DE19853861A1 - Color photographic copy material containing a pyrrolo(1,2-b)-1,2,4-triazole blue-green coupler and giving a yellow density corresponding to 1-15% of the blue-green density - Google Patents

Abstract

A color photographic copy material with a pyrrolo(1,2-b)-1,2,4-triazole blue-green coupler of the type described in EP628867 in a red-sensitive layer has a blue sensitive layer 'associated' with a red-sensitive emulsion such that a yellow density is provided over the entire density range on red illumination, this yellow density corresponding to 1-15% of the blue-green density. By 'associated' is meant that the red-sensitive Ag halide emulsion is in the blue-sensitive (or a neighboring) layer such that the development oxidation product only reacts with the yellow coupler in this layer. The pyrrolo(1,2-b)-1,2,4-triazole blue-green coupler is of formula (I): R1 = H or a substituent; X = H or a splitting group; Y = OR2 or NR3R4; R2 = alkyl or a group of formula (II); R3 = alkyl; R4 = H or as for R3; R5, R6, R8 and R9 = H or a substituent; R7 = a substituent; and Z = non-metallic members of a 3-8-membered ring and is optionally further substituted

Description

The invention relates to a color photographic copy material, which is used as a cyan coupler contains at least one pyrrolo [1,2-b] -1,2,4-triazole.

Color photographic copying materials are especially supervising materials or displays that generally have a positive image. They are therefore not Recording material such as color photographic films.

Pyrrolo [1,2-b] -1,2,4-triazoles are z. B. from EP 628 867 known cyan couplers, the very pure cyan dyes with relatively short wavelength absorption band and very high extinction and therefore savings on silver halo enable genide. The cyan dyes of these couplers also have a great deal good stability when stored in the absence of light.

The disadvantage is that with these couplers blue and blue shades color shift as be given. This is the print compatibility with conventional copy material is no longer given.

The object of the invention is to eliminate this disadvantage to the advantages of this To be able to exploit couplers.

Surprisingly, it has now been found that in a material of the genann th species with at least one red-sensitive, at least one cyan coupler containing, at least one green-sensitive, at least one magenta containing and at least one blue-sensitive, at least one yellow coupler containing silver halide emulsion layer containing at least one pyrrolo [1 , 2-b] - 1,2,4-triazole blue-green coupler of the formula (I)

wherein
R _{1 is} hydrogen or a substituent,
X is a hydrogen atom or a leaving group and
Y OR ₂ or

mean, where
R ₂

or alkyl,
R _{3 is} alkyl,
R _{4 is} hydrogen or R ₃ ,
R ₅ , R ₆ , R ₈ and R _{9 are} hydrogen or a substituent,
R _{7 is} a substituent and
Z the remaining non-metallic members of a 3- to 8-membered ring be interpreted, where Z may be further substituted,
in the at least one red-sensitive layer, this object can be achieved by assigning the at least one blue-sensitive layer a red-sensitized silver halide emulsion which provides a yellow density amount over the entire density range at redness which amounts to 1 to 15%, preferably 3 to 30%. the cyan density corresponds.

Associated means that the red sensitized silver halide emulsion is in the blue sensitive or a neighboring layer is located so that in this Developed developmental oxidation product (EOP) layer only in the at least one blue-sensitive layer with a coupler, namely the yellow coupler couples.

The red sensitized silver halide emulsion is preferably in the white at least one blue-sensitive layer itself.

In this case, the invention can be realized by using a silver halide nidemulsion becomes both blue and red sensitized or by adding two separately blue- or red-sensitized silver halide emulsions mixed with each other the. Finally, the red sensitized silver halide emulsion can also be used in a separate layer can be used together with the yellow coupler.

The red-sensitized silver halide emulsion, that of the blue-sensitive layer is assigned, in particular, is chosen so that it is about the red sensitive Speed of the cyan coupler layer corresponds. This can be z. B. Sensibili Satormenge or done on grain size.  

Suitable pyrrolo [1,2-b] -1,2,4-triazole cyan couplers of the formula (I) are:

Suitable blue sensitizers correspond to the formula II

wherein
R ₁₁ to R ₁₃ and R ₁₆ to R _{18 are} H, alkyl, alkoxy, halogen, 2-thienyl, 3-thienyl, 1-pyrolyl, 2-pyrrolyl, phenyl, 1-indolyl, 2-furanyl, 3-furanyl or carbazolyl .
R ₁₄ and R _{15 are} alkyl, sulfoalkyl, carboxyalkyl,
- (CH ₂ ) _n SO ₂ N ^θ -COR ₁₉ , - (CH ₂ ) _n SO ₂ N ^θ SO ₂ R ₁₉ ,
- (CH ₂ ) _n CON ^θ SO ₂ R ₁₉ or - (CH ₂ ) _n CON ^θ COR ₁₉ ,
X ₁ and X ₂ O, S, Se, NR ₂₀ ,
M a counterion,
n a number 2 to 4 and
R ₁₉ and R _{20 are} C ₁ -C ₄ -alkyl or
R ₁₁ and R ₁₂ and R ₁₂ and R ₁₃ , R ₁₆ and R ₁₇ and R ₁₇ and R _{18 are} the remaining members of a fused benzene or naphthalene ring.

Preferred blue sensitizers correspond to the formula III

wherein
R ₂₁ and R _{23 are} hydrogen
R _{22 is} halogen, in particular chlorine or fluorine, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-furanyl, 1-indolyl or phenyl or
R ₂₁ and R ₂₂ together or R ₂₂ and R ₂₃ together form the remaining members of a fused benzene or naphthalene ring,
R _{24 is} hydrogen,
R _{25 is} halogen, in particular chlorine or fluorine, phenyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-furanyl, 1-indolyl or
R ₂₄ and R ₂₅ together form the remaining members of a fused benzene or naphthalene ring,
X ₃ S or O
M is a counterion, in particular triethylammonium and
l and m represent a number 2 to 4.

Suitable compounds of the formula III are the following with 1 and m = 3 and triethylammonium as counterion:

Suitable red sensitization correspond to the formula IV

wherein
X ₁ , X ₂ , R ₁₁ to R ₁₈ and M have the meaning given for formula II,
R _{26 is} H, alkyl, halogen, dialkylamino or alkylthio and
R ₂₇ and R _{28 are} H or alkyl.

The red sensitizers preferably correspond to the formula V

wherein
R ₁₄ , R ₁₅ , X ₃ and M have the abovementioned meaning,
R ₂₉ to R ₃₄ are each independently H, CH ₃ , OCH ₃ , Cl, 1-pyrrolyl, 1-indolyl, 2-thienyl, 3-thienyl, 2-furanyl, 3-furanyl, N-carbazolyl, phenyl or R ₂₉ and R ₃₀ , or R ₃₀ and R ₃₁ , and R ₃₂ and R ₃₃ , or R ₃₃ and R ₃₄ together, the remaining members of a benzo, 1,2-naphtho or 2,3-Naphthoringes be interpreted.

Suitable red sensitizers are

Examples of color photographic copy materials are color photographic paper, color reversal photographic paper and semi-transparent display material. An over See Research Disclosure 37038 (1995), Research Disclosure 38957 (1996) and Research Disclosure 40145 (1997).

The photographic copying materials consist of a support on which at least a photosensitive silver halide emulsion layer is applied. As a carrier In particular, thin films and films are suitable. An overview of carrier material rials and auxiliary layers applied to their front and back is in Rese arch Disclosure 37254, Part 1 (1995), p. 285 and Research Disclosure 38957, Part XV (1996), p. 627.  

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

Depending on the type of photographic copy material, these layers may be arranged different Lich. This is illustrated for the main products:
Color photographic paper and color photographic display material in the following order on the support usually each have a blue-sensitive, yellow-coupling silver halide emulsion layer, a green-sensitive, magenta-coupling silver halide emulsion layer, and a red-sensitive blue-green coupling silver halide emulsion layer; a yellow filter layer is not required.

Deviations from the number and arrangement of the photosensitive layers can to achieve certain results. For example, you can Color papers also contain differently sensitized intermediate layers over which the Gradation can be affected.

Essential constituents 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 and Research Disclosure 38957, part ILA (1996), p. 598.

Information on suitable silver halide emulsions, their preparation, ripening, Sta stabilization and spectral sensitization including appropriate spectral sensitization See Research Disclosure 37254, Part 3 (1995), p. 286, in Research Disclosure 37038, Part XV (1995), p. 89 and Research Disclosure 38957, Part V. A (1996), p. 603.  

As red sensitizers for the red-sensitive layer, moreover, penta methyncyanines having naphthothiazole, naphthoxazole or benzthiazole as basic end groups which can be substituted with halogen, methyl or methoxy groups and 9,11-alkylene, especially 9,11-neopentylene bridged, may be used , The N, N'-substituents may be C ₄ -C ₈ -alkyl groups. The methine chain may additionally carry substituents. It is also possible to use pentamethines having only one methyl group on the cyclohexene ring. The red sensitizer can be supersensitized and stabilized by addition of heterocyclic mercapto compounds.

The red-sensitive layer may additionally be between 390 and 590 nm, preferably be spectrally sensitized at 500 nm, so as to improve the differentiation of the To cause reds.

The spectral sensitizers may be in dissolved form or as a dispersant of fotogra be added to the emulsion. Both solution and dispergate may be added such as wetting agents or buffers.

The spectral sensitizer or a combination of spectral sensitizers can be added before, during or after the emulsion preparation.

Photographic copying materials contain either silver chlorobromide emulsions with up to 80 mol% AgBr or silver chlorobromide emulsions with more than 95 mol% AgCl.

For color couplers see Research Disclosure 37254, part 4 (1995), p. 288, Research Disclosure 37038, Part II (1995), p. 80, and Re search Disclosure 38957, Part X. B (1996), p. 616. The maximum absorption of is the dyes formed by the couplers and the color developer oxidation product for copying materials preferably in the following ranges: yellow coupler 440 to 450 nm, magenta couplers 540 to 560 nm, cyan couplers 640 to 670 nm.  

The more common in copying materials in association with a blue-sensitive layer The yellow couplers used are almost always two-equivalent couplers of the Pi valoylacetanilide and cyclopropylcarbonylacetanilide series.

The customary in copying magenta couplers are almost always those of the A series of anilinopyrazolones, pyrazolo [5.1-c] (1,2,4) triazoles or pyra zolo [1,5-b] (1,2,4) triazole.

The usually between layers of different spectral sensitivity angeges arranged non-photosensitive intermediate layers may contain agents that an undesirable diffusion of developer oxidation products from a lichtemp sensitive in another photosensitive layer with different spectral Prevent sensitization.

Suitable compounds (white couplers, scavengers or EOP scavengers) can be found in Research Disclosure 37254, Part 7 (1995), p. 292, in Research Disclosure 37038, Part III (1995), p. 84, in Research Disclosure 38957, Part X. D (1996), p. 621 et seq and in DE 196 34 702 and DE 197 14 614.

The photographic material may further include UV absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, anti-oxidants, D _min dyes, plasticizers (latices), biocides and additives to improve coupler and dye stability, to reduce color fog and to reduce yellowing and other things. Suitable compounds are found in Research Disclosure 37254, Part 8 (1995), p. 292, Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 et seq. And Re Disclosure 38957, Parts VI, VIII, IX and X (1996), pp. 607 and 610 et seq.

The layers of color photographic materials are usually cured, i. h., that used binders, preferably gelatin, by suitable chemical Networked process.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), P. 294, Research Disclosure 37038, Part XII (1995), p. 86, and Research Disclosure 38957, Part II.B (1996), p. 599.

After imagewise exposure, color photographic materials become their character processed according to different methods. Details of the Ver Driven and required chemicals are described in Research Disclosure 37254, Part 10 (1995), p. 294, in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95 ff and in Research Disclosure 38957, parts XVIII, XIX and XX (1996), p. 630 et seq published together with exemplary materials.

Examples example 1

A color photographic recording material suitable for a high-speed processing was prepared by applying the following layers in the order indicated on a backing of polyethylene coated paper on both sides. The quantities are in each case based on 1 m ² . For silver halide application, the appropriate amounts of AgNO ₃ are added.

Layer structure 1

Layer 1:
(Substrate layer)
0.10 g of gelatin
Layer 2:
(blue-sensitive layer)
blue-sensitive silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average grain diameter 0.75 μm) from 0.4 g AgNO ₃

, spectrally sensitized with 0.6 mg of compound III-6
1.25 g of gelatin
0.50 g yellow coupler GB-1
0.30 g tricresyl phosphate (TKP)
0.10 g stabilizer ST-1
Layer 3:
(Intermediate layer)
0.10 g of gelatin
0.06 g of EOP scavenger SC-1
0.06 g EOP scavenger SC-2
0.12 g TKP
Layer 4:
(green-sensitive layer)
green-sensitive silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average grain diameter 0.45 μm) from 0.2 g AgNO ₃

, spectrally sensitized with 0.12 mg of compound GS-1
1.10 g of gelatin
0.05 g of magenta coupler PP-1
0.10 g magenta coupler PP-2
0.15 g stabilizer ST-2
0.20 g Stabilizer ST-3
0.40 g TKP
Layer 5:
(UV protective layer)
1.05 g of gelatin
0.20 g UV absorber UV-1
0.05 g UV absorber UV-2
0.22 g UV absorber UV-3
0.06 g of EOP scavenger SC-1
0.06 g EOP scavenger SC-2
0.25 g TKP
Layer 6:
(red-sensitive layer)
red-sensitive silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average grain diameter 0.48 μm) of 0.28 g AgNO ₃

, spectrally sensitized with 0.04 mg of compound N-1 and stabilized with 0.56 mg of stabilizer ST-4
1.00 g of gelatin
0.40 g cyan coupler BG-1
0.40 g TKP
Layer 7:
(UV protective layer)
1.05 g of gelatin
0.20 g UV absorber UV-1
0.05 g UV absorber UV-2
0.22 g UV absorber UV-3
0.15 g TKP
Layer 8:
(Protective layer)
0.90 g of gelatin
0.05 g whitener W-1
0.07 g of polyvinylpyrrolidone
1.20 ml of silicone oil
2.50 mg polymethylmethacrylate spacer, mean particle size 0.8 μm
0.30 g instant hardener H-1

Layer structure 2

Layer structure 2 differs from layer structure 1 only in layer 6.
Layer 6:
(red-sensitive layer)
red-sensitive silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average grain diameter 0.48 μm) of 0.20 g AgNO ₃ , spectrally sensitized with 0.03 mg of compound IV-1 and stabilized with 0 , 4 mg stabilizer ST-4
1.00 g of gelatin
0.30 g of cyan coupler I-1
0.40 g TKP

Layer structure 3

Layer structure 3 differs from layer structure 1 only in layer 2.
Layer 2:
(blue-sensitive layer)
blue-sensitive silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, mean grain diameter 0.75 μm) of 0.40 g of AgNO ₃ spectrally sensitized with 0.6 mg of Compound III-6; Addition of a red-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average diameter 0.65 μm) from 0.02 g AgNO ₃ , spectrally sensitized with 0.005 mg of the compound IV-1 and stabilized with 0 , 05 mg ST-4
1.25 g of gelatin
0.50 g yellow coupler GB-1
0.10 g stabilizer ST-1
0.30 g TKP

Layer structure 4

Layer structure 4 differs from layer structure 2 only in layer 2.
Layer 2:
(blue-sensitive layer)
blue-sensitive silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average grain diameter 0.48 μm) of 0.20 g AgNO ₃ , spectrally sensitized with 0.6 mg of Compound III-6; Addition of a red-sensitive silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average diameter 0.65 μm) of 0.05 g AgNO ₃ , spectrally sensitized with 0.01 mg of compound IV-1 and stabilized with 0.1 mg ST-4
1.25 g of gelatin
0.05 g yellow coupler GB-1
0.30 g TKP
0.10 g stabilizer ST-1

Layer structure 5

Layer structure 5 differs from layer structure 2 only in layer 4.
Layer 4:
(green-sensitive layer)
green-sensitive silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average grain diameter 0.45 μm) of 0.2 g AgNO ₃ , spectrally sensitized with 0.12 mg of compound GS-1
1.10 g of gelatin
0.15 g purple couplet PP-3
0.15 g stabilizer ST-2
0.20 g Stabilizer ST-3
0.4 g TKP

Layer structure 6

Layer structure 6 differs from layer structure 5 only in layer 2.
Layer 2:
(blue-sensitive layer)
blue-sensitive silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, mean grain diameter 0.75 μm) of 0.05 g AgNO ₃ , spectrally sensitized with 0.6 mg of Compound III-6; Addition of a red-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, mean grain diameter 0.65 microns) from 0.05 g of AgNO ₃ , spectrally sensitized with 0.01 mg of compound IV-1 and stabilized with 0.1 mg ST-4
1.25 g of gelatin
0.50 g yellow coupler GB-1
0.30 g TKP
0.10 g stabilizer ST-1

Example 1 uses the following compounds:

processing

A negative with a shot of the MacBeth color chart comes with a standard one Printer exposed on the samples; The filtering is chosen so that the Gray field N5 of the MacBeth board in copy neutral gray with density 0.7 again is given. Processing was performed as described below in process AP94 (Agfa). Then color swatches # 18 (teal), # 6 (bluish tint Green), # 2 (light skin) and # 1 (dark skin) of the copy (Gretag SPM 100-II) and the respective difference ΔE {color difference in the CieLab system between Original and print}.  

a) Color developer - 45 s - 35 ° C

triethanolamine 9.0 g N, N-diethyl 4.0 g diethylene glycol 0.05 g 3-methyl-4-amino-N-ethyl-N-methanesulfonamidoethyl-aniline sulfate 5.0 g potassium 0.2 g triethylene 0.05 g potassium carbonate 22 g potassium hydroxide 0.4 g Ethylenediaminetetraacetic acid disodium salt 2.2 g potassium chloride 2.5 g 1,2-dihydroxybenzene-3,4,6-trisulfonsäuretrinatriumsalz 0.3 g Fill in AL = L <with water to 1 000 ml; pH 10.0

b) Bleach-fix bath - 45 s - 35 ° C

ammonium 75 g sodium bisulfite 13.5 g ammonium acetate 2.0 g Ethylenediaminetetraacetic acid (ferric ammonium salt) 57 g Ammonia 25% 9.5 g Fill in AL = L <with vinegar to 1 000 ml; pH 5.5

c) watering - 2 min - 33 ° C

d) drying

It can be seen from the table that by using a pyrrolo [1,2-b] - 1,2,4-triazole cyan coupler caused deterioration in color rendering at # 18 is significantly improved by the inventive measure. in the Range of # 6 and in the area of skin tones is also an improvement too recognize.

Claims (5)

A color photographic copy material comprising at least one red-sensitive, at least one cyan coupler-containing, at least one green-sensitive, at least one magenta coupler-containing and at least one blue-sensitive, at least one yellow coupler-containing silver halide emulsion layer containing at least one pyrrolo [1,2-b] -1,2 , 4-triazo cyan coupler of the formula (I)
wherein
R _{1 is} hydrogen or a substituent,
X is a hydrogen atom or a leaving group and
Y OR ₂ or
mean, where
R2
or alkyl,
R _{3 is} alkyl
R _{4 is} hydrogen or R ₃ ;
R ₅ , R ₆ , R ₈ and R _{9 are} hydrogen or a substituent,
R _{7 is} a substituent and
Z is the remaining non-metallic members of a 3- to 8-membered ring, where Z may be further substituted,
in the at least one red-sensitive layer, characterized in that the at least one blue-sensitive layer is assigned a rotsensi bilisierte silver halide emulsion which provides over the entire density range at red exposure a yellow density amount corresponding to 1 to 15% of Blaugründichte 2. Color photographic copy material according to claim 1, characterized in that it contains in the at least one blue-sensitive layer a Blausensibi initiator of the formula II:
wherein
R ₁₁ to R ₁₃ and R ₁₆ to R _{18 are} H, alkyl, alkoxy, halogen, 2-thienyl, 3-thienyl, 1-pyrolyl, 2-pyrrolyl, phenyl, 1-indolyl, 2-furanyl, 3-furanyl or carbazolyl .
R ₁₄ and R _{15 are} alkyl, sulfoalkyl, carboxyalkyl,
- (CH ₂ ) _n SO ₂ N ^θ -COR ₁₉ , - (CH ₂ ) _n SO ₂ N ^θ SO ₂ R ₁₉ ,
- (CH ₂ ) _n CON ^θ SO ₂ R ₁₉ or - (CH ₂ ) _n CON ^θ COR ₁₉ ,
X ₁ and X ₂ O, S. Se, NR ₂₀ ,
M a counterion,
n a number 2 to 4 and
R ₁₉ and R _{20 are} C ₁ -C ₄ -alkyl or
R ₁₁ and R ₁₂ and R ₁₂ and R ₁₃ , R ₁₆ and R ₁₇ and R ₁₇ and R _{18 are} the remaining members of a fused benzene or naphthalene ring. 3. A color photographic printing material according to claim 1, characterized in that the Rotsensibilisator in the at least one blue-sensitive layer of formula IV corresponds
wherein
X ₁ and X _{2 are} O, S, Se or NR ₂₀
R ₁₁ to R ₁₃ and R ₁₆ to R _{18 are} H, alkyl, alkoxy, halogen, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, phenyl, 1-indolyl, 2-furanyl, 3-furanyl or carbazolyl .
R ₁₄ and R _{15 are} alkyl, sulfoalkyl, carboxyalkyl,
- (CH ₂ ) _n SO ₂ N ^θ COR ₁₉ , - (CH ₂ ) _n SO ₂ N ^θ SO ₂ R ₁₉ ,
- (CH ₂ ) _n CON ^θ SO ₂ R ₁₉ or - (CH ₂ ) _n CON ^θ COR ₁₉ ,
M a counterion,
n is a number 2 to 4,
R ₁₉ and R _{20 are} C ₁ -C ₄ -alkyl,
R _{26 is} H, alkyl, halogen, dialkylamino or alkylthio and
R ₂₇ and R _{28 are} H or alkyl or
R ₁₁ and R ₁₂ and R ₁₂ and R ₁₃ , R ₁₆ and R ₁₇ and R ₁₇ and R _{18 are} the remaining members of a fused benzene or naphthalene ring. 4. color photographic copy material according to claim 1, characterized in that it contains in the at least one blue-sensitive layer, a blue sensitizer of the formula III:
wherein
R ₂₁ and R _{23 are} hydrogen
R _{22 is} halogen, in particular chlorine or fluorine, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-furanyl, 1-indolyl or phenyl or
R ₂₁ and R ₂₂ together or R ₂₂ and R ₂₃ together form the remaining members of a fused benzene or naphthalene ring,
R _{24 is} hydrogen,
R _{25 is} halogen, in particular chlorine or fluorine, phenyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-furanyl, 1-indolyl or
R ₂₄ and R ₂₅ together form the remaining members of a fused benzene or naphthalene ring,
X ₃ S or O
M is a counterion, in particular triethylammonium and
l and m represent a number 2 to 4. 5. The color photographic printing material according to claim 1, characterized in that the red sensitizer in the at least one blue-sensitive layer corresponds to the formula V:
wherein
R ₁₄ and R _{15 are} alkyl, sulfoalkyl, carboxyalkyl,
- (CH ₂ ) _n SO ₂ N ^θ -COR ₁₉ , - (CH ₂ ) _n SO ₂ N ^θ SO ₂ R ₁₉ ,
- (CH ₂ ) _n CON ^θ SO ₂ R ₁₉ or - (CH ₂ ) _n CON ^θ COR ₁₉ ,
R ₂₉ to R ₃₄ are each independently H, CH ₃ , OCH ₃ , Cl, 1-pyrrolyl, 1-indolyl, 2-thienyl, 3-thienyl, 3-furanyl, 3-furanyl, N-carbazolyl, phenyl or R ₂₉ and R ₃₀ , or R ₃₀ and R ₃₁ , and R ₃₂ and R ₃₃ , or R ₃₃ and R ₃₄ together form the remaining members of a benzo, 1,2-naphtho or 2,3-Naphthoringes
X ₃ O or S
M a counterion and
R _{19 is} C ₁ to C ₄ alkyl.