Thermosensitive recording material

Abstract: A thermosensitive recording material having a high whiteness and capable of forming clear colored images with an excellent resistance to oil and plasticizers is provided with a thermosensitive colored image-forming layer formed on a substrate sheet and comprising a substantially colorless dye precursor, a binder and a color-developing agent comprising at least one aromatic compound selected from those of the formula (II): in which formula (II), X represents a member selected from oxygen and sulfur atoms; R 1 represents an aromatic group substituted with at least one substituent selected from nitro group, alkyl groups substituted with at least one halogen atom, alkyloxy groups, aryloxy groups, aralkyloxy groups, alkylcarbonyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups and aralkyl groups, A represents a multivalent group; and n represents an integer of 2 or more.

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosensitive recording material on which colored images are formed by heating. More particularly, the present invention relates to a thermosensitive recording material capable of forming thereon colored images resistant to fading and thus exhibiting a high degree of persistency during extended storage thereof. The thermosensitive recording material of the present invention is capable of recording thereon colored images exhibiting an excellent resistance to moisture, heat, oily and fatty substances, and plasticizers, and thus has superior persistency when stored over a long period of time and a high whiteness, and therefore is useful as colored image-recording sheets, sheets for use in facsimiles, word processors, CRT image printers and cash dispensers, as passenger tickets, commuter passes, labels such as POS labels, cards such as prepaid cards, and as transit passes. 2. Description of the Related Arts It is known that a conventional thermosensitive recording material comprises a supporting substrate, for example, a paper sheet, synthetic paper sheet, or plastic resin film and a thermosensitive colored image-forming layer formed on a surface of the supporting substrate and comprising an electron-donative dye precursor, for example, a leuco basic dye, an electron-acceptive color-developing agent consisting of an organic acid substance, for example, a phenolic compound, and a binder. When the thermosensitive colored image-forming layer is heated imagewise, colored images are recorded thereon by a reaction of the dye precursor with the color-developing agent. This type of thermosensitive recording material is disclosed in Japanese Examined Patent Publication Nos. 43-4,160 and 45-14,039 and Japanese Unexamined Patent Publication No. 48-27,736, and is widely employed in practice. Namely, the thermosensitive recording material is advantageous in that colored images can be easily formed by heating alone, and the recording apparatus can be made compact and small in size, has a relatively low price, and can be easily maintained. Therefore, this type of thermosensitive recording material is appreciated as a useful information-recording material for recording outputs of printers used with, for example, computers, facsimile machines, automatic ticket-vending machines, scientific measurement recorders, and CRT medical measurement recorders. Nevertheless, the conventional dye-forming type thermosensitive recording materials in which the thermosensitive colored image-forming layer comprises a conventional color-developing agent together with the dye precursor and the binder is disadvantageous in that the resultant colored images fade with the lapse of time, presumably because of a reversible reaction of the dye precursor with the color-developing agent. This fading of the colored images is accelerated by exposure to light, high temperatures, and high humidity and is specifically promoted by contact with an oily or fatty substance or a plasticizer, to such an extent that the faded images cannot be recognized. Many attempts have been made to retard or inhibit the fading of the colored images formed on a conventional thermosensitive colored image-forming layer containing a substantially colorless dye precursor comprising a lactone ring compound. For example, Japanese Unexamined Patent Publication Nos. 60-78,782, 59-167,292, 59-114,096 and 59-93,387 disclose a thermosensitive colored image-forming layer containing a phenolic antioxidant. Japanese Unexamined Patent Publication No. 56-146,794 discloses a protective layer formed from a hydrophobic polymeric compound emulsion on a thermosensitive colored image-forming layer. Japanese Unexamined Patent Publication No. 58-199,189 discloses formation of both an intermediate layer and a top layer on a thermosensitive colored image-forming layer; the former being formed from a water-soluble polymeric compound solution or a hydrophobic polymeric compound emulsion and the latter being formed from a solvent-soluble hydrophobic polymer on the intermediate layer. Japanese Unexamined Patent Publication No. 62-164,579 discloses a thermosensitive colored image-forming layer containing an epoxy compound in addition to a phenolic color-developing agent. Japanese Unexamined Patent Publication No. 62-169,681 discloses metal salts of specific salicylic acid derivatives usable as a color-developing agent. Japanese Unexamined Patent Publication No. 62-19,485 discloses that a compound having a certain chemical structure similar to that of the present invention is usable as a material for mainly pressure-sensitive recording paper sheets. In the thermosensitive colored image-forming layer containing the phenolic antioxidant, the resultant colored images exhibit a higher resistance to heat and moisture to a certain extent compared to the colored images formed on a convention colored image-forming layer free from the phenolic antioxidant, but the improvement effect of the phenolic antioxidant is not satisfactory. Also, the phenolic antioxidant does not have the capability to enhance the resistance of the colored images to the oily or fatty substances, for example, salad oil, and plasticizers, for example, dioctyl phthalate. The resistance of the colored images to oily or fatty substance or a plasticizer is determined in such a manner that the colored images are brought into contact with an oily or fatty substance, for example, a salad oil or a plasticizer, and left in contact therewith for a predetermined time, and then a retention of the color density of the tested colored images is measured in comparison with an initial color density thereof. When the protective layer or the intermediate and top layers are formed on the thermosensitive colored image-forming layer, the resultant colored images exhibit a significantly enhanced persistency when the salad oil or the dioctyl phthalate is brought into contact with the colored image-forming surface of the recording material. Nevertheless, when the salad oil or the dioctyl phthalate is brought into contact with an edge face of the recording material, it penetrates the inside of the recording material and causes a complete fading of the colored images. Therefore, the provision of the protecting layer or the intermediate and top layer cannot completely eliminate the undesirable color-fading of the images. The addition of the epoxy compound to the phenolic color-developing agent, is not totally appreciated, because it takes a long time to stabilize the colored images formed on the colored image-forming layer after a heat-recording operation, and therefore, if salad oil, or a plasticizer is brought into contact with the colored image-forming layer immediately after the heat-recording operation, the resultant colored images fade to a great extent. The addition of the metal salts of the specific salicylic acid derivative to the colored image-forming layer effectively enhances the resistances of the colored image-forming layer to the oily or fatty substances and to the plasticizers. When the resultant thermosensitive recording sheet is subjected to a colored image-recording procedure and then to a heat resistance test, however, an undesirable color-development occurs on non-image-formed white portions of the recorded sheet. Also, the utilization of the specific salicylic acid derivative metal salts is disadvantageous in that this chemical has a complicated chemical structure and thus is expensive. The compound disclosed in Japanese Unexamined Patent Publication No. 62-19,485 and having a certain chemical structure similar to that of the present invention, exhibits a color-developing activity equal to or lower than that of the conventional phenolic color-developing compounds. Also, the thermosensitive recording paper sheet prepared by using the above-mentioned material is disadvantageous in that the colored images formed thereon are easily faded when brought into contact with salad oil or a plasticizer, as shown in Comparative Examples 3 and 4 hereinafter. Furthermore, EP-A-0535887, which is a document according to Art. 54(3) and (4) EPC, discloses a color-developing agent comprising at least one compound of the following formula: wherein X is an O or S atom, R is limited to unsubstituted aromatic hydrocarbon groups and aromatic hydrocarbon groups substituted by at least one substituent selected from lower alkyl groups and halogen atoms, A is a multivalent group and n is an integer of 2 or more. SUMMARY OF THE INVENTION An object of the present invention is to provide a thermosensitive recording material capable of forming colored images thereon having excellent resistance to oily and fatty substances, plasticizers, moisture, and heat, and thus exhibiting superior persistency over a long time, and a high whiteness. Another object of the present invention is to provide a thermosensitive recording material useful for thermorecording type tickets of automatic ticket-vending machines, commuter passes, and coupon tickets, which must have high persistency of the colored images recorded thereon, and for label sheets to be used in a POS bar code price-indicating system in which the label sheets are frequently attached to a surface of a polyvinyl chloride film containing a plasticizer and for wrapping fresh food or meat containing an oily or fatty substance; the label sheets of which are unavoidably brought into contact with the plasticizer and/or oily or fatty substance. A further object of the present invention is to provide a thermosensitive recording material useful as facsimile recording sheets, word processor recording sheets, and CRT image printing sheets, which all must have high persistency of colored images recorded thereon. The above-mentioned objects can be attained by the thermosensitive recording material of the present invention, which comprises a sheet substrate and a thermosensitive colored image-forming layer formed on a surface of the sheet substrate and comprising a substantially colorless dye precursor, a color-developing agent reactive with the dye precursor upon heating to thereby develop a color, and a binder, characterized in that the color-developing agent comprises at least one aromatic compound selected from those of the formula (II): in which formula (II), X represents a member selected from oxygen and sulfur atoms; R 1 represents an aromatic group substituted with at least one substituent selected from nitro group, alkyl groups substituted with at least one halogen atom, alkyloxy groups, aryloxy groups, aralkyloxy groups, alkylcarbonyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups and aralkyl groups, A represents a multivalent group; and n represents an integer of 2 or more. DESCRIPTION OF THE PREFERED EMBODIMENTS The thermosensitive recording material of the present invention comprises a substrate sheet and a thermosensitive colored image-forming layer formed on a surface of the substrate sheet and comprising a substantially colorless dye precursor, a color-developing agent reactive with the dye precursor upon heating to thereby develop a color, and a binder. In the present invention, the color-developing agent comprises at least one specific aromatic sulfonylamino(thio)carbonylamino compound, selected from those of the formula (II), each having, per molecule thereof, at least two functional groups of the formula (I): in which X is as defined above. Namely, the aromatic compounds of the formula (II) having at least two functional groups of the formula (I) per molecule thereof serve as a color-developing agent for the substantially colorless dye precursor upon heating to develop a color. The aromatic compounds with two or more functional groups of the formula (I) do not have a common acidic functional group such as phenolic hydroxyl group and carboxyl group. However, these aromatic compounds exhibit a strong color-developing capability for the dye precursors such as leuco basic dyes. Also, these aromatic compounds capable of maintaining the color-developed dye at the coloring form and preventing the fading of the coloring dye. In the advantageous properties of the aromatic compound having two or more functional groups of the formula (I), the strong color-developing activity thereof is presumed to be a result of a strong interaction of the sulfonyl(thio)urea group of the formula (I) with the dye. This strong interaction can be realized only by a functional sulfonyl(thio)urea group. This will be understood from the following facts. Namely, organic compounds having a functional group of the formula (V): wherein X is as defined above, and which is different from the sulfonyl(thio)urea group in the lack of -SO 2 - group; organic compounds having a functional group of the formula (VI): wherein X is as defined above, and which is different from the sulfonyl(thio)urea group in the lack of -NH- group; and organic compounds having a functional group of the formula (VII): wherein X is as defined above and which is different from the sulfonyl(thio)urea group in the substitution of the -NH- group by a group, exhibit a significantly poorer color-developing activity for the dye precursor than that of the compound having the functional groups of the formula (I), and the resultant colored images exhibit a poor persistency which cannot stand comparison with that of the colored images formed by using the specific color-developing compound of the present invention. The excellent persistency of the colored images formed on the thermosensitive recording material is necessarily derived from the specific color-developing aromatic compounds of the formula (II). This necessity can be established from the fact that although an aromatic compound having only one functional group of the formula (I) per molecule thereof exhibits a satisfactorily high color-developing activity, the resultant colored images exhibit a considerably poorer resistance to salad oil and a plasticizer than that of the colored images formed by using the specific color-developing aromatic compounds of the present invention of the formula (II). In the present invention, the aromatic compound having at least two functional groups of the formula (I) per molecule thereof is selected from those of the formula (II): in which X represents an oxygen or sulfur atom, R 1 represents an aromatic group substituted with at least one substituent selected from the group consisting of nitro group, alkyl groups substituted with at least one halogen atom, for example, trifluoromethyl group, alkyloxy groups, for example, methoxy, and ethoxy groups, aryloxy groups, for example, phenoxy group, aralkyloxy groups, alkyl carbonyl groups, for example, acetyl group alkenyl and alkynyl groups, having an unsaturated bond, for example, ethynyl and allyl groups, cycloalkyl groups, for example, cyclopropyl and cyclohexyl groups, aryl groups, for example, phenyl and tolyl groups, and aralkyl groups, for example, benzyl and phenetyl groups, A represents a multivalent group and n represents an integer of 2 or more. In the color-developing aromatic compounds of the formula (II), the multivalent group represented by A is not limited to specific groups as long as it has a di or more valency, and is preferably selected from the group consisting of: (a) carbonyl, thiocarbonyl and sulfonyl group; (b) multivalent aliphatic hydrocarbon groups; (c) multivalent, hetero-atom-containing aliphatic groups derived from aliphatic hydrocarbon compounds having at least one hetero-atom located in a backbone chain per molecule thereof; (d) multivalent aliphatic groups derived from aliphatic hydrocarbon compounds having at least one member selected from the group consisting of carbonyl, thiocarbonyl, imide, imino, and sulfonyl groups and ester structures, located in a backbone chain per molecule thereof; (e) multivalent aliphatic aromatic groups derived from aliphatic hydrocarbon compounds having at least one member selected from the group consisting of unsubstituted and substituted aromatic hydrocarbon groups, located in a backbone chain per molecule thereof; (f) multivalent organic groups derived from aliphatic hydrocarbon compounds having at least one member selected from the group consisting of unsubstituted and substituted aromatic hetero-cyclic groups, located in a backbone chain per molecule thereof; (g) multivalent aromatic groups derived from unsubstituted and substituted aromatic hydrocarbon compounds; (h) multivalent aromatic heterocyclic groups derived from unsubstituted and substituted heterocyclic compounds; and (i) multivalent organic groups derived from organic compounds in which two or more aromatic or aromatic heterocyclic groups are bonded to each other through one or more multivalent groups selected from the above-mentioned groups (a) to (d). The color-developing aromatic compounds of the formula (II) are preferably selected from the group consisting of, for example, bis(p-methoxybenzenesulfonylaminocarbonylamino) ketone, 1,2-bis(p-methoxybenzenesulfonylaminocarbonylamino) ethane, 1,5-bis(p-methoxybenzenesulfonylaminocarbonylamino)-3-oxapentane, 1,3-bis(p-methoxybenzenesulfonylaminocarbonylamino)-2-propane, 1,5-bis(p-methoxybenzenesulfonylaminocarbonylamino)-3-(2-(p-methoxybenzenesulfonylaminocarbonylamino)ethyl)-3-azapentane, 1,3-bis(p-methoxybenzenesulfonylaminocarbonylaminomethyl)benzene, 4,4'-bis(p-methoxybenzenesulfonylaminocarbonylamino) diphenylmethane, 4,4'-bis(p-methoxybenzenesulfonylaminothiocarbonylamino)diphenylmethane, 4,4'-bis(p-nitrobenzenesulfonylaminocarbonylamino) diphenylmethane, 4,4'-bis(m-trifluoromethylmethoxybenzenesulfonylaminocarbonylamino)diphenylmethane, 4,4'-bis(p-phenoxybenzenesulfonylaminocarbonylamino) diphenylmethane, 4,4'-bis(p-benzyloxybenzenesulfonylaminocarbonylamino)diphenylmethane, 4,4'-bis(p-acetylbenzenesulfonylaminocarbonylamino) diphenylmethane, 4,4'-bis(p-benzoylbenzenesulfonylaminocarbonylamino) diphenylmethane, 4,4'-bis(p-allyloxybenzenesulfonylaminocarbonylamino)diphenylmethane, 4,4'-bis(p-allylbenzenesulfonylaminocarbonylamino) diphenylmethane, 4,4'-bis(p-ethynylbenzenesulfonylaminocarbonylamino) diphenylmethane, 4,4'-bis(p-cyclohexylbenzenesulfonylaminocarbonylamino)diphenylmethane, 4,4'-bis(p-phenylbenzensulfonylaminocarbonylamino) diphenylmethane, 4,4'-bis(p-benzylbenzenesulfonylaminocarbonylamino) diphenylmethane, 4,4'-bis(o-methoxybenzenesulfonylaminocarbonylamino) diphenylmethane, 4,4'-bis(p-methoxybenzenesulfonylaminothiocarbonylamino)diphenylmethane, 2,2-bis(4'-(p-methoxybenzenesulfonylaminocarbonylamino)phenyl)propane, 1,2-bis(4'-(p-methoxybenzenesulfonylaminocarbonylamino)phenyloxy)ethane, 3,3'-bis(p-methoxybenzenesulfonylaminocarbonylamino) diphenylsulfone, 4,4'-bis(p-methoxybenzenesulfonylaminocarbonylamino) diphenylether, 2,5-bis(p-methoxybenzenesulfonylaminocarbonylaminomethyl)furan, 1,3-bis(p-methoxybenzenesulfonylaminocarbonylamino) benzene, and 1,5-bis(p-methoxybenzenetoluenesulfonylaminocarbonylamino)naphthalene. The color-developing aromatic compounds of the present invention of the formula (II) can be produced, for example, by the following reactions (1) to (3): In the above-mentioned reactions (1), (2) and (3), R represents the monovalent organic group as defined for R 1 of the formula (II), X is as defined above, M represents the multivalent group as defined for A of the formula (II), R 5 represents a member selected from the group consisting of lower alkyl groups and aryl groups, and n is as defined above. In the thermosensitive colored image-forming layer of the present invention, the content of the color-developing aromatic compound of the formula (II) is preferably in the range of from 10 to 50% based on the total dry weight of the thermosensitive colored image-forming layer. When the content is less than 10% by weight, the resultant thermosensitive colored image-forming layer exhibits an unsatisfactorily poor color-developing activity. Also, even if the content of the color-developing aromatic compound is raised to a level above 50% by weight, the color-developing activity of the resultant thermosensitive colored image-forming layer is saturated and no further improvement in the color-developing activity is obtained and it causes an economical disadvantage. In the thermosensitive colored image-forming layer of the present invention, the color-developing agent comprises one or two or more of the above-mentioned specific aromatic compounds. The dye precursor usable for the present invention comprises at least one member selected from conventional triphenylmethane, fluoran, and diphenylmethane leuco dyes, for example, 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-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-(o,p-dimethylphenylamino) fluoran, 3-(N-ethyl-N-p-toluidino)-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran, 3-diethylamino-7-(o-chloroanilino)fluoran, 3-diethylamino-7-(m-trifluoromethylanilino)fluoran, 3-diethylamino-6-methyl-7-chlorafluorane, 3-diethylamino-6-methylfluoran, 3-cyclohexylamino-6-chlorofluoran, 3-(N-ethyl-N-hexylamino)-6-methyl-7-(p-chloroanilino)fluoran, 2-chloro-3-methyl-6-(N,N-dibutylamino-anilino)fluoran, 3-(p-anilinoanilino)-6-methyl-7-anilinofluoran, 3,6-bis(dimethylamino)fluoran-9-spiro-3'-(6'-dimethylaminophthalide, 3,3-bis(2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl)-4,5,6,7-tetrachlorophthalide, and bis(p-dimethylaminostyryl)-p-toluenesulfonylmethane. In the thermosensitive colored image-forming layer of the present invention, the color-developing agent optionally contains at least one other or a conventional color-developing compound in addition to the aromatic compounds having two or more functional groups of the formula (I), unless the color-forming performance of the colored image-forming layer is disturbed thereby. The other color-developing compound is preferably selected from the N-aryl sulfonylurea compounds of the formula (VIII): wherein R 6 represents a member selected from the group consisting of hydrogen and halogen atoms, and lower alkyl groups preferably having 1 to 4 carbon atoms, aryl groups, for example, phenyl and tolyl group, alkoxyl groups preferably having 1 to 4 carbon atoms, acetyl group and nitro group, R 7 represents a member selected from the group consisting of unsubstituted phenyl and naphthyl groups and substituted phenyl and naphthyl groups having at least one substituent selected from the group consisting of alkoxyl, acetyl, nitro and lower alkyl groups and halogen atoms, m represents an integer of 1 to 5, the substituents represented by R 6 may be the same as or different from each other. The color-developing N-aryl sulfonylurea compounds of the formula (VIII) are preferably selected from the group consisting of: N-(p-toluenesulfonyl)-N'-phenylurea, N-(p-toluenesulfonyl)-N'-(p-methoxyphenyl)urea, N-(p-toluenesulfonyl)-N'(o-tolyl)urea, N-(p-toluenesulfonyl)-N'-(m-tolyl)urea, N-(p-toluenesulfonyl)-N'-(p-tolyl)urea, N-(p-toluenesulfonyl)-N'-(o-chlorophenyl)urea, N-(p-toluenesulfonyl)-N'-benzylurea, N-(p-toluenesulfonyl)-N'-(1-naphthyl)urea N-(benzenesulfonyl)-N'-phenylurea, N-(o-toluenesulfonyl)-N'-phenylurea, N-(p-toluenesulfonyl)-N'-(o-diphenyl)urea, N-(p-toluenesulfonyl)-N'-(p-ethoxycarbonylphenyl)urea, N-(p-methoxybenzenesulfonyl)-N'-phenylurea, N-(3-nitrobenzenesulfonyl)-N'-phenylurea, N-(3-nitro-4-methoxybenzenesulfonyl)-N'-phenylurea, N-(benzenesulfonyl)-N'-(p-methoxyphenyl)urea, N-(toluenesulfonyl)-N'-(4-nitro-1-naphthyl)urea, N-(benzenesulfonyl)-N'-p-acetylphenylurea, N-(p-acetylbenzenesulfonyl)-N'-(m-tolyl)urea, and N-(p-methoxybenzenesulfonyl)-N'-benzylurea. The conventional color-developing compounds usable for the present invention are preferably selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane (namely bisphenol A), 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,4-bis(1-methyl-1-(4'-hydroxyphenyl)ethyl)benzene, 1,3-bis(1-methyl-1-(4'-hydroxyphenyl)ethyl)benzene, dihydroxydiphenylether (disclosed in JP-A-1-180,382), benzyl p-hydroxybenzoate (disclosed in JP-A-52-140,483), bisphenol S, 4-hydroxy-4'-isopropyloxy-diphenylsulfone (disclosed in JP-A-60-13,852), 1,1-di(4-hydroxyphenyl)-cyclohexane, 1,7-di(4-hydroxyphenylthio)-3,5-dioxaheptane (disclosed in JP-A-59-52,694), and 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone (disclosed in JP-A-60-208,286). The above-mentioned other or conventional color-developing compounds can be employed alone or as a mixture of two or more thereof. When the other or conventional color-developing compound is employed, its content in the colored image-forming layer is preferably 5 to 40% by weight. The binder serves to bond the components in the colored image-forming layer to the substrate sheet and preferably comprises at least one member selected from water-soluble polymeric materials, for example, polyvinyl alcohols of various molecular weight, starch and starch derivatives, cellulose derivatives, for example, methoxy cellulose, carboxymethyl cellulose, methyl cellulose and ethyl cellulose, sodium polyarcylate, polyvinyl pyrrolidine, acrylic acid amide-acrylic acid ester copolymers, acrylic acid amide-acrylic acid ester-methacrylic acid terpolymers, alkali salts of styrene-maleic anhydride copolymers, polyacrylic acid amide, sodium alginate, gelatine and casein, and water-insoluble polymeric materials, for example, polyvinyl acetate resins, polyurethane resins, styrene-butadiene copolymer resins, polyacrylic acid resins, polyacrylic acid ester resins, vinyl chloride-vinyl acetate copolymer resins, polybutyl acrylate, ethylene-vinyl acetate copolymer resins and styrene-butadiene-acrylic compound-terpolymer resins, used in the form of a latex. In the thermosensitive colored image-forming layer of the present invention, the dye precursor is present in an amount of 5 to 20% of weight together with 5 to 50% of the color-developing compound of the formula (I) and the binder is present in an amount of 5 to 20% by weight, based on the total dry weight of the colored image-forming layer. The thermosensitive colored image-forming layer of the present invention optionally further comprises a heat-fusible organic substance, usually referred to as a sensitizer, non-basic inorganic and organic pigments, antioxidants, for example, hindered phenol compounds, ultraviolet ray-absorbers, and waxes. The sensitizing agent comprises at least one organic compound having a melting point of from 50°C to 150°C, for example, phenyl 1-hydroxy-2-naphthoate (disclosed in JP-A-57-191,089), p-benzylbiphenyl (JP-A-60-82,382), benzylnaphthylether (JP-A-58-87,094), dibenzyl terephthalete (JP-A-58-98,285), benzyl p-benzyloxybenzoate (JP-A-57-201,691), diphenyl carbonate, ditolyl carbonate (JP-A-58-136,489), m-terphenyl (JP-A-57-89,994), 1,2-bis(m-tolyloxy)ethane (JP-A-60-56,588), 1,5-bis(p-methoxyphenoxy)-3-oxapentane (JP-A-62-181,183), oxalic acid diesters (JP-A-64-1,583) 1,4-bis(p-tolyloxy)benzene (JP-A-2-153,783), diphenyl sulfone (melting point: 124°C), phenyl p-toluenesulfonate (m.p.: 96°C), p-tolyl mesitylenesulfonate (m.p.: 100 to 102°C), 4,4'-diallyloxydiphenylsulfone (m.p.: 145°C), 4,4'-diisopentyloxydiphenylsulfone (m.p.: 100°C), 4,4'-dimethoxydiphenylsulfone (m.p.: 130°C), bis(4-(2-((C 14 , C 16 or C 18 )alkanoyl(or alkenoyl)oxy)ethoxy)phenyl)sulfone, 2,2-bis(4-benzenesulfonyloxyphenyl)propane (m.p.: 114°C), 2,2-bis(4-methanesulfonyloxyphenyl)propane (m.p.: 101°C), p-toluenesulfonanilide (m.p.: 102°C) and N-benzyl-o-sulfophthalimide. The thermosensitive colored image-forming layer optionally contains an antioxidant, for example, hindered phenolic compound and/or ultraviolet ray-absorbers. The antioxidant and ultraviolet ray-absorbers are preferably selected from those disclosed in JP-A-57-151,394, JP-A-58-160,191, JP-A-58-69,096, JP-A-59-2,884, JP-A-59-95,190, JP-A-60-22,288, JP-A-60-255,485, JP-A-61-44,686, JP-A-62-169,683, JP-A-63-17,081, JP-A-1-249,385, and JP-A-4-144,786 for example, 1,1,3-tris(2'-methyl-3'-cyclohexyl-4'-hydroxyphenyl)butane; 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, p-octylphenyl salicylate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, ethyl-2-cyano-3,3'-diphenyl acrylate, and tetra(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarbonate. The inorganic and organic pigments usable for the present invention are preferably selected from inorganic fine particles of, for example, calcium carbonate silica, zinc oxide, titanium dioxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, anhydrous clay, talc, surface-modified calcium carbonate, and silica and organic fine particles of, for example, urea-formaldehyde resins, styrene-methacrylate copolymer resins and polystyrene resins. The waxes usable for the present invention preferably comprises at least one member selected from, for example, paraffin waxes, carnauba wax, microcrystalline waxes, polyethylene waxes, amide type waxes, bisimide type waxes, higher fatty acid amide waxes, for example, stearic acid amide, ethylene-bis-stearoamide wax, higher fatty acid esters and metal salts, for example, zinc stearate, aluminum stearate, calcium stearate, and zinc oleate. In the colored image-forming layer of the present invention, the sensitizing agent is preferably contained in an amount of 10 to 40% by weight, the wax and organic or inorganic pigment are optionally contained in amounts of 2 to 20% by weight and 2 to 50% by weight, respectively, and the antioxidant and ultraviolet ray-absorber are optionally contained in an amount of 1 to 10%, based on the total dry weight of the colored image-forming layer. The sheet substrate usable for the present invention is not limited to a specific group of materials, and usually the sheet substrate comprises a member selected from fine paper sheets, coated paper sheets having a clay or latex-coated layer, cast-coated paper sheets, paper boards, plastic resin films, synthetic paper sheets comprising a plastic resin such as a polyolefin resin and a multi-layer structure, and laminated composite sheets. Preferably, the sheet substrate has a basis weight of 40 to 170 g/m 2 . The colored image-forming layer can be formed on a surface of sheet substrate, by applying a coating liquid containing the above-mentioned components, and by drying and solidifying the coating liquid layer on the sheet substrate. The colored image-forming layer is preferably present in a dry weight of from 1 to 15 g/m 2 , more preferably 2 to 10 g/m 2 . In the present thermosensitive recording material, a protective layer and/or a layer for printing may be formed on the colored image-forming layer. The thermosensitive recording material of the present invention is provided with a specific thermosensitive colored image-forming layer characterized by containing a specific color-developing agent. This specific color-developing agent comprises at least one aromatic compound having at least two functional sulfonylamino(thio)carbonylamino groups of the formula (I), and causes not only the resultant thermosensitive colored image-forming layer to exhibit a high whiteness and a satisfactory thermosensitivity, but also the resultant colored images on the colored image-forming layer exhibit an excellent resistance to oily and fatty substances and a plasticizer even immediately after the color development, and thus have a superior storage persistency. EXAMPLES The present invention will be further explained by the following specific examples, which are merely representative and do not in any way restrict the scope of the present invention. Synthesis Example 1 (Preparation of 4,4'-bis(p-methoxybenzenesulfonylaminocarbonylamino)diphenylmethane) (1) Synthesis of p-methoxysulfonamide p-Methoxybenzenesulfonylchloride having a molecular weight of 206.5 was dissolved in an amount of 0.1 mole in 200 ml of a concentrated aqueous ammonia solution, and the resultant solution was agitated at room temperature for 3 hours. Then, the solution was neutralized by using a diluted aqueous hydrochloric acid, and a reaction product was extracted with ether. The resultant ether phase was washed with water and dried in the presence of a drying agent consisting of anhydrous magnesium carbonate for one night. The reaction product mixture was filtered, and the solvent was evaporated away from the resultant product. A white solid product was obtained. The product was subjected to a mass spectrometric analysis. As a result, a molecular ion peak (m/l = 187) was confirmed and it was identified that the resultant product was the aimed compound. (2) Synthesis of 4,4'-bis(p-methoxybenzenesulfonylaminocarbonylamino)diphenylmethane p-Methoxysulfonamide prepared by the above-mentioned method in an amount of 13.2g (0.07 mole) was mixed in the form of a fine powder with 8.0g (0.032 mole) of 4,4'-diphenylmethanediisocyanate, and the mixed powder was heated at a temperature of 140°C within a nitrogen gas stream. The mixture was dissolved and liquefied with the lapse of the heating time, and thereafter was solidified as a result of the reaction. After the heating for one hour, the heating procedure was stopped, the resultant mixture was cooled, and the resultant reaction product was extracted by an 1N aqueous sodium hydroxide solution. The extract solution was neutralized so as to cause the reaction product to be precipitated, and the precipitated solid product was filtered and dried. By repeating the above-mentioned procedures, a white solid product was obtained in an amount of 14.1g. In the temperature range of upto 220°C, the white solid product did not exhibit a certain melting point. The white solid product was subjected to a high speed liquid chromatographic analysis. It was confirmed that the white solid product has a different peak than that of p-methoxysulfonamide and 4,4'-diphenylmethane diisocyanate. Also, NMR spectral analysis and IR spectral analysis identified the resultant white solid product as the aimed compound. NMR spectral analysis (in deuterated DMSO) δ = 3.85 (s, 8H, hydrogen in methoxy and hydrogen in methylene overlapped each other) δ = 7.13 - 7.85 (m, 18H, hydrogen in aromatic cyclic structures and in NH). In addition, a peak was appeared at δ = about 9.2 which was assumably derived from the -NH group adjacent to sulfonyl group. IR spectral analysis (KBr tablet method) In this analysis, the following characteristic absorptions were confirmed. 1740 cm -1 (derived from carbonyl group in urea group) 1345 cm -1 , 1160 cm -1 (derived from sulfonyl group). Synthesis Example 2 (Preparation of 4,4'-bis(m-nitrobenzenesulfonylaminocarbonylamino)diphenylmethane (1) Synthesis of m-nitrobenzenesulfonamide The same synthesis procedures as in Synthesis Example 1-(1) were carried out with the following exceptions. 22.2g of m-nitrobenzenesulfonylchloride having a molecular weight of 221.5 were used in an amount of 0.10 mole in place of 20.7g of p-methoxybenzenesulfonylchloride. The resultant light yellow solid product was subjected to the mass spectrometer analysis. As a result, a molecular ion peak (m/l = 202) was confirmed and it was identified that the resultant solid product was the aimed compound. (2) Synthesis of 4,4'bis(m-nitrobenzenesulfonylaminocarbonylamino)diphenyl methane The same procedures as in Synthesis Example 1-(2) were carried out with the following exceptions. In the synthesis reaction, 13.2g of p-methoxy sulfonamide were replaced by 14.2g of m-nitrobenzenesulfonamide. A slightly yellowish solid product was obtained in an amount of 15.0g. This slightly yellowish solid product did not exhibit a clear melting point in a temperature range of upto 220°C. The high speed liquid chromatography confirmed that the reaction product exhibited a peak different from m-nitrobenzenesulfonamide and 4,4'-diphenylmethanediisocyanate. Also, NMR spectral analysis and IR spectral analysis identified the resultant slightly yellowish solid product as the aimed compound. NMR spectral analysis (in deuterated DMSO) δ = 3.89 (s, 2H), 7.07 - 9.10 (m, 18H hydrogen in aromatic cyclic structure and in NH). Also, a peak was appeared at δ = about 10.5 which was assumably derived from the NH group located adjacent to the sulfonyl group. IR spectral analysis (KBr tablet method) 1740 cm -1 (derived from carbonyl group in urea group) 1355 cm -1 , 1155 cm -1 (derived from sulfonyl group) Example 1 A thermosensitive recording paper sheet was prepared by the following procedures. (1) Preparation of an aqueous dye precursor dispersion A A mixture was prepared in the following composition. Component Part by weight 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran 20 10% aqueous solution of polyvinyl alcohol 10 Water 70 The mixture was dispersed by using a paint shaker to an extent such that the resultant dispersed solid particles had an average size of 1 µm or less. (2) Preparation of an aqueous color-developing agent dispersion B Component Part by weight 4,4'-bis(p-methoxybenzenesulfonylaminocarbonylamino) diphenylmethane 10 Diphenylsulfone 10 10% aqueous solution of polyvinyl alcohol 10 Water 70 The mixture was dispersed by using a paint shaker to such an extent that the resultant dispersed solid particles had an average size of 1 µm or less. (3) Preparation of a pigment-coated paper sheet A coating liquid was prepared by mixing an aqueous dispersion, prepared by dispersing 85 parts by weight of anhydrous clay available under the trademark of Ansilex, from Engelhard Corporation, in 320 parts by weight of water, with 40 parts by weight of an aqueous emulsion of a styrene-butadiene copolymer in a solid concentration of 50% by weight and 50 parts by weight of a 10% aqueous oxidized starch solution. The coating liquid was coated on a surface of a fine paper sheet having a basis weight of 48 g/m 2 , to form a coating layer having a dry weight of 7.0 g/m 2 , whereby a coated paper sheet was obtained. (4) Formation of thermosensitive colored image-forming layer A coating liquid was prepared by evenly mixing 50 parts by weight of the aqueous dye precursor dispersion A and 200 parts by weight of the aqueous color-developing agent dispersion B with 30 parts by weight of a calcium carbonate pigment, 20 parts by weight of a 25% aqueous zinc stearate dispersion, 15 parts by weight of 30% aqueous paraffin dispersion, and 100 parts by weight of a 10% aqueous polyvinyl alcohol solution, by agitating the mixture. A surface of the pigment coated paper sheet was coated with the resultant coating liquid and dried. A thermosensitive colored image-forming layer was formed in a weight of 5.0 g/m 2 , to provide a thermosensitive recording paper sheet. (5) Super calender treatment The recording sheet was treated by a super calender, and the calendered surface of the recording sheet had a Bekk smoothness of 900 to 1200 seconds. (6) Whiteness measurement and color-forming test The whiteness of the non-image-formed white portions of the recording sheet was measured by using a Hunter whiteness tester with a blue filter. Also, the specimen of the resultant thermosensitive recording sheet was subjected to a colored image-developing test by using a dynamic color-developing tester provided by modifying a thermosensitive facsimile printer with an applied energy of 0.49 mj/dot. The resultant colored images were subjected to a measurement of a color density by a Macbeth Reflection Color Density Tester RD-914, (trademarks). The measured color density of the colored images on the specimen is referred to as an original color density (D 0 ) of the colored images. The values of the measured whiteness and original color density are shown in Table 1. (7) Oil and plasticizer resistance test Specimens of the colored image-formed recording paper sheet were subjected to an oil or plasticizer resistance test in which salad oil or dioctyl terephthalate (a typical plasticizer) was applied to the colored image-formed surface of the specimen within 30 minutes from the completion of the color-developing operation. The salad oil or plasticizer-applied specimen was left to stand at room temperature for 3 hours. The salad oil or plasticizer was wiped away from the specimen, and the color density of the black colored images retained on the specimen was measured by the Macbeth Reflection Color Density Tester. The measured color density is referred to as a color density (D 1 ) after oil or plasticizer resistance test. The resistance of the colored images to the salad oil or plasticizer is represented by a color density retention calculated from the following equation. Color density retention (%) = [(color density (D 1 ) after oil or plasticizer resistance test)/(original color density (D 0 ))] × 100 The test results are shown in Table 1. Example 2 A thermosensitive recording sheet was produced by the same procedures as in Example 1 except that in the formation of the thermosensitive colored image-forming layer, a coating liquid was prepared by mixing 40 parts by weight of the dispersion A and 60 parts by weight of the dispersion B with 40 parts by weight of calcium carbonate pigment, 20 parts by weight of a 25% aqueous zinc stearate dispersion, 15 parts by weight of a 30% aqueous paraffin dispersion, 120 parts by weight of a 10% aqueous polyvinyl alcohol and 3 parts by weight of a melting agent (trademark: Dapro U 99, made by Sannopuco), while stirring the mixture. The coating liquid was coated on a surface of a synthetic paper sheet (trademark: YUPO FPG 110, made by OJI Yukagoseishi K.K.), to form a thermosensitive colored image-forming layer having a dry weight of 8.5 g/m 2 . A thermosensitive recording paper sheet was obtained. The test results are shown in Table 1. Example 3 A thermosensitive recording sheet was produced by the same procedures as in Example 1 except that in the preparation of the dispersion A, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran was replaced by 3-(N-isopentyl-N-ethylamino)-6-methyl-7-anilinofluoran. The test results are shown in Table 1. Comparative Example 1 A thermosensitive recording sheet was produced by the same procedures as in Example 1 except that in the preparation of the dispersion B, 4,4'-bis(p-methoxybenzenesulfonylaminocarbonylamino)diphenylmethane was replaced by 2,2-bis(4-hydroxyphenyl)propane, namely Bisphenol A. The test results are shown in Table 1. Comparative Example 2 A thermosensitive recording sheet was produced by the same procedures as in Example 1 except that in the preparation of the dispersion B, 4,4'-bis(p-methoxybenzenesulfonylaminocarbonylamino)diphenylmethane was replaced by 4,4'-bis(benzenaminothiocarbonylamino)benzene. The test results are shown in Table 1. Comparative Example 3 A thermosensitive recording sheet was produced by the same procedures as in Example 1 except that in the preparation of the dispersion B, 4,4'-bis(p-methoxybenzenesulfonylaminocarbonylamino)diphenylmethane was replaced by N-(p-nitrobenzoyl)-p-toluenesulfonamide (having a melting point of 206°C and disclosed in JP-A-62-19,485. The test results are shown in Table 1. Comparative Example 4 A thermosensitive recording sheet was produced by the same procedures as in Example 1 except that in the preparation of the dispersion 4, 4,4'-bis(p-methoxybenzenesulfonylaminocarbonylamino)diphenylmethane was replaced by N-(o-carboxybenzoyl)-p-toluenesulfonamide having a melting point of 161°C and disclosed in JP-A-62-19,485. Item Original color density (D 0 ) Color density retention (%) Example No. Salad oil resistance Plasticizer resistance Example 1 1.32 91 82 2 1.35 94 84 3 1.35 94 85 Comparative Example 1 1.42 22 12 2 0.90 32 20 3 0.79 21 17 4 0.41 35 22 Table 1 clearly indicates that the colored images formed by using the specific color-developing agent of the present invention exhibited a significantly higher oil and plasticizer resistance than those when a typical conventional color-developing agent, namely bisphenol A in Comparative Example 1 was used. Also, each of Examples 1, 2 and 3, the resultant colored images exhibited a significantly higher color density (D 0 ) and oil and plasticizer resistance than those when a color-developing compound having a sulfonyl group was used in Comparative Example 2, and when a color-developing compound in which one -NH group disappeared from a -SO 2 NHC(X)NH- group was employed in Comparative Examples 3 and 4.

Claims: A thermosensitive recording material comprising: a substrate sheet; and a thermosensitive colored image-forming layer formed on a surface of the substrate sheet and comprising a substantially colorless dye precursor, a color-developing agent reactive with the dye precursor upon heating to thereby develop a color, and a binder, wherein the color-developing agent comprises at least one aromatic compound selected from those of the formula (II): in which formula (II), X represents a member selected from oxygen and sulfur atoms; R 1 represents an aromatic group substituted with at least one substituent selected from nitro group, alkyl groups substituted with at least one halogen atom, alkyloxy groups, aryloxy groups, aralkyloxy groups, alkylcarbonyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups and aralkyl groups, A represents a multivalent group; and n represents an integer of 2 or more. The thermosensitive recording material as claimed in claim 1, wherein the multivalent group represented by A in the formula (II) is selected from: (a) carbonyl, thiocarbonyl and sulfonyl group; (b) multivalent aliphatic hydrocarbon group; (c) multivalent, hetero-atom-containing aliphatic groups derived from aliphatic hydrocarbon compounds having at least one hetero-atom located in a backbone chain per molecule thereof; (d) multivalent aliphatic groups derived from aliphatic hydrocarbon compounds having at least one member selected from carbonyl, thiocarbonyl, imide, imino, and sulfonyl groups and ester structures, located in a backbone chain per molecule thereof; (e) multivalent aliphatic aromatic groups derived from aliphatic hydrocarbon compounds having at least one member selected from unsubstituted and substituted aromatic hydrocarbon groups, located in a backbone chain per molecule thereof; (f) multivalent organic groups derived from aliphatic hydrocarbon compounds having at least one member selected from unsubstituted and substituted aromatic heterocyclic groups, located in a backbone chain per molecule thereof; (g) multivalent aromatic groups derived from unsubstituted and substituted aromatic hydrocarbon compounds; (h) multivalent aromatic heterocyclic groups derived from unsubstituted and substituted aromatic heterocyclic compounds; and (i) multivalent organic groups derived from organic compounds in which two or more aromatic or aromatic heterocyclic groups are bonded to each other through one or more multivalent groups selected from the above-mentioned groups (a) to (d).

Inventors: SEGAWA TAKAKO, SHIRAI AYAKO, TAKAHASHI YOSHIYUKI, TOYOFUKU KUNITAKA, SEGAWA, TAKAKO, SHIRAI, AYAKO, TAKAHASHI, YOSHIYUKI, TOYOFUKU, KUNITAKA
Applicants: OJI PAPER CO, OJI PAPER COMPANY LIMITED
Application year: 1993
Main classification: B41M5
IPC codes: B41M5