Fluoran compound, process for preparation thereof and heat sensitive recording materials comprising said compound

Abstract: Disclosed are a novel fluoran compound represented by the formula (I): and a heat-sensitive recording paper which is obtained by using the fluoran compound as a chromogenic compound and is excellent in preserving stability.

Description: Background of the Invention 1. Field of the Invention The present invention relates to a novel fluoran compound which is useful as a chromogenic compound in a heat-sensitive recording materials, to a process for the preparation of the compound and heat-sensitive recording materials comprising said compound. 2. Description of the Prior Art A heat-sensitive recording system utilizing a color reaction between a colorless or pale colored electron donative compound (chromogenic compound) and an organic or inorganic electron acceptor (developer) has been widely popularized. In the recording system, fluoran compounds have widely been used as the chromogenic compunds. Many fluoran compounds are known in the prior art, for example those having the formulas (A), (B) and (C). Japanese Patent Publication SHO 48-43296 (1973) Japanese Patent Publication SHO 51-23204 (1976) Japanese Patent Laid-Open Publication SHO 60-35053 (1985) Japanese Patent Laid-Open Publication SHO 61-195891(1986)---- However, in the case of applying to the heat-sensitive recording material, the compound of the formula (A) has the defect that the compound itself colors gray to dark gray when mixed with a developer such as bisphenol A and provides only a gray to dark gray colored (soiled) paper by applying the mixture to a paper. The compound of the formula (B) or the formula (C) provides a paper having relatively high whiteness immediately after application. However, the coated paper has a disadvantage of coloring to gray or brown by moisture, light or heat. The heat-sensitive recording material has recently been used indoors as in the case of facsimile and additionally in the open air under more severe conditions as in the case of, for example, prepaid cards such as telephone cards. Consequently, the heat-sensitive recording materials are required to further enhance preserving stability. Object of the Invention The object of the present invention is to provide a novel fluoran compound having an excellent preserving stability as a chromogenic compound for use in the heat-sensitive recording materials, and additionally to provide a process for the preparation of a novel fluoran compound and heat-sensitive recording materials comprising a novel fluoran compound of this invention. Summary of the Invention One aspect of the present invention relates to a novel fluoran compound represented by Formula (I): Another aspect of the present invention relates to a process for the preparation of the fluoran compound of this invention by reacting a benzoic acid derivative represented by Formula (II): with a diphenylamine derivative represented by Formula (III): wherein R is a lower alkyl group. Further aspect of the present invention relates to a heat-sensitive recording materials comprising the fluoran compound of this invention. Brief Description of the Drawings Figure 1 illustrates an IR absorption spectrum (KBr tablet) of the fluoran compound of Formula (I). In this drawing, axis of ordinate indicates transmittance and axis of abscissa indicates wave number (cm⁻¹). Figure 2 illustrates an X-ray diffraction diagram on crystal powder of the fluoran compound of Formula (I). In this drawing, axis of ordinate indicates strength of diffraction and axis of abscissa indicates an angle of diffraction (2ϑ). Detailed Description of the Invention The benzoic acid derivative of Formula (II) for use in the preparation of the fluoran compound of Formula (I) can be prepared, for example, by reaction of 3-N-cyclohexyl-N-n-propylaminophenol with phthalic anhydride in the absence or presence of a solvent such as benzene, toluene, xylene and tetrachloroethylene. A Lewis acid, such as zinc chloride, may also be added to the reaction. The diphenylamine derivatives of Formula (III) has a lower alkyl group represented by R. Examples of the lower alkyl group are preferably methyl group and ethyl group, and methyl group is preferred in particular. The fluoran compound of Formula (I) can be prepared by reacting the benzoic acid derivative of Formula (II) with the diphenylamine derivatives of Formula (III) in the presence of a dehydrating condensation agents such as concentrated sulfuric acid, mixture of concentrated sulfuric acid and oleum, polyphosphoric acid, phosphorus pentoxide and anhydrous aluminum chloride, more preferably in concentrated sulfuric acid, and thereafter bringing the reaction mixture to an alkaline pH. The time and temperature of the dehydrating condensation reaction is not critical and is usually carried out at 0 to 100 °C for from several hours to 100 hours. When the reaction is carried out in concentrated sulfuric acid, the preferred reaction temperature is in the range of 0 to 50°C. The reaction time depends upon the selected reaction temperature and hence the reaction is conducted for a sufficient time to permit the reaction to go to completion. After the dehydrating condensation reaction is completed, the alkali treatment is usually carried out by the addition of a base, e.g., aqueous potassium hydroxide or sodium hydroxide solution to adjust the pH to an alkaline value, e.g., 9 to 12. The treatment can be conducted in the temperature range of 0 to 100 °C. The alkali treatment may also be conducted in the presence of an organic solvent other than water, for example, bezene and toluene. When preparing a heat-sensitive recording material of the present invention, the fluoran compound of the present invention is pulverized in water to form an aqueous dispersion. The aqueous dispersion is mixed with an aqueous dispersion of pulverized developer, and binder is added to the thus obtained mixture. Representative examples of developers which are suitable for use in the heat sensitive recording materials of the present invention include phenols such as bisphenol A, halogenated bisphenol A, alkylated bisphenol A, dihydroxyphenyl sulfone, halogenated dihydroxyphenyl sulfone, alkylated hydroxybenzoic acid esters, and hydroquinone monoethers; organic developers such as salicylic acid derivatives, salicylamide derivatives, urea derivatives, and thiourea derivatives; and inorganic developers such as acid clay, attapulgite, activated clay, aluminum chrolide and zinc bromide. Exemplary binder used for the heat-sensitive recording material of the present invention includes polyvinyl alcohol, modified polyvinyl alcohol, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, gum arabic, salt of styrene-maleic anhydride copolymer, and isobutylene-acrylic acid-maleic anhydride copolymer. Other additives can also be employed, exemplary other additives include fillers such as talc, kaolin and calcium carbonate, and if necessary, may also include sensitizers such as higher fatty acid amides, aromatic carboxylic acid esters, aromatic sulfonic acid esters, aromatic ethers, aralkyl ethers, aromatic hydrocarbons, aromatic substituted aliphatic hydrocarbons and other generally known sensitizers for the heat-sensitive recording materials; UV-absorbers; and defoamers. The coating liquid obtained by the addition of the above additives can be applied to a suitable substrate such as paper, plastic sheet and resin coated paper and used as the heat-sensitive recording material. The heat-sensitive recording system of the present invention can of course be used in an organic solvent system without any problem in place of the above aqueous dispersion system. The fluoran compound of Formula (I) can be used singly as the chromogenic compound. Further, in order to adjust the developed hue, other chromogenic compounds such as triphenylmethanelactones, fluorans and spiropyrans can also be added depending upon the demand. The fluoran compound of Formula (I ) has a melting point of 257 to 258 °C. The melting point is extraordinarily higher than those of known compounds, for example, from 195 to 198 °C of the compound of Formula (A), from 195 to 197 °C of the compound of Formula (B), and from 124 to 126 °C of the compound of the formula (C). The fluoran compound of Formula (I ) has also very low solubility in organic solvents, for example, hydrocarbons such as benzene and toluene, esters such as ethyl acetate, and ketones such as acetone. For example, the solubility of the compound of Formula (I) was compared with known fluoran compounds of Formulas (A), (B) and (C). The results are shown in Table 1. Solubility is indicated by weight percent in toluene at 25 °C. Compound Solubility (I) 0.5% or less (A) 8% (B) 5% (C) 12% A heat-sensitive paper having a high whiteness without soil can be obtained by using the compound of Formula (I ) having the above properties for the heat-sensitive recording material. The paper is extremely excellent in the preserving stability such as resistnace to moisture and solvents. For example, a heat-sensitive recording paper prepared by using bisphenol A as a developer and the compound of the invention of Formula (I) as a chromogenic compound is compared with the heat-sensitive recording papers prepared by using the compounds of Formulas (A), (B) or (C) on the moisture-heat resistnace and oil resistance of uncolored portion. Results are illustrated in Table 2. The moisture and heat resistnace test was carried out by keeping the heat-sensitive paper prepared from each compound at 60 °C for 24 hours in the relative humidity of 90 % and thereafter by visually observing the soil of the paper. The oil resistance test was carried out by bringing the heat-sensitive recording paper into contact with dioctyl phthalate and allowing to stand for a week and thereafter by visually observing the soil of the paper. Compound Immediately after application Moisture and heat resistance Oil resistance (I) ○ ○ ○ (A) ▵ × × (B) ○ × × (C) ○ × × Note: ○ Paper with a high whiteness without soil ▵ Paper soiled to pale gray × Paper soiled to gray The fluoran compound of Formula (I) differs from the fluoran compounds Formulas (A), (B) or (C) only in the substituent on the amino group at the 3 position of the fluoran structure. For example, the compound of Formula (I ) differs from the compound of Formula (B) in the substituent on the amino group at the 3 position being n-propyl group instead of methyl group. Although, these differences in chemical structure are small, as mentioned above, the fluoran compound of Formula (I) has a very high melting point and extremely low solubility in organic solvents as compared to the fluoran compounds of Formulas (A), (B) and (C). The preserving stability of the heat-sensitive paper can be greatly improved as described above by using the fluoran compound of Formula (I) of the present invention for the heat-sensitive recording material. As to the solubility in organic solvents, the solubility is generally thought to increase in organic solvents, in particular hydrocarbon solvents, by changing to a longer alkyl chain in such a manner that a methyl group is replaced by a n-propyl group. However, it is surprising that the fluoran compound of the formula (I) of the present invention has much lower solubility in toluene as compared with the fluoran compound of Formula (B). As an example of such replacement by the longer chain, the compound of Formula (D): which differs from methylamino substituted compound at the 3 position of the Formula (B) by an isoamylamino group and which has high solubility in organic solvents, in particular hydrocarbons such as toluene has been known as disclosed in Japanese Patent Laid-Open Publication SHO 54-34909 (1979). However, the fluoran compound of Formula (I) which has a n-propyl group on the amino group, that is, the compound of the present invention has a conventionally unknown characteristic that the solubility in toluene is extremely low as compared with the fluoran compound of Formula (B). Thus, the heat-sensitive recording paper having an excellent preserving stability can be provided by using the fluoran compound of the invention as the chromogenic compound. The present invention will hereinafter be illustrated further in detail by way of examples. However, it is to be understood that the invention is not intended to be limited to the specific embodiments. Example 1. [Preparation of the compound of Formula (I)] After dissolving 20 g of 2-(4′-N-cyclohexyl-N-n-propylamino-2′-hydroxybenzoyl)benzoic acid, i.e., the compound of Formula (II), in 100 m ℓ of concentrated sulfuric acid at 10 °C , 11 g of 4-methoxy-2-methyl-diphenylamine, i.e., the compound of Formula (III) wherein R is methyl was added at the same temperature and stirred at 10 to 25 °C for 48 hours. The reaction mixture was poured into 600 m ℓ ice water. The precipitated solid was collected, washed with water and added to 500 m ℓ of an 10 % aqueous sodium hydroxide solution. The mixture was stirred at 60 to 70 °C for 2 hours and filtered. The solid obtained was washed with water, with 100 m ℓ of isopropanol and then washed twice with toluene. Thus, 20 g of the desired 3-N-cyclohexyl-N-n-propylamino-6-methyl-7-anilinofluoran was obtained as almost colorless crystals. The yield was 69 %. Melting point was 257 to 258 °C. The IR absorption spectrum (KBr tablet) is illustrated in Figure 1. The X-ray diffraction diagram of crystal powder of the compound is illustrated in Figure 2. Example 2. [Preparation of heat-sensitive recording paper using the compound of Formula (I)] A mixture composed of 10 g of 3-N-cyclohexyl-N-n-propylamino-6-methyl-7-anilinofluoran, 5 g of a 10 % aqueous polyvinyl alcohol solution and 37.5 g of water was pulverized to a particle size of 3 µ with a sand mill. Separately, bisphenol A was dispersed in a similar manner to obtain a 38 % developer dispersion. To 65.8 g of the developer dispersion, 50 g of the above aqueous dispersion of 3-N-cyclohexyl-N-n-propylamino-6-methyl-7-anilinofluoran, 18.3 g of a 60 % aqueous dispersion of precipitated calcium carbonate, 88 g of 10 % aqueous polyvinyl alcohol solution and 51.9 g of water were added and mixed. The mixture thus obtained was coated to a white free paper by using a wire rod No. 10 and allowed to dry at room temperature to obtain a heat-sensitive recording paper having a very high whiteness without soil. The heat-sensitive recording paper thus obtained very quickly developed a slightly reddish black color by heating. The developed image had good preserving properties such as heat resistance, moisture-heat resistance, and light resistance. The heat-sensitive recording paper was allowed to stand at 60 °C for 24 hours in a 90 % relative humidity. After the test, the paper retained the whiteness obtained immediately after application and no soil was found at all. The applied surface of the heat-sensitive recording paper was brought into contact with dioctyl phthalate and stored for a week. After the test, no soil of the paper was observed at all. Results are illustrated in Table 2. Comparative Example Heat-sensitive recording papers were prepared by carrying out the same procedures as described in Example 2 except that 3-N-cyclohexyl-N-n-propylamino-6-methyl-7-anilinofluoran was replaced by 3-N,N-diethylamino-6-methyl-7-anilinofluoran, i.e., the compound of formula (A), 3-N-cyclohexyl-N-methylamino-6-methyl-7-anilinofluoran, i.e., the compound of Formula (B), and 3-N-cyclohexyl-N-octylamino-6-methyl-7-anilinofluoran, i.e., the compound of the formula (C), respectively. The moisture and heat resistance test and the oil resistance test were conducted. The results are illustrated in Table 2. The coated surface of the heat-sensitive recording paper prepared by using the compound of Formula (A) was already soiled to pale gray immediately after coating.

Claims: A fluoran compound represented by the formula (I): A process for the preparation of the fluoran compound of claim 1 which comprises reacting a benzoic acid derivative represented by the formula (II): with a diphenylamine derivative represented by the formula (III): wherein R is a lower alkyl group. Heat-sensitive recording materials comprising the fluoran compound of claim 1.

Inventors: HASEGAWA KIYOHARU, NAKATSUKA MASAKATSU, OTSUJI ATSUO, TAKAGI MASATOSHI, YAMAGUCHI AKIHIRO, HASEGAWA, KIYOHARU, NAKATSUKA, MASAKATSU, OTSUJI, ATSUO, TAKAGI, MASATOSHI, YAMAGUCHI, AKIHIRO
Applicants: MITSUI TOATSU CHEMICALS, MITSUI TOATSU CHEMICALS, INC.
Application year: 1990
Main classification: C07D493
IPC codes: B41M5, C07D493