Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2000-02-11
2001-08-28
Chea, Thorl (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
C430S581000, C430S584000, C430S585000, C430S588000
Reexamination Certificate
active
06280921
ABSTRACT:
DESCRIPTION
The present invention relates to cyanine dyes corresponding to formula (I), to a colour photographic material which contains cyanine dyes of formula (I), and to the use of compounds of formula (I) as spectral sensitisers.
Improving the spectral sensitivity of photographic materials constitutes a permanent challenge. It is known that polymethine dyes can be used in order to increase the sensitivity beyond the range of intrinsic sensitivity of the silver halide which is used. Cyanine dyes are particularly suitable for this purpose.
Cyanines based on thienyl-substitituted benzoxazoles are known from the prior art, such as DE 1063028, JP 09/106028, JP 09/138476, JP 09/311398 and JP 10123650 for example.
EP 0 599 383 discloses cyanine dyes which, as a constituent of silver halide emulsion layers, are used in particular to prevent the formation of colour stains after processing when tab grain emulsionsd are used. These are cyanine dyes, the benzo nucleus of which is linked to a furanyl or pyrrolyl substituent.
However, there is a need for cyanine dyes which, particularly when they are used in tab grain emulsions, exhibit both increased spectral sensitivity and good stability on storage, especially after storage under conditions of high temperature and high humidity.
The underlying object of the present invention is to provide cyanine dyes which are distinguished by their particularly high spectral sensitivity and at the same time by their good long-term stability on storage, even under tropical conditions. As far as possible, the materials should retain their sensitivity even after long-term storage under tropical conditions.
It has surprisingly been found that cyanine dyes which contain benzoxazole, which correspond to formula (I), and which comprise at least one benzthienyl substituent, exhibit outstanding spectral sensitivity, whilst at the same time exhibiting good stability on storage even under tropical conditions. In addition, it has proved possible significantly to increase the spectral sensitivity of tab grain emulsions.
The present Application relates to cyanine dyes of formula (I)
wherein
R1, R2, R3 R4, R5 and R6, independently of each other, each represent a substituent, with the proviso that at least one of the radicals R1, R2, R3 represents a benzthienyl substituent,
x represents O, S, Se, NR7, CH═CH or C(CH3)2, wherein R7 represents an alkyl radical which is optionally substituted,
S1, S2 independently of each other, represent alkyl, sulphoalkyl, carboxyalkyl, —(CH2)1—SO2—Y—SO2-alkyl, —(CH2)1—SO2—Y—CO-alkyl, —(CH2)1—CO—Y—SO2-alkyl, —(CH2)1—CO—Y—O—alkyl, —(CH
2
)
1
—NH—SO
3
⊖
, —(CH
2
)
1
—N(alkyl-SO
3
⊖
or —(CH
2
)
1
—N(Aryl)—SO
3
⊖
, with the proviso that 1=1 to 6 and Y denotes NH or N—,
n denotes 0, 1, 2, 3,
L1, L2, L3 represent a substituted or unsubstituted methine group, which may be a constituent of one or more carbocyclic rings, and
M represents a counterion which may be necessary for charge compensation.
Unless a more special definition is given, a substituent in the sense of the present invention is to be understood, for example, as H, a halogen, preferably F, Cl or Br, an aryl, an alkyl—aryl, a hetaryl, an alkyl, an alkenyl, or OR10, wherein R10 represents a C1 to C6 alkyl, particularly methyl, ethyl and propyl. Furthermore, the term “substituent” can also denote condensed-on ring systems, which may optionally be substituted. Thus R6 may form a condensed-on ring system with R5, or R5 may form a condensed-on ring system with R4, for example. The term “condensed-on ring systems” is to be understood preferably to comprise benzo or naphtho ring systems.
Unless defined otherwise, “alkyl” in the sense of the present Application should be understood to comprise linear or branched, cyclic or straight-chain, substituted or unsubstituted hydrocarbon groups. The preferred alkyl groups are alkyl groups comprising 1 to 20 C atoms, particularly 1 to 6 C atoms. Open-chain alkyl groups which are particularly suitable include methyl, ethyl, n-propyl, n-butyl and n-pentyl radicals, and branched alkyl radicals which are particularly suitable include those with branched methyl or ethyl groups. Other suitable substituents include partially or completely halogenated alkyl groups, such as CF3 or —CH2CF2CF2H in particular. Substituents such as OH are also preferred.
Unless defined otherwise, “alkenyl” in the sense of the present invention should be understood to denote linear or branched, cyclic or straight-chain, substituted or unsubstituted, unsaturated hydrocarbon radicals, such as ethenyl, 2-propenyl and isopropenyl for example.
Unless defined otherwise, “aryl” in the sense of the present Application should be understood to denote aromatic hydrocarbon groups, which are preferably 5- or 6-membered ring systems but which can also exist in monocyclic form or as condensed ring systems also. These ring systems can be either substituted or unsubstituted ring systems. Phnely and naphthyl groups are particularly preferred, for example. Suitable substituents include the groups cited above, preferably halogen, alkyl, and OR10 with the meaning given above.
Unless defined otherwise, “hetaryl” in the sense of the present Application should be understood to denote aromatic systems which contain at least one hetero atom. These systems may comprise both substituted and unsubstituted ring systems. Typical examples include pyridine, pyridazine, pyrimidine, pyrazines, oxazole, isoxazole, thiazoles, 3,4-oxdiazole, 1,2,4-oxdiazole, imidazole, 1,2,3-triazole and 1,2,4-triazole. Heterocyclic substituents which are particularly preferred include 2-furanyl, 3-furanyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-thienyl, 3-thienyl and N-indolyl.
Unless defined otherwise, and depending on the substituent and thus on the charge relationship, the following entitites are suitable as counterions M in the sense of the present invention: tosylate, I-, Br-, Cl-, or preferably diazabicyclooctane (DABCOH+) or diazabicycloundecane (DBUH+), or pyridine or H+, and particularly Na+, Li+, K+and most preferably Et3N+H.
n represents 0,1,2,3, preferably 0,1 or 2.
Compounds of formula (I) which are particularly preferred are the compounds of formula (Ia) listed below:
wherein
Y1 represents a benzthienyl group which is bonded to the nucleus via the 2-, 3-, 4-, 5-, 6- or 7-positions,
Y2, Y3 and Y4 independently of each other represent H, halogen, in particular F, Cl or Br, a substituted or unsubstituted 1-, 2-, 3-pyrrolyl, 2- or 3-thienyl, 2-, 3-, 4-, 5-, 6-, or 7-benzthienyl, N-indolyl, phenyl or 2- or 3-furanyl residue, alkyl, preferably having 1 to 6 C atoms, in particular methyl, ethyl or propyl, or
Y2 and Y3 or Y3 and Y4 may be a constituent of a fused benzo or naphtho ring,
X represents O, S, Se, NR7, CH═CH or C(CH3)2, wherein R7 represents an alkyl radical which is optionally substituted,
S1, S2 independently of each other, represent alky, sulphoalkyl, carboxyalkyl, —(CH2)1—SO2—Y—SO2-alkyl, —(CH2)1—SO2—Y—CO-alkyl, —(CH2)1—CO—Y—SO2-alkyl, —(CH2)1—CO—Y—O-alkyl or —(CH2)1—NH—SO3È, —(CH2)1—N(alkyl)—SO3È or —(CH2)1—N(Aryl)—SO3È, with the proviso that l=1 to 6 and Y denotes NH or N—,
n denotes 0, 1, 2, 3,
L1, L2 , L3 represent a substituted or unsubstituted methine group, which may be a constituent of one or more carbocyclic rings, and
M represents a counterion which may be necessary for charge compensation.
A list of typical compounds which are particularly preferred according to the present invention is given below:
The preparation of dyes I-2 and I-28 will be explained with reference to the following reaction schemes:
Scheme 1: synthesis of dye I-2. Starting from p-acetylphenol 1 (manufactured by Fluka) the preparation of 2 was effected analogously to the method described in J.Chem.Eng.Data 26, 23 d (1981), 3 was synthesised according to J. Heterocyclic Chem. 25, 1417 (1988), and compounds 4, 5 and 6 were prepared analogously to the instructions on pages 70/71, 363 and 523 of the text by L.F.Tietze and Th. Eicher,
Georg Thieme Ver
Michael Missfeldt
Stefan Herrmann
AGFA-GEVAERT
Chea Thorl
Connolly Bove & Lodge & Hutz LLP
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