DE19638568A1 - Colour photographic material useful e.g. for colour negative - Google Patents

Abstract

Colour photographic material with silver halide emulsion layer(s) spectrally sensitised with a 5-indolyl-, 5-isoindolyl- or 5-carbazolyl- substituted benzothiazole monomethine cyanine dye of formula (I). In (I), R1 - R5 = hydrogen (H), halogen, alkyl, methoxy, aryl, 1-, 2- or 3-pyrrolyl, 2- or 3-furanyl, 2- or 3-thienyl, 1-indolyl, N-carbazolyl or 2-isoindolyl; or R3 R4 or R4 R5 = group completing an optionally substituted benzene ring; or R3 R4 = group completing an optionally substituted condensed naphthalene ring system; R6, R7 = alkyl, thioalkyl, carboxyalkyl, -(CH2)n-SO2-NH-SO2-alkyl, -(CH2)n-SO2-NH-CO-alkyl, -(CH2)n-CO-NH-SO2-alkyl or -(CH2)n-CO-NH-CO-alkyl; n = 1-6; X = oxygen (-O-), sulphur (-S-), selenium (-Se-) or alkylamino (-NR8-); R8 = optionally substituted alkyl; a, c, d = H or an aromatic group; and/or b = group completing a condensed benzene ring with a or c; c = group completing a condensed benzene ring with b or d; A = optional anion.

Description

The invention relates to a color photographic recording material with mind least a silver halide emulsion layer, which with a Monomethincyanin dye is spectrally sensitive.

The improvement in spectral sensitivity of photographic materials is a permanent challenge. By using polymethine dyes it is possible to increase the sensitivity beyond the intrinsic sensitivity range to expand. Cyanine dyes are particularly suitable for this. For AgCl emul ion is the requirement for a spectral sensitizer for the blue spectral range (400-500 nm) of the same importance as for the green and red Spectral range, since their intrinsic sensitivity range is predominantly in the ultra violet spectral range is located, so that AgCl unlike AgBr emulsions are only slightly sensitive to blue. In EP-A-0 683 427 Benzthiazolmonomethincyanine described that have at least one 5-membered Heterocycle (furanyl, thienyl, pyrrolyl) as a substituent on the benzo nucleus and lead to good blue sensitivity on AgCl emulsions.

It has now been found that by using benzothiazole monomethine cyanines of the general formula I which have at least one substituted or un substituted indolyl or a substituted or unsubstituted isoindolyl or a substituted or unsubstituted carbazolyl substituent on benzo wear core, a higher sensitivity to blue is achieved.

The invention relates to a color photographic recording material at least one silver halide emulsion layer, which with a Monomethincya Nin dye is spectrally sensitized, characterized in that the mono methine cyanine dye corresponds to the following general formula I:

in what mean
R¹, R², R³, R⁴ and R⁵ (same or different): H, halogen, alkyl, methoxy, aryl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-furanyl, 3-furanyl, 2-thienyl, 3 Thienyl, 1-indolyl, N-carbazolyl or 2-isoindolyl,
or R⁴ together with R³ or R⁵ the necessary residue to complete an optionally substituted condensed benzene ring
or R⁴ together with R³ the residue necessary to complete an optionally substituted fused naphthalene ring system;
R⁶ and R⁷ (identical or different): alkyl, sulfoalkyl, carboxyalkyl, - (CH₂) _n - SO₂-NH-SO₂-alkyl, (CH₂) _n -SO₂-NH-CO-alkyl, - (CH₂) _n -CO- NHSO₂- alkyl, - (CH₂) _n -CO-NH-CO-alkyl (n = 1-6);
X -O-, -S-, -Se-, -NR⁸- (R⁸ = optionally substituted alkyl);
a H, an aromatic residue or together with b the residue required to complete a fused-on benzene ring;
b either together with a or together with c the residue necessary to complete a fused-on benzene ring;
c H, an aromatic radical or together with b or d the radical required to complete a fused-on benzene ring;
d H, an aromatic radical or together with c the radical required to complete a fused-on benzene ring;
A an anion which may be present.

An alkyl radical represented by one of the radicals R¹ to R⁵ and R⁸ is straight-chain or branched and contains up to 4 carbon atoms. Preferred example of this is Methyl. An alkyl radical represented by or contained in R⁶ or R⁷ is straight-chain or branched and contains up to 6 carbon atoms.

An aryl radical represented by one of the radicals R¹ to R⁵ is preferred Phenyl.  

Examples of substituents on one with the participation of the radicals R³, R⁴ and R⁵ completed fused benzene ring or naphthalene ring system Halogen, especially chlorine, alkyl and alkoxy.

If a fused benzene ring is completed with the participation of a and b is then c and d are preferably H or both together also for the completion of a condensed benzene ring required rest. If with the participation of b and c a condensed Benzene ring is completed, then preferably at least one of the radicals a and d for an aromatic residue. An aromatic represented by a, c or d The radical is in particular an unsubstituted phenyl radical or a phenyl radical which is substituted for example with halogen, alkyl or alkoxy. A participant Delivery of two of residues a, b, c and d completed fused benzene ring can be substituted, e.g. B. with halogen, alkyl or alkoxy.

In a preferred embodiment of the present invention, the Monomethine cyanine dye of the following general formula IA

wherein X, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, c, d and A have the same meaning as in formula I, but R¹, R², R³, R⁴ and R⁵ are not isoindolyl, and wherein R⁹ represents H, halogen, alkyl, alkoxy or aryl.

Monomethine cyanine dyes of the formulas I and IA are particularly preferred, where R⁴ is chlorine or methyl.

Also particularly preferred are monomethine cyanine dyes of the formula IA, wherein R⁴ is 1-indolyl or N-carbazolyl.

Likewise particularly preferred are monomethine cyanine dyes of the formula IA, where R⁹ is chlorine.  

Suitable examples of sensitizing dyes according to the invention are given below listed below:

Synthesis of dye I-5

The synthesis of 3 from 1 and 2 was carried out analogously to that in J. former Soc., Perkin Trans. 1, 1989, 2407.

Production of the quaternary salt 4

2.64 g (10 mmol) 3 are heated in 5 ml dichlorobenzene with 1.22 g (10 mmol) 1,3-propanesulfone at 160 ° C for 6 h. After cooling to room temperature, 30 ml of acetone are added, the mixture is refluxed for 0.5 h, allowed to cool to room temperature, suction filtered, washed thoroughly with acetone and boiled with 30 ml of methanol for 1 h without intermediate drying.
Yield: 2.68 g (69.3% of theory)

Preparation of I-5

3.87 g (10 mmol) 4 are suspended together with 3.34 g (10 mmol) 5 in 30 ml form amide at room temperature and mixed with 3.1 g (30 mmol) acetic anhydride. For this purpose, 3.3 g (33 mmol) of triethylamine are metered in with cooling, so that 20 ° C. is not exceeded. After stirring at room temperature for 14 h, the precipitated dye is filtered off with suction and washed with acetone and boiled with 40 ml of methanol for 1 h without further drying.
Yield: 4.04 g (52% of theory).

The quaternary salt 5 was after the in Res. Discl. 182, 301-303 (1979) made method.

Examples of color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the sil over color bleaching process.

The photographic materials consist of a support on which at least one photosensitive silver halide emulsion layer is applied. As a carrier thin films and foils are particularly suitable. An overview of carriers materials and auxiliary layers applied to their front and back are in Research Disclosure 37254, Part 1 (1995), p. 285.

The color photographic materials usually contain at least one red sensitive, green-sensitive and blue-sensitive silver halide emulsions layer and, if necessary, intermediate layers and protective layers.

Depending on the type of photographic material, these layers can be arranged differently. This is shown for the most important products:
Color photographic films such as color negative films and color reversal films have 2 or 3 red-sensitive, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers on the support in the order given below. The layers of the same spectral sensitivity differ in their photographic sensitivity, the less sensitive sub-layers generally being closer to the support than the more sensitive sub-layers.

Between the green sensitive and blue sensitive layers is more common a yellow filter layer, which prevents blue light from entering the to get layers below.

The possibilities of the different layer arrangements and their out effects on photographic properties are described in J. Inf. Rec. Mats., 1994, Vol. 22, pages 183-193.

Color photographic paper, which is usually much less sensitive to light as a color photographic film, points in the order given below usually a blue-sensitive, yellow-coupling silver halo on the carrier genide emulsion layer, a green-sensitive, purple-coupling silver halide emulsion layer and a red-sensitive, cyan-coupling silver halide emulsion layer on; the yellow filter layer can be omitted.

Deviations in the number and arrangement of the photosensitive layers can occur to achieve certain results. For example, you can all highly sensitive layers in one layer package and all low sensitivity layers to another layer package in a photographic film be summarized to increase the sensitivity (DE 25 30 645).

Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.

Information on suitable binders can be found in Research Disclosure 37254, Part 2 (1995), p. 286.

Information about suitable silver halide emulsions, their preparation, maturation, Stabilization and spectral sensitization including suitable spectrals sensitizers can be found in Research Disclosure 37254, Part 3 (1995), pp. 286 and in Research Disclosure 37038, Part XV (1995), p. 89.

Photographic materials with camera sensitivity usually contain Silver bromide iodide emulsions, which may also contain small amounts of silver  can contain chloride. Photographic copy materials contain either Silver chloride bromide emulsions with up to 80 mol% AgBr or silver chloride bromide emulsions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288 and in Research Disclosure 37038, Part II (1995), p. 80. The maximum absorption of that from the couplers and the color developer oxidation Product-formed dyes are preferably in the following areas: Yellow coupler 430 to 460 nm, purple coupler 540 to 560 nm, cyan coupler 630 up to 700 nm.

In color photography films, to improve sensitivity, Graininess, sharpness and color separation are often used in compounds React with the developer oxidation product to release compounds that are photographically effective, e.g. B. DIR couplers that have a development inhibitor columns.

Information on such connections, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290 and in Research Disclosure 37038, Part XIV (1995), p. 86.

Mostly hydrophobic color couplers, but also other hydrophobic components of the layers, are usually in high-boiling organic solvents dissolved or dispersed. These solutions or dispersions are then in one emulsified aqueous binder solution (usually gelatin solution) and lie after drying the layers as fine droplets (0.05 to 0.8 µm through knife) in the layers.

Suitable high-boiling organic solvents, methods for incorporation into the layers of a photographic material and other methods, chemical Introducing connections into photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.

The usually between layers of different spectral sensitivity arranged non-light-sensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a  photosensitive to another photosensitive layer with different prevent spectral sensitization.

Suitable connections (white coupler, scavenger or EOP catcher) can be found in Research Disclosure 37254, Part 7 (1995), p. 292 and in Research Disclosure 37038, Part III (1995), p. 84.

The photographic material can also UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, anti-oxidants, D _Min dyes, additives to improve the stability of dyes, couplers and whites as well as to reduce the color fog, plasticizers (latices) , Biocide and others included.

Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), P. 292 and in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XIII (1995), pp. 84ff.

The layers of color photographic materials are typically hardened, i.e. H., the binder used, preferably gelatin, is by suitable cross-linked chemical processes.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 and in Research Disclosure 37038, Part XII (1995), page 86.

After imagewise exposure, color photographic materials become their character ter processed according to different processes. Details of the Procedures and chemicals required for this are in Research Disclosure 37254, part 10 (1995), p. 294 and in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95ff published together with exemplary materials.  

example 1

Using the sensitizing dye I-5, a light-sensitive material was prepared as follows:
14.9 mg of dye I-5 dissolved in 25 ml of methanol are added to 100 g of a silver chloride emulsion after 45 min at 40 ° C. After stirring for 60 min at 40 ° C., 6 mg of ST-A dissolved in 6 ml of water, 112.5 mg of potassium bromide dissolved in 12 ml of water and 2.2 mg of ST-B dissolved in 5 ml of dilute sodium hydroxide solution are added. After stirring for 10 minutes at 40 ° C., 50 ml of water, 81 g of a 20% by weight gelatin solution, 14.0 g of coupler K-1 and 6.2 g of coupler K-2 are emulsified in 204 g of water and 33, 3 g of oil-forming agent O-1 (polymeric mixed ester of adipic acid and a mixture of 1,3- and 1,4-butanediol and 2-ethylpropanediol), and 0.32 g of wetting agent NM-1 dissolved in 8 ml of water. After a further 15 minutes, the emulsion is poured and then hardened.

In the same way, other recording materials with the difference that that instead of the sensitizing dye I-5 according to the invention, other Sensi lizing dyes were used, as can be seen in Table 1. Of that The sensitivity was determined for the recording materials produced. Here samples of the materials were exposed behind a gradient wedge and one Color negative processing according to "The Journal of Photograpic Science 1974, pages 597, 598 ". The results are summarized in Table 1.

Table 1

The following compounds were used in Example 1:

As can be seen from Table 1, the sensitizers according to the invention perform to higher sensitivity.

Claims (6)

1. Color photographic recording material having at least one silver halide gene emulsion layer which is spectrally sensitized with a monomethine cyanine dye, characterized in that the monomethine cyanine dye corresponds to the following general formula I: in what mean
R¹, R², R³, R⁴ and R⁵ (same or different): H, halogen, alkyl, methoxy, aryl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-furanyl, 3-furanyl, 2-thienyl, 3 -Thienyl, 1-indolyl, N-carbazolyl or 2-isoindolyl,
or R⁴ together with R³ or R⁵ the necessary residue to complete an optionally substituted ankonden based benzene ring
or R⁴ together with R³ the residue necessary to complete an optionally substituted fused naphthalene ring system;
R⁶ and R⁷ (identical or different): alkyl, sulfoalkyl, carboxyalkyl, - (CH₂) _n -SO₂-NH-SO₂-alkyl, - (CH₂) _n -SO₂-NH-CO-alkyl, - (CH₂) _n - CO -NH-SO₂-alkyl, - (CH₂) _n -CO-NH-CO-alkyl (n = 1-6);
X -O-, -S-, -Se-, -NR⁸- (R⁸ = optionally substituted alkyl);
a H, an aromatic residue or together with b the required residue to complete a condensed benzene ring;
b either together with a or together with c the residue necessary to complete a fused-on benzene ring;
c H, an aromatic radical or together with b or d the radical required to complete a fused-on benzene ring;
d H, an aromatic radical or together with c the radical required to complete a fused-on benzene ring;
A an anion which may be present. 2. Recording material according to claim 1, characterized in that the monomethine cyanine dye of the following general formula IA speaks ent in what mean
R¹, R², R³, R⁴ and R⁵ (same or different): H, halogen, cyano, alkyl, methoxy, aryl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-furanyl, 2-thienyl, 3-thienyl , 1-indolyl or N-carbazolyl,
or R⁴ together with R³ or R⁵ is the radical required to complete an optionally substituted condensed benzene ring,
or R⁴ together with R³ the necessary residue to complete an optionally substituted fused naphthalene ring system;
R⁶ and R⁷ (identical or different): alkyl, sulfoalkyl, carboxyalkyl, - (CH₂) _n -SO₂-NH-SO₂-alkyl, - (CH₂) _n -SO₂-NH-CO-alkyl, - (CH₂) _n -CO -NH-SO₂-alkyl, - (CH₂) _n -CO-NH-CO-alkyl (n = 1-6);
X -O-, -S-, -Se-, -NR⁸- (R⁸ = optionally substituted alkyl);
R⁹ H, halogen, alkyl, alkoxy or aryl;
c H, an aromatic residue or together with d the rest required to complete a condensed benzene ring;
d H, an aromatic radical or together with c the radical required to complete a fused-on benzene ring;
A an anion which may be present. 3. Recording material according to one of claims 1 and 2, characterized characterized in that in formulas I and IA R⁴ for chlorine or methyl stands. 4. Recording material according to claim 2, characterized in that in Formula IA R⁴ is 1-indolyl or N-carbazolyl. 5. Recording material according to claim 2, characterized in that in Formula IA R⁹ represents chlorine. 6. Recording material according to one of claims 1 to 5, characterized records that the silver chloride content in the silver halide is the silver halo gene emulsion layer is not less than 90 mol%.