Two-color thermosensitive recording material

Claim 2

In a two-color thermosensitive recording material capable of forming two different colors when heated at different temperatures, comprising a support material, a high-temperature color-forming layer formed on said support material, a decolorization layer overlaying said high-temperature color-forming layer, and a low-temperature color-forming layer overlaying said decolorization layer, said high-temperature color-forming layer being capable of forming color when heated at a predetermined coloring temperature, said low-temperature color-forming layer being capable of forming color which is different from the color formed by said high-temperature color-forming layer when heated at a predetermined coloring temperature which is lower than said coloring temperature for said high-temperature color-forming layer, and said decolorization layer being capable of decolorizing the color developed in said low-temperature color-forming layer when heated up to a predetermined temperature for preventing the color developed in said low-temperature color-forming layer being mixed with the color developed in said high-temperature color-forming layer, the improvement wherein said high-temperature color-forming layer comprises a first leuco dye and a color developer capable of inducing color formation in said first leuco dye upon application of heat thereto, said decolorizing layer comprises a decolorizing agent selected from the group consisting of aliphatic amines and morpholine derivatives represented by general formula (Ia), (Ib) and (Ic), ##STR11## wherein X represents ##STR12## ##STR13## wherein Y represents ##STR14## and R represents alkylene, ##STR15## wherein Z represents ##STR16## or higher alkyl, said low-temperature color-forming layer comprises a second leuco dye and a thiourea derivative of general formula (II) serving as a color developer capable of inducing color formation in said second leuco dye upon application of heat thereto, ##STR17## wherein R 1 and R 2 each represent hydrogen, halogen, trifluoromethyl or alkyl having 1 to 4 carbon atoms.

Claim 3

A two-color thermosensitive recording material as claimed in claim 1, further comprising an intermediate layer comprising as the main components a thermo-fusible material and a water-soluble polymeric binder agent between said decolorization layer and said low-temperature color-forming layer.

Claim 4

A two-color thermosensitive recording material as claimed in claim 2, wherein said first leuco dye employed in said high-temperature color-forming layer and said second leuco dye employed in said low-temperature color-forming layer each are selected from the group consisting of triphenylmethane-type leuco compounds, fluoran-type leuco compounds, phenothiazine-type leuco compounds, auramine-type leuco compounds and spiropyran-type leuco compounds.

Claim 5

A two-color thermosensitive recording material as claimed in claim 2, wherein said first leuco dye in said high-temperature color forming layer and said second leuco dye in said low-temperature color forming layer each are selected from the group consisting of:

Claim 6

3-bis(p-dimethylaminophenyl)-phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (or Crystal Violet Lactone), 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-chlorophthalide, 3,3-bis(p-dibutylaminophenyl)-phthalide, 3-cyclohexylamine-6-chlorofluoran, 3-dimethylamino-5,6-dimethylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7,8-benzfluoran, 3-diethylaminobenzo[α]fluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-(N-p-tolyl-N-ethylamino)-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 2-[N-(3'-trifluoromethylphenyl)amino]-6-diethylaminofluoran, 2-[3,6-bis(diethylamino)-9-(o-chloroanilino)xanthylbenzoic acid lactam], 3-diethylamino-6-methyl-7-(m-trichloromethylanilino)-fluoran, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenyl)phthalide, 3-(2'methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chloro-5'-methylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)-fluoran, 3-pyrrolidino-7-trifluoromethylanilinofluoran, 3-diethylamino-5-chloro-7-(N-benzyl-trifluoromethylanilino)fluoran, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluoran, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-ethyl-p-toluidino)-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-(o-methoxycarbonylphenylamino)-fluoran, 3-diethylamino-5-methyl-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-piperidinofluoran, 2-chloro-3-(N-methyltoluidino)-7-(p-n-butylanilino)-fluoran, 3-diethylamino-7-(o-chloroanilino)fluoran, 3-dibutylamino-7-(o-chloroanilino)fluoran, 3-dimethylamino-7-(o-chloroanilino)fluoran, 3-dipropylamino-7-(o-chloroanilino)fluoran, 3-dimethylamino-7-(o-fluoranilino)fluoran, 3-diethylamino-7-(o-fluoroanilino)fluoran, 3-dipropylamino-7-(o-fluoroanilino)fluoran, 3-dibutylamino-7-(o-fluoroanilino)fluoran, 3-N-methyl-N-amylamino-6-methyl-7-anilinofluoran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)-fluoran, benzoyl leuco methylene blue, 6'-chloro-8'-methoxy-benzoindolino-spiropyran, 6'-bromo-3'-methoxy-benzoindolino-spiropyran, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-chlorophenyl)phthalide, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)phthalide, 3-(N-benzyl-cyclohexylamino)-5,6-benzo-7-α-naphthylamino-4'-bromofluoran, and 3-diethylamino-6-methyl-7-methyl-7mesidino-4',5'-benzofluoran.

Claim 7

3-bis(p-dimethylaminophenyl)-phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (or Crystal Violet Lactone), 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-chlorophthalide, 3,3-bis(p-dibutylaminophenyl)-phthalide, 3-cyclohexylamine-6-chlorofluoran, 3-dimethylamino-5,6-dimethylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7,8-benzfluoran, 3-diethylaminobenzo[α]fluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-(N-p-tolyl-N-ethylamino)-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 2-[N-(3'-trifluoromethylphenyl)amino]-6-diethylaminofluoran, 2-[3,6-bis(diethylamino)-9-(o-chloroanilino)xanthylbenzoic acid lactam], 3-diethylamino-6-methyl-7-(m-trichloromethylanilino)-fluoran, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenyl)phthalide, 3-(2'methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chloro-5'-methylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)-fluoran, 3-pyrrolidino-7-trifluoromethylanilinofluoran, 3-diethylamino-5-chloro-7-(N-benzyl-trifluoromethylanilino)fluoran, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluoran, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-ethyl-p-toluidino)-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-(o-methoxycarbonylphenylamino)-fluoran, 3-diethylamino-5-methyl-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-piperidinofluoran, 2-chloro-3-(N-methyltoluidino)-7-(p-n-butylanilino)-fluoran, 3-diethylamino-7-(o-chloroanilino)fluoran, 3-dibutylamino-7-(o-chloroanilino)fluoran, 3-dimethylamino-7-(o-chloroanilino)fluoran, 3-dipropylamino-7-(o-chloroanilino)fluoran, 3-dimethylamino-7-(o-fluoranilino)fluoran, 3-diethylamino-7-(o-fluoroanilino)fluoran, 3-dipropylamino-7-(o-fluoroanilino)fluoran, 3-dibutylamino-7-(o-fluoroanilino)fluoran, 3-N-methyl-N-amylamino-6-methyl-7-anilinofluoran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)-fluoran, benzoyl leuco methylene blue, 6'-chloro-8'-methoxy-benzoindolino-spiropyran, 6'-bromo-3'-methoxy-benzoindolino-spiropyran, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-chlorophenyl)phthalide, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)phthalide, 3-(N-benzyl-cyclohexylamino)-5,6-benzo-7-α-naphthylamino-4'-bromofluoran, and 3-diethylamino-6-methyl-7-methyl-7mesidino-4',5'-benzofluoran.

Claim 8

A two-color thermosensitive recording material as claimed in claim 2, wherein said thermo-fusible material contained in said intermediate layer is selected from the group consisting of amide derivatives and aromatic hydrocarbons having a melting point ranging from 60° C. to 120° C.

Claim 9

A two-color thermosensitive recording material as claimed in claim 2, wherein said thermo-fusible material contained in said intermediate layer is selected from the group consisting of stearamide, methylolstearamide, ethylenebisstearamide, N-stearylcarbamoylebenzene, terephthalic acid monomethylstearamide, dimethylterephthalate, benzoic acid p-chlorophenyl ester, benzoic acid p-cyanophenyl ester and methylbezoic phenyl ester, 2,6-diisopropylnaphthalene, phenanthrene, terphenyl, triphenylmethane, acenaphthene, fluorene and fluoranthene.

Claim 10

A two-color thermosensitive recording material as claimed in claim 2, wherein said water-soluble polymeric binder agent is selected from the group consisting of polyvinyl alcohol, polyacrylamide, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, starch, starch derivatives, isobutylene-maleic anhydride copolymer alkali salt and styrene/maleic anhydride copolymer alkali salt.

Claim 11

A two-color thermosensitive recording material as claimed in claim 1, wherein said first leuco dye employed in said high-temperature color-forming layer and said second leuco dye employed in said low-temperature color-forming layer each are selected from the group consisting of triphenylmethane-type leuco compounds, fluoran-type leuco compounds, phenothiazine-type leuco compounds, auramine-type leuco compounds and spiropyran-type leuco compounds.

Claim 12

A two-color thermosensitive recording material as claimed in claim 1, wherein said first leuco dye in said high-temperature color forming layer and said second leuco dye in said low-temperature color-forming layer each are selected from the group consisting of: 3,3-bis(p-dimethylaminophenyl)-phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (or Crystal Violet Lactone), 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-chlorophthalide, 3,3-bis(p-dibutylaminophenyl)-phthalide, 3-cyclohexylamino-6-chlorofluoran, 3-dimethylamino-5,7-dimethylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfluoran, 3-diethylamino-7,8-benzfluoran, 3-diethylaminobenzo[α]fluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-(N-p-tolyl-N-ethylamino)-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 2-[N-(3'-trifluoromethylphenyl)amino]-6-diethylaminofluoran, 2-[3,6-bis(diethylamino)-9-(o-chloroanilino)xanthylbenzoic acid lactam], 3-diethylamino-6-methyl-7-(m-trichloromethylanilino)-fluoran, 3-(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenyl)phthalide, 3-(2'-methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chloro-5'-methylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)-fluoran, 3-pyrrolidino-7-trifluoromethylanilinofluoran, 3-diethylamino-5-chloro-7-(N-benzyl-trifluoromethylanilino)fluoran, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluoran, 3-diethylamino-5-chloro-7-(α-phenylethylamino)fluoran, 3-(N-ethyl-p-toluidino)-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-(o-methoxycarbonylphenylamino)-fluoran, 3-diethylamino-5-methyl-7-(α-phenylethylamino)fluoran, 3-diethylamino-7-piperidinofluoran, 2-chloro-3-(N-methyltoluidino)-7-(p-n-butylanilino)-fluoran, 3-diethylamino-7-(o-chloroanilino)fluoran, 3-dibutylamino-7-(o-chloroanilino)fluoran, 3-dimethylamino-7-(o-chloroanilino)fluoran, 3-dipropylamino-7-(o-chloroanilino)fluoran, 3-dimethylamino-7-(o-fluoroanilino)fluoran, 3-diethylamino-7-(o-chloroanilino)fluoran, 3-dipropylamino-7-(o-fluoroanilino)fluoran, 3-dibutylamino-7-(o-fluoroanilino)fluoran, 3-N-methyl-N-amylamino-6-methyl-7-anilinofluoran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)-fluoran, benzoyl leuco methylene blue, 6'-chloro-8'-methoxy-benzoindolino-spiropyran, 6'-bromo-3'-methoxy-benzoindolino-spiropyran, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-chlorophenyl)phthalide, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)phthalide, 3-(N-benzyl-cyclohexylamino)-5,6-benzo-7-α-naphthylamino-4'-bromofluoran, and 3-diethylamino-6-methyl-7-methyl-7mesidino-4',5═-benzofluoran.

Claim 13

A two-color thermosensitive recording material as claimed in claim 1, wherein said second leuco dye in said low-temperature color forming layer is a leuco dye represented by the formula, ##STR18## wherein R 3 and R 4 each represent alkyl having 1 to 4 carbon atoms and R 3 represents chlorine or fluorine atom.

Claim 14

A two-color thermosensitive recording material as claimed in claim 1, wherein said color developer in said high-temperature color forming layer is selected from the group consisting of 4-hydroxyphenoxide, 4-t-butylphenol, 4-hydroxyacetophenone, resorcinol, α-naphthol, thymol, β-naphthol, catechol, hydroquinone, pyrogallol, phloroglucinol, phloroglucinolcarboxylic acid, 4,4'-sec-butylidenediphenol, 4,4'-isopropylidene-bis(2-t-butylphenol), 4-t-octylcatechol, 4'-sec-butylidenediphenol, 2,2'-dihydroxydiphenyl, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2-bis(4'-oxyphenyl)propane (Bisphenol A) and 3,5-xylenol.

Claim 15

A two-color thermosensitive recording material as claimed in claim 1, wherein said aliphatic amine contained in said decolorizing layer are thermo-fusible aliphatic amines having a melting point in the range of from 45° C. to 200° C.

Claim 16

A two-color thermosensitive recording material as claimed in claim 12, wherein said aliphatic amine is selected from the group consisting of stearylamine, behenyl amine, distearylamine, di-n-dodecylamine, triethylenediamine, octamethylenediamine and stearyldiethanolamine.

Claim 17

A two-color thermosensitive recording material as claimed in claim 1, wherein said thiourea derivative is selected from the group consisting of N,N'-diphenylthiourea, N-p-ethylphenyl-N'-phenylthiourea, N-p-butylphenyl-N'-phenylthiourea, N,N'-di-m-chlorphenylthiourea, N,N'-di-p-chlorophenylthiourea, N,N'-di-m-trifluoromethylphenylthiourea and N,N'-di-m-methylphenylthiourea.