Heat-sensitive recording materials and phenol compounds

Abstract

Heat-sensitive recording materials contain an electron-donating chromogenic compound and an electron-attracting compound. The recording materials also contain at least one compound represented by the following formula: ##STR1## wherein R.sub.1 and R.sub.3 mean a hydrogen atom or an alkyl, aralkyl or aryl group, R.sub.2 and R.sub.4 denote an alkyl, alkenyl, aralkyl or aryl group, X.sub.1, X.sub.2, Y.sub.1 and Y.sub.2 stand for an oxygen or a sulfur atom, and --Z.sub.1 -- and --Z.sub.2 -- are a specific aromatic group. Also provided are phenol compounds represented by the following formula: ##STR2## wherein R.sub.1, R.sub.2, X.sub.1 and Y.sub.1 have the same meanings as defined above; R.sub.5 and R.sub.6 are a hydrogen or halogen atom or an alkyl, alkoxy, aralkyl, aryl or hydroxyl group; p and q stand for an integer of 1-4; R.sub.5 and R.sub.6 may be either the same or different when p and q represent an integer of 2 or greater; and --Z.sub.3 -- means a specific divalent group.

Description

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION

This invention relates to heat-sensitive recording materials, and especially to heat-sensitive recording materials capable of producing color images with improved storage stability. This invention is also concerned with novel phenol compounds, and in particular with novel phenol compounds useful as color-developing agents or additives for recording materials (for example, heat-sensitive recording materials) or as monomers or additives for high molecular materials.

Heat-sensitive recording materials making use of the color-producing reaction between an electron-donating chromogenic compound and an electron-attracting compound (color-developing agent) have been well known conventionally (for example, Japanese Patent Publication Nos. 4160/1968 and 14039/1970). These heat-sensitive recording materials are relatively inexpensive and, moreover, have the merit that recording equipment therefor are compact and maintenance-free. They have hence found utility in a wide variety of fields such as facsimiles, recorders and printers.

As electron-attracting compounds, phenol compounds are widely used. Among these, 2,2-bis(4'-hydroxyphenyl)propane (also called "bisphenol A") is extensively used for its availability at low cost. Bisphenol A is, however, accompanied by the drawback that heat-recording materials using bisphenol A as an electron-attracting compound cannot produce color images with good storage stability. In addition, heat-sensitive recording materials with bisphenol A as an electron-attracting compound also involve the drawback that their color-producing sensitivity is low. Heat-sensitive recording materials using, as an electron-attracting compound, a phenol compound other than bisphenol A have also been proposed, for example, 4-hydroxybenzoate esters (Japanese Patent Laid-Open No. 144193/1981 and Japanese Patent Publication No. 30640/1989), aralkyloxyphenols (Japanese Patent Publication No. 31678/1990 and Japanese Patent Laid-Open No. 225789/1985) and hydroxybenzophenones (Japanese Patent Laid-Open No. 193388/1982).

The use of 4-hydroxybenzoate esters, for example, benzyl 4-hydroxybenzoate as an electron-attracting compound, however, leads to the drawback that the density of a produced color image drops with time. It is also accompanied by the drawback that white crystals of benzyl 4-hydroxybenzoate are formed on the produced color image thereby to present a powdered appearance (the so-called "whitening phenomenon"). The use of aralkyloxyphenols, for example, 4-benzyloxyphenol as an electron-attracting compound also results in the drawback that the density of a produced color image drops as time goes on. When hydroxybenzophenones, for example, 4-hydroxybenzophenone is used as an electron-attracting compound, the resulting color image has poor storage stability (for example, hydrothermoresistance and waterproofness) so that they are not considered to have sufficient quality or properties for practical use.

On the other hand, heat-sensitive recording materials containing--as a method for improving the color-producing sensitivity--a thermofusible compound (sensitizer) in addition to an electron-donating chromogenic compound and an electron-attracting compound are also widely used. Proposed as thermofusible compounds include terphenyls (Japanese Patent Publication No. 7958/1988), benzyl 4-benzyloxybenzoate (Japanese Patent Publication No. 30878/1988), naphthol derivatives (Japanese patent Publication No. 42590/1988), aminophenol derivatives (Japanese Patent Laid-Open No. 211494/1983), benzylbiphenyls (Japanese Patent Publication No. 11437/1990), diaryloxyalkane derivatives (Japanese Patent Laid-Open Nos. 56588/1985 and 16888/1986), oxalate ester derivatives (Japanese Patent Laid-Open No. 1583/1989), etc. However, it is the current situation that, although heat-sensitive recording materials containing one or more of these thermofusible compounds have been improved to some extent in color-producing sensitivity, they are accompanied by the problem of the extremely poor storage stability of produced color images, said storage stability being usually still inferior to that of color images produced without the addition of any thermofusible compound.

Accordingly, there is now a strong demand for the provision of heat-sensitive recording materials free of the drawbacks or problems described above, namely, for the provision of heat-sensitive recording materials capable of producing color images with excellent storage stability and, further, heat-sensitive recording materials having good color-producing sensitivity and capable of producing color images with excellent storage stability.

SUMMARY OF THE INVENTION

An object of this invention is, therefore, to provide a heat-sensitive recording material significantly improved in the storage stability of resulting color images. Another object of this invention is to provide a heat-sensitive recording material which is good in color-producing sensitivity and is excellent in the storage stability of resulting color images. A further object of this invention is to-provide a novel phenol compound useful as a color-developing agent or an additive for heat-sensitive recording materials.

With a view toward meeting the demand described above, the present inventors have conducted extensive research on heat-sensitive recording materials and also on electron-attracting compounds and additives for heat-sensitive recording materials.

In one aspect of this invention, there is thus provided a heat-sensitive recording material containing an electron-donating chromogenic compound and an electron-attracting compound, comprising at least one of the compounds represented by the following formula ##STR3## wherein R.sub.1 and R.sub.3 individually mean a hydrogen atom or an alkyl, aralkyl or aryl group, R.sub.2 and R.sub.4 individually denote an alkyl, alkenyl, aralkyl or aryl group, X.sub.1, X.sub.2, Y.sub.1 and Y.sub.2 stand for an oxygen or a sulfur atom, and --Z.sub.1 -- and --Z.sub.2 are a group represented by the following formulae (i) or (ii): ##STR4## wherein R.sub.5, R.sub.6 and R.sub.7 individually mean a hydrogen or halogen atom or an alkyl, alkoxy, aralkyl, aryl or hydroxyl group, p, q and r stand for an integer of 1-4, R.sub.5, R.sub.6 and R.sub.7 may be either the same or different when p, q and r individually represent an integer of 2 or greater, the rings A and A' individually denote a benzene or naphthalene ring, the ring D represents a naphthalene ring, and --B--0 represents a group containing at least one group selected from the class consisting of --R.sub.8 CR.sub.9 -- (in which R.sub.8 and R.sub.9 individually represent a hydrogen atom or an alkyl, trifluoromethyl or aryl group or are combined together to form a ring), --O--, --S--, a phenylene group, --CO--, a single bond, --C.sub.m H.sub.2m --, m being an integer of 2-10, --CR.sub.10 .dbd.CR.sub.11 -- (in which R.sub.10 and R.sub.11 are individually a hydrogen atom or an alkyl or aryl group), --SO--, and --SO.sub.2 --.

In another aspect of this invention, there is also provided a phenol compound represented by the following formula (3): ##STR5## wherein R.sub.1 means a hydrogen atom or an alkyl, aralkyl or aryl group, R.sub.2 denotes an alkyl, alkenyl, aralkyl or aryl group, R.sub.5 and R.sub.6 are a hydrogen or halogen atom or an alkyl, alkoxy, aralkyl, aryl or hydroxyl group, p and q stand for an integer of 1-4, R.sub.5 and R.sub.6 may be either the same or different when p and q individually represent an integer of 2 or greater, X.sub.1 and Y.sub.1 individually represent an oxygen or sulfur atom, and --Z.sub.3 -- means a group containing at least one group selected from the class consisting of --R.sub.8 CR.sub.9 -- (in which R.sub.8 and R.sub.9 individually represent a hydrogen atom or an alkyl, trifluoromethyl or aryl group or are combined together to form a ring), --O--, --S--, a phenylene group, --CO--, --C.sub.m H.sub.2m --, m being an integer of 2-10, --CR.sub.10 .dbd.CR.sub.11 -- (in which R.sub.10 and R.sub.11 are individually a hydrogen atom or an alkyl or aryl group), --SO-- and --SO.sub.2 --.

The heat-sensitive recording material according to the present invention can promptly produce a color at low temperatures so that it is suitable for use in high-speed recording. Moreover, the color image so produced has excellent storage stability (heat resistance, hydrothermoresistance, waterproofness and oil resistance).

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

Where the ring A and/or the ring A' in the group represented by the formula (i) in the compound according to the present invention, said compound being represented by the formula (1) or (2), is a benzene ring, the position of substitution by each phenolic hydroxyl group and/or carbamate group substituted on the benzene ring may be preferably the ortho-, meta- or para-position, more preferably the meta- or para-position, both relative to the --B-- group in the formula (i). Where the ring A and/or ring A' is a naphthalene ring, the position of substitution by each phenolic hydroxyl group and/or carbamate group substituted on the naphthalene ring may be preferably the 2-, 3-, 4-, 5-, 6-, 7- or 8-position when the --B-- group is substituted to the 1-position (.alpha.-position) of the naphthalene ring. When the --B-- group is substituted to the 2-position (.beta.-position) of the naphthalene ring, on the other hand, the position of substitution by each phenolic hydroxyl group and/or carbamate group substituted on the naphthalene ring may be preferably the 1-, 3-, 4-, 5-, 6-, 7- or 8-position.

In the naphthalene ring in the group represented by the formula (ii), the positions of substitution by phenolic hydroxyl and/or carbamate groups may be on the same benzene ring or the different benzene rings in the naphthalene ring.

In the compound represented by the formula (1) or (2), R.sub.1 and R.sub.3 are a hydrogen atom or an alkyl, aralkyl or aryl group; preferably a hydrogen atom or a C.sub.1-20 alkyl, C.sub.5-14 cycloalkyl, C.sub.7-20 aralkyl or substituted or unsubstituted phenyl group; more preferably a hydrogen atom or a C.sub.1-4 alkyl, cyclopentyl, cyclohexyl, cycloheptyl, benzyl or phenyl group; still more preferably a hydrogen atom or a C.sub.1-4 alkyl group; most preferably a hydrogen atom.

In the compound represented by the formula (1) or (2), R.sub.2 and R.sub.4 are an alkyl, alkenyl, aralkyl or aryl group; preferably a substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted aralkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted heteroaromatic group.

The alkyl and alkenyl groups represented by R.sub.2 or R.sub.4 may contain one or more substituents, for example, may be monosubstituted or multisubstituted by substituent(s) such as C.sub.1-20 alkoxy, C.sub.2-20 alkoxyalkyloxy, C.sub.2-20 alkenyloxy, C.sub.7-20 aralkyloxy, C.sub.8-20 aralkyloxyalkoxy, C.sub.6-20 aryloxy, C.sub.7-20 aryloxyalkoxy and/or hetero-atom-containing cycloalkyl group(s) and/or halogen atom(s).

Further, the aryl groups contained in these substituents may be substituted further by one or more C.sub.1-6 alkyl, C.sub.1-6 alkoxy, C.sub.7-10 aralkyl, C.sub.7-10 aralkyloxy and/or hydroxyl groups and/or one or more halogen atoms.

The aryl group in the aralkyl or aryl group represented by R.sub.2 or R.sub.4 may contain one or more substituents, for example, one or more C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.7-16 aralkyl, C.sub.6-16 aryl, C.sub.1-20 alkoxy, C.sub.2-20 alkoxyalkyl, C.sub.2-20 alkoxyalkyloxy, C.sub.2-20 alkenyloxy, C.sub.3-20 alkenyloxyalkyl, C.sub.3-20 alkenyloxyalkyloxy, C.sub.7-20 aralkyloxy, C.sub.8-20 aralkyloxyalkyl, C.sub.8-20 aralkyloxyalkyloxy, C.sub.6-20 aryloxy, C.sub.7-20 aryloxyalkyl, C.sub.7-20 aryloxyalkyloxy, C.sub.2-20 alkylcarbonyl, C.sub.3-20 alkenylcarbonyl, C.sub.8-20 aralkylcarbonyl, C.sub.7-20 arylcarbonyl, C.sub.2-20 alkoxycarbonyl, C.sub.3-20 alkenyloxycarbonyl, C.sub.8-20 aralkyloxycarbonyl, C.sub.7-20 aryloxycarbonyl, C.sub.2-20 alkylcarbonyloxy, C.sub.3-20 alkenylcarbonyloxy, C.sub.8-20 aralkylcarbonyloxy, C.sub.7-20 arylcarbonyloxy, C.sub.14-20 aralkyloxyaralkyl, C.sub.1-20 alkylthio, C.sub.7-20 aralkylthio, C.sub.6-20 arylthio, nitro, formyl, hydroxyl and/or cyano groups and/or one or more halogen atoms.

The aryl groups contained in these substituents may be substituted further by one or more C.sub.1-6 alkyl, C.sub.1-6 alkoxy, C.sub.7-10 aralkyl, C.sub.7-10 aralkyloxy and/or hydroxyl groups and/or one or more halogen atoms.

Specific examples of R.sub.2 and R.sub.4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclohexylmethyl, 2-cyclohexylethyl, bornyl, isobornyl, 2-norbornanemethyl, 1-adamantylmethyl, vinyl, allyl, 3-butenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 2-heptenyl, 6-nonenyl, 1-cyclohexenyl, cinnamyl, 2-methoxyethyl, 2-ethoxyethyl, 2-isopropoxyethyl, 2-n-butoxyethyl, 2-n-hexyloxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n-propoxypropyl, 3-n-butoxypropyl, 3-n-hexyloxypropyl, 3-cyclohexyloxypropyl, 2-methoxyethoxyethyl, 2-ethoxyethoxyethyl, 2-allyloxyethyl, 2-benzyloxyethyl, 2-phenethyloxyethyl, 2-(4'-methylbenzyloxy)ethyl, 2-(4'-chlorobenzyloxy)ethyl, 2-benzyloxymethoxyethyl, 2-phenoxyethyl, 2-(4'-chlorophenoxy)ethyl, 2-(4'-methylphenoxy)ethyl, 2-(4'-methoxyphenoxy)ethyl, 2-phenoxyethoxyethyl, 2-tetrahydrofurfuryl, 2-chloroethyl, 3-chloropropyl, 2,2,2-trichloroethyl, benzyl, .alpha.-methylbenzyl, .alpha.-ethylbenzyl, phenethyl, .alpha.-methylphenethyl, .alpha.,.alpha.-dimethylphenethyl, 4-(4'-methylphenethyl), 4-methylbenzyl, 3-methylbenzyl, 2-methylbenzyl, 4-isopropylbenzyl, 4-allylbenzyl, 4-benzylbenzyl, 4-phenethylbenzyl, 4-phenylbenzyl, 4-(4'-methylphenyl)benzyl, 4-methoxybenzyl, 4-n-butoxybenzyl, 3,4-dimethoxybenzyl, 4-methoxymethylbenzyl, 4-allyloxybenzyl, 4-vinyloxymethylbenzyl, 4-benzyloxybenzyl, 4-phenethyloxybenzyl, 4-phenoxybenzyl, 3-hydroxybenzyl, 2-hydroxybenzyl, 4-hydroxy-3-methoxybenzyl, 4-chlorobenzyl, 3-chlorobenzyl, 2-chlorobenzyl, 2-furfuryl, diphenylmethyl, phenyl, 1-naphthyl, 2-naphthyl, 3-furyl, 3-thienyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 4-isopropylphenyl, 4-n-butylphenyl, 4-sec-butylphenyl, 4-tert-butylphenyl, 4-n-pentylphenyl, 4-isopentylphenyl, 4-n-hexylphenyl, 4-n-octylphenyl, 4-tert-octylphenyl, 4-n-decylphenyl, 4-n-dodecylphenyl, 4-cyclopentylphenyl, 4-cyclohexylphenyl, 2-cyclohexylphenyl, 4-allylphenyl, 4-benzylphenyl, 2-benzylphenyl, 4-cumylphenyl, 4-(4'-methoxycumyl)phenyl, 4-(4'-chlorobenzyl)phenyl, 4-phenylphenyl, 3-phenylphenyl, 2-phenylphenyl, 4-( 4'-methoxyphenyl)phenyl, 2-(2'-methoxyphenyl )phenyl, 4-(4'-chlorophenyl)phenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 2-ethoxyphenyl, 4-isopropoxyphenyl, 4-n-butoxyphenyl, 4-n-hexyloxyphenyl, 4-n-octyloxyphenyl, 4-n-dodecyloxypehenyl, 4-cyclohexyloxyphenyl, 1-(2-methylnaphthyl), 1-(4-methoxynaphthyl), 1- (4-n-butoxynaphthyl), 1-(5-ethoxynaphthyl), 2-(6-ethoxynaphthyl), 2-(6-n-hexyloxynaphthyl), 2-(7-methoxynaphthyl), 2-(7-n-butoxynaphthyl), 4-methoxymethylphenyl, 4-ethoxymethylphenyl, 4-n-butoxymethylphenyl, 3-methoxymethylphenyl, 4-(2'-methoxyethyl)phenyl, 4-(2'-ethoxyethyloxy)phenyl, 4-(2'-n-butoxyethyloxy)phenyl, 4-vinyloxyphenyl, 4-allyloxyphenyl, 4-(5'-pentenyloxy)phenyl, 1-(4-allyloxynaphthyl), 4-allyloxymethylph 4-(2'-allyloxyethyloxy)phenyl, 4-benzyloxyphenyl, 2-benzyloxyphenyl, 4-phenethyloxyphenyl, 4-(4'-chlorobenzyloxy)phenyl, 4-(4'-methylbenzyloxy)phenyl, 4-(4'-methoxybenzyloxy)phenyl, 1-(4-benzyloxy)naphthyl, 2-(6-benzyloxynaphthyl), 2-(7-benzyloxynaphthyl), 4-(benzyloxymethyl)phenyl, 4-(2'-benzyloxyethyloxy)phenyl, 4-phenoxyphenyl, 3-phenoxyphenyl, 4-(4'-methylphenoxy)phenyl, 4-(4'-methoxyphenoxy)phenyl, 4-(4-chlorophenoxy)phenyl, 1-(4-phenoxynaphthyl), 4-phenoxymethylphenyl, 4-(2'-phenoxyethyloxy)phenyl, 4-[2'-(4'-methylphenyl)oxyethyloxy]phenyl, 4-[2'-4'-methoxyphenyl)oxyethyloxy]phenyl, 4-[2'-(4'-chlorophenyl)oxyethyloxy]phenyl, 4-acetylphenyl, 2-acetylphenyl, 4-ethylcarbonylphenyl, 4-n-butylcarbonylphenyl, 4-n-hexylcarbonylphenyl, 4-n-octylcarbonylphenyl, 4-cyclohexylcarbonylphenyl, 1-(4-acetylnaphthyl), 4-allylcarbonylphenyl, 4-benzylcarbonylphenyl, 4-(4'-methylbenzyl)carbonylphenyl, 4-phenylcarbonylphenyl, 4-(4'-methylphenyl)carbonylphenyl, 4-(4'-chlorophenyl)carbonylphenyl, 1-(4-phenylcarbonylnaphthyl), 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 4-n-propoxycarbonylphenyl, 4-n-butoxycarbonylphenyl, 4 -n-hexyloxycarbonylphenyl, 4-n-decyloxycarbonylphenyl, 4-cyclohexyloxycarbonyphenyl, 1-(4-ethoxycarbonynaphthyl), 2-(6-methoxycarbonylnaphthyl), 2-(6-n-butoxycarbonylnaphthyl), 4-allyloxycarbonylphenyl, 4-benzyloxycarbonylphenyl, 4-phenethyloxycarbonylphenyl, 2-(6-benzyloxycarbonylnaphthyl), 4-phenyloxycarbonylphenyl, 4-(4'-ethylphenyl)oxycarbonylphenyl, 4-(4'-chlorophenyl)oxycarbonylphenyl, 2-(6-phenyloxycarbonylnaphthyl), 4-acetyloxyphenyl, 4-ethylcarbonyloxyphenyl, 4-n-propylcarbonyloxyphenyl, 4-n-pentylcarbonyloxyphenyl, 4-n-octylcarbonyloxyphenyl, 4-cyclohexylcarbonyloxyphenyl, 1-(4-acetyloxynaphthyl), 1-(5-acetyloxynaphthyl), 2-(6-ethylcarbonyloxynaphthyl), 4-allylcarbonyloxyphenyl, 4-benzylcarbonyloxyphenyl, 4-phenethylcarbonyloxyphenyl, 2-(6-benzylcarbonyloxynaphthyl), 4-phenylcarbonyloxyphenyl, 4-(4'-methylphenyl)carbonyloxyphenyl, 4-(2'-methylphenyl)carbonyloxyphenyl, 4-(4'-chlorophenyl)carbonyloxyphenyl, 4-(2'-chlorophenyl)carbonyloxyphenyl, 1-(4-phenylcarbonyloxynaphthyl), 2-(6-phenylcarbonyloxynaphthyl), 4-(4'-benzyloxy)cumylphenyl, 4-methylthiophenyl, 4-ethylthiophenyl, 4-n-butylthiophenyl, 4-n-hexylthiophenyl, 4-cyclohexylthiophenyl, 4-benzylthiophenyl, 4-(4'-chlorobenzylthio)phenyl, 4-phenylthiophenyl, 4-(4'-methylphenylthio)phenyl, 4-(4'-methoxyphenylthio)phenyl, 4-(4'-chlorophenylthio)phenyl, 1-(4-methylthionaphthyl), 2-(6-ethylthionaphthyl), 2-(6-phenylthionaphthyl), 4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl 2,-chlorophenyl, 4-bromophenyl, 1-(4-chloronaphthyl), 2-(4-chloronaphthyl), 2-(6-bromonaphthyl), 4-nitrophenyl, 3-nitrophenyl, 4-formylphenyl, 3-formylphenyl, 2-formylphenyl, 4-hydroxyphenyl, 3-hydroxyphenyl 2-hydroxyphenyl, 4-cyanophenyl, 2-cyanophenyl, 2-chloro-4-nitrophenyl, 4-chloro-2-nitrophenyl, 6-chloro-3-methylphenyl, 2-chloro-6-methylphenyl, 4-chloro-2-methylphenyl, 4-chloro-3-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,6-dimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,4,6-trichlorophenyl, 2-methoxy-4-methylphenyl, 2,6-dimethoxyphenyl, 3,5-dimethoxyphenyl, 3,5-diethoxyphenyl, 3,5-di-n-butoxyphenyl, 3,4,5-trimethoxyphenyl, and 1-(2,4-dichloronaphthyl). X.sub.1, X.sub.2, Y.sub.1 and Y.sub.2 individually represent an oxygen atom or a sulfur atom.

In the formulae (i) and (ii), the ring A and ring A' individually represent a benzene ring or naphthalene ring while the ring D indicates a naphthalene ring. More preferably, the ring A and ring A' are each a benzene ring.

In the formulae (i) and (ii), p, q and r individually represent an integer of 1-4. When p, q and r individually represent an integer of 2 or greater, R.sub.5, R.sub.6 and R.sub.7 may be either the same or different. Namely, when p (q or r) is 2, for example, two R.sub.5 s (R.sub.6 s or R.sub.7 s) may be the same alkyl group or different alkyl groups, or may be an alkyl group and a halogen atom, respectively.

In the formulae (i) and (ii), R.sub.5, R.sub.6 and R.sub.7 individually represent a hydrogen or halogen atom or an alkyl, alkoxy, aralkyl, aryl or hydroxyl group; preferably a hydrogen, fluorine, chlorine or bromine atom or a C.sub.1-20 alkyl, C.sub.5-14 cycloalkyl, C.sub.1-20 alkoxy, C.sub.7-20 aralkyl, phenyl or hydroxyl group; more preferably a hydrogen, fluorine or chlorine atom or a C.sub.1-4 alkyl, cyclohexyl, C.sub.1-4 alkoxy, benzyl, phenyl or hydroxyl group, with a hydrogen atom being particularly preferred.

In the formula (i), --B-- represents a group containing at least one group selected from the class consisting of --R.sub.8 CR.sub.9 -- (in which R.sub.8 and R.sub.9 individually represent a hydrogen atom or an alkyl, trifluoromethyl or aryl group or are combined together to form a ring), --O--, --S--, a phenylene group, --CO--, a single bond, C.sub.m H.sub.2m --, m standing for an integer of 2-10, --CR.sub.10 .dbd.CR.sub.11 -- (in which R.sub.10 and R.sub.11 are individually a hydrogen atom or an alkyl or aryl group), --SO--, and --SO.sub.2 --.

R.sub.8 and R.sub.9 individually represent a hydrogen atom or an alkyl, trifluoromethyl or aryl group or are combined together to form a ring, preferably a hydrogen atom, a C.sub.1-20 alkyl, trifluoromethyl or phenyl group or a C.sub.5-14 cycloalkane ring formed of R.sub.8 and R.sub.9 ; more preferably a hydrogen atom, a C.sub.1-4 alkyl, trifluoromethyl or phenyl group, or a cyclopentane, cyclohexane, cycloheptane or cyclooctane ring formed of R.sub.8 and R.sub.9.

m stands for an integer of 2-10, with an integer of 2-6 being more preferred.

R.sub.10 and R.sub.11 individually represent a hydrogen atom or an alkyl or aryl group, preferably a hydrogen atom or a C.sub.1-20 alkyl or phenyl group, more preferably a hydrogen atom or a C.sub.1-4 alkyl group.

In particular, --B-- is preferably a group containing at least one group selected from the class consisting of --R.sub.8 CR.sub.9 -- (in which R.sub.8 and R.sub.9 individually represent a hydrogen atom or an alkyl, trifluoromethyl or aryl group or are combined together to form a ring), --O--, --S--, a phenylene group, --CO--, and a single bond. Of these, --R.sub.8 CR.sub.9 (in which R.sub.8 and R.sub.9 individually represent a C.sub.1-4 alkyl group) , --O--, --S--, ##STR6## --OOC-- and single bond are preferred.

Specific examples include ##STR7##

In the formulae (1) and (2) of this invention, particularly preferred --Z.sub.1 -- and --Z.sub.2 -- are the groups represented by the following formulae (iii) to (ix), respectively: ##STR8## wherein R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, p, q and r have the same meanings as defined above.

Among the compounds according to this invention, which are represented by the formula (1), the compounds represented by the formula (3) are novel compounds found by the present inventors.

In the compounds represented by the formula (3) according to this invention, the position of substitution by each phenolic hydroxyl group or carbamate group is preferably the ortho-, meta- or para-position, more preferably the meta- or para-position, both relative to --Z.sub.3 --.

Of the compounds (3) according to the present invention, preferred examples include those represented by the following formula (3-a) to (3-i), respectively: ##STR9## wherein R.sub.1, R.sub.2, R.sub.5, R.sub.6, X.sub.1, Y.sub.1, P and q have the same meanings as defined above.

In the formulae (3-a) to (3-i), examples of R.sub.1, R.sub.2, R.sub.5, R.sub.6, X.sub.1, Y.sub.1, P and q are as described above. In particular, R.sub.1 is preferably a hydrogen atom or a C.sub.1-4 alkyl group, notably a hydrogen atom, R.sub.5 and R.sub.6 are preferably a hydrogen atom or a C.sub.1-4 alkyl group, notably a hydrogen atom, and X.sub.1 is preferably an oxygen atom.

In the formulae (3-a) to (3-i), --Z.sub.3 -- represents a group containing at least one group selected from the class consisting of --R.sub.8 CR.sub.9 -- (in which R.sub.8 and R.sub.9 individually represent a hydrogen atom or an alkyl, trifluoromethyl or aryl group or are combined together to form a ring), --O--, --S--, a phenylene group, --CO--, --C.sub.m H.sub.2m -- (in which m stands for an integer of 2-10), --CR.sub.10 .dbd.CR.sub.11 -- (in which R.sub.10 and R.sub.11 individually represent a hydrogen atom or an alkyl or aryl group), --SO--, and --SO.sub.2 --.

In --Z.sub.3 --, R.sub.8 and R.sub.9 may individually represent a hydrogen atom or an alkyl, trifluoromethyl or aryl group or may be combined together to form a ring; preferably a hydrogen atom, a C.sub.1-20 alkyl, trifluoromethyl or phenyl group or a C.sub.5-14 cycloalkane ring formed of R.sub.8 and R.sub.9 ; most preferably a hydrogen atom, a C.sub.1-4 alkyl, trifluoromethyl or phenyl group, or a cycloheptane, cyclohexane or cyclopentane ring formed by R.sub.8 and R.sub.9. A methyl group is especially preferred. m stands for an integer of 2-10, more preferably an integer of 2-6. R.sub.10 and R.sub.11 individually represent a hydrogen atom or an alkyl or aryl group, preferably a hydrogen atom or a C.sub.1-20 alkyl or phenyl group, more preferably a hydrogen atom or a C.sub.1-4 alkyl group.

More preferred --Z.sub.3 -- is a group containing at least one group selected from the class consisting of --R.sub.8 CR.sub.9 -- (in which R.sub.8 and R.sub.9 individually represent a hydrogen atom or an alkyl, trifluoromethyl or aryl group or are combined together to form a ring), --O--, --S--, 1,4-phenylene and --CO--. Particularly preferred is a group containing at least one group selected from the class consisting of --R.sub.8 CR.sub.9 -- (in which R.sub.8 and R.sub.9 individually represent a C.sub.1-4 alkyl group), --O--, --S--, ##STR10## and --OOC--.

Among the compounds (3) according to the present invention, particularly preferred compounds are those represented by the following formulae (4) to (8), respectively: ##STR11## wherein R.sub.8 and R.sub.9 individually represent a C.sub.1-4 alkyl group, and R.sub.2, X.sub.1 and Y.sub.1 have the same meanings as defined above. ##STR12## wherein R.sub.2, X.sub.1 and Y.sub.1 have the same meanings as defined above. ##STR13## wherein R.sub.2, X.sub.1 and Y.sub.1 have the same meanings as defined above. ##STR14## wherein R.sub.2, X.sub.1 and Y.sub.1 have the same meanings as defined above. ##STR15## wherein R.sub.2, X.sub.1 and Y.sub.1 have the same meanings as defined above.

Among the compounds represented by the formula (4), the compounds represented by the formula (4-1) or (4-2) are particularly preferred. ##STR16## wherein R.sub.2 and Y.sub.1 have the same meanings as defined above.

Among the compounds represented by the formula (5), the compounds represented by the following formula (5-1) or (5-2) are particularly preferred. ##STR17## wherein R.sub.2 and Y.sub.1 have the same meanings as defined above.

Among the compounds represented by the formula (6), the compounds represented by the following formulae (6-1) are particularly preferred. ##STR18## wherein R.sub.2 and Y.sub.1 have the same meanings as defined above.

Among the compounds represented by the formula (7), the compounds represented by the following formula (7-1) or (7-2) are particularly preferred. ##STR19## wherein R.sub.2 has the same meaning as defined above.

Among the compounds represented by the formula (8), the compounds represented by the following formula (8-1) are particularly preferred. ##STR20## wherein R.sub.2 has the same meaning as defined above.

The phenol compounds represented by the formula (1), (2) or (3), said compounds pertaining to the present invention, can be prepared in a manner known per se in the art [for example, the process disclosed in Methoden Der Organischen Chemie, 8, 137(1952), Shin Jikken Kagaku Koza (New Textbook of Experimental Chemistry), 14, 1658,1836, Maruzen (1977), or Angewandte Chemie International Edition, 6, 281(1967)].

The compounds represented by the formula (1), which pertain to the present invention, can each be prepared typically from an aminophenol derivative, which is represented by the following formula (a): ##STR21## wherein R.sub.1 and Z.sub.1 have the same meanings as defined above, and a chloroformate ester, chlorothioformate ester or chlorodithioformate ester represented by the following formula (b): ##STR22## wherein R.sub.2, X.sub.1 and Y.sub.1 have the same meanings as defined above.

The compounds represented by the formula (2), which relate to the present invention, can each be prepared typically from a phenol derivative, which is represented by the following formula (c);

HO--Z.sub.2 --Y.sub.2 --H (c) wherein Y.sub.2 and Z.sub.2 have the same meanings as defined above, and from an isocyanate or thioisocyanate derivative, which is represented by the following formula (d): X.sub.2 .dbd.C.dbd.N--R.sub.4 (d) wherein R.sub.4 and X.sub.2 have the same meanings as defined above, or a chloroformic amide derivative represented by the following formula (e): ##STR23## wherein R.sub.3, R.sub.4 and X.sub.2 have the same meanings as defined above.

The novel phenol compounds represented by the formula (3), which also relate to the present invention, can each be prepared typically from an aminophenol derivative, which is represented by the following formula (aa): ##STR24## wherein R.sub.1, R.sub.5, R.sub.6, Z.sub.3, p and q have the same meanings as defined above, and a chloroformate ester, chlorothioformate ester or chlorodithioformate ester represented by the above formula (b) .

The aminophenol derivative useful as a raw material upon preparation of the novel phenol compound (3) of the present invention can be prepared in a manner known per se in the art.

For example, an aminophenol derivative, which is represented by the following formula (4-a): ##STR25## wherein R.sub.1, R.sub.5, R.sub.6, R.sub.8, R.sub.9, p and q have the same meanings as defined above, can be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in Journal of American Chemical Society, 68, 2600 (1946), British Patent 1,028,156, Japanese Patent Laid-Open No. 114942/1987, 116546/1987 or 172364/1989, or the like, namely, by decomposing the diazonium salt of a corresponding dianilinoalkane, by reacting a corresponding diphenol alkane with a corresponding aniline, by reacting a corresponding monoalkenylaniline with a corresponding phenol in the presence of a catalyst, or by reacting a corresponding monoalkenylphenol and a corresponding aniline in the presence of a catalyst.

Further, aminophenol derivatives represented by the following formula (5-a): ##STR26## wherein R.sub.1, R.sub.5, R.sub.6, p and q have the same meanings as defined above can each be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in Pharmaceutical Bulletin, 5, 397 (1952), Journal of the Society of Synthetic Organic Chemistry, Japan, 24, 44 (1966), U.S. Pat. No. 3,240,706 or the like, namely, by, for example, reacting a nitrochlorobenzene with a dihydroxybenzene in the presence of a base and then reducing the resultant nitrophenoxyphenol.

Aminophenol derivatives represented by the following formula (6-a): ##STR27## wherein R.sub.1, R.sub.5, R.sub.6, p and q have the same meanings as defined above can each be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in Indian Journal of Chemistry, 15B, 661 (1977), U.S. Pat. No. 3,443,943 or the like, namely, by reacting a nitrochlorobenzene with a hydroxythiophenol in the presence of a base and then reducing the resultant hydroxyphenyl-nitrophenyl sulfide.

In addition, aminophenol derivatives represented by the following formula (7-a): ##STR28## wherein R.sub.1, R.sub.5, R.sub.6, p and q have the same meanings as defined above can each be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in Japanese Patent Laid-Open No. 14441/1974 or the like, namely, by reacting a hydroxybiphenylcarboxylic acid with a nitrophenol in the presence of a catalyst and then reducing the resultant nitrophenyl hydroxybiphenylcarboxylate.

Aminophenol derivatives represented by the following formula (8-a): ##STR29## wherein R.sub.1, R.sub.5, R.sub.6, p and q have the same meanings as defined above can each be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in Journal of Organic Chemistry, 37, 1425 (1972), Journal of Organic Chemistry, 38, 3160 (1973) or the like, namely, by reacting a dihydroxybenzene with a nitrobenzoic acid and then reducing the resultant hydroxyphenyl nitrobenzoate.

Furthermore, the compounds represented by the formula (b) can each be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in Methoden Der Organischen Chemie, 8, 101 (1952), Journal of American Chemical Society, 72, 1254 (1950), Angewandte Chemie International Edition, 4, 281 (1967), Chemical Review, 73, 75 (1973) or the like, namely, by the reaction between phosgene or thiophosgene and an alcohol, phenol, thiol or thiophenol.

Upon production of the phenol compound (3) of the present invention, a conventional reaction process can be employed for the reaction between the aminophenol derivative represented by the formula (aa) and the compound represented by the formula (b). For example, they can be reacted by adding the compound (b) dropwise to the compound (aa) under stirring. Upon conducting the reaction, the molar ratio of the compound (aa) to the compound (b) is generally in a range of about 1 to about 0.5-2, preferably in a range of about 1 to about 0.8-1.5, more preferably in a range of about 1 to about 0.8-1.2.

Although the reaction may be conducted in a solventless manner, it is generally more preferable to carry it out using a solvent.

Examples of solvents usable in the reaction include hydrocarbon solvents such as hexane, octane, benzene, toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate, butyl acetate and amyl acetate; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran and dioxane; halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, Perclene, chlorobenzene and dichlorobenzene; and mixed solvents thereof. The reaction can also be conducted in the presence of both one of the solvents or mixed solvents and water.

The reaction temperature generally ranges from 0.degree. C. to 200.degree. C., with about 0.degree.-100.degree. C. being preferred. The reaction time is generally in a range of from several minutes to several tens of hours although it varies significantly depending on reaction conditions such as reaction temperature.

During the reaction, hydrogen chloride is by-produced. Use of a dehydrochlorinating agent, for example, an organic base such as dimethylaniline or an inorganic base such as sodium hydrogencarbonate, sodium carbonate, potassium hydrogencarbonate or potassium carbonate is preferred. It is particularly preferred to use an inorganic base. When such an inorganic base is employed, the inorganic base can be used as an aqueous solution without any problems.

After the completion of the reaction, the phenol compound (3) of the present invention can be isolated by collecting the reaction product in a manner known per se in the art and then purifying it in accordance with a conventional procedure, for example, recrystallization or column chromatography.

Among the compounds (1) of the present invention, those of the formula (1) in which --Z.sub.1 -- is represented, for example, by the formula (viii) can be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in Chemical and Pharmaceutical Bulletin, 26, 2508 (1978).

Among the compounds (1) of the present invention, those of the formula (1) in which --Z.sub.1 -- is represented, for example, by the formula (ix) can be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in Synthesis, 277 (1979).

Among the compounds (2) of the present invention, those of the formula (2) in which --Z.sub.2 -- is represented, for example, by the formula (iii) can be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in Collection of Czechoslovak Chemical Communication, 42, 1651 (1977) or U.S. Pat. No. 3,632,631.

Among the compounds (2) of the present invention, those of the formula (2) in which --Z.sub.2 -- is represented, for example, by the formula (iv) or (v) can be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in U.S. Pat. No. 3,371,109.

Among the compounds (2) of the present invention, those of the formula (2) in which --Z.sub.2 -- is represented, for example, by the formula (viii) can be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in U.S. Pat. No. 3,632,631.

Among the compounds (2) of the present invention, those of the formula (2) in which --Z.sub.2 -- is represented, for example, by the formula (ix) can be prepared in a manner known per se in the art, for example, in accordance with the process disclosed in Journal of Agricultural and Food Chemistry, 13, 537 (1965), 14, 555 (1966), 16, 561 (1968) or 19, 432,441 (1971).

The heat-sensitive recording material according to the present invention features the inclusion of at least one compound represented by the formula (1) or (2) in a heat-sensitive recording material which contains an electron-donating chromogenic compound and an electron-attracting compound. Describing in more detail the constitution of the heat-sensitive recording material of this invention, it is a heat-sensitive recording material which contains an electron-donating chromogenic compound and, as an electron attracting compound, at least one compound represented by the formula (1) or (2), or a heat-sensitive recording material which contains an electron-donating chromogenic compound, an electron-attracting compound and at least one compound represented by the formula (1) or (2).

As will be described later, these heat-sensitive recording materials additionally contain various known additives which have been used to produce conventional heat-sensitive materials, for example, a thermofusible compound.

Each compound represented by the formula (1) or (2), which pertains to the present invention, features the inclusion of a phenolic hydroxyl group and a carbamate group in its molecule. The present invention relates to a heat-sensitive recording material containing an electron-donating chromogenic compound and an electron-attracting compound, in which one or more of the compounds represented by the formula (1) or (2) are contained as the electron-attracting compound. The heat-sensitive recording material of this invention has very strong color-producing ability and provides a color image with excellent storage stability (hydrothermoresistance, waterproofness, etc.). Among the compounds represented by the formula (1) or (2) and useful in the heat-sensitive recording material according to this invention, those having a melting point not lower than about 60.degree. C. are preferred. By using as an electron-attracting compound a compound--whose melting point is about 60.degree. C. to 150.degree. C., preferably about 80.degree. C. to 130.degree. C.--out of the compounds represented by the formula (1) or (2), it is possible to provide a heat-sensitive recording material which is not only excellent in the storage stability of a color image to be produced but also good in color-producing sensitivity.

Further, a compound which is represented by the formula (1) or (2) and has a melting point of 150.degree. C. or higher can also provide a heat-sensitive recording material not only excellent in the storage stability of a color image to be produced but also good in color-producing sensitivity, provided that another electron-attracting compound and/or a thermofusible compound having a melting point of about 60.degree. C. to 150.degree. C., said thermofusible compound being to be described subsequently, is used in combination.

As a compound containing a phenolic hydroxyl group and a carbamate group in its molecule, 3-ethoxycarbonylaminophenol, 4-phenyloxycarbonylaminophenol or the like can be mentioned. As a result of a study conducted by the present inventors, it has, however, been found that a heat-sensitive recording material using the above compound, which contains only one benzene ring in its molecule, as an electron-attracting compound or a heat-sensitive recording material using, as an electron-attracting compound, the above compound in combination with another known electron-attracting compound is hardly considered to be good in the storage stability of a color image to be produced.

Japanese Patent Publication No. 59796/1990 proposes heat-sensitive recording materials which use, as an electron-attracting compound (color-developing agent), a blocked phenol compound obtained by the reaction of an isocyanate compound and a phenol compound. The blocked phenol compounds disclosed in the above patent publication are, however, compounds which do not contain any hydroxyl group in their molecules. Accordingly, heat-Sensitive recording materials containing as electron-attracting compounds these blocked phenol compounds, for example, 4-tert-butylphenyloxycarbonylaminobenzene or 2,4-bis(4'-tert-butylphenyloxycarbonylamino)toluene have very poor color-producing ability and cannot produce any color even when heated at high temperatures, for example, at 150.degree. C. These blocked phenol compounds are therefore not considered to have any practical function as an electron-attracting compound. From the foregoing, it is unique and also surprising that the heat-sensitive recording material according to this invention, which contains as an electron-attracting compound at least one compound represented by the formula (1) or (2), is excellent in the storage stability of a color image to be produced.

Further, Japanese Patent Laid-Open No. 18084/1990 proposes, as thermofusible compounds (sensitizers) for heat-sensitive recording materials, carbamate compounds having one of several specific structures. The carbamate compounds disclosed in the above patent publication are considerably different from the compounds of the formula (1) or (2), the latter compounds pertaining to the present invention, in that the former compounds do not contain any phenolic hydroxyl group in their molecules. Because of this, heat-sensitive recording materials containing as a sensitizer one of the compounds disclosed in the above patent publication, for example, 1,6-bis(phenyloxycarbonylamino)hexane are very poor in the storage stability (for example, heat resistance, hydrothermoresistance and waterproofness) of a color image to be produced, compared with heat-sensitive recording materials according to the present invention, the latter heat-sensitive recording materials containing an electron-donating chromogenic compound, an electron-attracting compound (for example, bisphenol A) and a compound of the formula (1) or (2). As has been described above, the excellent storage stability of a color image produced on the heat-sensitive recording material according to the present invention cannot be inferred from any conventional compounds or conventional technology and, although the mechanism has not been fully elucidated, is believed to be attributed to certain advantageous effects inherent to the compound of the formula (1) or (2) which pertains to the present invention and contains both a phenolic hydroxyl group and a carbamate group in its molecule.

Specific examples of the compounds according to the present invention, which are represented by the formula (1) or (2), include, but are not limited to, the following compounds.

1. 2-(4'-Hydroxyphenyl)-2-(4"-methoxycarbonylaminophenyl)propane 2. 2-(4'-Hydroxyphenyl)-2-(4"-n-propoxycarbonylaminophenyl)propane 3. 2-(4'-Hydroxyphenyl)-2-(4"-n-butoxycarbonylaminophenyl)propane 4. 2-(4'-Hydroxyphenyl)-2-(4"-n-decyloxycarbonylaminophenyl)propane 5. 2-(4'-Hydroxyphenyl)-2-(4"-n-hexadecyloxycarbonylaminophenyl)propane 6. 2-(4'-Hydroxyphenyl)-2-(4"-cyclohexyloxycarbonylaminophenyl)propane 7. 2-(4'-Hydroxyphenyl)-2-(4"-cyclohexylmethyloxycarbonylaminophenyl)propane 8. 2-(4'-Hydroxyphenyl)-2-[4"-(2-tetrahydrofurfuryl)oxycarbonylaminophenyl]propane 9. 2-(4'-Hydroxyphenyl)-2-[4"-(2-methoxyethyl)oxycarbonylaminophenyl]propane 10. 2-(4'-Hydroxyphenyl)-2-[4"-(2-n-butoxyethyl)oxycarbonylaminophenyl]propane 11. 2-(4'-Hydroxyphenyl)-2-[4"-(3-ethoxypropyl)oxycarbonylaminophenyl]propane 12. 2-(4'-Hydroxyphenyl)-2-[4"-(3-n-hexyloxypropyl)oxycarbonylaminophenyl]propane 13. 2-(4'-Hydroxyphenyl)-2-[4"-(2-methoxyethoxyethyl)oxycarbonylaminophenyl]propane 14. 2-(4'-Hydroxyphenyl)-2-[4"-(2-phenoxyethyl)oxycarbonylaminophenyl]propane 15. 2-(4'-Hydroxyphenyl)-2-{4"-[2-(4-chlorophenoxy)ethyl]oxycarbonylaminophenyl}propane 16. 2-(4'-Hydroxyphenyl)-2-[4"-(3-chloropropyl)oxycarbonylaminophenyl]propane 17. 2-(4'-Hydroxyphenyl)-2-(4"-allyloxycarbonylaminophenyl)propane 18. 2-(4'-Hydroxyphenyl)-2-(4"-benzyloxycarbonylaminophenyl)propane 19. 2-(4'-Hydroxyphenyl)-2-[4"-(4-methylbenzyl)oxycarbonylaminophenyl]propane 20. 2-(4'-Hydroxyphenyl)-2-[4"-(4-phenoxybenzyl)oxycarbonylaminophenyl]propane 21. 2-(4'-Hydroxyphenyl)-2-[4"-(4-chlorobenzyl)oxycarbonylaminophenyl]propane 22. 2-(4'-Hydroxyphenyl)-2-[4"-(3-hydroxybenzyl)oxycarbonylaminophenyl]propane 23. 2-(4'-Hydroxyphenyl)-2-[4"-(2-phenylethyl)oxycarbonylaminophenyl]propane 24. 2-(4'-Hydroxyphenyl)-2-(4"-phenyloxycarbonylaminophenyl)propane 25. 2-(4'-Hydroxyphenyl)-2-[4"-(2-naphthyl)oxycarbonylaminophenyl]propane 26. 2-(4'-Hydroxyphenyl)-2-[4"-(4-phenylphenyl)oxycarbonylaminophenyl]propane 27. 2-(4'-Hydroxyphenyl)-2-[4"-(4-methylphenyl)oxycarbonylaminophenyl]propane 28. 2-(4'-Hydroxyphenyl)-2-[4"-(3-methylphenyl)oxycarbonylaminophenyl]propane 29. 2-(4'-Hydroxyphenyl)-2-[4"-(4-cyclohexylphenyl)oxycarbonylaminophenyl]propane 30. 2-(4'-Hydroxyphenyl)-2-[4'-(4-cumylphenyl)oxycarbonylaminophenyl]propane 31. 2-(4'-Hydroxyphenyl)-2-[4"-(4-methoxyphenyl)oxycarbonylaminophenyl]propane 32. 2-(4'-Hydroxyphenyl)-2-[4"-(4-phenoxyphenyl)oxycarbonylaminophenyl]propane 33. 2-(4'-Hydroxyphenyl)-2-[4"-(4-chlorophenyl)oxycarbonylaminophenyl]propane 34. 2-(4'-Hydroxyphenyl)-2-[4"-(2-chlorophenyl)oxycarbonylaminophenyl]propane 35. 2-(4'-Hydroxyphenyl)-2-[4"-(4-nitrophenyl)oxycarbonylaminophenyl]propane 36. 2-(4'-Hydroxyphenyl)-2-[4"-(4-acetylphenyl)oxycarbonylaminophenyl]propane 37. 2-(4'-Hydroxyphenyl)-2-[4"-(4-ethoxycarbonylphenyl)oxycarbonylaminophenyl]propane 38. 2-(4'-Hydroxyphenyl)-2-[4"-(4-benzyloxyphenyl)oxycarbonylaminophenyl]propane 39. 2-(4'-Hydroxyphenyl)-2-[4"-(4-phenylcarbonylphenyl)oxycarbonylaminophenyl]propane 40. 2-(4'-Hydroxyphenyl)-2-[4"-(2-chloro-4-nitrophenyl)oxycarbonylaminophenyl]propane 41. 2-(4'-Hydroxyphenyl)-2-[4"-(2,4-dimethylphenyl)oxycarbonylaminophenyl]propane 42. 2-(3'-Methyl-4'-hydroxyphenyl)-2-(4"-ethoxycarbonylaminophenyl)propane 43. 2-(3'-Methyl-4'-hydroxyphenyl)-2-[4"-(4-methoxybenzyl)oxycarbonylaminophenyl]propane 44. 2-(3'-Ethyl-4'-hydroxyphenyl)-2-[4"-(4-tert-butylphenyl)oxycarbonylaminophenyl)]propane 45. 2-(3',5'-Dimethyl-4'-hydroxyphenyl)-2-[4"-(2-methylphenyl)oxycarbonylaminophenyl]propane 46. 2-(3'-Methyl-4'-hydroxyphenyl)-2-(3"-methyl-4'-isobutoxycarbonylaminophenyl)propane 47. 2-(4'-Hydroxyphenyl)-2-[3"-methyl-4"-(4-allylphenyl)oxycarbonylaminophenyl]propane 48. 2-(4'-Hydroxyphenyl)-2-[3"-chloro-4"-(3-methoxyphenyl)oxycarbonylaminophenyl]propane 49. 2-(4'-Hydroxyphenyl)-2-[3",5"-dimethyl-4"-(4-tert-butylcyclohexyl)oxycarbonylaminophenyl]propane 50. 1-(4'-Hydroxyphenyl)-1-(4"-phenyloxycarbonylaminophenyl)cyclopentane 51. 1-(4'-Hydroxyphenyl)-1-[4"-(4-methylcyclohexyl)oxycarbonylaminophenyl]cyclohexane 52. 1-(4'-Hydroxyphenyl)-1-(4"-isopropoxycarbonylaminophenyl)cycloheptane 53. 1-(4'-Hydroxyphenyl)-1-[4"-(2-acetylphenyl)oxycarbonylaminophenyl]cyclooctane 54. 1-(4'-Hydroxyphenyl)-1-(4"-sec-butoxycarbonylaminophenyl)methane 55. 1-(4'-Hydroxyphenyl)-1-[4"-(1-naphtyl)oxycarbonylaminophenyl]methane 56. 2-(4'-Hydroxyphenyl)-2-(4"-tert-butoxycarbonylaminophenyl)butane 57. 2-(4'-Hydroxyphenyl)-2-[4"-(3-furyl)oxycarbonylaminophenyl]isohexane 58. 1-(4'-Hydroxyphenyl)-1-(4"-n-pentyloxycarbonylaminophenyl)-1-phenylmethane 59. 1-(4'-Hydroxyphenyl)-1-[4"-(3-thienyl)oxycarbonylaminophenyl]-1-phenylethane 60. 2-(4'-Hydroxyphenyl)-2-(4"-phenyloxycarbonylaminophenyl)hexafluoropropane 61. 2-(4'-Hydroxyphenyl)-2-(4"-N-phenyloxycarbonyl-N-methylaminophenyl)propane 62. 2-(4'-Hydroxyphenyl)-2-(4"-phenylthiolcarbonylaminophenyl)propane 63. 2-(4'-Hydroxyphenyl)-2-(4"-phenyloxythiocarbonylaminophenyl)propane 64. 2-(4'-Hydroxyphenyl)-2-(4"-ethoxycarbonylamino-1"-naphtyl)propane 65. 2-(3'-Hydroxyphenyl)-2-(4"-methoxycarbonylaminophenyl)propane 66. 2-(3"-Hydroxyphenyl)-2-(4"-n-butoxycarbonylaminophenyl)propane 67. 2-(3'-Hydroxyphenyl)-2-[4"-(2-phenoxyethoxyethyl)oxycarbonylaminophenyl]propane 68. 2-(3'-Hydroxyphenyl)-2-[4"-benzyloxycarbonylaminophenyl) propane 69. 2-(3'-Hydroxyphenyl)-2-[4"-(4-chlorobenzyl)oxycarbonylaminophenyl]propane 70. 2-(3'-Hydroxyphenyl)-2-(4"-phenyloxycarbonylaminophenyl)propane 71. 2-(3'-Hydroxyphenyl)-2-[4"-(1-naphtyl)oxycarbonylaminophenyl]propane 72. 2-(3'-Hydroxyphenyl)-2-[4"-(2-phenylphenyl)oxycarbonylaminophenyl]propane 73. 2-(3'-Hydroxyphenyl)-2-[4"-(2-methylphenyl)oxycarbonylaminophenyl]propane 74. 2-(3'-Hydroxyphenyl)-2-[4"-(2-cyclohexylphenyl)oxycarbonylaminophenyl]propane 75. 2-(3'-Hydroxyphenyl)-2-[4"-(2-ethoxyphenyl)oxycarbonylaminophenyl]propane 76. 2-(3'-Hydroxyphenyl)-2-[4"-(3-phenoxyphenyl)oxycarbonylaminophenyl]propane 77. 2-(3'-Hydroxyphenyl)-2-[4"-(4-chlorophenyl)oxycarbonylaminophenyl]propane 78. 2-(3'-Hydroxyphenyl)-2-[4"-(2-chlorophenyl)oxycarbonylaminophenyl]propane 79. 2-(3'-Hydroxyphenyl)-2,-[4"-(4-bromophenyl)oxycarbonylaminophenyl]propane 80. 2-(3'-Hydroxyphenyl)-2-[4"-(4-benzyloxyphenyl)oxycarbonylaminophenyl]propane 81. 2-(3'-Hydroxyphenyl)-2-[4"-(4-cumylphenyl)oxycarbonylaminophenyl]propane 82. 2-(3'-Hydroxyphenyl)-2-[4"-(2,4-dimethylphenyl)oxycarbonylaminophenyl]propane 83. 2-(3'-Hydroxyphenyl)-2-(3",5"-dimethyl-4"-phenyloxycarbonylaminophenyl)propane 84. 1-(3'-Hydroxyphenyl)-1-(4"-isopentyloxycarbonylaminophenyl)cyclohexane 85. 1-(3'-Hydroxyphenyl)-1-[4"-(2-acetylphenyl)oxycarbonylaminophenyl]cyclohexane 86. 1-(3'-Hydroxyphenyl)-1-[4"-(4-acetyloxyphenyl)oxycarbonylaminophenyl]methane 87. 2-(3'-Hydroxyphenyl)-2-(4"-phenyloxycarbonylaminophenyl)butane 88. 2-(3'-Hydroxyphenyl)-2-(4"-methoxycarbonylaminophenyl)isohexane 89. 1-(4'-methyl-3'-hydroxyphenyl)-1-(4"-methyl-3"-phenyloxycarbonylaminophenyl)methane 90. 1-(4'-methyl-3'-hydroxyphenyl)-1-[4"-methyl-3"-(4-chlorophenyl)oxycarbonylaminophenyl]methane 91. 2-(4'-Hydroxyphenyl)-2-(3"-n-propoxycarbonylaminophenyl)propane 92. 2-(4'-Hydroxyphenyl)-2-[3"-(4-methylcyclohexyl)oxycarbonylaminophenyl]propane 93. 2-(4'-Hydroxyphenyl)-2-[3"-(2-cyclohexylethyl)oxycarbonylaminophenyl]propane 94. 2-(4'-Hydroxyphenyl)-2-[3"-(2-ethoxyethyl)oxycarbonylaminophenyl]propane 95. 2-(4'-Hydroxyphenyl)-2-[3"-(2-isopropoxyethyl)oxycarbonylaminophenyl]propane 96. 2-(4'-Hydroxyphenyl)-2-(3"-phenyloxycarbonylaminophenyl)propane 97. 2-(4'-Hydroxyphenyl)-2-[3"-(4-ethylphenyl)oxycarbonylaminophenyl]propane 98. 2-(4'-Hydroxyphenyl)-2-[3"-(4-methoxyphenyl)oxycarbonylaminophenyl]propane 99. 2-(4'-Hydroxyphenyl)-2-[3"-(2-fluorophenyl)oxycarbonylaminophenyl]propane 100. 2-(4'-Hydroxyphenyl)-2-[3"-(2-ethylphenyl)oxycarbonylaminophenyl]propane 101. 1-(4'-Hydroxyphenyl)-1-(3"-ethoxycarbonylaminophenyl)cyclohexane 102. 1-(4'-Hydroxyphenyl)-1-(3"-phenyloxycarbonylaminophenyl)cyclohexane 103. 2-(4'-Hydroxyphenyl)-2-[3"-(4-benzylphenyl)oxycarbonylaminophenyl]isohexane 104. 1-(2'-Hydroxyphenyl)-1-(4"-n-propoxycarbonylaminophenyl)methane 105. 1-(2'-Hydroxyphenyl)-1-(4"-cyclohexyloxycarbonylaminophenyl)methane 106. 1-(2'-Hydroxyphenyl)-1-(4"-benzyloxycarbonylaminophenyl)methane 107. 1-(2'-Hydroxyphenyl)-1-[4"-(2-methoxyphenyl)oxycarbonylaminophenyl]methane 108. 1-(4'-Hydroxyphenyl)-1-[2"-(4-methylphenyl)oxycarbonylaminophenyl]methane 109. 2-(4'-Hydroxyphenyl)-2-(4"-ethyl-2"-phenyloxycarbonylaminophenyl)propane 110. 1-(2'-Hydroxy-5'-methylphenyl)-1-(2"-hydroxy-3"-phenyloxycarbonylaminophenyl)methane 111. 1-(2',5'-Dihydroxyphenyl)-1-(3"-phenyloxycarbonylaminophenyl)methane 112. 1-(2',5'-Dihydroxyphenyl)-1-(4"-methyl-3"-methoxycarbonylaminophenyl)methane 113. 1-(2',5'-Dihydroxyphenyl)-1-(4"-methyl-3"-phenyloxycarbonylaminophenyl)methane 114. 1-(2'-Hydroxy-5'-n-butylphenyl)-1-(2"-benzyloxycarbonylaminophenyl)methane 115. 1-(2'-Hydroxy-5'-n-pentylphenyl)-1-(2"-phenyloxycarbonylaminophenyl)methane 116. 1-(2'-Hydroxy-5'-cumylphenyl)-1-(2"-methoxycarbonylaminophenyl)methane 117. 4-Hydroxyphenyl-4'-methoxycarbonylaminophenyl ether 118. 4-Hydroxyphenyl-4'-ethoxycarbonylaminophenyl ether 119. 4-Hydroxyphenyl-4'-n-butoxycarbonylaminophenyl ether 120. 4-Hydroxyphenyl-4'-n-hexyloxycarbonylaminophenyl ether 121. 4-Hydroxyphenyl-4'-n-hexadecyloxycarbonylaminophenyl ether 122. 4-Hydroxyphenyl-4'-(2-methoxyethyl)oxycarbonylaminophenyl ether 123. 4-Hydroxyphenyl-4'-(3-methoxypropyl)oxycarbonylaminophenyl ether 124. 4-Hydroxyphenyl-4'-(2-allyloxyethyl)oxycarbonylaminophenyl ether 125. 4-Hydroxyphenyl-4'-benzyloxycarbonylaminophenyl ether 126. 4-Hydroxyphenyl-4'-phenyloxycarbonylaminophenyl ether 127. 4-Hydroxyphenyl-4'-(3-ethylphenyl)oxycarbonylaminophenyl ether 128. 4-Hydroxyphenyl-4'-(4-phenylphenyl)oxycarbonylaminophenyl ether 129. 4-Hydroxyphenyl-4'-(3-phenylphenyl)oxycarbonylaminophenyl ether 130. 4-Hydroxyphenyl-4'-(4-cyclopentylphenyl)oxycarbonylaminophenyl ether 131. 4-Hydroxyphenyl-4'-(3-chlorophenyl)oxycarbonylaminophenyl ether 132. 4-Hydroxyphenyl-4'-(2-benzyloxyphenyl)oxycarbonylaminophenyl ether 133. 4-Hydroxyphenyl-4'-(2,6-dimethylphenyl)oxycarbonylaminophenyl ether 134. 4-Hydroxyphenyl-4'-phenylthiolcarbonylaminophenyl ether 135. 4-Hydroxy-1-naphthyl-4'-ethoxycarbonylaminophenyl ether 136. 3-Hydroxyphenyl-4'-methoxycarbonylaminophenyl ether 137. 3-Hydroxyphenyl-4'-ethoxycarbonylaminophenyl ether 138. 3-Hydroxyphenyl-4'-n-octyloxycarbonylaminophenyl ether 139. 3-Hydroxyphenyl-4'-(3-chlorobenzyl)oxycarbonylaminophenyl ether 140. 3-Hydroxyphenyl-4'-phenyloxycarbonylaminophenyl ether 141. 3-Hydroxyphenyl-4'-(4-isopropylphenyl)oxycarbonylaminophenyl ether 142. 3-Hydroxyphenyl-4'-(4-allylcarbonylphenyl)oxycarbonylaminophenyl ether 143. 3-Hydroxyphenyl-4'-(4-methylthiophenyl)oxycarbonylaminophenyl ether 144. 3-Hydroxyphenyl-4'-(4-methoxyphenyl)oxycarbonylaminophenyl ether 145. 3-Hydroxyphenyl-440 -(3-chlorophenyl)oxycarbonylaminophenyl ether 146. 3-Hydroxyphenyl-3'-methyl-4'-phenyloxycarbonylaminophenyl ether 147. 4-Hydroxyphenyl-3'-n-butoxycarbonylaminophenyl ether 148. 4-Hydroxyphenyl-3'-cyclohexyloxycarbonylaminophenyl ether 149. 4-Hydroxyphenyl-3'-(3-n-butoxypropyl)oxycarbonylaminophenyl ether 150. 4-Hydroxyphenyl-3'-(3-methylbenzyl)oxycarbonylaminophenyl ether 151. 4-Hydroxyphenyl-3'-phenyloxycarbonylaminophenyl ether 152. 4-Hydroxyphenyl-3'-(4-methylphenyl)oxycarbonylaminophenyl ether 153. 4-Hydroxyphenyl-3'-(4-phenoxyphenyl)oxycarbonylaminophenyl ether 154. 4-Hydroxyphenyl-3'-(3-nitrophenyl)oxycarbonylaminophenyl ether 155. 3-Methyl-4-Hydroxyphenyl-3'-phenyloxycarbonylaminophenyl ether 156. 3-Isopropyl-4-Hydroxyphenyl-3'-phenyloxycarbonylaminophenyl ether 157. 4-Hydroxyphenyl-4'-ethoxycarbonylaminophenyl sulfide 158. 4-Hydroxyphenyl-4'-isobutoxycarbonylaminophenyl sulfide 159. 4-Hydroxyphenyl-4'-n-hexadecyloxycarbonylaminophenyl sulfide 160. 4-Hydroxyphenyl-4'-cyclohexyloxycarbonylaminophenyl sulfide 161. 4-Hydroxyphenyl-4'-(2-methoxyethyl)oxycarbonylaminophenyl sulfide 162. 4-Hydroxyphenyl-4'-(2-benzyloxyethyl)oxycarbonylaminophenyl sulfide 163. 4-Hydroxyphenyl-4'-allyloxycarbonylaminophenyl sulfide 164. 4-Hydroxyphenyl-4'-(2-methylbenzyl)oxycarbonylaminophenyl sulfide 165. 4-Hydroxyphenyl-4'-phenyloxycarbonylaminophenyl sulfide 166. 4-Hydroxyphenyl-4'-(2-naphthyl)oxycarbonylaminophenyl sulfide 167. 4-Hydroxyphenyl-4'-(4-phenylphenyl)oxycarbonylaminophenyl sulfide 168. 4-Hydroxyphenyl-4'-(4-methylphenyl)oxycarbonylaminophenyl sulfide 169. 4-Hydroxyphenyl-4'-(4-chlorophenyl)oxycarbonylaminophenyl sulfide 170. 4-Hydroxyphenyl-4'-(4-methoxycarbonylphenyl)oxycarbonylaminophenyl sulfide 171. 4-Hydroxyphenyl-4'-(4-cumylphenyl)oxycarbonylaminophenyl sulfide 172. 4-Hydroxyphenyl-4'-phenylthiolcarbonylaminophenyl sulfide 173. 3-Hydroxyphenyl-4'-methoxycarbonylaminophenyl sulfide 174. 3-Hydroxyphenyl-4'-(2-chloroethyl)oxycarbonylaminophenyl sulfide 175. 3-Hydroxyphenyl-4'-benzyloxycarbonylaminophenyl sulfide 176. 3-Hydroxyphenyl-4'-phenyloxycarbonylaminophenyl sulfide 177. 3-Hydroxyphenyl-4'-(4-n-butylphenyl)oxycarbonylaminophenyl sulfide 178. 3-Hydroxyphenyl-4'-(4-formylphenyl)oxycarbonylaminophenyl sulfide 179. 3-Hydroxyphenyl-4'-(2,5-dimethylphenyl)oxycarbonylaminophenyl sulfide 180. 3-Hydroxyphenyl-3'-methyl-4'-phenyloxycarbonylaminophenyl sulfide 181. 4-Hydroxyphenyl-3'-n-hexyloxycarbonylaminophenyl sulfide 182. 4-Hydroxyphenyl-3'-cyclohexyloxycarbonylaminophenyl sulfide 183. 4-Hydroxyphenyl-3'-(2-n-hexyloxyethyl)oxycarbonylaminophenyl sulfide 184. 4-Hydroxyphenyl-3'-(4-allylbenzyl)oxycarbonylaminophenyl sulfide 185. 4-Hydroxyphenyl-3'-phenyloxycarbonylaminophenyl sulfide 186. 4-Hydroxyphenyl-3'-(4-allyloxyphenyl)oxycarbonylaminophenyl sulfide 187. 4-Hydroxyphenyl-3'-(4-hydroxyphenyl)oxycarbonylaminophenyl sulfide 188. 4-Hydroxyphenyl-3'-(3,4-dimethylphenyl)oxycarbonylaminophenyl sulfide 189. 3-Methyl-4-Hydroxyphenyl-3'-phenyloxycarbonylaminophenyl sulfide 190. 3-Isopropyl-4-Hydroxyphenyl-3'-phenyloxycarbonylaminophenyl sulfide 191. 4"-Methoxycarbonylaminophenyl-4-(4,-hydroxy)phenylbenzoate 192. 4"-Phenyloxycarbonylaminophenyl-4-(4'-hydroxy)phenylbenzoate 193. 3"-Phenyloxycarbonylaminophenyl-4-(4'-hydroxy)phenylbenzoate 194. 4'-Hydroxyphenyl-4-ethoxycarbonylaminobenzoate 195. 4'-Hydroxyphenyl-4-phenyloxycarbonylaminobenzoate 196. 4-Hydroxy-4'-n-octyloxycarbonylaminobiphenyl 197. 4-Hydroxy-4'-(2,6-dimethylcyclohexyl)oxycarbonylaminobiphenyl 198. 4-Hydroxy-4'-(2-ethoxyethoxyethyl)oxycarbonylaminobiphenyl 199. 4-Hydroxy-4'-(2-benzyloxyethyl)oxycarbonylaminobiphenyl 200. 4-Hydroxy-4'-benzyloxycarbonylaminobiphenyl 201. 4-Hydroxy-4'-phenyloxycarbonylaminobiphenyl 202. 4-Hydroxy-4'-(2-naphthyl)oxycarbonylaminobiphenyl 203. 4-Hydroxy-4'-(4-phenylphenyl)oxycarbonylaminobiphenyl 204. 4-Hydroxy-4'-(4-tert-octylphenyl)oxycarbonylaminobiphenyl 205. 4-Hydroxy-4'-(4-isopropoxyphenyl)oxycarbonylaminobiphenyl 206. 4-Hydroxy-4'-(4-chlorophenyl)oxycarbonylaminobiphenyl 207. 4-Hydroxy-4'-(4-cyanophenyl)oxycarbonylaminobiphenyl 208. 4-Hydroxy-2'-phenyl-4'-methoxycarbonylaminobiphenyl 209. 4-Hydroxy-3,5-diphenyl-4'-phenyloxycarbonylaminobiphenyl 210. 3-Hydroxy-4'-methoxycarbonylaminobiphenyl 211. 3-Hydroxy-4'-(2-chlorobenzyl)oxycarbonylaminobiphenyl 212. 3-Hydroxy-4'-phenyloxycarbonylaminobiphenyl 213. 3-Hydroxy-4'-(4-n-propylphenyl)oxycarbonylaminobiphenyl 214. 3-Hydroxy-4'-(2-chlorophenyl)oxycarbonylaminobiphenyl 215. 3-Hydroxy-3'-methyl-4'-phenyloxycarbonylaminobiphenyl 216. 3-Hydroxy-5'-phenyl-4'-methoxycarbonylaminobiphenyl 217. 4-Hydroxy-3'-n-nonyloxycarbonylaminobiphenyl 218. 4-Hydroxy-3'-cyclohexyloxycarbonylaminobiphenyl 219. 4-Hydroxy-3'-phenyloxycarbonylaminobiphenyl 220. 4-Hydroxy-3'-(4-fluorophenyl)oxycarbonylaminobiphenyl 221. 2-Hydroxy-2'-methoxycarbonylaminobiphenyl 222. 1-Hydroxy-4-methoxycarbonylaminonaphthalene 223. 1-Hydroxy-4-(2-ethylhexyl)oxycarbonylaminonaphthalene 224. 1-Hydroxy-4-benzyloxycarbonylaminonaphthalene 225. 1-Hydroxy-4-(4'-methylphenyl)oxycarbonylaminonaphthalene 226. 1-Hydroxy-4-(4'-phenylphenyl)oxycarbonylaminonaphthalene 227. 1-Hydroxy-5-methoxycarbonylaminonaphthalene 228. 1-Hydroxy-5-cyclohexyloxycarbonylaminonaphthalene 229. 1-Hydroxy-5-(4'-acetyloxyphenyl)oxycarbonylaminonaphthalene 230. 2-Hydroxy-7-methoxycarbonylaminonaphthalene 231. 2-Hydroxy-7-phenyloxycarbonylaminonaphthalene 232. 2-Hydroxy-7-(4'-methoxycarbonylphenyl)oxycarbonylaminonaphthalene 233. 2-Hydroxy-6-(4'-isopropoxyphenyl)oxycarbonylaminonaphthalene 234. 2-Hydroxy-8-phenyloxycarbonylaminonaphthalene 235. 2-Hydroxy-8-(4'-cumylphenyl)oxycarbonylaminonaphthalene 236. 1-(4'-hydroxyphenyl)-4-(4"-methoxycarbonylaminophenyl)benzene 237. 1-(4'-hydroxyphenyl)-4-(4"-phenyloxycarbonylaminophenyl)benzene 238. 4-Hydroxy-4'-n-butoxycarbonylaminobenzophenone 239. 4-Hydroxy-4'-(2-naphthyl)oxycarbonylaminobenzophenone 240. 3-Hydroxy-2'-cyclohexyloxycarbonylaminobenzophenone 241. 2-Hydroxy-3'-(4-methylphenyl)oxycarbonylaminobenzophenone 242. 2-Hydroxy-5-methyl-3'-(4-tert-butylphenyl)oxycarbonylaminobenzophenone 243. 3-Hydroxy-2'-(4-cyclohexylphenyl)oxycarbonylamino-5'-chlorobenzophenone 244. 4-Hydroxy-3,5-di-tert-butyl-4'-(4-cumylphenyl)oxycarbonylaminobenzophenone 245. 1-(4'-Hydroxyphenyl)-2-(4"-allyloxycarbonylaminophenyl)ethane 246. 1-(4'-Hydroxyphenyl)-2-[4"-(4-phenylphenyl)oxycarbonylphenyl]ethane 247. 1-(2',5'-Dihydroxyphenyl)-2-[3"-methoxy-4"-(4-methoxyphenyl)oxycarbonylaminophenyl]ethane 248. 1-(3'-Hydroxyphenyl)-3-[3"-(2-methoxyethyl)oxycarbonylaminophenyl]propane 249. 1-(3'-Hydroxyphenyl)-3-[4"-(3-methoxymethylphenyl)oxycarbonylaminophenyl]propane 250. 1-(4'-Hydroxyphenyl)-2-[4"-(2-n-butoxyethyl)oxycarbonylaminophenyl]ethene 251. 1-(4'-Hydroxyphenyl)-2-[4"-(4-allyloxyphenyl)oxycarbonylaminophenyl]ethene 252. 3-(4'-Hydroxyphenyl)-4-[4"-(2-methoxyethoxyethyl)oxycarbonylaminophenyl]-3-hexene 253. 3-(4'-Hydroxyphenyl)-4-[4"-(4-benzyloxyphenyl)oxycarbonylaminophenyl]-3-hexene 254. 3-(4'-Hydroxyphenyl)-4-[3"-(2-benzyloxyphenyl)oxycarbonylamino-4"-hydroxyphenyl]-3-hexene 255. 1-(4"-Hydroxyphenyl)-4-[4"-(2-allyloxyethyl)oxycarbonylaminophenyl]oxybenzene 256. 1-(4'-Hydroxyphenyl)-4-[4"-(4-octyloxyphenyl)oxycarbonylaminophenyl]oxybenzene 257. 4'-(2-Benzyloxyethyl)oxycarbonylaminophenyl2-hydroxybenzoate 258. 4'-(4-Phenoxyphenyl)oxycarbonylaminophenyl2-hydroxybenzoate 259. 3'-(2-Benzyloxyethoxyethyl)oxycarbonylamino-4'-chlorophenyl 4-hydroxy-3,5-di-tert-butylbenzoate 260. 3'-(4-Acetylphenyl)oxycarbonylamino-4'-chlorophenyl 4-hydroxy-3,5-di-tert-butylbenzoate 261. 1-(4'-Hydroxyphenyl)-2-[2"-hydroxy-4"-(2-phenoxyethyl)oxycarbonylaminophenylcarbonyl]ethane 262. 1-(4'-Hydroxyphenyl)-2-[2"-hydroxy-4"-(4-benzylcarbonylphenyl)oxycarbonylaminophenylcarbonyl]ethane 263. 1-(4'-Hydroxyphenyl)-2-[2"-hydroxy-4"-(2-tetrahydrofurfuryl)oxycarbonylaminophenylcarbonyl]ethene 264. 1-(4'-Hydroxyphenyl)-2-[2"-hydroxy-4"-(4-methoxycarbonylphenyl)oxycarbonylaminophenylcarbonyl]ethene 265. 1-(4'-Hydroxyphenyl)-2-[4"-(2-chloroethyl)oxycarbonylaminophenyl]ethene 266. 1-(4'-Hydroxyphenyl)-2-[4"-(4-acetyloxycarbonylphenyl)oxycarbonylaminophenyl]ethene 267. 1-(2',4',6'-Trihydroxyphenylcarbonyl)-1-(4"-benzyloxycarbonylaminophenyl)methane 268. 1-(2',4',6'-Trihydroxyphenylcarbonyl)-1-[4"-(4-phenylcarbonyloxyphenyl)oxycarbonylaminophenyl]methane 269. 3-(4'-Hydroxyphenyl)-4-[4"-(4-chlorobenzyl)oxycarbonylaminophenyl]hexane 270. 3-(4'-Hydroxyphenyl)-4-[4"-(4-methylthiophenyl)oxycarbonylaminophenyl]hexane 271. 1-(4'-Hydroxyphenyloxy)-2-[4"-(4-allylbenzyl)oxycarbonylaminophenyloxy]ethane 272. 1-(4'-Hydroxyphenyloxy)-4-[4"-(4"-chlorophenyl)oxycarbonylaminophenyloxy]butane 273. 1-(4'-Hydroxyphenyloxy)-5-[4"-(3-hydroxybenzyl)oxycarbonylaminophenyloxy]pentane 274. 1-(4'-Hydroxyphenyloxy)-6-[4"-(4-nitrophenyl)oxycarbonylaminophenyloxy]hexane 275. 1-(4'-Hydroxyphenylcarbonyl)-1-[4"-(4-hydroxy-3methoxybenzyl)oxycarbonylaminophenylcarbonyl]methane 276. 1-(4'-Hydroxyphenylcarbonyl)-1-[4"-(2,4-dimethylphenyl)oxycarbonylaminophenylcarbonyl]methane 277. 1-(3'-Methoxy-4'-hydroxyphenylcarbonyl)-1-[4"-(4-chlorobenzyl)oxycarbonylaminophenylcarbonyl]methane 278. 1-(3'-Methoxy-4'-hydroxyphenylcarbonyl)-1-[4"-(2,4,6-trichlorophenyl)oxycarbonylaminophenylcarbonyl]methane 279. 1-(4'-Hydroxyphenylcarbonyl)-1-[3"-(2-furfuryl)oxycarbonylaminophenylcarbonyloxy]methane 280. 1-(4'-Hydroxyphenylcarbonyl)-1-[3"-(2,4,6-trimethoxyphenyl)oxycarbonylaminophenylcarbonyloxy]methane 281. 2-(4'-Hydroxyphenyl)-2-(4"-methylaminocarbonyloxyphenyl]propane 282. 2-(4'-Hydroxyphenyl)-2-(4"-n-octylaminocarbonyloxyphenyl)propane 283. 2-(4'-Hydroxyphenyl)-2-(4"-cyclohexylaminocarbonyloxyphenyl)propane 284. 2-(4'-Hydroxyphenyl)-2-[4"-(2-tetrahydrofurfuryl)aminocarbonyloxyphenyl]propane 285. 2-(4'-Hydroxyphenyl)-2-[4"-(2-methoxyethyl)aminocarbonyloxyphenyl]propane 286. 2-(4'-Hydroxyphenyl)-2-[4"-(2-methoxyethoxyethyl)aminocarbonyloxyphenyl]propane 287. 2-(4'-Hydroxyphenyl)-2-[4"-(3-chloropropyl)aminocarbonyloxyphenyl]propane 288. 2-(4'-Hydroxyphenyl)-2-(4"-allylaminocarbonyloxyphenyl)propane 289. 2-(4'-Hydroxyphenyl)-2-[4"-(4-methylbenzyl)aminocarbonyloxyphenyl]propane 290. 2-(4'-Hydroxyphenyl)-2-(4"-phenylaminocarbonyloxyphenyl) propane 291. 2-(4'-Hydroxyphenyl)-2-[4"-(1-naphthyl)aminocarbonyloxyphenyl]propane 292. 2-(4'-Hydroxyphenyl)-2-[4"-(4-phenylphenyl)aminocarbonyloxyphenyl ]propane 293. 2-(4'-Hydroxyphenyl)-2-[4"-(4-methylphenyl)aminocarbonyloxyphenyl]propane 294. 2-(4'-Hydroxyphenyl)-2-[4"-(4-methoxyphenyl)aminocarbonyloxyphenyl]propane 295. 2-(4'-Hydroxyphenyl)-2-[4"-(4-chlorophenyl)aminocarbonyloxyphenyl]propane 296. 2-(4'-Hydroxyphenyl)-2-[4"-(4-acetylphenyl)aminocarbonyloxyphenyl]propane 297. 2-(4'-Hydroxyphenyl)-2-[4"-(4-ethoxycarbonylphenyl)aminocarbonyloxyphenyl]propane 298. 2-(4'-Hydroxyphenyl)-2-[4"-(4-phenylcarbonylphenyl)aminocarbonyloxyphenyl] propane 299. 2-(4'-Hydroxyphenyl)-2-[4"-(2-chloro-6-methylphenyl)aminocarbonyloxyphenyl]propane 300. 2-(4'-Hydroxyphenyl)-2-[4"-(2,4-dimethylphenyl)aminocarbonyloxyphenyl]propane 301. 2-(3'-Methyl-4'-hydroxyphenyl)-2-(3"-methyl-4"-ethylaminocarbonyloxyphenyl)propane 302. 2-(3'-Methyl-4'-hydroxyphenyl)-2-(3"-methyl-4"-phenylaminocarbonyloxyphenyl)propane 303. 2-(3',5'-Di-tert-butyl-4'-hydroxyphenyl)-2-(3",5"-di-tert-butyl-4"-n-butylaminocarbonyloxyphenyl)propane 304. 2-(3'-chloro-4'-hydroxyphenyl)-2-(3"-chloro-4"-phenylaminocarbonyloxyphenyl)propane 305. 1-(4'-Hydroxyphenyl)-1-(4"-phenylaminocarbonyloxyphenyl)cyclopentane 306. 1-(4'-Hydroxyphenyl)-1-(4"-methylaminocarbonyloxyphenyl)cyclohexane 307. 1-(4'-Hydroxyphenyl)-1-(4"-phenylaminocarbonyloxyphenyl)cyclohexane 308. 1-(4'-Hydroxyphenyl)-1-(4"-n-propylaminocarbonyloxyphenyl)cycloheptane 309. 1-(4'-Hydroxyphenyl)-1-(4"-phenylaminocarbonyloxyphenyl)cyclooctane 310. 1-(4'-Hydroxyphenyl)-1-(4"-methylaminocarbonyloxyphenyl)methane 311. 1-(4'-Hydroxyphenyl)-1-(4"-benzylaminocarbonyloxyphenyl)methane 312. 1-(4'-Hydroxyphenyl)-1-(4"-phenylaminocarbonyloxyphenyl)methane 313. 2-(4'-Hydroxyphenyl)-2-(4"-methylaminocarbonyloxyphenyl)butane 314. 2-(4'-Hydroxyphenyl)-2-(4"-phenylaminocarbonyloxyphenyl)isohexane 315. 1-(4'-Hydroxyphenyl)-1-(4"-phenylaminocarbonyloxyphenyl)-1-phenylethane 316. 1-(3'-Methyl-4'-hydroxyphenyl)-1-(3"-methyl-4"-phenylaminocarbonyloxyphenyl)methane 317. 1-(3'-Methyl-4'-hydroxyphenyl)-1-(3"-methyl-4"-(4-chlorophenyl)aminocarbonyloxyphenyl)methane 318. 2-(4'-Hydroxyphenyl)-2-(4"-phenylaminocarbonyloxyphenyl)hexafluoropropane 319. 2-(4'-Hydroxyphenyl)-2-(4"-dimethylaminocarbonyloxyphenyl)propane 320. 2-(4'-Hydroxyphenyl)-2-(4"-N-phenyl-N-methylaminocarbonyloxyphenyl)propane 321. 2-(4'-Hydroxyphenyl)-2-(4"-phenylaminothiocarbonyloxyphenyl)propane 322. 2-(3'-Hydroxyphenyl)-2-(4"-methylaminocarbonyloxyphenyl)propane 323. 2-(4'-Hydroxyphenyl)-2-(3"-ethylaminocarbonyloxyphenyl)propane 324. 2-(2'-Hydroxyphenyl)-2-(4"-phenylaminocarbonyloxyphenyl)propane 325. 2-(4'-Hydroxyphenyl)-2-(2"-n-butylaminocarbonyloxyphenyl)propane 326. 1-(4'-Hydroxyphenyl)-1-(2"-phenylaminocarbonyloxyphenyl)methane 327. 1-(2'-Hydroxyphenyl)-1-(4"-n-butylaminocarbonyloxyphenyl)methane 328. 1-(2'-Hydroxyphenyl)-1-[2"-(4-methylphenyl)aminocarbonyloxyphenyl)methane 329. 4-Hydroxyphenyl-4'-methylaminocarbonyloxyphenyl ether 330. 4-Hydroxyphenyl-4'-n-hexylaminocarbonyloxyphenyl ether 331. 4-Hydroxyphenyl-4'-n-hexadecylaminocarbonyloxyphenyl ether 332. 4-Hydroxyphenyl-4'-cyclohexylaminocarbonyloxyphenyl ether 333. 4-Hydroxyphenyl-4'-(2-methoxyethyl)aminocarbonyloxyphenyl ether 334. 4-Hydroxyphenyl-4'-benzylaminocarbonyloxyphenyl ether 335. 4-Hydroxyphenyl-4'-phenylaminocarbonyloxyphenyl ether 336. 4-Hydroxyphenyl-4'-(4-methylphenyl)aminocarbonyloxyphenyl ether 337. 4-Hydroxyphenyl-4'-(3-chlorophenyl)aminocarbonyloxyphenyl ether 338. 4-Hydroxyphenyl-4'-(2,4-dimethylphenyl)aminocarbonyloxyphenyl ether 339. 4-Hydroxyphenyl-4'-phenylaminothiocarbonyloxyphenyl ether 340. 2-Hydroxyphenyl-2'-methylaminocarbonyloxyphenyl ether 341. 2-Hydroxyphenyl-2'-(4-methylbenzyl)aminocarbonyloxyphenyl ether 342. 2-Hydroxyphenyl-2'-phenylaminocarbonyloxyphenyl ether 343. 2-Hydroxyphenyl-2'-(4-methoxyphenyl)aminocarbonyloxyphenyl ether 344. 2-Hydroxyphenyl-2'-(4-chlorophenyl)aminocarbonyloxyphenyl ether 345. 2-Hydroxyphenyl-2'-(3-chlorophenyl)aminocarbonyloxyphenyl ether 346. 4-Hydroxyphenyl-4'-ethylaminocarbonyloxyphenyl sulfide 347. 4-Hydroxyphenyl-4'-n-octylaminocarbonyloxyphenyl sulfide 348. 4-Hydroxyphenyl-4'-cyclohexylaminocarbonyloxyphenyl sulfide 349. 4-Hydroxyphenyl-4'-(2-phenoxyethyl)aminocarbonyloxyphenyl sulfide 350. 4-Hydroxyphenyl-4'-allylaminocarbonyloxyphenyl sulfide 351. 4-Hydroxyphenyl-4'-(4-methylbenzyl)aminocarbonyloxyphenyl sulfide 352. 4-Hydroxyphenyl-4'-phenylaminocarbonyloxyphenyl sulfide 353. 4-Hydroxyphenyl-4'-(2-chlorophenyl)aminocarbonyloxyphenyl sulfide 354. 4-Hydroxyphenyl-4'-(4-acetyloxyphenyl)aminocarbonyloxyphenyl sulfide 355. 4-Hydroxyphenyl-4'-(4-chloro-3-methylphenyl)aminocarbonyloxyphenyl sulfide 356. 4-Hydroxyphenyl-4'-(2,4-dimethylphenyl)aminocarbonyloxyphenyl sulfide 357. 3-Methyl-4-Hydroxyphenyl-3'-methyl-4'-phenylaminocarbonyloxyphenyl sulfide 358. 3,5-Dichloro-4-Hydroxyphenyl-3',5'-dichloro-4'-phenylaminocarbonyloxyphenyl sulfide 359. 4-Hydroxyphenyl-4'-phenylaminothiocarbonyloxyphenyl sulfide 360. 2-Hydroxyphenyl-2'-methylaminocarbonyloxyphenyl sulfide 361. 2-Hydroxyphenyl-2'-phenylaminocarbonyloxyphenyl sulfide 362. 2-Hydroxy-3,5-dichlorophenyl-2'-phenylaminocarbonyloxy-3',5'-dichlorophenyl sulfide 363. 4-Hydroxyphenyl-4'-phenylaminocarbonyloxyphenyl sulfoxide 364. 4-Hydroxyphenyl-4'-phenylaminocarbonyloxyphenyl sulfone 365. 4"-Methylaminocarbonyloxyphenyl-4-(4'-hydroxy)phenylbenzoate 366. 4"-Phenylaminocarbonyloxyphenyl 4-(4'-hydroxy)phenylbenzoate 367. 4-Hydroxyphenyl 4-n-butylaminocarbonyloxybenzoate 368. 4-Hydroxyphenyl 4-phenylaminocarbonyloxybenzoate 369. 4-Hydroxy-4'-ethylaminocarbonyloxybiphenyl 370. 4-Hydroxy-4'-cyclohexylaminocarbonyloxybiphenyl 371. 4-Hydroxy-4'-(2-methoxyethyl)aminocarbonyloxybiphenyl 372. 4-Hydroxy-4'-benzylaminocarbonyloxybiphenyl 373. 4-Hydroxy-4'-phenylaminocarbonyloxybiphenyl 374. 4-Hydroxy-4'-(4-methoxyphenyl)aminocarbonyloxybiphenyl 375. 3,5-Di-tert-butyl-4-hydroxy-3',5'-di-tert-butyl-4'-phenylaminocarbonyloxybiphenyl 376. 2-Hydroxy-2'-n-propylaminocarbonyloxybiphenyl 377. 2-Hydroxy-2'-phenylaminocarbonyloxybiphenyl 378. 1-Hydroxy-4-methylaminocarbonyloxynaphthalene 379. 1-Hydroxy-4-phenylaminocarbonyloxynaphthalene 380. 1-Hydroxy-4-methylaminothiocarbonyloxynaphthalene 381. 1-Hydroxy-5-methylaminocarbonyloxynaphthalene 382. 2-Hydroxy-1-methylaminocarbonyloxynaphthalene 383. 2-Hydroxy-5-ethylaminocarbonyloxynaphthalene 384. 2-Hydroxy-8-methylaminocarbonyloxynaphthalene 385. 2-Hydroxy-8-phenylaminocarbonyloxynaphthalene 386. 1,8-Dihydroxy-4-n-butylaminocarbonyloxynaphthalene 387. 1,8-Dihydroxy-4-methylaminothiocarbonyloxynaphthalene

Examples of the colorless or slightly-colored electron-donating chromogenic compounds usable in the present invention include triarylmethane compounds, diarylmethane compounds, Rhodamine-lactam compounds, fluoran compounds, indolylphthalide compounds, pyridine compounds, spiro compounds and fluorene compounds.

Specific examples of the triarylmethane compounds include 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide [also called "crystal violet lactone"], 3,3-bis(4-dimethylaminophenyl)phthalide, 3-(4-dimethylaminophenyl)-3-(1,3-dimethylindol-3-yl)phthalide, 3-(4 -dimethylaminophenyl)-3-(2-methylindol-3-yl)phthalide, 3,3-bis(9-ethylcarbazol-3-yl)-6-dimethylaminophthalide, 3-(4-dimethylaminophenyl)-3-(1-methylpyrrol-3-yl)-6-dimethylaminophthalide and 3,3-bis[2,2-bis(4-dimethylaminophenyl)ethenyl]-4,5,6,7-tetrachlorophthalide.

Specific examples of the diarylmethane compounds include 4,4-bis-dimethylaminobenzhydrinbenzyl ether, N-halophenyl-leucoauramines and N-2,4,5-trichlorophenylleucoauramine.

Specific examples of the Rhodamine-lactam compounds include Rhodamine-B-anilinolactam, Rhodamine-(4-nitroanilino)lactam and Rhodamine-B-(4-chloroanilino)lactam.

Specific examples of the fluoran compounds include 3,6-dimethoxyfluoran, 3-dimethylamino-7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-6,7-dimethylfluoran, 3-N-cyclohexyl-N-n-butylamino-7-methylfluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-n-octylaminofluoran, 3-diethylamino-7-di-n-hexylaminofluoran, 3-diethylamino-7-anilinofluoran, 3-diethylamino-7-(2-chloroanilino)fluoran, 3-diethylamino-7-(3-chloroanilino) fluoran, 3-diethylamino-7-(2,3-dichloroanilino)fluoran, 3-diethylamino- 7-(3-trifluoromethylanilino)fluoran, 3-di-n-butylamino-7-(2-chloroanilino)fluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-di-n-butylamino-6-chloro-7-anilinofluoran, 3-diethylamino-6-methoxy-7-anilinofluoran, 3-di-n-butylamino-6-ethoxy-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3-morpholino-6-methyl-7-anilinofluoran, 3-dimethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-di-n-butylamino-6-methyl-7-anilinofluoran, 3-di-n-pentylamino-6-methyl-7-anilinofluoran, 3-di-n-octylamino-6-methyl-7-anilinofluoran, 3-N-ethyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-n-propyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-n-propyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-isopropyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-n-butyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-n-butyl-N-n-ethylamino-6-methyl-7-anilinofluoran, 3-N-n-butyl-N-n-propylamino-6-methyl-7-anilinofluoran, 3-N-isobutyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-isobutyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-isopentyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-n-hexyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-n-octyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-N-n-propylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-N-n-butylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-N-n-pentylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-N-n-hexylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-N-n-heptylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-N-n-octylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-N-n-decylamino-6-methyl-7-anilinofluoran, 3-N-2'-methoxyethyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-2'-methoxyethyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-2'-ethoxyethyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-2'-ethoxyethyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-3'-methoxypropyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-3'-ethoxypropyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-2'-methoxyethyl-N-isobutylamino-6-Methyl-7-anilinofluoran, 3-N-2'-tetrahydrofurfuryl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-(4'-methylphenyl)-N-ethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-ethyl-7-anilinofluoran, 3-di-ethylamino-6-methyl-7-(2',6'-dimethylphenylamino)fluoran, 3-di-n-butylamino-6-methyl-7-(2',6'-dimethylphenylamino)fluoran, 3-di-n-butylamino-7-(2',6'-dimethylphenylamino)fluoran and 2,2-bis[4'-(3-N-cyclohexyl-N-methylamino-6-methylfluoran)-7-ylaminophenyl]propane.

Specific examples of the indolylphthalide compounds include 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-octyl-2-methylindol-3-yl)phthalide, 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3-(2-ethoxy-4-dibutylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3-(2-ethoxy-4-diethylaminophenyl)-3-(1octyl-2-methylindol-3-yl)phthalide.

Specific examples of the pyridine compounds include 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-octyl-2methylindol-3-yl)-4- and -7-azaphthalides, 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4- and -7-azaphthalides, 3-(2-hexyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4- and -7-azaphthalides, 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-phenylindol-3-yl)-4- and -7-azaphthalides, and 3-(2-butoxy-4-diethylaminophenyl)-3-(1-ethyl-2-phenylindol-3-yl)-4- and -7-azaphthalides.

Specific examples of the spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxybenzo)spiro-pyran and 3-propyl-spiro-dibenzopyran.

Specific examples of the fluorene compounds include 3',6'-bisdiethylamino-5-diethylaminospiro(isobenzofuran-1,9'-fluoren)-3-on and 3',6'-bisdiethylamino-7-diethylamino-2-methylspiro(1,3-benzooxazine-4,9'-fluorene).

These electron-donating chromogenic compounds can be used either singly or, to adjust the tone of color images to be produced or to obtain a multi-color heat-sensitive recording material or for other purposes, in combination.

In the heat-sensitive recording material according to the present invention, it is generally desirable to use the electron-attracting compound in an amount of 50-700 parts by weight, preferably 100-500 parts by weight per 100 parts by weight of the electron-donating chromogenic compound. As has already been mentioned above, the heat-sensitive recording material according to this invention can also use, as an electron-attracting compound, an electron-attracting compound other than the compound represented by the formula (1) or (2) in combination with the latter compound.

In particular, a heat-sensitive recording material using, as an electron-attracting compound, the compound represented by the formula (1) or (2) in combination with another electron-attracting compound is excellent in the storage stability (hydrothermo-resistance, waterproofness, oil resistance, etc.) of color images to be produced, and is preferred.

In this case, it is generally desirable to control the proportion of the compound represented by the formula (1) or (2) to at least 5 wt. %, preferably 20 wt. % or more, more preferably 30 wt. % or more, all based on the whole electron-attracting compounds.

Examples of electron-attracting compounds other than the compounds represented by the formula (1) or (2) include organic electron-attracting compounds such as phenol derivatives, organic acids and metal salts thereof, complexes and urea derivatives; and inorganic electron-attracting compounds such as acid clay.

Specific examples of these compounds include organic electron-attracting compounds, for example, phenol derivatives such as 4-tert-butylphenol, 4-tert-octylphenol, 4-phenylphenol, 1-naphthol, 2-naphthol, hydroquinone, resorcinol, 4-tert-octylcatechol, 2,2'-dihydroxydiphenyl, 2,2-bis(4'-hydroxyphenyl)propane [also called "bisphenol A"], 1,1-bis(4'-hydroxyphenyl)cyclohexane, 2,2-bis(4'-hydroxy-3'-methylphenyl)propane, ethyl 2,2-bis(4'-hydroxyphenyl)acetate, n-butyl 4,4-(4'-hydroxyphenyl)pentanoate, benzyl 4-hydroxybenzoate, phenethyl 4-hydroxybenzoate, phenoxyethyl 2,4-dihydroxybenzoate, dimethyl 4-hydroxyphthalate, hydroquinonmonobenzyl ether, bis(3-methyl-4-hydroxyphenyl) sulfide, bis(2-methyl-4-hydroxyphenyl) sulfide, bis(3-phenyl-4-hydroxyphenyl) sulfide, bis(3-cyclohexyl-4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfone, bis(3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-methyldiphenyl sulfone, 4-hydroxy-4'-chlorodiphenyl sulfone, 4-hydroxy-4'-n-propoxydiphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4-hydroxy-4'-n-butoxydiphenyl sulfone, 3,4-dihydroxy-4'-methyldiphenyl sulfone, bis(2-hydroxy-4-tert-butylphenyl) sulfone, bis(2-hydroxy-4-chlorophenyl) sulfone, 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 1,7-di(4-hydroxyphenylthio)-3,5-dioxaheptane and 1,5-di(4-hydroxyphenylthio)-3-oxapentane, organic acids such as salicyclic acid, 3-isopropylsalicyclic acid, 3-cyclohexylsalicyclic acid, 3,5-di-tert-butylsalicyclic acid, 3,5-di-.alpha.-methylbenzylsalicyclic acid, 3-methyl-5-.alpha.-methylbenzylsalicyclic acid, 4-[2'-(4-methoxyphenyloxy)ethyloxy]-salicylic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, monobenzyl phthalate and monophenyl phthalate and metallic salts thereof (ex. nickel, zinc, aluminum and calcium salts), complexes such as zinc thiocyanate/antipyrine complexes and molybdic acid/acetylacetone complexes and urea derivatives such as phenylthiourea, di(3-trifluoromethylphenyl)thiourea and 1,4-di(3'-chlorophenyl)-3-thiosemicarbazide; and inorganic electron-attracting compounds such as acid clay, attapulgite, activated clay, aluminum chloride, zinc chloride and zinc bromide. Among them, phenol derivatives are particularly preferred as electron-attracting compounds.

These electron-attracting compounds can be used either singly or in combination.

In addition, in the heat-sensitive recording material according to the present invention, a thermo-fusible compound (a compound whose melting point is 60.degree.-150.degree. C., preferably about 80.degree.-130.degree. C.) can be added further to improve the color-producing sensitivity, if desired. This is preferred as it makes it possible to obtain a heat-sensitive recording material which is good in color-producing sensitivity and excellent in the storage stability of a color image to be produced. Particularly preferred are heat-sensitive recording materials using, as an electron-attracting compound, the compound represented by the formula (1) or (2) and the above-mentioned, known, electron-attracting compound (for example, one of the various phenol derivatives) in combination and heat-sensitive recording materials added further with a thermofusible compound.

In this case, it is generally desirable to use the thermofusible compound in an amount of 10-700 parts by weight, preferably 20-500 parts by weight per 100 parts by weight of the electron-donating chromogenic compound. Specific examples of such thermofusible compounds include nitrogen-containing compounds such as stearic acid amide, palmitic acid amide, stearyl urea, N-ethylcarbazole and 4-methoxydiphenylamine; esters such as benzyl 4-benzyloxybenxoate, phenyl 2-naphthoate, phenyl 1-hydroxy-2-naphthoate, dibenzyl oxalate, di(4-methylbenzyl) oxalate, di(4-chlorobenzyl) oxalate, diphenacyl glutarate, di(4-methylphenyl) carbonate and dibenzyl terephthalate; hydrocarbon compounds such as 4-benzylbiphenyl, m-terphenyl, fluorene and fluoranthene; and ether compounds such as 2-benzyloxynaphthalene, 2-(4'-methylbenzyloxy)naphthalene, 1,4-diethoxynaphthalene, 1,2-bis(3'-methylphenoxy)ethane, 1-phenoxy-2-(4-ethylphenoxy)ethane, 4-(4'-methylphenoxy)biphenyl, 1,4-bis(2'-chlorobenzyloxy)benzene, 4,4'-di-n-butoxydiphenyl sulfone, 1,2-diphenoxybenzene, 1,4-bis(3'-methylphenyloxymethyl)benzene and 4-chlorobenzyloxy(4'-ethoxybenzene). The ester compounds, hydrocarbon compounds and ether compounds are particularly preferred as thermofusible compounds.

These thermofusible compounds can be used either singly or in combination.

To produce the heat-sensitive recording material according to this invention, a conventional process can be followed without the need for relying upon any special process. In the heat-sensitive recording materials according to this invention, no particular limitation is imposed on the method for the formation of the recording layer. For example, a coating formulation for the heat-sensitive recording layer can be coated on a base by a suitable coating means such as an air knife coater, blade coater, bar coater, gravure coater, curtain coater or wire bar, and then dried to form a recording layer.

The coating formulation for the heat-sensitive recording layer can be prepared, generally, by separately grinding and dispersing an electron-donating chromogenic compound, the compound represented by the formula (1) or (2), etc., normally to 3 .mu.m or smaller, preferably to 1.5 .mu.m or smaller in a water-soluble binder in an apparatus such as a ball mill or sand mill and then mixing the resultant dispersions.

Specific examples of usable water-soluble binders include polyvinyl alcohol, hydroxyethylcellulose, hydroxypropylcellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylamide, methylol-modified polyacrylamide, starch derivatives, casein, gelatin, methylcellulose, carboxymethylcellulose, gum arabic, and carboxyl-modified polyvinyl alcohol.

The recording layer of the heat-sensitive recording material according to this invention can be added, as needed, with a pigment, a water-insoluble binder, a metal soap, a wax, a surfactant, an ultraviolet absorber, a hindered phenol, a defoaming agent, etc.

Usable examples of pigments include zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, titanium oxide, talc, agalmatolite, kaolin, diatomaceous earth, aluminum hydroxide, magnesium hydroxide, alumina, silica, amorphous silica, urea-formaldehyde filler, polyethylene particles, and cellulose filler.

As the water-insoluble binder, a synthetic rubber latex or synthetic resin emulsion is usually employed. Known examples include styrene-butadiene rubber latex, acrylonitrile-butadiene latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion. They can be used as needed.

As the metal soap, a higher fatty acid metal salt is used. Usable examples include zinc stearate, calcium stearate, and aluminum stearate.

Illustrative examples of waxes include paraffin wax, microcrystalline wax, carboxyl-modified paraffin wax, carnauba wax, polyethylene wax, polystyrene wax, and higher fatty acid esters.

Examples of surfactants include alkali metal sulfosuccinates and fluorine-containing surfactants.

Examples of ultraviolet absorbers include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives.

Preferred as the hindered phenol is a phenol derivative with a branched alkyl group substituted to at least one of the ortho positions relative to the phenolic hydroxyl group. Examples include 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,1,3tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, 1,1,3-tris(2-ethyl-4-hydroxy-5-tert-butylphenyl)butane, 1,1,3-tris(3,5-di-tert-butyl-4-hydroxyphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)propane, 2,2-methylene-bis-(6-tert-butyl-4-methylphenol), 2,2-methylene-bis-(6-tert-butyl-4-ethylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2-methyl-6-ethylbenzyl)isocyanuric acid, and bis(2-methyl-4-hydroxy-5-tert-butylphenyl) sulfide.

No particular limitation is imposed on the amount of the coating formulation to be applied. It can be coated in an amount sufficient to give a dry weight in a range of 1.5-12 g/m.sup.2, preferably 2.5-10 g/m.sup.2. As the base, a paper sheet, plastic sheet, a synthetic paper sheet or the like can be used.

Various techniques known in the production of heat-sensitive recording materials can be applied as needed. For example, a protective layer can be arranged on the upper and/or lower surfaces of the heat-sensitive recording layer, or a prime coat can be provided between the base and the heat-sensitive recording layer. Further, tackifying treatment can also be applied.

The present invention will hereinafter be described specifically by the following preparation examples and examples. It should however be borne in mind that this invention is by no means limited to or by the examples In the examples, all designations of "%" mean wt. %.

Preparation Example 1 (Preparation of Exemplified Compound No. 1)

Methyl chloroformate (22.7 g) was added dropwise to a suspension of 45.4 g of 2-(4'-hydroxyphenyl)-2-(4"-aminophenyl)propane and 10.6 g of sodium carbonate in 300 ml of ethyl acetate. After they were reacted at room temperature under stirring for 12 hours, the reaction mixture was filtered. Water (200 ml) was added to the resultant filtrate to wash the same. That procedure was repeated until the water layer became neutral. The reaction mixture was allowed to separate into layers. The ethyl acetate layer was collected and, then, ethyl acetate was distilled off under reduced pressure at 40.degree. C., whereby a slightly yellowish crude product was obtained in a solid form. The product was recrystallized from 150 ml of toluene and then dried at 40.degree. C. for 24 hours, whereby 51.3 g of 2-(4'-hydroxyphenyl)-2-(4"-methoxycarbonylaminophenyl)propane were obtained as white crystals.

yield: 90%. Melting Point: 104.degree.-105.5.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3):1.6(s,6H) , 3.8(s,3H), 5.1(s,1H) , 6.5-7.4(m,9H).

Preparation Example 2(Preparation of Exemplified Compound No. 2)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by n-propyl chloroformate, 2-(4'-hydroxyphenyl)-2-(4"n-propoxycarbonylaminophenyl)propane was obtained.

Melting Point: 146.degree.-147.5.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 0.8-1.1(t,3H), 1.6(s,6H) 1.7-1.9(m,2H), 4.0-4.2(t,2H), 5.4(s,1H), 6.5-7.4(m,9H).

Preparation Example 3 (Preparation of Exemplified Compound No. 3)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by n-butyl chloroformate, 2-(4'-hydroxyphenyl)-2-(4"-n-butoxycarbonylaminophenyl)propane was obtained.

Melting Point: 89.degree.-91.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 0.9-1.1(t,3H), 1.3-1.9(m,10H), 4.1-4.3(m,2H), 5.4-5.6(br,1H), 6.6-7.4(m,9H).

Preparation Example 4 (Preparation of Exemplified Compound No. 5)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by n-hexadecyl chloroformate, 2-(4'-hydroxyphenyl)-2-(4"-n-hexadecyloxycarbonylaminophenyl)propane was obtained.

Melting Point: 63.5.degree.65.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 0.9-1.1(t,3H), 1.1-2.0(m,36H), 4.1-4.3(t,2H), 5.4-5.6(br,1H) , 6.6-7.4(m,9H). Preparation Example 5 (Preparation of Exemplified Compound No. 6)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by cyclohexyl chloroformate, 2-(4'-hydroxyphenyl)-2-(4"-cyclohexyloxycarbonylaminophenyl)propane was obtained.

Melting Point: 136.degree.-137.5.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.1-2.1(m,16H), 4.7-4.9(br,1H), 5.3-5.5(br,1H), 6.5-7.5(m,9H).

Preparation Example 6 (Preparation of Exemplified Compound No. 9)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 2-methoxyethyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"-(2-methoxyethyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 84.degree.-86.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 3.4(s,3H), 3.6-3.8(m,2H), 4.2-4.4(m,2H), 5.8-6.0(br,1H), 6.6-7.4(m,9H) . Preparation Example 7 (Preparation of Exemplified Compound No. 14)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 2-phenoxyethyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"-(2-phenoxyethyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 98.degree.-100.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 4.1-4.3(m,2H), 4.4-4.6(m,2H), 5.3-5.5(br,1H), 6.6-7.4(m,14H).

Preparation Example 8 (Preparation of Exemplified Compound No. 17)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by allyl chloroformate, 2-(4'-hydroxyphenyl)-2-(4"-allyloxycarbonylaminophenyl)propane was obtained.

Melting Point: 109.degree.-111.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 4.6-4.8(d,2H), 5.1-5.5(m,3H), 5.7-6.2(m,1H), 6.6-7.4(m,9H).

Preparation Example 9 (Preparation of Exemplified Compound No. 18)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by benzyl chloroformate, 2-(4'-hydroxyphenyl)-2-(4"-benzyloxycarbonylaminophenyl)propane was obtained.

Melting Point: 69.degree.-74.degree. C. .sup.1 H-NMR, .delta.(CDCl .sub.3): 1.6(s,6H), 5.0-5.2(m,2H) , 5.3(s,1H), 6.6-7.4(m,14H).

Preparation Example 10 (Preparation of Exemplified Compound No. 23)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 2-phenylethyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"-(2-Phenylethyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 121.degree.-123.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 2.8-3.1(t,2H) , 4.2-4.5(t,2H), 5.4-5.5(br,1H), 6.6-7.4(m,14H) .

Preparation Example 11 (Preparation of Exemplified Compound No. 24)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by phenyl chloroformate, 2-(4'-hydroxyphenyl)-2-(4"-phenyloxycarbonylaminophenyl)propane was obtained.

Melting Point: 116.degree.-120.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 5.3(s,1H), 6.6-7.5(m,14H).

Preparation Example 12 (Preparation of Exemplified Compound No. 26)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 4-phenylphenyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"-(4-phenylphenyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 171.degree.-173.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 5.3(s,1H), 6.6-7.5(m,18H) .

Preparation Example 13 (Preparation of Exemplified Compound No. 27)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 4-methylphenyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"-(4-methylphenyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 146.degree.-148.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 2.4(s,3H), 4.5(br,1H), 6.6-7.4(m,13H).

Preparation Example.sup. 14 (Preparation of Exemplified Compound No. 28)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 3-methylphenyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"-(3-methylphenyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 133.degree.-136.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 2.4(s,3H), 5.0(br,1H), 6.6-7.4(m,13H).

Preparation Example 15 (Preparation of Exemplified Compound No. 30)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 4-cumylphenyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"-(4-cumylphenyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 146.degree.-148.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.5-1.7(m,12H), 4.8(s,1H), 6.6-7.4(m,18H).

Preparation Example 16 (Preparation of Exemplified Compound No. 31)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 4-methoxyphenyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"-(4-methoxyphenyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 125.degree.-127.degree. C. .sup.1 H-NMR, 6(CDCl.sub.3): 1.6(s,6H) , 3.8(s,3H), 5.0(br,1H), 6.6-7.4(m,13H).

Preparation Example 17 (Preparation of Exemplified Compound No. 33)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 4-chlorophenyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"-(4-chlorophenyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 162.degree.-164.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 4.6(s,1H), 6.6-7.4(m, 13H).

Preparation Example 18 (Preparation of Exemplified Compound No. 34)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 2-chlorophenyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"(2-chlorophenyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 97.degree.-99.degree. C. .sup.1 H-NMR, .delta.(CDCl .sub.3): 1.6(s,6H), 4.6(s,1H), 6.6-7.4(m,13H).

Preparation Example 19 (Preparation of Exemplified Compound No. 41)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by 2,4-dimethylphenyl chloroformate, 2-(4'-hydroxyphenyl)-2-[4"-(2,4-dimethylphenyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 156.degree.-157.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 2.2(s,3H), 2.4(s,3H), 5.0-5.1(br, 1H), 6.6-7.4(m,12H).

Preparation Example 20 (Preparation of Exemplified Compound No. 62)

In a similar manner to Preparation Example 1 except for the replacement of methyl chloroformate by S-phenyl chlorothioformate, 2-(4'-hydroxyphenyl)-2-(phenylthiolcarbonylaminophenyl)propane was obtained.

Melting Point: 118.degree.-121.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 5.3(s,1H), 6.6-7.5(m,14H).

Preparation Example 21 (Preparation of Exemplified Compound No. 65)

Methyl chloroformate (11.4 g) was added dropwise to a suspension of 22.7 g of 2-(3'-hydroxyphenyl)-2-(4"-aminophenyl)propane and 5.3 g of sodium carbonate in 100 ml of ethyl acetate. After they were reacted at room temperature under stirring for 12 hours, the reaction mixture was filtered. Water (200 ml) was added to the resultant filtrate to wash the same. That procedure was repeated until the water layer became neutral. The reaction mixture was allowed to separate into layers. The ethyl acetate layer was collected and, then, ethyl acetate was distilled off under reduced pressure at 40.degree. C., whereby a slightly yellowish crude product was obtained in a solid form. The product was recrystallized from 100 ml of toluene and then dried at 40.degree. C. for 24 hours, whereby 26.2 g of 2-(3'-hydroxyphenyl)-2-(4"-methoxycarbonylaminophenyl)propane were obtained as white crystals.

yield: 92%. Melting Point: 137.degree.-139.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(t,3H), 3.8(s,3H), 5.1(s,1H), 6.5-7.4(m,9H).

Preparation Example 22 (Preparation of Exemplified Compound No. 66)

In a similar manner to Preparation Example 21 except for the replacement of methyl chloroformate by n-butyl chloroformate, 2-(3'-hydroxyphenyl)-2-(4"-n-butoxycarbonylaminophenyl)propane was obtained.

Melting Point: 101.degree.-104.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 0.8-1.1(t,3H), 1.6(s,6H), 1.7-1.9(m,2H) , 4.0-4.2(t,2H), 5.0(s,1H), 6.5-7.4(m,9H).

Preparation Example 23 (Preparation of Exemplified Compound No. 70)

In a similar manner to Preparation Example 21 except for the replacement of methyl chloroformate by phenyl chloroformate, 2-(3'-hydroxyphenyl)-2-(4"-phenyloxycarbonylaminophenyl)propane was obtained.

Melting Point: 119.degree.-124.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,6H), 5.0(br, 1H), 6.6-7.5(m,14H).

Preparation Example 24 (Preparation of Exemplified Compound No. 77)

In a similar manner to Preparation Example 21 except for the replacement of methyl chloroformate by 4-chlorophenyl chloroformate, 2-(3'-hydroxyphenyl)-2-[4"-(4-chlorophenyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 112.degree.-116.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,3H), 5.0(br,1H), 6.6-7.5(m,13H).

Preparation Example 25 (Preparation of Exemplified Compound No. 78)

In a similar manner to Preparation Example 21 except for the replacement of methyl chloroformate by 2-chlorophenyl chloroformate, 2-(3'-hydroxyphenyl)-2-[4"-(2-chlorophenyl)oxycarbonylaminophenyl]propane was obtained.

Melting Point: 95.degree.-101.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.6(s,3H), 5.0(br,1H), 6.6-7.5(m,13H).

Preparation Example 26 (Preparation of Exemplified Compound No. 117)

Methyl chloroformate (5.2 g) was added dropwise to a suspension of 10.0 g of 4-(4'-aminophenoxy)phenol and 4.6 g of sodium hydrogencarbonate in 50 ml of ethyl acetate. They were reacted at room temperature under stirring for 12 hours. Water (100 ml) was thereafter added to the reaction mixture to wash the same. That procedure was repeated until the water layer became neutral. The reaction mixture was allowed to separate into layers. The ethyl acetate layer was collected and, then, ethyl acetate was distilled off under reduced pressure at 40.degree. C., whereby a slightly yellowish crude product was obtained in a solid form. The product was recrystallized from 500 ml of toluene and then dried at 40.degree. C. for 24 hours, whereby 11.0 g of 4-hydroxyphenyl-4'-methoxycarbonylaminophenyl ether were obtained as white crystals.

yield: 85%. Melting Point: 104.degree.-108.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.1(s,3H), 6.7-7.8(m,6H), 7.3-7.8(m,2H), 8.2(s,1H), 8.3-8.4(br,1H).

Preparation Example 27 (Preparation of Exemplified Compound No. 118)

In a similar manner to Preparation Example 26 except for the replacement of methyl chloroformate by ethyl chloroformate, 4-hydroxyphenyl-4'-ethoxycarbonylaminophenyl ether was obtained.

Melting Point: 117.degree.-118.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.2(t,3H), 4.2(q,2H), 6.8-7.0(m,6H), 7.4-7.7(m,2H), 8.1(s,1H), 8.2-8.4(br,1H).

Preparation Example 28 (Preparation of Exemplified Compound No. 119)

In a similar manner to Preparation Example 26 except for the replacement of methyl chloroformate by n-butyl chloroformate, 4-hydroxyphenyl-4'-n-butoxycarbonylaminophenyl ether was obtained.

Melting Point: 118.degree.-119.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.2-4.3(m,9H), 6.8-7.1(m,6H), 7.3-7.6(m,2H), 8.0(s,1H), 8.3-8.4(br,1H).

Preparation Example 29 (Preparation of Exemplified Compound No. 120)

In a similar manner to Preparation Example 26 except for the replacement of methyl chloroformate by n-hexyl chloroformate, 4-hydroxyphenyl-4'-n-hexyloxycarbonylaminophenyl ether was obtained.

Melting Point: 120.degree.-122.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.1-4.1(m,13H), 6.4-6.9(m,6H), 7.4-7.6(m, 2H), 8.1-8.3(br,1H), 8.3(s,1H)

Preparation Example 30 (Preparation of Exemplified Compound No. 121)

In a similar manner to Preparation Example 26 except for the replacement of methyl chloroformate by n-hexadecyl chloroformate, 4-hydroxyphenyl-4'-n-hexadecyloxycarbonylaminophenyl ether was obtained.

Melting Point: 123.degree.-124.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.1-4.5(m,33H), 6.9-7.8(m,8H), 8.1(s,1H), 8.2-8.4(br,1H).

Preparation Example 31 (Preparation of Exemplified Compound No. 122)

In a similar manner to Preparation Example 26 except for the replacement of methyl chloroformate by 2-methoxyethyl chloroformate, 4-hydroxyphenyl-4'-(2-methoxyethyl)oxycarbonylaminophenyl ether was obtained.

Melting Point: 89.degree.-90.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.5(s,3H), 3.6-4.2(m,4H), 6.9-7.1(m,6H), 7.4-7.8(m,2H), 8.1(s,1H), 8.4-8.5(br,1H).

Preparation Example 32 (Preparation of Exemplified Compound No. 125)

In a similar manner to Preparation Example 26 except for the replacement of methyl chloroformate by benzyl chloroformate, 4-hydroxyphenyl-4'-benzyloxycarbonylaminophenyl ether was obtained.

Melting Point: 148.degree.-150.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 4.2(s,2H), 6.9-7.8(m,13H), 8.2(s,1H), 9.0-9.2(br,1H)

Preparation Example 33 (Preparation of Exemplified Compound No. 126)

In a similar manner to Preparation Example 26 except for the replacement of methyl chloroformate by phenyl chloroformate, 4-hydroxyphenyl-4'-phenyloxycarbonylaminophenyl ether was obtained.

Melting Point: 158.degree.-161.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 6.8-7.6(m,13H), 8.2(s,1H), 8.9-9.2(br,1H).

Preparation Example 34 (Preparation of Exemplified Compound No. 128)

In a similar manner to Preparation Example 26 except for the replacement of methyl chloroformate by 4-phenylphenyl chloroformate, 4-hydroxyphenyl-4'-(4-phenylphenyl)oxycarbonylaminophenyl ether was obtained.

Melting Point: 264.degree.-270.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 6.4-7.9(m,17H), 8.2(s,1H), 8.9-9.2(br,1H).

Preparation Example 35 (Preparation of Exemplified Compound No. 131)

In a similar manner to Preparation Example 26 except for the replacement of methyl chloroformate by 3-chlorophenyl chloroformate, 4-hydroxyphenyl-4'-(3 -chlorophenyl)oxycarbonylaminophenyl ether was obtained.

Melting Point: 121.degree.-125.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 6.8-7.9(m,12H), 8.4(s,1H), 8.7-9.1(br,1H).

Preparation Example 36 (Preparation of Exemplified Compound No. 134)

In a similar manner to Preparation Example 26 except for the replacement of methyl chloroformate by S-phenyl chlorothioformate, 4-hydroxyphenyl-4'-phenylthiolcarbonylaminophenyl ether was obtained.

Melting Point: 138.degree.-140.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 6.6-7.9(m,13H), 8.1(s,1H), 9.0-9.2(br,1H).

Preparation Example 37 (Preparation of Exemplified Compound No. 136)

Methyl chloroformate (11.3 g) was added dropwise to a suspension of 20.0 g of 3-(4'-aminophenoxy)phenol and 9.2 g of sodium hydrogencarbonate in 100 ml of ethyl acetate. They were reacted at room temperature under stirring for 9 hours. Water (100 ml) was thereafter added to the reaction mixture to wash the same. That procedure was repeated until the water layer became neutral. The reaction mixture was allowed to separate into layers. The ethyl acetate layer was collected and, then, ethyl acetate was distilled off under reduced pressure at 40.degree. C., whereby a slightly brownish crude product was obtained in a solid form. The product was recrystallized from 700 ml of toluene and then dried at 40.degree. C. for 24 hours, whereby 21.7 g of 3-hydroxyphenyl-4'-methoxycarbonylaminophenyl ether were obtained as white crystals.

yield: 80%. Melting Point: 95.degree.-96.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.1(s,3H), 6.7-7.1l(m,6H), 7.3-7.8(m,8H), 8.5(s,1H), 9.0-9.3(br,1H).

Preparation Example 38 (Preparation of Exemplified Compound No. 137)

In a similar manner to Preparation Example 37 except for the replacement of methyl chloroformate by ethyl chloroformate, 3-hydroxyphenyl-4'-ethoxycarbonylaminophenyl ether was obtained.

Melting Point: 126.degree.-128.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.2(t,3H), 4.1(q,2H), 6.3-7.8(m,8H), 8.3-8.7(m,2H).

Preparation Example 39 (Preparation of Exemplified Compound No. 138)

In a similar manner to Preparation Example 37 except for the replacement of methyl chloroformate by n-octyl chloroformate, 3-hydroxyphenyl-4'-n-octyloxycarbonylaminophenyl ether was obtained.

Melting Point: 102.degree.-104.degree. C.

Preparation Example 40 (Preparation of Exemplified Compound No. 140)

In a similar manner to Preparation Example 37 except for the replacement of methyl chloroformate by phenyl chloroformate, 3-hydroxyphenyl-4'-phenyloxycarbonylaminophenyl ether was obtained.

Melting Point: 132.degree.-134.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 6.3-6.7(m,5H), 6.9-7.8(m,8H), 8.5(s,1H), 9.0-9.3(br,1H).

Preparation Example 41 (Preparation of Exemplified Compound No. 144)

In a similar manner to Preparation Example 37 except for the replacement of methyl chloroformate by 4-methoxyphenyl chloroformate, 3-hydroxyphenyl-4'-(3methoxyphenyl)oxycarbonylaminophenyl ether was obtained.

Melting Point: 133.degree.-136.degree. C.

Preparation Example 42 (Preparation of Exemplified Compound No. 145)

In a similar manner to Preparation Example 37 except for the replacement of methyl chloroformate by 3-chlorophenyl chloroformate, 3-hydroxyphenyl-4'-(3chlorophenyl)oxycarbonylaminophenyl ether was obtained.

Melting Point: 101.degree.-110.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 6.5-7.6(m,5H), 6.9-7.8(m,7H), 8.6(s,1H), 9.0-9.3(br,1H).

Preparation Example 43 (Preparation of Exemplified Compound No. 157)

Ethyl chloroformate (8.3 g) was added dropwise to a suspension of 14.9 g of 4-amino-4'-hydroxydiphenyl sulfide and 6.0 g of sodium hydrogencarbonate in 50 ml of ethyl acetate. They were reacted at room temperature under stirring for 12 hours. Water (200 ml) was thereafter added to the reaction mixture to wash the same. That procedure was repeated until the water layer became neutral. The reaction mixture was allowed to separate into layers. The ethyl acetate layer was collected and, then, ethyl acetate was distilled off under reduced pressure at 40.degree. C., whereby a slightly yellowish crude product was obtained in a solid form. The product was recrystallized from 500 ml of toluene and then dried at 40.degree. C. for 24 hours, whereby 17.3 g of 4-hydroxyphenyl-4'-ethoxycarbonylaminophenyl sulfide were obtained as white crystals.

yield: 87%. Melting Point: 87.degree.-88.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.3(t,3H), 4.2(q,2H), 5.3(br,1H), 6.7-6.9(m,3H), 7.0-7.4(m,6H).

Preparation Example 44 (Preparation of Exemplified Compound No. 158)

In a similar manner to Preparation Example 43 except for the replacement of ethyl chloroformate by isobutyl chloroformate, 4-hydroxyphenyl-4'-isobutoxycarbonylaminophenyl sulfide was obtained.

yield: 64%. Melting Point: 114.degree.-116.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 0.9(d,6H), 1.8-2.0(m,1H), 3.9(d,2H), 5.1(br,1H), 6.7-6.9(m,3H), 7.1-7.4(m,6H).

Preparation Example 45 (Preparation of Exemplified Compound No. 159)

In a similar manner to Preparation Example 43 except for the replacement of ethyl chloroformate by n-hexadecyl chloroformate, 4-hydroxyphenyl-4'-n-hexadecyloxycarbonylaminophenyl sulfide was obtained.

yield: 83%. Melting Point: 114.degree.-116.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.3(br,31H), 4.1(t,2H), 5.0(br,1H), 6.7-6.9(m,3H), 7.2-7.4(m,6H).

Preparation Example 46 (Preparation of Exemplified Compound No. 161)

In a similar manner to Preparation Example 43 except for the replacement of ethyl chloroformate by 2-methoxyethyl chloroformate, 4-hydroxyphenyl-4'-(2-methoxyethyl)oxycarbonylaminophenyl sulfide was obtained.

Melting Point: 82.degree.-84.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 3.4(s,3H), 3.6-3.7(m,2H), 4.3-4.4(m,2H), 5.2(br,1H), 6.6-6.9(m,3H), 7.1-7.7 (m,6H).

Preparation Example 47 (Preparation of Exemplified Compound No. 165)

In a similar manner to Preparation Example 43 except for the replacement of ethyl chloroformate by phenyl chloroformate, 4-hydroxyphenyl-4'-phenyloxycarbonylaminophenyl sulfide was obtained.

Melting Point: 151.degree.-153.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 4.9(br,1H), 6.7-6.9(m,3H), 7.1-7.6(m,11H)

Preparation Example 48 (Preparation of Exemplified Compound No. 172)

In a similar manner to Preparation Example 43 except for the replacement of ethyl chloroformate by S-phenyl chlorothioformate, 4-hydroxyphenyl-4'-phenylthiolcarbonylaminophenyl sulfide was obtained.

Melting Point: 243.degree.-248.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 5.1(br,1H), 6.8-6.9(m,3H), 7.3-7.8(m,11H)

Preparation Example 49 (Preparation of Exemplified Compound No. 192)

Phenyl chloroformate (15.0 g) was added dropwise to a suspension of 26.4 g of 4"-aminophenyl-4-(4'-hydroxy)phenylbenzoate and 8.0 g of sodium hydrogencarbonate in 120 ml of ethyl acetate. They were reacted at room temperature under stirring for 12 hours. Water (300 ml) was thereafter added to the reaction mixture to wash the same. That procedure was repeated until the water layer became neutral. The reaction mixture was allowed to separate into layers. The ethyl acetate layer was collected and, then, ethyl acetate was distilled off under reduced pressure at 40.degree. C., whereby a slightly yellowish crude product was obtained in a solid form. The product was recrystallized from 900 ml of toluene and then dried at 40.degree. C. for 24 hours, whereby 27.7 g of 4"-phenyloxycarbonylaminophenyl-4-(4'-hydroxy)phenylbenzoate were obtained as white crystals.

yield: 75%. Melting Point: >300.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 6.8-7.6(m,17H), 8.2(s,1H), 8.9-9.2(br,1H)

Preparation Example 50 (Preparation of Exemplified Compound No. 193)

Phenyl chloroformate (7.5 g) was added dropwise to a suspension of 13.2 g of 3"-aminophenyl-4-(4'-hydroxy)phenylbenzoate and 4.0 g of sodium hydrogencarbonate in 50 ml of ethyl acetate. They were reacted at room temperature under stirring for 12 hours. Water (200 ml) was thereafter added to the reaction mixture to wash the same. That procedure was repeated until the water layer became neutral. The reaction mixture was allowed to separate into layers. The ethyl acetate layer was collected and, then, ethyl acetate was distilled off under reduced pressure at 40.degree. C., whereby a slightly yellowish crude product was obtained in a solid form. The product was recrystallized from 900 ml of toluene and then dried at 40.degree. C. for 24 hours, whereby 13.9 g of 3"-phenyloxycarbonylaminophenyl-4-(4'-hydroxy)phenylbenzoate were obtained as white crystals.

yield: 75%. Melting Point: >300.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 6.8-7.6(m,17H), 8.2(s,1H), 8.9-9.2(br,1H)

Preparation Example 51 (Preparation of Exemplified Compound No. 194)

Ethyl chloroformate (7.7 g) was added dropwise to a suspension of 14.9 g of 4'-hydroxyphenyl-4-aminobenzoate and 6.0 g of sodium hydrogencarbonate in 50 ml of ethyl acetate. They were reacted at room temperature under stirring for 12 hours. Water (200 ml) was thereafter added to the reaction mixture to wash the same. That procedure was repeated until the water layer became neutral. The reaction mixture was allowed to separate into layers. The ethyl acetate layer was collected and, then, ethyl acetate was distilled off under reduced pressure at 40.degree. C., whereby a slightly yellowish crude product was obtained in a solid form. The product was recrystallized from 500 ml of toluene and then dried at 40.degree. C. for 24 hours, whereby 14.9 g of 4'-hydroxyphenyl-4-ethoxycarbonylaminobenzoate were obtained as white crystals.

yield: 76%. Melting Point: >300.degree. C. .sup.1 H-NMR, .delta.(CDCl.sub.3): 1.2(t,3H), 4.2(q,2H) 6.8-7.0 (m,6H), 7.4-7.7(m, 2H), 8.1(s,1H), 8.2-8.4(br,1H).

[Evaluation methods for heat-sensitive recording paper]

(Storage stability test of produced color image)

Using a color-producing apparatus for heat-sensitive recording paper ("TH-PMD" trade name; manufactured by Okura Denki K.K.), a color image having a color density of 0.9 as measured by a Macbeth densitometer ("TR-524 Model") was formed on a heat-sensitive recording paper produced in each of the below-described examples. Each heat-sensitive recording paper was then observed as to whether the image area presented the whitening phenomenon or not, and was then subjected to the below-described storage stability tests.

1. Heat resistance test

After each heat-sensitive recording paper had been stored at 60.degree. C. for 24 hours, the density of the produced color image was measured by the Macbeth densitometer so that the percent remainder of the produced color image was determined.

2. Hydrothermoresistance test

After each heat-sensitive recording paper had been stored at 60.degree. C. and 90% R.H. for 24 hours, the density of the produced color image was measured by the Macbeth densitometer so that the percent remainder of the produced color image was determined.

3. Waterproofness test

After each heat-sensitive recording paper had been stored at 25.degree. C. for 24 hours in water, the density of the produced color image was measured by the Macbeth densitometer so that the percent remainder of the produced color image was determined.

4. Oil resistance test

Each heat-sensitive recording paper and a paper, which was coated with dioctyl-phthalate-containing capsules were brought into a contiguous relationship and then caused to pass through a pressure roll. After the heat-sensitive recording paper had been stored at 25.degree. C. for 1 week, the density of the color image so produced was measured by the Macbeth densitometer so that the percent remainder of the produced color image was determined.

The percent remainder of each produced color image after each test was determined in accordance with the following formula: ##EQU1##

A greater value indicates better storage stability of produced color image.

(Color-producing performance test)

Each heat-sensitive recording paper was maintained for 5 seconds in contact with a metal block heated at a surface temperature of 150.degree. C. The density of a color image so produced was measured using the Macbeth densitometer ("TR-524" Model). A greater value indicates a higher color density. From the practical viewpoint, the density of each color image so produced is considered to be sufficient as long as it is not smaller than 1.

(Temperature-dependent color-producing performance test)

Each heat-sensitive recording paper was maintained for 5 minutes in contact with metal blocks heated at varied surface temperatures. The densities of color images so produced were measured using the Macbeth densitometer ("TR-524" Model). A greater value indicates a higher color density.

EXAMPLES 1-34

______________________________________(Production method of heat-sensitive recording papers)______________________________________(Composition of Liquid A)Electron-donating chromogenic compound 10 g10% Aqueous solution of polyvinyl 10 galcohol ("Kuraray-117", trade name;product of Kuraray Co., Ltd.)Water 80 gTotal 100 g(Composition of Liquid B)Electron-attracting compound 20 gPrecipitated calcium carbonate 40 g("TP-123", trade name; product ofOkutama Kogyo K.K.)10% Aqueous solution of polyvinyl 60 galcohol ("Kuraray-117", trade name;product of Kuraray Co., Ltd.)Water 130 gTotal 250 g______________________________________

Liquid A and Liquid B were separately dispersed to an average particle size of 1.5 .mu.m or smaller in a sand grinding mill, whereby dispersions were prepared.

Mixed were the dispersion of 100 g of Liquid A, the dispersion of 250 g of Liquid B, and 23 g of 30% paraffin wax. The coating formulation so prepared was coated on a wood free paper to give a dry coat weight of 5.0.+-.0.5 g/m.sup.2 and then dried, whereby a heat-sensitive recording paper was produced.

Using the electron-donating chromogenic compounds and electron-attracting compounds [the compounds represented by the formula (1) or (2)], both shown in Tables 1(1) to 1(5), heat-sensitive recording papers were produced in the manner described above.

TABLE 1(1)______________________________________ Electron-attract- ing compound [Compound of Electron-donating formula (1) orEx. chromogenic compound (2)]______________________________________ 1 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 12 3-Diethylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 183 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 244 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 285 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 336 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 667 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 708 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 779 3-N-n-propyl-N-methylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 78______________________________________ TABLE 1(2)______________________________________ Electron-attract- ing compound [Compound of Electron-donating formula (1) orEx. chromogenic compound (2)]______________________________________10 3-N-isobutyl-N-methylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 9611 3-di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 9812 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 9913 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 24 & Exemplified Compound No. 70 (50%:50%)14 3-Di-n-butylamino-6-methyl Exemplified 7-anilinofluoran Compound No. 11715 3-Diethylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 11916 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 12017 3-N-isopentyl-N-ethylamino- Exemplified6-methyl-7-anilinofluoran Compound No. 121______________________________________ TABLE 1(3)______________________________________ Electron-attract- ing compound [Compound of Electron-donating formula (1) orEx. chromogenic compound (2)]______________________________________18 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 12219 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 12520 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 12621 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 12822 3-N-n-propyl-N-methylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 13123 3-N-isobutyl-N-methylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 13624 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 13725 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 140______________________________________ TABLE 1(4)______________________________________ Electron-attract- ing compound [Compound of Electron-donating formula (1) orEx. chromogenic compound (2)]______________________________________26 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 120 & Exemplified Compound No. 126 (50%:50%)27 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 15828 3-N-2'-methoxyethyl-N- Exemplified isobutylamino-6-methyl-7- Compound No. 165 anilinofluoran29 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 17230 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 22131 3-Di-n-butylamino-7-(2- Exemplified chloroanilino)fluoran Compound No. 23432 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 28133 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 352______________________________________ TABLE 1(5)______________________________________ Electron-attract- ing compound [Compound of Electron-donating formula (1) orEx. chromogenic compound (2)]______________________________________34 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 381______________________________________

Comparative Examples 1-8

In each comparative example, heat-sensitive recording paper was produced in the above-described manner by using the electron-donating chromogenic compound and electron-attracting compound shown in Table 2.

TABLE 2(1)______________________________________Comp. Electron-donating Electron-attract-Ex. chromogenic compound ing compound______________________________________1 3-Di-n-butylamino-6-methyl- Bisphenol A 7-anilinofluoran2 3-Di-n-butylamino-6-methyl- Benzyl 4-hydroxy- 7-anilinofluoran benzoate3 3-N-isopentyl-N-ethylamino- 4-Benzyloxyphenol 6-methyl-7-anilinofluoran______________________________________ TABLE 2(2)______________________________________Comp. Electron-donating Electron-attract-Ex. chromogenic compound ing compound______________________________________4 3-Di-n-butylamino-6-methyl- 4-Hydroxybenzo- 7-anilinofluoran phenone5 3-Di-n-butylamino-6-methyl- 3-Ethoxycarbonyl- 7-anilinofluoran aminophenol6 3-Di-n-butylamino-6-methyl- 4-Phenoxycarbo- 7-anilinofluoran nylaminophenol7 3-Di-n-butylamino-6-methyl- 4-tert-Butyl- 7-anilinofluoran phenyloxycarbo- nylaminobenzene8 3-Di-n-butylamino-6-methyl- 2,4-Bis(4'-tert- 7-anilinofluoran butylphenyloxy- carbonylamino toluene______________________________________

Tables 3(1) to 3(3) present the results of incubation and waterproofness tests of color images produced on the heat-sensitive recording papers obtained in Examples 1-34 and Comparative Examples 1-6, respectively, and also show whether the color images were subjected to whitening or not.

TABLE 3(1)______________________________________Storage Stability Test of Produced Color Image Percent rema- Percent rema-Heat- inder after inder aftersensitive hydrothermo- waterproof-recording resistance ness testpaper test (%) (%) Whitening______________________________________Example 1 94 92 Not occurredExample 2 96 95 Not occurredExample 3 98 98 Not occurredExample 4 98 96 Not occurredExample 5 100 97 Not occurredExample 6 95 93 Not occurredExample 7 100 97 Not occurredExample 8 98 96 Not occurredExample 9 99 97 Not occurredExample 10 98 97 Not occurredExample 11 99 98 Not occurredExample 12 98 97 Not occurredExample 13 98 96 Not occurredExample 14 81 90 Not occurredExample 15 96 92 Not occurredExample 16 98 94 Not occurredExample 17 91 91 Not occurredExample 18 79 93 Not occurredExample 19 100 89 Not occurred______________________________________ TABLE 3(2)______________________________________Storage Stability Test of Produced Color Image Percent rema- Percent rema-Heat- inder after inder aftersensitive hydrothermo- waterproof-recording resistance ness testpaper test (%) (%) Whitening______________________________________Example 20 100 95 Not occurredExample 21 97 91 Not occurredExample 22 100 96 Not occurredExample 23 99 100 Not occurredExample 24 98 93 Not occurredExample 25 100 100 Not occurredExample 26 96 96 Not occurredExample 27 89 88 Not occurredExample 28 88 89 Not occurredExample 29 89 86 Not occurredExample 30 90 85 Not occurredExample 31 87 89 Not occurredExample 32 90 88 Not occurredExample 33 88 89 Not occurredExample 34 87 87 Not occurred______________________________________ TABLE 3(3)______________________________________Storage Stability Test of Produced Color Image Percent rema- Percent rema-Heat- inder after inder aftersensitive hydrothermo- waterproof-recording resistance ness testpaper test (%) (%) Whitening______________________________________Comp. Ex. 1 36 38 Not occurredComp. Ex. 2 26 25 OccurredComp. Ex. 3 30 25 OccurredComp. Ex. 4 24 20 Not occurredComp. Ex. 5 28 18 Not occurredComp. Ex. 6 30 21 Not occurred______________________________________

As is apparent from Tables 3(1) to 3(3), the heat-sensitive recording papers of the present invention, which used the compound represented by the formula (1) or (2) as an electron-attracting compound, are extremely superior in the storage stability (hydrothermoresistance and waterproofness) of produced color images compared with the heat-sensitive recording materials produced using the conventional electro-attracting compound.

Tables 4(1) to 4(3) present the results of a color-producing performance test of the heat-sensitive recording papers obtained in Examples 1-34 and Comparative Examples 7-8.

TABLE 4(1)______________________________________Color-Producing Performance Test Density of Density ofHeat-sensitive color-unproduced produced colorrecording paper area image______________________________________Example 1 0.04 1.15Example 2 0.04 1.16Example 3 0.04 1.17Example 4 0.04 1.15Example 5 0.04 1.16Example 6 0.04 1.16Example 7 0.04 1.16Example 8 0.04 1.15Example 9 0.04 1.16Example 10 0.04 1.15Example 11 0.04 1.17Example 12 0.04 1.17Example 13 0.04 1.16Example 14 0.04 1.15Example 15 0.04 1.16Example 16 0.04 1.17Example 17 0.04 1.15Example 18 0.04 1.16______________________________________ TABLE 4(2)______________________________________Color-Producing Performance Test Density of Density ofHeat-sensitive color-unproduced produced colorrecording paper area image______________________________________Example 19 0.04 1.16Example 20 0.04 1.16Example 21 0.04 1.15Example 22 0.04 1.16Example 23 0.04 1.15Example 24 0.04 1.17Example 25 0.04 1.17Example 26 0.04 1.16Example 27 0.04 1.15Example 28 0.04 1.14Example 29 0.04 1.14Example 30 0.04 1.15Example 31 0.04 1.16Example 32 0.04 1.16Example 33 0.04 1.15Example 34 0.04 1.17Comp. Ex. 7 0.04 0.04Comp. Ex. 8 0.04 0.04______________________________________

As is evident from Tables 4(1) to 4(3), carbamate compounds without any intramolecular hydroxyl group can be considered to have absolutely no color-producing ability and to have practically no function as color-attracting compounds.

It is understood, on the other hand, that the compounds of this invention, which are represented by the formula (1) or (2), namely, the compounds with intramolecular hydroxyl and carbamate groups are electron-attracting compounds having valuable practical utility.

Table 5 presents the results of a color-producing performance test of the heat-sensitive recording materials, which were obtained in Examples 3, 15, 27 and 32 and Comparative Example 1, at varied temperatures.

TABLE 5______________________________________Color-Producing Performance Test at Varied TemperatureHeat-sensitiverecording Temperature (.degree.C.)paper 100 105 110 115 120 130______________________________________Example 3 0.04 0.25 0.82 1.05 1.17 1.17Example 15 0.05 0.28 0.80 1.06 1.15 1.15Example 27 0.05 0.26 0.80 1.04 1.15 1.15Example 32 0.04 0.27 0.83 1.06 1.16 1.16Comp. Ex. 1 0.05 0.10 0.15 0.21 0.35 1.10______________________________________

As is clearly envisaged from Table 5, the heat-sensitive recording materials according to the present invention promptly produced the color at lower temperatures than the heat-sensitive recording material using the conventional electron-attracting compound and are considered to be heat-sensitive recording materials of high sensitivity suited for high-speed recording.

EXAMPLES 35-71

______________________________________(Production method of heat-sensitive recording papers)______________________________________(Composition of Liquid A')Electron-donating chromogenic compound 10 g10% Aqueous solution of polyvinyl 10 galcohol ("Kuraray-117", trade name;product of Kuraray Co., Ltd.)Water 80 gTotal 100 g(Composition of Liquid B')Electron-attracting compound 20 g(bisphenol-A)Precipitated calcium carbonate 40 g("TP-123", trade name; product ofOkutama Kogyo K.K.)10% Aqueous solution of polyvinyl 60 galcohol ("Kuraray-117", trade name;product of Kuraray Co., Ltd.)Water 130 gTotal 250 g(Composition of Liquid C')Compound of formula (1) or (2) 20 g10% Aqueous solution of polyvinyl 10 galcohol ("Kuraray-117", trade name;product of Kuraray Co., Ltd.)Water 220 gTotal 250 g______________________________________

Liquid A'-Liquid B' and Liquid C' were separately dispersed to an average particle size of 1.5 .mu.m or smaller in a sand grinding mill, whereby dispersions were prepared.

Mixed were the dispersion of 100 g of Liquid A', the dispersion of 250 g of Liquid B', the dispersion of 250 g of Liquid C' and 23 g of 30% paraffin wax. The coating formulation so prepared was coated on a wood free paper to give a dry coat weight of 5.0.+-.0.5 g/m.sup.2 and then dried, whereby a heat-sensitive recording paper was produced.

Using the electron-donating chromogenic compounds and the compounds represented by the formula (1) or (2), both shown in Tables 6(1) to 6(5), heat-sensitive recording papers were produced in the manner described above.

TABLE 6______________________________________ Compound of Electron-donating formulaEx. chromogenic compound (1) or (2)______________________________________35 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 136 3-Diethylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 1837 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 24______________________________________ TABLE 6(2)______________________________________ Compound of Electron-donating formulaEx. chromogenic compound (1) or (2)______________________________________38 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 2839 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 3340 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 6641 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 7042 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 7743 3-N-n-propyl-N-methylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 7844 3-N-isobutyl-N-methylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 9645 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 9846 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 99______________________________________ TABLE 6(3)______________________________________ Compound of Electron-donating formulaEx. chromogenic compound (1) or (2)______________________________________47 3-Di-n-butylamino-6-methyl Exemplified 7-anilinofluoran Compound No. 24 & Exemplified Compound No. 70 (50%:50%)48 3-Di-n-butylamino-6-methyl Exemplified 7-anilinofluoran Compound No. 11749 3-Diethylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 11950 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 12051 3-N-isopentyl-N-ethylamino- Exemplified6-methyl-7-anilinofluoran Compound No. 12152 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 12253 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 12554 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 12655 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 128______________________________________ TABLE 6(4)______________________________________ Compound of Electron-donating formulaEx. chromogenic compound (1) or (2)______________________________________56 3-N-n-propyl-N-methylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 13157 3-N-isobutyl-N-methylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 13658 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 13759 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 14060 3-Di-n-butylamino-6-methyl Exemplified 7-anilinofluoran Compound No. 120 & Exemplified Compound No. 126 (50%:50%)61 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 15862 3-N-2'-methoxyethyl-N- Exemplified isobutylamino-6-methyl-7- Compound No. 165 anilinofluoran63 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 17264 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 193______________________________________ TABLE 6(5)______________________________________ Compound of Electron-donating formulaEx. chromogenic compound (1) or (2)______________________________________65 3-N-isopentyl-N-ethylamino- Exemplified 6-methyl-7-anilinofluoran Compound No. 19466 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 22167 3-Di-n-butylamino-7-(2- Exemplified chloroanilino)fluoran Compound No. 23468 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 28169 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 35870 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 37571 3-Di-n-butylamino-6-methyl- Exemplified 7-anilinofluoran Compound No. 381______________________________________

Comparative Examples 9-10

In each comparative example, heat-sensitive recording paper was produced in the above-described manner by using the electron-donating chromogenic compound shown in Table 7 and Liquids A' and B' without using Liquid C'.

TABLE 7______________________________________ Electron-donatingComp. Ex. chromogenic compound______________________________________ 9 3-Di-n-butylamino-6-methyl- 7-anilinofluoran10 3-N-isopentyl-N-ethylamino- 6-methyl-7-anilinofluoran______________________________________

Comparative Examples 11-19

In each comparative example, heat-sensitive recording paper was produced in substantially the same manner as described above except that 3-di-n-butylamino-6-methyl-7-anilinofluoran was used as the electron-donating chromogenic compound in Liquid A' and the compound shown in Table 8 was used in place of the compound of the general formula (1) or (2) in Liquid C'.

TABLE 8______________________________________Comp. Ex. Compound in Liquid C'______________________________________11 4-Benzylbiphenyl12 m-Terphenyl13 3-Ethoxycarbonylaminophenol14 4-Phenyloxycarbonylaminophenol15 4-tert-Butylphenyloxycarbonylamino- benzene16 4-Cumylphenyloxycarbonylaminobenzene17 1,6-Bis(phenyloxycarbonylamino)hexane18 1,1-Bis(4-ethoxycarbonylaminophenyl)- methane19 Di-(4-ethoxycarbonylaminophenyl)ether______________________________________

Tables 9(1) to 9(3) present the results of incubation, waterproofness and oil resistance tests of color images produced on the heat-sensitive recording papers obtained in Examples 35-71 and Comparative Examples 9-19.

TABLE 9(1)______________________________________Storage Stability Test of Produced Color Image Percent rema- Percent rema- Percent rema-Heat- inder after inder after inder aftersensitive hydrothermo- waterproof- oil resis-recording resistance ness test tance testpaper test (%) (%) (%)______________________________________Example 35 100 98 99Example 36 100 97 96Example 37 99 97 98Example 38 99 100 98Example 39 100 97 99Example 40 98 99 99Example 41 100 97 100Example 42 98 96 97Example 43 100 97 99Example 44 98 99 99Example 45 100 98 99Example 46 99 97 98Example 47 98 98 98______________________________________ TABLE 9(2)______________________________________Storage Stability Test of Produced Color Image Percent rema- Percent rema- Percent rema-Heat- inder after inder after inder aftersensitive hydrothermo- waterproof- oil resis-recording resistance ness test tance testpaper test (%) (%) (%)______________________________________Example 48 81 90 90Example 49 96 90 94Example 50 98 92 94Example 51 91 94 96Example 52 79 91 95Example 53 100 93 99Example 54 100 89 85Example 55 97 95 96Example 56 100 91 100Example 57 99 96 98Example 58 98 100 89Example 59 100 93 92Example 60 96 96 93Example 61 95 93 90Example 62 95 94 89Example 63 96 94 88Example 64 98 93 90Example 65 98 92 91Example 66 97 90 90______________________________________ TABLE 9(3)______________________________________Storage Stability Test of Produced Color Image Percent rema- Percent rema- Percent rema-Heat- inder after inder after inder aftersensitive hydrothermo- waterproof- oil resis-recording resistance ness test tance testpaper test (%) (%) (%)______________________________________Example 67 95 92 86Example 68 95 91 88Example 69 94 92 90Example 70 94 93 87Example 71 90 90 91Comp. Ex. 9 36 38 20Comp. Ex. 10 42 45 29Comp. Ex. 11 18 15 16Comp. Ex. 12 16 13 12Comp. Ex. 13 19 18 11Comp. Ex. 14 20 19 15Comp. Ex. 15 21 20 17Comp. Ex. 16 23 21 19Comp. Ex. 17 22 20 16Comp. Ex. 18 20 17 17Comp. Ex. 19 19 18 18______________________________________

As is apparent from Tables 9(1) to 9(3), the heat-sensitive recording materials according to the present invention are excellent in the storage stability (hydrothermoresistance, waterproofness and oil resistance) of produced color images.

Table 10 shows the results of a color-producing performance test of the heat-sensitive recording papers, which were obtained in Examples 37, 49, 61 and 68 and Comparative Example 9, at varied temperatures.

TABLE 10______________________________________Color-Producing Performance Test at Varied TemperaturesHeat-sensitive Temperature (.degree.C.)recording paper 95 100 105 110 120 130______________________________________Example 37 0.10 0.68 1.10 1.26 1.35 1.35Example 49 0.10 0.68 1.10 1.26 1.35 1.35Example 61 0.10 0.66 1.11 1.20 1.35 1.35Example 68 0.10 0.65 1.12 1.22 1.35 1.35Comp. Ex. 9 0.05 0.05 0.10 0.15 0.35 1.10______________________________________

As is understood clearly from Table 10, the heat-sensitive sensitive recording materials according to the present invention promptly produced the color at lower temperatures than the heat-sensitive recording material composed of the conventional electron-attracting chromogenic compound and electron-attracting compound and are considered to be heat-sensitive recording materials of high sensitivity suitable for high-speed recording.

EXAMPLES 72-108

(Production method of heat-sensitive recording papers)

In each example, heat-sensitive recording paper was produced in the above-described manner by using 100 g of Liquid A", 250 g of Liquid B", 250 g of Liquid C" and 23 g of 30% paraffin wax Liquids A", B" and C" had been prepared using the electron-donating chromogenic compound, thermofusible compound and the compound of the formula (1) or (2), all shown in Table 11.

______________________________________(Composition of Liquid A")Electron-donating chromogenic compound 10 g10% Aqueous solution of polyvinyl 10 galcohol ("Kuraray-117", trade name;product of Kuraray Co., Ltd.)Water 80 gTotal 100 g(Composition of Liquid B")Electron-attracting compound 20 g(bisphenol-A)Precipitated calcium carbonate 40 g("TP-123", trade name; product ofOkutama Kogyo K.K.)10% Aqueous solution of polyvinyl 60 galcohol ("Kuraray-117", trade name;product of Kuraray Co., Ltd.)Water 130 gTotal 250 g(Composition of Liquid C")Thermofusible compound 5 gCompound of formula (1) or (2) 15 g10% Aqueous solution of polyvinyl 10 galcohol ("Kuraray-117", trade name;product of Kuraray Co., Ltd.)Water 220 gTotal 250 g______________________________________ TABLE 11(1)______________________________________ Thermo- Compound of Electron-donating fusible formulaEx. chromogenic compound compound (1) or (2)______________________________________72 3-Di-n-butylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 173 3-Diethylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 18______________________________________ TABLE 11(2)______________________________________ Thermo- Compound of Electron-donating fusible formulaEx. chromogenic compound compound (1) or (2)______________________________________74 3-Di-n-butylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 2475 3-N-isopentyl-N-ethylamino- A Exemplified 6-methyl-7-anilinofluoran Compound No. 2876 3-Di-n-butylamino-6-methyl- B Exemplified 7-anilinofluoran Compound No. 3377 3-N-isopentyl-N-ethylamino- C Exemplified 6-methyl-7-anilinofluoran Compound No. 6678 3-N-isopentyl-N-ethylamino- D Exemplified 6-methyl-7-anilinofluoran Compound No. 7079 3-N-isopentyl-N-ethylamino- C Exemplified 6-methyl-7-anilinofluoran Compound No. 7780 3-N-n-propyl-N- A Exemplified methylamino-6-methyl-7- Compound No. anilinofluoran 7881 3-N-Isobutyl-N-methylamino- E Exemplified 6-methyl-7-anilinofluoran Compound No. 9682 3-Di-n-butylamino-6-methyl- D Exemplified 7-anilinofluoran Compound No. 9883 3-N-Isopentyl-N-ethylamino- D Exemplified 6-methyl-7-anilinofluoran Compound No. 99______________________________________ TABLE 11(3)______________________________________ Thermo- Compound of Electron-donating fusible formulaEx. chromogenic compound compound (1) or (2)______________________________________84 3-Di-n-butylamino-6-methyl- D Exemplified 7-anilinofluoran Compound No. 24 & Exemplified Compound No. 70 (50%:50%)85 3-Di-n-butylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 11786 3-Diethylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 11987 3-Di-n-butylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 12088 3-N-Isopentyl-N-ethylamino- A Exemplified 6-methyl-7-anilinofluoran Compound No. 12189 3-Di-n-butylamino-6-methyl- B Exemplified 7-anilinofluoran Compound No. 12290 3-N-Isopentyl-N-ethylamino- C Exemplified 6-methyl-7-anilinofluoran Compound No. 12591 3-N-Isopentyl-N-ethylamino- D Exemplified 6-methyl-7-anilinofluoran Compound No. 12692 3-N-Isopentyl-N-ethylamino- C Exemplified 6-methyl-7-anilinofluoran Compound No. 128______________________________________ TABLE 11(4)______________________________________ Thermo- Compound of Electron-donating fusible formulaEx. chromogenic compound compound (1) or (2)______________________________________93 3-N-n-Propyl-N- A Exemplified methylamino-6-methyl-7- Compound No. anilinofluoran 13194 3-N-Isobutyl-N-methylamino- E Exemplified 6-methyl-7-anilinofluoran Compound No. 13695 3-Di-n-butylamino-6-methyl- D Exemplified 7-anilinofluoran Compound No. 13796 3-N-Isopentyl-N-ethylamino- D Exemplified 6-methyl-7-anilinofluoran Compound No. 14097 3-Di-n-butylamino-6-methyl- D Exemplified 7-anilinofluoran Compound No. 120 & Exemplified Compound No. 126 (50%:50%)98 3-Di-n-butylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 15899 3-N-2'-methoxyethyl-N-iso- A Exemplified butylamino-6-methyl-7- Compound No. anilinofluoran 165100 3-N-isopentyl-N-ethylamino- B Exemplified 6-methyl-7-anilinofluoran Compound No. 172101 3-Di-n-butylamino-6-methyl- C Exemplified 7-anilinofluoran Compound No. 193______________________________________ TABLE 11(5)______________________________________ Thermo- Compound of Electron-donating fusible formulaEx. chromogenic compound compound (1) or (2)______________________________________102 3-N-isopentyl-N-ethylamino- D Exemplified 6-methyl-7-anilinofluoran Compound No. 194103 3-Di-n-butylamino-6-methyl- E Exemplified 7-anilinofluoran Compound No. 221104 3-Di-n-butylamino-7-(2- A Exemplified chloroanilino)fluoran Compound No. 234105 3-Di-n-butylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 281106 3-Di-n-butylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 358107 3-Di-n-butylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 375108 3-Di-n-butylamino-6-methyl- A Exemplified 7-anilinofluoran Compound No. 381______________________________________

Incidentally, the thermofusible compounds A, B, C, D and E used in Tables 11(1) to 11(5) indicate the following compounds:

A: 2-Benzyloxynaphthalene B: Di(4-methylbenzyl) oxalate C: 1,2-Bis(3'-methylphenoxy)ethane D: 4-(4'-Methylphenoxy)biphenyl E: 4-Benzylbiphenyl

Comparative Examples 20-24

In each comparative example, heat-sensitive recording paper was produced in the above-described manner from 100 g of Liquid A", 250 g of Liquid B", 250 g of Liquid D" in place of Liquid C", and 23 g of 30% paraffin wax. Liquid A" had been prepared by employing the electron-donating chromogenic compound shown in Table 12 while Liquid D" had been obtained using the thermofusible compound shown in Table 12 in accordance with the below-described composition.

______________________________________(Composition of Liquid D")______________________________________Thermofusible compound 20 g10% Aqueous solution of polyvinyl 10 galcohol ("Kuraray-117", trade name;product of Kuraray Co., Ltd.)Water 220 gTotal 250 g______________________________________ TABLE 12______________________________________Comp. Electron-donating ThermofusibleEx. chromogenic compound substance______________________________________20 3-Di-n-butylamino-6-methyl- A 7-anilinofluoran21 3-N-Isopentyl-N-ethylamino- A 6-methyl-7-anilinofluoran22 3-Di-n-butylamino-6-methyl- B 7-anilinofluoran23 3-Di-n-butylamino-6-methyl- C 7-anilinofluoran24 3-Di-n-butylamino-6-methyl- D 7-anilinofluoran______________________________________

Incidentally, the thermofusible compounds A, B, C and D employed in Table 12 indicate the following compounds:

A: 2-Benzyloxynaphthalene B: Di(4-methylbenzyl) oxalate C: 1,2-Bis(3'-methylphenoxy)ethane D: 4-(4'-Methylphenoxy)biphenyl

Comparative Examples 25-26

In each comparative example, heat-sensitive recording paper was produced in the same manner as described above except that 3-di(n-butylamino)-6-methyl-7-anilinofluoran was used as the electron-donating chromogenic compound in Liquid A" and 3-ethoxycarbonylaminophenol (Comparative Example 25) or 4-phenyloxycarbonylaminobenzene (Comparative Example 26) was employed instead of the compound of the formula (1) or (2) in Liquid C".

Tables 13(1) to 13(5) present the results of heat resistance, incubation, waterproofness and oil resistance tests of color images produced on the heat-sensitive recording papers obtained in Examples 72-108 and Comparative Examples 20-26, respectively.

TABLE 13(1)______________________________________Storage Stability Test of Produced Color Image Percent rema- Percent inder after Percent PercentHeat- remainder hydro- remainder remaindersensitive after heat thermo- after water- after oilrecording resistance resistance proofness resistancepaper test (%) test (%) test (%) test (%)______________________________________Example 72 93 86 84 89Example 73 91 88 85 84Example 74 93 88 87 86Example 75 92 90 86 84Example 76 94 87 86 89Example 77 91 91 88 87Example 78 90 90 86 84Example 79 93 91 86 87Example 80 90 88 90 89______________________________________ TABLE 13(2)______________________________________Storage Stability Test of Produced Color Image Percent rema- Percent inder after Percent PercentHeat- remainder hydro- remainder remaindersensitive after heat thermo- after water- after oilrecording resistance resistance proofness resistancepaper test (%) test (%) test (%) test (%)______________________________________Example 81 90 86 84 83Example 82 91 85 85 86Example 83 93 88 87 88Example 84 90 90 88 88Example 85 90 88 88 89Example 86 93 86 87 88Example 87 91 90 85 88Example 88 90 98 84 86Example 89 90 85 90 83______________________________________ TABLE 13(3)______________________________________Storage Stability Test of Produced Color Image Percent rema- Percent inder after Percent PercentHeat- remainder hydro- remainder remaindersensitive after heat thermo- after water- after oilrecording resistance resistance proofness resistancepaper test (%) test (%) test (%) test (%)______________________________________Example 90 93 86 86 89Example 91 90 88 86 87Example 92 91 91 88 84Example 93 94 90 86 89Example 94 92 91 86 84Example 95 93 87 87 86Example 96 91 90 85 84Example 97 93 88 84 87Example 98 90 88 84 83______________________________________ TABLE 13(4)______________________________________Storage Stablility Test of Produced Color Image Percent rema- Percent inder after Percent PercentHeat- remainder hydro- remainder remaindersensitive after heat thermo- after water- after oilrecording resistance resistance proofness resistancepaper test (%) test (%) test (%) test (%)______________________________________Example 99 89 87 83 82Example 100 88 87 82 82Example 101 89 86 85 82Example 102 91 85 83 82Example 103 90 84 82 82Example 104 88 83 82 82Example 105 90 88 84 83Example 106 94 87 85 84Example 107 90 88 85 84Example 108 91 90 89 88______________________________________ TABLE 13(5)______________________________________Storage Stability Test of Produced Color Image Percent rema- Percent inder after Percent PercentHeat- remainder hydro- remainder remaindersensitive after heat thermo- after water- after oilrecording resistance restistance proofness resistancepaper test (%) test (%) test (%) test (%)______________________________________Comp. Ex. 20 30 15 20 10Comp. Ex. 21 42 28 32 21Comp. Ex. 22 30 15 18 11Comp. Ex. 23 29 17 16 12Comp. Ex. 24 32 18 21 15Comp. Ex. 25 30 19 18 14Comp. Ex. 26 29 19 18 16______________________________________

As is clearly envisaged from Tables 13(1) to 13(5), the heat-sensitive recording materials according to the present invention are excellent in the storage stability (heat resistance, hydrothermoresistance, waterproofness and oil resistance) of produced color images.

Table 14 presents the results of a color-producing performance test of the heat-sensitive recording papers, which were obtained in Examples 74, 86, 98 and 105 and Comparative Example 20, at varied temperatures.

TABLE 14______________________________________Color-Producing Performance Test at Varied TemperaturesHeat-sensitive Temperature (.degree.C.)recording paper 75 80 85 90 95 100______________________________________Example 74 0.05 0.10 0.80 0.93 1.09 1.21Example 86 0.05 0.10 0.80 0.93 1.09 1.21Example 98 0.05 0.11 0.82 0.95 1.10 1.20Example 105 0.05 0.11 0.81 0.92 1.12 1.22Comp. Ex. 20 0.05 0.07 0.10 0.20 0.92 1.19______________________________________

As is understood clearly from Table 14, the heat-sensitive recording materials according to the present invention promptly produced the color at lower temperatures than the conventional heat-sensitive recording material and are considered to be heat-sensitive recording materials of high sensitivity suitable for high-speed recording.

Claims

1. A phenol compound represented by the following formula (3): ##STR30## wherein R.sub.1 means a hydrogen atom or an alkyl, aralkyl or aryl group, R.sub.2 denotes an alkyl, alkenyl, aralkyl or aryl group, R.sub.5 and R.sub.6 are a hydrogen or halogen atom or an alkyl, alkoxy, aralkyl, aryl or hydroxyl group, p and q stand for an integer of 1-4, R.sub.5 and R.sub.6 may be either the same or different when p and q individually represent an integer of 2, or greater, X.sub.1 and Y.sub.1 individually represent an oxygen or sulfur atom, and --Z.sub.3 means a group containing at least one group selected from the class consisting of --O--, --S--, a phenylene group, --CO--, --CR.sub.10 .dbd.CR.sub.11 --, in which R.sub.10 and R.sub.11 are individually a hydrogen atom or an alkyl or aryl group, --SO-- and --SO.sub.2 -- or, when R.sub.1 is a hydrogen atom, --Z.sub.3 -- may also be --R.sub.8 CR.sub.9 --, wherein R.sub.8 and R.sub.9 individually represent an alkyl group having 1-4 carbon atoms.

2. The compound of claim 1, wherein in the formula (3), R.sub.1, R.sub.5 and R.sub.6 are each a hydrogen atom, X.sub.1 is an oxygen atom, and --Z.sub.3 -- is --R.sub.8 CR.sub.9 --.

3. The compound of claim 2, wherein in the formula (3), R.sub.8 and R.sub.9 are each a methyl group.

4. The compound of claim 1, which is represented by one of the following formula (4-1) or (4-2): ##STR31## wherein R.sub.2 and Y.sub.1 have the same meanings as defined above.

5. A phenol compound represented by the following formula (5-0): ##STR32## wherein R.sub.1 means a hydrogen atom or an alkyl, aralkyl or aryl group, R.sub.2 denotes an alkyl, alkenyl, aralkyl or aryl group, R.sub.5 and R.sub.6 are either the same or different and individually represent a hydrogen or halogen atom, or an alkyl, alkoxy, aralkyl, aryl or hydroxyl group, and Y.sub.1 represents an oxygen or sulfur atom.

6. The compound of claim 5, wherein in the formula (5-0), R.sub.1, R.sub.5 and R.sub.6 are each a hydrogen atom.

7. The compound of claim 6, wherein in the formula (5-0), Y.sub.1 is an oxygen atom.

8. The compound of claim 6, which is represented by one of the following formulae (5-1 or (5-2): ##STR33## wherein R.sub.2 and Y.sub.1 have the same meanings as defined above.

9. A phenol compound represented by the following formula (6-0): ##STR34## wherein R.sub.1 means a hydrogen atom or an alkyl, aralkyl or aryl group, R.sub.2 denotes an alkyl, alkenyl, aralkyl or aryl group, R.sub.5 and R.sub.6 are either the same or different and individually represent a hydrogen or halogen atom, or an alkyl, alkoxy, aralkyl, aryl or hydroxyl group, and Y.sub.1 represents an oxygen or sulfur atom.

10. The compound of claim 9, wherein in the formula (6-0), R.sub.1, R.sub.5 and R.sub.6 are each a hydrogen atom.

11. The compound of claim 10, wherein in the formula (6-0), Y.sub.1 is an oxygen atom.

12. A compound represented by the following formula (6-1): ##STR35## wherein R.sub.2 is an alkyl, alkenyl, aralkyl or aryl group and Y.sub.1 is an oxygen or sulfur atom.

13. A phenol compound represented by the following formula (7-0): ##STR36## wherein R.sub.1 means a hydrogen atom or an alkyl, aralkyl or aryl group, R.sub.2 denotes an alkyl, alkenyl, aralkyl or aryl group, R.sub.5 and R.sub.6 are either the same or different and individually represent a hydrogen or halogen atom, or an alkyl, alkoxy, aralkyl, aryl or hydroxyl group, p and q each individually stand for an integer of 1-4, wherein R.sub.5 and R.sub.6 may be the same or different when p and q individually represent an integer of 2-4, and X.sub.1 and Y.sub.1 individually represent an oxygen or sulfur atom.

14. The compound of claim 13, wherein in the formula (7-0), R.sub.1, R.sub.5 and R.sub.6 are each a hydrogen atom and X.sub.1 is an oxygen atom.

15. The compound of claim 14, wherein in the formula (7-0), Y.sub.1 is an oxygen atom.

16. A compound of claim 13, which is represented by one of the following formulae (7-1) or (7-2): ##STR37## wherein R.sub.2 has the same meaning as defined above.

17. A compound represented by the following formula (8-0): ##STR38## wherein R.sub.1 means a hydrogen atom or an alkyl, aralkyl or aryl group, R.sub.2 denotes an alkyl, alkenyl, aralkyl or aryl group, R.sub.5 and R.sub.6 are either the same or different and individually represent a hydrogen or halogen atom, or an alkyl, alkoxy, aralkyl, aryl or hydroxyl group, p and q stand for an integer of 1-4, wherein R.sub.5 and R.sub.6 may be the same or different when p and q individually represent an integer of 2-4, and X.sub.1 and Y.sub.1 individually represent an oxygen or sulfur atom.

18. The compound of claim 17, wherein in the formula (8-0), R.sub.1, R.sub.5 and R.sub.6 are each a hydrogen atom and X.sub.1 is an oxygen atom.

19. The compound of claim 18, wherein in the formula (8-0), Y.sub.1 is an oxygen atom.

20. A compound of claim 17, which is represented by the following formula (8-1): ##STR39## wherein R.sub.2 has the same meaning as defined above.