Reversibly color-changeable materials

• US 5,068,062 A
• Filed: 04/05/1989
• Issued: 11/26/1991
• Est. Priority Date: 04/07/1988
• Status: Expired due to Fees

• Current Assignee: Teijin Limited
• Original Assignee: Teijin Limited
• Inventors: Okada, Masuhiro, Matsumura, Shunichi, Itoh, Seiji, Inata, Hiroo
• Primary Examiner(s): Barr, Josephine
• Application Number:
  US07/333,257
• Time in Patent Office: 965 Days
• Field of Search: 252/500, 252/518, 350/356, 350/357, 523/457-459, 524/401, 524/80, 524/423, 524/414, 524/413, 524/417, 524/403
• US Class Current: 252/586
• CPC Class Codes: C08F 8/44 Preparation of metal salts or ammonium salts
• CPC Class Codes: C08G 59/28 containing acyclic nitrogen atoms
• CPC Class Codes: C08G 59/40 characterised by the curing agents used
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials

Abstract

An electrochromic resin composition comprising (A) 100 parts by weight of a network comprising a crosslinked polymer containing 4,4'"'"'-diaminodiphenylmethane units in a form in which the amino groups in the formula are quaternized, and (B) 5 to 150 parts by weight of an electrolytic material uniformly dispersed in the network (A). The crosslinked polymer containing the units with the amino groups therein being in the quaternized state is useful as an electrochromic or photochromic material.

Claims

1. An electrochromic resin composition comprising

(a) 100 parts by weight of a network comprising a crosslinked polymer containing bonded units represented by the following formula (I) ##STR18## wherein R represents a hydrogen atom or a monovalent hydrocarbon group selected from the group consisting of alkyl, aralkyl, cycloalkyl and aryl groups, X and Y, independently from each other, represent a halogen atom, a nitro group, a monovalent hydrocarbon group selected from the group consisting of alkyl, aralkyl, cycloalkyl and aryl groups or a monovalent hydrocarbon-O-group wherein the monovalent hydrocarbon is selected from the group consisting of an alkyl, aralkyl, cycloalkyl and aryl groups, m and n, independently from each other, represent 0, 1, 2, 3 or 4, a, b, d and e are bonds which, independently from each other, are bonded to a hydrogen atom or to an aliphatic or alicyclic carbon, provided that at least one of these bonds is bonded to the aliphatic or alicyclic carbon,

in a form in which the amino groups in the formula are quaternized, and

(B) 5 to 150 parts by weight of an electrolytic material uniformly dispersed in the network (A) wherein the electrolyte is an alkali metal salt or an ammonium salt of an organic or inorganic acid.

2. The resin composition of claim 1 in which the aliphatic or alicyclic carbon to which at least one of the bonds a, b, d and e in formula (I) is bonded is present in the bonded units of formula (I) incorporated in the network chain of the crosslinked polymer, or in the bonded units of formula (I) as a pendant group from the network chain of the crosslinked polymer.

3. The resin composition of claim 1 in which bonds a and d in formula (I) are bonded to the aliphatic or alicyclic carbon whereby the bonded units of formula (I) are incorporated in the network chain of the crosslinked polymer.

4. The resin composition of claim 1 in which in formula (I), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, X and Y, independently from each other, represent a fluorine, chlorine, bromine, a nitro group, an alkyl group having 1 to 5 carbons atoms, or an alkoxy group having 1 to 5 carbon atoms, m and n, independently from each other, represent 0 or 1, and a, b, d and e are as defined above.

5. The resin composition of claim 1 in which the crosslinked polymer is a crosslinked epoxy resin derived from a mixture composed of

(a) an epoxyamine compound represented by the following formula (II-1) ##STR19## wherein R, X, Y, m and n are as defined with regard to formula (I), and R¹, R², R³ and R⁴ are identical or different and each represents a hydrogen atom, a monovalent hydrocarbon group having a 1,2-epoxy moiety, or a monovalent hydrocarbon group selected from the group consisting of alkyl, alkenyl, cycloalkenyl, cycloalkyl and alkyl groups which may be substituted by a substituent inert to the 1,2-epoxy moiety, with the proviso that at least one of R¹, R², R³ and R⁴ is the monovalent hydrocarbon group having a 1,2-epoxy moiety, and

(b) a compound selected from the group consisting of amine compounds having at least two active hydrogens, polycarboxylic acids, intramolecular anhydrides of the polycarboxylic acids, polyphenols and poly(cyclic iminoethers), and in which the amino groups in formula (II-1) are in the quaternized state.

6. The resin composition of claim 5 in which the crosslinked polymer is a crosslinked epoxy resin obtained by ring-opening polymerization of an epoxyamine compound of formula (II-1) in which at least two of R¹ to R⁴ are monovalent hydrocarbon groups having a 1,2-epoxy moiety or a mixture of it with another epoxy compound, and the amino group in formula (II-1) are quaternized.

7. The resin composition of claim 1 in which the crosslinked polymer is a crosslinked resin derived from a mixture composed of

(a'"'"') an amine compound represented by the following formula (II-2) ##STR20## wherein R, X, Y, m and n are as defined hereinabove, and R⁵, R⁶, R⁷ and R⁸, independently from each other, represent a hydrogen atom or a monovalent hydrocarbon group selected from the group consisting of alkyl, aralkyl, cycloalkyl and aryl groups which may be substituted by a substituent other than a 1,2-epoxy group with the proviso that at least two of R⁵, R⁶, R⁷ and R⁸ are hydrogen atoms, and

(b'"'"') a compound selected from the group consisting of poly(cyclic iminoethers), polyepoxy compounds and polyisocyanates, and in which the amino groups in formula (II-2) are in the quaternized state.

8. The resin composition of claim 1 in which the crosslinked polymer is a crosslinked resin obtained by addition-polymerization of an ethylenically unsaturated compound represented by the following formula (II-3) ##STR21## wherein R, X, Y, m and n are defined hereinabove, R⁹, R¹⁰, R¹¹ and R¹², independently from each other represent a hydrogen atom, a monovalent hydrocarbon group having an ethylenically unsaturated bond selected from the group consisting of aralkyl, aryl, alkenyl or cycloalkenyl groups, or a monovalent hydrocarbon group having no ethylenically unsaturated bond selected from the group consisting of alkyl and cycloalkyl groups, with the proviso that at least two of R⁹ through R¹² are said monovalent hydrocarbon groups having an ethylenically unsaturated bond,

or a mixture of it with another ethylenically unsaturated compound and in which the amino groups in formula (II-3) are in the quaternized state.

9. An electrochromic display element comprising a pair of display electrodes each comprising a conductive transparent substrate and a conductive thin plate thereon, the two electrodes being arranged with an electrolyte medium therebetween;

wherein one of the display electrodes is an electrode having a color formation layer composed of the resin composition of claim 1 as the conductive thin film, and the other display electrode is an electrode having a color formation layer composed of a transition metal oxide or a resin composition containing a viologen as the conductive thin film.

10. The electrochromic resin of claim 1 wherein the electrolyte is selected from the group consisting of the KBr, KCl, CI, LiCl, K₂ SO₄, LiClO₄, KBF₄, KH₂ PO₄, KNO₃, CH₃ COOK, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, tetramethyl ammonium perchlorate, tetrabutyl ammonium bromide, tetraethyl ammonium perchlorate and tetrabutyl ammonium perchlorate.

11. The resin composition of claim 1 wherein when R, X or Y is a hydrocarbon group or Y is a monovalent hydrocarbon-O-group the monovalent hydrocarbon group is selected from the group consisting of alkyl having 1 to 5 carbon atoms, aralkyl having 1 to 3 carbons in the alkyl group and the aryl is phenyl, cycloalkyl having 5-12 carbon atoms and aryl of from 6 to 12 carbon atoms.

12. The resin composition of claim 5 wherein the epoxyamine compound (a) is bis-N(4-N,N-di(2,3-epoxypropyl)aminophenyl)methane, bis(3-chloro-4,N,N-di(2,3-epoxypropyl)amino-phenyl)methane or bis(2-methyl-4,N,N-di(2,3-epoxypropyl)aminophenyl)methane.

13. The resin composition of claim 5 wherein compound (b) is an amine compound having at least two active hydrogens.

14. The resin composition of claim 13 wherein compound (b) is 4,4'"'"'-diamino-diphenyl methane.

15. The resin composition of claim 5 wherein compound (b) is an aliphatic or alicyclic polycarboxylic acid.

16. The resin composition of claim 5 wherein compound (b) is an intramolecular anhydride of an aliphatic or alicyclic polycarboxylic acid.

17. The resin composition of claim 5 wherein compound (b) is a polyphenol.

18. The resin composition of claim 5 wherein compound (b) is a poly (cyclic iminoether).

19. The resin composition of claim 7 wherein the amine compound (a'"'"') is 4,4'"'"'-diaminodiphenyl methane.

20. The resin composition of claim 8 wherein the monovalent hydrocarbon group having an ethylenically unsaturated bond is an allyl group.