Organic compounds -- part of the class 532-570 series – Organic compounds – Azo
Reexamination Certificate
1999-10-14
2003-09-16
Harlan, Robert D. (Department: 1713)
Organic compounds -- part of the class 532-570 series
Organic compounds
Azo
C534S732000, C546S255000
Reexamination Certificate
active
06620920
ABSTRACT:
BACKGROUND OF THE INVENTION
The invention relates to photoaddressable side group polymers in which a high birefringence can be induced by irradiation, so that they are suitable for the production of components for storage of optically available information or as optically switchable components.
FIELD OF THE INVENTION
Photoaddressable side group polymers which have been recommended are special branched polymers: side groups of different types, of which one type (called “A”) can absorb electromagnetic radiation and another type (called “M”) is a mesogenic group anisotropic in shape, are positioned on a linear backbone, connected via molecular parts which act as spacers.
So that the interaction of the mesogenic groups is not impeded, in the past the mesogenic groups have usually been coupled to the spacing group via an oxygen atom, because it has been assumed to date that higher-valency atoms with their substituents in this position impede the interaction and therefore the photoaddressability because of their steric requirement.
The mechanism of photoaddressed orientation is probably based on the possibility of achieving an orientation of the mesogenic groups and therefore a change in the state of order by electromagnetic radiation. However, the photoaddressable polymers known to date still have the disadvantage that the changes in the state of order which can be produced are too small, the change in the state of order takes place too slowly and/or the patterns written in slowly fade again during storage.
The object of the invention was therefore to provide polymers which do not have these disadvantages or have them to a lesser extent.
SUMMARY OF THE INVENTION
Surprisingly, a connection has now been found between the experimentally determinable interaction of the group A, which can absorb electromagnetic radiation, with respect to a standard and the quality of the photoaddressability of the polymer. This finding allows the suitability of the groups A to be tested before their incorporation into the polymer.
The invention thus relates to polymers which have a main chain which acts as a backbone and, branching therefrom, covalently bonded side groups of the formulae
—S
1
—T
1
—Q
1
—A (I) and
—S
2
—T
2
—Q
2
—M (II)
wherein
S
1
and S
2
denote the atoms O or S or the radical NR
0
,
R
0
denotes hydrogen or C
1
-C
4
-alkyl,
T
1
and T
2
denote the radical (CH
2
)
y
, which can optionally be interrupted by
—O—, —NR
0
— or —OSiR
0
2
O— and/or can optionally be substituted by methyl or ethyl,
Q
1
and Q
2
denote a direct bond, —O—, —COO—, —OCO—, —CONR
0
—, —NR
0
CO— or —NR
0
—, or
S
1
T
1
Q
1
or S
2
T
2
Q
2
denotes a bivalent group of the formula
A denotes a unit which can absorb electromagnetic radiation,
M denotes a mesogenic unit anisotropic in shape and
y denotes an integer from 2 to 12,
characterized in that A has an extinction modulus E of greater than 0.2 (measured as described below).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
For the purposes of the invention, the value &Dgr;&Dgr;E is measured on a compound of the formula H—Q
1
—A or HS
1
T
1
Q
1
A wherein Q
1
, S
1
, T
1
and A have the abovementioned meaning and H represents the hydrogen radical.
The extinction modulus &Dgr;&Dgr;E is determined from the changes in extinction &Dgr;E of the longwave flank of the absorption band of 3 solutions of the following substances, that is to say
Solution A H—Q
1
—A or HS
1
T
1
Q
1
A is dissolved in the lowest possible concentration in a solvent which has the lowest possible polarity. The concentration is preferably chosen here such that the steepest possible edge results when the absorption is measured. In the case of dyestuffs, which as a rule have a high molar extinction, this concentration is preferably 10
−3
molar.
Solution B The standard is dissolved in the same solvent in the highest possible concentration, preferably 1 molar, and the absorption edge is recorded.
Solution C This solution comprises H—Q
1
—A or HS
1
T
1
Q
1
A and the standard in the concentrations of solutions A and B.
3 absorption edges are thus obtained: that of the standard, which in general is at a short wavelength, and the absorption edge of solution A and the edge of solution C, which is shifted parallel to this to a long wavelength.
On the longest-wavelength edge, that is to say of solution C, the wavelength belonging to the extinction 0.8 defines the reference wavelength &lgr; The extinction values E of the three solutions A, B and C are now in each case read off at the wavelengths &lgr; and &lgr;+50, where
E
solution C
>E
solution A
>E
solution B
.
To determine the value of &Dgr;E, the following differences are obtained for the wavelengths &lgr; and &lgr;+50:
&Dgr;
E
A
=E
(&lgr;)
solution A
−E
(&lgr;+50)
solution A
&Dgr;
E
B
=E
(&lgr;)
solution B
−E
(&lgr;+50)
solution B
&Dgr;
E
C
=E
(&lgr;)
solution C
−E
(&lgr;+50)
solution C
From these three differences, the increase in extinction of the dyestuff due to the presence of the standard is obtained as the difference &Dgr;&Dgr;E:
&Dgr;&Dgr;
E=&Dgr;E
C
−(&Dgr;
E
B
+&Dgr;E
A
)
The standard should be as polar and/or polarizable as possible. The polarity of the solvent should be as low as possible.
In a preferred form, 1,3-dinitrobenzene is used as the standard and dioxane is used as the solvent.
As explained above, A should be able to absorb electromagnetic radiation. The absorption maxima (&lgr;
max
) of preferred groups A can be in the near IR, in the range of visible light or in the UV, preferably in the wavelength range of 320-1500 nm, in particular 350 to 800 nm. Where the terms “chromophore” or “dyestuff” are used in the context of this invention, they are not limited to the wavelength range of visible light, but are based on the groups A.
Groups A, which give &Dgr;&Dgr;E values above 0.2, can be chosen from the radicals of the following classes of dyestuffs (cf. for example, G. Ebner and D. Schulz, Textilfarberei und Farbstoffe [Textile Dyeing and Dyestuffi], Springer-Verlag, Berlin Heidelberg 1989):
I. Azo dyestuffs
1. Monoazo dyestuffs, such as, for example
C.I. Mordant Yellow 1
C.I. Mordant Blue 78
C.I. Disperse Blue 79
C.I. Disperse Yellow 5
2. Disazo dyestufs, such as, for example,
C.I. Mordant Yellow 16
C.I. Disperse Yellow 23
C.I. Basic Brown 1
C.I. Disperse Yellow 7
II. Quinonoid dyestuffs
1. Quinonoid disperse and mordant dyestuffs, such as, for example,
C.I. Disperse Orange 11
C.I. Disperse Blue 5
C.I. Disperse Blue 7
C.I. Mordant Violet 26
C.I. Mordant Blue 23
III. Metal complex dyestuffs
C.I. Ingrain Blue 14
IV. Meroquinonoide dyestuffs
1. Diphenylmethane dyestuffs, such as, for example, Basic Yellow 3
2. Triphenylmethane dyestuffs, such as, for example,
C.I. Basic Violet 3
C.I. Basic Green 4
C.I. Mordant Blue 1
C.I. Mordant Blue 28
3. Quinoneimine dyestuffi, such as, for example,
C.I. Solvent Blue 22
4. Acridine dyestuffs, such as, for example, Acridine Orange 2 G
5. Thioxanthene dyestuffs, such as, for example, Pyronin G, C.I. 45005
6. Phenazine dyestuffs, such as, for example, C.I. Solvent Blue 7
7. Phenoxazine dyestuffs, such as, for example,
C.I. Mordant Blue 10
8. Phenothiazine dyestuffs, such as, for example,
C.I. Mordant Blue 51
9. Squaric acid dyestuffs, such as, for example, those known from EP-A 0 145 401
Polymethine dyestuffs comprising cationo, aniono and mero (=neutro)cyanines and hemicyanines, such as, for example,
C.I. Disperse Yellow 31
C.I. Disperse Blue 354
C.I. Disperse Red 196
C.I. Disperse Yellow 99
VI. Nitro and nitroso dyestuffs,
such as, for example,
C.I. Disperse Yellow 42
C.I. Disperse Yellow 1
VII. Heterocyclic dyestuffs
1. Perinones, such as, for example,
C.I. Disperse Yellow 58
2. Naphthalimides, such as, for example,
Disperse Yellow 11
3. Quinophthalone, such as, for example,
Disperse Yellow 54, Disperse Yellow 64
4. Coumarins, such as, for example,
those known from DE 15 94 845, 16 70 999, 20 65 076
5. Pyrazolines, such as, for example,
those known from DE 11 55 418, 14
Berneth Horst
Claussen Uwe
Kostromine Serguei
Neigl Ralf
Rübner Joachim
Bayer Aktiengesellschaft
Foley & Lardner
Harlan Robert D.
LandOfFree
Monomers for photoadressable side group polymers of high... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Monomers for photoadressable side group polymers of high..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Monomers for photoadressable side group polymers of high... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3040598