JPS5852356A - Fluoran derivative, production thereof and recording paper containing the same - Google Patents

Abstract

NEW MATERIAL:Fluoran serivatives of formulaIwherein R<1> is H, lower alkyl; R<2> is halogen; R<3> is lower alkyl. USE:Color coupler for heat-sensitive or pressure-sensitive recording paper. PREPARATION:A diphenylamine derivative of formulaI(wherein R<2> is halogen; R<3> is lower alkyl; R<4> is H, lower alkyl) is reacted with a keto carboxylic acid derivative of formula II (wherein R<1>, R<5> are the same or different groups, and each is H, lower alkyl) in the presence of a dehydration-condensation agent such as conc. sulfuric acid at -20-180 deg.C, perf. 0-50 deg.C to produce the desired compound. Usually, the reaction is completed in 1-50hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel fluoran derivative, a method for producing the same, and a recording paper containing the compound.

The fluoran derivative of the present invention is a novel compound that has not been described in any literature, and is represented by the following general formula (1).

[In the formula, R1 represents a hydrogen atom or a lower alkyl group, B2 represents a halogen atom, and R3 represents a lower alkyl group.

] In the above general formula (1), examples of the lower alkyl group include methyl, ethyl, pyl, -isopropyl,
Examples of the halogen atom include a luptyl, 5ac-butyl, and tart-butyl group, and examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

The fluoran derivatives of the present invention are almost colorless substances in themselves, but when brought into contact with electron-accepting substances such as organic acids, acid clay, activated clay, phenol-formaldehyde resin, bisphenol A, etc. It has the property of developing color. The fluoran derivatives of the present invention are compounds useful as color formers for heat-sensitive or pressure-sensitive recording papers.

Examples of compounds similar to the fluoran derivative represented by the above general formula (1) include 3-diethylamino-6-methyl-7-anilinofluoran (hereinafter referred to as "compound A") represented by the formula, 3-diethylamino-6-methyl-7-anilinofluoran represented by the formula -diethylamino-7-anilinofluorane (hereinafter referred to as "compound B") and the like are known [see Berly Patent No. 744,705].

However, when Compound A or Compound B is used as a coloring agent for heat-sensitive or pressure-sensitive recording paper, there are various drawbacks. That is, when Compound A or Compound B is used as a coloring agent for thermal recording paper, Compound A or Compound B has already developed a black or green color during the production of thermal recording paper, and as a result, the stain on the background of the recording paper is extremely dark. color (this phenomenon is referred to as "
It is extremely difficult to produce a practical thermosensitive recording paper. Moreover, thermal recording paper containing Compound A or Compound B as a coloring agent has low coloring sensitivity;
It will not develop a deep color unless heated to 30°C or higher. Furthermore, when compound A or compound B is used as a coloring agent for pressure-sensitive recording paper, compound A or compound B may be unstable with respect to the mineral acids used in the production of pressure-sensitive recording paper. It is difficult to produce a practical pressure-sensitive recording paper that avoids color development of Compound A or Compound B during production. On the other hand, when the fluoraci derivative of the present invention is used as a coloring agent for heat-sensitive or pressure-sensitive recording paper, the above drawbacks do not occur. That is, when the compound of the present invention is used as a coloring agent for pressure-sensitive recording paper, self-coloring does not occur during the production of heat-sensitive recording paper, and it has excellent storage stability and can be used for 1 to 2 months after production. Even so, there is no risk that the Mukuroki Kamakami will be colored. Furthermore, this thermal recording paper has excellent color development sensitivity.
Even at a relatively low 1i of around 20°C, the color develops sufficiently deep. Furthermore, when the compound of the present invention is used as a coloring agent for pressure-sensitive recording paper, the compound of the present invention is stable against the mineral acids used in the production of the recording paper. Practical pressure-sensitive recording paper can be manufactured without color development.

The 5-fluoride derivative of the present invention can be produced by various methods, and a preferred example thereof is as follows: [In the formula, R4 represents a hydrogen atom or a lower alkyl group.

R2 and R3 are the same as above 2] Diphenylamine derivatives represented by the general formula [wherein R5 represents a hydrogen atom or a lower alkyl group].

R1 is the same as above. ] is easily produced by reacting with a ketocarboxylic acid derivative represented by

In the reaction between the compound of general formula (2) and the compound of general formula (3), the ratio of the two to be used is not particularly limited and can be appropriately selected within a wide range, but usually 0.00% of the former is used for the latter. It is preferable to use 5 to 2 times the molar amount, preferably about the same molar amount. The reaction is carried out in the presence of a dehydration condensation agent. Examples of dehydration condensation agents include concentrated sulfuric acid, fuming sulfuric acid, phosphoric anhydride, polyphosphoric acid, etc., and such dehydration condensation agents are usually used in a large excess amount relative to the compound of general formula (2).

The reaction can be carried out under cooling, at room temperature, or under heating, but is usually -20 to 180°C, preferably 0 to 50°C.
The reaction proceeds suitably at a temperature of 0.degree. C. and is generally completed in about 1 to 50 hours.

The general formula used as a starting material in the above reaction (!
The diphenylamine derivative represented by ) can be easily produced, for example, as shown in the reaction formula below.

(41(Ml +!1 ↑ (61fit
(7) [In the formula, X represents a halogen atom and Y represents an acyl group. B2, R3 and R4 are the same as above. ]
The diphenylamine derivative represented by general formula (2) is
Aniline derivatives represented by general formula (4) and general formula (6)
), or an aniline derivative represented by the general formula (@) is reacted with a genobenzene derivative represented by the general formula Tel, and then a halogenobenzene derivative represented by the general formula (1) is produced. It is produced by deacylating a diphenylamine derivative.

In the reaction between the compound of general formula (4) and the compound of general formula (5), the ratio of both to be used can be appropriately selected within a wide range, and usually the latter is used in an amount of 1 to 10 times the molar amount of the former.
It is preferable to use about equimolar amounts. The reaction is carried out in the presence of a basic compound such as potassium carbonate using copper powder, cuprous chloride, cuprous bromide, cuprous oxide, cuprous acetate, etc. as a catalyst. In addition, the reaction is usually 100 to 250
The reaction between the compound of general formula (6) and the compound of general formula (5) is carried out under heating at about ) is carried out under the same reaction conditions as the reaction of the compound of the general formula (Kl).Deacylation of the compound of the general formula (]) is carried out, for example, by the reaction of the compound of the general formula (1).
A lower alcohol such as methanol or ethanol may be added to the compound, and the mixture may be heated to a flowing temperature together with an alkali hydroxide such as sodium hydroxide or potassium hydroxide. The heating time may normally be about 5 to 50 hours.

The thus obtained compound of the present invention can be easily isolated from the reaction mixture (by conventional isolation methods such as recrystallization, vacuum distillation, etc.). 1 will be given.

The heat-sensitive or pressure-sensitive recording paper of the present invention contains a full 5th:Jll conductor represented by the above general formula (1) as a coloring agent.

In producing the heat-sensitive recording paper of the present invention, the sub-recording paper is produced by applying a coating liquid in which an organic acid or phenolic substance and a coloring agent are dispersed in a binder onto a support. Ru. Organic acids, phenolic substances, binders and supports are those conventionally known in this field, such as
Those described in Japanese Patent Publication No. 14531, Japanese Patent Publication No. 52-20142, etc. can be widely used. The amount of the compound of the present invention used as a color former is preferably about the same amount as that of conventionally used color formers.

Further, in manufacturing the pressure-sensitive recording paper of the present invention, a wide variety of conventionally known methods can be applied. For example, the pressure-sensitive recording paper of the present invention is disclosed in US Pat. No. 2,548,366 and US Pat.
It is manufactured according to the method described in Specification No. 57, Specification No. 2800458, etc.

In the present invention, a full 5th derivative of general formula (1) is used as a coloring agent, but other components (for example, an electron-accepting solid acid, etc.) are widely used as described in the above-mentioned US patent specification. Can be used. The amount of the compound of the present invention to be used as a coloring agent is preferably about the same amount as that of a conventionally used coloring agent.

Examples will be given below to further clarify the present invention.

Example Heavy diethylamino-6-di0-7-valatriylfur No. 5
Production of Compound I (α) 4 of 3-O-4-acetaminoanisole, 42 t of toluene, 29.1 f of potassium carbonate and 1.5 t of copper powder were heated under reflux for 24 hours, 4
Potassium hydroxide (No. 01) and methyl alcohol (No. 2501) are added, and the mixture is further heated under reflux for 24 hours. Then, the toluene layer was extracted with 500 ml of toluene, and the toluene layer was distilled under reduced pressure to obtain 4'-methyldiphene:L7E-38.2F (yield 77.0'll). )
get.

Boiling point 182~b Elemental analysis CHN C1 Theoretical value (IG) 73,20 5,57 5.3 now
6.75 Analysis value (%) 73.1+ 5.54 5
．． 37 6.81 (h) 10.4t of 2-chlor-
12
0ff) 4-diethylamino-2-hyde
'-Sibenlifuenone and 541 concentrated sulfuric acid in carbo
After stirring at room temperature for 4 hours, the precipitate was drained into 700-g of ice water, collected in a furnace, washed with a caustic sorter solution, and then recrystallized in a tornige sieve to give 3 of l f, 5 F (yield 58.89 G). −
Diethylamino-6-di0-7-valatriylfur No. 5
get shi. This compound is a slightly colored crystal (melting point 180.5~
181.5°C) and develops a black-purple color on silica gel. .

Elemental analysis CHN CL Theoretical value (CH) 72.86 5.33 5.48 6
．． 94 analysis value (IIG) 72.79 5.26 5
．． 54 6.98 Example 2 Production of diethylamino-6-di0-7-varanithylanilinofluorane (compound ■) (g) +7. ot of 3-ri0-4-acetaminoanisole, 50 to
p-koyoruzu0mbeshit! Shi,! Reacted in the same manner as in (a). 32.9 f (E rate 53.45 k) (02-ri OL-4-J) +! /-4'-tech'? L diphenylamine (boiling point 209-211'C/10 WHt)
get.

(A) 10 f of 2-ri 0-metho-4'-ethyldiphenyl-acid and 12.5 f of 4-! ;Ethylua! Example of No2-Hyde0oNakace2'-CarboNakashibeshifuenoshi in 561L/concentrated sulfuric acid! The reaction was carried out in the same manner as in (b) to produce 10.7F (yield: 53.
3*) Obtain. This compound is a slightly colored crystal (melting point 187.8
~189.0°C) and develops a black-purple color on silica gel.

Elemental analysis CHN CL Theoretical value (*) 73.20 5.57 5,34 6
．． 75 analysis value (ch) 73.14 5.54 5.3
7 6.81 Example 3 3-, ; Production of methylamino-6-chloro-valatrylfluor-5 (compound ■) ′
-Methyldiphenylamine20. Example t <b
19.0f (yield: 51.0f) was reacted in the same manner as above to obtain 3-dimethylamino-6-diO-7-valatriylfur.
21g') obtained. This compound is a slightly colored crystal (melting point 15
3.2-155.4°C) and develops a black-purple color on silica gel.

Example 4 Manufacturer of 3-, methylamino-6-ly0-7-methatolylfluorane (compound ■) 48.6f of 3-ly0-4-acetaminoanisole, 50f of metatolylfluorane, 55.32 of potassium carbonate and 2f of copper powder were reacted in the same manner as in Example (→) to give 2-di-4-methoxy-3'-methyldiphenylamide: J41.1 f (68,2) get.

(Boiling point 179-181℃/w#f) (A) 2or's 2-
Example 1'( 3-dimethylamino-6-di0-7-methatoryl was reacted in the same manner as in A). Fluorane is obtained with a yield of 17.6 fC (47.5*). Kono compound is a slightly colored crystal (melting point 219.5-221.2℃)
It develops a black-purple color on silica gel.

Example 5 Production of 3-diethylamino-6-riO-7-orthoethylanilinofur No. 5 (Compound ■) (a) 23.
59 3-0-4-acetaminoanisole, 25
Orthoethylbenzene of f, potassium 171Fo acid and 2.52 of copper powder were reacted in the same manner as in Example 1 (α) to produce 14.8f (yield 48.0%) of 2-0-4
(A) Next, 10 f of 2'-ethyldiphenylamine and 12.5 t of 4-diethylamino-2-hyde. Example 1 (A)
11.5F (yield: 57.3%) of 3-diethylamino-6-di0-7-orthoethylanilinofluorane was obtained.

This compound has slightly colored crystals (melting point 169.8-172.3).
°C) and develops a black-purple color on silica gel.

Example 6 Production of thermal recording paper 15 f (D compound ■, ■, ■, ■ or v for 7
Grind and disperse using a mixer in a 10% aqueous polyvinyl alcohol solution of 5F and 329 water (referred to as component A). 35F bisphenol A is similarly ground and dispersed in a 150fO10 polyvinyl alcohol aqueous solution and 65F water (component B). 3t component A and 67
Component B of f2 is mixed and applied to paper to a dry weight of about 5 f/-. No self-coloring occurred during the manufacturing process or storage of these recording papers. These recording papers can be heated with a thermal pen, etc., and may contain compounds ■, ■, ■,
When using either (1) or (2), the color developed to black very quickly.

A thermosensitive recording paper is obtained in the same manner as above except that Compound A or B is used. Self-coloring occurred during the manufacturing process of this recording paper, and the recording paper was colored pale purple when Compound A was used and pale green when Compound B was used.

Further, when the coloring temperature of these recording papers was investigated, the results shown in Table 1 below were obtained.

Table 1 ◎Extremely dark color develops 0 Dark color develops △Light color develops 100
F is dissolved in bicyclic diphenyl, and this is added to a solution of 2Of arabicum and 1601 in water to emulsify. Next, add a solution of 2Of acid-treated tatisi and 16Of water, add acetic acid under stirring to lower the pH to 5,
Add water of f to cause coacervation. The pH is further lowered to 4.4t, and then 4f of 37-formalin aqueous solution is added. The above operations are carried out at 50°C, and then the mixture is cooled to 10°C to form a gel, and then the PIT is raised to 9 and left to stand for several hours to complete the cell forming operation.

This aqueous dispersion is applied to the lower surface of the upper leaf, and a solid acid such as acid clay or phenol-formalin resin is applied to the upper surface of the lower leaf, respectively, to obtain pressure-sensitive copying paper. By applying local pressure with a typewriter, ballpoint pen, etc., this copying paper will turn black very quickly if it is made of acid clay, or green if it is made of phenol-formalin resin. do. The color development during the manufacturing process of these copy papers is extremely pale.

Pressure-sensitive copying paper is obtained in the same manner as above except that compound A or B is used. During the manufacturing process of this copy paper, a very dark color developed.

(that's all)

Claims (1)

[Claims] ■ General formula [In the formula, R1 represents a hydrogen atom or a lower alkyl group, R2 represents a hexagen atom, and R3 represents a lower alkyl group, respectively.
] A fluoran conductor represented by . [In the formula, R2 represents a halogen atom, R3 represents a lower alkyl group, and R4 represents a hydrogen atom or a lower alkyl group, respectively. Diphenylamino: JII conductor represented by the general formula 〇 [wherein R1 and R5 are the same or different and represent a hydrogen atom or a lower alkyl group. [In the formula, R1, R2 and R3 are the same as above. ] A method for producing a fluoran derivative represented by (2) General formula [In the formula, R1 represents a hydrogen atom or a lower alkyl group, R2 represents a halogen atom, and R3 represents a lower alkyl group, respectively. ] A heat-sensitive or pressure-sensitive recording paper characterized by containing a fluoran derivative represented by the following as a coloring agent.