Thermochromic materials

• US 4,425,161 A
• Filed: 11/24/1981
• Issued: 01/10/1984
• Est. Priority Date: 11/27/1980
• Status: Expired due to Term

• Current Assignee: The Pilot Ink Co. Ltd (Berkshire Hathaway Incorporated)
• Original Assignee: The Pilot Ink Co. Ltd (Berkshire Hathaway Incorporated)
• Inventors: Inagaki, Hiroshi, Nakasuji, Norikazu, Kataoka, Takashi, Kito, Tsutomu, Shibahashi, Yutaka
• Primary Examiner(s): Hayes, Lorenzo B.
• Assistant Examiner(s): YARBROUGH, AMELIA
• Application Number:
  US06/324,701
• Time in Patent Office: 777 Days
• Field of Search: 106/21, 427/148, 427/150, 282/27.5
• US Class Current: 106/31.17
• CPC Class Codes: B41M 5/282 using thermochromic compounds
• CPC Class Codes: B41M 5/305 with reversible electron-donor electron-acceptor compositions
• CPC Class Codes: C09D 11/50 Sympathetic, colour changing or similar inks
• CPC Class Codes: C09D 5/26 Thermosensitive paints

Abstract

A thermochromic material is described which comprises (a) an electron-donating, chromatic organic compound, (b) a compound capable of reversibly accepting an electron or electrons from the electron-donating, chromatic organic compound, (c) a compound controlling the temperature and sensitivity of coloration/decoloration of the thermochromic material and (d) a N-radical, P-radical, O-radical or S-radical cationic compound having an aromatic ring or rings which improves by light-fastness.

Claims

1. In a reversible thermochromic material comprising (a) one or more electron-donating, chromatic organic compounds selected from the group consisting of diaryl phthalides, aryl phthalides, indolylphthalides, polyarylcarbinols, leucoauramines, acrylauramines, arylauramines, rhodamine B lactams, indolines, spiropyrans, fluorans, thiofluorans, phenothiazines, triphenylmethanes, diarylarylfurans, spiroxanthenearylfurans, and chromenoindoles, (b) one or more compounds, compounds, which are capable of reversibly accepting electrons of said organic compound, selected from the group consisting of phenolic hydroxy group-containing compounds and derivatives thereof and carboxyl group-containing compounds and derivatives thereof, and (c) one or more compounds, which are controlling the temperature and sensitivity of coloration/decoloration of said thermochromic material, selected from the group consisting of alcohols, esters, ketones, esters, acid amides and carboxylic acids, the ratio of each component to others (a):

(b);

(c) being 1;

0.1 to 10;

1 to 100 by weight,

the improvement which comprises said thermochromic material further containing (d) one or more radical cationic compound selected from the group consisting of N-radical cationic, P-radical cationic, O-radical cationic and S-radical cationic compounds having aromatic ring(s), in an amount of from 0.01 to 5 parts by weight per 1 part by weight of said electron-donating chromatic organic compound, said radical cationic compound interacting with said electron-donating, chromatic organic compound to stabilize said compound, resulting in a thermochromic mateiral with an improved resistance to light.

2. A thermochromic material as set forth in claim 1, wherein said radical cationic compound is selected from the group consisting of aminium salts and diimonium salts represented by the following general formulas (N-I) and (N-II), respectively:

space="preserve" listing-type="equation">[R.sup.1 --C.sub.6 H.sub.4).sub.n --N--(R.sup.2).sub.3-n ].X.sup.-(N-I)

wherein

n=1, 2 or 3;

R¹ =a hydrogen atom, an alkyl group (containing 1 to 18 carbon atoms), or a dialkylamino group (each alkyl group thereof containing 1 to 18 carbon atoms);

R² =a hydrogen atom, an alkyl group (containing 1 to 18 carbon atoms), or a di(substituted phenyl) amino group (the substituent including a hydrogen atom and an alkyl group containing 1 to 18 carbon atoms), provided that when n=1, two R² groups may be combined to form any one of the following groups;

##STR181## (wherein R³, R⁴, R⁵ and R⁶ =hydrogen atoms, or an alkyl group (containing 1 to 18 carbon atoms)); and

X^- =perchlorate (ClO₄^-), fluoroborate (BF₄^-), trichloroacetate (CCl₃ COO^-), trifluoroacetate (CF₃ COO^-), picrate ((NO₂)₃ C₆ H₂ O^-), hexafluoroarsenate (AsF₆^-), hexachloroantimonate (SbCl₆^-), hexafluoroantimonate (SbF₆^-), benzenesulfonate (C₆ H₅ SO₃^-), alkylsulfonate (RSO₃^-, the alkyl group thereof containing 1 to 18 carbon atoms), phosphate (PO₄^3-), sulfate (SO₄^2-), chloride (Cl^-) or bromide (Br^-), ##STR182## wherein ##STR183## l=1 or 2;

m=1 or 2;

R⁷ =a hydrogen atom, an alkyl group (containing 1 to 18 carbon atoms), a dialkylamino group (each alkyl group thereof containing 1 to 18 carbon atoms) or a diethanolamino group;

R⁸ =a hydrogen atom, an alkyl group (containing 1 to 18 carbon atoms), a dialkylamino group (each alkyl group thereof containing 1 to 18 carbonatoms) or a diethanolamino group;

R⁹ =a phenyl group, an alkyl group (containing 1 to 18 carbon atoms), a 4-dialkylaminophenyl group (each alkyl group thereof containing 1 to 18 carbon atoms) or a 4-diethanolaminophenyl group;

R¹⁰ --a phenyl group, an alkyl group (containing 1 to 18 carbon atoms), a 4-dialkylaminophenyl group (each alkyl group thereof containing 1 to 18 carbon atoms) or a 4-diethanolaminophenyl group; and

X^- --the same as for the general formual (N-I).

3. A thermochromic material as set forth in claim 1, wherein said thermochromic material contains one or more of

ultraviolet absorbers selected from the group consisting of 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, phenyl salicylate, p-tertbutylphenyl salycilate, p-octylphenyl salycilate, 2-(2'"'"'-hydroxy-5'"'"'-methyl-phenyl)benzotriazole, 2-(2'"'"'-hydroxy-3'"'"',5'"'"'-di-tertbutylphenyl)benzotriazole, 2-(2'"'"'hydroxy-8'"'"'tert-butyl-1'"'"',5'"'"'-methylphenyl)5-chlorobenzotriazole, 2-(2'"'"'-hydroxy-3'"'"',5'"'"'-di-tertbutylphenyl)-5-chlorobenzotriazole, 2-(2'"'"'-hydroxy-3'"'"',5'"'"'-tertbutylphenyl)-5-chlorobenzotriazole, 2-(2'"'"'-hydroxy-4'"'"'-octoxyphenyl)benzotriazole, 2'"'"'-ethylhexyl-2-cyano-8-phenyl cinnamate and resorcinol monobenzoate;

visible light absorbers selected from the group consisting of monoazo-, bisazo-, metal complex salt type monoazo-, anthraquinone-, phthalocyanine- and triphenylmethane-based dyes, and monoazo-, bisazo-, metal complex salt type monoazo-, anthraquinone-, indigo-, thioindigo-, phthalocyanine-, triphenylmethane- and xanthene-based pigments;

antioxidants selected from the group consiting of 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 2,2'"'"'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'"'"'-isopropylidene-bisphenol, 2,6-bis(2'"'"'-hydroxy-3'"'"'-tert-butyl-5'"'"'-methylbenzyl)-4-methyl-phenol, 4,4'"'"'-thiobis-(3-methyl-6-tertbutylphenol), tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane, p-hydroxyphenyl-3-naphthylamine, 2,2,4-trimethyl-1,2-dihydroxyquinoline, thiobis(β

-naphthol), mercaptobenzothiazole, mercaptobenzimidazole, aldol-α

-naphthylamine, bis-(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 2,2,6,6-tertramethyl-4-piperidylbenzoate, dilauryl-8,8'"'"'-thiodipropionate, distearyl-8,8'"'"'-thiodipropionate and tris(4-nonylphenol)phosphite;

singlet oxygen quenchers selected from the group consisting of 1,4-diazabicyclo [2,2,2]octane (DABCO), β

-carotene, 1,3-cyclohexadiene, 2-diethylaminomethylfuran, 2-phenylaminomethylfuran, 9-diethylaminomethylanthrathene, 5-diethylaminomethyl-6-phenyl-3,4-dihydroxypyran, nickel dimethyl dithiocarbamate, nickel dibutyl dithiocarbamate, nickel 3,5-di-tert-butyl-4-hydroxybenzyl o-ethylphosphate, nickel 3,5-di-tert-butyl-4-hydroxybenzyl o-butylphosphate, nickel-[2,2'"'"'-thiobis(4-tertoctylphenolate)](n-butylamine), nickel [2,2'"'"'-thiobis(4-tertoctylphenolate](2-ethylhexylamine), nickel bis[2,2'"'"'-thio-bis(4-tert-octylphenolate)], nickel bis[2,2'"'"'-sulfone-bis(4-octylphenolate)], nickel bis-(2-hydroxy-5-methoxyphenyl-N-n-butylaldoimine), nickel bis-(dithiobenzyl), and nickel bis(dithiobiacetyl); and

superoxide anion quenchers selected from the group consisting of super oxide dimustase and complexes of cobalt (III) and nickel (II),

in an amount of from 0.5 to 10% by weight of the whole.

4. A thermochromic material as set forth in claim 1, wherein said thermochromic material is in microcapsules having a size not exceeding 30 μ

m.

5. A thermochromic material as set forth in claim 2, wherein said thermochromic material is in microcapsules having a size not exceeding 30 μ

m.

6. A thermochromic material as set forth in claim 3 wherein said thermochromic material is in microcapsules having a size not exceeding 30 μ

m.