JPH0710828A - New bis(arylsulfonylureido) aromatic compound - Google Patents

Abstract

PURPOSE:To obtain a new compound capable of forming a colored image having excellent oil resistance and plasticizer resistance when used as a color-developing agent for a heat-sensitive recording material. CONSTITUTION:A compound of the formula I (A is group of the formula II to the formula VI), e.g. alpha,alpha'-bis(p-toluenesulfonylureidophenyl)-1,4- diisopropylbenzene. The compound can be produced by reacting p-toluenesulfonyl isocyanate of the formula VII with a diamino compound of the formula VIII in an organic solvent. A heat-sensitive color-developing layer of a heat-sensitive recording material can be formed by using the compound together with a dye precursor (leuco dye), a thermoplastic aromatic compound having a melting point of 60-150 deg.C and a binder for fixing these components on a substrate. The heat-sensitive color-developing layer is preferably further incorporated with organic or inorganic pigments. As necessary, the layer may be incorporated with known phenolic or organic oxygen color-developing agent, antioxidant, ultraviolet absorber or waxes.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel bis (arylsulfonylureido) aromatic compound. More specifically, the present compound is useful as a developer for a thermosensitive recording material that forms a colored image by heating, and does not cause the image once colored to disappear, and has excellent storage stability of recording. It is useful as a color-developing substance in a thermosensitive recording medium.

[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. A recorded image can be formed by applying heat energy to such a thermal recording material.
Such a thermosensitive recording medium is disclosed, for example, in Japanese Examined Patent Publication No. 43-4160.
No. 4, JP-B-45-14039, and JP-A-48-27.
No. 736, etc., and has been widely put into practical use.

The thermosensitive recording medium having the above-mentioned structure has a compact recording apparatus, is inexpensive, 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 CRT medical treatment. Widely used in measurement printers. However, in a conventional dye-type thermosensitive recording medium formed by coating a thermosensitive coloring layer containing a color-developing dye substance, a color-developing substance and a binder on a support, the coloring reaction Is reversible, it is known that the color image disappears over time. This decoloring is accelerated under exposure to light, high humidity and high temperature, and further progresses rapidly due to contact with a plasticizer and oil, and the image is decolorized to an unreadable level.

Therefore, a wide range of attempts have been made to solve the problem of decolorization by introducing a new compound into the color forming system. For example, one using a dimerized fluorane dye found in JP-A No. 62-121769, one using a metal salt of a specific salicylic acid derivative found in JP-A No. 62-169681 as a color developer, and further a fluoran-based dye. As a color-developing system which does not use a leuco dye, Japanese Patent Application Laid-Open No.
-Amino-1-imino-4,5,6,7-tetrachloro-1H-isoindole and 4,4 ', 4 "-triisocyanate-2,5 disclosed in US Pat.
There is known one using a non-reversible heat-sensitive material composed of dimethoxytriphenylamine.

When the above-mentioned dimerized fluoran dye is used, even if it is used together with a phenol type developer, the storability of a color image is improved correspondingly. However, it has the drawbacks that the obtained heat-sensitive recording material has a considerably low whiteness and the thermal response, that is, the sensitivity is low. 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 drawback that the chemical structure is complicated and expensive.

Further, 3-amino-1-imino-4,
Regarding the heat-sensitive material consisting of 5,6,7-tetrachloro-1H-isoindole and 4,4 ′, 4 ″ -triisocyanate-2,5-dimethoxytriphenylamine,
The colored image part is certainly robust, but the non-image part,
That is, when the white paper portion comes into contact with the plasticizer, it develops a red color, and there is a drawback that the image quality is significantly impaired.

[0007]

The present invention solves the above-mentioned problems of the prior art and forms a thermosensitive coloring layer having high whiteness and excellent sensitivity when used as a developer for a thermosensitive recording medium. In addition, it is intended to provide a novel developer compound capable of forming a color image having excellent long-term storage stability such as oil resistance, plasticizer resistance, moisture resistance and heat resistance.

The heat-sensitive recording material using the novel developer 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 foods packaged with a polyvinyl chloride film that cannot be avoided for use 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 are able to exhibit storage stability improving effects such as oil resistance and plasticizer resistance of a color image within a short time after formation of the color image. We have designed, synthesized, and investigated various novel developer compounds, and as a result, succeeded in producing compounds useful as novel developer compounds.

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

[Chemical 2] Is a bis (arylsulfonylureido) aromatic compound represented by.

The compound of the formula (I) according to the present invention specifically includes the compounds of the following formulas (Ia), (Ib), (Ic), (Id) and (Ie).

[Chemical 3]

[0012]

The compound of the present invention acts as a developer for a thermosensitive recording medium. That is, the compound 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 developing ability with respect to a dye precursor, that is, 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 the present invention can be synthesized, for example, by the following reactions (1) to (2).

[Chemical 4] [However, A in the above formula is the same as the above rule]

The above synthetic reactions (1) and (2) are carried out in an organic solvent. The reaction solvent for the synthetic reactions (1) and (2) is not particularly limited as long as it reacts with the isocyanates and does not 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. The reaction product in an aromatic solvent,
Contacting at a particularly high temperature may cause a decrease in whiteness. Preferred solvents include, for example, aliphatic halides such as dichloromethane, chloroform, carbon tetrachloride, and trichlorethylene, aliphatic nitriles such as acetonitrile, and propionitrile, ethyl acetate, propyl acetate, and butyl acetate. Examples thereof include aliphatic esters, ethylene glycol dimethyl ether, dibutyl ether, and aliphatic ethers such as dioxane, and aliphatic ketones such as cyclohexanone.

The compound of the formula (1) of the present invention is a dye precursor (leuco dye), 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 these components together with a binder for fixing 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,
Antioxidants, UV absorbers, or waxes can be included.

The leuco dye used as a dye precursor together with the developer of the present invention can be selected from conventionally known ones such as triphenylmethane type compounds, fluorane type compounds and diphenylmethane type compounds. The dye precursor is, for example, 3-
(4-Diethylamino-2-ethoxyphenyl) -3-
(1-Ethyl-2-methylindol-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-chlorofluorane, 3-diethylamino-6-methylfluorane, and 3-Cyclohexylamino-6-chlorofluorane, 3- (N-ethyl-N-hexylamino) -6
One or more selected from -methyl-7- (p-chloroanilino) fluorane and the like can be used.

As the above-mentioned sensitizer, for example, 1-hydroxy-2-naphthoic acid phenyl ester (JP-A-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), diphenyl sulfone (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 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.

Regarding 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 Polymers, acrylic acid amides / acrylic acid esters / methacrylic acid terpolymers, styrene / maleic anhydride copolymers alkaline salts, polyacrylamides, sodium alginates, gelatin, and water-soluble polymeric materials such as casein, and
Polyvinyl acetate, polyurethane, styrene / butadiene copolymer, polyacrylic acid, polyacrylic ester,
Each latex such as vinyl chloride / vinyl acetate copolymer, polybutyl methacrylate, ethylene / vinyl acetate copolymer, and styrene / butadiene / acrylic copolymer can be used.

These compounds are dispersed or dissolved in fine particles, mixed at an appropriate ratio, and coated on a sheet-like substrate to form a thermosensitive coloring layer. A coating layer such as a protective layer or a printing layer may be further formed on the thermosensitive color developing layer.

[0021]

EXAMPLES The present invention will be specifically described with reference to the following examples. Example 1 [α, α'-bis (p-toluenesulfonylsulfone
Raidphenyl) -1,4-diisopropylbenzene
(Synthesis of Compound (Ia)) In a three-necked flask equipped with a dropping funnel and a thermometer, 6.
89 g of α, α'-bis (4-aminophenyl) -1,
4-Diisopropylbenzene was added and this was dissolved in 200 ml of acetonitrile. While vigorously stirring this solution with a magnetic stirrer, 8.20 g of p-toluenesulfonyl isocyanate was added dropwise thereto with a dropping funnel. An exothermic reaction occurred with the dropping, and a white solid was deposited. This mixed solution was further heated and stirred at 70 ° C. for 1 hour, then the reaction solution was cooled to room temperature and filtered by 14.1
g white solid was obtained. Its melting point was 235-239 ° C.

The white solid obtained by NMR and IR
I confirmed that my body was the target. Results of NMR measurement (in heavy DMSO) (numbers are ppm values):
 δ = 1.58 (s, 12H), 2.40 (s, 6H),
7.08 (s, 4H), 7.13 (d, 4H), 7.2
5 (d, 4H), 7.45 (d, 4H), 7.88
(D, 4H) and other peaks that are thought to be due to NH
Ku appeared at δ = 8.8 and 10.4.

Example 2 [4,4'-bis (p-toluene)
Sulfonyl ureido) -2,2'-dimethylbibenzyl
(Synthesis of Compound (Ib)) The same synthetic operation as in Example 1 was performed. However, α, α ′
Instead of -bis (4-aminophenyl) -1,4-diisopropylbenzene, 4.80 g of 4,4'-diamino-2,2'-dimethylbibenzyl was used. As the solvent, 150 ml of tetrahydrofuran was used instead of 200 ml of acetonitrile. As a result, 11.4 g of a white solid was obtained. Its melting point was 196-200 ° C.

The white solid obtained by NMR and IR
I confirmed that my body was the target. Results of NMR measurement (in heavy DMSO) (numbers are in ppm) Values:
 δ = 2.16 (s, 6H), 2.40 (s, 6H),
2.67 (s, 4H), 6.9 to 7.2 (m, 6H),
7.43 (d, 4H), 7.86 (d, 4H),
In addition, δ = 8.6 with a peak that seems to be due to N-H
Appeared near and 10.4.

Example 3 [2,2'-bis (p-toluene)
Sulfonyluido) diphenyl disulfide (compound
Synthesis of (Ic))] The same synthesis operation as in Example 1 was performed. However, α, α ′
Instead of -bis (4-aminophenyl) -1,4-diisopropylbenzene, 4.96 g of 2,2'-diaminodiphenyl disulfide was used. Also, the solvent is 20
Instead of 0 ml acetonitrile, 150 ml 1,4-
Dioxane was used. As a result, 12.2 g of a white solid was obtained. Its melting point was 166-169 ° C.

The white solid obtained by NMR and IR
I confirmed that my body was the target. Results of NMR measurement (in heavy DMSO) (numbers are in ppm) Values:
 δ = 2.40 (s, 6H), 6.9 to 7.4 (m, 6)
H), 7.43 (d, 4H), 7.86 (d, 4H),
In addition, the peak that seems to be due to NH is δ = 8.
It appeared around 6 and 11.4.

Example 4 [2,7-bis (p-toluene)
Rufonylureido) fluorene (compound (Id))
Synthesis ] The same synthetic operation as in Example 1 was performed. However, α, α ′
Instead of -bis (4-aminophenyl) -1,4-diisopropylbenzene, 3.92 g of 2,7-diaminofluorene was used. As the solvent, 150 ml of chloroform was used instead of 200 ml of acetonitrile.
As a result, 10.9 g of a white solid was obtained. Its melting point (decomposition) was 283 ° C.

The white solid obtained by NMR and IR
I confirmed that my body was the target. Results of NMR measurement (in heavy DMSO) (numbers are in ppm) Values:
 δ = 2.40 (s, 6H), 3.80 (s, 2H),
7.1 to 8.0 (m, 14H), other, due to N-H
It seems that the peaks are around δ = 8.9 and 10.1.
Appeared in.

Example 5 [9,9-bis {4- (p-tolu]
Ensulfonylureido) phenyl} fluorene (compound
Synthesis of Product (Ie))] The same synthetic operation as in Example 1 was performed. However, α, α ′
Instead of -bis (4-aminophenyl) -1,4-diisopropylbenzene, 6.97 g of 9,9-bis (4
-Aminophenyl) fluorene was used. As a result, 1
3.7 g of white solid was obtained. Its melting point is 225-230
It was ℃.

The white solid obtained by NMR and IR
I confirmed that my body was the target. Results of NMR measurement (in heavy DMSO) (numbers are in ppm) Values:
 δ = 2.40 (s, 6H), 7.00 (d, 4H),
7.22 (d, 4H), 7.3 to 8.0 (m, 16)
H) and other peaks that are thought to be due to NH
= Appeared near 8.8 and around 10.3.

Thermal recording paper production example 1 A thermal recording paper was prepared by the following operation. (1) Sand dispersion A prepared Ingredient Weight (parts) 3- (N-isopentyl -N- ethylamino) -6-methyl-7-anilinofluoran 20 polyvinyl alcohol 10% solution 10 Water 70 The composition It grind | pulverized using the grinder until the average particle diameter became 1 micrometer or less.

[0032] (2) Dispersion B prepared Ingredient Weight (parts) alpha,. Alpha .'- bis (p- toluenesulfonyl urethane Idofeniru) -1,4-diisopropylbenzene (Compound (Ia)) 10 diphenylsulfone 10 Polyvinyl alcohol 10 % Liquid 10 water 70 The above composition was pulverized using a sand grinder until the average particle size 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.
40 parts of a styrene-butadiene copolymer emulsion (solid content: 50%) and 50 parts of a 10% oxidized starch aqueous solution were mixed with the resulting dispersion to prepare a coating liquid. The coating liquid onto the base paper basis weight 48 g / m ^2, the coating amount after drying was coated so as to 7.0 g / m ^2, to prepare a pigment undercoat paper.

(4) Formation of Thermosensitive Coloring Layer 30 parts of calcium carbonate pigment, 20 parts of 25% zinc stearate dispersion, 3 parts of solution A and 200 parts of solution B were used.
15 parts of 0% paraffin dispersion and 100 parts of 10% polyvinyl alcohol aqueous solution were mixed and stirred to prepare a coating liquid. 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 coloring layer, thereby preparing a thermosensitive recording paper.

(5) Calender treatment The thermal 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 With respect to the samples thus obtained, a dynamic color development tester obtained by modifying a commercially available heat-sensitive facsimile machine manufactured by Hitachi,
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 is prepared from this color-developed sample, and within 30 minutes after color development, salad oil or dioctyl terephthalate (representative plasticizer) is applied to the test piece and allowed to stand at room temperature for 3 hours. The plasticizer was wiped off, the residual image density 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.

Production Examples 2 to 5 of Thermal Recording Paper In each of Production Examples 2 to 5 of thermal recording paper, Production Example 1 described above was used.
A heat-sensitive recording paper was produced by the same operation as above. However, in the preparation of the dispersion liquid B, the compounds synthesized in Examples 2 to 5 were used instead of the α, α′-bis (p-toluenesulfonylureidophenyl) -1,4-diisopropylbenzene (compound (Ia)). Ib), (Ic), (Id) and (Ie) were used. 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, α, α′-bis (p-toluenesulfonylureidophenyl) -1,
Instead of 4-diisopropylbenzene (compound (Ia)), 2,2-bis (4-hydroxyphenyl) propane (ie bisphenol A) was used. The test results are shown in Table 1.

[0039]

[Table 1]

The bis (arylsulfonylureido) aromatic compounds of formula (I) of the present invention are novel, well characterized compounds as described in detail in Examples 1-5. Further, as is clear from Production Examples 1 to 5 of thermal recording paper and Comparative Example 1 of production of thermal recording paper, when the compound of the present invention is used as a developer for a thermal recording material, it represents a conventional developer. Compared with bisphenol A, the obtained color image shows remarkably excellent oil resistance and plasticizer resistance.

[0041]

The bis (arylsulfonylureido) aromatic compound of the formula (I) of the present invention is a novel compound.
Further, in a heat-sensitive recording material using the compound of the present invention as a color developer, the color-developed image has good dynamic sensitivity and shows excellent oil resistance and plasticizer resistance.

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[Procedure amendment]

[Submission date] July 8, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

The above synthesis reaction (1) is carried out in an organic solvent. The reaction solvent of the synthesis reaction (1) is not particularly limited as long as it does not inhibit the above reaction by reacting with isocyanates, but in order to keep the whiteness of the produced compound high, a non-aromatic It is preferable to use a system solvent.
When the reaction product is brought into contact with an aromatic solvent at a particularly high temperature, the whiteness of the reaction product may be lowered. Preferred solvents include, for example, aliphatic halides such as dichloromethane, chloroform, carbon tetrachloride, and trichlorethylene, aliphatic nitriles such as acetonitrile, and propionitrile, ethyl acetate, propyl acetate, and butyl acetate. Examples thereof include aliphatic esters, ethylene glycol dimethyl ether, dibutyl ether, and aliphatic ethers such as dioxane, and aliphatic ketones such as cyclohexanone.

Claims (1)

[Claims] 1. The following chemical formula (I): A novel bis (arylsulfonylureido) aromatic compound represented by: