DE1054325B - Supersensitized silver halide photographic emulsion - Google Patents

Description

The invention relates to a supersensitized silver halide photographic emulsion.

It is known in the manufacture of photographic emulsions that by incorporating certain dyes of the cyanine class the spectral sensitivity of photographic emulsions of the halosilver gelatin genus can be changed. It is also known that the achieved by means of a certain dye Sensitization varies somewhat with the type of emulsion into which the dye is incorporated. Furthermore, a certain emulsion can be sensitized by means of a certain dye Change in the state conditions in the emulsion. So the sensitivity can through Increasing the silver ion concentration and / or by decreasing the hydrogen ion concentration (i.e. Increase in alkalinity). It is thus possible, for example, to increase the sensitivity of spectrally sensitized Emulsions coated panels can be increased by placing them in water or in aqueous ammonia solutions to be bathed. Such methods of changing the sensitivity of a sensitized Emulsion by increasing the silver ion concentration and / or reducing the hydrogen ion concentration are generally "hypersensitization"? called. However, hypersensitized emulsions are generally not very stable.

According to the invention it has now been found that other means of changing the sensitivity of certain Emulsions containing dicarbocyanine dyes can be used. Since doing the state conditions in the emulsion, d. H. the hydrogen ion concentration and / or the silver ion concentration little or not at all should be changed, the present method is to be distinguished as;,> Supersensibilisierungcf are designated.

R-N (-CH = CH) - C = CH-CH = CH-CH = CH-C

^v 'η -1

Supersensitized
photographic silver halide emulsion

Applicant:

Eastman Kodak Company,
Rochester, NY (V. St. A.)

Representative: Dr.-Ing. W. Wolff, patent attorney,
Stuttgart-N, Lange Str. 51

Claimed priority:
V. St. v. America October 12, 1955

Burt Haring Carroll, Jean Elmore Jones

and John Spence, Rochester, N.Y. (V. St. A.),

have been named as inventors

According to the invention, the photographic emulsions contain certain (known) dicarbocyanine dyes and, as supersensitizers for these bistriazinylamino-stilbene compounds. It is essential that such emulsions containing bis-triazinylamino-stilbene compounds are particularly suitable for color photography.
The dicarbocyanine dyes useful according to the invention can advantageously be represented by the following general formula

7 "v

= N -R ₁ I.

are illustrated in which R and R ₁ each have an alkyl group, e.g. methyl, ethyl, / S-oxyethyl, carboxy-methyl, jff-carboxyethyl, carbomethoxymethyl, carboethoxymethyl group, etc., η is a positive integer, namely 1 or 2, X represents an acid residue, for example chlorine, iodine, bromine, perchlorate, p-toluenesulfonate, benzenesulfonate, ethylsulfonate, methylsulfonate, etc., Z denotes the non-metallic atoms required to complete a 5- or 6-membered heterocyclic nucleus, eg a heterocyclic nucleus of the benzothiazole series, such as benzothiazole , 4-, 5-, 6- or 7-chlorobenzothiazole, 4-, 5- or 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 4- or 5-phenylbenzothiazole, 4-, 5- or 6-methoxybenzothiazole, or 6-iodobenzothiazole, 4- or 5-ethoxybenzothiazole, 5,6-dimethylbenzothiazole, 5-oxybenzothiazole, 6-oxybenzothiazole, etc. or a heterocyclic nucleus of the naphthothiazole series, e.g. α- or / 3-naphthothiazole, 7- or 8-methoxy α-naphthothiazole, 5-methoxy-yS-naphthothiazole , 5-ethoxy-a-naphthothiazole, etc. or a heterocyclic nucleus of the benzoselenazole series, for example benzoselenazole, 5- or 6-methoxybenzoselenazole, 5-chlorobenzoselenazole, etc. or a heterocyclic nucleus of the naphthoselenazole series, for example a- or / 5-naphthoselenazole, uswelenazole . Or a heterocyclic nucleus of the benzoxazole series, e.g. benzoxazole, 5- or 6-oxybenzoxazole, 5-chlorobenzoxazole, 5- or 6-methoxy

809 788/304

jenzoxazole, 5-phenylbenzoxazole, 5-bromobenzoxazole, etc.) that of a heterocyclic nucleus of the naphthoxazole series, for example α- or ε-naphthoxazole, etc. Z ₁ denotes the nonmetallic atoms required to complete a heterocyclic nucleus, namely a heterocyclic atom Nucleus of the benzoxazole series (e.g. as mentioned above under Z), a heterocyclic nucleus of the naphthoxazole series (e.g. as mentioned above in Z m), a heterocyclic nucleus of the benzoselenazole series (as in Z), a heterocyclic nucleus of the naphthoselenazole series (as in Z ), a heterocyclic nucleus of the naphthothiazole series (for example as mentioned above under Z), a heterocyclic nucleus of the 2-quinoline series, eg 2-quinoline, 5- or 7-methyl-2-quinoline, 8-3-methyl-2 -quinoline, 6- or S-chloro ^ -quinoline, 4-chloro-2-quinoline, 5-, 6- or 7-ethoxy-2-quinoline, 6- or 7-oxy-2-quinoline, 6-methoxy- 2-quinoline, etc., of a heterocyclic nucleus of the 4-quinone series, e.g. B. 4-quinoline, 6-methoxy-4-quinone, 7- or 8-methyl-4 ~ quinoline, etc., of a heterocyclic nucleus of the benzimidazole series, eg benzimidazole, 5-chlorobenzimidazole, 5,6-dichlorobenzimidazole, 1,7 -Trimethylene benzimidazole, etc. or a heterocyclic nucleus of the 5,6-benzoquinoline series, e.g. 5,6-benzo-2-quinoline, etc. The bistriazinylamino-stilbene compounds suitable for carrying out the invention have already been used as fluorescent substances or as bleaching agents (optical) used. Accordingly, they are well-known compounds. Particularly useful compounds of this class are those of the general formula

, N,

N N

R ₇

-NH

η of R ₆ , R ₇ , R ₂ and R ₃ each have a hydrogen atom or a monovalent substituent, e.g. a hydroxyl, \ ryloxyl, e.g. phenoxyl, o-toloxyl, p-sulfophenoxyl etc., alkoxyl, e.g. Methoxy, ethoxyl, etc., a halogen atom, e.g. chlorine, bromine, etc., a heterocyclic radical, e.g. morpholinyl, piperidyl, etc., an alkylthio group (e.g. methylthio, ethylthio, etc.), an irylthio group (e.g. phenylthio, tolylthio, etc. .), a BEeterocyclylthio group (e.g. benzothiazylthio, etc.),; an amino group, an alkylamino group (e.g. methylimino, ethylamino, propylamino, dimethylamino, diethylamino, dodecylamino, cyclohexylamino, ß-oxyethylamino, diethylamino, , /? - sulfoäthylaminousw.),; An arylamino group (e.g. aniline, o-, m- and p- sulfomiline, o-, m- and p-chloroaniline, o-, m- and p-anisylamine,) -, m- and p-toludine, o-, m- and p-carboxyaniline, oxyaniline, sulfonaphthylamine, o-, m- and p-aminoaniline, p-acetamidaniline, etc.), R ₄ and R ₅ each have a hydrogen

■ - ^ s atom or one which makes the compound water-soluble

Group, e.g. a sulfo, carboxyl group, etc. (also such as the alkali salts or amine salts of these groups).

Many of these compounds illustrated by Formula II are known substances. Also are

the manufacturing process known. Below are representative compounds that come under the formula II fall, listed. The invention is of course not limited in any way to these specific compounds limited. Structural formulas are only for the first

three compounds are indicated, but it will be understood that throughout this specification the same numbering system was used.

.N-

Y ₂ NI! "-N N
V / '

NH

NH- C

CH = CH

SO ₃ H

SO ₃ H

-SO _a H

NH-f Y-NH ₂
NN

NH

SO, H

4,4 '- Bis - [4- (3' - sulfoaniline) - 6 - amino - s - triazin-2-ylamino] stilbene-2,2'-disulfonic acid

N
HO-CH ₂ CH ₂ NH- 'Jj- NH-

N
NN

i — CH = CH- '

V-NH- / Y-NH-CH ₂ CH ₂ -OH

NN

SOoH

SO, H

NH-CH ₂ CH ₂ -OH NH-CH ₂ CH ₂ -OH

4,4 '- bis - [4,6 - di - (β - oxyethylamino) - s - triazine -2 -ylamino] stilbene-2,2'-disulfonic acid

HO - ^ ^N V - NH - / Y - CH = CH

N N

I.
NH

NC ₂ H ₆

CH ₉

-NH - / 'T ^0H
NN

SCLH

SO ₃ H

NH

NC ₂ H ₅
CH,

SO, H

SO ₃ H

4,4'-bis- {4- [4 '- (N'-4 "-sulfobenzyl-N'-ethyl) -aminoanilm] -6-oxy-s-triazm ^

4. 4,4'-Bis- [4- (4'-sulfoaniline) -6 - ^ - oxyethylamino-s-triazin-2-ykmino] -stben-2,2'-disulfonic acid

5. 4,4'-Bis- [4,6-dianiline-s-triazinyl-2-ylamino] -stilbene-2,2'-disulfonic acid

6. 4,4'-Bis- [4-phenoxy-6 - (/ S-oxyethylamino) -s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

7. 4,4'-bis (4,6-dianiline-s-triazin-2-ylamino) stilbene

8. 4,4'-bis (4,6-dioxy-s-triazin-2-ylamino) -stilbene-2,2'-disulfonic acid

9. 4,4'-bis (4-aniUn-6-oxy-s-triazin-2-ylamino) -stilbene-2,2'-disulfonic acid

10. 4,4'-Bis- [4- (2'-chloraninn) -6-oxy-s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

11. 4,4'-Bis- [4- (5'-sulfonaphthylamino) -6-oxy-s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

12. 4 ₎ 4'-Bis- [4-n-dodecylamino-6 - (^ - sulfoethylamino) -s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

13. 4,4'-Bis- [4-N-morpholinyl-6- (4'-sulfoaniline) -s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

14. 4,4'-Bis- [4,6-di- (N-morphoHnyl) -s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

15. 4,4'-bis- {4- [4 '- (5 "-keto-3" -methyl-2 "-pyrazolin-1" -yl) -aniline] -o-oxy-s-triazine ^ -ylaminoj-stilbene ^^ '- disulfonic acid

16. 4- [4-Ethylamino-6- (di- / 3-oxyethyl) -amino-s-triazin-2-ylamino] -4 '- [4-methylamino-6- (jS-oxyethylamino) -s-triazine -2-ylaimno] -stilbene-2,2'-disulfonic acid

17. 4- [4- methylamine) -6- (ß- oxyäthylamino) -s - triazin-2-ylamino] -4 '- [4-ethylamino-6- (2'-anisidine) -s-triazine-2- ylamino] stilbene-2,2'-disulfonic acid

18. 4- [4-Ethylamino -6- (ß- oxyäthylamino) -s-triazin-2-ylamino] - 4 '- (4,6 - diamino - s - triazin - 2 - ylamino) stilbene-2,2' -disulfonic acid

19. 4,4'-Bis- [4-chloro-6-di - ((S-oxyethyl) -amino-s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

20. 4,4 '- Bis - [4 - aniline -6- ( β-oxyethylamino) - s - triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

21. 4,4'-Bis- [4- (4'-acetamidaniline) -6 - (/ 5-oxyethylamino) -s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

22. 4,4'-Bis- [4-amino-6- (3'-carboxyphenylamino) -s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

23. 4- [4-Phenoxy-6- (β-oxyethylamino) -s-triazin-2-ylamino] -4 '- [4-chloro-6-di - (/ 3-oxyethyl) -amino-s-triazine -2-ylamino] stilbene-2,2'-disulfonic acid

24. 4,4'-Bis- [4-ethyltnio-o- (/ 3-oxyethylamino) -s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

25. 4,4'-Bis- [4-phenylthio-6 - (^ - oxyethylamino) -s-triazin-2-ylamino] -stilbene-2,2'-disulfonic acid

26. 4,4'-bis (s-triazin-2-ylamino) stilbene-2,2'-disulionic acid

27. 4,4'-Bis (4-oxy-6-amino-s-triazin-2-ylamino) -stilbene-2,2'-disulfonic acid

28. 4,4'-Bis (4-chloro-6-trimethylolnethyl-amino-s-triazin-2-ylamino) -stilbene-2,2'-disulfonic acid.

Compounds which are particularly suitable according to the invention are described in one or more of the following patent specifications listed:

U.S. Patents 2,171,427, 2,473,475, 2,595,030, 2,660,578.

British patents 595 065, 623 849, 624051, 624 052, 678 291, 681 642, 705 406.

These products were previously only used in the text sector and are sold under trade names such as Leucophor B, Calconuor White MR, Tinopal (SP, WR, BV277, 2B, GS, NG), Blancofor SC, Hiltamine (BSP, N, SoL, 6T6) or the like.

According to the invention, one or more dicarbocyanine dyes according to formula are combined in the emulsion with one or more s-triazinylamino compounds, as illustrated by Formula II, added. The invention is directed in particular on the commonly used silver-halide gelatin emulsions. Nonetheless the supersensitization combinations can also be used in halogen silver emulsions in which as a carrier a substance other than gelatin, e.g. B. a synthetic resin or cellulosic material is used, as far as this has no harmful effect on the light-sensitive materials. The dicarbocyanine dyes and the s-Triazinylamino-stilbene compounds can be used in different concentrations depending on the desired effects be applied.

In general, the optimal concentration or near optimal concentration is that of the invention used dicarbocyanine dyes in the range of 0.01 to 0.3 g per mole of halosilver the emulsion.

7 8

The s-triazinyl used according to the invention is. The so supersensitized emulsion can then on

Amino-stilbene compounds can preferably be in a suitable carrier, e.g. B. Glass, CelMosederivatfilm,

Concentration of about 0.03 to 10.0 g per mole of halogen resin film or paper, in the appropriate thickness

silver of the emulsion can be used. to be shed. The emulsion is then left

In general, the proportions of the Di-5 can dry. The details of such potting processes

carbocyanine dye to the s-triazinylamino-stilbene are known to the person skilled in the art. The specified

Drive connection in the combinations according to the invention and quantitative ratios are only used

within fairly wide limits, for example in many cases of explanation. The invention is of course based on

from 1: 1 to 1: 300 (weight ratios) vary. any halogen silver emulsion directed to the one

The procedures for the incorporation of the sensitizing io combination of the dicarbocyanine color specified above

Dyes in halogen silver emulsions are made up of specialist substances and contains s-triazinylamino-stilbene compounds,

man known. The s-triazinylamino-stilbene compounds in this respect achieved a supersensitizing effect

can be dispersed directly in the emulsions. The following examples serve to further elucidate

will. They can also be in water (or in an orga- refinement of the invention.

niche solvents, e.g. B. methanol, ethanol, etc., 15 According to Table I below, different if the water solubility is not sufficiently great) given portions of the same batch of a photographic are dissolved and then added in the form of their solutions. Although the dicarbocyanine dyes in the dye, as he z. B. illustrated by Formula I. Emulsions can be dispersed immediately, and 2. a combination of a dicarbocyanine dye usual, the same in the form of their solutions in suitable ao substances with bis- (s-triazin-2-ylamino) -stilbene (in neutral Add solvents. For many of the dyes, aqueous solution) is added. Then the According to formula I, methanol, ethanol and emulsion were briefly kept at about 40 ° C and on Pyridine or the like as satisfactory. A carrier can also be cast. After settling by cooling Solvent mixtures, ζ. B. with methanol or was the layer dried. The samples were through Acetone diluted pyridine can be used. The di- 25 is a filter that essentially absorbs light from a wave carbocyanine dye and the s-triazinylamino-stilbene length is less than about 580 πιμ impermeable (additional compounds are in the finished emulsions games 1 to 14 and 17 to 31, Wratten filter No. 25) or dispersed. If possible, you should pass through a filter in the emulsions that is suitable for wavelengths above about 495 πιμ be evenly distributed. The following procedure (Examples 15 and 16, Wratten No. 12 filter) failed turns out to be satisfactory. 3 ° is cool in an Eastman IB sensitometer

Stock solutions of the dicarbocyanine dyes and the exposed. The film strips were 3 minutes with a

Stilbene compounds are prepared by making the same solution of the following composition
in suitable solvents, such as those mentioned above. ,, ...,

are to be applied, to be deleted. Then the N-methyl-p-ammophenol sulfate 2.0 g

liquid halosilver gelatin emulsion the desired 35 «ydrocninon S, U g

th quantities of the stock solutions of one of the dyes Dried Sodium Suffite 90.0 g

(or the stilbene compounds) slowly with stirring sodium carbonate (monohydrate) 52.5 g

admitted. Stirring is continued until the potassium bromide is 5.0 g

Dye is evenly incorporated into the emulsion. Water aut 1 1

The desired amount of the supply 40 is then developed.

solution of the stilbene compound (or the dye, if the sensitivity (red or blue), gamma value and

the stilbene compound was added first) slowly fog densities were measured on each of the samples,

added while stirring the same. The results are shown in table I below

Stirring continues until the second solution is thoroughly incorporated.

List I

example

Sensitizing dye plus additives (g / mol AgX)

Red exposure
or blue exposure

30 / E

sensitivity

Gamma value

veil

a S.S 'diethellene dicarbocyanine bromide (0.075)

b Dye a (0.075) plus Calcofluor White MR * (0.13)

c SjS'-diethyloxathiadicarbocyanin iodide (0.050)

d dye c (0.050) plus compound 4 (3.0)

e dye c (0.050) plus compound 1 (3.0)

f dye c (0.050) plus compound 5 (3.0)

g dye c (0.050) plus compound 6 (3.0)

h dye c (0.050) plus compound 2 (3.0)

i dye c (0.0375)

j dye c (0.0375) plus compound 6 (2.5)

k dye c (0.050)

1 dye c (0.050) plus Calcofluor White MR * (3.0).

m dye a (0.050)

η dye a (0.050) plus Calcofluor White MR * (3.0).

20th
25th

3.7
20.5

6.7
24.5
22nd
27.5
32
111

Nile
34.5

5.1
16.5

2.3

2.0

1.3

2.7

2.4

2.9

2.9

2.8

3.0

2.1

Nile

2.4

0.73

2.4

0.22 0.31 0.06 0.06 0.05 0.05 0.06 0.06 0.06 0.06 0.05 0.06 0.07 0.06

*) Calcofluor White MR is a bis (s-triazin-2-ylamino) -stilbene-2,2'-disulfonic acid (e.g. sodium salt)

ίο

example

Sansibilizing dye plus additives (g / mol AgX)

Red exposure or blue exposure

30 / E Gamma- Sensation value opportunity

veil

(3.0)

ο dye c (0.050)

ρ dye c (0.050) plus Calcofluor White MR *

q dye c (0.050).

r dye c (0.050) plus Calcofluor White MR * (3.0)

s S-ethyl-S'-zS-oxyathyloxathiadicarbocyanine iodide (0.050)

t dye s (0.050) plus Calcofluor White MR * (3.0)

u S.S'-diethyl-S-phenyloxathiadicarbocyanine-p-toluene sulfonate (0.050)

ν dye u (0.050) plus Calcofluor White MR * (3.0)

w S-Ethyl-S'-zS-oxyathyl-S-phenyloxathiadicarbocyanine bromide (0 050)

χ Dye w (0.050) plus Calcofluor White MR * (3.0)

y S ^ '- Diethyloxadicarbocyanine iodide (0.050)

ζ dye y plus compound 27 (0.30)

a 'S ^' - diethyl S ^ '- diphenyloxadicarbocyanine perchlorate (0.050)

b 'dye a' (0.050) plus compound 27 (0.30),

c 'S.S'-diethyl-oJ.o' ^ '- dibenzoxadicarbocyanine iodide (0.050)

d 'dye c (0.050) plus compound 27 (0.30)

e 'S.S'-dimethyl- ^ S ^ S'-dibenzothiadicarbocyanine chloride (0.050)

f 'dye e' (0.050) plus compound 27 (0.30)

g 'S.S'-diethyl-o ^ o' ^ '- dibenzothiadicarbocyanine iodide (0.050)

h 'dye g' (0.050) plus compound 27 (0.30)

i 'S.l'-diethyl-S.o-benzoselen ^' - dicarbocyanine iodide (0.050)

j 'dye i' (0.050) plus compound 27 (0.30)

k '3,3'-diethyl ~ 4', 5'-benzoselenthiadicarbocyanin iodide (0.050)

Γ dye k '(0.050) plus compound 27 (0.30)

m 'S.S'-diethyl-ö' ^ '- benzoselenthiadicarbocyaninjodid (0.050)

n 'dye m' (0.050) plus compound 27 (0.30)

o 'S.S'-diethyl- ^ S.o'J'-dibenzothiadicarbocyanine iodide (0.050)

p 'dye o' (0.050) plus compound 27 (0.30)

q 'S.l'-Diethyl-o ^ -benzothia ^' - dicarbocyanine iodide

r 'dye q' (0.050) plus compound 27 (0.030)

s' S.l'-diethyl- ^ S.S'.o'-dibenzothia - ^ - dicarbocyanine iodide (0.050)

t 'dye s' (0.050) plus compound 27 (0.30)

u 'S.l'-diethyl-oJ-benzothia ^' - dicarbocyanin iodide (0.050)

v 'dye u' (0.050) plus compound 27 (0.30)

w 'S ^' - diethyl- ^ S ^ '^' - dibenzothiadicarbocyanine iodide (0.050)

x 'dye w' (0.050) plus compound 27 (0.30)

y '(3 - ethyl - 2 - benzothiazole) (3 - ethyl -1,7- trimethylene - 2 - benzimidazole) penta-

methine vanin iodide (0.050)

z 'dye y' (0.050) plus compound 27 (0.30)

a "S.S'-diethyl-ö ^ -benzothiacarbocyanin iodide (0.050)

b "dye a" (0.050) plus compound 27 (0.30)

c "l'.S-diethyl ^ .S-benzothia ^ '- dicarbocyanine iodide (0.050)

d "dye c" (0.050) plus compound 27 (0.30)

3,3'-Diethyl-4 S ^ '. S'-dibenzoselendicarbocyanine iodide (0.050)

f "dye e" (0.050) plus compound 27 (0.30)
* Calcofluor White MR is a bis (s-triazin-2-ylammo) -stilbene-2,2'-disulfonic acid (e.g. sodium salt).

4.65

11.9
4.25

13.7

11.9

22.0
Nile
4.15
4.55
9.25
7.7

19.0
3.8
9.1
4.2
6.0
0.93
4.1
2.6
4.4
0.97
3.3.
2.4
3.5
2.8
3.5
1.6
3.3

Nile
3.9

Nile
4.2

Nile
1.6
3.2
5.2

8.2
11.1
2.2
5.2
3.8
8.4
1.7
4.4

1.5
2.0
1.3
2.3
2.8
2.3
Nile
1.3
1.5
1.9
2.0
2.1
1.4
2.1
1.3
1.5
0.79
1.4
1.6

1.1

0.66

1.9

1.8

0.98

1.8

0.9

1.2

1.0

Nile

1.6

Nile

1.1
Nile
1.4
1.8
1.2

1.9
2.3
1.4
1.3
2.3
1.9
1.2
2.0

0.06 0.06 0.06 0.07 0.06 0.07 0.06 0.08 0.06 0.08 0.06 0.06 0.06 0.07 0.06 0.07 0.06 0.07 0.05 0.06 0.07 0.06 0.05 0.06 0.05 0.06 0.06 0.06 0.06 0.06 0.13 0.10 0.09 0.08 0.05 0.07

0.05 0.06 0.06 0.06 0.07 0.07 0 06 0.06

In accordance with the above list, the layers of Examples 2 to 6 were prepared from the same batch of a bromide silver gelatin emulsion, the layers of the example from the same batch of a chlorobromosilver gelatin emulsion, the layers of Example 7 from the same batch of silver chlorobromide gelatin emulsion that Layers of Examples 8 and 9 from the same batch of silver bromide gelatin emulsion, the layers of Example 10 from the same batch of a silver bromide gelatin emulsion, the layers of Examples 11 to 11 from the same batch of silver bromide gelatin emulsion, the layers of Examples 15 and 16 from the same Batch of silver bromide gelatin emulsion and the layers of Examples 17 to 31 from the same batch made of a bromide silver gelatin emulsion.

For the stilbene compounds alone are in the list no measured values given, as there were a large number of test castings among those used in the list Concentrations indicated that the stilbene compounds, when used on their own, did not have a positive measurable effect (sensitometric).

The invention is particularly applicable to the developable halogen-silver gelatin emulsions commonly used, z. B. on -Chlorsilber-, chlorobromosilver, chloroiodosilver, chlorobromoiodosilver, and bromine silver Silver bromide gelatin emulsions, directed. Emulsions can also be used according to the invention in which the latent image is mainly formed inside the halogen silver grains, such as these

z. From U.S. Patent 2,456,956.

809 788 / 304-

11 12

The emulsions prepared according to the invention coupler 10: a-o-methoxybenzoyl-a-chloro-4- [a- (2,4-di-

can in the usual way on a suitable carrier, tert. amylphenoxy) -n-butyramid] -acetanilide (U.S. Patent

ί. On glass, cellulose nitrate film, cellulose acetate film, 2,728,658).

Polyvinyl acetal synthetic resin film, paper or metal, coupler 11: a- {3- [a- (2,4-di-tert.amylphenoxy) -acet-

be josed. 5 amide] benzoyl} -2-methoxyacetanilide.

The supersensitization combinations according to coupler 12: 3-Benzoylacetamide-4-methoxy-2 ', 4'-di-

Invention containing photographic halosilver tert-amylphenoxyacetanilide.

; emulsions such as those given above, coupler 13: 4-benzoylacetamide-3-methoxy-2 ', 4'-di-

You can also add other additives, such as chemical sensitization tert-amylphenoxyacetanilide.

iators, e.g. B. Sulfur sensitizers, such as allylthio- io The following examples serve to illustrate the advantages achieved with: arbamide, urea, allyl isothiocyanate, cystine, the new supersensitization combinations, etc. (See, for example, United States patent materials containing the dye-producing documents 2,540,085, 2,597,856 and 2,597,915), various compounds containing palladium compounds such as palladium chloride 15. [USA. Patent 2,540,086), KaliumchlorpaUadat Example 32 [USA. Patent 2,598,079), etc. or mixtures contraceptive A photographic chlorobromide-gelatin Emulierartiger sensitizers, fog, sion, a coupler dispersion of a color forming 1. B. ammonium chloroplatinate (U.S. Patent Compound, e.g., Coupler 5 and 2,566,245 above), ammonium chloroplatinate (U.S. Patent 20, an ultraviolet absorbing thiazolidone compound, 2,566,263), benzotriazole, nitrobenzimidazole, 5-nitro- e.g. B. 5-Benzal-3-n-cetyl-2-phenyHmino-4-tHazolidon, ent-: ndazole, benzidine, mercaptans, etc. the Photographic Process ", Macmülan Pub., (0.075 g / mol AgX). Part of one of the 3,460) or mixtures of the same, further hardening agent, like sensitized emulsion was Leucophor B" vie formaldehyde (US Pat. No. 1,763,533) , Chromium-25 (10 g / mol AgX) was added, while the other part was alum (US Pat. 1763 533), Glyoxal (US Pat. No. 1,763,533), Glyoxal (US Pat - on separate paper, provided with a baryta layer: entschrift 406 750) etc., finally also dyestuff carrier cast. The samples were contained in a Sensitoiuppler, as they are exposed, for example, from the USA.- meter and known in the reverse process by means of patents 2,423,730 and 2,640,776, 30 first developer of the composition: Dder also mixtures of such additives. _ _{Cal (Na} t _riuni hexametaphosphate .. 2.0 g

Likewise, m the emulsions given above 4-N-methylaminophenol sulfate 0.9 g

Dispersants for dye couplers, such as hydroquinone 2 35 ε

^ S! o, ^a n I f ^en ₊ ^USA -f ^atents , ^scripts ? ^{322 02} J ™ ^Α Anhydrous sodium sulfite ". '.'. '.'. '.'. '.'. '. See 2 304 940 above that 35 anhydrous sodium carbonate 10.0 |

Such halogen silver emulsions can also Y ^ j " _m i, r ^; j η" ^? ~

■ «,. ι-η -ι 1 λ,. ι ,, ι ι. -ι -π- jtvanuiiiuxoinici υ, 00 κ

fhiazolidone or other ultraviolet absorbing sodium chloride 0 2Oe

contain bindings such as those from the USA.- c MetWlhpnyntriarni ' VtO? I.

Patent specification 2,739,888 have become known. While water on .. ". '.'. '.'.". '. ".'.". ". '.'. '.'. ' 11 certain emulsion additives, for example certain 40

iiltraviolet absorbing compounds and certain 6 minutes developed.

Dye-forming compounds have a desensitizing effect after treatment in a conventional stop bath and Effect or a de-sensitization We wash the layers with a photo label have, it has been shown according to the invention that the lamp is exposed and in a bath of the following increases Combinations of such adverse effects 45 composition:

largely absent. Typical dye-producing compounds - benzyl alcohol 15 ecm

fertilize that can be used in this way, Calgon (sodium hexametaphosphate) .. 2.0 g

are for example those from the United States patent anhydrous sodium carbonate 20.0 g

2,322,027 known compounds and the following: Sodium hydroxide 2.0 g

Coupler 1: 1-Oxy-2 - [(5- (2 ', 4'-di-tert.amylphenoxy) - 50 anhydrous sodium sulfite 2 ^ 0 g

n-butyl] naphthamide (U.S. Patent 2,474,293). Developer substance * 4.0 g

Coupler 2: 1-Oxy ^ -phenylazo - ^ - (p-tert.butylphene-hydroxylamine hydrochloride 4.0 g

oxy) -2-naphthanilide (U.S. Patent 2,521,908). Potassium bromide 0.1 g

Coupler 3: 2- (2,4-Di-tert. Amylphenoxyacetamino) - water on 11

4, o-dichloro-S-methylphenol (USA. Ser. No. 285,544). 55 * _N _äthyl-N- _i 3-methane-sulfoiiamidäthyl-3-methyl-4-amino-

Coupler 4: 2- (a-Di-tert-amylphenoxy-n-butyryl-aniline.

amino -) - 4,6-dichloro-t-methylphenol. color developed.

Coupler 5: 6- (a- [4- [a- (2,4-Di-tert.amylphenoxy) -butyr- After treatment in a conventional stop bath, the

amidJ-phenoxyJ-acetamid ^^ - dichloro-S-methylphenol. Sample bleached with ferricyanide and bromide and put in

Coupler 6: 2- (3 '- (2 ", 4" -Diamylphenoxy) acetamide] - 60 in a bath of the type described in U.S. Pat. No. 2,706,687

benzamide ^ -chloro-S-methylphenol. written genre fixed. The relative sensitive

Coupler 7: 1- (2 ', 4', 6'-trichlorophenyl) -3- [3 "- (2 '", 4' "- properties for red and blue (optical density 0.3 above the

di-tert-amylphenoxyacetamide) benzamide] -5-pyrazolone haze value) for each of the samples were measured.

(U.S. Patent 2,600,788). The following results were achieved:

Coupler 8: 1- (2 ', 4', 6'-trichlorophenyl) -3- [3 "- (2 '", 4'"- 6 ₅ di-tert.amylphenoxyacetamide) benzamide] -4- (p - methoxyphenylazo) -5-pyrazolone.

Coupler 9: N - (4 - benzoylacetaminobenzenesulfonyl) -

N - (γ - phenylpropyl) - ρ - toluidine (USA. Patent specification dye c alone

2 298 443). 70 dye c plus leucophor B

Sensitivity to red

0.81 2.29

blue

0.86 0.85

The layers described in the following examples were prepared in essentially the same manner as in the Example 32 given above. However, no ultraviolet absorbing compound was used. The emulsions were cast on a cellulose acetate support instead of paper. It was either Leucophor B or Calcofluor White MR (both 10 g per mole of AgX) as in the following list II specified used. About the effect of the stilbene compounds counteracting a decrease in sensitivity To measure, series of the layers were 30 minutes and 60 minutes at 40 ° C before potting held for comparison with a series of fresh grouts (without delay). The layers were subsequently exposed in the usual way and in a solution of the following composition:

Water (21.1 to 23.9 ° C) 800 ecm

Calgon 2.0 g

Anhydrous sodium sulfite 4.0 g

Developer substance * 3.0 g

Sodium carbonate (monohydrate) 20.0 g

Potassium bromide 2.0 g

Water on 11

* 2-Ammo-5-diethylaminotoluene hydrochloride

color developed.

The samples were then rinsed, fixed, bleached with potassium dichromate, etc. in the usual way. The results are compiled in the following list:

List II

example

33 a
33 b
34
35 a
35 b
36

additions

no

Leucophor B

Calcofluor White MR.

no

Leucophor B

Calcofluor White MR.

no

Leucophor B

Calcofluor White MR.

Delay time in minutes

no

no

no

30 at 40 ° C 30 40 ⁰ C 30 40 ⁰ C 60 40 ° C 60 at 4O ⁰ C 60 ⁰ C at 40

sensitivity

Red i blue

nü 1.11

1.30

Nile

0.62

0.98

Nile

0.44

0.69

0.80 0.87 0.80 0.83 0.88 0.81 0.86 0.91 0.70

In exactly the same way as described for the sample according to Schedule I, dye c (0.05 g / MoIAgX) together (in the same concentration) with the compound in a standard silver bromide-gelatin emulsion 7 (8.0 g / mol AgX) incorporated. The relative sensitivity (for red), the gamma and the fog density for each of these layers are:

Example 39 gamma veil 4.5
5.3 0.06
0.06 Dye c alone
plus connection 7 Relative
Sensitive
speed 100
245

Although it has been shown that the dicarbocyanine dyes of the formula I corresponding tricarbocyanine dyes (e.g. S ^ '- diethyl thiatricarbocyanine iodide) sometimes with advantage in combination with the compounds according to formula II (e.g. with the compound 4 or Calcofluor White MR) can be used, these combinations prove to be in the generally not as beneficial as those given above. A corresponding series of layers of a usual one The bromide silver gelatin emulsion was prepared as indicated above for the layers according to Schedule I. The following results were achieved:

Dye g "
(0.015) ..
Dye g "
plusVerbir Example 40 alone Red sensitivity
opportunity
(30 / E) gamma veil ² 5 (0.015)
idung4 (3.0) 1.3
3.5 2.7
2.5 0.07
0.07

Dye g "is S.S'-diethyl thiatricarbocyanine iodide. Example 41

35 Dye g "
(0.010)
Dye g "
Calcofluor
(3.0) .... alone plus
MR Red sensitivity
opportunity
(30 / E) gamma 4th
7th veil (0.010)
White 3.3
13.7 1
2 0.06
0.07 40

In Examples 40 and 41 are the proportions

given in g / mol AgX.

The dicarbocyanine dyes of Formula I comprise a well known class of optical sensitizers. Processes for making these dyes have been previously described. It will be in this context

for example to U.S. Patents 2,131,865, 2 213 238, 2 218 450 and 2 269 234 and British Patent 562 567 are referred to. The following examples serve to further explain these known processes.

Example 42
S.S'-diethyl-S.S'-diphenyloxadicarbocyanine perchlorate

= CH-CH = CH-CH = CH-C

C ₂ H ₅

-C ₆ H ₆

ClO ₄

A mixture of 3.65 g (2MoI) 3-ethyl-2-methyl-heated to reflux temperature. The cool reaction mixture

5-phenylbenzoxazolium iodide and 1.74 g (1 mol plus 100 ° / “were stirred with ether. The liquids were

Excess) 1,3,3-triethoxypropene in 10 ecm acetic acid decanted. The remaining residue was washed with hot

anhydride was stirred up to 70% acetone with shaking for about 5 minutes. After cooling, the solid

bodies collected on a filter and washed with acetone and then with water. After a recrystallization The dye was converted from methyl alcohol into the perchlorate form by adding a hot aqueous solution Sodium perchlorate solution converted into a hot methyl alcoholic solution of the dye. Afterward the dye was recrystallized from methyl alcohol. The copper colored crystals melted at 234 to 236 ° C under decay.

Example 43 S-Ethyl-S'-ß-oxyethyloxathiadicarbocyanine iodide

= CH-CH = CH-CH = CH-C

C ₂ H ₅

CH ₂ CH ₂ OH

A mixture of 5.48 g (1 mol) 3- / 3-oxyethyl-2-methylbenzothiazolium bromide, 7.14 g (1 mol) 3-ethyl-2- (4-methoxy-1,3-butadienyl) -benzoxazolium iodide and 4.04 g (1 mol plus 100% excess) triethylamine in 50 ecm absolute ethyl alcohol was stirred at room temperature for 5 minutes. The reaction mixture was nitrated, the residue was washed thoroughly with water and then with a small amount of ethyl alcohol. The dye yield was 53% in the raw material and 35 ° / ₀ after two recrystallizations from methyl alcohol. The green crystals melted at 250 to 251 ° C with disintegration.

Example 44 S.S'-Diethyl-S-phenyloxathiadicarbocyanine-p-toluenesulfonate

C ₆ H ₅ -

= CH-CH = CH-CH = CH-C

C ₂ H ₅

A mixture of 3.49 g (1 mol) of 3-ethyl-2-methyl-Denzothiazolium p-toluenesulfonate, 4.77 g (1 mol) of 3-ethyl I- (4-methoxy-1,3 butadienyl) - 5-phenylbenzoxazolium-D-toIuolsulfonat and 2.02 g (1 mol plus 100% excess) triethylamine in 35 ecm absolute ethyl alcohol were stirred for 5 minutes at room temperature. After the reaction mixture had been removed, it was filtered. The residue was washed with ethyl alcohol. The dye yield was 100% in the raw state and 74% after recrystallization twice from methyl alcohol. The green needles melted at 221 to 222 ⁰ C with disintegration.

3-Ethyl 2- (4-methoxy-1,3-butadienyl) -5-phenylbenzoxazolium p-toluenesulfonate was prepared as follows: The by heating 99.5 g of 2-methyl-

5-phenyl-benzoxazole and 100 g of ethyl-p-toluenesulfonate (overnight at 11O ⁰ C) obtained crude quaternary salt was dissolved in 500 cc of acetic acid. 132 g of 1,3,3-trimethoxypropene were then added. The reaction mixture was refluxed for 30 minutes. After cooling, the intermediate product was collected on a filter with stirring and washed first with ether and then with acetone, yield 74 g.

example

S-ethyl-S'-zS-oxyethyl-S-phenyloxathiadicarbocyanine bromide λ O _x

= CH-CH = CH-CH = CH-C

C ₂ H ₅

CH ₅₁ CH ₅₁ OH

A hot solution of 2.75 g (1 mol) of 3 - /? - oxyethyl-2-methylbenzothiazolium bromide in 50 ecm of absolute ethyl alcohol, while stirring, was rapidly : temperature cooled. Then 4.77 g (1 mol) of 5-ethyl-2- (4-methoxy-1,3-butadienyl) -5-phenylbenzoxazoium p-toluenesulfonate were added and 2.02 g (1 mol) plus 10% excess triethylamine were added. The reaction mixture v was stirred for 10 minutes at room temperature. The dye was collected on a filter and used with Washed methyl alcohol. The dye yield was 77% in the raw state and 49% after two recrystallizations from methyl alcohol. The blue needles with a green reflex melted below at 255 to 256 ° C ZerfaU.

The melting points of the dyes used in the above lists are given below in exactly the same manner as illustrated in Examples 43 to 46.

dye Melting point in ⁰ C y 229 to 230 under decay e ' 215 to 216 under decay G' 236 to 237 under decay i ' 178 to 180 under decay k ' 177 to 178 under decay m ' 220 to 221 under decay O' 186 to 187 under decay q ' 189 to 191 under decay and shrinkage from about 180 onwards s' 208 to 209 under decay u ' 191 to 195 under decay and shrinkage from about 165 on c " 225 to 227 under ZerfaU e " 215 to 216 under ZerfaU

IO

The dye y 'was prepared according to the method known from US Pat. No. 2,269,234 (under Ver ao Turning of the intermediate product according to Example 1 and the quaternary benzimidazole salts according to the USA patent 2 320 439). The dye melted at 149-155 ° C with decomposition.

As already stated above, the bis-triazinylamino-stilbene compounds represented by the formula II

Cl

bonds a well-known class of "optical" Bleach. Methods for making the same have been used sufficiently described in the patents cited above. For further explanation, the manufacturing process of compound 9 given above. -

step 1
Three solutions were made as follows:

a) 260 g of purified diaminostilbene disulfonic acid in 11 Water.

H ₉ N

-CH =

NH,

SOoH

SO _a H

b) 259 g of cyanuric acid chloride in 461 g of acetone.

c) 42.6 g of sodium carbonate in 500 ecm of water.

Solutions b) and c) were added to ^{solution a) at 0 ° C. with vigorous stirring.} The proportions were adjusted so that the mixture remains neutral or slightly acidic. The implementation is finished when an amino nitrogen test is negative.

At this time the following connection exists:

Cl

n n

Cl-C

-NH- /

> - CH = CH

NH-

SO ₃ H SO, H

NN
I Il
-C C-Cl

Level 2

Separate solutions were added to this reaction product. The temperature was allowed to rise to 20 to 25 ° C and

gen d) and e), as indicated, added at 0 to 10 ° C. 40 continues stirring until no more free aniline

d) 206 g of aniline hydrochloride in 2751 water. is present.

e) 100 g of sodium carbonate in 650 ecm of water. At this point in time the following connection exists:

Cl

Cl

NN
I ii

C.KHN-C C - NH- <

-CH = CH-

SO, H

NH-

-C

N
I!
C-

-NHC ₆ H ₈

level 3

There were 550 ecm of a 15% sodium carbonate solution added to the reaction mixture from stage 2. The mixture was heated to the boiling point and that Acetone distilled off. Heating was continued for a few hours after the acetone was removed. The mixture was diluted to 10 1 and filtered hot.

The filtrate was salted out and filtered off in a filter press without washing. The optical bleach concentrate was then dried at 70 to 80 ° C. It had the following chemical structure:

OH

OH

N N

I Il "

C ₈ H ₅ -NH-C C -NH- <f

H CH = CH- \ - NH- / ■ N
If Λ -
SO ₃ N Il
C.
S. _> C.
■ λ / so _£ N _ / "\ _f c H * N

(Compound 9)

809 788/304

In a manner similar to that indicated by obsn, compound 27 was made using concentrated ammonia in place of the aniline used in making compound 9. Compound 28 was prepared in a similar manner by using tris (oxymethyl) aminomethane in place of the uilin, but step 3 was omitted. The compound 26 is produced by a condensation similar to stage 1 in the production of the compound 9. The tetrachloro compound obtained was then reduced by means of a zinc-acetic acid reduction mixture to a compound in which R ₂ , R ₃ , R ₆ and R _{7 of} the formula II are in hydrogen. Compound 7 was prepared in the same way as compound 5 (U.S. Pat. No. 2,582,357) using 4,4'-diaminostilbene in place of the corresponding stilbene disulfonic acid. For the tactical implementation of the invention are also `` compounds suitable, as they are explained by the above iOrmel II, if R ₂ , R ₃ , R ₆ and / or R ₇ e is a heterocyclylamino group, z. B. 2-Benzothiazyl-.mino, 2-pyridylamino, etc., mean.

In the drawing, the sensitizing effect achieved with three of the new combinations in bromide-iodide-gelatin emulsion is explained. Each of the figures of the drawing is a schematic representation of one or two (Fig. 1) spectrograms. The sensitivity of the sdiglich the dicarbocyanine Formally nthaltenden emulsion according to Figure 1 is dash-dotted lines of qualification;. Estellt, while the sensitivity of both a ^ carbocyanine dye of the formula I as well as the triazine ^r Getting Connected according to Formula II containing the same Emulion is represented by a solid curve . No curve is given for the emulsion containing only the triazine compound according to formula II, since it has been shown that these compounds on their own generally have little or no measurable senibization effect in the case of the emulsions. The same sensitizing dye became fair to the layers . 2 and 3 are used as used in FIG. However, curve A according to FIG. 1 is no longer shown in FIGS. 2 and 3, since it would only represent a repetition.

In Fig. I, curve A shows the sensitivity of an ibal bromoiodosilver gelatin emulsion containing 3,3'-di-Lthyloxathiadicarbocyaninjodid, while curve B shows the sensitivity of the same emulsion when this with S ^ '- diethyloxathiadicarbocyanine iodide and 4 , 4'-bis- [4- (4'-sulfoaniline) -6 - ^ - oxyäthylaminos-triazin - 2 - ylamino] - stilbene - 2,2 '- disulfonic acid is sensitized.

In Fig. 2, curve C shows the sensitivity of a conventional bromiodilver gelatin emulsion, the 3,3'-diethyloxathiadicarbocyanine iodide and 4,4'-bis- (4,6-dianiline-s-triazine-2-ylamino) stilbene -2,2'-disulfonic acid contains.

ίο In Fig. 3, curve D shows the sensitivity of a conventional bromoiodosilver gelatin emulsion when it is treated with 3,3'-diethyloxathiadicarbocyanine iodide and 4,4'-bis- (4-phenoxy-o-jiS-oxy äthylamino-s- triazin - 2 - ylamino) - stilbene-2,2'-disulfonic acid is sensitized. The sensitometric measured values for the layers of FIGS. 1, 2 and 3 are given in Examples 2, 4 and 5 of Table I given above.

A bis (s-triazin-2-ylamino) stilbene compound is intended to be a compound of the following structure

20 D-NH

NH-D ₁

CH = CH

25 are understood, where R ₄ and R ₅ each have the meanings given above and D and D ₁ each denotes an s-triazin-2-yl nucleus.

The disulfonic acids according to formula II are generally used in neutral aqueous solution as indicated above, ie the free acids are at least partially neutralized by means of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylamine, etc. before they are used in the emulsions. The corresponding disulfonic acid salts are formed. It is possible in this manner, the _pH value of the aqueous solutions so set that it is approximately the same as the p _H value of the emulsions.

Claims (19)

Patent claims: 1. Supersensitized photographic silver halide emulsion, characterized in that it is a Supersensitization combination of at least one dicarbocyanine dye of the following general terms Formula: 40 45 and at least one triazine compound. Here, R and R _{1 are} each an alkyl group, η is a positive integer, namely 1 or 2, X is an acid radical, Z is the benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, the to complete a heterocyclic nucleus Benzoselenazole or the naphthoselenazole series required non-metallic atoms and Z ₁ those to complete a heterocyclic nucleus of -C- = N -R ₁ Naphthothiazole, the benzoxazole, the naphthoxazole, the benzoselenazole, the naphthoselenazole, the 2-quinoline, 4-quinoline, benzimidazole or of the 5,6-benzoquinone series require non-metallic atoms. 2. Halogen silver emulsion according to claim 1, characterized in that the supersensitization combination at least one bis (s-triazin-2-ylamino) stilbene of the general formula ,, - NH - CH = CH- ■ < N N R ₇ contains, in which R ₂ , R ₃ , R ₆ and R ₇ each have a hydrogen atom, a hydroxyl group, an aryloxyl group, an alkoxyl group, a halogen, a heterocyclic radical, an alkylthio group, an arylthio group, a heterocyclylthio group, an amino group, a .N _x NU- »V ^]
NN Alkylamino group or an arylamino group and R ₄ and R ₅ each represent a hydrogen atom or sulfo groups. 3. Halogen overemulsion according to claim 1, characterized in that the supersensitization compo- combination of at least one bis (s-triazin-2-ylamino) stilbene of the general formula D-NH-i > - CH = CH -1 VNH-D ₁ ολ υ ο Γ \ XT Z ₁ ^ R —Ν (—CH = contains, in which D and D ₁ each represent an s-triazin-2-yl nucleus. 4. Bromiodosilver or bromochlorosilver gelatin emulsion according to Claims 1 to 3, characterized in that that they are a supersensitizing combination of at least one dicarbocyanine dye general formula C TT C ¹ TJ Γ * ΧΤ PXT Γ * ΧΤ Γ ¹
= Ks ± ± - UxI ^ UxI - UxI = UxI U ⁼ N - R ₁ in which R and R ₁ each represent an alkyl group containing 1 or 2 carbon atoms, η 1 or 2, X forms an acid _{radical and Z and Z 1 have} the meaning given above and are composed of at least one bis (s-triazin-2-ylamino ) stilbene of the general formula D-NH-C > -CH = CH contains, in which D and D ₁ each represent an s-triazin-2-yl nucleus. 5. Developable silver halide gelatin photographic emulsion according to claims 1 to 4, characterized in that it is a supersensitization combination from a dicarbocyanine dye of the general formula SO, H SOoH 7th 7th "V RN C = CH-CH = CH-CH = CH-C == N - R ₁ D-NH- < in which R and R ₁ each have an alkyl group containing 1 or 2 carbon atoms, X an acid radical, Z the nonmetallic atoms required to complete a heterocyclic nucleus of the benzothiazole series and Z ₁ the nonmetallic atoms required to complete a heterocyclic nucleus of the benzoxazole series, and from at least one bis (s-triazin-2-ylamino) stilbene compound of the general formula SO ₃ H SO ₃ H 40 D-NH V VCH = CH- / VNH-D ₁ SO ₃ H SO ₃ H 45 contains, in which D and D ₁ each represent an s-triazin-2-yl nucleus. 6. halogen silver - gelatin - emulsion according to claims 1 to 5, characterized in that it a supersensitization combination of 3,3'-diethyloxathiadicarbocyanine iodide and of at least one bis (s-triazin-2-ylamino) stilbene compound of the general formula contains, in which D and D ₁ each represent an s-triazin-2-yl nucleus. 7. Halosilver gelatin emulsion according to claims 1 to 6, characterized in that it is a supersensitization combination of 3,3'-diethyloxathiadicarbocyanine iodide and 4,4'-bis (4,6-dianiHn-s-triazin -2-ylamino) - stilbene-2,2 '- disulfonic acid contains. 8. Halosilver gelatin emulsion according to Claims 1 to 6, characterized in that it a supersensitization combination of 3,3'-diethyloxathiadicarbocyanine iodide and 4,4'-bis (4,6-di - /? - oxyäthylamino-s-triazin-2-ylarrdno) -stilbene-2,2'-disulfonic acid contains. 9. Halogen silver gelatin emulsion according to Claims 1 to 6, characterized in that it a supersensitization combination of 3,3'-diethyloxathiadicarbocyanine iodide and 4,4'-bis (4-phenoxy-6- / 3-oxyethylamino-s-triazin-2-ylamino) stilbene-2,2'-disulfonic acid contains. 10. Halosilver gelatin emulsion according to claim 1, characterized in that it is a supersensitization combination from a dicarbocyanine dye of the general formula R-N -C = CH-CH = CH-CH = CH-C = / ^{Χ r} -Ri in which R and R ₁ each have an alkyl group containing 1 or 2 carbon atoms, X is an acid radical, Z is the non-metallic atoms required to complete a heterocyclic nucleus of the benzothiazole series, and Z _{1 is} the non-metallic atoms required to complete a heterocyclic nucleus of the benzimidazole series, and from at least one bis (s-triazin-2-ylamino) stilbene compound of the general formula -CH = CH NH-D ₁ SO ₃ H SO "H contains, in which D and D ₁ each represent an s-triazin-2-yl nucleus. 11. Halosilver gelatin emulsion according to claim 1, characterized in that it is a supersensitization combination from (3-ethyl-2-benzothiazole) - (3-ethyl-l, 7-trimethyle-2-benzimidazole) pentamethine cyanine iodide and of at least one bis (s-triazin-2-ylamino) stilbene compound of the general formula D-NH- NH-D ₁ IO contains, in which D and D ₁ each represent an s-triazin-2-yl nucleus. 12. Halosilver gelatin emulsion according to claim 1, characterized in that it is a super-sensitivity combination from (3-ethyl-2-benzothiazole) - (3-ethyl-1,7-trimethylene-2-benzimidazole) -pentamethinecyaninjodid and 4,4'-bis- (4-oxy-6-aminos-triazine-2 -ylamino) -stilbene-2,2'-disulfonic acid contains. 13. Halosilver gelatin emulsion according to claim 1, characterized in that it is a supersensitization combination from a dicarbocyanine dye of the general formula R-N C = CH-CH = CH-CH = CH-C NR ₁ in which R and R ₁ each represent an alkyl group containing 1 or 2 carbon atoms, X an acid radical and Z the nonmetallic atoms required to complete a heterocyclic nucleus of the benzoxazole series, and of at least one bis (s-triazin-2-ylamino) stilbene compound the general formula D-NH- CH = CH - NH-D ₁ SO ₃ H SO, H contains, in which D and D ₁ each represent an s-triazin-2-yl nucleus. 14. Halosilver gelatin emulsion according to Claims 1 to 13, characterized in that it a supersensitization combination of 3,3'-diethyloxadicarbocyanine iodide and at least one Bis- (s-triazin-2-ylamino) -stilbene compound of the general formula D-NH CH = CH- -NH-D ₁ SOoH SO _S H in which D and D ₁ each denote an s-triazin-2-yl nucleus. 15. Halogen silver gelatin emulsion according to Claims 1 to 14, characterized in that it a supersensitization combination of 3,3'-diethyloxadicarbocyanine iodide and 4,4'-bis- (4-oxyo-amino-s-triazine ^ -ylaminoJ-stilbene ^^ '- disuUonic acid contains. 16. Halogen silver emulsion for achieving a color image according to claim 1, characterized in that that they 1. a dispersion of a reactable with a primary aromatic amino developer substance, color-producing compound, 2. a dicarbocyanine dye of the general formula R-N (-CH = CH) - C = CH-CH = CH-CH = CH-C == N-R ₁ in which R and R ₁ each have an alkyl group, η 1 or 2, X an acid radical, Z and Z _{1 have} the meanings given above, and 3. contains a bis (s-triazin-2-ylamino) stilbene. 17. Halogen silver emulsion according to claim 16, characterized in that it is a bis (s-triazin-2-ylamino) -stilbene compound of the general formula CH = CH- < N N R ₇ contains, in which R ₂ , R ₃ , R ₆ and R ₇ each represent a hydrogen, a hydroxyl group, an aryloxyl group, an alkoxyl group, a halogen atom, a heterocyclic radical, an alkylthio group, an arylthio group, a heterocyclylthio group, an amino group, an alkylamino group or an arylamino group and R ₄ and R ₅ each represent a hydrogen or a sulfo group. NH- (\ - -R, N N 18. Halogen silver emulsion according to claim 16, characterized in that a developable Halogen silver gelatin emulsion 1. A dispersion of a primary aromatic amino developing agent convertible, dye-generating compound, 2. a dicarbocyanine dye of the general formula R-N (-CH = CH) - C = CH-CH = CH-CH = CH-CNR ₁ * ■ 'it - 1 ^x in which R and R ₁ each have an alkyl group containing 1 or 2 carbon atoms, η 1 or 2, X an acid radical, Z and Z _{1 have} the meanings given above, and 3. a bis (s-triazin-2-ylamino) - stilben of the general formula D-NH- / > -CH = NH-D ₁ SO, H SO, H contains, in which D and D ₁ each represent an s-triazin-2-yl nucleus. 19. Halogen silver emulsion according to claim 16, characterized in that a fully developable Halogen silver gelatin emulsion 1. A dispersion of a primary aromatic amino developing agent convertible, color-generating compound, 2. a dicarbocyanine dye of the general formula R —N C = CH-CH = CH-CH = CH-C == N -R ₁ in which R and R ₁ each have an alkyl group containing 1 or 2 carbon atoms, X an acid radical, Z and Z _{1 have} the meanings given above, and 3. a bis- (s-triazin-2-ylamino) -stilbene compound of the general formula D-NH CH = CH- NH-D ₁ SO ₃ H SO ₃ H contains, in which D and D ₁ each represent an s-triazin-2-yl nucleus. A priority document was displayed when the registration was announced. 1 sheet of drawings © 809 788/304 3.59