Polymerizable dichroic azo dyes
AssigneeRolic AG
InventorsThomas Peglow, Franco Mola, Zoubair Cherkaoui, Mario Schawab
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Abstract
The present invention is directed towards polymerizable dichroic azo dyes comprising azo-chromophores having at least one standard mesogenic ring system attached to said chromophores and at least one polymerizable group leading to dyes having sufficient solubilty and a very high order parameter.
Claims54
A polymerizable dichroic azo dye of the general formula I:
- wherein:
- A represents a dichroic residue, which may comprise one or more polymerizable groups PG, exhibiting at least partial absorption in the visible region between 400 nanometer and 800 nanometer and comprising at least one azo-binding group that is linked to at least one radical of formula a) to f) shown below,
- which radical of formula a) to f) may be unsubstituted, mono- or poly-substituted by fluorine, chlorine, hydroxy, —NR1, R2 or by a straight chain or branched alkyl residue having 1-10 carbon atoms, which alkyl residue is unsubstituted, mono- or poly-substituted by fluorine, and wherein one or more of the non-adjacent CH2 groups may independently be replaced by —O—, —CO—O—, —O—CO—, —NR1—CO—, —CO—NR1—, —NR1—CO—O—, —O—CO—NR1—, —CH═CH—, —C≡C—, —O—CO—O—, wherein R1 and R2 independently represent hydrogen or lower alkyl,
- wherein the broken line (i) symbolizes the possible linkages to the azo-binding group and wherein
- R represents hydrogen or lower alkyl;
- E each independently represents hydrogen, lower alkyl, lower acyl or a polymerizable group selected from acryloyl or methacryloyl;
- B represents a group of substructure II
- wherein the broken line (ii) symbolizes the linkage to said dichroic residue and wherein:
- D1, D2, D3 each independently represents an aromatic or alicyclic group, which is unsubstituted or substituted by fluorine, chlorine, cyano, nitro, or by a straight chain or branched alkyl residue having 1-10 carbon atoms, which alkyl residue is unsubstituted, mono- or poly-substituted by fluorine and wherein one or more of the non-adjacent CH2 groups may independently be replaced by Q, whereby Q represents —O—, —CO—, —CO—O—, —O—CO—, —Si(CH3)2—O—Si(CH3)2—, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C—, —O—CO—O— and R has the meaning given above;
- S1 represents a single covalent bond or a spacer unit, such as a straight-chain or branched alkylene residue, which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 24 carbon atoms, wherein one or more of the non-adjacent CH2 groups may independently be replaced by Q, wherein Q has the meaning given above and wherein heteroatoms are not directly linked to each other;
- Z1, Z2, Z3 each independently represents a single covalent bond or a spacer unit, such as a straight-chain or branched alkylene residue, which is unsubstituted, mono-substituted by cyano or halogeno, or poly-substituted by halogeno, having 1 to 8 carbon atoms, wherein one or more of the non-adjacent CH2 groups may independently be replaced by Q or —CR═C—CO—, wherein Q and R have the meaning given above;
- m1, m2 independently are 0 or 1;
- and
- P represents hydrogen, halogeno, cyano, nitro or a polymerizable group PG;
- and
- with the proviso that the compound of formula I comprises at least one polymerizable group.
A polymerizable dichroic azo dye according to any preceding claim wherein the polymerizable groups PG are each independently preferably selected from the formulae CH2═CY—, CH2═CY—COO—, CH2═CH—CO—NH—, CH2═C(Ph)-CO—NH—, CH2═CH—O—, CH2═CH—OOC—, Ph-CH═CH—, CH2═CH-Ph-, CH2═CH-Ph-O—, CH2═CH-Ph-OCO—, R3-Ph-CH═CH—COO—, R2-0° C.—CH═CH-Ph-O—, N-maleinimidyl,
- wherein Y each independently represents hydrogen, chloro or methyl, R2 is hydrogen or lower alkyl, R3 is hydrogen or lower alkoxy, Ph- is phenyl and -Ph- is 1,4-phenylene.
A polymerizable dichroic azo dye according to any preceding claim, wherein rings D1, D2, D3, D4 and D5 independently of each other are unsubstituted, saturated five- or six-membered alicyclic rings or six- or ten-membered aromatic rings, which are unsubstituted, mono- or poly-substituted by fluorine or chlorine or nitro or by a straight chain or branched alkyl residue having 1-6 carbon atoms, which alkyl residue is unsubstituted, mono- or poly-substituted by fluorine, and wherein one or more of the non-adjacent CH2 groups may independently be replaced by —O—, —CO—O—, —O—CO—, —NR2—CO—, —CO—NR2—, —NR2—CO—O—, —O—CO—NR2—, —CH═CH—, —C≡C—, —O—CO—O—, wherein R2 represents hydrogen or lower alkyl.
A polymerizable dichroic azo dye according to any preceding claim, wherein the S1 and S2 comprise a single bond, or a straight-chain or branched alkylene grouping, such as —(CH2)r—, and also —(CH2)r—O—(CH2)s—, —(CH2)r—CO—O—(CH2)s—, —(CH2)r—O—CO—(CH2)s—, —(CH2)r—NR2—CO—(CH2)s—, —(CH2)r—NR2—CO—O—(CH2)s—, —(CH2)r—(OCH2CH2)s—(CH2)t— wherein r, s and t are each a n integer from 1 to 20, the sum of r+s+t≦21, wherein R2 represents hydrogen or lower alkyl, and which are attached to the dichroic residue and the polymerizable group, respectively, such that heteroatoms are not directly linked to each other.
A polymerizable dichroic azo dye according to any preceding claim, wherein Z1, Z2, Z3, Z4 and Z5 are a single covalent bond or a straight-chain or branched alkylene residue, which is unsubstituted, mono-substituted or poly-substituted by fluoro, having 1 to 8 carbon atoms, wherein one or more of the non-adjacent CH2 groups may independently be replaced by —O—, —CO—, —CO—O—, —O—CO—, —NR2—CO—, —CO—NR2—, —NR2—CO—O—, —O—CO—NR2—, —CH═CH—, —C≡C—, —O—CO—O—, —CR2═C—CO—, wherein R2 represents hydrogen or lower alkyl.
A polymerizable dichroic azo dye according to any preceding claim, wherein E represents hydrogen, methyl, acetyl, acryloyl and methacryloyl, especially hydrogen, methyl and acetyl.
A polymerizable dichroic azo dye according to any preceding claim, wherein the sum of the integers m1+m2 is 0 or 1.
A polymerizable dichroic azo dye of the general formula I:
- wherein
- A is a dichroic residue of general formula IIIa,
- T-X1-G1-N═N—(—Ar1—N═N—)q1—(—Ar2—N═N—)q2—(—Ar3—N═N—)q3—(—Ar4—N═N—)q4-G2-X2— IIIa
- wherein
- G1 and G2 independently of each other represent 1,4-phenylene, which is unsubstituted, mono- or disubstituted by chlorine or —CH3, or unsubstituted 1,4-naphthylene;
- or a group of formula b) or c)
- wherein the broken lines (i) symbolize the linkage to the azo-binding group;
- and wherein
- E independently represents hydrogen, methyl and acetyl;
- R independently represents hydrogen, methyl, ethyl, propyl and isopropyl;
- X1 and X2 independently of each other represent a covalent bond, CH2—CH2—, —CO—O—, —O—CO—, —CH2—O—, —O—CH2—, —NR— or —CH2—NR—, —NR—CH2—, —NR—CO— or —CO—NR—, wherein R has the meaning given above;
- B represents a group of substructure XXIII
- wherein the broken line (ii) symbolizes the linkage to said dichroic residue;
- and wherein
- Ar1, Ar2, Ar3, Ar4 are independently of each other 1,4-phenylene, which is unsubstituted, mono- or disubstituted by chlorine or —CH3, or unsubstituted 1,4-naphthylene, with the proviso that if G1 and G2 are optionally substituted 1,4-phenylen at least one of Ar1, Ar2, Ar3 or Ar4 is unsubstituted 1,4-naphthylene;
- q1, q2, q3, q4 independently are 0 or 1, with the proviso that the sum of the integers q1+q2+q3+q4+0, 1, or 2;
- P and P1 independently of each other represent hydrogen, halogeno, cyano, nitro or a polymerizable group PG, wherein PG includes CH2═CY—COO—, CH2═CH—O— and CH2═CH—OOC—, wherein Y is hydrogen or methyl;
- D1, D3, D4 and D5 independently of each other represent 1,4-phenylene, which is unsubstituted, mono- or poly-substituted by fluorine, chlorine, methyl, methoxy, acyl or —CO—O—CH3;
- Z1, Z3, Z4 and Z5 independently of each other represent selected from a group consisting of a single covalent bond, —CO—O—, —O—CO—, —CH2—O— or —O—CH2—;
- S1 and S2 represent independently of each other a single bond, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, or dodecylene and
- m1, m3, m4 are independently of each other 0 or 1.
Use of a polymerizable dichroic azo dye according to any preceding claim for the preparation of mesogenic, polymerizable mixtures.
A mesogenic, polymerizable mixture comprising at least one polymerizable dichroic azo dye of formula I according to any preceding claim.
Dependencies are inferred from the claim text.