Polymerisable liquid crystal material and polymerised liquid crystal film
A polymerisable LC material comprising one or more di- or multireactive mesogenic compounds and one or more compounds of formula UVI, and one or more compounds of formula UVII, Further, a method for its preparation, a polymer film with improved thermal durability and UV stability obtainable from a corresponding polymerisable LC material, a method of preparation of such polymer film, and the use of such polymer film and said polymerisable LC material for optical, electro-optical, decorative or security devices.
1. A polymerizable LC material, comprising at least one di- or multireactive mesogenic compound and one or more compounds of formula UVII,
wherein the individual radicals have the following meanings:
R 1 to R 5 are each independently selected from the group consisting of H, alkyl, —OH, alkylaryl, alkylheteroaryl, cycloalkyl, cycloheteroalkyl, alkenyl, aryl and —SO 3 H, and
R 6 and R 7 denote each and independently a hydrogen atom, a hydroxy group, or a halogen atom; and
one or more compounds of formula UVI-a:
2. The polymerisable LC material according to claim 1 , further comprising one or more compounds of formula UVI,
in which
R 11 on each occurrence, independently of one another, denotes H, F, or a straight-chain alkyl having 1-20 C atoms or branched alkyl having 3-20 C atoms, in which one —CH 2 — group or, if present, a plurality of —CH 2 — groups may be replaced by —O— or —C(═O)—, but two adjacent —CH 2 — groups cannot be replaced by —O—, and one or, if present, a plurality of —CH 2 — groups may be replaced by —CH═CH— or —C≡C—, and in which one H atom or a plurality of H atoms may be replaced by F, OR 13 , N(R 13 )(R 14 ) or R 15 ,
R 12 on each occurrence, independently of one another, denotes a straight-chain alkyl having 1-20 C atoms or branched alkyl having 3-20 C atoms, in which one —CH 2 — group or a plurality of —CH 2 — groups may be replaced by —O— or —C(═O)—, but two adjacent —CH 2 — groups cannot be replaced by —O—, a hydrocarbon radical which contains a cycloalkyl or alkylcycloalkyl unit and in which one —CH 2 —group or a plurality of —CH 2 — groups may be replaced by —O— or —C(═O)—, but two adjacent —CH 2 — groups cannot be replaced by —O—, and in which one H atom or a plurality of H atoms may be replaced by OR 13 , N(R 13 )(R 14 ) or R 15 , or an aromatic or heteroaromatic hydrocarbon radical, in which one H atom or a plurality of H atoms may be replaced by F, OR 13 , N(R 13 )(R 14 ) or R 15 ,
R 13 on each occurrence, independently of one another, denotes a straight-chain alkyl or acyl group having 1 to 10 C atoms or branched alkyl or acyl group having 3 to 10 C atoms or an aromatic hydrocarbon or carboxylic acid radical having 6-12 C atoms,
R 14 on each occurrence, independently of one another, denotes a straight-chain alkyl or acyl group having 1 to 10 C atoms or branched alkyl or acyl group having 3 to 10 C atoms or an aromatic hydrocarbon or carboxylic acid radical having 6 to 12 C atoms,
R 15 on each occurrence, independently of one another, denotes a straight-chain alkyl group having 1 to 10 C atoms or branched alkyl group having 3 to 10 C atoms, in which one —CH 2 — group or a plurality of —CH 2 — groups may be replaced by —O— or —C(═O)—, but two adjacent —CH 2 — groups cannot be replaced by —O—,
S 11 and S 12 on each occurrence, independently of one another, denote a straight-chain alkylene group having 1 to 20 C atoms or a branched alkylene group having 3 to 20 C atoms, in which one —CH 2 — group or, if present, a plurality of —CH 2 — groups may be replaced by —O— or —C(═O)—, but two adjacent —CH 2 — groups cannot be replaced by —O—, and one or, if present, a plurality of —CH 2 — groups may be replaced by —CH═CH— or —C≡C— and in which one H atom or a plurality of H atoms may be replaced by F, OR 13 , N(R 13 )(R 14 ) or R 15 , or denote a single bond,
X 11 denotes C,
Y 11 to Y 14 each, independently of one another, denote methyl or ethyl,
Z 11 to Z 14 on each occurrence, independently of one another, denote —O—, —(C═O)—, —O—(C═O)—, —(C═O)—O—, —O—(C═O)—O—, —(N—R 13 )—, —N—R 13 —(C═O)— or a single bond if S 11 is a single bond, but both Z 11 and Z 12 do not simultaneously denote —O—, and, however, if S 12 is a single bond, both Z 13 and Z 14 do not simultaneously denote —O—, and, however, if —X 11 [—R 11 ] o — is a single bond, both Z 12 and Z 13 do not simultaneously denote —O—,
p denotes 1 o 2,
o denotes (3-p),
n*p denotes an integer from 3 to 10,
in the case where p=1,
m denotes (10-n),
and in the case where p=2,
n denotes an integer from 2 to 4, and
m denotes (4-n),
denotes an organic radical having (m+n) bonding sites,
and, in the case where p=1, —X 11 [—R 11 ] o — may alternatively also denote a single bond.
3. The polymerisable LC material according to claim 1 , wherein the one or more compounds of formula UVII are selected from the group of compounds of the following subformulae
4. The polymerisable LC material according to claim 1 , wherein the at least one di- or multireactive mesogenic compound is selected of formula DRM
P 1 -Sp 1 -MG-Sp 2 -P 2 DRM
wherein
P 1 and P 2 independently of each other denote a polymerisable group,
Sp 1 and Sp 2 independently of each other are a spacer group or a single bond,
and MG is a rod-shaped mesogenic group, which is preferably selected of formula MG
(A 1 -Z 1 ) n -A 2 - MG
wherein
A 1 and A 2 denote, in case of multiple occurrence independently of one another, an aromatic or alicyclic group, which optionally contains one or more heteroatoms selected from N, O and S, and is optionally mono- or polysubstituted by L 1 ,
L 1 is P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O) NR 00 R 000 , —C(═O) OR 00 , —C(═O)R 00 , —NR 00 R 000 , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12 C atoms, straight chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 3 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,
R 00 and R 000 independently of each other denote H or alkyl with 1 to 12 C-atoms,
Z 1 denotes, in case of multiple occurrence independently of one another, —O—, —S—, —CO—, —COO—, —OCO—, —S—CO—, —CO—S—, —O—COO—, —CO—NR 00 —, —NR 00 —CO—, —NR 00 —CO—NR 000 , —NR 00 —CO—O—, —O—CO—NR 00 —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —(CH 2 ) n1 , —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 00 —, —CY 1 ═CY 2 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond,
Y 1 and Y 2 independently of each other denote H, F, Cl or CN,
n is 1, 2, 3 or 4, and
n1 is an integer from 1 to 10.
5. The polymerisable LC material according to claim 1 , wherein at least one direactive mesogenic compound is selected from the following formulae,
wherein
P 0 is, in case of multiple occurrence independently of one another, an acryl, methacryl, oxetane, epoxy, vinyl, heptadiene, vinyloxy, propenyl ether or styrene group,
L has on each occurrence identically or differently one of the meanings given for L 1 in formula DRM,
r is 0, 1, 2, 3 or 4,
x and y are independently of each other 0 or identical or different integers from 1 to 12,
Z is each and independently, 0 or 1, with z being 0 if the adjacent x or y is 0.
6. The polymerisable LC material according to claim 1 , comprising at least one monoreactive mesogenic compound, which is selected from formula MRM,
P 1 -Sp 1 -MG-R MRM
wherein P 1 , Sp 1 and MG have the meanings as given in formula DRM,
R is F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O) NR x R y , —C(═O)X, —C(═O)OR x , —C(═O)R y , —NR x R y , —OH, —SF 5 , optionally substituted silyl, straight chain alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 3 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl,
X is halogen, preferably F or Cl, and
R x and R y are independently of each other H or alkyl with 1 to 12 C-atoms.
7. The polymerisable LC material according to claim 1 , comprising at least one monoreactive mesogenic compound, which is selected from the following formulae,
wherein P 0 , L, r, x, y and z are defined as given in claim 5 ,
R 0 is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 or more, preferably 1 to 15 C atoms or denotes Y 0 ,
Y 0 is F, Cl, CN, NO 2 , OCH 3 , OCN, SCN, SF 5 , or mono-oligo- or polyfluorinated alkyl or alkoxy with 1 to 4 C atoms,
R 01 and R 02 is H, alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 or more, preferably 1 to 15 C atoms or denotes Y 0 ,
Z 0 is —COO—, —OCO—, —CH 2 CH 2 —, —CF 2 O—, —OCF 2 —, —CH═CH—, —OCO—CH═CH—, —CH═CH—COO—, or a single bond,
A 0 is, in case of multiple occurrence independently of one another, 1,4-phenylene that is unsubstituted or substituted with 1, 2, 3 or 4 groups L, or trans-1,4-cyclohexylene,
u and v are independently of each other 0, 1 or 2,
W is 0 or 1, and
wherein the benzene and naphthalene rings can additionally be substituted with one or more identical or different groups L.
8. The polymerisable LC material according to claim 1 , comprising one or more compounds of formula ND,
wherein
U 1,2 are independently of each other selected from
including their mirror images, wherein the rings U 1 and U 2 are each bonded to the group-(B) q-via the axial bond, and one or two non-adjacent CH 2 groups in these rings are optionally replaced by O and/or S, and the rings U 1 and U 2 are optionally substituted by one or more groups L,
L has on each occurrence identically or differently one of the meanings given for L 1 in formula DRM,
Q 1,2 are independently of each other CH or SiH,
Q 3 is C or Si,
B is in each occurrence independently of one another-C≡C—, —CY 1 ═CY 2 — or an optionally substituted aromatic or heteroaromatic group,
Y 1,2 are independently of each other H, F, Cl, CN or R 0 ,
q is an integer from 1 to 10, preferably 1, 2, 3, 4, 5, 6 or 7,
A 1-4 are independently of each other selected from non-aromatic, aromatic or heteroaromatic carbocyclic or heterocyclic groups, which are optionally substituted by one or more groups R 5 , and wherein each of -(A 1 -Z 1 ) m —U 1 —(Z 2 -A 2 ) n - and -(A 3 -Z 3 ) o —U 2 —(Z 4 -A 4 ) p - does not contain more aromatic groups than non-aromatic groups and preferably does not contain more than one aromatic group,
Z 1-4 are independently of each other-O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —CO—NR 00 —, —OCH 2 —, —CH 2 O—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, —CH 2 CH 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —CH═CH—, —CY 1 ═CY 2 —, —CH═N—, —N═CH—, —N═N—, —CH═CR 0 —, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, CR 0 R 00 or a single bond,
R 0 and R 00 are independently of each other H or alkyl with 1 to 12 C-atoms,
m and n are independently of each other 0, 1, 2, 3 or 4,
and p are independently of each other 0, 1, 2, 3 or 4,
R 1-5 are independently of each other identical or different groups selected from H, halogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O) NR 0 R 00 , —C(═O)X 0 , —C(═O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , P-Sp-, optionally substituted silyl, or carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or denote P or P-Sp-, or are substituted by P or P-Sp-, wherein the compounds comprise at least one group R 1-5 denoting or being substituted by P or P-Sp-,
P is a polymerisable group,
Sp is a spacer group or a single bond.
9. The polymerisable LC material according to claim 1 , comprising 5 to 99% by weight of di- or multireactive polymerisable mesogenic compounds.
10. The polymerisable LC material according to claim 1 , comprising 5 to 80% by weight of monoreactive polymerizable mesogenic compounds.
11. The polymerisable LC material according to claim 1 , comprising one or more additives selected from the group consisting of surfactants, further stabilisers, catalysts, sensitizers, inhibitors, chain-transfer agents, co-reacting monomers, reactive thinners, surface-active compounds, lubricating agents, wetting agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, degassing or defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments and nanoparticles.
12. A process for the preparation of a polymerisable LC material, comprising the steps of mixing one or more compounds of formula UVI-a with at least one di- or multireactive mesogenic compound,
13. A process for the preparation of a polymer film, comprising the steps of:
providing a layer of a polymerisable LC material comprising at least one di- or multireactive mesogenic compound and one or more compounds of formula UVI-a,
and
one or more compounds of formula UVII,
wherein the individual radicals have the following meanings:
R 1 to R 5 are each independently selected from the group consisting of H, alkyl, —OH, alkylaryl, alkylheteroaryl, cycloalkyl, cycloheteroalkyl, alkenyl, aryl and —SO 3 H, and
R 6 and R 7 denote each and independently a hydrogen atom, a hydroxy group, or a halogen atom onto a substrate, photopolymerising the polymerisable LC material, and optionally removing the polymerised LC material from the substrate and/or optionally providing it onto another substrate.
14. A polymer film obtainable from a polymerisable LC material comprising at least one di- or multireactive mesogenic compound and one or more compounds of formula UVI-a,
and
one or more compounds of formula UVII,
wherein the individual radicals have the following meanings:
R 1 to R 5 are each independently selected from the group consisting of H, alkyl, —OH, alkylaryl, alkylheteroaryl, cycloalkyl, cycloheteroalkyl, alkenyl, aryl and —SO 3 H, and
R 6 and R 7 denote each and independently a hydrogen atom, a hydroxy group, or a halogen atom by a process comprising the steps of providing a layer of the polymerisable LC material onto a substrate, photopolymerising the LC material, and optionally, removing the polymerised LC material from the substrate and/or optionally providing it onto another substrate.
15. The polymer film according to claim 14 , wherein the LC material is uniformly aligned.
16. An optical component or device comprising at least one polymer film according to claim 14 .
17. An optical component or device comprising a polymerisable LC material according to claim 1 .
18. The polymerisable LC material according to claim 2 , wherein the one or more compounds of formula UVI are selected from the following subformulae: