Coumarin and quinolinone derivatives for the production of...

Details Coumarin and quinolinone derivatives for the production of... Coumarin and quinolinone derivatives for the production of...

1997-03-27

2001-03-13

Zitomer, Fred (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S258000, C526S259000, C526S263000, C526S264000, C526S265000, C526S266000, C526S267000

Reexamination Certificate

active

06201087

ABSTRACT:

The invention is concerned with novel linear and cyclic polymers or oligomers of coumarin and quinolinone derivatives having a photoreactive ethene group as well as their use as orienting layers for liquid crystals.
The orienting layer has a particular significance in (electro-optical) liquid crystal indicators. It serves the purpose of guaranteeing a uniform and trouble-free alignment of the molecular axes and thus guarantees a high contrast. The alignment of the liquid crystals in such indicators can be brought about in different ways. It is usually effected by rubbing a glass plate which is coated with an organic polymer layer or by obliquely vaporizing a glass plate with a silicon oxide layer. Aligned layers which are essentially uniform can be produced in this manner.
It is, however, also possible to obtain a structured orientation of the liquid crystals. This can be achieved, for example, by coating a glass plate with a polymer containing admixed photochemically-orientable colouring molecules or photochemically-isomerizable molecules, as is described, for example, in EP-A-0 445 629. However, these methods have the disadvantage that on the one hand the solubility of such orientable molecules in the polymer is limited and on the other hand the stability of the orientation in the long term can not be guaranteed to a sufficient extent.
A further possibility for the production of high resolution orientation patterns in liquid crystal layers is described in Jpn. J. Appl. Phys. Vol. 31 (1992), 2155. Dimerization of polymer-bonded photoreactive cinnamic acid groups induced by irradiation with linear polarized light for the structured orientation of liquid crystals is used in this procedure.
These polymers are, however, still not optimal. Photochemical concurrent (side) reactions as bring about trans/cis isomerism are disturbing to the orientation capacity and long-term stability. For example, a longer irradiation with UV light of an already finished orienting layer leads to the destruction of the originally present orientation. Multiple irradiations in which an already existing orienting layer having a predetermined registered pattern is irradiated once more in order to orientate the still non-irradiated region in another direction can only be carried out when the previously irradiated sites are covered by a mask. Otherwise, the already oriented regions of the layer can lose their structure by photochemical side-reactions.
The task is therefore to search for photoreactive polymers which are capable of producing high resolution orienting patterns and which lead to significantly more stable orienting structures for liquid crystalline materials.
It has surprisingly been found that polymers which contain coumarin or quinolinone derivatives as photoreactive units fulfil these requirements and are excellently suited as orienting layers for liquid crystals. In addition to a significantly higher (e.g. photochemical) stability of the orienting layer a substantially improved orienting of the liquid crystal is achieved and this leads e.g. to a clearly improved contrast.
The object of the present invention is accordingly polymers of the general formula
wherein
M
1
and M
2
signify monomer units for homo- or copolymers;
x and y indicate mole fractions of the comonomers, with in each case 0<x≦1 and 0≦y<1 and x+y=1;
p signifies 4 to 30,000;
S
1
and S
2
signify spacer units;
Q
1
signifies a structural unit of the formula
—A—(Z
1
—B)
z
—Z
2
—  IIa;
Q
2
signifies a structural unit of the formula
—A—(Z
1
—B)
z
—R
1
—  IIb;
A and B each independently signify pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or optionally substituted 1,4-phenylene;
Z
1
and Z
2
each independently signify a single covalent bond, —CH
2
-ch
2
—, —CH
2
O—, —OCH
2
—, —CONR—, —RNCO—, —COO— or —OOC—;
R signifies hydrogen or lower alkyl;
R
1
signified hydrogen, optionally substituted alkyl or alkoxy with in each case 1 to 12 carbon atoms, cyano, nitro or halogen;
z signifies 0 or 1;
C signifies a photochemically dimerizable coumarin or quinolinone derivative; and
m and n each independently signify 0 or 1.
The monomer units M
1
and M
2
set forth in general formula I are units for the formation of homopolymers or copolymers and have—in the scope of the present invention—the structures which are usual in polymer chemistry. Such monomer units are, for example, ethylene, acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, acryloylphenylene, acrylamide, methacrylamide, 2-chloroacrylamide, 2-phenylacrylamide, vinyl ether, vinyl ester, styrene derivative, maleic acid derivative, fumaric acid derivative, itaconic acid derivative, siloxane, epoxide, ethyleneimine derivative and the like.
When n=0, M
2
can also signify acrylonitrile, methacrylonitrile, methylacrylate, methylmethacrylate, hydroxyalkylacrylate or hydroxyalkylmethacrylate.
Preferred monomer units are acrylate, methacrylate, 2—Chloroacrylate, acrylamide, methacrylamide, 2-chloroacrylamide, styrene derivative, maleic acid derivative or siloxane.
Under the term “copolymers” there are to be understood not only statistical copolymers, for example from different acrylic acid and methacrylic acid derivatives, but also alternating copolymers, for example alternating copolymers from maleic acid derivatives with styrene or vinyl ethers. Statistical copolymers are preferably used. Homopolymers embrace linear and cyclic polymers such as, for example, cyclic polysiloxanes.
The spacer units S
1
and S
2
link the individual units with one another. Thus, spacer S
1
links the monomer unit with the compound of formula IIa (Q
1
) or, where m=0, with the coumarin or quinolinone derivative (C), while S
2
links the monomer unit M
2
with the compound of formula IIb (Q
2
). Compound Q
1
is linked by Z
2
with the coumarin or quinolinone derivative C.
Such spacer units are known per se. The term “spacer units” embraces in the scope of the present invention a single covalent bond, —(CH
2
)
s
—, —O(CH
2
)
s
—, —(CH
2
)
s
O—, —O(CH
2
)
s
O—, —OOC(CH
2
)
s
—, —COO(CH
2
)
s
—, —(CH
2
)
s
COO—, —(CH
2
)
s
OOC— or —(CH
2
)
s
NR
2
—, wherein s is a whole number of 1 to 12, preferably 1 to 8, carbon atoms, one of the —CH
2
— groups can be replaced by —CHR
3
—, R
2
signifies hydrogen or lower alkyl, especially hydrogen, and R
3
signifies lower alkyl; cycloalkylene with 3 to 8, preferably 5 or 6, carbon atoms, piperidinediyl, piperazinediyl, phenylene, which can be substituted with lower alkyl, lower alkoxy, cyano, nitro or halogen; other spacer units are carbonate (—OCOO—), ester (—COO—, —OOC—), amide (—CONR
2
—, —R
2
NCO—), ether (—O—), amino (—NR
2
—), carboxylamine (—OCONR
2
—, —R
2
NCOO—) or urea (—R
2
NCONR
4
—), in which R
4
signifies hydrogen or a lower alkyl, especially hydrogen.
Spacer units can be especially also a combination of the mentioned groups. Thus, for example, the amide function of acrylamide or the ester function of methacrylic acid can be looked upon as part of the spacer. Likewise, for example, an alkyl group can be combined with a carboxyl, an ether or amino group to an alkylcarboxyl, or alkyloxycarbonyl, an alkoxy, an alkylamino spacer or also to a 4-hydroxy-piperidinyl spacer.
Examples of preferred spacer units are the single bond, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene 1,2-propylene, 1,3-butylene, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, piperidine-1,4-diyl, piperazine-1,4-diyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, ethyleneoxy, ethyleneoxycarbonyl, ethylenecarboxyl, propyleneoxy, propyleneoxycarbonyl, propylenecarboxyl, butyleneoxy, butyleneoxycarbonyl, butylenecarboxyl, pentyleneoxy, pentyleneoxycarbonyl, pentylenecarboxyl, hexyleneoxy, hexyleneoxycarbonyl, hexylenecarboxyl, heptyleneoxy, heptyleneoxycarbonyl, heptylenecarboxyl, octyleneoxy, octyleneoxycarbonyl, octylenecarboxyl, ethylamino, propylamino, butylamino, pentylamino, hexyla

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