U.S. patent number 10,385,215 [Application Number 15/308,504] was granted by the patent office on 2019-08-20 for polymerizable dichroic dyes.
This patent grant is currently assigned to ROLIC AG. The grantee listed for this patent is ROLIC AG. Invention is credited to Cedric Klein, Frederic Lincker, Frederic Reveaud.
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United States Patent |
10,385,215 |
Klein , et al. |
August 20, 2019 |
Polymerizable dichroic dyes
Abstract
New dichroic dyes having a composition with slave materials. The
dyes may be used for a dichroic polymer network, a dichroic liquid
crystalline polymer film (LCP film) or a dichroic liquid
crystalline polymer gel, which for instance find application as
electro-optical or optical devices.
Inventors: |
Klein; Cedric
(Herrlisheim-pres-Colmar, FR), Lincker; Frederic
(Schiltigheim, FR), Reveaud; Frederic (Mulhouse,
FR) |
Applicant: |
Name |
City |
State |
Country |
Type |
ROLIC AG |
Zug |
N/A |
CH |
|
|
Assignee: |
ROLIC AG (Zug,
CH)
|
Family
ID: |
50732947 |
Appl.
No.: |
15/308,504 |
Filed: |
May 18, 2015 |
PCT
Filed: |
May 18, 2015 |
PCT No.: |
PCT/EP2015/060833 |
371(c)(1),(2),(4) Date: |
November 02, 2016 |
PCT
Pub. No.: |
WO2015/177062 |
PCT
Pub. Date: |
November 26, 2015 |
Prior Publication Data
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|
|
Document
Identifier |
Publication Date |
|
US 20170058126 A1 |
Mar 2, 2017 |
|
Foreign Application Priority Data
|
|
|
|
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May 21, 2014 [EP] |
|
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14169195 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K
19/603 (20130101); C09K 19/3861 (20130101); C09B
1/585 (20130101); C09K 19/56 (20130101); C09K
19/586 (20130101); C09B 69/101 (20130101); C09B
1/22 (20130101); C09K 19/3809 (20130101); C09B
1/473 (20130101); C09K 2019/0448 (20130101); C09K
2219/03 (20130101) |
Current International
Class: |
C09B
69/10 (20060101); C09B 1/473 (20060101); C09B
1/22 (20060101); C09K 19/60 (20060101); C09B
1/58 (20060101); C09K 19/04 (20060101); C09K
19/56 (20060101); C09K 19/58 (20060101); C09K
19/38 (20060101) |
References Cited
[Referenced By]
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Other References
Ringsdorf et al., "Orientational Ordering of Dyes in the Glassy
State of Liquid-Crystalline Side Group Polymers", Jul. 1986, Liquid
Crystals, vol. 1 Issue 4, 319-325. (Year: 1986). cited by examiner
.
International Search Report of PCT/EP2015/060833, dated Jul. 31,
2015 [PCT/ISA/210]. cited by applicant .
Written Opinion of PCT/EP2015/060833, dated Nov. 26, 2016
[PCT/ISA/237]. cited by applicant .
Jia, Y., et al., "Synthesis and characterization of side-chain
liquid crystalline polymer containing dichroic dye monomer",
European Polymer Journal, vol. 39, 2003, pp. 1701-1706. cited by
applicant.
|
Primary Examiner: Kelly; Cynthia H
Assistant Examiner: Malloy; Anna
Attorney, Agent or Firm: Sughrue Mion, PLLC
Claims
The invention claimed is:
1. A composition comprising at least a dichroic dye of formula (I)
and at least one slave material which is selected from the group
consisting of a liquid crystal and a polymerizable liquid crystal:
##STR00032## wherein X.sup.2, X.sup.1 are independently from each
other NR, R represents hydrogen, unbranched or branched lower alkyl
radical, Y.sup.1, Y.sup.2 independently from each other are a
single bond, Z.sup.1 is O, Z.sup.2 is a single bond, n2 is 1, n1,
n3, n4, n5, n6 are 0, W.sup.1, W.sup.4, W.sup.5, W.sup.6 are
hydrogen, W.sup.2, W.sup.3 independently from each other are
unsubstituted or substituted, straight chain or branched
C.sub.1-C.sub.30 alkyl, in which one --CH-- or --CH.sub.2-- group
may be replaced by one or more linking group consisting of --O--,
--S--, --NR.sup.1--, --CH(OR.sup.1)--, --CO--NR.sup.1--,
--NR.sup.1--CO--, --CO--O--, --O--CO--, --SO.sub.2-- or an aromatic
group which is unsubstituted or substituted by one or more straight
chain or branched lower alkyl radical, --F, --Cl or --OR.sup.1, and
wherein R.sup.1 represents hydrogen, straight chain or branched
lower alkyl radical, PG is a polymerizable group consisting of
CH.sub.2.dbd.CQ-COO--, wherein Q is hydrogen or methyl; or a
dichroic dye of formula (I), wherein X.sup.1 is S X.sup.2 is single
bond or NR, R has the same meaning as mentioned above, Y.sup.1 is
S, Y.sup.2 is a single bond or NR, Z.sup.1, Z.sup.2 are single
bond, n1, n6 are 1, n2, n3, n4, n5, are 0, W.sup.2, W.sup.3,
W.sup.4, W.sup.5 are hydrogen W.sup.1, W.sup.6 are independently
from each other are unsubstituted or substituted, straight chain or
branched C.sub.1-C.sub.30 alkyl, in which one --CH-- or
--CH.sub.2-- group may be replaced by one or more linking group
consisting of --O--, --S--, --NR.sup.1--, --CH(OR.sup.1)--,
--CO--NR.sup.1--, --NR.sup.1--CO--, --CO--O--, --O--CO--,
--SO.sub.2-- or an aromatic group which is unsubstituted or
substituted by one or more straight chain or branched lower alkyl
radical, --F, --Cl or --OR.sup.1, and wherein R.sup.1 having the
same meaning as mentioned above, PG is a polymerizable group
consisting of CH.sub.2.dbd.CQ-COO--, wherein Q is hydrogen or
methyl; or a dichroic dye of formula (I), wherein X.sup.1, X.sup.2
are independently from each other NR Y.sup.1, Y.sup.2 are
independently from each other NR, R has the same meaning as
mentioned above, Z.sup.1, Z.sup.2 are independently from each other
a single bond or O n2, n5 are 1, n1, n3, n4, n6, are 0, W.sup.1,
W.sup.6 are hydrogen W.sup.2, W.sup.3 W.sup.4, W.sup.5 are
independently from each other unsubstituted or substituted,
straight chain or branched C.sub.1-C.sub.30 alkyl, in which one
--CH-- or --CH.sub.2-- group may be replaced by one or more linking
group consisting of --O--, --S--, --NR.sup.1--, --CH(OR.sup.1)--,
--CO--NR.sup.1--, --NR.sup.1--CO--, --CO--O--, --O--CO--,
--SO.sub.2-- or an aromatic group which is unsubstituted or
substituted by one or more straight chain or branched lower alkyl
radical, --F, --Cl or --OR.sup.1, and wherein R.sup.1 having the
same meaning as mentioned above, PG is a polymerizable group
consisting of CH.sub.2.dbd.CQ-COO--, wherein Q is hydrogen or
methyl.
2. A composition according to claim 1, wherein said composition
additionally comprises at least one chiral polymerizable liquid
crystalline compound or at least one chiral component.
3. A process for the preparation of a dichroic polymer network, a
dichroic liquid crystalline polymer film (LCP film) or a dichroic
liquid crystalline polymer gel, which process comprises
polymerizing a composition according to claim 1.
4. A dichroic polymer network, a dichroic liquid crystalline
polymer film (LCP film) or a dichroic liquid crystalline polymer
gel comprising a composition according to claim 1.
5. An electro-optical or optical device, comprising a dichroic
polymer network, a dichroic liquid crystalline polymer film (LCP
film) or a dichroic liquid crystalline polymer gel according to
claim 4.
6. An electro-optical or optical device according to claim 5, which
is represented by a polarizer, an optical film, a security or an
authentication device.
7. A dichroic polymer network, a dichroic liquid crystalline
polymer film (LCP film) or a dichroic liquid crystalline polymer
gel comprising a composition according to claim 2.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
This is a National Stage of International Application No.
PCT/EP2015/060833 filed May 18, 2015, claiming priority based on
European Patent Application No. 14169195.6 filed May 21, 2014.
FIELD OF THE INVENTION
The present invention relates to new dichroic dyes, their
composition with slave materials and their use for a dichroic
polymer network, a dichroic liquid crystalline polymer film (LCP
film) or a dichroic liquid crystalline polymer gel, which for
instance find application as electro-optical or optical
devices.
SUMMARY OF THE INVENTION
The present invention relates in a first aspect to a dichroic dye
of formula (I):
##STR00001## wherein X.sup.1 is NR or S, X.sup.2 is a single bond,
NR, S or O, Y.sup.1, Y.sup.2 independently from each other are a
single bond, NR, S or O, Z.sup.1, Z.sup.2 independently from each
other are a single bond, NR, S or O, R represents hydrogen,
unbranched or branched lower alkyl radical, W.sup.1, W.sup.2,
W.sup.3, W.sup.4, W.sup.5, W.sup.6 independently from each other
are H, unsubstituted or substituted, unbranched or branched
C.sub.1-C.sub.30 alkyl radical, in which one or more --CH-- or
--CH.sub.2-- group may be replaced by a linking group, PG is a
polymerizable group, n1, n2, n3, n4, n5, n6 independently from each
other signifies 0, 1, 2, 3, 4, 5 or 6 whereby the sum of n1, n2,
n3, n4, n5 and n6 is .gtoreq.1, with the proviso that if n1, n2,
n3, n4, n5 or n6=0, the connected W.sup.1, W.sup.2, W.sup.3,
W.sup.4, W.sup.5, W.sup.6 have to be saturated by hydrogen.
DETAILED DESCRIPTION OF THE INVENTION
The wording linking group, as used in the context of the present
invention is selected from the group consisting of --O--, --S--,
--NR.sup.1--, --CH.dbd.N--, --N.dbd.N--, --CH(OR.sup.1)--, --CO--,
--CO--NR.sup.1--, --NR.sup.1--CO--, --NR.sup.1--CO--O--,
--O--CO--NR.sup.1--, --NR.sup.1--CO--NR.sup.1--, --CO--O--,
--O--CO--, --O--CO--O--, --SO--, --SO.sub.2--,
--Si(R.sup.1).sub.2--, --O--Si(R.sup.1).sub.2--,
--O--Si(R.sup.1).sub.2--O--, --C.dbd.C--, --C.ident.C--, an
aromatic or alicyclic group which is unsubstituted or substituted
by one or more straight chain or branched lower alkyl radical,
halogens, --OR.sup.1, --SR.sup.1, --NR.sup.1R.sup.2, --CN,
--NO.sub.2, --SOR.sup.1, --SO.sub.2R.sup.1, --SO.sub.3.sup.- the
negative charge of the --SO.sub.3.sup.- group being balanced by a
cation or mixture of cations selected from the group consisting of
H.sup.+, Li.sup.+, Na.sup.+, K.sup.+ and
[NR.sup.1R.sup.2R.sup.3R.sup.4].sup.+, and wherein
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently from each other
represent hydrogen, straight chain or branched lower alkyl
radical,
with the proviso that oxygen atoms of the linking groups are not
directly linked to each other.
It is understood that the term "aromatic" includes optionally
substituted carbocyclic and heterocyclic groups comprising five-,
six- or ten-membered ring systems, such as furane, benzene,
pyridine, pyrimidine, naphthalene or tetraline units. In the scope
of the present invention, preferred aromatic ring is selected from
the group consisting of benzene, naphthalene or tetraline, even
more preferred aromatic ring is benzene.
It is understood that the term "alicyclic" includes non-aromatic
carbocyclic or heterocyclic ring systems having 3 to 10 carbon
atoms, such as cyclopropane, cyclobutane, cyclopentane,
cyclopentene, cyclohexane, cyclohexene, 1,3 dioxane, cyclohexadiene
and decaline. In the scope of the present invention, preferred
alicyclic ring is selected from the group consisting of
cyclobutane, cyclopentane, cyclopentene, cyclohexane or
cyclohexene, even more preferred alicyclic ring is cyclohexane.
It is understood that the phrase "straight chain or branched
C.sub.1-C.sub.30 alkyl radical" includes groups selected from the
group comprising methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
sec-butyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl,
cyclohexyl, heptyl, octyl, nonyl, decyl, 3-methylpentyl, allyl,
but-3-en-1-yl, pent-4-en-1-yl, hex-5-en-1-yl, propynyl, butynyl,
pentynyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,
sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, cyclopentyloxy,
hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, nonyloxy,
3-methylpentyloxy, allyloxy, but-3-enyloxy, pent-4-enyloxy,
cylohexylmethoxy, cyclopentylmethoxy, methoxycarbonyl,
ethoxycarbonyl, propoxycarbonyl, isopropoxy-carbonyl,
butoxycarbonyl, isobutoxycarbonyl, sec-butoxy-carbonyl,
tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl,
cyclopentyloxy-carbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl,
octyloxycarbonyl, nonyloxycarbonyl, 3-methylpentyloxycarbonyl,
allyloxycarbonyl, but-3-enyloxycarbonyl, pent-4-en-yl-oxy-carbonyl,
cylohexylmethoxy-carbonyl, cyclopentylmethoxycarbonyl, acetoxy,
ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy,
butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy,
tert-butylcarbonyloxy, pentylcarbonyloxy, isopentylcarbonyloxy,
cyclopentylcarbonyloxy, hexylcarbonyloxy, cyclohexylcarbonyloxy,
octylcarbonyloxy, nonylcarbonyloxy, 3-methylpentylcarbonyloxy,
but-3-enyloxy, pent-4-enyloxy, acetyl, ethylcarbonyl,
propylcarbonyl, isopropylcarbonyl, butylcarbonyl, isobutylcarbonyl,
sec-butylcarbonyl, pentylcarbonyl, isopentylcarbonyl,
cyclohexylcarbonyl, octyl, carbonyl, nonylcarbonyl, methoxyacetoxy,
1-methoxy-2-propoxy, 3-methoxy-1-propoxy, 2-methoxyethoxy,
2-isopropoxyethoxy, 1-ethoxy-3-pentyloxy, 3-butynyloxy,
4-pentynyloxy, 5-chloropentynyl, 4-pentynecarbonyloxy,
6-propyloxyhexyl, 6-propyloxyhexyloxy, 2-fluoroethyl,
trifluoromethyl, 2,2,2-trifluoroethyl, 1H,1H-pentadecafluorooctyl,
1H,1H,7H-dodecafluoroheptyl, 2-(perfluorooctyl)ethyl,
2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl,
2-(perfluorodecyl)ethyl, perfluoropropyl, perfluorobutyl,
perfluoroheptyl, perfluorooctyl, perfluorononyl. 1-fluoropropoxy,
1-fluoropentyloxy, 2-fluoropropoxy, 2,2-difluoropropoxy,
3-fluoropropoxy, 3,3-difluoropropoxy, 3,3,3-trifluoropropoxy,
trifluoromethoxy or variations thereof.
The term "polymerizable group", as used in the context of the
present invention is selected from the group consisting of
CH.sub.2.dbd.CQ-, CH.sub.2.dbd.CQ-COO--, CH.sub.2.dbd.CH--CO--NH--,
CH.sub.2.dbd.C(Ph)-CO--NH--, CH.sub.2.dbd.CH--O--,
CH.sub.2.dbd.CH--OOC--, Ph-CH.dbd.CH--, CH.sub.2.dbd.CH-Ph-,
CH.sub.2.dbd.CH-Ph-O--, R.sup.5-Ph-CH.dbd.CH--COO--,
R.sup.5--OOC--CH.dbd.CH-Ph-O--, N-maleinimidyl, wherein Q is
hydrogen, chloro, or methyl, R.sup.5 is straight chain or branched
C.sub.1-C.sub.8 alkyl or alkoxy, Ph- is phenyl and -Ph- is
1,4-phenylene. In the scope of the present invention, preferred
polymerizable group is selected from the group consisting of
CH.sub.2.dbd.CQ-, CH.sub.2.dbd.CQ-COO--, CH.sub.2.dbd.CH--CO--NH--,
CH.sub.2.dbd.C(Ph)-CO--NH--, CH.sub.2.dbd.CH--O--,
CH.sub.2.dbd.CH--OOC--, CH.sub.2.dbd.CH-Ph-O--, wherein Q is
hydrogen, chloro, or methyl, more preferred polymerizable group is
selected from the group consisting of CH.sub.2.dbd.CQ-,
CH.sub.2.dbd.CQ-COO--, CH.sub.2.dbd.CH--CO--NH--,
CH.sub.2.dbd.CH--OOC--, wherein Q is hydrogen or methyl, even more
preferred polymerizable group is selected from the group consisting
of CH.sub.2.dbd.CQ-COO--, wherein Q is hydrogen or methyl.
The term "lower alkyl or lower alkyl radical", as used in the
context of the present invention is selected from the group
consisting of straight chain or branched, cyclic or straight-chain,
optionally substituted by one or more cyano group, one or more
hydroxyl group or one or more halogen atoms C.sub.1-C.sub.8 alkyl
radical. Preferred lower C.sub.1-C.sub.8 alkyl radical is selected
from the group consisting of methyl, ethyl, 2-cyanoethyl,
2-hydroxyethyl, propyl, isopropyl, cyclopropyl, 2-hydroxypropyl,
butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl,
neopentyl, cyclopentyl, hexyl, cyclohexyl, 3-metylpentyl, heptyl,
octyl, 2-ethylhexyl, 2-fluoroethyl, trifluoromethyl,
2,2,2-trifluoroethyl, 2-(perfluorobutyl)ethyl,
2-(perfluorohexyl)ethyl, perfluoropropyl, perfluorobutyl,
perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl
and the like, more preferred lower C.sub.1-C.sub.8 alkyl radical is
selected from the group consisting of methyl, ethyl, propyl,
isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hexyl,
cyclohexyl, octyl, 2-ethylhexyl, trifluoromethyl,
2-(perfluorohexyl)ethyl, perfluoropropyl, perfluorobutyl and the
like, even more preferred lower C.sub.1-C.sub.8 alkyl radical is
selected from the group consisting of methyl, ethyl, propyl,
isopropyl, butyl, hexyl, cyclohexyl, 2-ethylhexyl, trifluoromethyl,
2-(perfluorohexyl)ethyl, perfluoropropyl and the like.
Preferred the term "lower alkyl" includes straight chain and
branched hydrocarbon radicals having 1 to 6 carbon atoms,
preferably 1 to 3 carbon atoms. Methyl, ethyl, propyl and isopropyl
groups are especially preferred.
More preferably, the term "lower acyl" includes acetyl, propionyl,
butyryl and isobutyryl groups. Acetyl is especially preferred.
It is understood that the term "halogen" includes fluoro, chloro,
bromo and iodo, preferably fluoro and chloro.
It is understood that the term "optionally substituted" includes
optionally mono-substituted by lower alkyl, nitro, cyano or halogen
or poly-substituted by lower alkyl and/or cyano and/or halogen.
The wording "dichroic dye" refers to compounds exhibiting positive
or negative dichroism. A dichroic dye includes a chromophore system
to which ring systems, additional polymerizable groups and/or
spacer units may be attached [i.e. formula (I)].
Preferred is dichroic dye of formula (I), wherein
X.sup.1 is NR or S,
X.sup.2 is a single bond, NR or S,
Y.sup.1, Y.sup.2 independently from each other are a single bond,
NR or S,
R has the same meaning as mentioned above,
Z.sup.1, Z.sup.2 independently from each other are a single bond, S
or O,
W.sup.1, W.sup.2, W.sup.3, W.sup.4, W.sup.5, W.sup.6 independently
from each other are H, unsubstituted or substituted, straight chain
or branched C.sub.1-C.sub.30 alkyl, in which one --CH-- or
--CH.sub.2-- group may be replaced by one or more linking group
consisting of --O--, --S--, --NR.sup.1--, --N.dbd.N--,
--CH(OR.sup.1)--, --CO--NR.sup.1--, --NR.sup.1--CO--,
--O--CO--NR.sup.1--, --CO--O--, --O--CO--, --O--CO--O--, --SO--,
--SO.sub.2--, --C.dbd.C--, --C.ident.C--, an aromatic or alicyclic
group which is unsubstituted or substituted by one or more straight
chain or branched lower alkyl radical, --F, --Cl, --Br, --I,
--OR.sup.1, --SR.sup.1, --NR.sup.1R.sup.2, --CN, --NO.sub.2,
--SOR.sup.1, --SO.sub.2R.sup.1, and wherein R.sup.1, R.sup.2 having
the same meaning as mentioned above, with the proviso that oxygen
atoms of the linking groups are not directly linked to each other,
PG is a polymerizable group consisting of CH.sub.2.dbd.CQ-,
CH.sub.2.dbd.CQ-COO--, CH.sub.2.dbd.CH--CO--NH--,
CH.sub.2.dbd.C(Ph)-CO--NH--, CH.sub.2.dbd.CH--O--,
CH.sub.2.dbd.CH--OOC--, CH.sub.2.dbd.CH-Ph-O--, wherein Q is
hydrogen, chloro, or methyl, n1, n2, n3, n4, n5, n6 independently
from each other signifies 0, 1 or 2 whereby the sum of n1, n2, n3,
n4, n5 and n6 is .gtoreq.1, with the proviso that if n1, n2, n3,
n4, n5 or n6=0, the connected W.sup.1, W.sup.2, W.sup.3, W.sup.4,
W.sup.5, W.sup.6 as to be saturated by hydrogen.
More preferred is a dichroic dye of formula (I), wherein
X.sup.1 is NR or S,
X.sup.2 is a single bond, NR or S,
Y.sup.1, Y.sup.2 independently from each other are a single bond,
NR or S,
R has the same meaning as mentioned above,
Z.sup.1, Z.sup.2 independently from each other are a single bond, S
or O,
W.sup.1, W.sup.2, W.sup.3, W.sup.4, W.sup.5, W.sup.6 independently
from each other are H, unsubstituted or substituted, straight chain
or branched C.sub.1-C.sub.30 alkyl, in which one --CH-- or
--CH.sub.2-- group may be replaced by one or more linking group
consisting of --O--, --S--, --NR.sup.1--, --CH(OR.sup.1)--,
--CO--NR.sup.1--, --NR.sup.1--CO--, --O--CO--NR.sup.1--, --CO--O--,
--O--CO--, --SO.sub.2--, an aromatic or alicyclic group which is
unsubstituted or substituted by one or more straight chain or
branched lower alkyl radical, --F, --Cl, --Br, --OR.sup.1,
--SO.sub.2R.sup.1, and wherein R.sup.1 having the same meaning as
mentioned above, with the proviso that oxygen atoms of the linking
groups are not directly linked to each other, PG is a polymerizable
group consisting of CH.sub.2.dbd.CQ-, CH.sub.2.dbd.CQ-COO--,
CH.sub.2.dbd.CH--CO--NH--, CH.sub.2.dbd.CH--OOC--, wherein Q is
hydrogen or methyl. n1, n2, n3, n4, n5, n6 independently from each
other signifies 0 or 1 whereby the sum of n1, n2, n3, n4, n5 and n6
is .gtoreq.1, with the proviso that if n1, n2, n3, n4, n5 or n6=0,
the connected W.sup.1, W.sup.2, W.sup.3, W.sup.4, W.sup.5, W.sup.6
as to be saturated by hydrogen.
Even more preferred a dichroic dye of formula (I), wherein
X.sup.1 is NR or S,
X.sup.2 is a single bond, NR or S,
Y.sup.1, Y.sup.2 independently from each other are a single bond,
NR or S,
R has the same meaning as mentioned above,
Z.sup.1, Z.sup.2 independently from each other are a single bond, S
or O,
W.sup.1, W.sup.2, W.sup.3, W.sup.4, W.sup.5, W.sup.6 independently
from each other are H, unsubstituted or substituted, straight chain
or branched C.sub.1-C.sub.30 alkyl, in which one --CH-- or
--CH.sub.2-- group may be replaced by one or more linking group
consisting of --O--, --S--, --NR.sup.1--, --CH(OR.sup.1)--,
--CO--NR.sup.1--, --NR.sup.1--CO--, --CO--O--, --O--CO--,
--SO.sub.2-- or an aromatic group which is unsubstituted or
substituted by one or more straight chain or branched lower alkyl
radical, --F, --Cl or --OR.sup.1, and wherein R.sup.1 having the
same meaning as mentioned above, with the proviso that oxygen atoms
of the linking groups are not directly linked to each other, PG is
a polymerizable group consisting of CH.sub.2.dbd.CQ-COO--, wherein
Q is hydrogen or methyl, n1, n2, n3, n4, n5, n6 independently from
each other signifies 0 or 1 whereby the sum of n1, n2, n3, n4, n5
and n6 is .gtoreq.1, with the proviso that if n1, n2, n3, n4, n5 or
n6=0, the connected W.sup.1, W.sup.2, W.sup.3, W.sup.4, W.sup.5,
W.sup.6 as to be saturated by hydrogen.
In addition, even more preferred a dichroic dye of formula (I),
wherein
X.sup.2, X.sup.1 are independently from each other NR,
R has the same meaning as mentioned above,
Y.sup.1, Y.sup.2 independently from each other are a single
bond,
Z.sup.1 is O,
Z.sup.2 is a single bond,
n2 is 1,
n1, n3, n4, n5, n6 are 0,
W.sup.1, W.sup.4, W.sup.5, W.sup.6 are hydrogen
W.sup.2, W.sup.3 are independently from each other are
unsubstituted or substituted, straight chain or branched
C.sub.1-C.sub.30 alkyl, in which one --CH-- or --CH.sub.2-- group
may be replaced by one or more linking group consisting of --O--,
--S--, --NR.sup.1--, --CH(OR.sup.1)--, --CO--NR.sup.1--,
--NR.sup.1--CO--, --CO--O--, --O--CO--, --SO.sub.2-- or an aromatic
group which is unsubstituted or substituted by one or more straight
chain or branched lower alkyl radical, --F, --Cl or --OR.sup.1, and
wherein R.sup.1 having the same meaning as mentioned above, PG is a
polymerizable group consisting of CH.sub.2.dbd.CQ-COO--, wherein Q
is hydrogen or methyl; or even more preferred a dichroic dye of
formula (I), wherein X.sup.1 is S, X.sup.2 is single bond or NR, R
has the same meaning as mentioned above, Y.sup.1 is S, Y.sup.2 is a
single bond or NR, Z.sup.1, Z.sup.2 are single bond, n1, n6 are 1,
n2, n3, n4, n5, are 0, W.sup.2, W.sup.3, W.sup.4, W.sup.5 are
hydrogen, W.sup.1, W.sup.6 are independently from each other are
unsubstituted or substituted, straight chain or branched
C.sub.1-C.sub.30 alkyl, in which one --CH-- or --CH.sub.2-- group
may be replaced by one or more linking group consisting of --O--,
--S--, --NR.sup.1--, --CH(OR.sup.1)--, --CO--NR.sup.1--,
--NR.sup.1--CO--, --CO--O--, --O--CO--, --SO.sub.2-- or an aromatic
group which is unsubstituted or substituted by one or more straight
chain or branched lower alkyl radical, --F, --Cl or --OR.sup.1, and
wherein R.sup.1 having the same meaning as mentioned above, PG is a
polymerizable group consisting of CH.sub.2.dbd.CQ-COO--, wherein Q
is hydrogen or methyl; or even more preferred is a dichroic dye of
formula (I), wherein X.sup.1, X.sup.2 are independently from each
other NR Y.sup.1, Y.sup.2 are independently from each other NR, R
has the same meaning as mentioned above, Z.sup.1, Z.sup.2 are
independently from each other a single bond or O n2, n5 are 1, n1,
n3, n4, n6, are 0, W.sup.1, W.sup.6 are hydrogen W.sup.2, W.sup.3
W.sup.4, W.sup.5 are independently from each other unsubstituted or
substituted, straight chain or branched C.sub.1-C.sub.30 alkyl, in
which one --CH-- or --CH.sub.2-- group may be replaced by one or
more linking group consisting of --O--, --S--, --NR.sup.1--,
--CH(OR.sup.1)--, --CO--NR.sup.1--, --NR.sup.1--CO--, --CO--O--,
--O--CO--, --SO.sub.2-- or an aromatic group which is unsubstituted
or substituted by one or more straight chain or branched lower
alkyl radical, --F, --Cl or --OR.sup.1, and wherein R.sup.1 having
the same meaning as mentioned above, PG is a polymerizable group
consisting of CH.sub.2.dbd.CQ-COO--, wherein Q is hydrogen or
methyl.
Further the present invention relates to a composition, preferably
a slave composition, more preferably a liquid crystalline
composition, comprising at least one dichroic dye (I) as described
above within the given preferences, and at least one slave
material, preferably a liquid crystal material or a polymerizable
liquid crystal.
In the context of the present application, a "slave material" shall
refer to any material that has the capability to establish
anisotropy upon contact with an aligned material, preferably
photo-aligned material. The nature of the anisotropy in the aligned
material and in the slave material may be different from each
other. For example, the slave material may exhibit light absorption
anisotropy for visible light and therefore can act as a polarizer,
whereas the anisotropy of the aligned material may only be related
to the molecular orientation.
A slave material may comprise polymerizable and/or
non-polymerizable compounds. Within the context of the present
application the terms "polymerizable" and "polymerized" shall
include the meaning of "cross-linkable" and "cross-linked",
respectively. Likewise, "polymerization" shall include the meaning
of "cross-linking".
Preferably, the slave material is a self-organizing material. More
preferred is that the slave material is a liquid crystal material
and in particular preferred is that the slave material is a liquid
crystal polymer material.
In the context of the present application, a "slave composition"
shall refer to a composition comprising a slave material.
Polymerizable liquid crystals (LCP) which are present in the
inventive compositions are well known to the skilled person e.g.
from EP 0331233, WO 95/24454, U.S. Pat. Nos. 5,567,349, 5,650,534,
WO 00/04110, WO 00/07975, WO 00/48985, WO 00/55110, WO 00/63154 and
WO 2011003846. For adjustment of liquid crystalline properties and
suppression of crystallization, mixtures of two or more LCP
components may be used. At least one of the LCP components may
optionally comprise more than one polymerizable group in the
chemical structure in order to achieve cross-linking. As an
alternative or to improve cross-linking abilities the addition of
isotropic compounds comprising two or more polymerizable groups, so
called cross-linkers, may also be possible. Furthermore well-known
additives such as, e.g. phenol derivatives for stabilization and
photoinitiators such as, e.g. Irgacure.RTM. may also be present in
the inventive mixture.
The number of dichroic dyes of formula (I) present in the
composition may depend mainly on the spectral working range of the
polarizer and on the solubility of the dyes. Colored polarizers,
which are absorbing in a selective spectral range or the whole
visible range may preferably be achieved by the presence of one or
more dyes in the composition.
Preferred composition of the invention consequently comprise at
least one polymerizable dichroic dye according to the general
formula (I), at least one polymerizable liquid crystal and
optionally additives, such as cross-linkers, stabilizers and
photoinitiator.
Particularly preferred are compositions comprising one to four
dichroic dyes of formula (I) and at least one polymerizable liquid
crystal and optionally additives such as cross-linkers, stabilizers
and photoinitiators.
In a further embodiment the compositions of the invention may
comprise in addition another dichroic or non-dichroic dye, which
resulting mixture may be used as a dichroic dye of a desired color
hue. No limitation is imposed in this context.
The total content of dichroic dyes of formula (I) in the inventive
composition may depend on different factors such as solubility in
the LCP host, influence on the liquid crystalline properties (e.g.
depression of clearing point) and absorption ability (extinction)
of the dyes involved. Preferred dye concentrations may be in the
range of 0.1 to 50 wt %, more preferably from 0.5 to 30 wt %, most
preferably from 0.5 to 20 wt %.
The dichroic dyes (I) according to the invention are also of value
in the manufacture of dyed cholesteric layers. When added to a
cholesteric mixture the dichroic dyes according to the invention
are able to contribute to the enhancement of special color effects
and therefore their further use in the formation of dyed
cholesteric devices is an additional and valuable asset.
Thus in a preferred embodiment, compositions of the invention as
described hereinabove may further comprise at least one chiral
polymerizable liquid crystalline compound or at least one chiral
component, to induce a cholesteric phase for the creation of dyed
cholesteric layers.
In a further aspect the invention also provides the use of said
composition for the preparation of a dichroic polymer network, a
dichroic liquid crystalline polymer film (LCP film) or a dichroic
liquid crystalline polymer gel.
In addition, the present invention relates to a process for the
preparation of a dichroic polymer network, a dichroic liquid
crystalline polymer film (LCP film) or a dichroic liquid
crystalline polymer gel, which process comprises polymerizing a
dichroic dye or a composition of the present invention.
Thus, in a further aspect the invention provides a dichroic polymer
network, a dichroic liquid crystalline polymer film (LCP film) or a
dichroic liquid crystalline polymer gel comprising dichroic dyes
and/or compositions according to the present invention. Such
dichroic polymer network, a dichroic liquid crystalline polymer
film (LCP film) or a dichroic liquid crystalline polymer gel may
readily be prepared by UV or thermal polymerization of the mixtures
of the present invention. A film comprising a composition according
to the present invention is formed on a substrate, for example, by
first preparing a solution of a composition, which is subsequently
applied to a support by different coating techniques, such as spin
coating, dip coating, meniscus coating, wire coating, slot coating,
offset printing, inkjet printing, flexo printing, gravure printing.
After evaporation of the solvent the obtained film is polymerized
using UV light to give a cross-linked dichroic liquid crystal film
of preferably 0.1 to 100 .mu.m thickness, more preferable 0.2 to 50
.mu.m thickness, even more preferable 0.5 to 20 .mu.m thickness. If
required such films may further be coated with other layers, such
as, e.g. protective layers for protection against oxygen,
UV-irradiation or mechanical stress. Such films may be used in the
manufacture of devices such as polarizers or optical filters.
Examples of substrates used in the preparation of dichroic LCP
films may include transparent substrates, such as glass or plastic
including an orientation layer, which is able to induce a uniform
orientation to the mixture. Such orientation layers may include
rubbed polyimide, or polyamide or preferably layers of
photo-orientable materials. A well-suited kind of photo-orientable
orientation layers are Linearly Photopolymerizable Polymers (LPP),
also sometimes referred to as Light Controlled Molecular
Orientation (LCMO). Backgrounds and manufacturing of such
orientation layers are disclosed in, for example, U.S. Pat. Nos.
5,389,698, 5,838,407, 5,602,661, 6,160,597, 6,144,428, all of the
applicant. Using LPP layers, segments (pixels) of locally varying
orientation may be formed. Thus, not only uniformly aligned
dichroic LCP layers but also structured complex orientation
patterns within the dichroic LCP layers may be produced.
Furthermore multilayer systems formed from stacks of alternating
LPP and LCP layers, wherein at least one of the LCP layers is a
dichroic LCP layer are feasible. Such layers or stacks of layers
may additionally be covered by other well-known functional layers,
such as, e.g. protecting layers against oxygen or humidity or
layers for protection against ultraviolet radiation.
It has been shown, e.g. in WO 99/64924, that photo-orienting
materials like LPPs may also be able to orient liquid crystals,
such as LCPs, if they are admixed to the mixture to be oriented
prior to illumination with polarized light. In this way,
orientation layers and LCP layers need not be formed separately.
Thus, an analogous preparation of a dichroic LCP film using an
inventive mixture, which in addition contains a photo-orientable
material, may also be possible.
In addition, the present invention relates to the use of said
composition of the present invention and a dichroic polymer
network, a dichroic liquid crystalline polymer film (LCP film) or a
dichroic liquid crystalline polymer gel of the present invention
for the preparation of electro-optical and optical devices,
preferably including security devices or multi-layer systems, such
as functional foils.
A further aspect of the invention provides an electro-optical or
optical device, preferably a security device or an optical film, or
a multi-layer system, such as a functional foil, comprising a
dichroic polymer network, a dichroic liquid crystalline polymer
film (LCP film) or a dichroic liquid crystalline polymer gel of the
present invention. Electro-optical or optical devices may include
structured or unstructured optical filters, polarizers, especially
linear or circular polarizers, etc. Examples of electro-optical or
optical devices are polarizers, optical films, security or
authentication devices may for instance be used to safeguard
banknotes, credit cards, securities, identity cards and the like
against forgery and copying.
The following non-limiting examples further describe the synthesis
of dichroic dyes of formula (I) of the present invention.
Variations on these falling within the scope of the invention will
be apparent to a person skilled in the art.
EXAMPLES
Abbreviations
DMSO=Dimethylsulfoxide
CDCl.sub.3'=deuterated chloroform
BOPP=biaxially oriented polypropylen
Example 1
##STR00002##
1-aminoanthraquinone (46.0 parts) commercial available such as from
Sigma Aldrich, is dissolved in concentrated sulfuric acid (98%, 200
mL) at 60.degree. C. When the product is completely dissolved, the
temperature is decreased to room temperature before slow addition
of ice (800.0 parts) with efficient stirring. To the resulting
slurry at 0-5.degree. C. is then added drop wise bromine (72.4
parts) over a period of 3 hours. The resulting mixture is stirred
at room temperature for 20 hours. Excess bromine is then removed by
bubbling nitrogen in the reaction mixture. The precipitate is then
filtered and washed with water (1000 mL). The wet press-cake is
stirred in 8 wt % aqueous sodium hydroxide solution (1000 mL) for
one hour, filtered, successively washed with water (1000 mL), 20 wt
% aqueous sodium bisulfite solution (400 mL), water (1000 mL) and
finally dried overnight at 500.degree. C. under vacuum to afford
70.0 parts of compound (1) as a red solid. NMR--.sup.1H
(DMSO-d.sup.6, 300 MHz, ppm): 8.2 (s, 1H), 8.2-8.1 (m, 2H), 7.8 (m,
2H).
Example 2
##STR00003##
Compound (1) (68.6 parts), tosylamine (62.9 parts), potassium
acetate (22.3 parts) and anhydrous copper acetate (1.7 parts) in
amyl alcohol (750 mL) are stirred and refluxed for 10 hours.
Temperature is decreased to room temperature and methanol (375 mL)
is added. The precipitate is filtered, successively washed with
methanol (500 mL) and water (1000 mL). The obtained press-cake is
dried overnight at 50.degree. C. under vacuum to afford 84.8 parts
of compound (2) as a dark brown solid. NMR--.sup.1H (DMSO-d.sup.6,
300 MHz, ppm): 11.9 (s, 1H), 8.2-8.1 (m, 3H), 7.9 (m, 2H), 7.7 (d,
2H), 7.3 (d, 2H), 2.3 (s, 3H).
Example 3
##STR00004##
6-chlorohexan-1-ol (20.0 parts) (commercial available such as from
Sigma Aldrich), dicyclohexylcarbodiimide (36.2 parts) and
methacrylic acid (15.2 parts) are dissolved in tetrahydrofurane
(200 mL). 4-Dimethylaminopyridine (2.0 parts) is added and the
mixture is stirred 24 hours at room temperature. The reaction
mixture is then filtered over celite and the filtrate is evaporated
to dryness. The residue is then purified by column chromatography
(SiO.sub.2; eluent: toluene) to afford 30.0 parts of compound (3)
as a colorless oil. NMR--.sup.1H (CDCl.sub.3, 300 MHz, ppm): 6.1
(s, 1H), 5.5 (s, 1H), 4.1 (t, 2H), 3.5 (t, 2H), 1.9 (s, 3H),
1.8-1.6 (m, 4H), 1.5-1.3 (m, 4H).
Example 4
##STR00005##
Compound (3) (30.0 parts), Hydroquinone (60.0 parts), potassium
iodide (3.0 parts) and potassium carbonate (30.0 parts) are stirred
in dimethylformamide (100 mL) and heated to 100.degree. C. for 10
hours. Temperature is decreased to room temperature, ethyl acetate
(250 ml) is added and the mixture is successively washed with 1 wt
% aqueous hydrochloric acid solution (3.times.250 ml) and saturated
aqueous sodium chloride solution (2.times.200 ml). The organic
layer is dried over sodium sulfate, filtered and evaporated. The
product is further purified by column chromatography (SiO.sub.2;
eluent: toluene then toluene/ethyl acetate: 95/5) to afford 31.4
parts of compound (4) as a colorless oil which solidify upon
standing. NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 8.8 (s, 1H),
6.7 (d, 2H), 6.6 (d, 2H), 6.0 (s, 1H), 5.6 (s, 1H), 4.1 (t, 2H),
3.8 (d, 2H), 1.9 (s, 3H), 1.7-1.5 (m, 4H), 1.5-1.3 (m, 4H).
Example 5
##STR00006##
Compound (4) (5.0 parts) is dissolved in N-methyl-2-pyrrolidone (50
mL) at room temperature. Sodium hydride (60% dispersion in mineral
oil, 0.54 part) is added and the resulting mixture is stirred 30
minutes at room temperature. Compound (2) (4.2 parts) and
2,6-di-tert-butyl-4-methylphenol (0.01 part) are then added and the
resulting mixture is heated at 135.degree. C. for 8 hours under
nitrogen. Temperature is decreased to room temperature, ethyl
acetate (250 mL) is added and the mixture is successively washed
with 1 wt % aqueous hydrochloric acid solution (2.times.250 mL) and
saturated aqueous sodium chloride solution (2.times.200 mL). The
organic layer is dried over sodium sulfate, filtered and
evaporated. The product is further purified by column
chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 95/5) to
afford 3.7 parts of compound (5) as a dark reddish-pink solid.
NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.9 (s, 1H), 8.2 (d,
2H), 7.9 (m, 2H), 7.4 (d, 2H), 7.3 (d, 2H), 7.2 (m, 4H), 6.9 (s,
1H), 6.0 (s, 1H), 5.6 (s, 1H), 4.1 (m, 4H), 2.3 (s, 3H), 1.9 (s,
3H), 1.8 (m, 2H), 1.7 (m, 2H), 1.5-1.3 (m, 4H).
Example 6
##STR00007##
Compound (5) (3.6 parts) is mixed with methanesulfonic acid (30 mL)
and stirred 24 hours at room temperature. The resulting solution is
poured in a mixture of ice and water (300.0 parts) and the pH is
slowly increased to 5-6 using an 8 wt % aqueous sodium hydroxide
solution. Ethyl acetate (300 mL) is added, the organic phase is
separated and successively washed with 5 wt % aqueous sodium
carbonate (2.times.200 mL) and saturated aqueous sodium chloride
solution (2.times.200 mL). The organic phase is dried over sodium
sulfate, filtered and evaporated. The product is further purified
by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate:
95/5) to afford 1.5 parts of compound (6) as a reddish-pink solid.
NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 8.2 (m, 2H), 7.8 (m,
2H), 7.2 (d, 2H), 7.1 (d, 2H), 6.4 (s, 1H), 6.0 (s, 1H), 5.6 (s,
1H), 4.1 (m, 2H), 4.0 (m, 2H), 1.9 (s, 3H), 1.7 (m, 2H), 1.6 (m,
2H), 1.5-1.3 (m, 4H).
Example 7
##STR00008##
Compound (2) (9.5 parts) and hydroquinone (11.1 parts) are added to
N-methyl-2-pyrrolidone (80 mL) and stirred at room temperature.
Potassium carbonate (3.1 parts) is added and the reaction mixture
is heated to 130.degree. C. for 20 hours. Temperature is decreased
to room temperature and the resulting mixture is poured in 5 wt %
aqueous hydrochloric acid solution (650 mL) with efficient
stirring. The precipitate is filtered, successively washed with 1
wt % aqueous hydrochloric acid solution (300 mL), water (1000 mL)
and finally dried overnight at 50.degree. C. under vacuum to afford
9.0 parts of compound (7) as a reddish-pink solid. NMR--.sup.1H
(DMSO-d.sup.6, 300 MHz, ppm): 12.9 (s, 1H), 9.8 (s, 1H), 8.2 (m,
2H), 7.9 (m, 2H), 7.4 (d, 2H), 7.3 (d, 2H), 7.0 (m, 4H), 6.9 (s,
1H), 2.3 (s, 3H).
Example 8
##STR00009##
Compound (7) (4.5 parts), 4-(6-acryloyloxy-hexyl-1-oxy)benzoic acid
(4.0 parts; synthesized according to U.S. Pat. No. 6,258,974 or
EP-1174411), dicyclohexylcarbodiimide (2.8 parts) and
2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in
tetrahydrofurane (75 mL). 4-Dimethylaminopyridine (0.4 part) is
added and the mixture is stirred 24 hours at room temperature. The
reaction mixture is then filtered over celite and the n-heptane
(200 mL) is added to the filtrate. Tetrahydrofurane is evaporated
under vacuum and the resulting precipitate is filtered and
successively washed with n-heptane (200 mL). The resulting product
is finally dried overnight at 500.degree. C. under vacuum to afford
5.3 parts of compound (8) as a dark reddish-pink solid.
NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.8 (s, 1H), 8.3 (d,
2H), 8.2 (m, 2H), 7.9 (m, 2H), 7.5 (d, 2H), 7.4 (d, 2H), 7.3 (d,
2H), 7.2 (d, 2H), 7.1 (d, 2H), 6.9 (s, 1H), 6.4-5.9 (m, 3H), 4.1
(m, 4H), 2.3 (s, 3H), 1.8 (m, 2H), 1.6 (m, 2H), 1.4 (m, 4H).
Example 9
##STR00010##
1,8-dichloroanthraquinone (5.0 parts) (commercial available such as
from Sigma Aldrich) and 4-hydroxybenzenethiol (9.1 parts) are added
to N-methyl-2-pyrrolidone (100 mL) and stirred at room temperature.
Potassium carbonate (3.0 parts) is added and the reaction mixture
is heated to 1000.degree. C. for 4 hours. Temperature is decreased
to room temperature and ethyl acetate (400 mL) is added. The
organic phase is successively washed with 1 wt % aqueous
hydrochloric acid solution (2.times.200 mL) and saturated aqueous
sodium chloride solution (2.times.200 mL). The organic phase is
dried over sodium sulfate, filtered, evaporated and the obtained
solid is finally dried overnight at 500.degree. C. under vacuum to
afford 6.8 parts of compound (9) as a yellow-orange solid.
NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 10.0 (s, 2H), 7.9 (d,
2H), 7.6 (t, 2H), 7.4 (d, 4H), 7.1 (d, 2H), 6.9 (d, 4H).
Example 10
##STR00011##
Compound (9) (2.6 parts), mono-2-(methacryloyl)ethyl succinate (3.3
parts), dicyclohexylcarbodiimide (3.0 parts) and
2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in
dichloromethane (100 mL). 4-Dimethylaminopyridine (0.4 part) is
added and the mixture is stirred 5 hours at room temperature. The
reaction mixture is then filtered over celite and the filtrate
poured in n-heptane (400 mL) with efficient stirring. The resulting
precipitate is filtered, successively washed with a mixture
composed of ethyl acetate/n-heptane (1/2; 300 mL), methanol (300
mL) and finally dried overnight at 50.degree. C. under vacuum to
afford 4.0 parts of compound (10) as an orange solid. NMR--.sup.1H
(CDCl.sub.3, 300 MHz, ppm): 8.1 (d, 2H), 7.7 (d, 4H), 7.4 (t, 2H),
7.3 (d, 4H), 7.2 (d, 2H), 6.1 (s, 2H), 5.6 (s, 2H), 5.4 (m, 8H),
2.9 (m, 4H), 2.8 (m, 4H), 1.9 (s, 6H).
Example 11
##STR00012##
1,8-dichloroanthraquinone (10.0 parts) and 4-aminobenzenethiol
(11.4 parts) are added to N-methyl-2-pyrrolidone (100 mL) and
stirred at room temperature. Potassium carbonate (12.5 parts) is
added and the reaction mixture is heated to 100.degree. C. for 4
hours. Temperature is decreased to room temperature and methanol
(250 mL) is added dropwise with efficient stirring. The resulting
precipitate is filtered, successively washed with methanol (250
mL), water (500 mL) and finally dried overnight at 50.degree. C.
under vacuum to afford 15.1 parts of compound (11) as a
yellow-orange solid. NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 7.9
(d, 2H), 7.6 (m, 2H), 7.2 (d, 4H), 7.1 (d, 2H), 6.7 (d, 4H), 5.6
(s, 4H).
Example 12
##STR00013##
Compound (11) (3.0 parts), mono-2-(methacryloyl)ethyl succinate
(4.6 parts), dicyclohexylcarbodiimide (4.0 parts) and
2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in
dichloromethane (150 mL). 4-Dimethylaminopyridine (0.5 part) is
added and the mixture is stirred 24 hours at room temperature. The
reaction mixture is then filtered over celite and the filtrate is
concentrated under vacuum. The product is purified by column
chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 50/50) to
afford after drying overnight at 50.degree. C. under vacuum 4.2
parts of compound (12) as an orange. NMR--.sup.1H (CDC.sub.3, ppm):
8.1 (d, 2H), 7.9 (s, 2H), 7.7 (d, 4H), 7.6 (d, 4H), 7.4 (t, 2H),
7.1 (d, 2H), 6.2 (s, 2H), 5.6 (s, 2H), 4.4 (m, 8H), 2.8 (m, 4H),
2.6 (m, 2H), 1.9 (s, 6H).
Example 13
##STR00014##
1,8-Dichloroanthraquinone (104.0 parts), tosylamine (250.0 parts),
potassium acetate (146.0 parts) and anhydrous copper acetate (5.0
parts) in amyl alcohol (1000 mL) are stirred and refluxed for 20
hours. Temperature is decreased to room temperature and methanol
(1000 mL) is added. The precipitate is filtered, successively
washed with methanol (1000 mL) and water (1000 mL). The obtained
press-cake is dried overnight at 50.degree. C. under vacuum to
afford 185.0 parts of compound (13) as an orange solid.
NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 11.7 (s, 2H), 7.9 (d,
4H), 7.8 (m, 6H), 7.4 (d, 4H), 2.3 (s, 6H).
Example 14
##STR00015##
Compound (13) (180.0 parts) is added portion-wise with efficient
stirring to concentrated sulfuric acid (98%, 500 mL) at room
temperature. The resulting mixture is heated to 60.degree. C. for 2
hours. Temperature is decreased to room temperature and the
obtained solution is slowly poured in a mixture of ice (1500 parts)
and water (1000 mL). After 30 minutes of stirring, the resulting
solid is filtered and washed with water (2000 mL). The filter cake
is then slurried in 5 wt % aqueous Sodium hydroxide solution (500
mL) and stirred at room temperature for 1 hour. The precipitate is
filtered, washed with water (1000 mL) and finally dried overnight
at 50.degree. C. under vacuum to afford 78.0 parts of compound (14)
as a red solid. NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 7.8
(broad, 4H), 7.6 (m, 2H), 7.3 (m, 2H), 7.1 (m, 2H).
Example 15
##STR00016##
Compound (14) (10.0 parts) is dissolved in N-methyl-2-pyrrolidone
(80 mL) and stirred at room temperature. N-bromosuccinimide (14.9
parts) dissolved in N-methyl-2-pyrrolidone (50 mL) is then added
dropwise over a period of 30 minutes and the resulting mixture is
stirred 2 hours at room temperature. Methanol (400 mL) is then
added dropwise. The precipitate is filtered, successively washed
with methanol (200 mL), water (200 mL) and finally dried overnight
at 500.degree. C. under vacuum to afford 15.8 parts of compound
(15) as a brown solid. NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm):
7.9 (broad, 4H), 7.6 (d, 2H), 6.9 (d, 2H).
Example 16
##STR00017##
Compound (15) (2.7 parts) and 4-hydroxybenzenethiol (2.6 parts) are
added to N-methyl-2-pyrrolidone (25 mL) and stirred at room
temperature. Potassium carbonate (2.8 parts) is added and the
reaction mixture is heated to 80.degree. C. for 1 hour. Temperature
is decreased to room temperature and a mixture composed of water
(200 mL) and acetic acid (20 mL) is added dropwise with stirring.
The precipitate is filtered, washed with water (1000 mL) and
finally dried overnight at 50.degree. C. under vacuum to afford 2.7
parts of compound (16) as a dark blue-violet solid. NMR--.sup.1H
(DMSO-d.sup.6, 300 MHz, ppm): 9.9 (s, 2H), 7.9 (broad, 4H), 7.4 (d,
4H), 7.0 (d, 2H), 6.9 (d, 4H), 6.7 (d, 2H).
Example 17
##STR00018##
Compound (16) (2.5 parts), 10-bromodecyl-1-methacrylate (3.8 parts;
synthesized from 10-bromodecan-1-ol in a similar way as compound
(3)), potassium carbonate (1.7 parts) and
2,6-di-tert-butyl-4-methylphenol (0.01 part) are mixed in
N-methyl-2-pyrrolidone (30 mL) and heated to 90.degree. C. for 3
hours. Temperature is decreased to room temperature and ethyl
acetate (300 mL) is added. The organic phase is successively washed
with water (2.times.150 mL) and saturated aqueous sodium chloride
solution (2.times.150 mL). The organic layer is dried over sodium
sulfate, filtered and evaporated. The product is further purified
by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate:
95/5) to afford 1.5 parts of compound (17) as a dark blue-violet
solid. NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 8.0 (broad, 4H),
7.5 (d, 4H), 7.1 (d, 4H), 7.0 (d, 2H), 6.7 (d, 2H), 6.0 (s, 2H),
5.6 (s, 2H), 4.1 (m, 4H), 4.0 (m, 4H), 1.9 (s, 6H), 1.7 (m, 4H),
1.6 (m, 4H), 1.4-1.2 (m, 24H).
Example 18
##STR00019##
Compound (14) (58.0 parts) is dissolved in concentrated sulfuric
acid (98%, 170 mL) at 60.degree. C. When the product is completely
dissolved, the temperature is decreased to room temperature before
slow addition of ice (850.0 parts) with efficient stirring. To the
resulting slurry at 0-5.degree. C. is then added dropwise bromine
(182.0 parts) over a period of 3 hours. The resulting mixture is
stirred at room temperature for 20 hours. Excess bromine is then
removed by bubbling nitrogen in the reaction mixture. The
precipitate is then filtered, successively washed with water (1000
mL), 8 wt % aqueous sodium hydroxide solution (1000 mL), 20 wt %
aqueous sodium bisulfite solution (400 mL), water (3000 mL) and
finally dried overnight at 50.degree. C. under vacuum to afford
119.0 parts of compound (18) as a reddish-brown solid. NMR--.sup.1H
(DMSO-d.sup.6, 300 MHz, ppm): 8.1 (s, 2H), 7.9 (broad, 4H).
Example 19
##STR00020##
Compound (18) (119.0 parts), tosylamine (150.0 parts), potassium
acetate (53.0 parts) and anhydrous copper acetate (4.0 parts) in
amyl alcohol (1700 mL) are stirred and refluxed for 10 hours.
Temperature is decreased to room temperature and methanol (850 mL)
is added. The precipitate is filtered, successively washed with
methanol (1000 mL) and water (2000 mL). The obtained press-cake is
dried overnight at 50.degree. C. under vacuum to afford 150.0 parts
of compound (19) as a dark blue solid. NMR--.sup.1H (DMSO-d.sup.6,
300 MHz, ppm): 11.0 (s, 2H), 8.0 (s, 2H), 7.9 (broad, 4H), 7.7 (d,
4H), 7.3 (d, 4H), 2.3 (s, 6H).
Example 20
##STR00021##
Compound (4) (4.0 parts) is dissolved in N-methyl-2-pyrrolidone (25
mL) at room temperature. Sodium hydride (60% dispersion in mineral
oil, 0.5 part) is added and the resulting mixture is stirred 30
minutes at room temperature. Compound (19) (3.0 parts) and
2,6-di-tert-butyl-4-methylphenol (0.01 part) are then added and the
resulting mixture is heated at 135.degree. C. for 24 hours under
nitrogen. Temperature is decreased to room temperature, ethyl
acetate (200 mL) is added and the mixture is successively washed
with 1 wt % aqueous hydrochloric acid solution (3.times.200 mL) and
saturated aqueous sodium chloride solution (3.times.200 mL). The
organic layer is dried over sodium sulfate, filtered and
evaporated. The product is further purified by column
chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 98/2) to
afford 2.0 parts of compound (20) as a dark blue-violet solid.
NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.3 (s, 2H), 7.4 (d,
4H), 7.3 (d, 4H), 7.2 (d, 4H), 7.1 (d, 4H), 6.8 (s, 2H), 6.0 (s,
2H), 5.6 (s, 2H), 4.1 (m, 8H), 2.3 (s, 6H), 1.9 (s, 6H), 1.8 (m,
4H), 1.6 (m, 4H), 1.4 (m, 8H).
Example 21
##STR00022##
Compound (19) (10.0 parts) is added portion-wise with efficient
stirring to concentrated sulfuric acid (98%, 60 mL) at room
temperature. The resulting mixture is heated to 60.degree. C. for 2
hours. Temperature is decreased to room temperature and the
obtained solution is slowly poured in a mixture of ice (300 parts)
and water (300 mL). After 30 minutes stirring, the resulting solid
is filtered and washed with water (500 mL). The filter cake is then
slurried in 5 wt % aqueous sodium hydroxide solution (300 mL) and
stirred at room temperature for 1 hour. The precipitate is
filtered, washed with water (500 mL) and finally dried overnight at
50.degree. C. under vacuum to afford 5.8 parts of compound (21) as
a blue-violet solid. NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 7.7
(broad, 8H), 7.5 (s, 2H).
Example 22
##STR00023##
Compound (21) (5.0 parts), 4-hydroxyphenyl boronic acid (4.9
parts), potassium carbonate (5.0 parts) and
tretakis-triphenylphosphine palladium (1.3 parts) are mixed in
N-methyl-2-pyrrolidone (90 mL) and deionized water (10 mL) and
heated to 100.degree. C. for 3 hours under nitrogen. Temperature is
decreased to room temperature and the reaction mixture is poured in
deionized water (800 mL). The precipitate is filtered, washed with
water (3.times.50 mL) and dried at 50.degree. C. under vacuum. The
resulting solid is dissolved in tetrahydrofurane (1000 mL) with
heating and filtered over celite while still hot. To the filtrate
is added toluene (500 mL) and tetrahydrofurane is evaporated under
vacuum. The precipitate is filtered, washed with toluene (300 mL)
and dried overnight at 50.degree. C. under vacuum to afford 4.6
parts of compound (22) as a dark blue solid. NMR--.sup.1H
(DMSO-d.sup.6, 300 MHz, ppm): 9.7 (s, 2H), 7.7 (s, 4H), 7.4 (broad,
4H), 7.3 (d, 4H), 6.9 (s, 2H), 6.8 (d, 4H).
Example 23
##STR00024##
Compound (22) (1.0 part), 10-bromodecyl-1-methacrylate (2.0 parts;
synthesized from 10-bromodecan-1-ol according to example 3),
potassium carbonate (0.76 part) and
2,6-di-tert-butyl-4-methylphenol (0.01 part) are mixed in
N-methyl-2-pyrrolidone (25 mL) and heated to 80.degree. C. for 3
hours. Temperature is decreased to room temperature and ethyl
acetate (300 mL) is added. The organic phase is successively washed
with 1 wt % aqueous hydrochloric acid solution (3.times.150 mL) and
saturated aqueous sodium chloride solution (3.times.150 mL). The
organic layer is dried over sodium sulfate, filtered and
evaporated. The product is further purified by column
chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 95/5) to
afford 1.4 parts of compound (23) as a dark blue-violet solid.
NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 7.7 (broad, 4H), 7.4 (d,
4H), 7.3 (broad, 4H), 7.1 (d, 4H), 6.9 (s, 2H), 6.0 (s, 2H), 4.1
(m, 4H), 4.0 (m, 4H), 1.9 (s, 6H), 1.8 (m, 4H), 1.6 (m, 4H),
1.4-1.2 (m, 24H).
Example 24
##STR00025##
Compound (19) (11.0 parts) and hydroquinone (16.0 parts) are added
to N-methyl-2-pyrrolidone (80 mL) and stirred at room temperature.
Potassium carbonate (4.5 parts) are added and the reaction mixture
is heated to 120-130.degree. C. for 5 hours. Temperature is
decreased to room temperature and the resulting mixture is poured
in 5 wt % aqueous hydrochloric acid (400 mL) with efficient
stirring. The precipitate is filtered, successively washed with 1
wt % aqueous hydrochloric acid solution (200 mL), water (1000 mL)
and finally dried overnight at 50.degree. C. under vacuum to afford
11.0 parts of compound (24) as a dark blue-violet solid.
NMR--.sup.1H (DMSO-d.sup.6, 300 MHz, ppm): 12.4 (s, 2H), 9.7 (s,
2H), 7.4 (d, 4H), 7.3 (d, 4H), 7.0 (m, 8H), 6.9 (s, 2H), 2.3 (s,
6H).
Example 25
##STR00026##
Compound (24) (7.0 parts), 4-(6-acryloyloxy-hexyl-1-oxy)benzoic
acid (7.7 parts; synthesized according to U.S. Pat. No. 6,258,974
or EP-1174411), dicyclohexylcarbodiimide (5.3 parts) and
2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in
dichloromethane (200 mL). 4-Dimethylaminopyridine (0.5 part) is
added and the mixture is stirred 5 hours at room temperature. The
reaction mixture is then filtered over celite and the filtrate
poured in methanol (400 mL) with efficient stirring. The resulting
precipitate is filtered, washed with methanol (300 mL) and purified
by column chromatography (SiO.sub.2; eluent: toluene/ethyl acetate:
90/10). The resulting product is finally dried overnight at
50.degree. C. under vacuum to afford 9.0 parts of compound (25) as
a dark blue-violet solid. NMR--.sup.1H (DMSO-d.sup.6, 300 MHz,
ppm): 12.3 (s, 2H), 8.1 (d, 4H), 7.5 (m, 8H), 7.4 (d, 4H), 7.2 (d,
4H), 7.1 (d, 4H), 6.9 (s, 2H), 6.4-5.9 (m, 6H), 4.1 (m, 8H), 2.3
(s, 6H), 1.8 (m, 4H), 1.6 (m, 4H), 1.4 (m, 8H).
Example 26
##STR00027##
Compound (24) (2.0 parts), mono-2-(methacryloyl)ethyl succinate
(1.5 parts), dicyclohexylcarbodiimide (1.3 parts) and
2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in
dichloromethane (75 mL). 4-Dimethylaminopyridine (0.4 part) is
added and the mixture is stirred 20 hours at room temperature. The
reaction mixture is then filtered over celite and the filtrate
poured in n-heptane (250 mL) with efficient stirring. The resulting
precipitate is filtered, successively washed with n-heptane (250
mL), methanol (250 mL) and finally dried overnight at 50.degree. C.
under vacuum to afford 2.7 parts of compound (26) as a dark
blue-violet solid. NMR--.sup.1H (CDCl.sub.3, 300 MHz, ppm): 12.3
(s, 2H), 7.5 (d, 4H), 7.3-7.0 (m, 14H), 6.1 (s, 2H), 5.6 (s, 2H),
4.4 (m, 8H), 2.9 (m, 4H), 2.8 (m, 4H), 2.4 (s, 6H), 1.9 (s,
6H).
Example 27
##STR00028##
Compound (19) (2.0 parts) and 4,4'-dihydroxybiphenyl (5.0 parts)
are added to N-methyl-2-pyrrolidone (25 mL) and stirred at room
temperature. Potassium carbonate (0.8 part) is added and the
reaction mixture is heated to 140.degree. C. for 5 hours.
Temperature is decreased to room temperature and the resulting
mixture is poured in 5 wt % aqueous hydrochloric acid solution (300
mL) with efficient stirring. The precipitate is filtered and washed
with water (300 mL). The solid is then stirred in hot methanol (300
mL), filtered, washed with methanol (200 mL) and finally dried
overnight at 50.degree. C. under vacuum to afford 2.3 parts of
compound (27) as a dark blue-violet solid. NMR--.sup.1H
(DMSO-d.sup.6, 300 MHz, ppm): 12.3 (s, 2H), 9.6 (s, 2H), 7.8 (d,
4H), 7.7 (d, 4H), 7.5 (d, 4H), 7.3 (d, 4H), 7.2 (d, 4H), 7.0 (d,
4H), 6.9 (s, 2H), 2.3 (s, 6H).
Example 28
##STR00029##
Compound (27) (2.0 parts), 4-(6-acryloyloxy-hexyl-1-oxy)benzoic
acid (2.0 parts; synthesized according to U.S. Pat. No. 6,258,974
or EP-1174411), dicyclohexylcarbodiimide (1.4 parts) and
2,6-di-tert-butyl-4-methylphenol (0.01 part) are dissolved in
tetrahydrofurane (100 mL). 4-Dimethylaminopyridine (0.2 part) is
added and the mixture is stirred 24 hours at room temperature. The
reaction mixture is then filtered over celite and the filtrate is
evaporated. The resulting solid is further purified by column
chromatography (SiO.sub.2; eluent: toluene/ethyl acetate: 95/5) and
finally dried overnight at 50.degree. C. under vacuum to afford 2.1
parts of compound (28) as a dark blue-violet solid. NMR--.sup.1H
(DMSO-d.sup.6, 300 MHz, ppm): 12.2 (s, 2H), 8.1 (d, 4H), 7.9 (m,
8H), 7.4 (m, 8H), 7.3 (m, 8H), 7.1 (d, 4H), 6.9 (s, 2H), 6.4-5.9
(m, 6H), 4.1 (m, 8H), 2.3 (s, 6H), 1.8 (m, 4H), 1.6 (m, 4H),
1.4-1.2 (m, 8H).
Preparation of Dichroic Mixtures M.sub.LCP
Dichroic mixtures M.sub.LCP were prepared as illustrated in table
1:
TABLE-US-00001 TABLE 1 Mixture composition LCP Photo- Mixture
Dichroic Dye component .sup.a) initiator .sup.b) Total Color
M.sub.LCP1 Compound (6) 88 wt % 2 wt % 100 wt % Pink- 10 wt % Red
M.sub.LCP2 Compound (8) 88 wt % 2 wt % 100 wt % Pink- 10 wt % Red
M.sub.LCP3 Compound (10) 88 wt % 2 wt % 100 wt % Yellow 10 wt %
M.sub.LCP4 Compound (12) 88 wt % 2 wt % 100 wt % Yellow 10 wt %
M.sub.LCP5 Compound (17) 88 wt % 2 wt % 100 wt % Blue 10 wt %
M.sub.LCP6 Compound (20) 88 wt % 2 wt % 100 wt % Blue 10 wt %
M.sub.LCP7 Compound (23) 88 wt % 2 wt % 100 wt % Blue 10 wt %
M.sub.LCP8 Compound (25) 88 wt % 2 wt % 100 wt % Blue 10 wt %
M.sub.LCP9 Compound (26) 88 wt % 2 wt % 100 wt % Blue 10 wt %
M.sub.LCP10 Compound (28) 88 wt % 2 wt % 100 wt % Blue 10 wt %
M.sub.LCP11 Compound (12) 88 wt % 2 wt % 100 wt % Grey 5 wt %
Compound (25) 4 wt % Compound (6) 1 wt % M.sub.LCP12 Compound (12)
88 wt % 2 wt % 100 wt % Green 6.7 wt % Compound (25) 3.3 wt %
M.sub.LCP13 Compound (25) 88 wt % 2 wt % 100 wt % Violet 5 wt %
Compound (6) 5 wt % M.sub.LCP14 Compound (10) 88 wt % 2 wt % 100 wt
% Grey 5 wt % Compound (17) 3.3 wt % Compound (8) 1.7 wt %
M.sub.LCP15 Compound (17) 88 wt % 2 wt % 100 wt % Violet 5 wt %
Compound (8) 5 wt % M.sub.LCP16 Compound (10) 88 wt % 2 wt % 100 wt
% Green 6 wt % Compound (17) 4 wt % wt % = weight %
a) LCP component used in the above mixtures is described in WO
2011003846, on page 29 and have the following structure:
##STR00030## b) Photoinitiator is Irgacure.RTM. 369 from BASF.
The mixtures M.sub.LCP1 to M.sub.LCP16 are used to produce
oriented, dichroic liquid crystal samples on plastic substrates as
described below.
Production of Dichroic LCP Layers:
Sixteen samples P.sub.1 to P.sub.16 are prepared, whereby each
single specimen comprised an alignment layer and a dichroic liquid
crystal polymer layer. The alignment layers are manufactured using
the linearly photo-polymerizable aligning (LPP) technique. The
dichroic liquid crystal polymer layers are oriented by the adjacent
LPP layers. The manufacturing processes of both layers are
described in the following.
For the production of an LPP orientation layer, suitable LPP
materials are described for example in patent publications EP 0 611
786, WO 96/10049, EP 0 763 552 and U.S. Pat. No. 6,107,427, and
include cinnamic acid derivatives and ferulic acid derivatives. For
the examples, the following LPP material is chosen, which is
described in WO2012/08504, example 1:
##STR00031##
A 4 wt % solution of the above mentioned LPP material in a mixture
of solvent composed of methylethylketone and cyclohexanone (80/20
w/w) is coated on a BOPP (50 .mu.m) substrate using a bar coater
(KBar 0). The foil is then warmed for 30 seconds at 80.degree. C.
in an oven. The resulting layer has a thickness of approximately
100 nanometers.
The coated film is then exposed to linearly polarized UV light from
a mercury high pressure lamp using an energy dose of 300
mJ/cm.sup.2 at room temperature.
The layer is then used as an orientation layer for a liquid crystal
material comprising dichroic dyes.
For the production of the dichroic LCP layers, the mixtures
M.sub.LCP1 to M.sub.LCP16 are dissolved in a mixture of solvent
composed of methylethylketone and cyclohexanone (80/20 w/w) to give
a 40 wt % solution. These LCP mixtures, which include dichroic
dyes, are then coated on top of the photo-exposed LPP layers using
a bar coater (KBar 2). The coated dichroic LCP layers are then
dried at 60.degree. C. for approximately 30 seconds in an oven. For
photo-initiated cross-linking of the liquid crystals and dye
components, the layers are exposed to isotropic light from a xenon
lamp using an energy dose of 1500 mJ/cm.sup.2 at room temperature
in an inert atmosphere. The resulting layer has a thickness of
approximately 3 micrometers.
The procedure described above gives photo-aligned dichroic LCP
layers on plastic substrates leading to sixteen different samples
P1 to P16 derived from the sixteen dichroic LCP mixtures M.sub.LCP1
to M.sub.LCP16.
Order parameters of samples P1 to P16:
The order parameter S of a dichroic dye is given by the following
expression: S=D.sub.//-D.sub..perp./D.sub.//+2D.sub..perp. wherein
D.sub.// and D.sub..perp. are the optical densities of a dichroic
dye in a liquid crystal measured for light polarizations parallel
and perpendicular to the liquid crystal director.
Table 2 shows the order parameters S of samples P.sub.1 to P.sub.16
measured at the indicated wavelength.
TABLE-US-00002 TABLE 2 Samples M.sub.LCP .lamda. (nm) S P.sub.1
M.sub.LCP1 584 0.47 P.sub.2 M.sub.LCP2 522 0.47 P.sub.3 M.sub.LCP3
452 0.45 P.sub.4 M.sub.LCP4 458 0.52 P.sub.5 M.sub.LCP5 616 0.55
P.sub.6 M.sub.LCP6 608 0.45 P.sub.7 M.sub.LCP7 672 0.55 P.sub.8
M.sub.LCP8 608 0.61 P.sub.9 M.sub.LCP9 574 0.43 P.sub.10
M.sub.LCP10 606 0.59 P.sub.11 M.sub.LCP11 582 0.57 P.sub.12
M.sub.LCP12 608 0.56 P.sub.13 M.sub.LCP13 584 0.46 P.sub.14
M.sub.LCP14 614 0.46 P.sub.15 M.sub.LCP15 614 0.49 P.sub.16
M.sub.LCP16 614 0.48
All samples P.sub.1 to P.sub.16 are cross-linked successfully. The
surfaces are completely dry and are more or less resistant against
scratches.
* * * * *