# US 5,350,633 A · Thermochromic composition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,350,633 A - Document ID: US5350633A - Status: Granted - Kind: A - Application number: 08/103,673 - Filed: 1993-08-10 - Granted: 1994-09-27 - Earliest claimed: 1992-09-08 - Assignees: Sakura Color Products Corporation - Inventors: Masaaki Sumii; Fumiko Sakai; Yasuyuki Yoshimura - Web page: https://patentgrep.com/patent/US5350633A ## CPC - B41M 5/284: {Organic thermochromic compounds} - Y10T 428/2985: Solid-walled microcapsule from synthetic polymer - B41M: PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING, (correction of typographical errors B41J; processes for applying transfer pictures or the like B44C1/16; fluid media for correction of typographical errors by coating C09D10/00; printing textiles D06P) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract A thermochromic composition which comprises (1) an electron-donating chromogenic organic compound, (2) an electron-accepting compound, and (3) at least one desensitizer selected from among carbazole derivatives of the following formulas: ##STR1## wherein R is an alkyl group containing 1 to 22 carbon atoms, a phenyl group or a benzyl group and X is a hydrogen atom, a halogen atom, --NH.sub.2, --NO.sub.2 or --CHO; ##STR2## wherein R is an alkyl group containing 1 to 22 carbon atoms and X is a hydrogen atom, a halogen atom, --NH.sub.2, --NO.sub.2 or --CHO. A thermochromic composition which comprises (1) an electron-donating chromogenic organic compound, (2) an electron-accepting compound, (3) at least one desensitizer selected from among carbazole derivatives mentioned above, and (4) a thermochromic transition temperature modifier. A thermochromic composition which comprises one of the thermochromic compositions mentioned above as enclosed in microcapsule. ## Claims ### Claim 1 A thermochromic composition which comprises: (1) an electron-donating chromogenic organic compound, (2) an electron-accepting compound and (3) at least one desensitizer selected from among carbazole derivatives of the following formulas: ##STR9## wherein R is an alkyl group containing 1 to 22 carbon atoms, a phenyl group or a benzyl group and X is a hydrogen atom, a halogen atom, --NH.sub.2, --NO.sub.2 or --CHO; ##STR10## wherein R is an alkyl group containing 1 to 22 carbon atoms and X is a hydrogen atom, a halogen atom, --NH.sub.2, --NO.sub.2 or --CHO. ### Claim 2 (depends on 1) A thermochromatic composition as claimed in claim 1, wherein said desensitizer is a carbazole derivative having a molecular weight within the range of 181 to 900. ### Claim 3 (depends on 1) A thermochromic composition as claimed in claim 1, wherein said desensitizer is a carbazole derivative having a melting point within the range of -50.degree. C. to 300.degree. C. ### Claim 4 (depends on 1) A thermochromic composition as claimed in claim 1, wherein said desensitizer comprises at least one carbazole derivative selected from the group consisting of N-methyl carbazole, N-ethyl carbazole, N-propyl carbazole, N-isobutyl carbazole, N-capryl carbazole, N-lauryl carbazole, N-myristyl carbazole, N-cetyl carbazole, N-stearyl carbazole, 3-chloro-N-methyl carbazole, N-ethyl-3-carbaldehyde, 3-nitro-N-propyl carbazole, 3-amino-N-lauryl carbazole, N-acetyl carbazole, N-propionyl carbazole, N-lauroyl carbazole, N-myristoyl carbazole, N-palmitoyl carbazole, N-stearoyl carbazole, 3-amino-N-lauroyl carbazole, 3-bromo-N-caproyl carbazole, N-phenyl carbazole and N-benzyl carbazole. ### Claim 5 (depends on 1) A thermochromic composition as claimed in claim 1, wherein said electron-donating chromogenic organic compound comprises at least one compound selected from the group consisting of diarylphthalides, polyarylcarbinols, leucoauramines, rhodamine B lactams, indolines, spiropyrans, and fluorans. ### Claim 6 (depends on 1) A thermochromic composition as claimed in claim 1, wherein said electron-donating chromogenic organic compound comprises at least one compound selected from the group consisting of crystal violet lactone, malachite green lactone, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl) phthalide, Michler's hydrol, crystal violet carbinol, malachite green carbinol, N-(2,3-dichlorophenyl) leucoauramine, N-benzoylauramine, N-acetylauramine, N-phenylauramine, rhodamine B lactam, 2-(phenyliminoethylidene) 3,3-dimethylindoline, N-3,3-trimethylindolinobenzospiropyran, 8-methoxy-N-3,3-trimethylindolinobenzospiropyran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-6-benzyloxyfluoran, 3-amino-5-methylfluoran, 2-methyl-3-amino-6,7-dimethylfluoran, 2-bromo-6-cyclohexylaminofluoran, 2-(o-chlorophenylamino)-6-dibutylaminofluoran, 1,3-dimethyl-6-diethylaminofluoran, 3,6-diphenylaminofluoran, 9-(diethylamino)-spiro(12H-benzoxanthene-12,1'(3'H)-isobenzofluoran)-3'-on e, 2-(N-phenyl-N-methylamino)-6-(N-ethyl-N-phenylamino)fluoran, 3-diethylamino-6-methyl-7-chlorofluoran and 3-diethylaminobenzo(a)-fluoran. ### Claim 7 (depends on 1) A thermochromic composition as claimed in claim 1, wherein said electron-accepting compound comprises at least one compound selected from the group consisting of phenols, phenol resins, metal phenolates, aromatic carboxylic acids, aliphatic carboxylic acids containing 2 to 5 carbon atoms, metal salts of carboxylic acids, acid phosphoric esters, metal salts of acid phosphoric esters, triazole compounds, thiourea, diphenylthiourea, di-o-toluoylthiourea, halohydrins, and benzothiazoles. ### Claim 8 (depends on 7) A thermochromic composition as claimed in claim 7, wherein said electron-accepting compound comprises at least one compound selected from the group consisting of bisphenol A, p-phenylphenol, dodecylphenol, o-bromophenol, ethyl p-hydroxybenzoate, methyl gallate, phenol resins, sodium phenolate, potassium phenolate, lithium phenolate, calcium phenolate, zinc phenolate, aluminum phenolate, magnesium phenolate, nickel phenolate, cobalt phenolate, tin phenolate, copper phenolate, iron phenolate, titanium phenolate, lead phenolate, molybdenum phenolate, phthalic acid, benzoic acid, acetic acid, propionic acid, sodium oleate, zinc salicylate, nickel benzoate, 1,2,3-triazole, 1,2,3-benzotriazole, thiourea, diphenylthiourea, and di-o-toluoylthiourea. ### Claim 9 A thermochromic composition which comprises: (1) an electron-donating chromogenic organic compound, (2) an electron-accepting compound, (3) at least one desensitizer selected from among carbazole derivatives of the following formulas: ##STR11## wherein R is an alkyl group containing 1 to 22 carbon atoms, a phenyl group or a benzyl group and X is a hydrogen atom, a halogen atom, --NH.sub.2, --NO.sub.2 or --CHO; ##STR12## wherein R is an alkyl group containing 1 to 22 carbon atoms and X is a hydrogen atom, a halogen atom, --NH.sub.2, --NO.sub.2 or --CHO, and (4) a thermochromic transition temperature modifier. ### Claim 10 (depends on 9) A thermochromic composition as claimed in claim 9, wherein said desensitizer is a carbazole derivative having a molecular weight within the range of 181 to 900. ### Claim 11 (depends on 9) A thermochromic composition as claimed in claim 9, wherein said desensitizer is a carbazole derivative having a melting point within the range of 50.degree. C. to 300.degree. C. ### Claim 12 (depends on 9) A thermochromic composition as claimed in claim 9, wherein said desensitizer comprises at least one carbazole derivative selected from the group consisting of N-methyl carbazole, N-ethyl carbazole, N-propyl carbazole, N-isobutyl carbazole, N-capryl carbazole, N-lauryl carbazole, N-myristyl carbazole, N-cetyl carbazole, N-stearyl carbazole, 3-chloro-N-methyl carbazole, N-ethyl-3-carbaldehyde, 3-nitro-N-propyl carbazole, 3-amino-N-lauryl carbazole, N-acetyl carbazole, N-propionyl carbazole, N-lauroyl carbazole, N-myristoyl carbazole, N-palmitoyl carbazole, N-stearoyl carbazole, 3-amino-N-lauroyl carbazole, 3-bromo-N-caproyl carbazole, N-phenyl carbazole and N-benzyl carbazole. ### Claim 13 (depends on 9) A thermochromic composition as claimed in claim 9, wherein said thermochromic transition temperature modifier comprises at least one compound selected from the group consisting of alcohols, esters, ketones, ethers, acid amides, fatty acids, aromatic hydrocarbons, thiols, sulfides, disulfides, sulfoxides, sulfones, azomethines, and fatty acid primary amine salts. ### Claim 14 (depends on 9) A thermochromic composition as claimed in claim 9, wherein said thermochromic transition temperature modifier comprises at least one compound selected from the group consisting of n-cetyl alcohol, n-octyl alcohol, cyclohexanol, hexylene glycol, ethyl myristate, stearyl laurate, dioctyl phthalate, methyl hexyl ketone, benzophenone, stearone, butyl ether, diphenyl ether, distearyl ether, oleamide, stearamide, N-octyl lauramide, caproanilide, lauric acid, stearic acid, 2-hydroxymyristic acid, isopropylbenzene, dodecylbenzene, biphenyl, trimethylbiphenyl, diphenylethane, dibenzyltoluene, propylnaphthalene, butyltetralin, n-decylmercaptan, n-myristylmercaptan, n-stearylmercaptan, isocetylmercaptan, dodecylbenzylmercaptan, di-n-octyl sulfide, di-n-decyl sulfide, diphenyl sulfide, diethylphenyl sulfide, dilauryl thiodipropionate, di-noctyl disulfide, di-n-decyl disulfide, diphenyl disulfide, dinaphthyl disulfide, diethyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfoxide, diethyl sulfone, dibutyl sulfone, diphenyl sulfone, dibenzyl sulfone, benzylidenelaurylamine, p-methoxybenzylidenelaurylamine, benzylidene-p-anisidine, stearylamine oleate, myristylamine stearate, and stearylamine behenate. ### Claim 15 (depends on 9) A thermochromic composition as claimed in claim 9, wherein said electron-donating chromogenic organic compound comprises at least one compound selected from the group consisting of diarylphthalides, polyarylcarbinols, leucoauramines, rhodamine B lactams, indolines, spiropyrans, and fluorans. ### Claim 16 (depends on 9) A thermochromic composition as claimed in claim 9, wherein said electron-donating chromogenic organic compound comprises at least one compound selected from the group consisting of crystal violet lactone, malachite green lactone, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, Michler's hydrol, crystal violet carbinol, malachite green carbinol, N(2,3-dichlorophenyl)leucoauramine, N-benzoylauramine, N-acetylauramine, N-phenylauramine, rhodamine B lactam, 2-(phenyliminoethylidene) 3,3-dimethylindoline, N-3,3-trimethylindolinobenzospiropyran, 8-methoxy-N-3,3-trimethylindolinobenzospiropyran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-6-benzyloxyfluoran, 3-amino-5-methylfluoran, 2-methyl-3-amino-6,7-dimethylfluoran, 2-bromo-6-cyclohexylaminofluoran, 2-(o-chlorophenylamino)-6-dibutylaminofluoran, 1,3-dimethyl-6-diethylaminofluoran, 3,6-diphenylaminofluoran, 9-(diethylamino)-spiro(12H-benzoxanthene-12,1'(3'H)-iso-obenzofluoran)-3'- one, 2-(N-phenyl-N-methylamino)-6-(N-ethyl-N-phenylamino)fluoran, 3-diethylamino-6-methyl-7-chlorofluoran, and 3-diethylaminobenzo(a)-fluoran. ### Claim 17 (depends on 9) A thermochromic composition as claimed in claim 9, wherein said electron-accepting compound comprises at least one compound selected from the group consisting of phenols, phenol resins, metal phenolates, aromatic carboxylic acids, aliphatic carboxylic acids containing 2 to 5 carbon atoms, metal salts of carboxylic acids, acid phosphoric esters, metal salts of acid phosphoric esters, triazole compounds, thiourea, diphenylthiourea, di-o-toluoylthiourea halohydrins, and benzothiazoles. ### Claim 18 (depends on 9) A thermochromic composition as claimed in claim 9, wherein said electron-accepting compound comprises at least one compound selected from the group consisting of bisphenol A, p-phenylphenol, dodecylphenol, o-bromophenol, ethyl p-hydroxybenzoate, methyl gallate, sodium phenolate, potassium phenolate, lithium phenolate, calcium phenolate, zinc phenolate, aluminum phenolate, magnesium phenolate, nickel phenolate, cobalt phenolate, tin phenolate, copper phenolate, iron phenolate, titanium phenolate, lead phenolate, molybdenum phenolate, phthalic acid, benzoic acid, acetic acid, propionic acid, sodium oleate, zinc salicylate, nickel benzoate, 1,2,3-triazole, 1,2,3-benzotriazole, thiourea, diphenylthiourea, and di-o-toluoylthiourea. ### Claim 19 (depends on 1) A microencapsulated thermochromic composition which comprises the thermochromic composition of claim 1 enclosed within a microcapsule.