USRE41281EExpiredUtilityPatentIndex 51
Liquid crystal display device
Est. expiryJul 1, 2016(expired)· nominal 20-yr term from priority
C09K 19/38C09K 19/2007C09K 2019/0448G02F 2413/03G02F 1/13363G02B 5/3016G02F 2413/15G02F 2413/07C09K 19/2014G02F 1/133638C09K 2323/05C09K 2323/00
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Claims
Abstract
The invention relates to a liquid crystal display device comprising a liquid crystal cell and at least one compensation film or a combination of polarizer and optical compensators comprising at least one compensation film, said compensation film comprising at least one layer of an isotropic polymer obtainable by polymerization of a mixture of a polymerizable mesogenic material comprising: a) compound having one or two more polymerizable functional group, in the presences b) an initiator, c) optionally a non-polymerizable compound having two or more polymerizable functional groups and d) optionally a stabilizer, characterized in that said layer of an anisotropic polymer has a hometropic or tilted hometropic molecular orientation. The invention also relates to methods of manufacturing said compensation films. The invention further relates to mixtures of chiral polymerizable mesogenic material used for manufacturing of said compensation films.
Claims
exact text as granted — not AI-modified1. A liquid crystal display device comprising:
a liquid crystal cell and at least one compensation film or a combination of polarizers and optical compensators comprising at least one compensation film,
said compensation film comprising at least one layer of an anisotropic polymer obtained by polymerization of polymerizable mesogenic material comprising
a) two or more mesogenic compounds having at least one rod-like or board-like mesogenic group and at least one polymerizable functional group, in the presence of
b) an initiator,
c) optionally a non-mesogenic compound having two or more polymerizable functional groups, and
d) optionally a stabilizer,
wherein said layer of an anisotropic polymer has a homeotropic or tilted homeotropic molecular orientation,
wherein said mesogenic compounds having at least one rod-like or board-like mesogen and at least one polymerizable functional group are compounds of formula I
P—(Sp—X) n —MG—R I
wherein
P is a polymerizable group,
Sp is a spacer group having 1 to 20 C atoms,
X is a group selected from —O—, —S—, —CO—, —COO—, —OCO—, —OCOO— or a single bond,
n is 1,
MG is a group according to formula II
—(A 1 —Z 1 ) m —A 2 —Z 2 —A 3 — II
wherein
A 1 , A 2 and A 3 are independently from each other:
1,4-phenylene or 1,4-phenylene in which one or more CH groups is replaced by N,
1,4-cyclohexylene or 1,4-cyclohexylene in which one or two non-adjacent CH 2 groups is replaced in each case by O or S,
1,4-cyclohexenylene, or
naphthalene-2,6-diyl,
wherein in each case the group is unsubstituted, or mono- or polysubstituted with halogen, cyano, nitro, alkyl having 1 to 7 C atoms, alkoxy having 1 to 7 C atoms, alkanoyl having 1 to 7 C atoms, alkyl having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl, alkoxy having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl, or alkanoyl having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl,
Z 1 and Z 2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH, —C≡C —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond,
m is 0, 1 or 2, and
R is alkyl having up to 25 C atoms, alkyl having up to 25 C atoms which is mono- or polysubstituted by halogen or CN, wherein, in each case, one or more non-adjacent CH 2 groups is optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S— or —C≡C— in such a manner that oxygen atoms are not linked directly to one another, or
alternatively R is halogen, cyano or has independently one of the meanings given for P—(Sp—X) n —,
wherein said polymerizable mesogenic material contains at least 75% by weight of compounds of formula I.
2. A liquid crystal display device as claimed in claim 1 , wherein said device it comprises a broad band reflective polarizer.
3. A liquid crystal display device as claimed in claim 2 , wherein the phase retardation of the compensation film is opposite in sign to the phase retardation of the broad band reflective polarizer over the range of viewing angles from 0 to ± 90 degrees.
4. A liquid crystal display device as claimed in claim 1 , wherein the compensation film is a composite film comprising two or more layers of an anisotropic polymer at least one of said layers having a homeotropic or tilted homeotropic orientation.
5. A liquid crystal display device as claimed in claim 4 , wherein at least one layer of said composite compensation film has an optical symmetry axis with a diffusion orientation than the optical symmetry axis of at least one other of said layers.
6. A compensation film comprising at least one layer of an anisotropic polymer with homeotropic or tilted homeotropic molecular orientation,
wherein said compensation film is obtained by
A) coating a mixture of a polymerizable mesogenic material comprising
a) two or more mesogenic compounds having at least one rod-like or board-like mesogenic group and at least one polymerizable functional group,
b) an initiator,
c) optionally a non-mesogenic compound having two or more polymerizable functional groups, and
d) optionally a stabilizer
on at least one substrate in the form of a layer,
B) aligning said mixture in a homeotropic or tilted homeotropic orientation,
C) polymerizing said mixture by exposing it to heat or actinic radiation,
D) optionally repeating steps A), B) and C) at least one more time, and
E) optionally removing said at least one substrate from the polymerized material,
wherein said mesogenic compounds having at least one rod-like or board-like mesogen and at least one polymerizable functional group are compounds of formula I
P—(Sp—X) n —MG—R I
wherein
P is a polymerizable group,
Sp is a spacer group having 1 to 20 C atoms,
X is a group selected from —O—, —S—, —CO—, —COO—, —OCO—, —OCOO— or a single bond,
n is 1,
MG is a group according to formula II
—(A 1 —Z 1 ) m —A 2 —Z 2 —A 3 — II
wherein
A 1 , A 2 and A 3 are independently from each other:
1,4-phenylene or 1,4-phenylene in which one or more CH groups is replaced by N,
1,4-cyclohexylene or 1,4-cyclohexylene in which one or two non-adjacent CH 2 groups is replaced in each case by O or S,
1,4-cyclohexenylene, or
naphthalene-2,6-diyl,
wherein in each case the group is unsubstituted, or mono- or polysubstituted with halogen, cyano, nitro, alkyl having 1 to 7 C atoms, alkoxy having 1 to 7 C atoms, alkanoyl having 1 to 7 C atoms, alkyl having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl, alkoxy having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl, or alkanoyl having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl,
Z 1 and Z 2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH, —C≡C —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond,
m is 0, 1 or 2, and
R is alkyl having up to 25 C atoms, alkyl having up to 25 C atoms which is mono- or polysubstituted by halogen or CN, wherein, in each case, one or more non-adjacent CH 2 groups is optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S— or —C≡C— in such a manner that oxygen atoms are not linked directly to one another, or
alternatively R is halogen, cyano or has independently one of the meanings given for P—(Sp—X) n —,
wherein said polymerizable mesogenic material contains at least 75% by weight of compounds of formula I.
7. A compensation film as claimed in claim 6 , wherein at least one substrate is a plastic film.
8. A compensation film as claimed in claim 6 , wherein the mixture of the polymerizable mesogenic material comprises at least one mesogen having one polymerizable functional group and at least one mesogen having two or more polymerizable functional groups.
9. A compensation film as claimed in claim 6 , wherein the mixture of the polymerizable mesogenic material comprises at least two mesogens having one polymerizable functional group.
10. A composition film as claimed in claim 6 , wherein the polymerized material forms a three-dimensional network.
11. A compensation film according to claim 6 , wherein the mixture of the polymerizable mesogenic material consists essentially of:
a1) 15 to 85% by weight of at least one mesogen according to formula I having one polymerizable functional group,
a2) 10 to 85% by weight of at least one mesogen according to formula I having two or more polymerizable functional groups,
b) 0.01 to 5% by weight of an initiator,
c) 0 to 20% by weight of a non-mesogenic compound having two or more polymerizable functional groups, and
d) 0 to 1000 ppm of a stabilizer,
wherein said polymerizable mesogenic material contains at least 75% by weight of compounds of formula I.
12. A compensation film according to claim 6 , wherein, the mixture of the polymerizable mesogenic material essentially consists of
a) 75 to 99% by weight of at least two mesogens according to formula I having one polymerizable functional group,
b) 0.01 to 5% by weight of an initiator,
c) 0 to 20% by weight of a non-mesogenic compound having two or more polymerizable functional groups, and
d) 0 to 1000 ppm of a stabilizer.
13. A mixture of a polymerizable mesogenic material comprising
a) 75 to 99% by weight of two more achiral mesogenic compounds having at least one rod-like or board-like mesogen and one polymerizable functional group in the presence of
b) 0.01 to 5% by weight of an initiator,
c) 0 to 20% by weight of a non-mesogenic compound having two or more polymerizable functional groups, and
d) 0 to 1000 ppm of a stabilizer,
wherein said two or more achiral mesogenic compound having at least one rod-like or board-like mesogen and one polymerizable functional group are compounds of formula I
P—(Sp—X) n —MG—R I
wherein
P is a polymerizable group,
Sp is a spacer group having 1 to 20 C atoms,
X is a group selected from —O—, —S—, —CO—, —COO—, —OCO—, —OCOO— or a single bond,
n is 0 or 1,
MG is a group according to formula II
—(A 1 —Z 1 ) m —A 2 —Z 2 —A 3 — II
wherein
A 1 , A 2 and A 3 are independently from each other:
1,4-phenylene or 1,4-phenylene in which one or more CH groups is replaced by N,
1,4-cyclohexylene or 1,4-cyclohexylene in which one or two non-adjacent CH 2 groups are replaced in each case by O or S,
1,4-cyclohexenylene, or
naphthalene-2,6-diyl,
wherein in each case the group is unsubstituted, or mono- or polysubstituted with halogen, cyano, nitro, alkyl having 1 to 7 C atoms, alkoxy having 1 to 7 C atoms, alkanoyl having 1 to 7 C atoms, alkyl having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl, alkoxy having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl, or alkanoyl having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl,
Z 1 and Z 2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH, —C≡C —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—, CH═CH— or a single bond,
m is 0, 1 or 2,
R is alkyl having up to 25 C atoms, alkyl having up to 25 C atoms which is mono- or polysubstituted by halogen or CN, wherein, in each case, one or more non-adjacent CH 2 groups is optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S— or —C≡C— in such a manner that oxygen atoms are not linked directly to one another, or
alternatively R is halogen or cyano.
14. In a method of compensating the viewing angle dependence of the phase retardation of light transmitted by a broad band reflective polarized by providing a compensation film to achieve said compensating, the improvement wherein said compensation film is a film according to claim 6 .
15. A liquid crystal display device according to claim 2 , wherein the bandwidth of said broad band reflective polarizer is at least 100 nm.
16. A liquid crystal display device according to claim 2 , wherein the bandwidth of said broad band reflective polarizer is at least 150 nm.
17. A liquid crystal display device according to claim 4 , wherein at least one of said layers of anisotropic polymer has an optical symmetry axis with a tilt angle, relative to the plane of the layer, of less than 90 degrees but greater than 45 degrees.
18. A liquid crystal display device according to claim 4 , wherein at least one of said layers of anisotropic polymer has an optical symmetry axis with a tilt angle, relative to the plane of the layer, of less than 90 degrees but greater than 60 degrees.
19. A liquid crystal display device according to claim 4 , wherein at least one of said layers of anisotropic polymer has an optical symmetry axis with a tilt angle, relative to the plane of the layer, of less than 90 degrees but greater than 75 degrees.
20. A liquid crystal display device according to claim 1 , wherein said layer of anisotropic polymer has an optical symmetry axis which is oriented perpendicular to the layer.
21. A liquid crystal display device according to claim 1 , wherein said layer of anisotropic polymer has an optical symmetry axis with a tilt angle, relative to the plane of said layer, of less than 90 degrees but higher than 45 degrees.
22. A liquid crystal display device according to claim 15 , wherein the phase retardation of the compensation film is opposite in sign to the phase retardation of the broad band reflective polarizer over viewing angles, measured from the normal plane of the film, of 0 to +/−85 degrees.
23. A liquid crystal display device according to claim 1 , wherein said polymerizable mesogenic material contains up to 20% of non-mesogenic compounds with two or more polymerizable functional groups selected from alkyldiacrylates or alkyldimethacrylates having alkyl groups with 1-20 C atoms.
24. A liquid crystal display device according to claim 1 , wherein said polymerizable mesogenic material exhibits a nematic or smectic phase.
25. A compensation film according to claim 6 , wherein said polymerizable mesogenic material exhibits a nematic or smectic phase.
26. A compensation film according to claim 6 , wherein polymerization is carried out in the smectic phase of said polymerizable mesogenic mixture.
27. A compensation film according to claim 26 , wherein polymerization is carried out in the smectic A phase of said polymerizable mesogenic mixture.
28. A compensation film according to claim 6 , wherein said polymerization mesogenic material contains 40-90% of at least one mesogenic according to formula I having one polymerizable functional group.
29. A device according to claim 1 , wherein said polymerizable mesogenic material further comprises one or more surface-active compounds.
30. A compensation film according to claim 6 , wherein said polymerizable mixture further comprises one or more surface-active compounds.
31. A mixture according to claim 13 , wherein said polymerizable mixture further comprises one or more surface-active compounds.
32. A mixture of a polymerizable mesogenic material comprising
a) at least two mesogenic compounds each having at least one rod-like or board-like mesogen, wherein one of said mesogenic compounds has one polymerizable functional group and another of said mesogenic compounds has two or more polymerizable functional groups,
b) 0.01 to 5% by weight of an initiator,
c) 0 to 20% by weight of a non-mesogenic compound having two or more polymerizable functional groups, and
d) 0 to 1000 ppm of a stabilizer,
wherein said at least two mesogenic compound are compounds of formula I
P—(Sp—X) n —MG—T I
wherein
P is a polymerizable group,
Sp is a spacer group having 1 to 20 C atoms,
X is a group selected from —O—, —S—, —CO—, —COO—, —OCO—, —OCOO— or a single bond,
n is 0 or 1,
MG is a group according to formula II
—(A 1 —Z 1 ) m —A 1 —Z 2 —A 3 — II
wherein
A 1 , A 2 and A 3 are independently from each other:
1,4-phenylene or 1,4-phenylene in which one or more CH groups is replaced by N,
1,4-cyclohexylene or 1,4-cyclohexylene in which one or two non-adjacent CH 2 groups is replaced in each case by O or S,
1,4-cyclohexenylene, or
naphthalene-2,6-diyl,
wherein in each case the group is unsubstituted, or mono- or polysubstituted with halogen, cyano, nitro, alkyl having 1 to 7 C atoms, alkoxy having 1 to 7 C atoms, alkanoyl having 1 to 7 C atoms, alkyl having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl, alkoxy having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl, or alkanoyl having 1 to 7 C atoms wherein one or more H atoms is replaced by F or Cl,
Z 1 and Z 2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH, —C≡C —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond,
m is 0, 1 or 2, and
R is, in this case of mesogenic compounds having one polymerizable functional group, straight chain or achiral branched alkyl having up to 25 C atoms, wherein, in each case, one or more non-adjacent CH 2 groups is optionally replaced, in each case independently from one another, by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S— or —C≡C— in such a manner that oxygen atoms are not linked directly to one another, or, in the case of mesogenic compounds having two or more polymerizable functional group, R is independently P—( Sp—X ) n ,
wherein component a) consists essentially of
a1) 15 to 85% by weight of said mesogenic compound having one polymerizable functional group, and
a2) 10 to 85% by weight of said mesogenic compound having two or more polymerizable functional groups, and
wherein said polymerizable mesogenic material contains at least 75% by weight of compounds of formula I.
33. A device according to claim 1 , wherein P is CH 2 ═CW—COO—, WCH≡CH—O—,
is H, CH 3 or Cl, k is 0 or 1, and Sp is a linear or branched alkylene group having 1-20 C atoms in which, optionally one or more non-adjacent CH 2 groups is in each case replaced by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)—, —CH(CN)—, —CH═CH— or —C≡C—.
34. A compensation film according to claim 6 , wherein P is CH 2 ═CW—COO—,
is H, CH 3 or Cl, k is 0 or 1, and Sp is a linear or branched alkylene group having 1-20 C. atoms in which, optionally one or more non-adjacent CH 2 groups is in each case replaced by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)—, —CH(CN)—, —CH═CH— or —C≡C—.
35. A mixture of polymerizable material according to claim 13 , wherein P is
is H, CH 3 or Cl, k is 0 or 1, and Sp is a linear or branched alkylene group having 1-20 C atoms in which, optionally one or more non-adjacent CH 2 groups is in each case replaced by —O—, —S—, —NH—, —N(CH 3 )—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)—, —CH(CN)—, —CH═CH— or —C≡C—.
36. A mixture according to claim 32 , wherein MG is selected from formulae II- 1 to II - 16 — Phe—Z 2 —Phe— II - 1 — Phe—Z 2 —Cyc— II - 2 — PheL—Z 2 —Phe— II - 3 — PheL—Z 2 —Cyc— II - 4 — Phe—Z 2 —PheL— II - 5 — Phe—Z 1 —Phe—Phe— II - 6 — Phe—Z 1 —Phe—Cyc— II - 7 — Phe—Z 1 —Phe—Z 2 —Phe— II - 8 — Phe—Z 1 —Phe—Z 2 —Cyc— II - 9 — Phe—Z 1 —Cyc—Z 2 —Phe— II - 10 — Phe—Z 1 —Cyc—Z 2 —Cyc— II - 11 — Phe—Z 1 —PheL—Z 2 —Phe— II - 12
— Phe—Z 1 —Phe—Z 2 —PheL— II - 13
— PheL—Z 1 —Phe—Z 2 —PheL— II - 14
— PheL—Z 1 —PheL—Z 2 —Phe— II - 15
— PheL—Z 1 —PheL—Z 2 —PheL— II - 16
wherein
Phe is 1 , 4 - phenylene,
PheL a 1 , 4 - phenylene group which is substituted by at least one group L,
L is F, Cl, CN or an optionally fluorinated alkyl, alkoxy or alkanoyl group having 1 to 4 C atoms, and
Cyc is 1 , 4 - cyclohexylene.
37. A mixture according to claim 36 , wherein L is F, Cl, CN, methyl, methoxy, ethyl, ethoxy, oxamethyl, oxaethyl, or trifluormethyl.
38. A mixture according to claim 36 , wherein L is F, Cl, CN, NO 2 , CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , COCH 3 , COC 2 H 5 , CF 3 , OCF 3 , OCHF, or OC 2 F 5 .
39. A mixture according to claim 32 , wherein MG is selected from formulae IIa to IIn
wherein
L is F, Cl, CN or an optionally fluorinated alkyl, alkoxy or alkanoyl group having 1 to 4 C atoms, and
r is 0 , 1 or 2 .
40. A mixture according to claim 39 , wherein the group
41. A mixture according to claim 32 , wherein one of said at least two polymerizable mesogenic compounds is selected from formula Ia and the other of said at least two polymerizable mesogenic compounds is selected from formulae Ib to Ig:
wherein
x and y are each independently 1 to 12 ,
A is a 1 , 4 - phenylene or 1 , 4 - cyclohexylene group,
R
1
is halogen, cyano or an optionally halogenated alkoxy group with 1 to 12 C atoms, and
L
1
and L
2
are each independently H, halogen, CN, or an alkyl, alkoxy or alkanoyl group with 1 to 7 C atoms.Cited by (0)
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