# US 9,039,946 B2 · Reversibly thermochromic compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,039,946 B2 - Document ID: US9039946B2 - Status: Granted - Kind: B2 - Application number: 11/921,604 - Filed: 2006-05-31 - Published: 2009-12-10 - Granted: 2015-05-26 - Earliest claimed: 2005-06-10 - Assignees: BASF SE - Applicants: Walter Fischer; Abdel-Ilah Basbas; Mara Destro; Manuele Vitali; Dario Lazzari; Mirko Rossi - Inventors: Walter Fischer; Abdel-Ilah Basbas; Mara Destro; Manuele Vitali; Dario Lazzari; Mirko Rossi - Web page: https://patentgrep.com/patent/US9039946B2 ## CPC - C07C 69/95: Esters of quinone carboxylic acids - C07C 69/94: of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings - C07C 317/24: having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton - C07C 317/44: having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton - C07C 323/22: containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton - C07C 323/52: the carbon skeleton being acyclic and saturated - C07D 209/56: Ring systems containing three or more rings - C07D 209/58: [b]- or [c]-condensed - C07D 307/77: ortho- or peri-condensed with carbocyclic rings or ring systems - C09K 9/02: Organic tenebrescent materials - C07C 2603/44: Naphthacenes; Hydrogenated naphthacenes - C09K 2211/1011: Condensed systems - C09K 2211/1029: containing one nitrogen atom as the heteroatom - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE ## Abstract The present invention pertains to a reversibly thermochromic system comprising a substituted or an unsubstituted 6,11-dihydroxy-naphthacene-5,12-dione and a base and to a reversibly thermochromic composition comprising the reversibly thermochromic system and a carrier material and to novel substituted 6,11-dihydroxy-naphthacene-5,12-diones. ## Claims ### Claim 1 A reversibly thermochromic system comprising a) a 6,11-dihydroxy-naphthacene-5,12-dione and b) a base with a molecular weight of at least 300, wherein the base b) is an secondary or tertiary amine where the secondary or tertiary amine is of formula NHR26R27 or NHR26R27R28 where R26, R27 and R28 are independently C1-C30alkyl, C7-C12aralkyl, C2-C30alkenyl, C8-C12aralkenyl, C2-C30alkynyl or C8-C12aralkynyl, which are unsubstituted or substituted by one or more COO—R21, CONR21R22, OCO—R23, NR21CO—R23, NR23R21, O—R23, S—R23, SO—R23 and/or S(═O)2—R23; or the aralkyl, aralkenyl and aralkynyl are substituted by C1-C30alkyl, C2-C30alkenyl and/or C2-C30alkynyl, R23 is C1-C30alkyl, C2-C30alkenyl, C2-C30alkynyl, C6-C10aryl, C7-C12aralkyl, C8-C12aralkenyl or C8-C12aralkynyl and R21 and R22 are independently H or as defined for R23 or the secondary or tertiary amine is of formula III wherein G4, G5, G6 and G7 are independently methyl or ethyl, E is hydrogen, C1-C18 alkyl or C3-C18alkenyl and E10 is a carbon atom which is unsubstituted or substituted by OH, ═O or by one or two organic residues containing in total 1-500 carbon atoms, wherein said reversibly thermochromic system demonstrates a reversibly thermochromic property. ### Claim 2 (depends on 1) A reversibly thermochromic system of claim 1, wherein component a) is a compound of formula (I) or one of the tautomers thereof wherein R1, R2, R3, R4, R5, R6, R7 and R8 independently are H, C1-C30alkyl, C7-C12aralkyl, C1-C30alkoxy, C1-C30alkylthio, C1-C30alkylsulfoxyl, C1-C30alkylsulfonyl, C2-C30alkenyl, C8-C12aralkenyl, C2-C30alkenyloxy, C2-C30alkenylthio, C2-C30 alkenylsulfoxyl, C2-C30alkenylsulfonyl, C2-C30alkynyl, C8-C12aralkynyl, C2-C30alkynyloxy, C2-C30alkynylthio, C2-C30alkynylsulfoxyl, C2-C30alkynylsulfonyl, C6-C10aryl, C6-C10aryloxy, C6-C10arylthio, C6-C10arylsulfoxyl, C6-C10arylsulfonyl, halogen, NO2, CN, COO—R9, OCO—R10, CO—NR9R11 or NR12CO—R13, whereby the alkyl, alkenyl, alkynyl, aryl and aralkyl are substituted or unsubstituted, or R2, R3, R6 and/or R7 are hydroxy; or two adjacent groups of R1, R2, R3, R4, R5, R6, R7 and R8 form a 5- or 6-membered alicyclic or heterocyclic ring structure together with the two carbon atoms they are directly connected to; or two of the substituents R1, R2, R3, R4, R5, R6, R7 and R8 are defined as follows: one substituent is the group and the other substituent is the group so the part of the one substituent with the open bracket and the part of the other substituent with the open bracket form together with the part of the molecule they are both attached to a monomer unit that is x times part in an oligomer or polymer; R10 and R13 are independently C1-C30alkyl, C2-C30alkenyl, C2-C30alkynyl, C6-C10aryl, C7-C12aralkyl, C8-C12aralkenyl, C8-C12aralkynyl or an organic polymer, whereby the alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl and aralkynyl are substituted or unsubstituted; R9 is H or as defined for R10; R11 and R12 are independently H or C1-C30alkyl, C2-C30alkenyl, C2-C30alkynyl, C6-C10aryl, C7-C12aralkyl, C8-C12aralkenyl or C8-C12aralkynyl, whereby the alkyl, alkenyl, alkynyl, aryl aralkyl, aralkenyl and aralkynyl are substituted or unsubstituted; V is independently CH2, S, SO or SO2; G is C1-C30 alkylene; L and L′ are A or B; if L is A, then L′ is B; if L is B, then L′ is A; A is 0, S or NR14; R14 is H, C1-C30alkyl, C2-C30alkenyl, C2-C30alkynyl, C6-C10aryl, C7-C12aralkyl, C8-C12aralkynyl or C8-C12aralkenyl; B is CO; G2 is C1-C30alkylene; said alkylene is optionally interrupted by O, S, SO, SO2, NR14 or G2 is one of the groups R15 is H or CH3; q, r and s are independently integers from 1 to 20; R16 is NH2, NHR14 or R17 and R18 are independently as defined for R14 or R19 and R20 are independently C1-C20alkylene; G3 has the same meanings as G2; T is H, if L is A; T is OH, if L=B; x and y are independently integers from 1 to 20; z is an integer from 0 to 20; the substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, aralkenyl and aralkynyl are substituted by halogen, hydroxy, nitro, cyano, COO—R21, CONR21R22, OCO—R23, NR21CO—R23, NR21R22, O—R23S—R23SO—R23 and/or S(═O)2—R23; or the substituted aryl, aralkyl, aralkenyl and aralkynyl are substituted by C1-C30alkyl, C2-C30alkenyl and/or C2-C30alkynyl; R23 is C1-C30alkyl, C2-C30alkenyl, C2-C30alkynyl, C6-C10aryl, C7-C12aralkyl, C8-C312aralkenyl or C8-C12aralkynyl; and R21 and R22 are independently H or as defined for R23. ### Claim 3 (depends on 2) A reversibly thermochromic system of claim 2, wherein R1, R2, R3, R4, R5, R6, R7 and R8 independently are H, C1-C30alkyl, C7-C12aralkyl, C1-C30alkoxy, C1-C30alkylthio, C1-C30alkylsulfoxyl, C1-C30alkylsulfonyl, C2-C30alkenyl, C8-C12aralkenyl, C2-C30alkenyloxy, C2-C30alkenylthio, C2-C30alkenylsulfoxyl, C2-C30alkenylsulfonyl, C2-C30alkynyl, C8-C12aralkynyl, C2-C30alkynyloxy, C2-C30alkynylthio, C2-C30alkynylsulfoxyl, C2-C30alkynylsulfonyl, C6-C10aryl, C6-C10aryloxy, C6-C10arylthio, C6-C0arylsulfoxyl, C6-C10arylsulfonyl, halogen, NO2, CN, COO—R9, OCO—R10, CO—NR9R11 or NR12CO—R13, whereby the alkyl, alkenyl, alkynyl, aryl and aralkyl are substituted or unsubstituted, or R2, R3, R6 and/or R7 are hydroxy: or two adjacent groups of R1, R2, R3, R4, R5, R6, R7 and R8 form a 5- or 6-membered alicyclic or heterocyclic ring structure together with the two carbon atoms they are directly connected to, whereby the ring structure optionally contains one or two carbonyl groups and/or one or two hetero atoms, that are O, N, S, Se and/or P; the said ring structure is unsubstituted or substituted by C1-C30alkyl, C2-C30alkenyl, C2-C30alkynyl, unsubstituted or substituted C6-C10aryl, halogen, hydroxy, nitro, cyano, COO—R21, CONR21R22, OCO—R23NR21CO—R23NR21R22, O—R23, S—R23, SO—R23, S(═O)2—R23 an organic poly- or oligomer, and/or an anellated 5- or 6-membered saturated or unsaturated ring structure that contains C and optionally one or two carbonyl groups and/or one or two hetero atoms, that are O, N, S, Se and/or P, the said anellated ring structure is unsubstituted or substituted by C1-C30alkyl, C2-C30alkenyl, C2-C30alkynyl, halogen, hydroxy, nitro, cyano, COO—R21, CONR21R22, OCO—R23, NR21COR23, NR21R22, O—R23, S—R23, SO—R23, S(═O)2—R23, and/or anellated 5- or 6-membered saturated or unsaturated ring structure that contains C and optionally one or two carbonyl groups and/or one or two hetero atoms, that are O, N, S, Se and/or P; or two of the substituents R1, R2, R3, R4, R5, R6, R7 and R8 are defined as follows: one substituent is the group and the other substituent is the group so the part of the one substituent with the open bracket and the part of the other substituent with the open bracket form together with the part of the molecule they are both attached to a monomer unit that is x times part in an oligomer or polymer; and q, r and s are independently integers from 1 to 5. ### Claim 4 (depends on 3) A reversibly thermochromic system of claim 3, wherein R1, R2, R3, R4, R5, R6, R7 and R8 independently are H, C1-C30alkyl, C7-C12aralkyl, C1-C30alkoxy, C1-C30alkylthio, C1-C30alkylsulfoxyl, C1-C30alkylsulfonyl, C2-C30alkenyl, C8-C12aralkenyl, C2-C30alkenyloxy, C2-C30alkenylthio, C2-C30alkenylsulfoxyl, C2-C30alkenylsulfonyl, C2-C30alkynyl, C8-C12aralkynyl, C2-C30alkynyloxy, C2-C30alkynylthio, C2-C30alkynylsulfoxyl, C2-C30alkynylsulfonyl, C6-C10aryl, C6-C10aryloxy, C6-C10arylthio, C6-C0arylsulfoxyl, C6-C10arylsulfonyl, halogen, NO2, CN, COO—R9, OCO—R10, CO—NR9R11 or NR12CO—R13, whereby the alkyl, alkenyl, alkynyl, aryl and aralkyl are substituted or unsubstituted, or R2, R3, R6 and/or R7 are hydroxy; or R2 and R3 form together the group CO—O—CO or CO—NR24—CO; or R2 and R3 are defined as follows: one substituent is the group and the other substituent is the group so the part of the one substituent with the open bracket and the part of the other substituent with the open bracket form together with the part of the molecule they are both attached to a monomer unit that is x times part in an oligomer or polymer; R24 is C2-C30 alkyl, C2-C30alkenyl, C2-C30alkynyl, C6-C10aryl, C7-C12aralkyl, C8-C12aralkenyl, C8-C12aralkynyl or q is an integer from 2 to 4; r and s are independently integers from 1 to 3; W is C6-C10arylene, C1-C30alkylene, C1-C30alk-1-enylene, NR11 or O; and R25 is H or C1-C4alkyl. ### Claim 5 (depends on 4) A reversibly thermochromic system of claim 4, wherein R1, R2, R3, R4, R5, R6, R7 and R8 independently are H, C1-C30alkyl, C7-C12aralkyl, C1-C30alkoxy, C1-C30alkylthio, C1-C30alkylsulfoxyl, C1-C30alkylsulfonyl, C6aryl, C6arylthio, C6arylsulfoxyl, C6arylsulfonyl, halogen, COO—R9 or OCO—R10, whereby the alkyl and aryl are substituted or unsubstituted, or R2 and R3 form together the group CO—O—CO or CO—NR24—CO; or R2 and R3 are defined as follows: one substituent is the group and the other substituent is the group so the part of the one substituent with the open bracket and the part of the other substituent with the open bracket form together with the part of the molecule they are both attached to a monomer unit that is x times part in an oligomer or polymer; R10 is C1-C30alkyl or C6aryl, whereby the alkyl and aryl is substituted or unsubstituted; R9 is H or as defined for R10; R24 is unsubstituted or substituted C2-C30alkyl or C6aryl; V is SO2; G1 is C2-C10alkylene; L and L′ are A or B; if L is A, then L′ is B; if L is B, then L′ is A; A is O; B is CO; G2 is C2-C10alkylene; G3 has the same meanings as G2; T is H, if L is A; T is OH, if L=B; x and y are independently integers from 1 to 10; z is an integer from 0 to 10; the substituted alkyl and substituted aryl are substituted by hydroxy, COO—R21, OCO—R23 and/or O—R23; or the aryl is substituted by C1-C15alkyl; R23 is C1-C15alkyl; and R21 is H or as defined for R23. ### Claim 6 (depends on 1) A reversibly thermochromic system of claim 1, wherein the ratio of component a) to component b) is 2:1 to 1:100 by weight. ### Claim 7 (depends on 1) A reversibly thermochromic composition, comprising i) a reversibly thermochromic system as defined in claim 1 and ii) a carrier material. ### Claim 8 (depends on 7) A reversibly thermochromic composition of claim 7, wherein the ratio of component i) to component ii) is 1:10000 to 1:1. ### Claim 9 (depends on 7) A reversibly thermochromic composition of claim 7, comprising as carrier material ii) polymers, solvents and/or waxes. ### Claim 10 (depends on 7) A reversibly thermochromic composition of claim 7, comprising as carrier material ii) plastic articles, films, papers, fibers, solvents, waxes, coatings and/or inks. ### Claim 11 (depends on 7) A reversibly thermochromic composition of claim 7, comprising further additives selected from the group consisting of antioxidants, UV-absorbers, light stabilizers, metal deactivators, processing stabilizers, thiosynergists, peroxide scavengers, oxygen scavengers, basic co-stabilizers, nucleating agents, fillers, reinforcing agents, flameproofing agents and additional colorants, with the proviso that the additional colorants do not suppress and do not mask the thermochromic effect. ### Claim 12 (depends on 11) A reversibly thermochromic composition of claim 11, comprising as further additives phenolic antioxidants, aminic antioxidants, phosphites, phosphonites, hydroxylamines, nitrones, benzofuranones, indolinones, 2-(2-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, 2-(2-hydroxyphenyl)-1,3,5-triazines, oxamides, sterically hindered amines, pigments and/or dyes. ### Claim 13 (depends on 1) A process for reversibly thermochromically coloring a carrier by applying thereto/incorporating therein the reversibly thermochromic system of claim 1 comprising a 6,11-dihydroxy-naphthacene-5,12-dione and a base with a molecular weight of at least 300, wherein the base is an secondary or tertiary amine where the secondary or tertiary amine is of formula NHR26R27 or NHR26R27R28 where R26, R27 and R28 are independently C1-C30alkyl, C7-C12aralkyl, C2-C30alkenyl, C8-C12aralkenyl, C2-C30alkynyl or C8-C12aralkynyl, which are unsubstituted or substituted by one or more COO—R21, CONR21R22, OCO—R23, NR21CO—R23, NR23R21, O—R23, S—R23, SO—R23 and/or S(═O)2—R23; or the aralkyl, aralkenyl and aralkynyl are substituted by C1-C30alkyl, C2-C30alkenyl and/or C2-C30alkynyl, R23 is C1-C30alkyl, C2-C30alkenyl, C2-C30alkynyl, C6-C10aryl, C7-C12aralkyl, C8-C12aralkenyl or C8-C12aralkynyl and R21 and R22 are independently H or as defined for R23 or the secondary or tertiary amine is of formula III wherein G4, G5, G6 and G7 are independently methyl or ethyl, E is hydrogen, C1-C18 alkyl or C3-C18alkenyl and E10 is a carbon atom which is unsubstituted or substituted by OH, ═O or by one or two organic residues containing in total 1-500 carbon atoms.