JPH11240863A - New phenylsulfonyl hydrazide derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject new compound useful as a color-developing agent, a charge regulation agent, or the like, for heat-sensitive recording material. SOLUTION: This compound is expressed by formula I (R1 and R2 are each H, an alkyl, an aryl or a halogen), e.g. the compound of formula II. The compound of formula I can be produced by reacting phthalic anhydride (or its nucleus-substituted substance) with p-phenylsulfonyl hydrazide (or its nucleus- substituted substance) in a polar organic solvent such as acetonitrile at room temperature or under heating for several hours, leaving the produced reaction product at room temperature or under cooling to effect the crystal precipitation and subjecting the crystal to filtration and purification. The compound has carboxyl group and is usable as a color developing agent for heat-sensitive recording material together with leuco dye and other additives and also usable as a charge regulation agent, intermediate for Pharmaceuticals, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel sulfonyl hydrazide derivative having a carboxyl group. Since this compound has a carboxyl group, it is a compound useful as a color developer, a charge control agent, and the like used in a thermosensitive recording material.

[0002]

2. Description of the Related Art A recording material such as a thermal paper is generally used in combination with a leuco dye and other chemicals such as an acidic developer and a sensitizer for coloring the leuco dye.
The performance required of the heat-sensitive recording material includes thermal responsiveness and stability of a recorded image, and various color developers have been developed to improve these performances. As an acidic developer, bisphenol A having a phenolic hydroxyl group, a benzoic acid derivative having a carboxyl group, and the like are generally used, but it has been difficult to obtain those satisfying most of them.

Japanese Patent Application Laid-Open No. 7-195938 describes an N-substituted anthranyl derivative having a sulfonylhydrazide skeleton, but there is still room for improvement. JP-A-9-254542 discloses that a compound having a sulfonylhydrazide skeleton is used as a sensitizer. However, as can be seen from the absence of a carboxyl group, the use of a compound as a color developer is described. It does not teach use.

Accordingly, it is an object of the present invention to provide a novel phenylsulfonylhydrazide derivative having excellent performance as a developer for a heat-sensitive recording material.

That is, the present invention is a novel phenylsulfonylhydrazide derivative represented by the following general formula (1).

Embedded image (Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aryl group or a halogen)

In the general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen. As the alkyl group, a lower alkyl group having 1 to 6 carbon atoms is preferable. The group is preferably a phenyl group or a lower alkyl-substituted phenyl group. Examples of the halogen include fluorine, chlorine, and bromine.

The phenylsulfonyl hydrazide derivative of the present invention can be produced by reacting unsubstituted or nucleus-substituted phenylsulfonyl hydrazide with R ₁ and phthalic anhydride unsubstituted or nucleus-substituted with R _2. .

This reaction can be carried out, for example, under the following conditions. Phthalic anhydride (or its nuclear substitute) and p
-Phenylsulfonyl hydrazide (or its nuclear substitute)
Is reacted in an organic polar solvent such as acetonitrile for several hours at room temperature or under warming conditions, resulting in a reaction almost as theoretical amount. The obtained reaction product is left at room temperature or under cooling to precipitate crystals, which are collected by filtration, washed with a solvent such as acetonitrile, purified, and dried under reduced pressure to obtain a highly pure compound of the present invention. Can be.

Specific examples of the phenylsulfonyl hydrazide derivative of the present invention include the following compounds 1 and _{2 in} which R ₂ is hydrogen and R ₁ is hydrogen or a methyl group in the general formula (1). Other preferred compounds include those in which R ₂ is hydrogen and R ₁ is an ethyl group, a propyl group, a phenyl group, a toluyl group, or chlorine in the general formula (1).

[Compound 1]

Embedded image

[Compound 2]

Embedded image

The phenylsulfonyl hydrazide derivative of the present invention can be used together with a leuco dye and other additives as a color developer for the above-mentioned heat-sensitive recording material, and can also be used for applications such as charge control agents and pharmaceutical intermediates. it can.

[0013]

The present invention will be described below in detail with reference to examples. Example 1 81.4 phthalic anhydride in a flask equipped with a stirrer
g and 500 g of acetonitrile, and 93.1 g of p-toluenesulfonylhydrazide was added while stirring at room temperature. After stirring at room temperature for 3 hours, the precipitated crystals were collected by filtration and washed twice with 300 g of acetonitrile.
Drying under reduced pressure at 5 ° C. for 5 hours gave 158.8 g of compound 1 as white crystals. The melting point of the obtained crystal was 194 ° C.
The crystal was subjected to elemental analysis and measured for its infrared absorption spectrum and nuclear magnetic resonance spectrum. As a result, it was confirmed that the crystal was Compound 1. The results of elemental analysis are shown in Table 1, and the infrared absorption spectrum (JIR-100) is shown in FIG.
FIG. 3 shows the nuclear magnetic resonance spectrum (JNM-LA400).

Example 2 81.4 phthalic anhydride was placed in a flask equipped with a stirrer.
g, 500 g of acetonitrile, and 86.1 g of benzenesulfonylhydrazide were added while stirring at room temperature. After stirring at room temperature for 3 hours, the precipitated crystals were collected by filtration, washed twice with 300 g of acetonitrile, and then washed at 40 ° C.
And dried under reduced pressure for 5 hours to obtain 153.7 g of compound 2 as white crystals. The melting point of the obtained crystal was 217 ° C. The crystal was subjected to elemental analysis and measured for its infrared absorption spectrum and nuclear magnetic resonance spectrum. As a result, it was confirmed that the crystal was Compound 2. Table 2 shows the results of elemental analysis.
FIG. 2 shows an infrared absorption spectrum (JIR-100).
FIG. 4 shows the nuclear magnetic resonance spectrum (JNM-LA400).

[0015]

[Table 1]

[0016]

[Table 2]

Hereinafter, a thermosensitive recording paper is produced using the phenylsulfonyl hydrazide derivative of the present invention as a color developer,
evaluated. Example 3 (1) Preparation of solution A 20 parts by weight of 7'-anilino-3 '-(dibutylamino) -6'-methylfluorane, 10% by weight aqueous solution of PVA 1
0 parts by weight and 70 parts by weight of water were pulverized and mixed using a paint shaker to prepare a liquid A having an average particle size of 1.0 μm. (2) Preparation of Solution B 20 parts by weight of compound 1 as a developer and 10% by weight of PVA
10 parts by weight of the aqueous solution and 70 parts by weight of water were pulverized and mixed using a paint shaker to prepare a liquid B having an average particle size of 1.0 μm. (3) Preparation of Solution C 20 parts by weight of parabenzylbiphenyl as a sensitizer,
10 parts by weight of a 0% by weight aqueous PVA solution and 70 parts by weight of water were pulverized and mixed using a paint shaker to obtain an average particle size of 1.0
A μm C solution was prepared. (4) Preparation of thermal recording paper 60 parts by weight of liquid A, 120 parts by weight of liquid B, 120 parts by weight of liquid C, 15 parts by weight of paraffin wax emulsion (Hydrin Z-7 manufactured by Chukyo Yushi), paraffin wax emulsion (hydrin manufactured by Chukyo Yushi) P-7) A coating liquid is prepared by mixing 20 parts by weight and 120 parts by weight of a 10% by weight aqueous PVA solution, and this coating liquid is applied on a base paper and dried.
A thermosensitive recording paper having a coating amount of 6 g / m ² after drying was prepared.

(5) Coloring test The thermosensitive recording paper prepared in this manner was tested at 27 V,
A dynamic color development test was performed at 1.9 ms, and at the same time, the color density of the background was measured. Then, using the printed test paper,
A test for moisture resistance test and a test for plasticizer resistance test were performed. In addition,
The dynamic color test uses a printing tester (Okura Electric)
The color density was measured using a Macbeth reflection densitometer RD-914. (6) Humidity resistance test method The thermosensitive recording paper subjected to the dynamic color test was subjected to a thermo-hygrostat (50).
(C °, relative humidity 90%) for 24 hours, and then the color density of the printed portion was measured using a Macbeth reflection densitometer RD-914. The residual rate is calculated by the following equation (1).
Was calculated by Residual rate = (AB) / C (1) (where A represents the dynamic color density after the humidity resistance test, and B
Indicates a value obtained by subtracting the color density of the background before the humidity resistance test from the color density of the background after the humidity resistance test, and C indicates the dynamic color density before the humidity resistance test. (7) Plasticizer resistance test method A vinyl chloride wrap is brought into close contact with the entire printing surface of the thermosensitive recording paper subjected to the dynamic color development test. The test thermosensitive recording paper was stored in a dryer (40 ° C.) for 24 hours, and then the color density of the printed portion was measured using a Macbeth reflection densitometer RD-914. The residual ratio was calculated by the following equation (2). Residual rate = (DE) / F (2) (where D represents the dynamic color density after the plasticizer resistance test,
E indicates a value obtained by subtracting the color density of the background before the plasticizer resistance test from the color density of the background after the plasticizer resistance test, and F indicates the dynamic color density before the plasticizer resistance test. Table 3 shows the results of the dynamic color test, the humidity resistance test, and the plasticizer resistance test.

Example 4 In preparing the solution B of Example 1, the compound 2 was used in place of the compound 1.
A heat-sensitive recording paper was prepared in exactly the same manner as in Example 3 except that was used, and a color development test was performed in the same manner as in Example 3. Table 3 shows the results.

Comparative Example 1 A thermosensitive recording paper was prepared in exactly the same manner as in Example 3 except that bisphenol A was used in place of compound 1 in the preparation of solution B in Example 1. A color development test was performed in the same manner as described above. Table 3 shows the results.

Comparative Example 2 In preparing the solution B of Example 1, Np-
A thermosensitive recording paper was prepared in exactly the same manner as in Example 3 except that tolyl-2-carboxybenzamide was used, and a color development test was performed in the same manner as in Example 3. Table 3 shows the results.

[0022]

[Table 3]

[0023]

The phenylsulfonyl hydrazide derivative of the present invention is a compound useful as a color developer, a charge adjusting agent, and the like used in a heat-sensitive recording material.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the compound obtained in Example 1.

FIG. 2 is an infrared absorption spectrum of the compound obtained in Example 2.

FIG. 3 is a nuclear magnetic resonance spectrum of the compound obtained in Example 1.

FIG. 4 is a nuclear magnetic resonance spectrum of the compound obtained in Example 2.

Claims (1)

[Claims] 1. A novel phenylsulfonylhydrazide derivative represented by the following general formula (1). Embedded image (Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aryl group or a halogen)