyl-Nn-hexyl) -amino-6-ethylaminofluorane, 3- (N-ethyl-Nn-hexyl) -amino-6-ethyl-7- (np-tolyl) -aminofluorane, 3- (N-methyl-N- (3-ethyl-hexyl) -amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-O-ethylhexyl) -amino -6-methyl-7-anilinofluorane, 3- (N-di-n-octyl) amino-6-methyl-7-anilino fluoro Rane, 3- (N-methyl-N-isoamyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamyl) amino-6-methyl-7- (Np-tolyl ) -aminofluorane, 3- (N-methyl-Nn-hexyl) -amino-6-methyl-7- (Np-tolyl) -aminofluorane, 3- (N-isoamyl-N-cyclohexylamino-6-methyl) -7-anilinofluorane and 3- (N-ethyl-Nn-amyl) -amino-7- (Nm-trifluoro) -methyl (phenyl) -aminofluorane. 69859 48