JPH072758A - New bis(arylsulfonylureido)benzene compound - Google Patents

Abstract

PURPOSE:To obtain a new compound consisting of a bis(arylsulfonylureido) benzene compound useful for developers, etc., of heat-sensitive recording body capable of forming color image having high sensitivity and good oil resistance, plasticizer resistance and storage stability by heating. CONSTITUTION:An arylsulfonylisocyanate (e.g. p-toluenesulfonyl isocyanate) expressed by formula I (R<3> is H, halogen or methyl) is made to react with an aromatic diamine compound (e.g. m-phenylenediamine) expressed by formula II (R<1> and R<2> are H, halogen or methyl) in a solvent such as acetonitrile while heating at 70 deg.C under stirring and the resultant reaction liquid is cooled to ambient temperature and the produced precipitation is filtered to provide the objective bis(arylsulfonylureido)benzene compound expressed by formula III and having high sensitivity and capable of forming color image and excellent in oil resistance and plasticizer resistance when used as a developer for heat- sensitive recording body.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel bis (arylsulfonylureido) benzene compound. The present invention relates to a heat-sensitive recording material that forms a color image by heating, and particularly to a heat-sensitive recording material that does not lose a once-colored image and is excellent in storage stability of recording.

[0002]

2. Description of the Related Art A heat-sensitive recording material which can utilize the compound of the present invention is generally a support such as paper, synthetic paper or plastic film, on which a color-forming substance such as an electron-donating leuco dye is added.
A thermosensitive coloring layer containing a color-developing substance such as an organic acidic substance such as an electron-accepting phenolic compound as a main component is provided. Such a heat-sensitive recording material can form a recorded image by applying heat energy. Such thermal recording materials are disclosed in JP-B-43-4160, JP-B-45-14039, JP-A-48-27736 and the like, and are widely put into practical use.

The thermosensitive recording medium as described above has a compact and inexpensive recording device and is easy to maintain. Therefore, the output of a computer, a facsimile, an automatic ticket vending machine, a printer of a scientific measuring instrument, or a CRT medical measuring instrument is used. Widely used for printers and the like. However, in a conventional dye-type thermosensitive recording medium prepared by coating a thermosensitive coloring layer containing a color-forming dye substance, a color-developing substance and a binder as an active ingredient on a support, the coloring reaction is Being reversible,
It is known that a color image disappears over time. This decolorization is accelerated under exposure to light, high humidity and high temperature, and further progresses promptly by contact with plasticizer and oil,
The image is erased to an unreadable level.

There have been extensive attempts to solve this problem of decolorization by introducing new compounds into the color forming system. For example, those using the dimerized fluorane dye found in JP-A-62-121769, JP-A-62-16
Japanese Patent Application Laid-Open No. 3899/1993, which uses a metal salt of a specific salicylic acid derivative found in 9681 as a developer, and a coloring system which does not use a fluoran-based leuco dye.
No. 6, etc., 3-amino-1-imino-4,
For example, a non-reversible heat-sensitive material composed of 5,6,7-tetrachloro-1H-isoindole and 4,4 ′, 4 ″ -triisocyanate-2,5-dimethoxytriphenylamine is used.

When the above-mentioned dimerized fluoran dye is used, even if it is used together with a phenol-based developer, the storability of a color image is improved correspondingly. However, it has the drawbacks that the resulting heat-sensitive recording material has a considerably low whiteness and a low thermal response, that is, a low sensitivity. When a specific metal salt of salicylic acid is used as a color developer, the oil resistance and plasticizer resistance of the obtained color image are improved, but the white paper color is observed in the heat resistance test, and the effective specific salicylic acid It has the disadvantage that the scientific structure is complicated and expensive.

Further, 3-amino-1-imino-4,
When a heat-sensitive material composed of 5,6,7-tetrachloro-1H-isoindole and 4,4 ′, 4 ″ -triisocyanato-2,5-dimethoxytriphenylamine was used, the colored image portion was certainly colored. Although it is tough, the non-image area, that is, the blank area, develops a red color when it comes into contact with the plasticizer, and the image quality is significantly impaired.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and a thermosensitive recording material obtained by using the same has high whiteness and excellent sensitivity, oil resistance and plasticizer resistance. Another object of the present invention is to provide a new developer compound capable of forming a colored image excellent in long-term storage stability of the colored image such as moisture resistance and heat resistance.

The heat-sensitive recording material using the novel developer compound of the present invention can be used not only as a heat-sensitive recording type ticket for an automatic ticket vending machine, but also as a coupon ticket or a commuter ticket which requires preservation. It is also highly suitable as a label for a POS bar code system that is attached to the packaging surface of a food packaged with a polyvinyl chloride film that cannot be avoided from contact with plasticizers and fats and oils. Further, the thermosensitive recording medium using the novel color developer of the present invention has excellent characteristics such that it can be used as a facsimile paper or a word processor paper for long-term storage, or an image printer paper for CRT.

[0009]

DISCLOSURE OF THE INVENTION The inventors of the present invention have developed a novel method in which storage stability improving effects such as oil resistance and plasticizer resistance of a color image are exhibited within a short time after formation of the color image. We have designed, synthesized, and studied various developer compounds, and as a result, have succeeded in producing a novel compound useful as a developer.

That is, the compound of the present invention has the following chemical formula (I)

[Chemical 2] A bis (arylsulfonylureido) benzene compound represented by

The compounds of formula (I) according to the present invention are 1,
It includes a 2-bis (arylsulfonylureido) benzene compound, a 1,3-bis (arylsulfonylureido) benzene compound, and a 1,4-bis (arylsulfonylureido) benzene compound. Of these compounds, two arylsulfonylureido groups bound to a benzene ring at a meta-substitution position,
That is, 1,3-bis (arylsulfonylureido)
Benzene compounds are preferred.

[0012]

The compound of the present invention acts as a developer for a thermosensitive recording medium. That is, the compound of formula (I) of the present invention does not have an acidic functional group such as a phenolic hydroxyl group or a carboxyl group, but has a strong color developing ability for a basic leuco dye. It is understood that this is because the urea group in the compounds of the present invention is activated by the sulfonyl group adjacent to it. Further, it is understood that the high storability of the image formed by the compound of the present invention and the leuco dye in various environments is due to the synergistic effect of the two arylsulfonylurea groups.

The compound of formula (I) of the present invention can be synthesized, for example, by the following reactions (1) to (3).

[Chemical 3]

The above reactions (1) and (2) are carried out in an organic solvent, and the reaction (3) is carried out under interfacial conditions or in a mixed solvent with water. The reaction solvent for the reactions (1) and (2) is not particularly limited as long as it reacts with isocyanates to inhibit the above reaction, but in order to keep the whiteness of the produced compound high, It is preferable to use a non-aromatic solvent. If the reaction product is brought into contact with an aromatic solvent at a particularly high temperature, the whiteness of the reaction product may be reduced.

Preferred reaction solvents include, for example, dichloromethane, chloroform, carbon tetrachloride, aliphatic halides such as trichloroethylene, acetonitrile, aliphatic nitriles such as propionitrile, ethyl acetate,
Aliphatic esters such as propyl acetate and butyl acetate,
Examples thereof include aliphatic ethers such as ethylene glycol dimethyl ether and dibutyl ether, and aliphatic ketones such as cyclohexanone.

The compound of formula (I) of the present invention includes a dye precursor (leuco dye) and a heat-fusible aromatic compound having a melting point of 60 ° C. to 150 ° C. (this is a substance generally known as a sensitizer). And a binder for fixing these components to the support to form the thermosensitive color forming layer of the thermosensitive recording medium. Furthermore, the heat-sensitive coloring layer preferably contains an organic or inorganic pigment, and if necessary, a conventionally known phenol-based or organic acid-based developer, antioxidant, ultraviolet absorber, or Waxes may be included.

The dye precursor used with the developer of the present invention can be selected from conventionally known leuco dyes such as triphenylmethane type, fluorane type and diphenylmethane type compounds. Examples of such dye precursors include 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-
Yl) -4-azaphthalide, crystal violet lactone, 3- (N-ethyl-N-isopentylamino)
-6-Methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluorane, 3- (N-ethyl-N-p-toluidino) -6-methyl-7-anilinofluorane, 3-
Pyrrolidino-6-methyl-7-anilinofluorane, 3
-Dibutylamino-6-methyl-7-anilinofluorane, 3- (N-cyclohexyl-N-methylamino)-
6-methyl-7-anilinofluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-diethylamino-7- (m-trifluoromethylanilino) fluorane, 3-diethylamino-6-methyl-7
-Chlorofluoran, 3-diethylamino-6-methylfluorane, and 3-cyclohexylamino-6-chlorofluorane, 3- (N-ethyl-N-hexylamino) -6-methyl-7- (p-chloroanilino ) One or more selected from fluoran and the like can be used.

As the above-mentioned sensitizer, for example, 1-hydroxy-2-naphthoic acid phenyl ester (Japanese Unexamined Patent Publication (Kokai) 57-57
-1910989), p-benzylbiphenyl (JP-A-60-82382), benzylnaphthyl ether (JP-A-58-87094), dibenzyl terephthalate (JP-A-58-98285), p-benzyloxybenzoic acid. Benzyl acid (JP-A-57-201691), diphenyl carbonate, ditolyl carbonate (JP-A-58-136489).
No.), m-terphenyl (JP-A-57-89994).
No.), 1,2-bis (m-tolyloxy) ethane (JP-A-60-56588), 1,5-bis (p-methoxyphenoxy) -3-oxapentane (JP-A-62-18).
1183), oxalic acid diesters (JP-A-64-1)
583), 1,4-bis (p-tolyloxy) benzene (JP-A-2-153787), diphenylsulfone (JP-B-59-25673), p-toluenesulfonic acid phenyl ester (JP-A-59-73990). ), Mesitylenesulfonic acid p-tolyl ester (JP-A-2-8)
No. 0285), 4,4'-diallyloxydiphenyl sulfone, 4,4'-diisopentyloxydiphenyl sulfone, 4,4'-dimethoxydiphenyl sulfone (Japanese Patent Publication No. 2-9951), 4,4'-di- n-Pentyloxydiphenyl sulfone (JP-A-60-47070)
And so on.

Examples of the above-mentioned organic or inorganic pigments include calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, calcined clay, talc, and surface treatment. In addition to inorganic fine powders such as calcium carbonate and silica, organic fine powders such as urea-formalin resin, styrene / methacrylic acid copolymer, and polystyrene resin can be used.

As the binder, polyvinyl alcohol having various molecular weights, starch and its derivatives, cellulose derivatives such as methoxycellulose, carboxymethylcellulose, methylcellulose and ethylcellulose,
Sodium polyacrylate, polyvinylpyrrolidone, acrylic acid amide / acrylic acid ester copolymer, acrylic acid amide / acrylic acid ester / methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt, polyacrylamide, alginic acid Water-soluble polymer materials such as soda, gelatin, and casein, as well as polyvinyl acetate, polyurethane, styrene / butadiene copolymer, polyacrylic acid, polyacrylic acid ester, vinyl chloride / vinyl acetate copolymer, polybutyl methacrylate , Ethylene / vinyl acetate copolymer, and styrene /
Each latex such as butadiene / acrylic copolymer can be used.

Each of the above components is dispersed or dissolved in fine particles, mixed at an appropriate ratio, and the resulting coating liquid is applied to a sheet-like substrate to form a thermosensitive color developing layer. A coating layer such as a protective layer or a printing layer may be further formed on the thermosensitive color developing layer.

[0022]

EXAMPLES The present invention will be specifically described with reference to the following examples.

Example 1 [1,3-bis (p-toluene)
Synthesis of Sulfonylureido) benzene (Compound 1) ] A three-necked flask equipped with a dropping funnel and a thermometer was charged with 5.4 g of m-phenylenediamine, and this was dissolved in 200 ml of acetonitrile. While vigorously stirring the solution with a magnetic stirrer, add 2 drops from the dropping funnel.
0.2 g of p-toluenesulfonyl isocyanate was added dropwise. An exothermic reaction occurred with the dropping, and a white solid was deposited. The mixture was further heated and stirred at 70 ° C. for 1 hour, then the obtained reaction solution was cooled to room temperature and filtered to obtain 24.1 g of a white solid. Its melting point is 176-1
It was 79 ° C.

It was confirmed by NMR and IR that the obtained white solid was the desired product. Results of NMR measurement (in heavy DMSO) (numbers are ppm values):
δ = 2.40 (s, 6H), 7.0-7.4 (m, 4)
H), 7.45 (d, 4H), 7.85 (d, 4H),
Other peaks that are thought to be due to NH are δ = 8.9.
Appeared near and at 9.8.

Results of IR measurement (KBr tablet method): 1671 cm ^-1 (derived from carbonyl group) 1159 cm ^-1 (derived from sulfone group)

Example 2 [2,4-bis (p-toluene)
Synthesis of sulfonylureido) toluene (Compound 2) ] The same synthetic operation as in Example 1 was performed. However, 6.1 g of 2,4-diaminotoluene was used instead of m-phenylenediamine. As a result, 24.4 g of a white solid was obtained. Its melting point was 206-210 ° C.

It was confirmed by NMR and IR that the obtained white solid was the desired product. Results of NMR measurement (in heavy DMSO) (numbers are ppm values):
δ = 2.03 (s, 3H), 2.38 (s, 6H),
7.0-7.4 (m, 3H), 7.42 (d, 4H),
7.852 (d, 4H) and other peaks that are thought to be due to N-H appeared around δ = 8.8 and around 10.0.

Results of IR measurement (KBr tablet method): 1663 cm ^-1 (derived from carbonyl group) 1175 cm ^-1 (derived from sulfone group)

Example 3 [2,6-bis (p-toluene)
Synthesis of sulfonylureido) toluene (Compound 3) ] The same synthetic operation as in Example 1 was performed. However, 6.1 g of 2,6-diaminotoluene was used instead of m-phenylenediamine. As a result, 23.8 g of a white solid was obtained. Its melting point was 176-179 ° C.

It was confirmed by NMR and IR that the white solid obtained was the desired product. Results of NMR measurement (in heavy DMSO) (numbers are ppm values):
δ = 1.93 (s, 3H), 2.40 (s, 6H),
7.0-7.4 (m, 3H), 7.42 (d, 4H),
7.85 (d, 4H) and other peaks that are thought to be due to N-H appeared near δ = 8.2 and around 10.0.

Example 4 [3,5-bis (p-toluene)
Combination of sulfonylureido) chlorobenzene (compound 4)
Synthesis ] The same synthetic operation as in Example 1 was performed. However, in place of m-phenylenediamine, 7.1 g of 3,5-diaminochlorobenzene was used. As a result, 25.0 g of a white solid was obtained. Its melting point was 215 to 220 ° C.

It was confirmed by NMR and IR that the obtained white solid was the desired product. Results of NMR measurement (in heavy DMSO) (numbers are ppm values):
δ = 2.40 (s, 6H), 7.14 (s, 2H),
7.36 (s, 2H), 7.43 (d, 4H), 7.8
5 (d, 4H), and other peaks that are considered to be caused by N-H appeared around δ = 9.1 and 10.0.

Example 5 [1,2-bis (p-toluene)
Synthesis of Sulfonylureido) benzene (Compound 5) ] The same synthetic operation as in Example 1 was performed. However, the same amount of o-phenylenediamine was used instead of m-phenylenediamine. As a result, 23.7 g of a white solid was obtained. Its melting point was 224-230 ° C.

It was confirmed by NMR and IR that the obtained white solid was the desired product. Results of NMR measurement (in heavy DMSO) (numbers are ppm values):
δ = 2.40 (s, 6H), 7.0-7.4 (m, 4)
H), 7.42 (d, 4H), 7.85 (d, 4H),
In addition, the peak that seems to be due to NH is δ = 8.
Appeared around 2 and 10.0.

Example 6 [3,4-bis (p-toluene)
Synthesis of sulfonylureido) toluene (Compound 6)] The same synthetic operation as in Example 1 was performed. However, 6.1 g of 3,4-diaminotoluene was used instead of m-phenylenediamine. As a result, 23.5 g of a white solid was obtained. Its melting point was 218-222 ° C.

It was confirmed by NMR and IR that the obtained white solid was the desired product. Results of NMR measurement (in heavy DMSO) (numbers are ppm values):
δ = 2.20 (s, 3H), 2.40 (s, 6H),
6.8-7.3 (m, 3H), 7.42 (d, 4H),
7.85 (d, 4H), and other peaks that are thought to be due to N-H appeared near δ = 8.1 and around 10.0.

Example 7 [3,4-bis (p-toluene)
Combination of sulfonylureido) chlorobenzene (compound 7)
Adult] was carried out in the same manner as the synthesis procedure as in Example 1. However, 7.1 g of 3,4-diaminochlorobenzene was used instead of m-phenylenediamine. As a result, 23.0 g of a white solid was obtained. Its melting point was 197-203 ° C.

It was confirmed by NMR and IR that the obtained white solid was the desired product. Results of NMR measurement (in heavy DMSO) (numbers are ppm values):
δ = 2.40 (s, 6H), 7.0-7.4 (m, 3)
H), 7.42 (d, 4H), 7.85 (d, 4H),
In addition, the peak that seems to be due to NH is δ = 8.
Appeared around 3 and 10.5.

Example 8 [1,4-bis (p-toluene)
Synthesis of Sulfonylureido) benzene (Compound 8) ] The same synthetic operation as in Example 1 was performed. However, the same amount of p-phenylenediamine was used instead of m-phenylenediamine. As a result, 23.9 g of a white solid was obtained. Its melting point was 241-245 ° C.

It was confirmed by NMR and IR that the obtained white solid was the desired product. Results of NMR measurement (in heavy DMSO) (numbers are ppm values):
δ = 2.40 (s, 6H), 7.25 (s, 4H),
7.42 (d, 4H), 7.85 (d, 4H), 8.7
6 (s, 2H) and other peaks that are thought to be due to N-H appeared around δ = 10.6.

Example 9 [2,5-bis (p-toluene)
Sulfonylureido) -4-chlorotoluene (compound
Synthesis of 9) ] The same synthesis operation as in Example 1 was performed. However, 7.8 g of 2,5-diamino-4-chlorotoluene was used instead of m-phenylenediamine. As a result, 24.3
g white solid was obtained. Its melting point was 242-248 ° C.

It was confirmed by NMR and IR that the obtained white solid was the desired product.

Example 10 [2,5-bis (p-toluene)
Sulfonylureido) -1,4-dichlorobenzene
Synthesis of (Compound 10) ] The same synthetic operation as in Example 1 was performed. However, 8.8 g of 2,5-diamino-1,4-dichlorobenzene was used instead of m-phenylenediamine. As a result, 2
5.7 g of white solid was obtained. Its melting point was 240 ° C. (decomposition).

It was confirmed by NMR and IR that the white solid obtained was the desired product.

Production Example 1 of Thermal Recording Paper A thermal recording paper was prepared by the following operation. (1) Dispersion A prepared Ingredient Weight (parts) 3- (N-isopentyl -N- ethylamino) -6-methyl-7-anilino fluoran 20 sand grinder polyvinyl alcohol 10% solution 10 Water 70 The composition And was pulverized until the average particle diameter was 1 μm or less.

[0046] (2) Dispersion B prepared Ingredient Weight (parts) 1,3-bis (p- toluenesulfonyl two Ruureido) benzene (Compound 1) 10 diphenylsulfone 10 polyvinyl alcohol 10% solution 10 Water 70 The composition Was crushed using a sand grinder until the average particle diameter became 1 μm or less.

(3) Preparation of Pigmented Undercoat Paper 85 parts of calcined clay (trademark: Ansilex) was added to 320 parts of water.
To 40 parts of styrene-butadiene copolymer emulsion (solid content 50%) and 50 parts of 10% oxidized starch aqueous solution to prepare a coating solution. It was coated on a base paper having a basis weight of 48 g / m ² so that the coating amount after drying was 7.0 g / m ² to prepare a pigment-undercoated paper.

(4) Formation of Thermosensitive Coloring Layer 30 parts of calcium carbonate pigment, 20 parts of 25% zinc stearate dispersion liquid were added to 50 parts of solution A and 200 parts of solution B.
A coating solution was prepared by mixing 15 parts of a 30% paraffin dispersion liquid, 10 parts of a 30% stearic acid amide dispersion liquid, and 100 parts of a 10% polyvinyl alcohol aqueous solution, and stirring the mixture. This coating solution was applied to one surface of the pigment-undercoated paper so as to have a coating amount after drying of 5.0 g / m ² and dried to form a thermosensitive color-developing layer to prepare a thermosensitive recording paper.

(5) Calender treatment The heat-sensitive recording paper obtained as described above was treated with a super calender, and the surface smoothness was 800 to 100.
It was set to 0 seconds.

(6) Color development test and plasticizer resistance test The samples thus obtained were tested using a dynamic color development tester obtained by modifying a commercial heat-sensitive facsimile machine manufactured by Hitachi, Ltd.
The sample was colored with an applied energy of 0.49 mj / dot.
The color density was measured with a Macbeth reflection densitometer RD-914 (this is referred to as original density). Then, a predetermined test piece was prepared from this color-developed sample, and within 30 minutes after color development, salad oil or dioctyl terephthalate (representative plasticizer) was applied to the test piece, and this was left at room temperature for 3 hours, and then an excess amount was applied. The oil or plasticizer was wiped off, the density of the residual image was measured with a Macbeth reflection densitometer, and the image retention rate was calculated according to the following formula.

[Equation 1] The test results are shown in Table 1.

Heat Sensitive Recording Paper Manufacturing Examples 2 to 10 In each of Heat Sensitive Recording Paper Manufacturing Examples 2 to 10, a heat sensitive recording paper was prepared in the same manner as in the above Manufacturing Example. However, in the preparation of Dispersion B, Compounds 2 to 10 synthesized in Examples 2 to 10 were used instead of 1,3-bis (p-toluenesulfonylureido) benzene (Compound 1). The test results are shown in Table 1.

Comparative Example 1 of Production of Thermal Recording Paper A thermal recording paper was produced by the same operation as in Production Example 1 of thermal recording paper. However, in the preparation of the dispersion liquid B, 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A) was used instead of 1,3-bis (p-toluenesulfonylureido) benzene (Compound 1). .
The test results are shown in Table 1.

[0053]

[Table 1]

As described in Examples 1-10,
The bis (arylsulfonylureido) benzene compounds of formula (I) according to the present invention are novel, well characterized compounds. In addition, thermal recording paper production examples 1 to 10,
As is clear from Comparative Example 1 for the production of thermal recording paper, when the compound of the present invention is used as a developer for a thermal recording material, it is compared with bisphenol A which is a representative of conventional developers.
The color image thus obtained shows remarkably excellent oil resistance. Also,
When the meta-substituted products (Compounds 1 to 4) are used, the color image also shows markedly excellent plasticizer resistance.

[0055]

The bis (arylsulfonylureido) benzene compound of the formula (I) of the present invention is a novel compound. Furthermore, when the compound of the present invention is used as a developer for a thermosensitive recording material, the thermosensitive coloring layer obtained shows good dynamic sensitivity, and the obtained color image shows excellent oil resistance and plasticizer resistance. Show.

Claims (2)

[Claims] 1. The following chemical formula (I): (In the formula (I), R ¹ _, R ² , and R ³ each independently represent a hydrogen atom, a halogen atom, or a methyl group.) A bis (arylsulfonylureido) benzene compound . 2. The compound according to claim 1, wherein the compound of formula (I) is a 1,3-bis (arylsulfonylureido) benzene compound.