A thermal recording medium

Abstract: A thermally sensitive recording medium which comprises, on a substrate, a thermally sensitive colour developing layer which comprises a colourless or pale coloured basic leuco dye and an organic colour developer, wherein the thermal colour developing layer includes (a) 0.01-0.9 parts by weight, based on 1 part by weight of colour developer, of one or more aminobenzenesulfonamide derivatives of formula (I) wherein X is oxygen or sulphur, R is a group selected from phenyl, naphthyl, aralkyl, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl and C 2 -C 6 alkenyl, which group is unsubstituted or substituted, Z is C 1 -C 6 alkyl or an electron attracting group, n is 0 or an integer from 1 to 4 and p is an integer from 1 to 5, provided that n+p≤5; and (b) 0.01-2 parts by weight, based on 1 part by weight of colour developer, of at least one methylolated fatty acid amide of formula (II) R 1 -CONHCH 2 OH wherein R 1 is C 11 -C 21 alkyl.

Description: This invention relates to a thermally sensitive recording medium which achieves excellent preservation of the developed image. In general, a thermally sensitive recording medium can be obtained by mixing a colourless or pale coloured basic leuco dye and a colour developer such as a phenolic compound, each of which has been dispersed to fine particles before mixing, adding a binder, a filler, a sensitizer, a slip agent and other additives to form a coating colour. The obtained coating colour is then used to coat a substrate such as paper, synthetic paper, film or plastic, and colour is developed by a momentary chemical reaction caused by heating with a thermal head, a hot stamp, a thermal pen, laser light or the like to obtain a recorded image. Thermally sensitive recording mediums can be used in a wide variety of fields such as facsimiles, terminal printers for computers, automatic ticket venders and measuring recorders and recently the number of applications has extended broadly to include slips for parcel delivery services and bar code labels, for example for foods. However, conventional dye type thermally sensitive recording mediums, which coat a thermally sensitive colour developing layer comprising a basic leuco dye, a colour developer and a binder on to a substrate, have been known to produce a developed image which tends to discolour over time. This discolouration is accelerated by exposure to light, high temperatures or very humid environments and particularly by immersion in water for a long time, contact with an oil e.g. salad oil or a plasticizer. After such treatment the developed image becomes unreadable. In order to suppress such discolouration of the developed image, various techniques have been disclosed regarding thermally sensitive recording media which use a basic leuco dye which is mainly composed of a colourless or pale coloured lactone ring compound. For instance, a thermally sensitive recording medium comprising a thermal colour developing layer in which a phenolic antioxidant is mixed is disclosed in JP-A-78782/85 and JP-A-114096/84. A thermally sensitive recording medium which uses a hydrophobic macromolecular emulsion as a protective layer is disclosed in JP-A-146794/81. A thermally sensitive recording medium which uses an epoxy compound together with a phenolic colour developer is disclosed in JP-A-164579/87. However, since these techniques are not sufficient for practical use, a new technique to stabilize a developed image against decolouration over time is still required. The object of this invention is to improve a thermally sensitive recording medium comprising a basic leuco dye and a phenolic colour developer, in order to provide excellent stability, especially when exposed to a plasticizer. The inventors have conducted intensive studies to develop a thermally sensitive recording medium having the above mentioned feature, and have consequently accomplished the present invention. The inventors have succeeded in improving the stability by including a specific stabilizer in the thermally sensitive colour developing layer. The present invention relates to a thermally sensitive recording medium which comprises, on a substrate, a thermally sensitive colour developing layer which comprises a colourless or pale coloured basic leuco dye and an organic colour developer, wherein the thermal colour developing layer includes (a) 0.01-0.9 parts by weight, based on 1 part by weight of colour developer, or one or more aminobenzenesulfonamide derivatives of formula (I) wherein X is oxygen or sulphur, R is a group selected from phenyl, naphthyl, aralkyl, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl and C 2 -C 6 alkenyl, which group is unsubstituted or substituted, Z is C 1 -C 6 alkyl or an electron attracting group, n is 0 or an integer from 1 to 4 and p is an integer from 1 to 5, provided that n+p≤5; and (b) 0.01-2 parts by weight, based on 1 part by weight of colour developer, of at least one methylolated fatty acid amide of formula (II) R 1 -CONHCH 2 OH wherein R 1 is C 11 -C 21 alkyl. In the thermally sensitive colour developing layer of this invention, "Z" is a substituted group which does not adversely effect the functioning of the stabilizer. Specifically, Z is a lower alkyl group of 1-6 carbon atoms such as methyl or ethyl, or an electron attracting group such as nitro or methoxy. R is preferably a phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, propenyl, isopropenyl, cyclohexyl or naphthyl group. R may be substituted by one or more substituents which are the same or different and is preferably substituted by one, two or three substituents. The substituted groups are those which do not adversely effect the stabilizing effect. Examples of such groups include lower alkyl groups of 1-6 carbon atoms such as methyl or ethyl, lower alkenyl groups of 2-6 carbon atoms such as isopropenyl, or electron attracting groups such as halogen atoms, for example a fluorine, bromine or chlorine atom, nitro, cyano or C 1 -C 6 alkoxy groups such as methoxy. As used herein, C 1 -C 6 alkyl is typically C 1 -C 4 alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl or t-butyl. C 2 -C 6 alkenyl is typically ethenyl, isopropenyl, propenyl, n-butenyl, s-butenyl or t-butenyl. C 1 -C 6 alkoxy is typically C 1 -C 4 alkoxy, for instance methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy or t-butoxy. C 3 -C 6 cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Practical examples of compounds of formula (I) include the following compounds (I-1) to (1-72). The compound (I-10) is preferred by reason of easy purchase and easy synthesis. In this invention, if the proportion of derivatives of aminobenzenesulfonamide indicated by general formula (I) is smaller than 0.01 parts based on 1 part of colour developer, a sufficient stabilizing effect can not be expected, and if it is bigger than 0.9 parts based on 1 part of colour developer, not enough colour developing density can be obtained. Therefore, for the preparation of a thermally sensitive recording medium which is satisfactory in terms of stabilizing effect and also in terms of colour developing density, it is desirable to use the derivatives of aminobenzenesulfonamide indicated by general formula (I) in a proportion of 0.01-0.9 parts based on 1 part of colour developer. Furthermore, in this invention, at least one kind of methylol fatty acid amide indicated by general formula (II) is included in the thermally sensitive colour developing layer with the compound of said general formula (I). In general formula (II), "R 1 " indicates a hydrocarbon group, concretely an alkyl group of 11 to 21 carbon atoms can be mentioned. R 1 is preferably C 11 , C 16 , C 17 or C 21 alkyl. As the specific examples of compounds indicated by general formula (II), the following compounds (II-1) to (II-4) can be mentioned, however, the invention is not intended to be limited to them. The compound (II-3) is preferred by reason of easy purchase and stabilizing effect when it is used with said compound (I-10). C 11 H 23 CONHCH 2 OH C 16 H 31 CONHCH 2 OH C 17 H 35 CONHCH 2 OH C 21 H 43 CONHCH 2 OH In this invention, if the proportion of methylolated fatty acid amide indicated by general formula (II) is smaller than 0.01 parts based on 1 part of colour developer, a sufficient stabilizing effect can not be expected, and if it is bigger than 2 parts based on 1 part of colour developer, not enough colour developing density can be obtained. Therefore, for the preparation of a thermally sensitive recording medium which is satisfactory in terms of stabilizing effect and also in terms of colour developing density, it is desirable to use the methylolated fatty acid amide indicated by general formula (II) in a proportion of 0.01-2 parts based on 1 part of colour developer. In this invention, it is obvious that the derivatives of aminobenzenesulfonamide indicated by general formula (I) which is used as a stabilizer is recognized as to have a colour developing ability, but it is inferior to that of an ordinary organic colour developer. However, by using the compound of general formula (I) in a specific proportion based on 1 part of organic colour developer, the compound of general formula (I) can function as a stabilizer. The reason for this phenomenon is not clear, but a hypothesis is suggested below. Generally, a thermal recording medium is composed of a basic leuco dye which acts as an electron donor and an organic acid substance which acts as an electron accepter. Electrons are exchanged between said basic leuco dye and colour developer by heat fusion, then a kind of complex is formed and a colour image can be obtained. The compound of general formula (I) is thought to strengthen the chemical bond between the basic leuco dye and the colour developer and stabilize the recorded image. On the other hand, the compound of general formula (II) is thought to strengthen the interaction between said complex and the compound of general formula (I) when it is mixed by heat fusion with the compound (II). Therefore, in this invention, a thermally sensitive recording medium having high stabilization can be obtained by using a compound of general formula (I) together with that of general formula (II). As a basic leuco dye used for the thermal recording medium of this invention, any known compound in the fields of conventional pressure sensitive or thermally sensitive recording paper can be used, and preferably triphenylmethane compounds, fluoran compounds, fluorene compounds and divinyl compounds can be used, however the invention is not intended to be limited to them. Examples of typical basic leuco dyes are indicated below. These basic leuco dyes can be used alone or by mixing with others. <triphenylmethane-based leuco dye> 3,3-bis( p -dimethylaminophenyl)-6-dimethylaminophthalide [another name is crystal violet lactone] 3,3-bis( p -dimethylaminophenyl)phthalide [another name is malachite green lactone] <fluoran-based leuco dye> 3-diethylamino-6-methylfluoran 3-diethylamino-6-methyl-7-anilinofluoran 3-diethylamino-6-methyl-7-( o,p- dimethylanilino)fluoran 3-diethylamino-6-methyl-7-chlorofluoran 3-diethylamino-6-methyl-7-( m -trifluoromethylanilino)fluoran 3-diethylamino-6-methyl-7-( o -chloroanilino)fluoran 3-diethylamino-6-methyl-7-( p -chloroanilino)fluoran 3-diethylamino-6-methyl-7-( o -fluoroanilino)fluoran 3-diethylamino-6-methyl-7- n -octylanilinofluoran 3-diethylamino-6-methyl-7- n -octylaminofluoran 3-diethylamino-6-methyl-7-benzylanilinofluoran 3-diethylamino-6-methyl-7-dibenzylanilinofluor'an 3-diethylamino-6-chloro-7-methylfluoran 3-diethylamino-6-chloro-7-anilinofluoran 3-diethylamino-6-chloro-7- p -methylanilinofluoran 3-diethylamino-6-ethoxyethyl-7-anilinofluoran 3-diethylamino-7-methylfluoran 3-diethylamino-7-chlorofluoran 3-diethylamino-7-( m -trifluoromethylanilino)fluoran 3-diethylamino-7-( o -chloroanilino)fluoran 3-diethylamino-7-( p -chloroanilino)fluoran 3-diethylamino-7-( o -fluoroanilino)fluoran 3-diethylamino-benzo[a]fluoran 3-diethylamino-benzo[c]fluoran 3-dibutylamino-6-methyl-fluoran 3-dibutylamino-6-methyl-7-anilinofluoran 3-dibutylamino-6-methyl-7-( o,p -dimethylanilino)fluoran 3-dibutylamino-6-methyl-7-( o -chloroanilino)fluoran 3-dibutylamino-6-methyl-7-( p -chloroanilino)fluoran 3-dibutylamino-6-methyl-7-( o -fluoroanilino)fluoran 3-dibutylamino-6-methyl-7-( m -trifluoromethylanilino)fluoran 3-dibutylamino-6-methyl-chlorofluoran 3-dibutylamino-6-ethoxyethyl-7-anilinofluoran 3-dibutylamino-6-chloro-7-anilinofluoran 3-dibutylamino-6-methyl-7- p -methylanilinofluoran 3-dibutylamino-7-( o -chloroanilino)fluoran 3-dibutylamino-7-( o -fluoroanilino)fluoran 3- n -dipentylamino-6-methyl-7-anilinofluoran 3- n -dipentylamino-6-methyl-7-(p-chloroanilino)fluoran 3- n -dipentylamino-7-( m -trifluoromethylanilino)fluoran 3- n -dipentylamino-6-chloro-7-anilinofluoran 3- n -dipentylamino-7-( p -chloroanilino)fluoran 3-pyrrolidino-6-methyl-7-anilinofluoran 3-pyperidino-6-methyl-7-anilinofluoran 3-(N-methyl-N-propylamino)-6-methyl-7-anilinofluoran 3-(N-methyl-N-cyclohexylamino)-6-methyl-7-anilinofluoran 3-(N-ethyl-N-cyclohexylamino)-6-methyl-7-anilinofluoran 3-(N-ethyl-N-xylamino)-6-methyl-7-(p-chloroanilino)fluoran 3-(N-ethyl- p -toluidino)-6-methyl-7-anilinofluoran 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran 3-(N-ethyl-N-isoamylamino)-6-chloro-7-anilinofluoran 3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-anilinofluoran 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluoran 3-(N-ethyl-N-ethoxypropylamino)-6-methyl-7-anilinofluoran 3-cyclohexylamino-6-chlorofluoran 2-(4-oxahexyl)-3-dimethylamino-6-methyl-7-anilinofluoran 2-(4-oxahexyl)-3-diethylamino-6-methyl-7-anilinofluoran 2-(4-oxahexyl)-3-dipropylamino-6-methyl-7-anilinofluoran 2-methyl-6- p -( p -dimethylaminophenyl)aminoanilinofluoran 2-methoxy-6- p -( p -dimethylaminophenyl)aminoanilinofluoran 2-chloro-3-methyl-6- p -( p -phenylaminophenyl)aminoanilinofluoran 2-chloro-6- p -( p -dimethylaminophenyl)aminoanilinofluoran 2-nitro-6- p -( p -diethylaminophenyl)aminoanilinofluoran 2-amino-6- p -( p -diethylaminophenyl)aminoanilinofluoran 2-diethylamino-6- p -( p -diethylaminophenyl)aminoanilinofluoran 2-phenyl-6-methyl-6- p -( p -phenylaminophenyl)aminoanilinofluoran 2-benzyl-6- p -( p -phenylaminophenyl)aminoanilinofluoran 2-hydroxy-6- p -( p -phenylaminophenyl)aminoanilinofluoran 3-methyl-6- p -( p -dimethylaminophenyl)aminoanilinofluoran 3-diethylamino-6- p -( p -diethylaminophenyl)aminoanilinofluoran 3-diethylamino-6- p -( p -dibutylaminophenyl)aminoanilinofluoran 2,4-dimethyl-6 -[(4-dimethylamino)anilino]-fluoran <fluorene-based leuco dye> 3,6,6'-tris(dimethylamino)spiro[fluorene-9,3'-phthalide] 3,6,6'-tris(diethylamino)spiro[fluorene-9,3'-phthalide] <divinyl-based leuco dye> 3,3-bis-[2-( p -dimethylaminophenyl)-2-( p -methoxyphenyl)ethenyl]-4, 5, 6, 7-tetrabromophthalide 3,3-bis-[2-( p -dimethylaminophenyl)-2-( p -methoxyphenyl)ethenyl]-4,5,6,7-tetrachlorophthalide 3,3-bis-[1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrabromophthalide 3,3-bis-[1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl]-4,5,6,7-tetrachlorophthalide <others> 3-(4 -diethylamino-2-ethoxyphenyl)-3 -(1-ethyl-2-methylindole-3-yl)-4-azaphthalide 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-octyl-2-methylindole-3-yl)-4-azaphthalide 3-(4-cyclohexylethylamino-2-methoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalide 3,3-bis(1-ethyl-2 -methylindole-3-yl)phthalide 3, 6-bis(diethylamino)fluoran-y-(3'-nitro)anilinolactam 3,6-bis(diethylamino)fluoran-y-(4'-nitro)anilinolactam 1,1-bis-[2',2',2",2"-tetrakis-( p -dimethylaminophenyl)-ethenyl]-2,2-dinitrilethane 1,1 -bis-[2',2',2",2"-tetrakis-( p -dimethylaminophenyl)-ethenyl]-2-β-naphthylethane 1,1-bis-[2',2',2",2"-tetrakis-( p -dimethylaminophenyl)-ethenyl]-2,2-diacetylethane bis-[2,2,2',2'-tetrakis-( p -dimethylaminophenyl)-ethenyl]-methylmalonatedimethyl ester In this invention, variation in the kind of basic leuco dye used has an unremarkable effect on the stability of the image, but gives a slight difference. The reason for this phenomenon is not clarified, however, it is considered that it is because the stability of the developed image is somewhat dependent on the polarity of the basic leuco dye (this can be detected by the developed state of thin-layer chromatography). For instance, the polarity of 3-diethylamino-6-methyl-7-anilinofluoran is relatively high, and in comparison with said compound the polarity of 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilionfluoran or 3-dibutylamino-6-methyl-7-anilinofluoran is low. It is considered that the developed image is dependent on the reactivity between the basic leuco dye and the colour developer. This influences the stabilization, which further influences the solubility with plasticizer. However, when a basic leuco dye having high polarity is used, it has a high reactivity with the developer and may cause problems regarding colouration of the background colour. Further plasicizer resistance is improved by use of a mixture of basic leuco dyes. Also the reason for said phenomenon is not clear, however, it is presumed that it is because the electron transfer complex forms a strong reactive substance in comparison with the use of a single basic leuco dye alone. As the specific examples of an organic colour developer used in the thermally sensitive recording medium of this invention, for instance the following compounds, which are disclosed in JP-A-207688/91, or in JP-A-24366/93 can be mentioned : bisphenol A type 4-hydroxybenzoic ester type 4-hydroxyphthalic diester type phthalic monoester bis- (hydroxyphenyl)sulfide type 4-hydroxyphenylarylsulfone type 4-hydroxyphenylarylsulfonate type 1, 3-di [2-(hydcoxyphenyl)-2-propyl]-benzene type 4-hydroxybenzoiloxybenzoic ester type bisphenolsulfone type Specific examples of typical known developers are indicated below, however, the invention is not intended to be limited to them. These developers can be used alone or can be used by mixing with others. <bisphenol A type> 4,4'-isopropylidenediphenol(another name is bisphenol A) 4,4'-cyclohexylidenediphenol p , p '-(1-methyl-normalhexylidene)diphenol 1,7-di(hydroxyqhenylthio)-3,5-dioxaheptane <4-hydroxybenzoic ester type> 4-hydroxybenzylbenzoate 4-hydroxyethylbenzoate 4-hydroxypropylbenzoate 4-hydroxyisopropylbenzoate 4-hydroxybutylbenzoate 4-hydroxyisobutylbenzoate 4-hydroxymethylbenzylbenzoate <4-hydroxyphthalic diester type> 4-hydroxydimethylphthalate 4-hydroxydiisopropylphthalate 4-hydroxydibenzylphthalate 4-hydroxydihexylphthalate <phthalic monoester type> monobenzylphthalate ester monocyclohexylphthalate ester monophenylphthalate ester monomethylphenylphthalate ester monomethylphenylphthalate ester monopropylbenzylphthalate ester monohalogenbenzylphthalate ester monoethoxybenzylphthalate ester <bis-(hydroxyphenyl)sulfide type> bis-(4-hydroxy-3-tert-butyl-6-methylphenyl)sulfide bis-(4-hydroxy-2,5-dimethylphenyl)sulfide bis-(4-hydroxy-2-methyl-5-ethylphenyl)sulfide bis-(4-hydroxy-2-methyl-5-isopropylphenyl)sulfide bis-(4-hydroxy-2,3-dimethylphenyl)sulfide bis-(4-hydroxy-2,5-dimethylphenyl)sulfide bis-(4-hydroxy-2,5-diisopropylphenyl)sulfide bis-(4-hydroxy-2,3,6-trimethylphenyl)sulfide bis-(2,4,5-trihydroxyphenyl)sulfide bis-(4-hydroxy-2-cyclohexyl-5-methylphenyl)sulfide bis-(2,3,4-trihydroxyphenyl)sulfide bis-(4,5-dihydroxy-2-tert-butylphenyl)sulfide bis-(4-hydroxy-2,5-diphenylphenyl)sulfide bis-(4-hydroxy-2-tert-octyl-5-methylphenyl)sulfide <4-hydroxyphenylarylsulfone type> 4-hydroxy-4'-isopropoxydiphenylsulfone 4-hydroxy-4'-propoxydiphenylsulfone 4-hydroxy-4'-n-butyloxydiphenylsulfone 4-hydroxy-4'-n-propoxydiphenylsulfone <4-hydroxyphenylarylsulfonate type> 4-hydroxyphenylbenzenesulfonate 4-hydroxyphenyl- p -tolylsulfonate 4-hydroxyphenylmethylenesulfonate 4-hydroxyphenyl- p -chlorobenzenesulfonate 4-hydroxyphenyl- p -tert-butylbenzenesulfonate 4-hydroxyphenyl- p -isopropoxybenzenesulfonate 4-hydroxyphenyl-1'-naphthalenesulfonate 4-hydroxyphenyl-2'-naphthalenesulfonate <1,3-di[2-(hydroxyphenyl)-2-propyl]-benzene type> 1,3-di[2-(4-hydroxyphenyl)-2-propyl]benzene 1,3-di[2-(4-hydroxy-3-alkylphenyl)-2-propyl]benzene 1,3-di[2-(2,4-dihydroxyphenyl)-2-propyl]benzene 1,3-di[2-(2-hydroxy-5-methylphenyl)-2-propyl]benzene <resorcinol type> 1,3-dihydroxy-6(α,α-dimethylbenzyl)-benzene <4-hydroxybenzoiloxybenzoic ester type> 4-hydroxybenzoiloxybenzylbenzoate 4-hydroxybenzoiloxymethylbenzoate 4-hydroxybenzoiloxyethylbenzoate 4-hydroxybenzoiloxypropylbenzoate 4-hydroxybenzoiloxybutylbenzoate 4-hydroxybenzoiloxyisopropylbenzoate 4-hydroxybenzoiloxytert-butylbenzoate 4-hydroxybenzoiloxyhexylbenzoate 4-hydroxybenzoiloxyoctylbenzoate 4-hydroxybenzoiloxynonylbenzoate 4-hydroxybenzoiloxycyclohexylbenzoate 4-hydroxybenzoiloxyβ-phenethylbenzoate 4-hydroxybenzoiloxyphenylbenzoate 4-hydroxybenzoiloxyα-naphthylbenzoate 4-hydroxybenzoiloxyβ-naphthylbenzoate 4-hydroxybenzoiloxysec-butylbenzoate <bisphenolsulfone type (I)> bis-(3-1-butyl-4-hydroxy-6-methylphenyl)sulfone bis-(3-ethyl-4-hydroxyphenyl)sulfone bis-(3-propyl-4-hydroxyphenyl)sulfone bis-(3-methyl-4-hydroxyphenyl)sulfone bis-(2-isopropyl-4-hydroxyphenyl)sulfone bis-(2-ethyl-4-hydroxyphenyl)sulfone bis-(3-chloro-4-hydroxyphenyl)sulfone bis-(2,3-dimethyl-4-hydroxyphenyl)sulfone bis-(2,5-dimethyl-4-hydroxyphenyl)sulfone bis-(3-methoxy-4-hydroxyphenyl)sulfone 4-hydroxyphenyl-2'-ethyl-4'-hydroxyphenylsulfone 4-hydroxyphenyl-2'-isopropyl-4'-hydroxyphenylsulfone 4-hydroxyphenyl-3'-isopropyl-4'-hydroxyphenylsulfone 4-hydroxyphenyl-3'-secbutyl-4'-hydroxyphenylsulfone 3-chloro-4-hydroxyphenyl-3'-isopropyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-aminophenyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-isopropylphenyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-octylphenyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3'-chloro-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3'-methyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3'-isopropyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3'-chloro-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3'-methyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-3'-isopropyl-4'-hydroxyphenylsulfone 2-hydroxy-5-t-butylphenyl-2'-methyl-4'-hydroxyphenylsulfone <bisphenolsulfone type (II)> 4,4'-sulfonyldiphenol 2,4'-sulfonyldiphenol 3,3'-dichloro-4,4'-sulfonyldiphenol 3,3'-dibromo-4,4'-sulfonyldiphenol 3,3',5,5'-tetrabromo-4,4'-sulfonyldiphenol 3,3'-diamino-4,4'-sulfonyldiphenol <others> p -tert-butylphenol 2,4-dihydroxybenzophenone novolak type phenol resin 4-hydroxyacetophenone p -phenylphenol benzyl-4-hydroxyphenylacetate p -benzylphenol In this invention, since a developer having plural phenolic hydroxyl groups has a tendency to produce background colour contamination (colouration of background colour) when it is coated as an aqueous solution or by the influence of a vapour contained in an atmosphere, a mono-phenolic developer is desirably used to obtain better background colour stabilization. Especially, the above mentioned mono-phenolic sulfone developer represented by 4-hydroxyphenylarysulfonate includes a sulfonyl group in its structure. A strong electron accepting portion is formed by the electron attracting effect of this sulfonyl group, indicating strong reactivity with a basic leuco dye and providing an excellent colour developing ability. Further, the obtained thermal recording medium is superior regarding the stability of the background colour. In this invention, conventional known sensitizers can be used as far as they do not adversely effect the necessary effects of the invention as mentioned above. As the specific examples of the sensitizer, the following compounds can be mentioned, however, the invention is not intended to be limited to them. These sensitizers can be used alone or can be used by mixing with others: montanic acid wax polyethylene wax 1,2-di-(3-methylphenoxy)ethane p -benzylbiphenyl β -benzyloxynaphthalene 4-biphenyl- p -tolyleter m -tarphenyl 1,2-diphenoxyethane dibenzyloxalate di( p -chlorobenzyl)oxalate di( p -methylbenzyl)oxalate dibenzylterephthalate p -benzyloxybenzylbenzoate di-p-tolylcarbonate phenyl-α-naphthylcarbonate 1,4-diethoxynaphthalene 1-hydroxy-2-naphthoeic acid phenyl ester o-xylylene-bis-(phenylether) 4-(m-methylphenoxymethyl)biphenyl As the binder to be used in this invention, full saponificated polyvinyl alcohol having 200-1900 polimerization degree, partially saponificated polyvinylalcohol, denatured polyvinylalcohol such as denatured polyvinylalcohol by carboxy, denatured polyvinylalcohol by amide, denatured polyvinylalcohol by sulfonic acid and denatured polyvinylalcohol by butylal, derivatives of cellulose such as hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and acetyl cellulose, copolymer of styrene-maleic anhydride, copolymer of styrene-butadiene, polyvinylchloride, polyvinylacetate, polyacrylamide, polyacrylicester, polyvinylbutylal, polystyrene and copolymers of these polymers, polyamide resin, silicon resin, petroleum resin, terpene resin, ketone resin, cumarone resin can be mentioned. These kinds of macromolecular compounds can be used by dissolving in water or in solvents such as alcohol, ketone, ester of hydrocarbon, and also can be used by dispersion in water or other solvent to an emulsion or paste. These methods can be used in combination, if necessary. In this invention, it is possible to add a metallic salt (Ca, Zn) of a p-nitrobenzoic acid, or a metallic salt (Ca, Zn) of monobenzylphthalate or derivatives of diphenylsulfone which is a known stabilizer which is beneficial regarding the oil resistance of the recording image, within a limit so as not to adversely effect the necessary effects of the invention as mentioned above. As a filler which can be used in this invention, the following inorganic or organic compounds can be mentioned: namely, silica, calcium, carbonate, kaoline, calcined kaoline, diatomaceous earth, talc, titanium oxide, zinc oxide, aluminium hydroxide, polystyrene resin, urea-formaldehyde resin, styrene-methacrylic acid copolymer, styrene-butadiene copolymer, hollow plastic pigment, and the like. Further, compounds such as a metallic salt of a fatty acid, lubricants such as wax, ultra violet ray absorbers such as benzophenone or triazole, waterproof agents such as glyoxal, dispersing agents, deformers, antioxidants and fluorescent dyes can be used. As a substrate, paper, synthetic paper, plastic film, non-woven cloth or metal foil can be used, or a hybrid sheet which is prepared by assembling these materials. And, in order to increase the preservability it is possible to prepare an over coating layer which comprises a macromolecular substance on the recording layer. Further, in order to increase the preservability and sensitivity, it is possible to prepare an undercoat layer between the recording layer and the substrate. EXAMPLES The present invention will be more clearly understood with reference to the following Examples. The thermally sensitive recording medium of this invention can be obtained by following procedure, that is ; prepare the coating colour of the thermally sensitive colour developing layer by dispersing a basic leuco dye, a colour developer, one or more kinds of aminobenzenesulfonamide derivative indicated by above mentioned general formula (I) as a stabilizer and also one or more kinds of methylol fatty acid amide indicated by above mentioned general formula (II) as a stabilizer. These are dispersed with a binder, then a filler and other additives are added as necessary. The coating colour is coated on the substrate and dried, thus the thermally sensitive recording medium can be obtained. The type and the amount of developer, basic leuco dye and other additives are decided according to the required features and to the recording property of the thermally sensitive recording medium, and in general preferable amount of these compounds are as follows, however, are not intended to be limited. That is, 0.1-2 parts of dye and 0.5-4 parts of filler based on 1 part of organic developer. The preferable amount of binder is 5-25% to the total amount of solid. And the compound indicated by general formula (I) is used in a proportion of 0.01-0.9 parts based on 1 part of developer, and the compound indicated by general formula (II) is used in a proportion of 0.01-2 parts based on 1 part of developer. The developer, dye and other additives to be added as necessary are ground to fine particles of micron size by means of a pulverizer such as a ball mill, an attritor or a sand grinder or an adequate emulsifying apparatus, and binder and other additives are added as necessary, thus the coating colour is prepared. As the coating method, a hand coating method, a sizing press coater method, a roll coater method, an air knife coater method, a blend coater method, a flow coater method, a comma direct method, a gravure direct method, a gravure reverse method or a reverse-roll coater method can be mentioned. Or, it is possible to dry after coating by spraying, blowing or immerssion. <preparation of thermally sensitive recording medium> The present invention is further illustrated by following Examples. In the Examples and Comparative examples, the term of "parts" and "%" means "parts by weight" and "Weight %", unless otherwise specified. Example 1 Example 1 is an experimental result which uses 4-hydroxy-4'-isopropoxydiphenylsulfone (D-8) as a developer, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran (S-205) as a basic leuco dye and compound (I-10) and (II-3) as a stabilizer in the thermal sensitive recording medium of the present invention. The dispersion of colour developer (solution A), the dispersion of basic leuco dye (solution B) and the dispersion of sensitizer (solution C) are separately ground to an average diameter of 1µm whilst wet by means of a sand grinder. Solution A (dispersion of colour developer) 4-hydroxy-4'-isopropoxydiphenylsulfone (D-8) 6.0 parts 10% polyvinylalcohol aqueous solution 18.8 parts water 11. 2 parts Solution B (dispersion of dye) 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran (S-205) 2.0 parts 10% polyvinylalcohol aqueous solution 4.6 parts water 2.6 parts Solution C (dispersion of stabilizer) compound (I-10) 4.0 parts 10% polyvinylalcohol aqueous solution 18.8 parts water 11.2 parts Solution D (dispersion of stabilizer) compound (II-3) 4.0 parts 10% polyvinylalcohol aqueous solution 18.8 parts water 11.2 parts Then the resulting dispersions are mixed together in the proportions below so as to prepare the coating colour. Solution A (dispersion of colour developer [D-8]) 36. 0 parts Solution B (dispersion of basic leuco dye [S-205]) 9. 2 parts Solution C (dispersion of stabilizer [compound (I-10)] 34. 0 parts Solution D (dispersion of stabilizer [compound (II-3)] 34. 0 parts Kaoline clay (50% dispersion) 12. 0 parts The prepared coating colours are applied to one side of 50g/m 2 sheet substrate, then dried and the sheet is processed by a super calender to surface smoothness of 500-600 second. Thus, the thermally sensitive recording medium with a coating weight of 6.0g/m 2 is obtained. Example 2 The thermally sensitive recording paper is prepared as in Example 1. In the preparation of solution A, 4,4'-isopropylidenediphenol (bisphenol A, briefly mentioned as BPA in tables) is used instead of 4-hydroxy-4'-isopropoxydiphenylsulfone (D-8). Example 3 The thermally sensitive recording paper is prepared as in Example 1. In this Example, two types of colour developer are used, that is, 4,4'-isopropylidenediphenol (bisphenol A) and 4-hydroxy-4'-isopropoxydiphenylsulfone (D-8) are used. Each dispersion is mixed and stirred as follows, and the coating colour is prepared. Solution A (dispersion of colour developer [bisphenol-A]) 18.0 parts Solution A (dispersion of colour developer [D-8]) 18.0 parts Solution B (dispersion of basic leuco dye [S-205]) 9.2 parts Solution C (dispersion of stabilizer [compound (I-10)] 34.0 parts Solution D (dispersion of stabilizer [compound (II-3)] 34.0 parts Kaoline clay (50% dispersion) 12.0 parts Examples 4-7 The thermally sensitive recording paper is prepared as in Example 1. In the preparation of solution B, 3-dibutylamino-6-methyl-7-anilinofluoran (ODB-2 ; Example 4), 3-diethylamino-6-methyl-7-anilinofluoran (ODB ; Example 5), 3-pyrrolidino-6-methyl-7-anilinofluoran (PSD-170 ; Example 6) and 3, 3-bis (p-dimethylaminophenyl)-6-dimethylaminophthalide (CVL ; Example 7) are used instead of 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran (S-205). Example 8 The thermally sensitive recording paper is prepared as in Example 1. As the dye, 3-(N-ethyl-N-isoamylamino)-6-methyl-7-anilinofluoran (S-205) and 3-dibutylamino-6-methyl-7-anilinofluoran (ODB-2) are used. Each dispersion is mixed and stirred as follows, and the coating colour is prepared. Solution A (dispersion of colour developer [D-8]) 36.0 parts Solution B (dispersion of basic leuco dye [S-205]) 4.6 parts Solution B (dispersion of basic leuco dye [OBD-2]) 4.6 parts Solution C (dispersion of stabilizer [compound (I-10)] 34.0 parts Solution D (dispersion of stabilizer [compound (II-3)] 34.0 parts Kaoline clay (50% dispersion) 12.0 parts Examples 9-12 The thermally sensitive recording paper is prepared as in Example 8. In the preparation of solution C, compounds (I-1), (1-13), (I-19) and (I-26) are used instead of compound (1-10). Example 13 The thermally sensitive recording paper is prepared as in Example 8. In the preparation of solution C, compounds (I-10) and (I-1) are used as the stabilizer. Each dispersion is mixed and stirred as follows, and the coating colour is prepared. Solution A (dispersion of colour developer [D-8]) 36.0 parts Solution B (dispersion of basic leuco dye [S-205]) 9.2 parts Solution C (dispersion of stabilizer [compound (I-1)] 17.0 parts Solution C (dispersion of stabilizer [compound (I-10)] 17.0 parts Solution D (dispersion of stabilizer [compound (II-3)] 34.0 parts Kaoline clay (50% dispersion) 12.0 parts Example 14 The thermally sensitive recording paper is prepared as in Example 8. In the preparation of solution D, compound (II-4) is used instead of (II-3). Example 15 The thermally sensitive recording paper is prepared as in Example 8. In the preparation of solution D, compounds (II-3) and (III-3) are used as the stabilizer. Each dispersion is mixed and stirred as follows, and the coating colour is prepared. Solution A (dispersion of colour developer [D-8]) 36.0 parts Solution B (dispersion of basic leuco dye [S-205]) 9.2 parts Solution C (dispersion of stabilizer [compound (I-10)] 34.0 parts Solution D (dispersion of stabilizer [compound (II-3)] 17.0 parts Solution D (dispersion of stabilizer [compound (II-4)] 17.0 parts Kaoline clay (50% dispersion) 12.0 parts Comparative Example 1 The thermally sensitive recording paper is prepared as in Example 1. However, in the preparation of the colour developing layer, solution C and D are not added. Comparative Example 2 The thermally sensitive recording paper is prepared as in Example 8. However, in the preparation of the colour developing layer, solution C and D are not added. Comparative Example 3 The thermally sensitive recording paper is prepared as in Example 8. However, in the preparation of the colour developing layer, solution D is not added. Comparative Example 4 The thermally sensitive recording paper is prepared as in Example 8. However, in the preparation of the colour developing layer, solution C is not added. Comparative Example 5 The thermally sensitive recording paper is prepared as in Example 15. However, in the preparation of the colour developing layer, solution C is not added. Comparative Example 6 The thermally sensitive recording paper is prepared as in Example 8. In the preparation of the colour developing layer, solution C is prepared as follows. compound (I-10) 0.030 parts 10% polyvinylalcohol aqueous solution 0.141 parts water 0.084 parts Then, each dispersion is mixed and stirred as follows, and the coating colour is prepared. Solution A (dispersion of colour developer [D-8]) 36.0 parts Solution B (dispersion of basic leuco dye [S-205]) 4.6 parts Solution B (dispersion of basic leuco dye [ODB-2]) 4.6 parts Solution C' (dispersion of stabilizer [compound (I-10)]) 0.255 parts Solution D (dispersion of stabilizer [compound (II-3)]) 34.0 parts Kaoline clay (50% dispersion) 12.0 parts Comparative Example 7 The thermally sensitive recording paper is prepared as in Example 8. In the preparation of the colour developing layer, solution D is prepared as follows. Solution D' (dispersion of stabilizer) compound (II-3) 0.030 parts 10% polyvinylalcohol aqueous solution 0.141 parts water 0.084 parts Then, each dispersion is mixed and stirred as follows, and the coating colour is prepared. Solution A (dispersion of colour developer [D-8]) 36.0 parts Solution B (dispersion of basic leuco dye [S-205]) 4.6 parts Solution B (dispersion of basic leuco dye [ODB-2]) 4.6 parts Solution C (dispersion of stabilizer [compound (I-10)]) 34.0 parts Solution D' (dispersion of stabilizer [compound (II-3)]) 0.255 parts Kaoline clay (50% dispersion) 12.0 parts Comparative Example 8 The thermally sensitive recording paper is prepared as in Example 8. In the preparation of the colour developing layer, solution C is prepared as follows. Solution C" (dispersion of stabilizer) compound (I-10) 9.0 parts 10% polyvinylalcohol aqueous solution 42.3 parts water 25.2 parts Then, each dispersion is mixed and stirred as follows, and the coating colour is prepared. Solution A (dispersion of colour developer [D-8]) 36.0 parts Solution B (dispersion of basic leuco dye [S-205]) 4.6 parts Solution B (dispersion of basic leuco dye [ODB-2]) 4.6 parts Solution C" (dispersion of stabilizer [compound (I-10)]) 76.5 parts Solution D (dispersion of stabilizer [compound (II-3)]) 34.0 parts Kaoline clay (50% dispersion) 12.0 parts Comparative Example 9 The thermally sensitive recording paper is prepared as in Example 8. In the preparation of the colour developing layer, solution D is prepared as follows. compound (II-3) 18.0 parts 10% polyvinylalcohol aqueous solution 84.6 parts water 50.4 parts Then, each dispersion is mixed and stirred as follows, and the coating colour is prepared. Solution A (dispersion of colour developer [D-8]) 36.0 parts Solution B (dispersion of basic leuco dye [S-205]) 4.6 parts Solution B (dispersion of basic leuco dye [ODB-2]) 4.6 parts Solution C (dispersion of stabilizer [compound (I-10)]) 34.0 parts Solution D" (dispersion of stabilizer [compound (II-3)]) 153.0 parts Kaoline clay (50% dispersion) 12.0 parts <Evaluation of thermally sensitive recording medium> Printing tests of thermally sensitive recording media prepared in the above mentioned Examples and Comparative Examples are carried out using TH-PMD (thermally sensitive recording paper testing apparatus, to which a thermal head [Kyosera Ltd.] is installed) made by Ohkura Denki Ltd., by 0.41mj/dot impressive energy. The Image density of the recorded portion of each specimen is measured by a Macbeth densitometer (RD-914 an amber filter is used), and the obtained results are regarded as the image density of untreated specimen. Wrapping film of polyvinylchloride (high wrap KMA ; product of Mitsui Toatsu Ltd.) is wound around a paper tube to form a single layer, a recording sheet of the thermally sensitive recording medium is stuck on it, then the wrapping film of polyvinylchloride is wound over the sheet to form a triple layer. This specimen is left for 4 hours in the chamber at 40°C, and then the Macbeth density of the image portion is measured. Similarly, the density of background colour is measured (refer to table 1 and table 2). As is clearly understood from the test results shown in tablel and 2, the specimens of thermally sensitive recording medium prepared by Examples 1-15 of this invention which use the compound indicated by general formula (I) and the compound indicated by general formula (II) have remarkably superior image stability to a plasticizer compared with those prepared by Comparative Examples 1 and 2 which use neither (I) nor (II), or with these prepared by Comparative Examples 3-5 which use only (I) or (II). Therefore, although the compounds indicated by general formula (I) and (II) do not act as a stabilizer when they are used alone, when they are used together they provide an excellent stabilizing effect. Comparative Example 6 includes 0.005 parts of a compound indicated by general formula (I) and Comparative Example 8 includes 1.5 parts of a compound indicated by general formula (I) based on 1 part of developer. On the other hand, Comparative Example 7 includes 0.005 parts of a compound indicated by general formula (II) and Comparative Example 9 includes 3 parts of a compound indicated by general formula (II) based on 1 part of developer. Every specimen prepared by the above mentioned Comparative Examples has a poor plasticizer resistance, further, when the proportion of one compound is too high (Comparative Example 8 and 9), the recording density is low too. Accordingly, even if compounds of general formula (I) and (II) are included together, the desired stabilization can not be obtained unless the proportion of them satisfy the following condition. That is ; 0.01-0.9 parts of a compound of general formula (I) of this invention based on 1 part of developer, and 0.01-2 parts of a compound of general formula (II) based on 1 part of developer. Further, from Example 1 and Example 2, it is indicated that the use of "D-8" as the developer is superior to the use of "BPA" as regards the colouring of the background colour. Similarly, a product having better plasticizer resistance can be obtained by using "D-8". In the case of the use of a single basic leuco dye, the difference in plasticizer resistance is caused by the difference in the basic leuco dye used: Example 6 which uses "PSD-170" shows the best result, however, it has a problem regarding background colour. On the contrary, Example 8 which uses "S-205" together with ODB-2" shows a good result for both plasticizer resistance and background colour. The thermally sensitive recording medium of this invention not only has sufficient colour developing sensitivity but also has excellent image stability, especially against a plasticizer. Therefore, since the recorded image does not fade on contact with a plasticizer included in a wrapping film or in leatherwork, the thermally sensitive recording medium can be broadly applied for practical use. Additionally, since the thermally sensitive recording medium of this invention includes a compound indicated by general formula (I) and (II), it is possible to provide plasticizer resistance without a protective layer. Therefore, it is an excellent product from an economic view point.

Claims: A thermally sensitive recording medium which comprises, on a substrate, a thermally sensitive colour developing layer which comprises a colourless or pale coloured basic leuco dye and an organic colour developer, wherein the thermal colour developing layer includes (a) 0.01-0.9 parts by weight, based on 1 part by weight of colour developer, of one or more aminobenzenesulfonamide derivatives of formula (I) wherein X is oxygen or sulphur, R is a group selected from phenyl, naphthyl, aralkyl, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl and C 2 -C 6 alkenyl, which group is unsubstituted or substituted, Z is C 1 -C 6 alkyl or an electron attracting group, n is 0 or an integer from 1 to 4 and p is an integer from 1 to 5, provided that n+p≤5; and (b) 0.01-2 parts by weight, based on 1 part by weight of colour developer, of at least one methylolated fatty acid amide of formula (II) R 1 -CONHCH 2 OH wherein R 1 is C 11 -C 21 alkyl. A medium according to claim 1 wherein, in formula (I), R is a group as defined in claim 1 which is substituted by one or more substituents which are the same or different and are selected from C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, nitro, cyano and halogen. A medium according to claim 1 or 2 wherein, in formula (I), R is a group as defined in claim 1 which is substituted by one or more substituents which are the same or different and are selected from methyl, ethyl, isopropenyl, methoxy, Cl, Br and F. A medium according to any one of the preceding claims wherein, in formula (I), R is a phenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, propenyl, isopropenyl, cyclohexyl or naphthyl group. A medium according to any one of the preceding claims wherein, in formula (I), R is substituted by one, two or three substituents. A medium according to any one of the preceding claims wherein, in formula (2), R 1 is C 11 , C 16 , C 17 or C 21 alkyl. A medium according to any one of the preceding claims which further includes, on the recording layer, an overcoating layer which comprises a macromolecular substance. A medium according to any one of the preceding claims which further includes, between the recording layer and the substrate, an undercoating layer. A medium according to any one of the preceding claims which comprises the leuco dye in an amount of 0.1 to 2 parts by weight based on 1 part by weight of organic colour developer, and which further includes 0.5 to 4 parts by weight of filler based on 1 part by weight of organic colour developer. A medium according to any one of the preceding claims which further comprises a binder in an amount of 5-25% by weight based on the total amount of solid.

Inventors: FUKUCHI TADAKAZU, HAMADA KAORU, KUDOH NOBUHIRO, NAGAI TOMOAKI, SEKINE AKIO, FUKUCHI, TADAKAZU, HAMADA, KAORU, KUDOH, NOBUHIRO, NAGAI, TOMOAKI, SEKINE, AKIO, Fukuchi, Tadakazu, c/o Res. Lab. of Product Dev., Hamada, Kaoru, c/o Res. Lab. of Product Dev., Kudoh, Nobuhiro, c/o Res. Lab. of Product Dev., Nagai, Tomoaki, c/o Res. Lab. of Product Dev., Sekine, Akio, Central Research Laboratory
Applicants: JUJO PAPER CO LTD, NIPPON PAPER INDUSTRIES CO., LTD.
Application year: 1996
Main classification: B41M5
IPC codes: B41M5