Dye-doped liquid-crystal medium comprising polymerizable compounds
A liquid-crystal (LC) medium containing one or more dyes and one or more polymerizable compounds, its use for optical, electro-optical and electronic purposes, in particular in LC displays, especially in colour LC displays of the PSA (polymer sustained alignment) or SA (self-aligning) mode containing a quantum dot colour filter (QDCF), an LC display of the PSA or SA mode containing the LC medium and containing a QDCF, and to a process of manufacturing the LC display.
1. An LC medium, comprising
0.01 to 3.0% by weight of one or more polymerizable compounds of formula I
P-Sp-A a -(Z a -A b ) z -R b
wherein each of the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
R b is P-Sp- or R,
R is F, Cl, —CN or a 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—, CR 0 ═CR 00 —, —C≡C—
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 or P-Sp-,
P is a polymerizable group,
Sp is a spacer group which is optionally substituted by P, or is a single bond,
A a , A b is an alicyclic, heterocyclic, aromatic or heteroaromatic group with 4 to 20 ring atoms, which is monocyclic or polycyclic and which is optionally substituted by one or more groups L or P-Sp-,
Z a is —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —(CH 2 ) n1 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —(CF 2 ) n1 —, —CH═CH—, —CF═CF—, —CH═CF—, —CF═CH—, —C≡C—, —CH═CH—CO—O—, —O—CO—CH═CH—, —CH 2 —CH 2 —CO—O—, —O—CO—CH 2 —CH 2 —, —CR 0 R 00 —, or a single bond,
R 0 , R 00 is H or alkyl having 1 to 12 C atoms,
L is F, Cl, —CN, P-Sp- or a 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—, CR 0 ═CR 00 —, —C≡C—
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-Sp-, F or Cl,
z is 0, 1, 2, 3 or 4,
n1 is 1, 2, 3 or 4,
and further comprising one or more compounds of formula II
wherein each of the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
R 1 , R 2 is H or a 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—, CR 0 ═CR 00 —, —C≡C—,
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 CN, CF 3 , F or Cl,
A 1 , A 2 is selected from the following formulae
Z 1 , Z 2 is —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 , L 2 , L 3 , L 4 is F, Cl, OCF 3 , CF 3 , CH 3 , CH 2 F or CHF 2 ,
Y H, F, Cl, CF 3 , CHF 2 or CH 3 ,
L C CH 3 or OCH 3 ,
a1 0, 1 or 2, and
a2 0 or 1,
and further comprising at least one dichroic dye absorbing green light and/or at least one dichroic dye absorbing red light,
wherein the LC comprises one or more dichroic dyes of formulae I*
wherein each of the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
are independently of each other
and, in case i is 2 or more, the terminal
may also be
and, in case j is 2 or more, the terminal
may also be
Z 11 and Z 12 denote a single bond, —N═N—, —OCO— or —COO—,
R 11 and R 12 denote alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy with 1 to 20 C-atoms, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl with 2 to 20 C-atoms, or alkylaminyl, dialkylaminyl, alkylcarbonyl, alkyloxycarbonyl, alkylcarbonyloxy or alkyloxycarbonyloxy with 3 to 20 C-atoms, or alkylcyclohexylalkyl with 8 to 25 C-atoms,
i and j are independently of each other 1, 2, 3 or 4.
2. The LC medium according to claim 1 , comprising one or more polymerizable compounds of formula I selected from the following formulae:
in which each of the individual radicals, on each occurrence identically or differently, and each, independently of one another, have the following meaning:
P 1 , P 2 , P 3 is a polymerizable group,
Sp 1 , Sp 2 , Sp 3 is a single bond or a spacer group, where one or more of the radicals P 1 -Sp 1 -, P 2 -Sp 2 - and P 3 -Sp 3 - may denote R aa , with the proviso that at least one of the radicals P 1 -Sp 1 -, P 2 -Sp 2 and P 3 -Sp 3 -present is different from R aa ,
R aa is H, F, Cl, CN or straight-chain alkyl having 1 to 25 C atoms or branched alkyl having 3 to 25 C atoms, in which one or more non-adjacent CH 2 groups may each be replaced, independently of one another, by —C(R 0 )═C(R 00 )—, —C≡C—, —N(R 0 )—, —O—, —S—, —CO—, —CO—O—, —O—CO—, or —O—CO—O— in such a way that 0 and/or S atoms are not linked directly to one another, and in which one or more H atoms may be replaced by F, Cl, CN or P 1 -Sp 1 -, and wherein R aa does not denote or contain a group P 1 , P 2 or P 3 ,
R 0 , R 00 is H or alkyl having 1 to 12 C atoms,
R y , R z is H, F, CH 3 or CF 3 ,
Z M1 is —O—, —CO—, —C(R y R z )— or —CF 2 CF 2 —,
Z M2 , Z M3 is —CO—O—, —O—CO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 — or —(CH 2 ) n —, where n is 2, 3 or 4,
L is F, Cl, CN or a straight-chain or branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or a straight-chain, optionally mono- or polyfluorinated alkenyl or alkynyl having 2 to 12 C atoms, or a branched, optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 3 to 12 C atoms,
L′, L″ is H, F or Cl,
k is 0 or 1,
r is 0, 1, 2, 3 or 4,
s is 0, 1, 2 or 3,
t is 0, 1 or 2, and
x is 0 or 1.
3. The LC medium according to claim 1 , comprising one or more dichroic dyes of the following formulae:
wherein R 11 , R 12 , A 11 and i have the meanings given for formula I*.
4. The LC medium according to claim 1 , comprising one or more dichroic dyes of the following formulae:
wherein R 11 and R 12 have the meanings given for formula I*.
5. The LC medium according to claim 1 , comprising one or more compounds of formula II selected from the group consisting of compounds of formulae IIA, IIB, IIC and IID
in which
R 2A and R 2B each, independently of one another, denote H, an alkyl or alkenyl radical having up to 15 C atoms which is unsubstituted, monosubstituted by CN, CF 3 , F or Cl, or at least monosubstituted by halogen, in which one or more CH 2 groups may be replaced by —O—, —S—,
—C≡C—, —CF 2 O—, —OCF 2 —, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another,
L 1 to L 4 each, independently of one another, denote F, Cl, CF 3 or CHF 2 ,
Y denotes H, F, Cl, CF 3 , CHF 2 or CH 3 ,
Z 2 , Z 2B and Z 2D each, independently of one another, denote a single bond, —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 —CH═CHCH 2 O—,
p denotes 0, 1 or 2, and
q on each occurrence, identically or differently, denotes 0 or 1.
6. An LC medium, comprising
0.01 to 3.0% by weight of one or more polymerizable compounds of formula I
P-Sp-A a -(Z a -A b ) z -R b I
wherein each of the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
R b is P-Sp- or R,
R is F, Cl, —CN or a 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—, CR 0 ═CR 00 —, —C≡C—,
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 or P-Sp-,
P is a polymerizable group,
Sp is a spacer group which is optionally substituted by P, or is a single bond,
A a , A b is an alicyclic, heterocyclic, aromatic or heteroaromatic group with 4 to 20 ring atoms, which is monocyclic or polycyclic and which is optionally substituted by one or more groups L or P-Sp-,
Z a is —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —(CH 2 ) n1 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —(CF 2 ) n1 —, —CH═CH—, —CF═CF—, —CH═CF—, —CF═CH—, —C≡C—, —CH═CH—CO—O—, —O—CO—CH═CH—, —CH 2 —CH 2 —CO—O—, —O—CO—CH 2 —CH 2 —, —CR 0 R 00 —, or a single bond,
R 0 , R 00 is H or alkyl having 1 to 12 C atoms,
L is F, Cl, —CN, P-Sp- or a 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—, CR 0 ═CR 00 —, —C≡C—,
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-Sp-, F or Cl,
z is 0, 1, 2, 3 or 4,
n1 is 1, 2, 3 or 4,
and further comprising one or more compounds of formula II
wherein each of the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
R 1 , R 2 is H or a 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—, CR 0 ═CR 00 —, —C≡C—,
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 CN, CF 3 , F or Cl,
A 1 , A 2 is selected from the following formulae
Z 1 , Z 2 is —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 , L 2 , L 3 , L 4 is F, Cl, OCF 3 , CF 3 , CH 3 , CH 2 F or CHF 2 ,
Y H, F, Cl, CF 3 , CHF 2 or CH 3 ,
L C CH 3 or OCH 3 ,
a1 0, 1 or 2, and
a2 0 or 1,
and further comprising at least one dichroic dye absorbing green light and/or at least one dichroic dye absorbing red light,
and one or more compounds of formula III
in which
R 11 and R 12 each, independently of one another, denote H, an alkyl or alkoxy radical having 1 to 15 C atoms, in which one or more CH 2 groups may each be replaced, independently of one another, by
—O—, —S—, —C≡C—, —CF 2 O—, —OCF 2 —, —CH═CH—, —OC—O— or —O—CO— in such a way that O atoms are not linked directly to one another, and in which one or more H atoms may be replaced by halogen,
A 3 on each occurrence, independently of one another, denotes
a) 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH 2 groups may be replaced by —O— or —S—,
b) a 1,4-phenylene radical, in which one or two CH groups may be replaced by N, or
c) a radical selected from the group consisting of spiro[3.3]heptane-2,6-diyl, 1,4-bicyclo[2.2.2]octylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl,
wherein the radicals a), b) and c) may be mono- or polysubstituted by halogen atoms,
n denotes 0, 1 or 2,
Z 1 on each occurrence independently of one another denotes —CO—O—, —O—CO—, —CF 2 O—, —OCF 2 —, —CH 2 O—, —OCH 2 —, —CH 2 —, —CH 2 CH 2 —, —(CH 2 ) 4 —, —CH═CH—CH 2 O—, —C 2 F 4 —, —CH 2 CF 2 —, —CF 2 CH 2 —, —CF═CF—, —CH═CF—, —CF═CH—, —CH═CH—, —C≡C— or a single bond,
L 11 and L 12 each, independently of one another, denote F, Cl, CF 3 or CHF 2 , and
W denotes O or S.
7. The LC medium according to claim 1 , additionally comprising one or more compounds of formula IV
in which
R 41 denotes an unsubstituted alkyl radical having 1 to 7 C atoms or an unsubstituted alkenyl radical having 2 to 7 C atoms, and
R 42 denotes an unsubstituted alkyl radical having 1 to 7 C atoms or an unsubstituted alkoxy radical having 1 to 6 C atoms, or an unsubstituted a alkenyl radical having 2 to 7 C atoms.
8. The LC medium according to claim 1 , additionally comprising one or more compounds of formula V
in which
R 51 and R 52 independently of one another, each denotes an unsubstituted alkyl radical having 1 to 7 C atoms or an unsubstituted alkoxy radical having 1 to 6 C atoms, or an unsubstituted alkenyl radical having 2 to 7 C atoms, alkoxy having 1 to 6 C atoms, or denotes alkoxyalkyl, alkenyl or alkenyloxy having 2 to 7 C atoms,
identically or differently, denote
Z 51 , Z 52 each, independently of one another, denote —CH 2 —CH 2 —, —CH 2 —O—, —CH═CH—, —C≡C—, —COO— or a single bond, and
n is 1 or 2.
9. An LC display comprising an LC medium according to claim 1 .
10. The LC display according to claim 9 , which is a PS-VA, PS-IPS, PS-FFS, PS-UB-FFS or SA-VA display.
11. An LC display comprising a quantum dot colour filter and an LC medium
wherein the LC medium comprises
0.01 to 3.0% by weight of one or more polymerizable compounds of formula I
P-Sp-A a -(Z a -A b ) z -R b I
wherein each of the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
R b is P-Sp- or R,
R is F, Cl, —CN or a 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—, CR 0 ═CR 00 —, —C≡C—,
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 or P-Sp-,
P is a polymerizable group,
Sp is a spacer group which is optionally substituted by P, or is a single bond,
A a , A b is an alicyclic, heterocyclic, aromatic or heteroaromatic group with 4 to 20 ring atoms, which is monocyclic or polycyclic and which is optionally substituted by one or more groups L or P-Sp-,
Z a is —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —(CH 2 ) n1 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —(CF 2 ) n1 —, —CH═CH—, —CF═CF—, —CH═CF—, —CF═CH—, —C≡C—, —CH═CH—CO—O—, —O—CO—CH═CH—, —CH 2 —CH 2 —CO—O—, —O—CO—CH 2 —CH 2 —, —CR 0 R 00 —, or a single bond,
R 0 , R 00 is H or alkyl having 1 to 12 C atoms,
L is F, Cl, —CN, P-Sp- or a 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—, CR 0 ═CR 00 —, —C≡C—
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-Sp-, F or Cl,
z is 0, 1, 2, 3 or 4,
n1 is 1, 2, 3 or 4,
and further comprising one or more compounds of formula II
wherein each of the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings
R 1 , R 2 is H or a 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—, CR 0 ═CR 00 —, —C≡C—,
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 CN, CF 3 , F or Cl,
A 1 , A 2 is selected from the following formulae
Z 1 , Z 2 is —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 , L 2 , L 3 , L 4 is F, Cl, OCF 3 , CF 3 , CH 3 , CH 2 F or CHF 2 ,
Y H, F, Cl, CF 3 , CHF 2 or CH 3 ,
L C CH 3 or OCH 3 ,
a1 0, 1 or 2, and
a2 0 or 1,
and further comprising at least one dichroic dye absorbing green light and/or at least one dichroic dye absorbing red light.
12. An LC display, comprising:
a first substrate including a pixel electrode defining pixel areas, the pixel electrode being connected to a switching element disposed in each pixel area and optionally including a micro-slit pattern, and optionally a first alignment layer disposed on the pixel electrode,
a second substrate including a common electrode layer, which may be disposed on the entire portion of the second substrate facing the first substrate, and optionally a second alignment layer,
an LC layer disposed between the first and second substrates and including an LC medium according to claim 1 , wherein the one or more polymerizable compounds of formula I are optionally present in polymerized form,
a quantum dot colour filter containing red, green and blue quantum dots provided between the LC layer and the first or second substrate, and
optionally a backlight.
13. The LC display according to claim 9 , wherein the one or more polymerizable compounds of formula I are present in polymerized form.
14. A process for the production of an LC display comprising:
a first substrate including a pixel electrode defining pixel areas, the pixel electrode being connected to a switching element disposed in each pixel area and optionally including a micro-slit pattern, and optionally a first alignment layer disposed on the pixel electrode,
a second substrate including a common electrode layer, which may be disposed on the entire portion of the second substrate facing the first substrate, and optionally a second alignment layer,
an LC layer disposed between the first and second substrates and including an LC medium according to claim 1 , wherein the one or more polymerizable compounds of formula I are optionally present in polymerized form,
a quantum dot colour filter containing red, green and blue quantum dots provided between the LC layer and the first or second substrate, and
optionally a backlight,
said process comprising providing said LC medium between the substrates of the display, and polymerizing the one or more polymerizable compounds of formula I by irradiation with UV light, while a voltage is applied to the electrodes.
15. The LC medium according to claim 1 , which contains 0.05 to 1% by weight of the one or more polymerizable compounds of formula I.
16. The LC medium according to claim 1 , which contains 0.1 to 0.5% by weight of the one or more polymerizable compounds of formula I.
17. The LC medium according to claim 1 , which contains 0.1 to 0.2% by weight of the one or more polymerizable compounds of formula I.
18. The LC medium according to claim 1 , wherein
P 1 , P 2 , P 3 is selected from vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane and epoxy, and/or
Sp 1 , Sp 2 , Sp 3 is —(CH 2 ) p1 —, —(CH 2 ) p1 —O—, —(CH 2 ) p1 —CO—O— or —(CH 2 ) p1 —O—CO—O—, wherein p1 is an integer from 1 to 12, where one or more of the radicals P 1 -Sp 1 -, P 2 -Sp 2 - and P 3 -Sp 3 - may denote R aa , with the proviso that at least one of the radicals P 1 -Sp 1 -, P 2 -Sp 2 and P 3 -Sp 3 -present is different from R aa , and/or
R aa is a straight-chain optionally mono- or polyfluorinated alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 12 C atoms, or a straight-chain optionally mono- or polyfluorinated alkenyl or alkynyl having 2 to 12 C atoms, or a branched optionally mono- or polyfluorinated alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 3 to 12 C atoms.
19. The LC display according to claim 12 , wherein, in the LC medium, the at least one dichroic dye absorbing green light and/or at least one dichroic dye absorbing red light do not substantially absorb light reflected by a blue backlight of the display.
20. The LC medium according to claim 1 , wherein the at least one dichroic dye absorbing green light and/or at least one dichroic dye absorbing red light do not substantially absorb light reflected by a blue backlight of a display.
21. The LC display according to claim 9 , comprising a quantum dot colour filter.