Polymerizable compounds and the use thereof in liquid-crystal displays
Polymerizable compounds, to processes and intermediates for the preparation thereof, liquid-crystal (LC) media comprising them, and the use of the polymerizable compounds and LC media for optical, electro-optical and electronic purposes, in particular in LC displays, especially in LC displays of the polymer sustained alignment type, or a stabilizers in LC media and LC displays.
1. A compound of formula I
P-Sp-A 1 -(Z 1 -A 2 ) z -R I
wherein individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
P a polymerizable acrylate or methacrylate group,
Sp a spacer group that is optionally substituted by one or more groups P or L a , or a single bond,
-A 1 -(Z 1 -A 2 ) z is
wherein the benzene rings are optionally substituted by one or more groups L, P-Sp-, L a or L a -Sp-
R P-Sp-,
L F, Cl, —CN, P-Sp-, L a , L a -Sp-, or straight chain alkyl having 1 to 25 C atoms or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH 2 -groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by P, F, Cl or L a -,
L a —C(R aa )(R bb )OH,
R aa , R bb straight-chain alkyl with 1 to 20 C atoms, branched alkyl with 3 to 20 C atoms, or cyclic alkyl with 3 to 12 C atoms, or R aa and R bb together with the C atom to which they are attached form a cyclic alkyl group with 3 to 12 C atoms, wherein in R aa and R bb one or more non-adjacent CH 2 -groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl,
wherein the compound of formula I contains at least one group L a or L a -Sp-.
2. The compound according to claim 1 , wherein R aa and R bb denote straight-chain alkyl with 1 to 12 C atoms or branched alkyl with 3 to 12 C atoms, or R aa and R bb together with the C atom to which they are attached form a cyclic alkyl group with 3 to 12 C atoms.
3. The compound according to claim 1 , wherein all groups P that are present in the compound have the same meaning.
4. The compound according to claim 1 , containing a group P-Sp- of the following formulae
P—CHL a - SL1
P—(CH 2 ) cc —O-CHL a - SL2
P—(CH 2 ) cc —CO—O-CHL a - SL3
P—(CH 2 ) cc —CHL a - SL4
cc is 1, 2, 3, 4, 5 or 6 and
L a is as defined in claim 1 .
5. The compound according to claim 1 , wherein A 1 -(Z 1 -A 2 ) z - is
wherein the benzene rings are optionally substituted by one or more groups L, P-Sp-, L a or L a -Sp-.
6. The compound according to claim 1 , of the following subformulae:
wherein
r1, r3, r7 are independently of each other 0, 1, 2 or 3,
r2 is 0, 1, 2, 3 or 4,
r4, r5, r6 are independently of each other 0, 1 or 2,
wherein r1+r7≥1, r1+r2+r3≥1, r4+r5≥1, r1+r3+r4≥1 and at least one of L denotes L a or L a -Sp-, and/or
wherein the compounds contain at least one group Sp that is substituted by L a .
7. A compound of the formula:
or a compound of formula I8-1 or I8-2 wherein P is replaced by Pg
Sp a spacer group that is optionally substituted by one or more groups P or L a , or a single bond,
P a polymerizable acrylate or methacrylate group,
Pg is —OH, a protected hydroxy group or a masked hydroxy group,
L F, Cl, —CN, P-Sp-, L a , L a -Sp-, or straight chain alkyl having 1 to 25 C atoms, or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH 2 -groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by P, F, Cl or L a -,
L a —C(R aa )(R bb )OH,
R aa , R bb straight-chain alkyl with 1 to 20 C atoms, branched alkyl with 3 to 20 C atoms, or cyclic alkyl with 3 to 12 C atoms, or R aa and R bb together with the C atom to which they are attached form a cyclic alkyl group with 3 to 12 C atoms, wherein in R aa and R bb one or more non-adjacent CH 2 -groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl,
r1, r3, r7 are independently of each other 0, 1, 2 or 3,
r2 is 0, 1, 2, 3 or 4,
r4, r5, r6 are independently of each other 0, 1 or 2,
wherein R denotes H or Pg-Sp,
wherein r1+r7≥1, r1+r2+r3≥1, r4+r5≥1, r1+r3+r4≥1 and at least one of L denotes L a or L a -Sp-, and/or
wherein the compounds contain at least one group Sp that is substituted by L a .
8. A liquid crystal (LC) medium comprising one or more compounds formula I as defined in claim 1 .
9. The LC medium of claim 8 , comprising
a polymerizable component A) comprising one or more compounds of formula I, and
a liquid-crystalline LC component B) comprising one or more mesogenic or liquid-crystalline compounds.
10. The LC medium of claim 9 , wherein component B) comprises one or more compounds of formulae CY and/or PY:
in which
a denotes 1 or 2,
b denotes 0 or 1,
R 1 and R 2 each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent CH 2 groups may be replaced by —O—, —CH═CH—, —CO—, —O—CO— or
—CO—O— in such a way that O atoms are not linked directly to one another,
Z x denotes —CH═CH—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —O—, —CH 2 —, —CH 2 CH 2 — or a single bond,
L 1-4 each, independently of one another, denote F, Cl, OCF 3 , CF 3 , CH 3 , CH 2 F, CHF 2 .
11. The LC medium according to claim 9 wherein component B) comprises one or more compounds of the following formulae:
in which the individual radicals, on each occurrence identically or differently, each, independently of one another, have the following meaning:
R A1 alkenyl having 2 to 9 C atoms or, if at least one of the rings X, Y and Z denotes cyclohexenyl, also one of the meanings of R A2 ,
R A2 alkyl having 1 to 12 C atoms, in which, in addition, one or two non-adjacent CH 2 groups may be replaced by —O—, —CH═CH—, —CO—, —OCO— or —COO— in such a way that O atoms are not linked directly to one another,
Z x —CH 2 CH 2 —, —CH═CH—, —CF 2 O—, —OCF 2 —, —CH 2 O—, —OCH 2 —, —CO—O—, —O—CO—, —C 2 F 4 —, —CF═CF—, —CH═CH—CH 2 O—, or a single bond,
L 1-4 each, independently of one another, H, F, Cl, OCF 3 , CF 3 , CH 3 , CH 2 F or CHF 2 H,
x 1 or 2,
z 0 or 1.
12. The LC medium according to claim 9 , wherein component B) comprises one or more compounds of the following formula:
in which the individual radicals have the following meanings:
R 3 and R 4 each, independently of one another, denote alkyl having 1 to 12 C atoms, in which, in addition, one or two non-adjacent CH 2 groups may be replaced by —O—, —CH═CH—, —CO—, —O—CO— or —CO—O— in such a way that O atoms are not linked directly to one another,
Z y denotes —CH 2 CH 2 —, —CH═CH—, —CF 2 O—, —OCF 2 —, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —C 2 F 4 —, —CF═CF— or a single bond.
13. The LC medium according to claim 8 , wherein the compounds of formula I are polymerized.
14. The LC medium according to claim 8 , containing from 50 to 1000 ppm of one or more compounds of formula I.
15. A process of preparing an LC medium according to claim 8 , comprising mixing one or more mesogenic or liquid-crystalline compounds, with one or more compounds of formula I and optionally with further liquid-crystalline compounds and/or additives.
16. An LC display comprising one or more compounds of formula I comprising an LC medium as defined in claim 8 .
17. The LC display of claim 16 , which is a VA, IPS, UB-FFS, TN, OCB, FFS or poli-VA display.
18. The LC display of claim 16 , which is a PSA display.
19. The LC display of claim 18 , which is a PS-VA, PS-OCB, PS-IPS, PS-FFS, PS-UB-FFS, PS-poli-VA or PS-TN display.
20. The LC display of claim 18 , comprising two substrates, at least one which is transparent to light, an electrode provided on each substrate or two electrodes provided on only one of the substrates, and located between the substrates a layer of an LC medium, comprising one or more compounds of formula I and optionally one or more additional compounds that are polymerizable, wherein the compounds of formula I and the additional polymerizable compounds are polymerized between the substrates of the display.
21. A process for the production of an LC display according to claim 20 , comprising providing an LC medium, comprising one or more compounds of formula I and optionally one or more additional compounds that are polymerizable, between the substrates of the display, and polymerizing the compounds of formula I and the additional polymerizable compounds.
22. A compound of the following formulae
Sp a spacer group that is optionally substituted by one or more groups P or L a , or a single bond,
P is a polymerizable group,
and at least one group Pg-Sp is a spacer group substituted by L a ,
L F, Cl, —CN, P-Sp-, L a , L a -Sp-, or straight chain alkyl having 1 to 25 C atoms or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH 2 -groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by P, F, Cl or L a ,
L a —C(R aa )(R bb )OH,
R aa , R bb straight-chain alkyl with 1 to 20 C atoms, branched alkyl with 3 to 20 C atoms, or cyclic alkyl with 3 to 12 C atoms, or R aa and R bb together with the C atom to which they are attached form a cyclic alkyl group with 3 to 12 C atoms, wherein in R aa and R bb one or more non-adjacent CH 2 -groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl,
r1, r3, r7 are independently of each other 0, 1, 2 or 3,
r2 is 0, 1, 2, 3 or 4,
r4, r5, r6 are independently of each other 0, 1 or 2,
wherein r1+r7≥1, r1+r2+r3≥1, r4+r5≥1, r1+r3+r4≥1,
wherein R denotes H or Pg-Sp, and Pg denotes OH, a protected hydroxyl group or a masked hydroxyl group, wherein the compounds contain at least one group L a or L a -Sp.
23. A process for preparing a compound of formula I of claim 1 , by esterification of a compound
wherein P is replaced by Pg
Sp a spacer group that is optionally substituted by one or more groups P or L a , or a single bond,
P is a polymerizable group,
L F, Cl, —CN, P-Sp-, L a , L a -Sp-, or straight chain alkyl having 1 to 25 carbon atoms or branched or cyclic alkyl having 3 to 25 C atoms, wherein one or more non-adjacent CH 2 -groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by P, F, Cl or L a -,
L a —C(R aa )(R bb )OH,
R aa , R bb straight-chain alkyl with 1 to 20 C atoms, branched alkyl with 3 to 20 C atoms, or cyclic alkyl with 3 to 12 C atoms, or R aa and R bb together with the C atom to which they are attached form a cyclic alkyl group with 3 to 12 C atoms, wherein in R aa and R bb one or more non-adjacent CH 2 -groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl,
r1, r3, r7 are independently of each other 0, 1, 2 or 3,
r2 is 0, 1, 2, 3 or 4,
r4, r5, r6 are independently of each other 0, 1 or 2,
wherein r1+r7≥1, r1+r2+r3≥1, r4+r5≥1, r1+r3+r4≥1,
wherein R denotes H or Pg-Sp, and
wherein Pg denotes OH, using corresponding acids, acid derivatives, or halogenated compounds containing a group P, in the presence of a dehydrating reagent, and the compounds 111-119 contain at least one group L a or L a -Sp.