DE1158835B - Photographic material suitable for color photography - Google Patents

Description

GERMAN

PATENT OFFICE

3 22962 IXa / 57b

REGISTRATION DATE: JANUARY 4, 1963

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: DECEMBER 5, 1963

The invention relates to a color photographic material whose spectrally (optically) sensitized silver halide photographic layer contains certain anthraquinone dyes.

In U.S. Patents 2,640,776 and 2,912,329, certain are spectrally sensitive making known dyes, which are particularly useful in combination with photographic silver halide emulsions which contain color couplers. This has less of an influence on the Color couplers instead of the indicated sensitizing dyes. This seems to be its cause in having a displacement of sensitizing dye from the silver halide grains is avoided to a certain extent by a color coupler.

It has now been shown according to the invention that certain combinations or mixtures of sensitizing (sensitizing) dyes and anthraquinone dyes, of which each of these two groups of substances is explained in more detail below, in the case of photographic silver halide emulsion layers actually give substantially stable sensitivity for a longer period of time.

For a better understanding of the nature and spirit of the invention, reference is made to the following description Reference is made in connection with the drawings.

Figures 1 through 23 show spectral sensitivity curves reproduced from wedge spectrograms of gelatin silver iodobromide emulsions matched with the various respectively indicated Carbocyanine dyes have been sensitized.

In practicing the invention, a silver halide emulsion containing an anthraquinone image dye is used contains, which has developing properties in relation to exposed halogen silver, with at least one carbocyanine dye of the formula

For color photography
suitable photographic material

Applicant:

International Polaroid Corporation,
Jersey City, NJ (V. St. A.)

Representative: Dr.-Ing. F. Wuesthöff, Dipl.-Ing. G. Pulse and Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Pechmann, patent attorneys, Munich 9, Schweigerstr. 2

Claimed priority:
V. St. v. America January 4, 1962 (No. 164 314)

Vivian May Walworth, Concord, Mass. (V. St. A.), has been named as the inventor

C C

ζ "~ cc & ζ

NGN
(CH ₂ ) _m (CH ₂ ) _m

RR ¹

sensitized. In the formula, G denotes a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m a positive integer from 1 to 4, η the number 0 or 1; R represents a hydrogen atom, a carboxyl or sulfonic acid group, X represents an anion; R ¹ denotes a carboxyl or sulfonic acid group when M = I, and a COo ⁰ or SOe ⁰ group when η = 0. Z denotes the atoms that are necessary for a naphthothiazole, benzothiazole, benzoselenazole, Naphthoselenazole, benzimidazole or benzooxazole rows to complete identical or mismatched heterocyclic ring system.

The heterocyclic ring systems of the formula can contain the substituents which are found in cyanine dyes are common, e.g. B. alkyl, alkoxy, aryl, benzyl, phenyl, naphthyl, chlorine, bromine, amino, Hydroxyl, cyano groups and the like.

Examples of the above-mentioned heterocyclic ring systems which can be used for the purposes of the invention suitable are 6-methylbenzothiazole, 5-ethoxy-6-methylbenzothiazole, 5-methylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethylbenzothiazole, 6-ethylbenzothiazole, 5 - ethoxybenzothiazole, 6 - ethoxy

309 767/325

benzothiazole, 6-phenylbenzothiazole, 5,6-dichlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 5-bromobenzotbiazole, 5-phenylbenzothiazole, 5-acetamidobenzothiazole, 5-iodobenzothiazole, 5-dimethylaminobenzothiazole, 5-chlorobenzoselenazole, / MSFaphthothiazole, / J-naphthoselenazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, benzoxazole, 5-chlorobenzoxazole, 5-phenylbenzoxazole, /? - naphthoxazole, etc. Groups. ίο

The anion X is the anionic acid residue found in cyanine dyes are common, ζ. B. chloride, bromide, iodide, methyl sulfate, ethyl sulfate, p-toluenesulfonate, benzenesulfonate, Acetate, propionate, cyanate, perchlorate and the like.

For the purposes of the invention carbocyanine sensitizing dyes are preferred compounds in which each η is a positive integer of 2, and especially where η - 0, R 'is a -CO represents a carboxylic acid group and R ₂ ⁰ group.

Carbocyanine sensitizing dyes of general Formula possessed by heterocyclic benzoxazole and benzimidazole ring systems generally used to sensitize the silver halide emulsions in the green range of the spectrum, while those which contain heterocyclic benzothiazole, naphthothiazole, Possess benzoselenazole or naphthoselenazole ring systems, are generally used, to give sensitization of the silver halide emulsion in the red region of the spectrum.

Certain of the preferred carboxyanine sensitizing dyes can be represented by the formula invention are suitable next to the ones mentioned above Substances the following:

C2H5 H

C ₂ H ₅

NCCN

\ s \ s \ /

ccc

/ I \ e

NHN

(CH ₂ ) ₄
SO ₃ H

(CHa) ₄

SOf

Anhydro-1, r-diethyl-3,3'-bis - ((3-suh ^o obutyl) -S ^^ 'jo ^ etrachlorobenzimidazole carbocyanine hydroxide

C ₂ H ₅ H

C ₂ H ₅

NCCN CCC

/ I

N H .N

(CHa) ₂
CO ₂ H

COf

Anhydro-3,3'-bis (/ 3-carboxyethyl> 1,1 '-diethyl-Sjo ^ ö'-tetrachlorobenzmidazole carbocyanine hydroxide

40

45

wherein each X is a selenium, oxygen, a nitrogen substituted with lower alkyl groups or is a sulfur atom. The substituents Y can be identical or different and can be preferably a lower alkyl group, a lower alkoxy group, a halogen atom such as chlorine or Bromine, a phenyl group or a hydrogen atom, which are located on the benzene nucleus in positions 5, 5 ', 6 and 6 'are located. Here, two adjacent substituents Y together give those hydrocarbon atoms which are necessary for a benzene ring. So that means a benzene ring in the 4-5, 5-6, 4'-5 'and 5'-6' positions is condensed. G means a hydrogen atom, a methyl or Ethyl group.

Examples of typical carbocyanine sensitizing dyes, which are used for the purposes of

y ^ yyO ^ 1,1 '-diethylbenzimidazole carbocyanine hydroxide

C ₂ H ₅

I I I I

NCCN

C ₂ H ₅

(CHa) ₄
SO ₃ H

(CH ₂ ) ₄

SO ₃ "

yy (o-sulfobutylj-benzimidazole carbocyanine hydroxide

CO ₂ ⁰

Anhydro-3,3'-bis ($ - rarboxyethyl) -5,5'-bis-phenyl-9-ethyoxacarbocyanine hydroxide

(CH ₂ ) ₂ CO ₂ ⁰

Attachment hydro-3,3'-bis (/ 3-carboxyethyl) selenacarbocyanine hydroxide

C ₂ H ₅ H

C ₂ H ₅

sol ³

Anhydro-1,1'-diethyl-3,3'-bis (o-sulfobutyl) -benzimidazole carbocyanine hydroxide

25th

sees

X / -X / X /

CCC

CaH ₅

Anhydro-5,5'-dichloro-9-ethyl-3,3'-bis (i? -Sulfoethyl) -thiacarbocyanine hydroxide

35

eof

Anhydro-3,3'-bis - (/? - carboxyethyl) -1.1 '-diethylbenzimidazole carbocyanine hydroxide

45

sees

CCC

/ I \ _@ / X

N CH ₃ N

(CH ₂ );
CO ₂ H

CO ₂

₂ ⁰

Anhydro-S ^ '- bis-ijS-carboxyethyl ^ -methyl-S ^' jojo'-tetrachlorothiacarbocyanine hydroxide

H H

I.
sees

x / x / x /

ccc

Anhydro-5,5'-dichloro-3,3'-bis-G? -Sulfoethyl) -thiacarbocyanine hydroxide

55

6o

Se C C X- / X Se \ @ / / \ / X / / \ N
I. I. I ^c C C (CH V \ / I. N
ι C ₂ H ₅ / (CHa) ₂ CO ₂ H Λ ₂ ) a CO ₂ ⁰

Anhydro-3,3'-bis- (i? -Carboxyethyl) -9-ethylselenacarbocyanine hydroxide

CO ₂ H

^ yC / yy
thiaselenacarbocyanine bromide

S C C

CCC

CH ₃

4,5-Benzo-3-ethyl-3 '- (/ 3-carboxyethyl) -5'-chloro-9-methylthiacarbocyanine iodide

The preparation and usual use of cyanine sensitizing dyes of the above Species is described e.g. B. U.S. Patents 2,213,995, 2,238,231, 2,503,776, 2 640 776, 2 912 329 and 2 945 763.

For the manufacture of photographic materials for subtractive color photography Various processes can be carried out using the new combinations according to the invention use. One such known method makes use of a photosensitive one Layer containing at least two groups of selectively sensitized very small photosensitive Contains elements arranged in the form of a light-sensitive grid or grid. In such an embodiment, each of the very small photosensitive emulsions are color image forming Components assigned in or behind the photosensitive emulsion section. In general, a suitable photosensitive filter contains very small red-sensitive emulsion units, very small green-sensitive emulsion units and very small blue-sensitive emulsion units, side by side, arranged directly next to one another in the form of a grid pattern are and cyan image-forming, purple image-forming and yellow images, respectively forming components are assigned.

Another known method makes use of a uniform multilayer Material in which at least two selective sensitized photosensitive layers on a single one Bearings lie on top of each other. A suitable arrangement of this type comprises a carrier having a red-sensitive emulsion layer, a green-sensitive and a blue-sensitive emulsion layer, with these emulsions being assigned components, the corresponding blue-green, purple and give yellow pictures.

According to the invention, one of the present contains sensitized with the relevant carbocyanine dyes Emulsion units as a color image-forming component an anthraquinone dye, which is a Ability to develop exposed silver halide and its typical properties are described in more detail below.

The last-mentioned anthraquinone dye can be used in the emulsion layer, e.g. B. in the form of particles or, preferably, in the form of a coating or layer of the dye behind the corresponding light-sensitive Emuiao sion unit. In this preferred embodiment the layer of dye can be applied from a coating solution containing e.g. B. about Contains 0.5 to 8 percent by weight of the dye in a colloidal binder such as gelatin is dispersed or in a synthetic polymeric matrix, such as cellulose acetate hydrogen phthalate, is resolved.

In preparing silver halide emulsions according to the invention, the sensitizing dyes can be used are added to the emulsion according to the usual methods, d. i.e., by having a Solution of the sensitizing dye in a suitable solvent is added to the emulsions. Suitable solvents are e.g. B. water, me-

ethanol, ethanol, pyridine, acetone or mixtures thereof. The amount of used. Sensitizing dye may be desired depending on the properties of the silver halide emulsion concerned Results and the like can be varied. Generally there is about 5 to 100 mg of dye per Liters of the silver halide emulsion are sufficient to obtain maximum sensitization.

The image-forming dyes can also be incorporated into the emulsions in a customary manner.

The invention is primarily directed to the gelatin-silver halide developer emulsions normally used, z. B. gelatin-silver chloride, -chlorobromide, -chlorobromoiodide, -iodochloride, -bromide and -bromoiodide developing emulsions. These normally used silver halide developing emulsions are emulsions that produce "surface grain" latent images. Man can, however, also use silver halide emulsions for the purposes of the invention, the latent Form images primarily within the silver halide grains. The preferred silver halide emulsions contain a silver iodobromide emulsion. It should be noted that silver halide emulsions can be used advantageously with changing halide concentration.

If desired, suitable antifoggants, hardeners, wetting agents, retarders, accelerators, Protectants, coating aids, chemical sensitizers and / or stabilizers be incorporated into the preparation of the emulsions. The emulsions can be in commonly applied as coatings on various types of rigid or flexible

Carriers, ζ. Β. on glass, paper, metal, films of polymeric substances, both synthetic and synthetic also those which are derived from naturally occurring products and the like. It is known that in general, numerous anthraquinone compounds show desensitizing effects, namely in both sensitized and unsensitized silver halide photographic emulsions. Such effects are the result of various conditions and are at least partially dependent of the circumstances and the components involved.

Several patents describe anthraquinone compounds which as such have a sufficient desensitizing effect to be used as photographic desensitizers (compare, for example, U.S. Patent 1753 911, in which anthraquinone carboxylic acids and sulfonic acids, e.g. -Nitroanthraquinone-2-carboxylate and sodium anthraquinone-2-sulfonate, are described as desensitizers). In U.S. Pat. No. 2,131,742, taurides of anthraquinone carboxylic acids and sulfonic acids have been described as desensitizers, e.g. B. anthraquinone-2-sulfo-tauride, anthraquinone-2-carbonyl-tauride, anthraquinone-l-sulfo-methyl-tauride, anthraquinone - 2 - sulfo - methyl - tauride, anthraquinone-2-chloro-3-sulfo-methyl- tauride, anthraquinone-2,6-disulf ο - methyl - tauride, anthraquinone - 2 - carbonyl - methyl-tauride and anthraquinone ^ -chlor-S-carbonylmethyl-tauride. U.S. Patent 2132169 explains the sarcosides of anthraquinone carbonic and sulfonic acid as desensitizers, e.g. B. anthraquinone-2-sulfosarcoside, anthraquinone-2-carboxylic sarcoside and anthraquinone-2-sulfophenylglycide. U.S. Patent 2,172,192 describes substituted ethers and thioethers of anthraquinone as desensitizers, e.g. B. sodium anthraquinone-2-phenoxy-2 ', 4'-disulfonate, sodium anthraquinone-2-phenoxy-4'-mono-sulfo-3-sulfonate, sodium anthraquinone-2-thioethane- ω -sulfo-3-sulfonate, sodium anthraquinone-2 -thioethane-to-sulfonate and sodium anthraquinone-2-thiophenol-4'-mono-sulfo-3-sulfonate.

In addition, many anthraquinone dyes have been shown to reduce the sensitizing effects of affect various optically sensitizing dyes, possibly by desorption of Sensitizing dye from the silver halide crystals of the silver halide emulsion as a result of a preferential absorption of anthraquinone dye on the silver halide crystals.

It has now surprisingly been found that the above-mentioned photographic desensitizing effects of anthraquinone compounds can be substantially reduced, if not eliminated, by using the above Sensitizing dyes in association with the desired anthraquinone compounds.

As a result of this knowledge, numerous anthraquinone dyes can be safely and effectively used as image dyes in photographic processes, preferably around cyan and magenta images as well as photographic developer substances.

This finding is particularly valuable for use in diffusion transfer photographic processes and for products using anthraquinone compounds which have both the properties of a dye and a photographic silver halide developing agent. Such processes and products using anthraquinone dyes which are both image dyes and silver halide developing agents are described in U.S. Patent 2,983,606.

In particular, it has been shown that the desensitization properties such image dyes can be severely limited by applying the guidelines of the invention.

Examples of the above-mentioned anthraquinone image dyes are as follows: N-monobenzoyl- 1,4-bis (β- [3 ', 4'-dihydroxyphenyl] -ethylamino) -anthraquinone and N - monobenzoyl -1,4 - bis - (β - [2 ', 5' - dihydroxyphenyl] - ethylamino) - anthraquinone (U.S. Patent 2,983,605) 1,4-bis (2 ', 5'-dihydroxyanilino) anthraquinone and 1,4-bis (jS- [2 ', 5'-dihydroxyphenyl] propylamino) - anthraquinone (U.S. Patent 2,983,606) 1,4-diamino-N - (, 3-2', 5'-dihydroxyphenyl-α - methylethyl) - 2,3 - anthraquinone - dicarboximide and 1 - amino - 4 - hydroxy - N - (β - 2 ', 5' - dihydroxyphenyl-α - methylethyl) - 2,3 - anthraquinone - dicaroximide, 4 - (l ', 5' - bis - [ 2 ", 5" - dihydroxyphenyl] - 3 "- pentyl) -amino-1-hydroxy-anthraquinone and l, 4-bis- (l ', 5'-bis- [2", 5 "- dihydroxyphenyl] - 3' - pentyl) - amino - anthraquinone, 1-amino ^ -anilino ^ -hydroquinonylsulfamylanthraquinone, 1,5 - bis - hydroquinonylcarbamylmethylamino - 4,8 - dihydroxyanthraquinone, 1 - aminoethylamino - 4 - hydroquinonylcarbamylmethylaminoethyl anthraquinone, 1-amino-4- (p- [N- (hydroquinonylcarbamylmethyl) -amino] -phenylamino) -2-anthraquinonesulfonic acid - sodium salt, 1,4 - bis-

(p-PST- (hydroquinoxylcarbamylmethyl) -amino] -phenylamino) -anthraquinone and 1,4-bis-hydroquinonylcarbamylmethylaminoanthraquinone, 1,4-bis- (a-methyl- β -hydroquinonyl-ethylamino) -anthraquinone, 1,4-bis - (α - methyl - β - hydroquinonyl - ethylamino) -5,8 - dihydroxyanthraquinone, 1 - (α - hydroxymethylpropylamino) - 4 - (a - methyl - β - hydroquinonyl - ethylamino) - anthraquinone, 1 - (α - hydroxymethyl - propylamino) -4- (a-methyl- | S-hydroquinonyl-methylamino) -5,8-dihydroxyanthraquinone, l-hydroxy-4- (a-methylhydroquinonyl - ethylamino) - anthraquinone, 1,4 - bis (γ - hydroquinonyl - a - methyl propylamino) - 5.8 - dihydroxyanthraquinone, 1,4 - bis - (α - methyl - γ - hydroquinonylpropylamino) anthraquinone, 1,5-bis-hydroquinonyl - methylamino - anthraquinone, 1,4 - bis - hydroquinonyl-methylaminoanthraquinone, l, 4-bis- (a-methyl- / S-hydroquinonyl-ethylamino) -6,7-dichloroanthraquinone, 1 - (α - methyl - β - hydroquinonyl - ethylamino) -4 - (α - ethyl - β - hydroquinonyl - ethylamino) - ant hrachinon, 1 - (a-methyl-ß-hydroquinonyl-ethylamino) -4 - (α - ethyl - β - hydroquinonyl - ethylamino) - 5,8 - dihydroxyanthraquinone, 1,4 - bis - (α - methyl - 2 ', 5 '- dihydroxybenzylamino) anthraquinone, 1,4-bis- (a-methyl- ß - hydroquinonyl - ethylamino) - 5.8 - bis - benzosulfonamidoanthraquinone, 1,4- bis - (<z - methyl - β - hydroquinonyl- ethylamino) -5-hydroxy-8-aminoanthraquinone, 1 - (α - hydroxymethyl - propylamino) - 4 - (α - methyl- ß - hydroquinonyl - ethylamino) - 5 - hydroxyanthraquinone, 1,4-bis - (ß -hydroquinonyl - ethylamino) anthraquinone, 1 - [p - (^ - hydroquinonylethyl) phenylaminolanthraquinone, 1 - (α - hydroxymethyl - propylamino) 4 - [ß - (4 '- methyl - 2', 5 '- dihydroxyphenyl) - a - methylethylamino ] - anthraquinone, 1 - ethylamino - 4 - [ β - (3 ', 4' - dihydroxyphenyl) - ethylamino] - anthraquinone, 1 - chlorine - 4 - (ß - hydroquinonyl - ethylamino) - anthra-

309 767/325

quinone, 1-hydroxy-4- [/ 3- (3 ', 4'-dihydroxyphenyl) -ethylamino] -anthraquinone, 1-chloro-5 - (/ miydroquinonyl-ethylamino) -anthraquinone, 1,4-bis- [8 - (3 ', 4'-dihydroxyphenyl) - ethylamino] - 5,8 - dihydroxyanthraquinone, 1,8-bis - [^ - (3', 4'-dihydroxyphenyl) -ethylamino] -anthraquinone, l- [jS- ( 3 ', 4'-dihydroxyphenyl) -. ethylamino] -anthraquinone, l - ^ - hydroquinonyl-ethylaminoanthraquinone, 1,5-bis- iö- (3 ', 4'-dihydroxyphenyl) - ethylamino] - anthraquinone, 1,5 - bis - (β - hydroquinonylethylamino) - anthraquinone, 1,8-bis- (JS-hydroquinonyl-ethylamino) -anthraquinone, 1- [j8- (3 ', 4'-dihydroxyphenyl) -ethylamino] -5-nitroanthraquinone, 1,5-bis- (a-methyl - ^ - hydroquinonyl-ethylamino) -anthraquinone, 1 - (| S-hydroxyethylamino) -4 - (/? - hydroquinonyl - ethylamino) - anthraquinone 1,4 - bis - [, S- (3 ', 4'-dihydroxyphenyl) -äthylamino] -anthraquinone, 1 - (β - hydroxyethylamino) - 4 - (α - methyl -β- hydroquinonyl - ethylamino) - 5.8 - dihydroxyanthraquinone, 1,4-bis (o - ethyl - β - hydroquinonyl - ethylamino ) - anthraquinone, 1 - methylamino - 4 - (/ 3 - hydroquinonylethylamino) anthraquinone and l - /? - hydroxyethylamino-4- (a-methyl- _j S-hydroquinonylethylamino) anthraquinone, 4,8-bis- ( 2 ^/ , 5'-dihydroxyanilino) -anthrarufin, 4- (2 ', 5'-dihydroxyanilino) -1-hydroxy-anthraquinone, 1,4-bis- (2', 5'-dihydroxyanilino) -anthraquinone and 8-chlo r-4- (2 ', 5'-dihydroxyanilino) -anthrarufin and 1- β- aminoethylamino-4- | S- (homogentisarnido) -ethylaminoanthraquinone, 1,4 - bis - β - (homogentisamido) - ethylaminoanthraquinone, 5 - amino - 4,8 - dihydroxy-1-homogentisamido-anthraquinone, 1,5-bishomogentisamido ^ S-dihydroxyanthraquinone, 1,5-bishomogentisamido-anthraquinone, 1,4-bis-homogentisamido-anthraquinone, 1 - homogentisamidoanthraquinone and 5,8-dimethyl -1,5-bis (N-methylhomogeneous isamido) -anthraquinone.

Particularly preferred anthraquinone dyes of the type mentioned above are compounds which have one or more amino groups in the α-position in the anthraquinone nucleus.

The invention is illustrated in more detail in connection with the following examples, which represent typical possible applications within the scope of the invention.

The carbocyanine sensitizing dye of Fig. 4, Anhydro-S ^ '- bis-ijS-carboxyethyO-S ^' - dichloro-9-methyl-thia-carbocyanine-hydroxide was prepared by dissolving 101 g of S-chloro-methyl-3 - (j8-carboxyethyl) -benzothiazoliumbromid in 100 ml of m-cresol and heated in an oil bath at 8O ⁰ C. to the solution, 121.5 g of triethyl ortho-acetate, and the mixture then heated for 10 minutes. 75.8 g of triethylamine were added to the resulting solution and the mixture was then heated ^{to 85 ° C. for 45 minutes.} The solution was then cooled and mixed with 500 ml of acetone in order to bring about the precipitation of the carbocyanine dye. The precipitated dye was separated, washed first with 3 liters of warm acetone, then with 3 liters of hot water and again with 3 liters of acetone and finally dried.

The dyes thus obtained to be used according to the invention, which are indicated in the drawing, were made in accordance with the previous example, with the Reaction mixtures were used, which are given in the following table.

figure Sensitizing dye 10.5 g
7.3 g
50 ml Components of the reaction mixture 1 Anhydro-3,3'-bis - (^ - carboxy-ethyl) -9-methyl-
thiacarbocyanine 5.0 g
4.6 g
50 ml 2-methyl-benzothiazole-ß-carboxy-
ethyl iodide
Triethyl orthoacetate and
anhydrous pyridine 2 Anhydro-3,3'-bis - (/ 3-carboxyethyl) -9-methyl-
selenium carbocyanine hydroxide 2.5 g
2.2 g
25 ml 2-methylbenzoselenazole / 3-carboxy-
ethobromide
Triethyl orthoacetate and
anhydrous pyridine 3 Anhydro-3,3'-bis (, 8-carboxyethyl) -5,5'-diethoxy-
6,6 ', 9-trimethyl-thiacarbocyanine hydroxide 7.9 g
8.1g
5.0 g
20 ml 2,6-dimethyl-5-ethoxybenzothiazole
jS-carboxyethobromide
Triethyl orthoacetate and
anhydrous pyridine 5 Anhydro-S ^ '- dichloro ^ -methyl-S ^' - bis-C / S-sulfo-
ethyl) thiacarbocyanine hydroxide 101g
100 ml
132 g
75.8 g 5-chloro-2-methyl-3- (| 5-sulfoethyl) -
benzothiazolium bromide
Triethyl ortho acetate
Triethylamine and
m-cresol 6th Anhydro-3,3'-bis - (/? - <^ rboxyäthyr) -5,5'-dichlor-
9-ethylthiacarbocyanine hydroxide 6.5 g
25 ml
8.7 g
7.0 ml 3-0? -Carboxyethyl) -5-chlorine-
2-methyl-benzothiazolium bromide
m-cresol
Triethyl orthopropionate and
Triethylamine 7th Anhydro-SjS'-bis-carboxymethyl-S ^ '- dichloro-
9-ethylthiacarbocyanine hydroxide S-carboxymethyl-S-chloro - ^ - methyl-
benzothiazolium bromide
m-cresol
Triethyl orthopropionate and
Triethylamine

continuation

figure Sensitizing dye Components of the reaction mixture 6.5 g S-carboxymethyl-S-chloro ^ -methyl- 8th Anhydro-S ^ '- bis-carboxymethyl-S ^' - dichloro- benzothiazolium bromide thiacarbocyanine hydroxide 25 ml m-cresol 5.5 ml Triethyl ortho formate and 5.5 ml Triethylamine 2.2 g 2-0S-carboxyethyl) -2-methyl- 9 Anhydro-3,3'-bis - (/ 3-carboxyethyl) -9-methyl- 5-phenyl-benzothiazolium bromide S ^ '- bis-phenyl-thiacarbocyanine-hydroxyd 10 ml m-cresol 3.0 ml Triethyl ortho acetate and 2.8 ml Triethylamine 10.0 g 5-chloro-2-methyl-3 - ((5-sulfobutyl) - 10 Anhydro-5,5'-dichloro-9-methyl-3,3'-bis- benzothiazolium betaine ((5-sulfobutyl) thiacarbocyanine hydroxide 25 ml m-cresol 11.5 ml Triethyl ortho acetate and 8.6 ml Triäthykmjn 10.0 g 5-chloro-2-methyl-3 - (<5-sulfobutyl) - 11 Anhydro-5,5'-dichloro-3,3'-bis (δ-sulfobutyl) - benzothiazolium betaine thiacarbocyanine hydroxide 25 ml m-cresol 10.5 ml Triethyl ortho formate and 8.6 ml Triethylamine 7.29 g S-Co-CarboxybutyO-S-chloro ^ -methyl- 12th Anhydro-S ^ '- bis-Ocarboxybutyty-S ^' - dichlor- benzothiazolium bromide 9-ethylthiacarbocyanine hydroxide 10 ml m-cresol 10.00 ml Triethyl orthopropionate and 5.5 ml Triethylamine 7.02 g 3- (y-carboxypropyl) -5-chloro- 13th Anhydro-S ^ '- bis-iy-carboxypropyD-S ^' - dichlor- 2-methyl-benzothiazolium bromide 9-ethyl-thiacarbocyanine hydroxide 10 ml m-cresol 10.0 ml Triethyl orthopropionate and 5.5 ml Triethylamine 7.29 g 3 - ((5-carboxybutyl) -5-chloro- 14th Anhydro-3,3'-bis - ((5-carboxybutyl) -5,5'-dichloro- 2-methyl-benzothiazolium bromide 9-methylthiacarbocyanine hydroxide 10 ml m-cresol 9.2 ml Triethyl ortho acetate and 5.5 ml Triethylamine 7.02 g 3- (y-carboxypropyl) -5-chloro- 15th Anhydro-3,3'-bis- (γ-carboxypropyl) -5,5'-dichloro- 2-methyl-benzothiazolium bromide 9-methylthiacarbocyanine hydroxide 10 ml m-cresol 9.2 ml Triethyl ortho acetate and 5.5 ml Triethylamine 4.0 g 3 - (/ S-carboxyethyl) -5-methoxy- 16 Anhydro-3,3'-bis (ß-carboxyethyl) - 2-methyl-benzothiazolium bromide S ^ '- dimethoxy - ^ - methyl selenium carbocyanine 5 ml m-cresol hydroxide 5.26 ml Triethyl ortho acetate and 4.0 ml Triethylamine 2.9 g 3 - (/ 5-carboxyethyl) -5-methoxy- 17th Anhydro-S ^ '- bis-dS-carboxyethyl) - 2-methyl-benzoselenazolium S ^ '- dimethoxy-fJ-ethylselenacarbocyanine-
hydroxide 5 ml uromici
m-cresol 3.8 ml Triethyl orthopropionate and 2.7 ml Triethylamine

All dyes indicated in the drawing were in a suitable solvent, such as Water, methanol, pyridine, methanol - pyridine, triethylamine and the like, added to a silver iodobromide emulsion containing 2 to 4 mole percent iodide and a photographic speed of 100 ASA

exhibited. The dyes were added at concentrations of 0.5 to 6 mg / g silver. Common wetting agents, such as saponin, anionic or nonionic surface-active substances, stabilizers, such as benzotriazoles, or substituted triazaindolizines and hardeners such as chrome alum or Aldehyde hardeners, were added in aliquots to the respective sensitized emulsions. The emulsions were then adjusted to a pH of about 6 to 8 on the outer surface an overcoat layer which disperses an anthraquinone dye developer in gelatin, and was on a film pad. The assembly was then dried.

The film units produced in this way were then used to measure the spectral sensitivity in exposed with a wedge spectrograph. The film units were developed after exposure by they were brought into contact with a developer preparation of the following composition:

Water 1860 g

Sodium carboxymethyl cellulose 117 g

Sodium sulfite 78 g

Sodium hydroxide 74.6 g

Sodium thiosulfate 14.5 g

Citric acid 38.5 g

Hydroquinone 52 g

The wedge spectrogram gives the spectral sensitivity for the individual substances indicated in the drawings.

A typical example to explain further details of fabrication and photographic Examination of the film unit with regard to the spectral sensitivity according to Fig. 9 is as follows:

2 ml of a saturated methanol solution of anhydro-S ^ '- bis-OS-carboxyäthyrj-S ^' - dichloro-9-äthylthiacarbocyanin hydroxide was added at 38 ⁰ C to 25 g of a silver iodobromide emulsion optionally containing 1.1 g of silver. The mixture was stirred thoroughly for 5 to 10 minutes. The resulting sensitized emulsion was admixed with 1.5 ml of 10% strength saponin, 1.5 ml of 10% strength sodium N-methyl-N-oleylaurate and 0.4 ml of 1% strength acetic acid with constant stirring. The resulting emulsion was applied to the outer surface of an anthraquinone image dye layer containing 91 mg / 0.09 m ^{2 of} gelatin with 80 mg / 0.09 m ^{2 of} 1,4-bis (a - methyl - β - hydroquinonylethylamino) - 5.8 - dihydroxyanthraquinone and was on a gelatin coated cellulose triacetate film backing.

This product was then exposed in a wedge spectrograph and developed by turning it into Was brought into contact with the above preparation. The spectrogram showed that spectral sensitivity, which is indicated in the drawing.

The carbocyanine dyes of FIGS. 2, 4, 10, 11, 18, 19 and 20 were tested with 1,4-bis- (α-methyl - /? - hydroquinonyl-ethylamino) -anthraquinone. The carbocyanine dyes of Figs. 1, 3, 5, 6, 7, 8, 9, 12, 13, 14, 15, 16 and 17 were tested with 1,4-bis (α-methyl- β -hydroquinonyl-ethylamino) -5,8-dihydroxyanthraquinone.

It should be noted that the carbocyanine dyes of Figures 18, 19 and 20 do not have acid substituents of the Have dyes according to the general formula. However, the dye of Fig. 19 corresponds to that The dye of Fig. 2 and the dye of Fig. 20 correspond to the dyes of Figs. 4 and 5 except for the above-mentioned substituents. Testing the spectral sensitivity of the corresponding dyes and the other dyes closely related thereto, given as examples, clearly show the considerable stability achieved with the present invention.

Figures 21, 22 and 23 show the spectral sensitivity characteristics of the carbocyanine dyes according to FIGS. 18, 19 and 20 in the absence of the sensitization caused by the presence of the indicated anthraquinone image dyes is imparted.

Claims (4)

PATENT CLAIMS: 1. A photographic material suitable for color photography, containing a light-sensitive silver halide emulsion and an anthraquinone image dye which has developing properties with respect to exposed silver halide, characterized in that the silver halide emulsion contains a carbocyanine dye of the formula H
C. Z C (CH ₂ ) _m
R. H
C. C C® (CH ₂ ) _m R ¹ contains, in which G is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, m is a positive integer from 1 to 4 and η is the number 0 or 1 and R is a hydrogen atom, a carboxyl or sulfonic acid group, X is an anion, R ¹ denotes a carboxyl or sulfonic acid group when η = 1, or a CO ₂ ³ or SO3 ⁰ group when η = 0, and Z represents the atoms that are necessary to form a heterocyclic ring system of the benzothiazoles benzoselenazoles naphthothiazole, To complete the naphthoselenazole, benzimidazole or benzooxazole series. 2. Color photographic material according to claim 1, characterized in that it is the Anthraquinone image dye in the silver halide emulsion or in a separate, transparent, contains dispersed layer immediately adjacent to the silver halide emulsion. 3. Color photographic material according to claim 1 and 2, characterized in that it as carbocyanine dye anhydro-3,3-bis - (/ 3-carboxyethyl) - 9 - methylselenecarbocyanine-hydroxyd, AhdS ^ 'bidbhrdi ydyyj ^ y 6,6 ', 9 -trimethyl-thiacarbocyanine hydroxide, anhy- dro-3,3'-bis - ((8-carboxyethyl) -5,5'-dichloro-9-methyl-thiaecarbocyanine hydroxide, Anhydro-3,3'-bis (/ 3-carboxyethyl) -5,5'-dichloro-9-ethyl-thiacarbocyanine hydroxide or anhydro-3,3'-bis (ß-carboxyethyl) - 5,5 '- dimethoxy - 9 - methyl - selenium carbocyanine hydroxide contains. 4. Color photographic material according to claim 1 to 3, characterized in that it contains the anthraquinone image dye l, 4-bis (a-methyl- ß - hydroquinonylethylamino) - anthraquinone or l, 4-bis (a-methyl- (S-hydroquinonyl -äthylammo) -5,8-dihydroxyanthraquinone contains. For this purpose 2 sheets of drawings