Asymmetric dichroic dye molecules having poly(arylazo) linking groups, a bis-substituted aryl thiazyl end group, and another end group

• US 4,565,424 A
• Filed: 01/06/1982
• Issued: 01/21/1986
• Est. Priority Date: 12/12/1980
• Status: Expired due to Fees

• Current Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Huffman, William A., Novack, James C.
• Primary Examiner(s): Higel, Floyd D.
• Application Number:
  US06/337,493
• Time in Patent Office: 1,476 Days
• Field of Search: 260/158, 252/299, 252/299.1, 252/299.01, 252/299.61, 252/299.62, 252/299.68, 350/349, 350/350 R, 534/754, 534/755, 534/757, 534/762, 534/763, 534/648
• US Class Current: 349/165
• CPC Class Codes: C09B 31/00 Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
• CPC Class Codes: C09B 35/50 Tetrazo dyes
• CPC Class Codes: C09K 19/60 Pleochroic dyes
• CPC Class Codes: C09K 19/601 Azoic

Abstract

A dichroic dyestuff having the formula

Q--A--Z

wherein:

A is a poly(arylazo) linking group wherein the aryl comprises 6 to 10 carbon atoms and has 4,4'"'"'-azo linkages;

Q is a bis-substituted aryl thiazyl substituent wherein the aryl comprises 6 to 10 carbon atoms;

and

Z is selected from the group consisting of naphthalene having an alkyl substituted amino in the 4 position, 2,3-dihydro-2,2'"'"'-substituted-perimidine and julolidine groups;

forms guest-host combinations with nematic liquid crystals. These dichroic dyes have absorption maxima at wavelengths greater than 600 nanometers and transmit less than 50% of incident light having wavelengths between 600 and 700 nanometers. Thus these dyes, when combined with dichroic dyes which have absorption maxima between 400 and 600 nanometers, and nematic liquid crystals, are useful to provide electro-optical displays which change from clear to a neutral black color or vice versa when an electric field is applied to the electro-optical display.

Claims

1. A dichroic dyestuff having the formula

View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 11, 12, 13, 14, 15, 16, 17, 18, 19)

2. The dichroic dyestuff of claim 1 wherein the poly(arylazo) linking group A has the formula:

##STR62## wherein m is 0, or an integer from about 1 to 6, and x is independently 0, 1, 2 or 4, provided that

where x is 4, the R groups are independently selected from the group consisting of alkyl or alkoxy groups having from about 1 to 8 carbon atoms;

where x is 2, the R groups are independently selected from the group consisting of alkyl or alkoxy groups having from about 1 to 8 carbon atoms, and the two R groups are not substituted on adjacent ring carbon atoms; and

when x is 1, in from 0 to m ##STR63## R is the group --C═

CH--CH═

CH-- which is substituted on two adjacent ring carbon atoms.

3. The dichroic dyestuff of claim 1 wherein the bis-substituted aryl thiazyl group Q has the formula:

##STR64## wherein B and B'"'"' are independently selected from the group consisting of H, C_n H_2n+1, OC_n H_2n+1, phenyl, phenoxy, trifluoromethylsulfonyl, cyano, and thiocyanato, wherein n is an integer from about 1 to 10.

4. The dichroic dyestuff of claim 1 wherein the bis-substituted aryl thiazyl group Q has the formula:

##STR65##

5. The dichroic dyestuff of claim 1 wherein the bis-substituted aryl thiazyl group Q has the formula ##STR66##

6. The dichroic dyestuff of claim 1 wherein Z has the formula:

##STR67## wherein R is selected from the group consisting of H and C_n H_2n+1 and wherein R₂ is C_n H_2n+1, wherein n is an integer from about 1 to 20.

7. The dichroic dyestuff of claim 1 wherein Z has the formula:

##STR68## wherein R₃ and R₄ are independenytly selected from the group consisting of alkyls and alkenes having about 1-20 carbon atoms, aryls, cycloaliphatic and heterocyclic rings, or R₃ and R₄ are combined and, together with the 2 carbon of the perimidine moiety, form cycloaliphatic or heterocyclic rings, said cycloaliphatic and heterocyclic rings having from 4 to 12 carbon atoms and said rings consisting of atoms selected from the group consisting of carbon, hydrogen, nitrogen, oxygen, and sulfur.

8. The dichroic dyestuff of claim 1 wherein Z is selected from the group consisting of:

##STR69## wherein R₅ is a lower alkyl having about 1 to 6 carbon atoms, and wherein the cyclopentyl and cyclohexyl rings are substituted in available positions by groups independently selected from the group consisting of H and lower alkyls having about 1-8 carbon atoms.

9. The dichroic dyestuff of claim 1 wherein Z is a julolidine group having the formula:

##STR70##

11. A composition of matter comprising a nematic liquid crystal material and, in admixture therewith, the dichroic dyestuff of claim 1.

12. The composition of claim 11 wherein said composition additionally comprises at least one dichroic dye having maximum absorption at wavelengths between about 400 and 600 nm.

13. The composition of claim 11 wherein said dichrioc dyestuff is present in an amount of about 0.5 to about 5 percent by weight.

14. The composition of claim 11 wherein there is additionally present an optically active compound in an amount sufficient to provide a cholesteric phase.

15. An improved "guest-host" type liquid crystal display device which is responsive to the absence or presence of an electric field, said device comprising a layer of a nematic liquid crystal composition and two conductive electrodes positioned, respectively, adjacent opposing surfaces of said layer, wherein the improvement comprises the presence of a dichroic dyestuff according to claim 1 in admixture with said liquid crystal composition.

16. An improved "guest-host" type liquid crystal display which is responsive to the absence or presence of an electric field, and which appears neutral black in the absence of said electric field and clear in the presence of said electric field, said device comprising:

(a) a "guest-host" layer comprising a nematic liquid crystal material and a plurality of dichroic dyes which together strongly absorb throughout the region between about 400 and 600 nm; and

(b) two conductive electrodes positioned, respctively, adjacent opposing surfaces of said layer;

wherein the improvement comprises the presence of a dichroic dyestuff according to claim 1 in admixture with said "guest-host", liquid crystal-dichroic dye mixture.

17. An improved "phase change" type liquid crystal display device which is responsive to the absence or presence of an electric field, said device comprising a layer of a nematic liquid crystal material in admixture with an optically active compound, and two conductive electrodes positioned, respectively, adjacent opposing surfaces of said layer, wherein the improvement comprises the presence of the dichroic dyestuff of claim 1 in admixture with said liquid crystal material.

18. An improved "phase-change" type liquid crystal display device which is responsive to the absence or presence of an electric field, and which appears neutral black in the absence of said electric field and clear in the presence of said electric field, said device comprising:

(a) a layer of a nematic liquid crystal material in admixture with a plurality of dichroic dyes which together absorb strongly throughout the region between about 400 and 600 nm, and an optically active compound; and

(b) two conductive electrodes positioned, respectively, adjacent opposing surfaces of said layer;

wherein the improvement comprises the presence of the dichroic dyestuff of claim 1 in admixture with said liquid crystal material.

19. A display device according to claims 15, 16, 17 or 18 wherein said device includes a means for applying an electric field across said electrodes.

10. A dichroic dyestuff having the formula