JP3529147B2 - New isophthalic acid compounds - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an isophthalic acid compound which is useful as a color developer for leuco dyes, and more particularly to a thermosensitive recording which is particularly excellent in the stability of a color image. The present invention relates to an isophthalic acid-based compound that can be used as a color developer for paper. 2. Description of the Related Art Various recording materials have been proposed which utilize a color-forming reaction between a colorless or light-colored leuco dye and a color developer which is colored upon contact by heat and pressure. One such heat-sensitive recording material does not require complicated processing such as development and fixing, and can be recorded in a short time with a relatively simple device, has less noise, and has advantages such as low cost. It is useful as various recording materials for electronic calculators, facsimile machines, ticket vending machines, label printers, recorders and the like. As a color-forming dye used in a heat-sensitive recording material, for example, a colorless or light-colored leuco dye having a lactone, lactam or spiropyran ring, and as a developer, an organic acid, a phenolic substance or the like is conventionally used. ing. Thermosensitive recording materials using this leuco dye and a developer are widely used because of their high image density and high whiteness of the background. On the other hand, as the demand for the heat-sensitive recording system has increased in recent years, the demand for improving the preservability of recording chemicals, light, heat, and the like has been increasing, and the development of a recording material capable of meeting the demand has been strongly desired. [0004] In order to cope with high storage stability of recorded images, high-reliability developers such as those disclosed in JP-A-58-82788 and JP-A-60-13852 are disclosed.
Phenol sulfone compound is disclosed in
No. 47292 discloses a metal salt of benzoic acid.
Substituted salicylic acid compounds have been proposed in, for example, JP-A-2-169681, but heat-sensitive recording materials using these compounds as a color developer are still insufficient in terms of the fastness of the image area to oils, fats, plasticizers, water and the like. Hard to say. The object of the present invention is to provide a novel isophthalic acid compound which is extremely practical as a developer for leuco dyes whose color images are not easily erased by oils, fats, plasticizers, etc. Is to provide. The present inventors have conducted various studies to achieve the above object, and as a result, an isophthalic acid compound represented by the following formula (1) is suitable for the purpose. This led to the completion of the present invention. [0007] The isophthalic acid compound of the present invention comprises 1,3,3
By reacting 5-benzenetricarboxylic acid with benzyl chloride in the presence of sodium hydroxide, it can be synthesized easily, with high purity, and relatively inexpensively. When a thermosensitive recording material is produced by using the compound of the present invention as a developer, the leuco dye used is applied alone or as a mixture of two or more kinds. Any of those applied to a recording material of, for example, triphenylmethanephthalide type, triallylmethane type, fluoran type, fentidian type, thioferoran type, xanthene type, indophthalyl type, spiropyran type, azaphthalide type And leuco compounds such as chromenopyrazole, methine, rhodamine anilinolactam, rhodamine lactam, quinazoline, diazaxanthene and bislactone are preferably used. [0010] Examples of such compounds include the following. 3,3-bis (p-dimethylaminophenyl) -phthalide 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide 3,3-bis (p-dibutylaminophenyl) -phthalide 3-cyclohexylamino-6-chlorofluoran 3-dimethylamino-5,7- Dimethylfluoran 3- (N-methyl-N-isoamylamino) -6-methyl-7-anilinofluoran 3- (N-methyl-N-isobutylamino) -6-methyl-7-anilinofluoran 3 -(Np-tolyl-N-ethylamino) -6-methyl-7-anilinofluoran 3- (N-methyl-N-amylamino) -6 Methyl -
7-anilinofluoran 3- (N, N-di-n-amylamino) -6-methyl-
7-anilinofluoran 3- (N-methyl-N-cyclohexylamino) -6
Methyl-7-anilinofluoran 3- (N-methyl-N-iso-propylamino) -6
-Methyl-7-anilinofluoran 3- (N-ethyl-N-iso-propylamino) -6
-Methyl-7-anilinofluoran 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluoran 3-diethylamino-7,8-benzfluoran 3-diethylamino-7 -Chlorofluoran 3-diethylamino-7-methylfluoran 3-diethylamino-6-methyl-7-chlorofluoran 3-pyrrolidino-6-methyl-7-anilinofluoran 3-diethylamino-6-methyl-7- (M-trichloroanilino) fluoran 3-diethylamino-7- (o-chloroanilino) fluoran 3-dibutylamino-7- (o-chloroanilino) fluoran 3-diethylamino-6-methyl-7-anilinofluoran 3-dibutyl Amino-6-methyl-7-anilinofluoran 3-diethylamino-6-methyl 7- (2 ', 4'
Dimethylanilino) fluoran 3- (N, N-diethylamino) -5-methyl-7-
(N, N-dibenzylamino) fluoranbenzoylleucomethylene blue 6'-chloro-8'-methoxybenzoindolinospiropyran 6'-bromo-8'-methoxybenzoindolinospiropyran 3- (2'-hydroxy-4 ' -Dimethylaminophenyl) -3- (2'-methoxy-5'-chlorophenyl)
Phthalide 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-nitrophenyl)
Phthalide 3- (2'-hydroxy-4'-diethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl)
Phthalide 3- (2'-methoxy-4'-dimethylaminophenyl) -3- (2'-hydroxy-4'-chloro-5'-
Methylphenyl) phthalide 3-morpholino-7- (N-propyltrifluoromethylanilino) fluoran 3-pyrrolidino-7-trifluoromethylanilinofluoran 3-diethylamino-5-chloro-7- (N-benzyl-tri Fluoromethylanilino) fluoran 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluoran 3-diethylamino-5-chloro-7- (α-phenylethylamino) fluoran 3- (N-ethyl-N- p-Toluidino) -7- (α-
Phenylethylamino) fluoran 3-diethylamino-7- (o-methoxycarbonylphenylethylfluoran 3-diethylamino-5-methyl-7- (α-phenylethylamino) fluoran 3-diethylamino-7-piperidinoaminofluoran 2-chloro-3- (N-methyltoluidino) -7- (p
-N-butylanilino) fluoran 3,6-bis (dimethylamino) fluorenespiro (9,3 ')-6'-dimethylaminophthalide 3- (N-ethyl-N-cyclohexylamino) -5
6-benzo-7-α-naphthylamino-4′-bromofluoran 3-diethylamino-6-chloro-7-anilinofluoran 3- (N-ethyl-N-2-ethoxypropylamino)
-6-methyl-7-anilinofluoran 3- (N-ethyl-N-tetrafurfurylamino) -6
-Methyl-7-anilinofluoran 3-diethylamino-6-methyl-7-mesitidino-
4 ', 5'-benzofluoran 3- (p-dimethylaminophenyl) -3- {1,1-
Bis (p-dimethylaminophenyl) ethylene-2-yl} phthalide, 3- (p-dimethylaminophenyl) -3- {1,1-
Bis (p-dimethylaminophenyl) ethylene-2-yl {-6-dimethylaminophthalide 3- (p-dimethylaminophenyl) -3- (1-p-
Dimethylaminophenyl-1-phenylethylene-2-
Yl) phthalide 3- (p-dimethylaminophenyl) -3- (1-p-
Dimethylaminophenyl-1-p-chlorophenylethylene-2-yl) -6-dimethylaminophthalide 3- (4'-dimethylamino-2'-methoxy) -3-
(1 "-p-dimethylaminophenyl-1" -p-chlorophenyl-1 ", 3" -butadiene-4 "-yl) benzophthalide 3- (4'-dimethylamino-2'-benzyloxy)
-3- (1 "-p-dimethylaminophenyl-1" -phenyl-1 ", 3" -butadiene-4 "-yl) benzophthalide 3-dimethylamino-6-dimethylamino-fluorene-9-spiro-3 '(6'-dimethylamino) phthalide 3,3-bis {2- (p-dimethylaminophenyl) ethylene-2- (p-methoxyphenyl) ethenyl}-
4,5,6,7-tetrachlorophthalide 3-bis {1,1-bis (4-pyrrolidinophenyl) ethylene-2-yl} -5,6-dichloro-4,7-dibromophthalidebis ( p-dimethylaminostyryl) -1-naphthalenesulfonylmethanebis (p-dimethylaminostyryl) -1-p-tolylsulfonylmethane and the like. In the present invention, the compound represented by the above formula [1] is used as a color developer and various compounds having electron accepting properties, such as phenolic compounds, thiophenolic compounds, thiourea derivatives, and organic compounds. Acids and metal salts thereof can be used in combination. Specific examples thereof include the following, but are not limited thereto. 4,4'-isopropylidene diphenol, 4,4'-isopropylidenebis-o-methylphenol, 4,4'-sec-butylidenebisphenol, 4,4'-isopropylidenebis (2-tert −
Butylphenol) zinc p-nitrobenzoate, 1,3
5, -tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzylisocyanuric acid, 2,2-
(3,4′-dihydroxyphenyl) propane, bis (4-historoxy-3-methylphenyl) sulfide,
4- (β- (p-methoxyphenoxy) ethoxy) salicylic acid, 1,7-bis (4-hydroxyphenylthio)
-3,5-dioxaheptane, 1,5-bis (4-hydroxyphenylthio) -3-oxapentane, monobenzyl phthalate monocalcium salt, 4,4′-cyclohexylidenediphenol, 4,4 ′ -Isopropylidenebis (2-chlorophenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-2-methylphenol), 1,3-Tris (2
-Methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-diphenolsulfone, 4-isopropoxy-4'- Hydroxydiphenylsulfone, 4-benzyloxy-4′-hydroxydiphenylsulfone, 4,4′-diphenolsulfoxide, isopropyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, stearyl gallate, lauryl gallate, octyl gallate, 1,3-bis (4-hydroxyphenylthio) propane, N, N-diphenylthiourea, N, N-di (m-chlorophenyl) thiourea, salicylanilide, methyl bis (4-hydroxyphenyl) acetate, bis ( Benzyl 4-hydroxyphenyl) acetate, 1,3-bis (4 Hydroxyphenyl) benzene, 1,4-bis (4-hydroxyphenyl) benzene, 2,4'-diphenol sulfone, 3,3'-diallyl-4,4'-hydroxyphenyl sulfone, 3,
4-dihydroxy-4′-methyldiphenyl sulfone,
Zinc 1-acetyloxy-2-naphthoate, zinc 2-acetyloxy-3-naphthoate, 2-acetyloxy-
Zinc 1-naphthoate, α, α-bis (4-hydroxyphenyl) α-methyltoluene, antipyrine complex of zinc thiocyanate, tetrabromobisphenol A, tetrabromobisphenol S, 4,4′-thiobis (2-methylphenol ), 4,4′-thiobis (2-chlorophenol) and the like. Here, the ratio of the leuco dye to the isophthalic acid-based compound of the above formula [1] is suitably about 1: 1 to 1: 6 (weight). The heat-sensitive recording material obtained by using the isophthalic acid-based compound of the present invention thus obtained as a color developer has the following characteristics. 1) The developed image is extremely stable without erasing the color over time or causing a white powder phenomenon. 2) By using the above-mentioned isophthalic acid-based compound, a heat-sensitive recording material having extremely excellent image stability, in which a color-developed image is not erased by an oil or a fat or a plasticizer, can be obtained. Next, the present invention will be described in more detail with reference to examples. All parts and percentages shown below are based on weight. Example 1 In a 300 ml Erlenmeyer flask, 40 ml of DMSO was added with 1,
Disperse 21.0 g of 3,5-benzenetricarboxylic acid. Next, put benzyl chloride 1 in the same Erlenmeyer flask.
Add 2.7 g and stir. 4.3 g of sodium hydroxide (93%) was added to a dropping funnel with a side tube at the top of an Erlenmeyer flask.
Dissolve in 0 ml of water. The Erlenmeyer flask is heated, and when the solution becomes transparent, an aqueous solution of sodium hydroxide is added dropwise (1 drop / 4 to 5 sec). A white precipitate forms with the addition. After the completion of the dropwise addition, a heating reaction was performed for 1 hour under the reflux condition of DMSO. After the heating was completed, the reaction solution was cooled, and the reaction solution was poured into 700 ml of water, stirred, and the precipitated white crystals were collected by filtration and sufficiently washed with water. After drying, it was recrystallized from ethanol to give 5-benzyloxycarbonylisophthalic acid 17.9.
g was obtained. 267 ° C. Elemental analysis values were as shown in [Table 1]. [Table 1] Application Example 1 The following mixtures were pulverized in a magnetic ball mill for 2 days to prepare [Solution A], [Solution B], and [Solution C]. [Solution A] 3-N, N-dibutylamino-6-methyl-7-anilinofluorane 20 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 60 parts [Solution B] 5-benzyloxycarbonylisophthalic acid 20 parts Polyvinyl 10% aqueous solution of alcohol 20 parts Water 60 parts [liquid C] 20 parts of calcium carbonate 20 parts methylcellulose 20 parts water 60 parts Next, [liquid A] 10 parts, [liquid B] 30 parts, [liquid C] 40
And Chukyo Yushi Zinc Stearate Dispersion (Product Name
10 parts of Hydrin Z730 (concentration: 30%) were mixed to form a thermosensitive color-forming layer forming solution, which was obtained from commercially available high-quality paper (basis weight: 52 g).
/ M ² ) is 0.5 g / m ² after drying.
After coating and drying to provide a heat-sensitive coloring layer, the surface of the layer was calendered so that the surface smoothness was 500 to 600 seconds to prepare a heat-sensitive recording material. Comparative Example 1 A heat-sensitive recording material was prepared in the same manner as in Example 1 except that the following [Liquid D] was used in place of the [Liquid B]. [Solution D] 4,4'-isopropylidene diphenol 20 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 60 parts The thermosensitive recording material prepared as described above was printed with a printing device manufactured by Matsushita Electronic Components. . The color density was measured with a Macbeth densitometer RD-914. The test conditions and test items are as follows. Power: 0.68 w / dot, line cycle: 10 ms / L
Ine 1) Oil resistance: After applying cottonseed oil (Kanto Chemical Reagents) to the image area and the background area, the densities were measured with a Macbeth densitometer RD-914 after storage for 16 hours under dry conditions at 40 ° C. 2) A vinyl chloride wrap film made of Shin-Etsu Polymer (Polymer Wrap 300) is superposed on the image area and the background area, and a load of 5 kg is applied. The densities after storage for 16 hours under a drying condition of 40 ° C. are measured with a Macbeth densitometer RD-914. Measured with The above results are shown in [Table 1]. [Table 1] As is apparent from the above results, the heat-sensitive recording material using the compound of the present invention has extremely high image stability against fats and oils, plasticizers and the like. As is apparent from the above description, when the isophthalic acid compound of the present invention is used as a developer for a leuco dye in a thermosensitive recording material, a color image can be easily formed with oils and fats, a plasticizer and the like. Shows extremely high image stability without decoloring.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-76180 (JP, A) JP-A-7-49590 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 69/767 C07C 69/80 B41M 5/12-5/22

Claims (1)

(57) [Claims] [Claim 1] A novel isophthalic acid-based compound represented by the following [Chemical Formula 1]. Embedded image