JPS594652A - Fluoran compound and heat or pressure-sensitive color recording sheet using it - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R1 and R2 are lower alkyl; R3 is methyl, or ethyl; X is halogen or nitro; n is 0-4; group shown by the formula II is group shown by the formula III or formula IV). EXAMPLE:2'-Anilino-3'-methoxy-6'-diethylamino-fluoran. USE:A color former for heat or pressure-sensitive recording sheets. Having improved color characteristics such as color sensitivity, color concentration, etc., solvent resistance, light resistance, water resistance, water-vapor resistance, etc. PROCESS:For example, a m-aminophenol derivative shown by the formula V is condensed with phthalic anhydride shown by the formula VI through dehydration, to give a 2-(4'-disubstituted amino-2'-hydroxybenzoyl)-benzoic acid derivative shown by the formula VII. This compound is then reacted with a diphenylamine derivative shown by the formula VIII in the presence of a condensation agent through dehydration. The reaction product is added to ice water, the prepared precipitate is filtered off, and treated with an alkali.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel fluoran compound and a recording sheet containing the same as a coloring agent. More specifically, the formula (wherein R1 and R2 represent lower alkyl, R3 represents methyl or ethyl, X represents halogen or nitro, and represents an integer from 0 to 4).

The present invention relates to a fluoran compound represented by the formula "eF: f- means "no" or "Xn side effect") and a heat-sensitive or pressure-sensitive recording sheet containing the same as a coloring agent.

A recording method that utilizes a color reaction caused by contact between a colorless or light-colored electron-donating compound and a colorless or light-colored electron-accepting compound has been known for a long time.

Among them, sensitive, thermal recording sheets, and pressure-sensitive recording sheets are representative.

A heat-sensitive recording sheet is prepared by supporting an electron-donating colorless dye (hereinafter referred to as a color former) and an electron-accepting substance (hereinafter referred to as a color developer) in a binder so that the two do not come into contact with each other on a support. When heated, the color forming agent and/or the color developer melt and come into contact with each other, causing a color reaction and producing a recorded image.

Pressure-sensitive recording paper consists of an upper sheet in which microcapsules of an organic solvent solution of a color former are coated on a support, and a lower sheet in which a color developer is coated on the other sheet surface. The microcapsules are placed facing each other, and the pressure of a pencil, typewriter, etc. is used to destroy the microcapsules, emit a coloring agent, and transfer it to the surface of the developer, causing a coloring reaction and producing a recorded image.

The coloring agent used in the heat-sensitive and pressure-sensitive recording sheets is required to be excellent in coloring sensitivity, coloring density, solubility in solvents, stability, and various fastnesses such as water resistance, light resistance, and moisture resistance after coloring.

Furthermore, in recent years, there has been a demand for color formers that produce black colored images due to the need to obtain copies from recording sheets.

However, despite the development and improvement efforts of each manufacturer, nothing that satisfies the above properties has yet to be obtained.

The present inventors have discovered that the novel fluoran derivative represented by formula (1) has excellent color development properties such as color development sensitivity and color density, high solubility in solvents, excellent stability, and various properties such as light resistance, water resistance, moisture resistance, etc. It was also found that it has excellent fastness.

In the compound of formula (1) of the present invention, specific examples of R1 and R2 include methyl, ethyl, propyl, butyl, and the like. R3 may be methyl or ethyl, and X may be chlorine, bromine or nitro. The compound represented by the formula (I) of the present invention can be prepared, for example, as follows.

The m-amine phenol derivative of the following formula (to) and the following formula (
The phthalic anhydride of III) is dehydrated and condensed to form the following formula (I
The 2-(4'-disubstituted amino-2'-hydroxy-benzoyl-benzoic acid derivative of V) is obtained.

n (In the formula, R□, R2, X and n have the same meanings as defined above.) Next, the compound of formula (IV) and the diphenylamine derivative of the following formula M are reacted in the presence of a dehydration condensation agent.

Next, the mixture is immersed in ice water, and the resulting precipitate is filtered off and treated with an alkali to obtain a crude fluoran compound.

By recrystallizing this from a suitable solvent, a fluoran compound represented by the formula (Il) is obtained as colorless or light-colored crystals.

(In the formula, R1 to Rs, X and n have the same meanings as defined above, and R4 represents hydrogen or lower alkyl.) Examples of dehydration condensation agents used in this reaction include sulfuric acid, phosphoric acid,
Polyphosphoric acid, phosphorus pentoxide, phosphorus pentachloride, phosphorus tribromide, anhydrous metal halides such as anhydrous aluminum chloride or anhydrous zinc chloride, boron trifluoride, and the like are used.

The condensation temperature is -10 to 150C, preferably 0 to 30C.
It is C. Paid hours can be arbitrarily selected from a few hours to 404 hours.

In addition, the alkaline treatment is, for example, 8% in an aqueous solution of caustic alkali.
What is necessary is just to stir at 0-100C for 2-3 hours.

Further, examples of the recrystallization solvent include benzene.

Aromatic hydrocarbons such as toluene, halobenzenes such as monochlorobenzene and dichlorobenzene, halogenated aliphatic hydrocarbons such as chloroform and bromoform, and alcohols such as isobutanol or isopropanol are used.

Note that the diphenylamine derivative of formula (2) can be produced, for example, as follows.

The compound of the following formula (Vl) and bromobenzene are condensed under the boiling point in the presence of an acid binder such as potassium carbonate, sodium carbonate or magnesium oxide and a copper catalyst (such as copper powder, copper oxide or copper acetate) to form the following formula: Compound (■) is obtained, and then this compound is hydrolyzed by refluxing water in an alcohol such as propatool to produce compound (2) M.

(Vl) (■) (In the formula, R3 and R4 have the same meanings as above, and R5 represents hydrogen or lower alkyl.) Heat-sensitive and pressure-sensitive recording sheets using the color forming agent of the present invention can be prepared, for example, by the following methods. It can be prepared by dispersing the binder in a dispersion medium and then mixing it, adding additives such as pigments and wax as necessary, applying it to a sheet, and drying it.

In addition, the pressure-sensitive recording sheet uses alkylated naphthalene as the coloring agent.
After dissolving alkylated diphenyl, alkylated diphenylalkane, chlorinated paraffin, etc. in a solvent, emulsifying it down to several microns in an aqueous solution containing an emulsifier, protective colloid, etc., and encapsulating it with gelatin, polyurethane, polyurea, etc. Add binder additives, etc. according to the requirements and apply to the sheet to make the upper sheet.

Color developers used in heat-sensitive and pressure-sensitive recording sheets include:
Examples include clay minerals such as acid clay, activated clay, and attapulgite kaolin, phenol derivatives, phenol resins, aromatic carboxylic acids or polyvalent metal salts thereof, and the like.

Further, materials for the recording sheet include paper, synthetic paper, synthetic resin film, and the like.

Examples will be shown below, but the present invention is not limited thereto. In addition, all parts in the examples indicate parts by weight.

Example I.

Synthesis of 2'-anilino-3'-methoxy-6-dinitylaminofluorane 15.7 jil-(4'-diethylamino-2'-hydroxy-benzoyl)-benzoic acid and Diphenylamine 11.5P with concentrated sulfuric acid + 5
79- and stirred at 10-20C for 24 hours. The reaction mixture is poured into a swamp of ice water, and the precipitate is filtered and washed thoroughly with water. The product was then dissolved in a 2% aqueous solution of caustic soda at a concentration of 400 ml.
ml, stirred at 80-90C for 3 hours, and filtered to obtain crude fluoran. After drying, recrystallize from toluene to obtain 16
．． Obtain 95' objective. Yield 69% IR1760Crn (lactone ring) NMR: 1.1 (t, 6H), 3.28 <q
, 4l-1), 3.8 < s +3 I-1), 6
1-8.6 (b, 14H)Mass 2M
492 (Molecular ion) This compound developed a bluish-purple color with silica gel and a dark blue color with bisphenol A.

Note that 2,4-dimethoxy-diphenylamine used in this example was produced as follows.

2.4-dimethoxyacetanilide 48.8p, bromobenzene 2507. Potassium carbonate 18.5i, copper powder 0.
59- is reacted under reflux for 12 hours.

Next, 18 P of potassium hydroxide and 70 g of ethanol were added, and the mixture was refluxed for 4 hours to cause hydrolysis. After ethanol is distilled off, potassium carbonate, copper powder, etc. are filtered off, and the furnace liquid is distilled to obtain 54.8 g of 2,4-dimethoxydiphenylamine (yield 95.8%), pale yellow. Liquid bp, 191-195 C7' 6. mmHg Example 2 Synthesis of 2'-anilino-3'-methoxy-6'-diethylami/-4,5,6,7-titrachlorofluoran 2-[4'-diethylamino-2'-hydroxybenzoyl] -3,4,5,6-tetrachlorobenzoic acid 2
2.5P and 2.4-dimethoxy-diphenylamine 11
．． 5g of the solution was dissolved in 130r of concentrated sulfuric acid and 30p of 28% fuming sulfuric acid and stirred at 10-20C for 20 hours.

The reaction mixture was poured into 1.8 ml of ice water, neutralized with 48% aqueous sodium hydroxide solution, added with 400 ml of 2% aqueous sodium hydroxide solution, stirred at 80-90C for 3 hours, and filtered to obtain crude fluoran. After drying, recrystallize from monochlorobenzene to obtain 1
9. Obtain 29-objectives.

Yield: 61%, Mass, M 628 (molecular ion) IR1745crn (lactone ring) This compound developed a green-blue color with silica gel and a green color with bisphenol A.

Example 3゜In Example 2, 2- [: 4'-diethylamino-2
'-Hydroxybenzoyl)-3,4,5,6-Tetrachlorobenzoic acid was replaced with 4-N,N-diethylamino-2-hydroxy-4-5'-benzo-benzophenone-2'-carboxylic acid. The following compound is obtained in the same manner as in Example 2.

Yield 58%, Mass M 542 (molecular ion) I
R, 1745 cm (5 ri) 7'fR) This compound developed a bluish-purple color with silica gel and a dark blue color with bisphenol A.

Next, we will show a fluoran compound represented by the following formula (VIU) obtained by the same method as above, and the color hue and IR of the same on silica gel, as well as the results of measurement.

λn Example 1' h RI R2R3 35 parts of bisphenol A, which is pulverized for 24 hours in a ball mill and used as "component A", is mixed with 10% PV.
150 parts of aqueous solution A and 65 parts of water are ground in a ball mill for 24 hours to obtain "component B." Mix 1 part of component Al and 15 parts of component B, and the solid content on the paper is 5! i'/yyL
' to obtain thermal recording paper. This heat-sensitive recording paper develops a dark blue color at a temperature of 150C, has no background coloration, and has excellent fastness.

Example 13゜Example 10 2'-anilino-3'-methoxy-6'-diethylaminofluorane 21 was dissolved in diisopropylnaphthalene 981 at 500 °C, and at this temperature gum arabic 2
Add 01 and 160g of water and emulsify. To this were added 20 g of acid-treated gelatin and 160 g of water, and the pH was adjusted to 5 with acetic acid.

Next, 50 oz of ice water was added to promote coacervation, forming a thick liquid film of gelatin-gum arabic on the -zb of the diisopropylnaphthalene oil droplets, and reducing the pI-T to 4.
．． 4, and then 37% formalin solution 41 is added to obtain a microcapsule warm body. Add this capsule liquid to 4 O
5 g-7 dry solids on paper with basis weight f/m”
It is coated to a thickness of m2 and dried to obtain a bed sheet. The thus obtained overlay sheet was overlaid with a color developer sheet using a paraphenylphenol-formaldehyde polymer as a color developer, and a color was developed at a pressure of 6ooky/d. A dark blue copying paper with excellent fastness was obtained, with water resistance of 80% and light resistance of 95%.

Patent Applicant Nippon Kayaku Co., Ltd. Procedural Sleeve 11-1 (10,000 people) % Formula % l Case Indication 1982 Patent Application No. 1 i 1797 No. 2 "0" Name Fluoran compound and color-forming heat-sensitive or Pressure Sensitive Record Sheet 3 Relationship with famous case to be amended Patent applicant 2-1 Marunouchi-chome, Chiyoda-ku, Tokyo (408) Nippon Kayaku Co., Ltd. Representative President Tsunekazu Sakano 4th generation Director Chiyoda, Tokyo Marunouchi-ku, 2-1-1-5 Date of amendment order September 28, 1980 6 No number of inventions to be increased by the amendment 7 Specification subject to amendment 8 Contents of the amendment As shown in the appendix Description 1, Title of the invention Fluoran compounds and color-forming heat-sensitive or pressure-sensitive recording sheets using the same. and Rs represent lower alkyl, R1 represents methyl or ethyl, X represents )-logen or nitro, and n represents an integer of O-4.

xn5 indicates 0 or 0. ) A heat-sensitive or pressure-sensitive recording sheet containing a fluoran compound represented by the following as a coloring agent.

The present invention relates to a novel fluoran compound and a recording sheet containing the same as a coloring agent. More specifically, it is represented by the formula (wherein R1 and R1 represent lower alkyl, R1 represents methyl or ethyl, and X represents) -logen or nitro. n represents an integer of 0-4.

xn4 relates to a fluoran compound represented by or to a heat-sensitive or pressure-sensitive recording sheet containing the same as a coloring abrasive.

A recording method that utilizes a color reaction caused by contact between a colorless or light-colored electron-donating compound and a colorless or light-colored electron-accepting compound has been known for a long time.

Among them, heat-sensitive recording sheets and pressure-sensitive recording sheets are representative.

A heat-sensitive recording sheet is prepared by supporting an electron-donating colorless dye (hereinafter referred to as a color former) and an electron-accepting substance (hereinafter referred to as a color developer) in a binder so that the two do not come into contact with each other on a support. When heated, the color forming agent and/or the color developer melt and come into contact with each other, causing a color reaction and producing a recorded image.

In addition, pressure-sensitive recording paper consists of an upper sheet in which microcapsules containing an IFfAm solution, which is a color former, is coated on a support, and a lower sheet in which a color developer is coated on the other sheet surface. The microcapsules are placed facing each other, and the pressure of a pencil, typewriter, etc. is used to destroy the microcapsules, emit a coloring agent, and transfer the coloring agent to the surface of the developer, causing a coloring reaction and producing a recorded image.

The coloring agent used in the heat-sensitive and pressure-sensitive recording sheets is required to be excellent in coloring sensitivity, coloring density, solubility in solvents, stability, and various fastnesses such as water resistance, light resistance, and moisture resistance after coloring.

Furthermore, in recent years, there has been a demand for color formers that produce black colored images due to the need to obtain copies from recording sheets.

However, despite the development and improvement efforts of each manufacturer, nothing has been found that addresses the above-mentioned properties.

The present inventors have discovered that the novel fluorane current conductor represented by formula (1) has excellent coloring characteristics such as coloring sensitivity and coloring density, high solubility in solvents, excellent stability, and light resistance, water resistance, moisture resistance, etc. It was also found that it has excellent fastness properties.

In the compound of formula (1) of the present invention, specific examples of l'L and R include methyl, ethyl, norobil, butyl, and the like. Ri can be methyl or ethyl, and X can be chlorine, bromine or nitro.

Specifically, the compound represented by formula (11) of the present invention is produced, for example, as follows.

Four m-inophenol vj of the following formula σl and the following formula (
The phthalic anhydride of III) is dehydrated and condensed to form the following formula (I
The 2-(4'-disubstituted aino-2'-hydroxy-benzoyl-benzoic acid wire conductor of V) is obtained.

n (In the formula, IR1+stone, X and n have the same meanings as defined above.) Next, the compound of formula (IV) and the diphenylamine derivative of the following formula M are reacted in the presence of a dehydration condensation agent.

Next, the mixture is poured into ice water, the resulting precipitate is filtered off, and then treated with an alkali to obtain a crude fluoran compound.

By recrystallizing this from a suitable solvent, a fluoran compound represented by the formula (Il) is obtained as colorless or light-colored crystals.

(In the formula, R11 to R, , , phosphorus pentoxide, phosphorus pentachloride, phosphorus tribromide,
Anhydrous metal halides such as anhydrous aluminum chloride or anhydrous lead chloride, boron trifluoride, and the like are used.

The condensation temperature is -10 to 150C, preferably 0 to 30C.
It is C. The condensation time can be arbitrarily selected from a range of several hours to 404 hours.

In addition, the alkaline treatment is, for example, 8% in an aqueous solution of caustic alkali.
What is necessary is just to stir at 0-100C for 2-3 hours.

Examples of recrystallization solvents include aromatic hydrocarbons such as benzene and toluene, halobenzenes such as monochlorobenzene and dichlorobenzene, halogenated aliphatic hydrocarbons such as chloroform and bromoform, isobutanol and impropatol. Alcohols are used.

Note that the diphenylanne derivative of formula M can be produced, for example, as follows.

The compound of the following formula (Vl) and bromobenzene are condensed under the boiling point in the presence of an acid binder such as potassium carbonate, sodium carbonate or magnesium oxide and a copper catalyst (such as copper powder, oxidized steel or acetic steel) to form the following formula: (~II) is obtained,
This compound is then hydrolyzed by refluxing it in water or an alcohol such as mechyl, ethanol or glopanol to produce a compound of formula (1).

(Vl) (■) (In the formula, Rx and L have the same meanings as in the above formula, and Rs represents water or lower alkyl.) Heat-sensitive and pressure-sensitive recording sheets using the coloring agent of the present invention can be produced, for example. After dispersing the binder in a dispersion medium, it can be prepared as follows.

The mixture is mixed, 6710 agents such as pigments and waxes are added as necessary, and the mixture is coated onto a sheet and dried.

In addition, the pressure-sensitive recording sheet uses a coloring agent, alkylated naphthalene,
After dissolving alkylated diphenyl, alkylated diphenylalkane, chlorinated paraffin, etc. in a bath agent, it is emulsified to several microns in an aqueous solution containing an emulsifier, protective colloid, etc. After encapsulation, binder additives and the like are added as required and applied to the sheet to form an upper sheet.

Color developers used in heat-sensitive and pressure-sensitive recording sheets include:
Examples include clay minerals such as acid clay, activated clay, and attapulgite kaolin, phenol derivatives, phenol resins, aromatic carboxylic acids or polyvalent metal salts thereof, and the like.

Further, materials for the recording sheet include paper, synthetic paper, synthetic resin film, and the like.

Examples will be shown below, but the present invention is not limited thereto. It should be noted that all parts in the examples indicate heavy f parts.

Example 1 Synthesis of 2'-Ayusuno-3'-methoxy6'-diethylamine-fluoran 2-(4'-diethylamino-2'-hydroxy-benzoyl)-benzoic acid 15.79- and 2.4- Dimethoxy-diphenylamine 11.5P to concentrated sulfuric acid 157? The mixture was dissolved in a bath and stirred at 10S-20C for 24 hours. The reaction mixture was poured into 11 pieces of ice water, and the precipitate was collected by filtration and thoroughly washed with water. Then, the product was added to 400 ml of 2 qb caustic soda aqueous solution.
In addition, the mixture was stirred at 80-90C for 3 hours and filtered to obtain crude fluoran. After drying, recrystallize from toluene to obtain 16.9
Obtain the 5' target. Yield 69% IR, 1760α (lactone ring) NM: 1.1 (t, 6H), 3.28 (q, 4
) T), 3.8 (a.

3I]), 6.1-8.6 (b, 1.Hl) Ma
aa: M 492 (molecular ion) This compound is 1! with silica gel! The color was purple and dark blue due to bisphenol A.

Note that 2,4-dimetho-1'' cydiphenylamine used in this example was produced as follows.

2.4-dimethoxyacetanilide 48.8i, bromobenzene 250P, potassium carbonate 18.5p% copper powder 0
．． 51 is allowed to react under reflux for 12 hours.

Next, 18 ff of potassium hydroxide and 70 ml of ethanol were added and refluxed for 4 hours for hydrolysis. After distilling off the ethanol, remove potassium carbonate, copper powder, etc. by filtration.
P liquid is distilled to obtain 2.4-dimethoxy-diphenylamine (54.8PC yield 95.8%), pale yellow liquid b
p, 191-195 c," 6 mmHg 21-hydro-dibenzoyl)-3,4,5,6-tetrachlorobenzoic acid 2
2.5P and 2.4-dimethoxydiphenylua? N11
．． 554 with 13 oz of sulfuric acid and 30 oz of 28% oleum. Melt and stir at 10 to 2 oct for 20 hours.

The reaction mixture was discharged into 11 ice water, neutralized with 48% aqueous sodium hydroxide solution, added with 400 vtl of 2% aqueous sodium hydroxide solution, stirred at 80-90c for 3 hours, and filtered to obtain crude fluoran. After drying, it is recrystallized from monochlorobenzene to obtain the desired product 19.2f.

Yield 61%, Mass3M 628 (molecular ion)
IR3745 Nishiki (lactone m) This compound developed a green-blue color with silica gel and green with bisphenol A.

Example 3 In Example 2, 2- (4'-diethyl minnow 2'-
Hydroxybenzoyl] = 4-N,N-diethylamine-2-hydroxy-4s'-benzo-benzophenone-instead of 3.4.5.6-tetrachlorobenzoic acid
The following compound is obtained in the same manner as in Example 2 using 2'-carboxylic acid.

Yield 58%, to 4assM 542 (molecular ion) I
R, 1745crn (Lacto 719) This compound develops evening purple in silica gel and dark blue in bisphenol.
child.

Next, a fluoran compound represented by the following formula (■) obtained by the same method as above, and its color hue and IR measurement results on silica gel will be shown.

λn Example h R+ Ri Rs X n
IRJla Sea Bream Example Embodiment 11 2'-Ayurina 3'-Metoya Sea 6'-
Diethylaminofluorane 30P'l'1Oqb PV
150 parts of A soap solution and 65 parts of water were crushed in a bowl for 24 hours to obtain 35 parts of bisphenol A as "component A".
50 parts of a 0% PVA aqueous solution and 65 parts of water were ground in a ball mill for 24 hours to obtain [-component B]. "Component Al
1 part and 15 parts of "Component B" are mixed, and the solid content of the paper is 5?
The heat-sensitive recording paper is discontinued so that it becomes /-. This thermosensitive recording paper develops a dark blue color at a temperature of 150°C, has no background coloration, and has an excellent fastness of M.

Example 13 2'-anilino-3'-methoxy6'
-diethylaminofluorane 2? Diisopropylnafculene 98? #Solution at 50c] -1 Gum arabic 20i and water 160 at this temperature? ' to emulsify by adding 7J []. Add acid-treated gelatin 20) and 16 oz of water to this and ply with acetic acid.
Set it to 5.

Next is ice water 500? Add and allow Core Cell Page to develop to form a warm liquid film of gelatin-gum arabic in place of diisoglobylnaphthalene oil/A and adjust the pH to:
After adjusting the temperature to 4.4, 37% Polmarin solution 41 was added to obtain a microcapsule warm body. 40% of this capsule liquid
? A paper with a basis weight of /nl has a dry solid content of 5? Apply it in such a manner that it becomes thick and dry to obtain an overlay sheet. The thus obtained overlay sheet was overlaid with a color developer sheet containing a phenylphenol-formaldehyde polymer, and the color was developed at a pressure of 5ook/7. Water resistance 80%,
A dark blue copy paper with excellent light fastness and light fastness of 95% was obtained.

Patent applicant: Nippon Kayaku Co., Ltd. 433-

Claims (1)

[Claims] Xn (In the formula, R1 and R2 represent lower alkyl, R3 represents methyl or ethyl. □ and the mountain represent lower alkyl, and R3 represents methyl or ethyl. ) A heat-sensitive or pressure-sensitive recording sheet containing a fluoran compound represented by C as a coloring agent.