Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1998-03-12
2002-08-27
Lambkin, Deborah C. (Department: 1613)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
active
06441191
ABSTRACT:
The present invention relates to the use of indolenine-cyanine dyestuffs as infrared-absorbing agents in hydrophilic colloidal layers, specifically those in recording materials, in particular photographic recording materials, and to such materials for IR detection processes which furthermore comprise hydrophilic colloidal layers with such indolenine-cyanine dyestuffs, and new indolenine-cyanine dyestuffs.
It is known to use colloidal layers which comprise dyestuffs, including infrared-absorbing dyestuffs, in photographic recording materials, in particular those based on silver halide. Photographic recording materials in general have a multi-layer structure. The dyestuff-containing layers can be employed in various positions in the multi-layer material. The photosensitive colloidal layer or layers comprising silver halides can comprise dyestuffs directly. In this context, infrared sensitive materials based on silver halide comprise one or more colloidal layers having one or more infrared-absorbing dyestuffs as sensitizers. However, layers comprising dyestuffs, in particular also infrared-absorbing dyestuffs, also function, for example, as auxiliary or filter layers.
For example, dyestuff-containing layers have the task, inter alia, of increasing the imaging sharpness of the recording materials. It is also known in this context to apply dyestuff-containing layers to the reverse of a photographic material to suppress halation effects caused by reflection of scattered light (antihalation layers).
It is furthermore also known that infrared-detecting apparatuses can advantageously be used for automatic process control or management, in particular also for automatic process control or management during the production and working or processing of recording materials. So that the material to be worked, for example the recording material, is capable of interaction with the control unit, it must have a suitable infrared absorption. Control detectors which operate in the range from 850 to 950 nm, which requires a corresponding absorption, for example of the recording material in this range, are typically used. The desired secondary actions are triggered off according to whether the detection system, which can comprise, for example, an infrared laser, detects an absorption or no absorption in a certain range. Analogue detection coupling is also possible. It is furthermore known that IR-detecting apparatuses can advantageously be employed for recognition of IR-absorbing materials. Thus, for example, documents, securities, letters and the like can be marked or coded by application of one or more IR-absorbing layers over the entire material or on selected positions.
Dyestuffs which are suitable for the above purposes must have, in particular, suitable absorption characteristics. For use in photographic recording materials, the dyestuffs must be decolorized completely during the photographic wet processing process, and/or they must be readily washed out of the photographic material, so that the developed material displays no residual coloration after processing. Furthermore, no stain of the baths should occur.
It is known to use infrared-absorbing dyestuffs of the heptamethine-cyanine type with indolenine end groups, in particular for infrared-sensitive photographic silver halide materials (see, for example, U.S. Pat. No. 4,876,181; EP-A-445 627; Chem. Abstr. 112:169019e (1990); Chem. Abstr. 112:108465a (1990)). However, these dyestuffs do not meet, or meet only in part, the requirements imposed. In particular, these indolenine-hepta-methine-cyanines have the disadvantage that, with all the proposed substitution patterns, they absorb in too short a wavelength, i.e. they are not capable of providing an adequate IR absorption in the range from 850 to 950 nm, which is important for IR detection purposes. In order to achieve an adequate absorption, suitable dyestuffs would often have to be employed in an uneconomically large amount. Furthermore, the dyestuffs are often not easily accessible by synthesis and/or are not adequately decolorized during the photographic processing process.
There is therefore a need for infrared-absorbing dyestuffs which can be employed in hydrophilic colloidal layers, for example of photographic recording materials, are easily accessible by synthesis, and have a suitable infrared absorption and adequate decolorizing properties during photographic processing.
It has now been found, surprisingly, that certain indolenine-cyaninedisulphonic acid derivatives meet these conditions. Individual representatives of these dyestuffs are already known per se (see Chem. Abstr. 111: 144195a (1989), Chem. Abstr. 115: 146699z (1991) and Chem. Abstr. 110:222544j (1989), but the use according to the invention does not yet belong to the prior art.
The present invention thus relates to the use of dyestuffs of the general formula I
in which
R
1
, R
2
and R
3
independently of one another are hydrogen, (C
1
-C
6
)-alkyl which is unsubstituted or monosubstituted by halogen or phenyl, or unsubstituted or mono- or disubstituted phenyl, and R
3
furthermore is also halogen or (C
3
-C
7
)-cycloalkyl, but wherein no sulpho or sulphonate groups, no carboxyl or carboxylate groups and no sulphato groups may occur as a substituent in phenyl groups, and M
⊕
is a monovalent cation or one equivalent of a polyvalent cation,
as infrared-absorbing agents in hydrophilic colloidal layers.
(C
1
-C
6
)-Alkyl groups and (C
1
-C
4
)-alkyl groups can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, 3-methylbutyl or n-hexyl. The same applies if alkyl groups are substituted or occur as substituents, for example on phenyl groups or in alkoxy groups. n-Alkyl groups are preferred, particularly preferably (C
1
-C
3
)-n-alkyl groups, such as methyl, ethyl and n-propyl. Methyl is a very particularly preferred alkyl group.
Alkyl which is substituted by halogen or phenyl is, for example, benzyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 2-chloro-2-methylpropyl, 4-chlorobutyl or 6-chlorohexyl.
A substituent on an alkyl group is preferably bonded to the terminal C atom of the alkyl group.
Substituted phenyl is preferably phenyl which is mono- or disubstituted by (C
1
-C
4
)-alkoxy, (C
1
-C
4
)-alkyl, halogen or (C
1
-C
4
)-alkoxycarbonyl. Monosubstituted phenyl can be substituted in the 2-, the 3- or the 4-position, and disubstituted phenyl can be substituted, for example, in the 2,3-, in the 3,4- or in the 3,5-position. Preferably, substituted phenyl is substituted in the 4-position.
Halogen is, in particular, fluorine, chlorine, bromine and iodine, chlorine being preferred, and (C
3
-C
7
)-cycloalkyl is, in particular, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
The sulphonate groups in the indolenine end groups of the dyestuffs of the general formula I can be in the 5- or the 6-position of the indole ring-system and can also be in different positions in the two end groups.
They are preferably in the 5-position of the indole ring-system. They are also preferably in the same position in the two end groups.
R
1
and R
2
are preferably hydrogen, (C
1
-C
4
)-alkyl, which can also be substituted by phenyl, or phenyl. R
1
and R
2
are particularly preferably (C
1
-C
3
)-n-alkyl, and furthermore benzyl, and very particularly preferably methyl. R
1
and R
2
also preferably have the same meaning.
R
3
is preferably hydrogen or (C
1
-C
4
)-alkyl, and furthermore (C
1
-C
4
)-alkyl, which is substituted by phenyl, phenyl, halogen or (C
3
-C
7
)-cycloalkyl. R
3
is particularly preferably hydrogen, (C
1
-C
3
)-n-alkyl, benzyl, phenyl or halogen, very particularly preferably hydrogen or methyl.
M
⊕
is, for example, a cation or cation equivalent of main group or sub-group elements, for example of the alkali metals lithium, sodium, potassium, rubidium and caesium, the alkaline earth metals magnesium, calcium, strontium and barium, or,
Lehmann Lutz Uwe
Lonsky Ralph
Honeywell International , Inc.
Lambkin Deborah C.
Synnestvedt & Lechner LLP
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