DE2046687B2 - SUPERSENSITIZED, LIGHT SENSITIVE, PHOTOGRAPHIC SILVER HALOGENIDE EMULSION WITH A CONTENT OF A SPECTRALLY SENSITIZING TRICARBOCYANINE DYE - Google Patents

Description

The invention relates to a supersensitized, photosensitive, photographic silver halide emulsion containing a spectral sensitizing agent ^ carbocyanine dye and at least one supersensitizing compound.

It is known e.g. B. from the book by M e e s and James: "The Theory of the Photographic Process", 3rd edition, published by The MacMillan Company. 1966, pp. 198 and 199, silver halide photographic emulsions to sensitize spectrally to the infrared region of the spectrum. To the spectral Sensitization to the infrared region of the spectrum is from the USA patent 2 875 058 known to use tricarbocyanines, which by polynuclear aromatic, sulfonic acid groups load-bearing connections, e.g. B. stilbene compounds, are oversensitized.

Disadvantageous ar the previously known, compared to the infrared region of the spectrum sensitized SiI-herhalide emulsions is that they either do not have a sufficiently high sensitivity to the blue region of the spectrum and, or that they gradually lose their sensitivity to the infrared region of the spectrum on storage.

The object of the invention is therefore to provide a photosensitive, silver halide photographic emulsion which is excellent in infrared sensitivity is characterized which retains even in storage and also excellent Has blue sensitivity.

The invention was based on the knowledge that such silver halide emulsions can then be obtained if you get them by adding certain tricarbocyanine dyes and certain supersensitizing compounds. It has been found that the required properties can be used for the production of silver halide emulsions Tricarbocyanine dyes, whose meso carbon atom is the methine chain, are very well suited is bonded to the nitrogen atom of an amino radical which is linked to the methine chain of the tricarbocyanine dye forms an enamine. The emulsion is used as a supersensitizing compound Supersensitization components known per se polynuclear aromatic compounds with at least a sulfonic acid or sulfonic acid salt residue, azaindenes and / or silver halide reducing agents added.

The invention accordingly provides a super-sensitized, photosensitive, photographic Silver halide emulsion containing a spectral sensitizing carbocyanine dye and at least one emulsion supersensitizing compound, which is characterized is that it contains (A) as a sensitizing dye at least one ^ carbocyanine dye of the formula

N - (CH = CH) _n ^ r C = CH - CH = CC - = C - CH = CH - C = (CH - CH) == N--

R ₁ ^ Q-

in which m and η each denote 1 or 2, R ₁ and R ₂ each represent an optionally substituted alkyl or aryl radical, Q the atoms required to complete an optionally substituted ethylene, trimethylene or o-phenyl radical, R ₃ and R ₄ each individually an optionally substituted alkyl or aryl radical or together the atoms required to complete a heterocyclic ring containing 5- or 6-ring atoms, Z ₁ and Z ₂ each represent the atoms required to complete a heterocyclic ring typical of cyanine dyes, and X an acid anion and (B) as a supersensitizing compound at least (a) a polynuclear aromatic compound known per se as a supersensitization component and having at least one sulfonic acid or sulfonic acid salt residue, (b) an azaindene and / or (c) a silver halide reducing agent.

The invention provides supersensitized silver halide photographic emulsions which which have excellent sensitivity to the infrared region of the spectrum, at the same time have a high sensitivity wedge to the blue region of the spectrum and furthermore the sensitivity to the infrared and blue regions of the spectrum even when stored maintained.

"Tricarbocyanine dyes" are understood here to mean those dyes that have a chromophores Amidiniumionsystcm have (cf. the book "The Theory of the Photographic Process" by Mees and James, 3rd Edition, 1966, p. 201). Such Dyes typically contain two nitrogen-containing heterocyclic rings through a straight chain methine with 7 methine residues linked together. The carbon atom of the central methine residue of the methine chain is referred to as the meso carbon atom of the methine chain.

An "enamine" is a connection with the rest

C = C

Understood. Reference is made to the book by Raphael, Taylor and Wynberg »Advance; in Organic Chemistry, Methods and Results ", Vol. 4 1963, Verlag Interscience, p. 3, and the book before Fieser and Fieser," Advance Organic Chemistry "Reinhold Publishing Corporation. 1961, pp. 494 to 499 If, in the structural formula given, R ₁ around K ₂ denotes optionally substituted alkyl radicals, these preferably have 1 to II, in particular 1 to 4 carbon atoms. The Alky! Residues can be of an aliphatic or cycloaliphatic nature. This means that R ₁ u'.id R ₂ example, the meaning of methyl, ethyl, propy! isopropyl. Butyl, hexyl, cyclohexyl, decyl or dodecyl radicals can have. Have R ₁ and 'R the meaning of substituted alkylrcsien mix voi

preferably 1 to 12, in particular 1 to 4 carbon atoms, these alkyl radicals can for example consist of hydroxyalkyl radicals, e.g. B. / J-hydroxyethyl or m-hydroxybutyl radicals, alkoxyalkyl radicals, e.g. B. / i-methoxyethyl ode ^r (u-Butoxybutylresten or carboxyalkyl most ^r, z. B. / i-Carboxyäthyl- or ω-Carboxybutylresten, Sulfoalkylresten, z. B. / f-Sulfoäthyl- or ω-Sulfobutylresten or Sulfatoalkylresten, e.g.-sulfatoethyl or ω-sulfatobutyl radicals or acyloxyalkyl radicals, e.g. ß-acetoxyethyl, γ-acetoxypropyl or ru-butyryloxybutyl radicals or alkoxycarbonylalkyl radicals, e.g. / J-methoxycarbonylethyl or m-ethoxy carbonylbutyl radicals , e.g. benzyl or phenethyl residues.

If R ₁ and R ₂ are optionally substituted aryl radicals, these radicals preferably consist of aryl radicals of the phenyl or naphthyl series. 7. B. phenyl, tolyl, naphthyl, methoxyphenyl or chlorophenyl radicals.

X can be an acid anion of the type conventional for cyanine dyes, e.g. B. a chloride, bromide, iodide, Thiocyanate, sulfamate, perchlorate, p-toluenesulfonate or methyl sulfate anion.

The acid anion can optionally be part of the _{radical or radicals R 1} or R ₂ , for example when R ₁ and _{/ or R 2} are sulfoalkyl or carboxyalkyl radicals.

Z ₁ and Z ₂ preferably represent the atoms required for the formation of 5- or o-membered heterocyclic rings, as are typical for cyanine dyes, these rings optionally also having a second hetero atom in addition to the nitrogen atom specified, /. B. may have an oxygen, sulfur, selenium or nitrogen atom.

_{Z 1} and Z ₂ preferably represent the atoms which are necessary to complete the optionally substituted heterocyclic rings indicated below, namely

a thiazole ring, e.g. B. a thiazole,
4-methylthiazole, 4-phenylthiiazole,
5-methylthiazole, 5-phenylthiazole,
4,5-dimei'ylthiazole, 4,5-diphenylthiazole,
4- (2-thienyl) thiazole, benzothiazole,
4-chlorobenzothiazole, 5-chlorobenzothiazole,
6-chlorobenzothiazole, 7-chlorobenzothiazole,
4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole,
6-bromobenzothiazole, 5-phenylbenzothiazole,
6-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole. 6-methoxybenzothi

azole,

5-iodobenzothiazole, 6-iodobenzothiazole,
4-Äthoxybenzothiazol-, 5-Äthoxybenzothiazol-, 'Tetrahydröbenzöthiazöl-, 5,6-Dimethoxybenzothiazol-,

5,6-dioxymethylene benzothiazole,
5-hydroxybenzothiazole, 6-hydroxybenzothiazole,

Naphtho [2, ld] thiazole, naphtho [1.2-d] thiazole, 5-methoxynaphthi, o [2,3-d] thiazole,
5-ethoxynaphtho [2,3-d] thiazole,
8-methoxynaphtho [2,3-d] thiazole,
7-methoxynaphthio [2,3-d] thiazole or one
4'-methoxythianaphtheno-7'.6'-4,5-tlliazole ring. an oxazole ring, e.g. B. a 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole,
4,5-diphenyloxazole, 4-ethyloxazole,

4,5-dimethyloxazole, 5-phenoxazole, Benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole-, 5,6-dimethylbenzoxazole-. 4,6-dimethylbenzoxazole, 5-methoxybenzoxazole,

5-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, naphtho [2.1 -d] oxazole or

Naphtho [l, 2-d] oxazole rings,
a selenazole ring, e.g. B. a 4-methylselenazole,

4-Phenylselenazole-, Benzcselenazole-, 5-chlorobenzoselenazoI-, 5-methoxybenzo-

selenazole,
5-hydroxybenzoseienazo 'tetrahydrobenzoselenazole-,

Naphtho [2, ld] selenazole or naphtho [1,2-d] selenazole ring, a thiazoline ring, e.g. B. a thiazoline or 4-methylthiazoline ring,
a pyridine ring, e.g. B. a 2-pyridine, 5-methyl! -2-pyridine, 4-pyridine or a 3-methyl-4-pyridine ring,
a quinoline ring, e.g. B. a 2-quinoline, S-methyl ^ -quinoline-, 5-ethyl-2-quinoline-, o-chloro ^ -quinoline-, S-chloro ^ -quinoline-, 6-methoxy-2-quinoline-, 8-ethoxy-2-quinoline, 8-hydroxy-2-quinoline, 4-quinoline, δ-methoxy-3-quinoline, T-methyM-quinoline, S-chloro-2-quinoline, 1-isoquinoline 3,4-dihydro-1-isoquinoline or a 3-isoquinoline ring,

a 3,3-dialkylindolenin ring, e.g. B. one 3,3-dimethylindolenine or a 3,3,5-trimethylindolenine ring, an imidazole ring, e.g. B. an imidazole, 1-alkylimidazole, l-alkyl-4-phenylimidazole, i-AlkyM.S-dimethylimidazo'-, benzimidazole-, 1 -alkylbenzimidazole-, 1 -aryl-S ^ -dichlorobenzimidazole-,

l-alkyl-lH-naphth [l, 2-d] imidazoI-, 1-Aryl-3H-naphth [1,2-d] imidazole or an 1-alkyl-5-methoxy-1 H-naphth [1,2-d] imidazole ring.

The ethylene, trimethylene or o-phenylene radical represented by Q can optionally be replaced by a Halogen atom and / or an alkyl or alkoxy radical be substituted by 1 to 4 carbon atoms.

If R ₃ and R ₄ are optionally substituted alkyl radicals, these preferably have 1 to 12 carbon atoms. They can be substituted by the substituents given _{for R 1} and R _2. For example, R ₃ and R _{4 can} be: methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl or dodecyl radicals or Alkoxycarbonylaklyk este, z. B. Methoxycarbonylmethyl, Äthoxycarbonylmethyl- or Äthoxycarbonyläthylreste. If R ₁ and R ₂ are aryl radicals, these preferably consist of optionally substituted aryl radicals of the phenyl or naphthyl series, e.g. B. phenyl, naphthyl, tolyl, hydro

quinolyl, chlorophenyl or alkoxyphenyl radicals, the alkoxy groups thereof preferably having 1 to 4 carbon atoms to have.

If R ₃ and R ₄ stand together for the

If a heterocyclic ring containing 5- or 6-ring atoms is present, this preferably exists from an optionally substituted morpholino, thiomorpholino, piperidino, piperazinyl, pyrrolidinyl, Indolinyl, tetrahydrochinoyl or decahydrochinoyl ring.

If R ₃ and R _{4 are} the atoms required to complete a piperazinyl ring, this preferably consists of a 4-alkyl-1-piperazinyl, 4-alkoxycarbonyl-1-piperazinyl, or 4-aryl-1-piperazinyl ring, this being Ring in the 4-position can be substituted, for example, by a methyl, ethyl, propyl or butyl radical or a methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl or butoxycarbonyl radical or a phenyl radical.

Particularly advantageous tricarbocyanine dyes are present when Z ₁ and Z ₂ represent the atoms required to complete benzoxazole, naphthothiazole or benzothiazole rings, when Q is also an ethylene radical and when R ₃ and R ₄ together represent the atoms required to complete a piperazinyl radical. represent in particular a 4-Älhoxycarbonyl-l-piperazinylrestes required atoms.

Particularly advantageous, typical tricarbocyanine dyes for the preparation of a supersensitized light-sensitive silver halide photographic emulsion according to the invention are the dyes listed in Table A below.

Table A.

HI

IV

VI

VII

VIII

IX

XI

XII

1 l- (4-ethoxycarbonyl-l-piperazinyl) -3,3'-diethyl-10,12-ethylene oxatricarbocyanine perchlorate

3,3'-Diethyl-10,12-ethylene-II- (4-methyll-piperazinyl joxatricarbocyanine perchlorate

3,3'-Diethyl-10.12-ethylene-11- (4-methyll-piperazinyl) thiatricarbocyanine perchlorate

1 l- (4-Ethoxycarbonyl-1-piperazinyl) -3.3'-diethyl-10.12-ethylene-5.5'-diphynoxatricarbocyanine perchlorate
Anhydro-11 - {4-ethoxycarbonyl-1-piperazinyl) -10,12-ethylene-3,3 '-di (3-sulfopropyl) -thiatricarbocyanine hydroxide

Anhydro-10,12-ethylene-11 - (4-methy 1-

l-piperazinyl) -3,3'-di (3-sulfopropyl) -

oxatricarboeyanine hydroxide

Anhydro-10,12-ethylene-11 - (4-methyl-

l-piperazinyl) -3,3'-di (3-sulfopropyl) -

thiatricarbocyanine hydroxide

1 l- (4-ethoxycarbonyl-1-piperazinyl) -

3,3'-diethyl-10,12-ethylthiatricarbo-

cyanine perchlorate

ll- (4-phenyl-l-piperazinyl) -3,3'-diethyl

10,12-orthophenylenethiatricarbocyanine-

p-toluenesulfonate

Anhydro-II-dibutylamino-10 ^ -ethylene-3,3'-di (3-sulfopropyl) thiatricarbocyanine hydroxide, sodium salt
3,3'-Diethyl-10,12-ethylene-H- (I -pyrrolidinyl) -thiatricarbocyanine iodide
10,12-ethylene-l, l ', 3,3,3 \ 3'-hexamethyl- !! - (l-pyrrolidinyl jindotricarbocyanine iodide

XIII

XIV

XV

XVI

XVII

XVIII XIX

XX

XXI

XXlI

XXIiI

XXIV

XXV

3,3'-diethyl-10,12-ethylene-ll-piperi-

dinothiatricarbocyanine codide

3,3'-diethyl-10, l 2-ethylene- 11-morpho-

linothiatricarbocyanin iodide

. "U'-Diethyl-II-piperidino-10.n-tri-

methylthiatricarbocyanin iodide

3.3'-diethyl-10,12-ethylene-ll- (l-indo-

vinyl ioxatricarbocyanine perchlorate

3,3'-diethyl-10,12-ethylcn-l l- [1- (1,2,3,4-tc-

trahydrocholy ^ oxatricarbocyanine per-

chlorate

1 l-diethylamino-S ^ '- diethyl-lO. ^ - ethyl thiatricarbocyanine perchlorate

I l-piäthylamino-10, I2-iithy! En-l, l 1.3,3-3 ', 3'-hexamethylindotricarbocyanine- perchlorate

3.3'-Diethyl-10,12-iithylen-l 1 - [I - (1.2,3.4-

tetrahydroquinolyl)] 4,5; 4 ', 5'-dibcnzo-

thiatricarbocyanine perchlorate

I1 -Diphenylamino-S ^ '- diethyl-10,12-ethylenoxatrica ^r bocyanine perchlorate

1 l-Dimethylamino-3,3'-diethyl-10,12-ethylthiatricarbocyanine perchlorate

SJ'-Diäihyl-lO. ^ - trimcthylcn-ü-thio-

morpholinooxathiatricarbocyanine per-

chlorate

3.3 '-Diethyl-10,12-ethylene-H- (I -decahydroquinolylH ^' - tricarbocyanine perchlorate

Anhydro-II- (4-ethoxycarbonylpiperazine-1 -y I) -10,12-ethyien-3,3'-bis (3-sulfopropyl> S.o ^ '^' - dibenzothiatricarbocyanine hydroxide, Triethylamine salt

The tricarbocyanine dyes used according to the invention can easily be prepared by Um Setting of one mole of a starting compound of formula II

Z ₁ - ..

N = (CH-CH) = fC-CH = CH-N-C

R ₁ QH ₅ X-

with one mole of an enamine salt of the formula III

RR ₄

H ₂ C-C-CH ₂

(III)

wherein a compound of the following formula IV will hold

\ λ

.: "N I (IV)

N = (CH-CH) = T = C-CH = CH-C = C-CH ₂ R. \ n / υθ

One mole of the compound of the formula IV can then be reacted with one mole of a compound of the formula V given below, whereby a tricarbocyanine dye of the given structural formula is obtained. In the formulas given, X, n, m, Z ₁ , Z ₂ , Q, R ₁ , R ₂ , Rj and R _{4 have} the meaning given.

CH ₃ -C

C ₆ H ₅

J-CH = CH-C = (CH-CH) _n = ^ f = N "

(V)

R,

The reactions are preferably carried out in a suitable solvent, e.g. B. acetone or acetic anhydride, preferably in the presence of a customary basic condensing agent, e.g. B. triethylamine. as well as at elevated temperatures, e.g. B. The reflux temperature of the reaction mixture. In detail can methods are used as they are, for example, in French patent 1410 864, the Belgian patent specification 674 800, the Belgian patent specification 702 840 and in the German Offenlcgschrift 2 046 672 will be described in more detail.

Polynuclear aromatic compounds with at least one sulfonic acid or sulfonic acid salt residue Aromatic compounds are to be understood here which have two or more condensed benzene rings have e.g. B. naphthalene or pyrene compounds, and also compounds that at least have two benzene rings or other aromatic rings directly linked together. z. B.

iY ^ V-v

<o

Diphenyl-. Phenyl and quaternyl compounds. and finally also those compounds in which at least two Benzolinge or other aromatic Rings are connected to one another via an aliphatic chain or an aliphatic radical. Such polynuclear aromatic compounds can be expressed by the following general formula reproduce

D-SO ₃ M (IVa)

in which D denotes a polynuclear aromatic radical as indicated above and M denotes a hydrogen atom or a water soluble cation salt residue, e.g. B. a metal atom, e.g. B. an alkali metal atom, for example a sodium or potassium atom or an ammonium residue or a triethylammonium, triethanolammonium or pyridinium radical.

Particularly advantageous polynuclear aromatic compounds of the type described, which are included under the given general formula IVa fall, are those of the following formula Va

CH = CH-D ₂

D ₁

(Va)

SO ₃ M

Herein D means a 1,3,5-triazin-6-ylamino radical and D _{2 means} an aromatic radical, e.g. B. a gege- yo bcnenfalls substituted benzene radical. M has the meaning already given.

Typical compounds which come under the formula V, in which D _{1 is} a 1,3,5-triazin-6-ylamino radical. ie a 1,3,5-triazin-2-ylamino radical. are compounds of the following general formula Vb

NH

SO ₃ M SO ₃ M

ι ji ^κ ιι

N N

(Vb)

wherein M has the meaning already given and R ₅ , R ₆ , R ₇ and R _{1 are} each a hydrogen atom or a hydroxyl radical, an aryloxy radical, e.g. B. phenoxy, o-toloxy or p-sulfophenoxy, an alkoxy, e.g. B. a methoxy or ethoxy radical or a halogen atom, for example a chlorine or bromine atom or a heterocyclic radical, e.g. B. a morpholinyl or piperidyl radical or an alkylthio radical, e.g. B. a methylthio or ethylthio or arylthio, z. B. a phenylthio or tolylthio or a heterocyclic thio, z. B. a benzothiazolylthio radical or an amino radical or an alkylamino radical, e.g. B. a methylamino, ethylamino, propylamino, dimethylamino, diethylamino, dodecylamino, cyclohexylamino, / i-hydroxyäthylamino, di-hydroxyäthylamino- or / I-sulfoäthylaminorest or an arylamino, z. B. an anilino or o-, m- or p-anisylamino radical or an o-, m- or p-chloroanilino radical or an o-, m- or p-ToIudino radical or an o-, m- or p-carboxyanilino radical or a Hydroxyanilino radical or a sulfonaphthylamino radical or an o-, m- or p-aminoanilino radical or a »n p-acetamidoanilino radical.
For the preparation of a supersensitized, light-sensitive, photographic silver halide emulsion, compounds of the formula Vb, for example, in which R ₁₁ . R ₅ . R ₆ and / or R _{7 represent} heterocyclic amino branches. for example 2-benzothiazolamino or 2-pyridylamino radicals.

Another class of polynuclear aromatic compounds with at least one sulfonic acid or Sulphonic acid salt residue useful in the preparation of a supersensitized silver halide photographic emulsion suitable for the invention can be represented by the following structural formula VI a:

(Via)

Herein R _{8 is} an acylamido radical, e.g. B. einci acetamido, sulfobenzamido, 4 - methoxy - 3 - sulfo benzamido, 2-ethoxybenzamido, 2,4-diethoxybenz amido, ρ - tolylamido, 4 - methyl - 2 - methoxybenz

• SiS -

amido-. 1-naphthoxylamino-, 2-naphihoylamino-, 2,4-dimethoxybenzamido. 2 - Phenylbei.zamido- or 2-Thienylbenzamidorcst or a Sulforcst, R ₉ an acylamido radical, as _{indicated for R 8} or a sulfoaryl radical, ζ. B. a sulfophenyl or p'-sulfodiphenyl radical and R ₁₀ a hydrogen atom or a sulfo: ^ st, where it applies that the compound has at least one sulfo radical, ie a sulfonic acid or sulfonic acid salt radical.

Compounds of the formula Vb. which can be used in an advantageous manner for the production of a supersensibilisicrtcn. Photographic silver halide emulsions according to the invention are, for example, from U.S. Patents 2,171,427, 2,473,475, 2,595,030. 2,660,578 and 2,945,762, and British patents 595,065, 623 849, 624 051, 624 052, 678 291. 681 642 and 705 406 known.

Compounds of the formula V are commercially available and are also used, for example, as optical Brighteners used in the textile industry.

The preparation of the Dibenzothiophendioxydverbindungen of formula VIa is for example from the U.S. Patent Nos. 2,573,652, 2,580,234 and 2,563,493, and also 2,937,089.

Hooray e

For making a photosensitive photographic Silver halide emulsions according to the invention suitable compounds of the formula IVa are also known from the USA Palentcriptions 2,937,089 and 2,950,196 (see in particular formulas II, III and IV of this patent specification).

Compounds of the formula Va in which D _{1 represents} a benzotriazolyl radical can be prepared, for example, by the processes known from U.S. Patents 2,713,057, 2,684,966, 2,784,197 and 2,784,183. Other similar compounds with a 2-benzotriazolyl radical. which can be used according to the invention are described in US Pat. No. 2,733,165. Such compounds fall under the formula IVa given above.

Typical polynuclear aromatic compounds with at least one sulfonic acid or sulfonic acid salt residue, those under the formulas IVa. Va and VIa fall, for example:

1. triazolostilbene compounds containing sulfonic acid residues, z. B. of the type known from U.S. Pat. No. 2,713,057,

CH = CH

SO, H

NH-

OH

SO ₃ H

N N

OH

4.4'-Di (4 ".6" -dihvdroxv-2 "-s-triazinvlamino) stilbene-2.2'-di: sulfonic acid.

3. 4,4'-Bis [4- (3'-sulfoanilino) -6-amino-s-triazin-2-ylamino] -rods.

4. Sulphonated triazinyl stilbene (Tinopal WR and 2 B as well as Calcofluor White-MR).

5. Sulphonated triazinyl stilbene, e.g. That of U.S. Patents 2,595,030 and British Patent 595 065 known type,

6. 4,4 '- bis [2 - (4 - sulfoanilino - 2 - β - hydroxyethylamino) - 1,3,5 - triazine - 6 - ylamino] stilbene-2,2'-disulfonic acid.

7. 4,4'-bis (2.4-hydroxy-1,3,5-triazin-6-ylamino) -dibenzyl-2,2'-disulfonic acid,

8.4 '- bis (2 - β - hydroxyäthylamino - 4 - anilino-1,3,5 - triazine - 6 - ylamino) - \ A - distyrylbenz-2,2'-disulfonic acid,

9. 5 - methoxy - 2 - (4 - styryl - 3 - sulfo) phenyl-1,2,3-benzotriazole, Sodium salt,

60

3,7 - bis (2 - phenylbenzamido) - 2,8 - disuifodibenzothiophene-5,5-dioxide,

11. 3,7 - bis (2 - thienylamido) - 2,8 - disuifodibenzothiophendioxyd, Sodium salt,

12. 3-14 - (4 - methoxy - 3 - sulfobenzamido) phenyl] -7 - (4 - methoxy - 3 - sulfobenzamido) dibenzothiophendioxyd, sodium salt,

13. Chrysene-6-sulfonic acid, sodium salt,

14. Pyrene-3-sulfonic acid. Sodium salt.

15. Phenanthrene-3-sulfonic acid. Sodium salt.

16. 2.3-Dimethylnaphthalene-1-sulfonic acid, sodium salt,

! 7. 4 - [4 - phenoxy - 6 - (ή - hydroxyäthylamino) -s - triazin - 2 - ylamino] - 4 '- [4 - chloro - 6 - di- (fi - hydroxyäthyUamino - s ■■ triazin - 2 - ylamino] -stilbene-2..T-disulfonic acid.

18. 2.8 - bis [4 - (4 - sulfoanilino) - 6 - hydroxy - s - triazin-2-ylamino] carbazole,

19.4.4 '- bis (4,6 - di (/ i - hydroxyäthylamino) - s - triazine-2ynbenzidine-2,2'-disulfonic acid,

20. 2-Laurylamino-4.o-di (4-sulfoanilino) -s-triazine.

21. 4,4 '- Bis14 - [4' - (N ', 4 "- sulfobenzyl - N' - ethyl) aminoanilino] -6-hydroxy-s-triazin-2-ylamino} -stilbene-2.2'-disulfonic acid ,

22. 5 - Acetamido - 2 - (4 - styryl - 3 - sulfo) phenyl-!, 2,3-benzotriazole, sodium salt,

23. 2,7 - Diacetamido - 3,6 - disulfodibenzothiophene-5,5-dioxide, Sodium salt,

24. 4 - sulfo - ο - terpiienyl. Sodium salt (Lour. Organ. Chem., 14, 163 (1949),

25. Pyrene - 3 - (4 - methoxy - 3 - sulfostyryl) ketone. Sodium salt,

26. 3,7 - bis (4 - methyl - 2 - methoxybenzamido) - 2,8 - disulfodibeiizothiophene-5,5-dioxide, Sodium salt.

As can be seen from the previous list of to produce a supersensitized photosensitive polynuclear aromatic photographic silver halide emulsions suitable for the invention Compounds with at least one sulfonic acid or sulfonic acid salt residue can be used Compounds, for example, in ^ orm their water

soluble alkali metal salts, ζ. B. in the form of their sodium and potassium salts or ammonium salts or Amine salts, ζ. B. triethylamine, triethanolamine, pyridine and aniline salts can be used. You can the emulsions in practically neutral aqueous solutions without changing the pH value of the emulsions, can be added.

Particularly advantageous silver halide reducing agents d. H. Compounds that are able to reduce silver halide are reducing dihydroxy compounds, ζ. B. from the group of benzenes, - / - lactors, pyronimides, tetronimides. Furans and Pyrroles that have at least two hydroxyl groups.

Typical dihydroxy compounds that act as supersensitizing agents Compounds for the preparation of a supersensitized light-sensitive photographic SiIb j'halide emulsion according to the invention can be used are hydroquinone, resorcinol, pyrocatechol, 3-methylpyrocatechol, toluhydroquinone, Naphthalenediols and the like, also - / - lactones, ζ. B. ascorbic acid, isoascorbic acid and the like, also 3-hydroxytetronimides; 3,4,5-trihydroxy-5,6-dihydro-pyronimide, also aminohexose reductones, ζ. Β. those in which the amino group can be represented by the following formula

R ²

R ¹ - N - ^3U

wherein R ¹ and R ² each denote an alkyl radical with preferably 1 to 8 carbon atoms or together the atoms required to complete a heterocyclic ring with preferably 5 to 6 ring atoms, with the proviso that the ^{heterocyclic ring formed by R 1} and R ^{2 in} addition to the existing one Nitrogen atom can optionally also have a second nitrogen atom or an oxygen atom. For example, R 'and R ^{2 can represent} the atoms required to complete a morpholino, piperazino, pyrrolino, pyridino, pyrimidino or piperidino ring.

Typical for the preparation of a light-sensitive silver halide photographic emulsion according to Invention as a supersensitizing compound suitable tetronimides, pyronimides and aminohexose reductones are compiled in Table B below.

Table B.
5-phenyl-3-hydroxytetronimide

HO-C =

OH

C ₆ H ₅ -CC = NH

[V

55

60

5- (4-carboxyphenyl) -3-hydroxytetronimide,
5- (3,4-dimethoxyphenyl) -3-hydroxytetron ^: mid,
5- (n-butyl) -3-hydroxytetronimide,

5- (2-furyl) -3-hydroxytetronimide,
S ^ dihd ^ iil 5,6-diphenyl-3,4,5-trihydroxy-5,6-dihydropyronimide

OH

/ V

C 1, H ₅ -CH C-OH

! I.

C ₆ H ₅ -CH C == NH \ / O

5,6-ni-n-butyl-3,4,5-trihydroxy-5,6-dihydropyronimide.

y
furan),

pyronimide.
5,6- (2-sulfophenyl) -3,4,5-trihydroxy-5,6-dihydropyronimide,

üimethylaminohexosercducton. Di-n-butylaminohexose reductone. Di-n-hexylaminohexose reductone. Morpholinohexose reductone. Piperazinohexose reductone.
Pyrrolinohexosercductone.
Piperidinohexose reductone.

For the preparation of a light-sensitive silver halide photographic emulsion according to the invention suitable tetronimides and pyronimides can be prepared, for example, by methods such as in British Patent 782 304 and Swiss Patent 322 985 and the Journal HeIv. Chim. Acta. 39. (1956) p. 1780. are described. The specified and other 3-hydroxytetronimides and also suitable SAS-trihydroxy-S.o-dihydropyronimides, those suitable for the preparation of a silver halide photographic emulsion according to the invention are also described in U.S. Patent 3,330,655.

That for the preparation of a light-sensitive silver halide photographic emulsion according to the invention Suitable aminohexose reductones are derived from sugars, in particular from n-gluose and also of other reducing hexose sugars containing 6 carbon atoms. 7 ß. n-galactose, D-Mannosc. D-fructose and 1-sorbose.

A typical method of production according to the invention Reductone that can be used consists in a reducing medium practically free of water a hexose reducing sugar and an aliphatic or cyclic secondary amine in the presence an acidic, reducton-forming catalyst, e.g. B. phosphoric acid. Boric acid. Acetic acid or succinic acid to heat. When the aminohexosereductone is formed, 3 molecules of water are released To make a supersensitized. light temp sensitive, photographic silver halide emulsions according to the invention suitable reductones as well as Processes for their production are known from US Pat. No. 2,936,308, for example.

If azaindenes are used as supersensitizing compounds, these can be e.g. B. from Tri azaindenes. Tetraazaindenes or pentaazaindenes exist. Particularly advantageous azaindenes are like this before, which are substituted by a hydroxyl and / or aminore:. Az which can be used according to the invention; Indenes are, for example, from the following USA patents 2,735,769, 2,743,181, 2,835,58

2 756 147, 2 743 180, 2 716 062, 2 772 164, 2 713 541, 2 852 357, 2 743 180, 2 566 658/9, 2 444 605 to 7 and 2 449 225 to 6 as well as from the Zeitschrift für Wissenschaftliche Photographic ^ 7 (1952), pp. 2 to 28, known. Particularly useful tetraazaindenes for the preparation of a light-sensitive silver halide photographic emulsion according to the invention are those of the following structural formula

OH

wherein R 'has the meaning of an alkyl radical, e.g. B. a methyl. Ethyl-. Propyl or butyl resies.

Typical azaindenes, which are particularly convincing, are for example:

4-hydroxy-2 -,; - hydroxy-ethyl-6-methyl-

1.3.3a.7-tetraazainden.

S-carbethoxy ^ -hydroxy-1,3,3a, 7-tetrazaindene,
7-hydroxy-1,2.3,4.6-pentazaindene.
Z.-t-bihydroxy-δ-methyl-UaJ-triazaindene.
4-Hydroxy-2 ->, - hydroxy propyl-6-methyl-

1.3.3a.7-tetrazainden.
4-hydroxy-2 (4-pyridyl) -6-methyl-

1J ^ aJ-tetrazainden.

4-hydroxy-6-methyl-1,2.3.3a.7-pentazaindcn,
5-amino-2- (p-carboxyphenyl) -7-hydroxy-

1,3.4.6-pentazainden.

2,4-dihydroxy-6-methyl-1.3a.7-triazaindene.
2,5-dimethyl-7-hydroxy-1,4,7a-triazaindene,
5-Amino-7-hydroxy-2-methyl-1,47a-triazaindene, S-carboxy ^ -hydroxy-1JaJ-tetrazaindene.
1,2-bis (4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene

5-yl) ethane,
l, 2,3,4-tetrakis (4-hydroxy-6-methyl-

1,3,3a, 7-tetraazainden-2-yl) butane.
^ -Amino-S-carboxy ^ -hydroxy-1,3,3a.7-tetraza-

in the,
4-Hydroxy-6-methyl-1.3.33,7-161 ^^^ 6 ^

It can optionally be particularly advantageous to combine the azaindenes with a silver halide reducing agent or advantageously together with one of the polynuclear aromatic polynuclear described To use compounds with at least one sulfonic acid or sulfonic acid salt residue. Such emulsions are characterized by particularly advantageous emulsion sensitivities, one in particular favorable infrared sensitivity, low fog and excellent storage stability.

Furthermore lan .: are often particularly advantageous Achieve results when a polynuclear aromatic compound with at least one Sulphonic acid or sulphonic acid salt residue and a SiI overhalide reducing agent is used. In some cases, it can be particularly advantageous to use both a polynuclear aromatic and a supersensitizer Compound with a sulfonic acid or sulfonic acid salt residue, an azaindene as well as a silver halide reducing agent to use.

The compounds used for supersensitization can be used separately or together with the enamine tricarbocyanine dye can be added to the light-sensitive silver halide emulsion.

The most favorable concentration of enamtricarbocyanine dye and super-sensitizing in each individual case Active compounds can be determined in a known manner by a series of tests.

It has proven to be expedient to add about 0.01 to 1 g of dye and about 25 to 2000 mg, preferably 50 to 1000 mg of the polynuclear aromatic compound with at least one Sulfonic acid or sulfonic acid salt residue or reducing agent and about 1 to 8 g, preferably 2 to 4 g of an azaindene per mole of silver to be used.

The conventionally known silver halides can be used to prepare the silver halide emulsions be e.g. B. silver chloride, silver bromide, silver bromoiodide. Silver chlorobromoiodide and mixtures of this. The emulsions can be coarse-grained or fine-grained emulsions or Medium grain size emulsions or mixed emulsions with different grain sizes Act. They can be prepared by customary known methods, d. h .. it can for example so-called single-nozzle emulsions or double-nozzle emulsions. Furthermore, the in accordance with super-sensitized emulsions so-called Lippmann emulsions consist of ammoniacal emulsions or in the presence of Thioeyanates or thioethers ripened emulsions.

like r.ie for example from the USA patents

2,222,264, 3,320,069 and 3,271,157 are known. Of furthermore, the emulsions can be those with cubic silver halide grains such as those shown in, for example the Journal of Photographic Science, Vol. 12, pp. 242ff ..

or the Journal of Photographic Science, Vol. 13, 1965, pp. 85 to 89, or British Patent 1,156,193.

The silver halide emulsions of the present invention can be used to remove the soluble salts washed emulsions, but also unwashed emulsions. This means that the soluble salts, for example can be removed by quenching and leaching the emulsion or that the Emulsion can be subjected to a coagulation wash, for example from the USA patents 2 618 556, 2 614 928, 2 565 418, 3 241969 and 2 489 341 are known.

The emulsions according to the invention can furthermore with the help of customary chemical sensitizers, z. B. reducing compounds, sulfur, selenium or tellurium compounds or Gold, platinum or palladium compounds or combinations of these compounds sensitize be. Typical chemical sensitization processes followed by the photographic processes of the present invention Silver halide emulsions who can be chemically sensitized are, for example, from USA.-Pa publications 1 623 499, 2 399 083, 3 297 447 unc

3,297,446 known.

Advantageously, the supersensitized silver halide emulsions according to the invention can also be used hold the sensitivity-increasing compounds ent, e.g. B. polyalkylene glycols, cationic upper Surface-active substances and thioethers or combinations thereof, for example from de: U.S. Patents 2,886,437, 3,046,134, 2,944,90 and 3,294,540.

The silver halide emulsions of the invention

Ιϋ

tons further protected from the appearance of veils! and to a loss of sensitivity, during storage of the emulsion. So can the emulsions usual known antifoggants and stabilizers, added alone or in the form of combinations be e.g. B. the thiazolium salts known from US Patents 131,038 and 2,694,716, those of U.S. Patents 2,886,437 and

2,444,605 known azaindenes from the USA patent 2,728,663 known mercury salts, the urazoles known from US Pat. No. 3,287,135, the sulfo catechols known from US Pat. No. 3,236,652, which are known from the British Patent 623 448 known oximes, also nitrone and nitroindazole and also those from the USA patents 2,403,927, 3,266,897 and 3,397,987 Mercaptotetrazoles, as well as the polyvalent ones described in US Pat. No. 2,839,405 Metal salts; also from the USA patent

3,220,839 known thiuronium salts and finally those from U.S. Patents 2,566,26? and 2,597,915 known palladium. Platinum and gold salts.

Optionally, the supersensitized silver halide photographic emulsions of the present invention can be used also contain developer compounds incorporated, e.g. B Hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives. Reductones and phenylenediamines or combinations of this. Optionally, the developer compounds can also be used in a different layer using a supersensitized light-sensitive silver halide photographic emulsion recording material produced according to the invention are incorporated.

The developer compounds can be in the form of solutions or in the form of dispersions, such as for example from US Pat. No. 2,592,368 and French Pat. No. 1,505,778 is to be added.

On the hardness of the supersensitized silver halide photographic emulsions of the present invention can use the customary known organic and inorganic hardeners and combinations of these are used, for example aldehydes and so-called blocked aldehydes, ketones, carboxylic acids and carboxylic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds. Epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides and also hardeners with two different hardening residues, e.g. B. an epoxy and an aldehyde radical or one Halogen and an aldehyde radical and curing agents consisting of polymers, e.g. B. oxidized polysaccharides, z. B. dialdehyde starch.

For the preparation of the photographic silver halide emulsions according to the invention, furthermore the usual known colloids can be used as carriers or binders. To manufacture the Hydrophilic binders suitable for emulsions can consist of naturally occurring substances, z. B. from proteins, such as gelatin, gelatin derivatives, cellulose derivatives, polysaccharides, e.g. dextran, gum arabic and the like, or from synthetic polymers, e.g. B. from water-soluble Polyvinyl compounds, e.g. B. poly (vinylpyrrolidone), also acrylamide polymers and other synthetic polymeric compounds, e.g. B. dispersed polyvinyl compounds in latex form, in particular those used to increase the dimensional stability of the silver halide emulsion photographic material produced. Synthetic ones suitable for the production of the emulsions Polymers are described, for example, in U.S. Patents 3,142,568, 3,193,386, 3,062,674, 3 220 844 uid 3 287 289 and also 3 411 911. As Particularly effective are the water-insoluble polymers of alkyl acrylates and alkyl methacrylates, Acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates proved, in particular those which have groups suitable for cross-linking, which facilitate curing,

and those repeating such as the polymers known from Canadian Patent 774 054 Have suIfobetain units.

The silver halide emulsions according to the invention can be used to produce a wide variety of recordings

tion materials are used, which are antistatic effective or conductive in an advantageous manner Have layers, e.g. B. layers mi. soluble salts, z. B. chlorides or nitrates or the vapor-deposited metal layers or layers from ionic polymers such as those from U.S. Patents 2,861,056 and 3,206,312 are known or layers with insoluble inorganic salts, such as those from the USA patent 3,428,451 are known.

The silver halide emulsions of the present invention can be applied to a wide variety of conventionally known ones Supports are applied, e.g. B. on films made of cellulose nitrate. Cellulose esters. Polyvinyl acetate, polystyrene. Polyesters, e.g. B. polyethylene terephthalate, polycarbonates and the like Glass. Paper and metal. A typical flexible layer support consists, for example, of a layer support made of paper, which is optionally partially acetylated can be. Furthermore, the paper layer carrier can, for example, be a barite layer or a Have a layer of an n-olefin polymer, in particular from a polymer of an n-olefin having 2 to 10 carbon atoms, e.g. B. a layer Polyethylene. Polypropylene, an ethylene butene copolymer and the like

Advantageously, the according to the invention Emulsions also plasticizers or plasticizers and lubricants, e.g. B. polyalcohols, z. B. glycerine and diols of the type known from US Pat. No. 2,960,404, also fatty acids or Esters such as those described in U.S. Patents 2,588,765 and 3,121,060, or Silicone resins, such as are known, for example, from British patent specification 955 061, contain.

Finally, the emulsions according to the invention can also contain surface-active compounds, z. B. saponin and / or anionic compounds such as alkylarylsulfonates, such as those for example from US Pat. No. 2,600,831 and / or amphoteric compounds such as for example, U.S. Patent 3,133,816.

Finally, those prepared using a supersensitized silver halide photographic emulsion Accounting materials produced according to the invention also contain matting agents, z. B. from strength. Titanium dioxide, zinc oxide. Silica. Polymer particles, such as those in

U.S. Patents 2,992,101 and 2,701,245, and the like.

The silver halide emulsions according to the invention can also be used can also be used for the production of photographic recording materials which contain optical brighteners, e.g. B. on Stilbene, triazine, oxazole and coumarin base. For the production of the recording materials can further water-soluble brighteners can be used, as for example in the German patent 972 067 and US Pat. No. 2,933,390 or, furthermore, dispersions of whitening agents, as for example from the German patent specification 1 150 274 and the USA patent specification 3 406 070 are known.

The silver halide emulsions according to the invention can also be used for the production of such recording materials used which light absorbing fabrics; and or contain filter dyes. as known, for example, from U.S. Patents 3,253,921, 2,274,782, 2,527,583, and 2,956,879 are. If necessary, such dyes can be fixed with the help of mordants, such as they are known, for example, from U.S. Patent 3,282,699.

The dyes used for the sensitization as well as the other emulsion additives can be added to the emulsions from aqueous solutions or from solutions of organic solvents, for example by processes as described in US Pat. No. 2,912,343, 3,342 605, 2 996 287 and 3 425 835. When using other dyes, these can be dissolved and added separately or together in a solvent To bathe dyes.

For the production of photographic recording materials using an inventive The supersensitized light-sensitive silver halide photographic emulsion can be of any variety common known coating processes are used, including dip coating, Coating with an air coating knife, curtain coating, extruder coating using a coating funnel. for example, as found in U.S. Patent 2,681,294 is known and the like. If necessary, two or more layers can be applied at the same time, as it is, for example, from the USA patent specification

2,761,791 and British Patent 837,095.

The emulsions according to the invention can also be used for the production of recording materials for Colloid transfer techniques such as that disclosed in U.S. Patent 2,716,059 is known, and also for the production of recording materials for the silver salt diffusion transfer process, as described, for example, in U.S. Patents 2,352,014, 2543,181, 3,020,155 and 2,861,885 is known. Finally, the emulsions can also be used to produce recording materials that are used to carry out of the color image transfer method such as that disclosed in U.S. patents 3 087 817, 3 185 567, 2 983 606. 3 253 915,

3,227,550, 3,227,551, 3,227,552, 3,415,644. 3,415,645 and 3,415,646 is known and also for the production of recording materials for the suction transfer process, as is known, for example, from U.S. Pat. No. 2,882,156.

The photosensitive silver halide emulsions according to the invention can advantageously be used use for the production of color photographic recording materials, i.e. for example such Recording materials containing color couplers, such as those from the USA patent specifications 2,376,679, 2,322,027, 2,801,171, 2,698,794, 3,227,554, and 3,046,129 are known. on the other hand The emulsions can also be used advantageously for the production of such color photographic recording materials which are developed in solutions containing color couplers, such as it for example from the USA patents

2 252 718. 2 592 243 and 2 950 970 is known.

Exposed silver halide photographic emulsions according to the invention can be developed according to the known customary development processes, in particular using the customary known alkaline developer solutions, their developer compounds from hydroquinones. Catechols, aminophenols. 3-pyrazolidones. Phenylenediamines, Ascorbic acid deriva.cn. Hydroxylamines ^ hydrazines and the like exist. The customary ones can also be used to develop the silver halide emulsions known edge development processes are used, as z. B. from the USA patent 3! 79 517 are received, as well as the so-called Stabilization Development Process. like for example from the »PSA Journal«. Vol. 16B, August ! 950, are known. Finally, they can also be developed with so-called monobaths, like them for example from the magazine »Phot., Sei. and Eng. ”, Vol. 2, No. 3 October 1958, and U.S. Patent 3,392,019 are known. If appropriate, the emulsions can also be made using so-called hardening developer.

such as, for example, the L SA. patent

3,232,761 are known. The development can finally also be carried out in developing devices using transport rollers, as are known, for example, from US Pat. No. 3,025,779. Finally, the development can also be carried out by what is known as a surface development process, as is described, for example, in Example 3 of US Pat ^{. No. 3,418,132.}

The supersensitized, photosensitive, silver halide photographic emulsions of the present invention can also be used to produce such recording materials, which are used for the production of planographic printing forms, as it is, for. B. from the USA patents 3 402 045 and 3 271 150 is known.

It has proven particularly advantageous to use the supersensitized emulsions according to the invention to be used for the production of color films for aerial photography with high resolution. Such For example, color films may consist of a film base on which in the following order the following layers have been applied:

1. an antihalation layer, consisting of a gelatin layer in which gray colloidal silver is dispersed.

2. a sensitive, blue-sensitive gelatin-silver bromoiodide emulsion layer, the a-pivalyl-u-phenoxyacetane couplers forming a non-diffusing, non-diffusing yellow dye as known, for example, from column 6 of US Pat. No. 3,408,194 is,

3. a gelatin layer containing 2,5-octylhydroquinone,

4. a gelatin layer containing a bleachable, blue-green colored dye,

5. a gelatin-silver bromoiodide emulsion with poor red sensitivity, the silver halide grains thereof from a silver bromoiodide core with a shell of silver bromide, practically of silver iodide is free, the emulsion contains a non-diffusing 1-hydroxynaphthamide color coupler contains, which leads to the formation of a non-diffusing, blue-green dye is capable. as for example in column 2 of the USA patent specification 2,474,293 and wherein the emulsion layer further comprises a non-diffusing, contains in the 2- and 5-substituted phenolic coupler, which to form a non-diffusing blue-green dye is capable and, for example, the constitution of a May have color couplers, as is known from Column 3 of U.S. Patent 2,895,826.

6. A gelatin layer containing 2,5-dioctylhydroquinone.

7. A gelatin layer containing a bleachable, magenta color shade.

8. a gelatin-silver bromoiodide emulsion layer that is slightly green-sensitive, whose silver halide grains consist of a core of silver bromoiodide and a shell of silver bromide, which are practically free made of silver iodide, with the emulsion layer contains a non-diffusing 3-benzamidol-phenyl-5-pyrazok> n color coupler, which for Formation of a slightly diluting purple-red Dye is capable, the non-diffusing color coupler, for example, a color coupler may be of the type known from column 3 of U.S. Patent 2,908,573,

9. a gelatin layer containing a bleachable, yellow-colored dye and

0. a gelatin layer in which a UV absorber is dispersed, as shown, for example, from Table A in column 4 of the USA. Patent 3 250 617 is known and in which also a pickling agent from U.S. Patent 2,882,156, that from the reaction product consists of aminoguanidine and a polymeric oxo compound.

The silver halide emulsions having a core and a shell silver halide grains internally produced in an advantageous manner by the fact that during the first 15% of the precipitation ι .Iodide-rich nuclei produced from silver bromocodide earth, whereupon an iodide-free silver halide LiIIc is precipitated, the pAg value being kept constant in order to obtain the desired grain size. The procedure is preferably such that the diameter of the silver halide grains is less than wa 0.75 microns, preferably below 0.5 microns

Hin such recording material can, for. B. in a camera used for aerial reconnaissance be used, with which earth recordings are made, whereupon the exposed material is wrong As part of a color development process, as described, for example, in the USA patent 3,046,129, column 23, line 34 to column 24, line 27. The one obtained during development Color image has an improved resolving power compared to the resolving power of a

Image obtained using a corresponding prior art recording material has been.

It has been shown that sensitization is a Silver halide emulsion versus the infrared

The range of the spectrum is generally higher when the silver halide grains of the emulsion are cubic Silver halide grains consist and not of octahedral silver halide grains.

As a result, according to a particularly advantageous embodiment of the Eriin Jung, the silver halide grains of the supersensitized. light-sensitive photographic silver halide emulsion; cubic silver halide grains.
Particularly advantageous antifoggants for infrared sensitized silver halide emulsions with cubic silver halide grains are 3,3'-alkylenebis (benzothiazolium salts), e.g. 3,3'-decamethylene bis (benzothiazolium bromide) or antifoggants consisting of a diselenide, e.g. B. 0.0 '- DiselcnobisfN - methylacetanilid) or a combination of these two antifoggants. Such antifoggants have been found to be particularly effective when the emulsion further contains a color coupler, e.g. B. one of the following color couplers

OH

1-QH _n -CO VO-CH-CONH

| -NHCOC, F ₇ -n

C ₅ H ₁₁ -I

OH

O I O

CONH- (CH ₂ ) ₄ O- <^ C? VC ₅ H ₁₁ -t

C ₅ H ₁₁ -I

these dissolved in a coupler solvent, e.g. B, dissolved in dibutyl phthalate or in tricresyl phosphate may be dispersed in the emulsion, or if the emulsion contains a so-called anti-stain agent (antistain agent) such as dioctyl hydroquinone. that in an advantageous manner also in one suitable solvent, e.g. B. Trieresyl phosphate dissolved may be dispersed in the emulsion.

The following examples are intended to illustrate the invention in more detail. The ones listed in the following tables Dyes are described in more detail in Table A.

example 1

Sensitive to different proportions of one and the same by means of a sulfur and a gold compound ized gelatin silver bromoiodide emulsion. their silver halide grains about 2.1 mole percent

.Iodide passed, the dyes 1 to 8 in the in the following Table I indicated concentrations were added.

For the supersensitization of the individual emulsions, either the sodium salt of the bis [s - triazin - 2 - ylamino] stilbene - 2,2 '- disulfonic acid in concentrations of 200 ml per mole of silver (in table I referred to as "stilbene") or the combination of this stilbene and 4-hydroxy-6-methyl-1,3.3a.7-tctrazaindene (referred to as "azaindens" in Table I) were added in concentrations of 2.0 g per mole of silver.

The individual supersensitized emulsions were then applied to a conventional cellulose acetate film carrier in such a way that 600 mg of silver and 1342 mg of gelatin were ^{applied to a carrier area of 0.0929 m 2.}

The recording materials obtained were then filtered through a conventional sensitometer (Kodak Wratten filters No. 35 and 38A) and a filter which absorbed infrared radiation, i.e. H. Radiation above about 700 nm. And a Kodak Wratten filter 89 B exposed to a tungsten light source, whereupon the specimens for 4 minutes at 20 ° C. in a developer of the following composition were developed:

Water, about 50 "C 500 ml

p-methylaminophenolsulfal 2.0 g

Sodium sulfite, dehydrated 90.0 g

Hydroquinone 8.0 g

Sodium carbonate, monohydrate .... 52.5 g

Potassium bromide 5.0 g

Topped up with cold water. . 1.0 1

The recording materials were then fixed, washed and dried in the usual way.

The following Table I shows the relative sensitivities obtained in the Exposure of the recording materials using the filters: Wratten 35 + 38A + CG on the one hand and the Wratten 89 B filter on the other hand. The waffle filters used are described in more detail in the company publication "Kodak-Wratten Filters for Scientific and Technical Use", published by Eastman Kodak Company, 22nd Edition, 1966.

Table I.

\ · -I rKs, t off concentration _ Stilbene Stilbene Stilbene Stilbene Stilbene Stilbene Stilbene Stilbene Relative blue | Relative infrared sensitivity .5 ί. JIILlCi 1 All I '^ IV'II in j: MoI Ag AU SiI 1 7.C Stilbene + azainds Stilbene + azainds Stilbene + azainds Stilbene + azainds Stilbene + azainds Stilbene + azainds Stilbene + azainds Stilbene + azainds Sensitivity 100 0.40 1 0.02 _ - - - - - - - 100 166 0.59 I. 0.02 151 132 0.12 I. 0.02 191 100 0.45 Il 0.04 100 295 0.13 11th 0.04 316 159 0.04 Il 0.04 331 100 0.23 III 0.04 100 3720 0.15 III 0.04 871 1450 0.03 πι 0.04 832 100 0.14 ι χ 0.02 100 159 0.16 ι ν 0.02 832 182 0.04 IV 0.02 209 100 0.15 'ν' 0.02 100 617 0.22 Y 0.02 132 575 0.09 V 0.02 145 100 0.80 Vl 0.02 100 479 0.50 Vl 0.02 1320 240 0.04 Vl 0.02 2090 100 0.69 VH 0.02 100 10,000 0.29 VII 0.02 200 575 0.06 VIl 0.02 550 100 2.20 VIII 0.02 100 11000 0.72 VIII 0.02 1510 11000 0.30 VIII 0.02 2000

The effective one results from the results obtained Using supersensitization of the tricarbocyanine dyes used in the present invention before. polynuclear aromatic compounds with at least one sulfonic acid or sulfonic acid salt residue.

The table also shows that <occurs in such supersensitized emulsions ting haze which is apparently haze produced by an enamine dye delt, can be decreased by using an azaindene.

309 508 '

The activity of silver halide reducing compounds as supersensitizers for one Emulsions containing f amintricarbocyanine dye are shown in Example 2 below.

B e i s ρ i e 1 2

Various proportions of a gelatin silver bromoiodide emulsion with 0.77 mole percent iodide of the substance described in the journal Phot. Journal, 79 (1939), p. 330. the dyes listed in the table below were added. The sodium salt of bis- [s - triazin - 2 - ylamino] stilbene - 2,2 '- disulfonic acid, a silver halide reducing compound in concentrations of 200 ml per mole of silver or the combination were added to the various emulsion fractions as a supersensitizing compound of stilbene compound and silver halide reducing compound incorporated. The silver halide reducing compounds used in detail consisted of piperidinohexose reductone, hydroquinone, 5-phenyl-3-hydroxy-tetronimide or ascorbic acid. The individual emulsion components were digested for 10 minutes at 52 ° C., after which the emulsion samples were applied to cellulose acetate film support in a concentration corresponding to 432 mg of silver per 0.09 m ^{2 of support area} .

Samples of the recording materials obtained were then passed through a Wratten filter in a sensitometer No. 89 B beliclHet, whereupon the examinees Developed for 3 minutes at 20 ° C in the developer described in Example 1, fixed, washed and were dried.

The results obtained are shown in the table below. The veil values were with the emulsions according to the invention all below 0.08.

Table II

40

45

additions Stilbene Stilbene Stilbene Stilbene Relative dye PHR ⁺ ) HQ ⁺⁺ ) PHTB ^{++ +} ) Infrared-
Sensation Stilbene + PHR Stilbene + HQ Stilbene + PHTB opportunity X Ascorbic acid - - - 100 X Stilbene 120 X Stilbene + ascorbic acid 330 X - 400 XI 100 XI 262 XI 132 XI 416 XII 100 XII 242 XII 200 XII 416 XIII 100 XIII 208 XIII 142 XIII 316 XIV 100 XTV 195

dye

XXII
XXII
XXIl
XXlI

26th

additions

XIV PHR ") Stilbene Stilbene Stilbene Stilbene Stilbene Stilbene Stilbene XIV Stilbene + PHR PHR Ascorbic acid Ascorbic acid Ascorbic acid Ascorbic acid Ascorbic acid Ascorbic acid XV --- Stilbene + PHR Stilbene + ascorbic acid Stilbene + ascorbic acid Stilbene 4- ascorbic acid Stilbene + ascorbic acid Stilbene + ascorbic acid Stilbene + ascorbic acid XV - - - - - XV XV XVl XVI XVI XVI XVIl XVIl XVIl XVII XVlII XVlII XVIIl XVIII XIX XIX XIX XIX XX XX XX XX XXI XXI XXI XXI

Stilbene

Ascorbic acid

Stilbene + ascorbic acid

j Infrared sensor wedge

110 230 100 250 160 416 100 230 160 272 100 156 170 210 100 190 170 200 100 220 170 416 100 220 200 470 100 795 316 891 100 501 126 631

*) = Piperidinohexose reductone.

⁺ ) = Piperidinohexose reductone.
⁺⁺ ) = hydroquinone.
+ +) = S-phenyl-B-hydroxy-tetronimide.

The results, compiled in Table II, show that silver halide photographic emulsions dissolve with an enamine tricarbocyanine dye excellent due to the addition of a polynuclear aromatic see connection with at least one sulfonic acid or sulfonic acid salt residue on the one hand or a silver On the other hand, let halide reducing agent supersensitize it. Compiled from the in Table II ten data also shows that with simultaneous use of a polynuclear aromatic see a compound with at least one sulfonic acid or sulfonic acid salt residue and a silver haigenide reducing agent a synergistic or superadditive effect is achieved.

Correspondingly favorable results were obtained if instead of the given Silberhalc Genid reducing agent andce reducing agent with at least two hydroxyl groups were used

■ -W

046 687

Example 3

Various proportions of a silver halide emulsion of the type described in Example 2, which had been spectrally sensitized by the addition of the dye II , were added to the sulfonated, polynuclear, aromatic compounds listed in Table III below in concentrations of 200 mg per mole of silver . The recording materials prepared using these emulsions were then tested according to the procedure described in Example 2. The following results were obtained:

Table 111

Stilbene

Without

Commercially available sulfonated triazinyl

style

4.4'-bis [(4-amino-6-anilino-s-triazin-2-yl) -amino] 2.2'-stilbene disulfonic acid,

Disodium salt

4,4'-Bis [(4-amino-6-phenoxy-s-triazin-2-yl) -amino] 2.2'-stiibcndi ^| ; iironic acid c.

Disodium salt

4,4'-bis (3-phenylureido) 2,2'-stilbene disulfone

acidic, disodium salt

4,4'-bis [4,6-bis (p-sulfoanilino) -s-triazin-2-yl] amino-2,2'-stilbene disulfonic acid.

Hexasodium salt

4.4'-Bis [(4-anilino-6-hydroxy-s-triazin-2-yl) amino] 2.2'-stilbene disulfonic acid.

Disodium salt

4,4'-bis [(4-hydroxy-6-phenoxy-s-iriazin-2-yl) amino] 2,2'-stilbene disulfonic acid.

Disodium salt

4.4'-bis [(4.6-bisanilino-s-triazin-2-yl) -amino] 2.2'-stilbene disulfonic acid,

Disodium salt

Relative

infrared

Sensible

lichkcit

100 166

115

166

120

126 151 151 151

see organic compounds for the supersensitization of photographic silver halide emulsions with an enamine tricarbocyanine dye are suitable.

The following Example 4 shows the supersensitization of emulsions with an enamine tricarbocyanine dye described with an azainden. From the following example 4 it follows further that it is particularly beneficial. for supersensitization ίο an enamine tricarbocyanine dye a combination to use from an azaindene and a sulfonated organic compound.

Example 4

There have been several recording materials starting out of one sensitized with a sulfur and a gold Gelatin-silver bromoiodide emulsion, the silver halide of which is approximately 2.5 mole percent consisted of iodide. The emulsions were in a layer thickness corresponding to 250 mg Silver and 574 mg gelatine per 0.0929 nr on cellulose acetate support applied. The silver halide grains of the emulsion were cubic Grains with an average size of about 0.3 microns. It was in detail after the British Patent 1,156,193.

The dyes tested in detail can be found in Tables IV and V below
individual iietcstct:

Connections were made in a ^4C

45

The results obtained show that the most varied of sulfonated polynuclear aromatics =

B =

C =

D =

E =
F =

Z =

Sodium salt of the bis [s-triazin-2-ylamino] style

bcn-2,2'-disulfonic acid,

Sodium salt of bis [s-triazin-2-ylamino] style

ben-2.2-disulfonic acid.

(Two different commercial products were

tc A and B used.)

Disodium salt of the 4.4'-bis [2-phenoxy-4- (2-hy-

droxyäthylamino) -13.5 - triazine - 6 - ylamino] -

stilbene-2.2'-disulfonic acid,

Sodium salt of 3,7 - bis (4 - methoxy - 3 - sulfo-

benzanv.do) -dibenzothiophendioxides.

Sodium salt of chrysene-6-sulfonic acid.

Disodium salt of 4,4 '- bis [4,6 - bis (o - chloro

anilino) - 2 - triazinylaminostilbene - 2.2 '- disul

fonsaure.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene.

Table IV

Mg dye; g Supersen
sensitizer / g tetra
azainden / Blue light exposure 3.8 veil Infrared exposure veil MoIAg MoIAg Mol Ag Relative
sensitivity 4.3 0.06 Relative
sensitivity 5.5 Without 229 4.1 0.08 - 4.9 0.08 1 (40) - - 100 4.3 0.14 100 4.7 0.14 1 (40) - 2.0 363 4.0 0.08 269 4.8 0.08 1 (40) A (300) 2.0 240 4.4 0.10 309 5.2 0.10 1 (40) B (300) 2.0 302 3.66 0.10 380 4.2 0.11 1 (40) C (300) 2.0 324 3.74 0.38 417 4.1 0.38 II (40) - - 100 4.5 0.22 100 4.8 0.22 II (40) - 2.0 398 4.1 0.10 141 5.0 0.10- 11 (40) A (300) 2.0 251 0.10 398 0.10 II (40) B (300) 2.0 316 289

g Supersen
sensitizer,
MoI Ag g Tclni-
azainden
MoI Ag continuation mg super Relative
Infrared
susceptibility 316 ichicxponicrur ΐ
veil lnfr
Relative
sensitivity '7 Table V veil 26th Inkuhicr irotcxposieru ig
Seemed 0.04 les material *! 0.11 Mg dye
Mol Ag C (300) 2.0 blue
Relative
sensitivity sensitizer
Mol Ag 100 295 4.2 I.
0.10 ■ 389 794 alerial 0.08 Relative
Infrared-
cmpf'mdliehkeil 6.8 j 0.10 0.04 ; ■ veil 0.15 II (40) - - 269 123 3.70 0.04. - 0.04 23 0.14 123 0.03 5.90 0.09 - - - Z (2000) 309 346 1.60 0.04 0.04! 1024 0.08 224 4.25 0.04 5.25 0.10 XXV (IOO) F (IOOO) - Z (2000)
+ A (300) 380 282 4.35 0.04 0.10 339 3.50 0.05 5.40 0.09 XXV (IOO) - 2.0 Z (2000)
+ B (300) 417 468 3.27 0.11 372 4.30 5.35 0.48 XXV (IOO) F (IOOO) 2.0 Z (2000)
4- C (300) 100 4.15 0.38 457 2.80 5.15 0.28 XXV (IOO) - 141 Fresh M. 0.22 89 4.30 0.26 Z (2000) 436 0.10 91 4.70 0.25 Z (2000)
+ A (300) 331 5.50 0.14 550 5.35 0.13 dye
(40 mc MoI Ag) Z (2000)
+ B (300) 417 4.90 0.13 331 5.20 0.07 I. Z (2000)
+ C (300) 234 4.70 0.08 479 5.20 0.22 I. Z (2000)
+ D (2000) 138 4.80 0.22 209 6.10 I. Z (2000)
+ D (300) 276 5.20 0, 100 4.90 0.31 Ϊ Z (2000)
+ E (300) 4.70 4.40 I. 4.10 107 II 4.80 ! I 4.60 II 5.40 II 5.60 II 4.20 I. 4.30 II II

*) Material incubated for one week at a temperature of 49 C and a relative humidity of 50%.

The results compiled in Tables IV and V show that azaindenes in the tricarbocyanine dyes described are excellent able to supersensitize and that further particularly good results are then obtained when a sulfonated polynuclear aromatic compound together with is used for a taming.

Corresponding favorable results were obtained when the aza used in Example 4 by appropriate concentrations of 7-hydroxy 2,3,4,6-pentazaindene or 2,4-dihydroxy-6-methyll, 3a, 7-triazaindene or other azaindenes was replaced.

The following Example 5 illustrates the supensitization of a photographic silver hair genide emulsion with a tricarbocyanine amine fiber by sulfonated. polynuclear, aromatic Compounds, silver halide reducing agents and an azaindene.

Example 5

According to the method described in Example 4 were three recording materials, starting from ν of a gelatin-silver halide emulsion containing cubic silver halide grains and cellulose acetate carrier, manufactured. The emulsion layers each contain 2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraza

den per mole of silver. Two of the three emulsion layers also contained 100 mg of dye II and 1000 mg of the dinairum salt of 4,4'-bis [(4,6-bis c-chloroanilino-s-triaan-2-yl) amino] -2,2'-stilbene disulfonic acid (Stilbene F) each per mole of silver. One of the emulsion layers contained Dye II, the

Stilbene F and also 500 mg ascorbic acid per mole of silver.

The three recording materials were exposed and developed as described in Example 4. Included the results compiled in the following table were obtained.

mc stilbene F
Mol Ag mg ascorbic acid
MoIAg Table VI Relative blue
sensitive wedge Relative red
sensitivity veil mg dye II /
Mol Ag 0
1000
1000 0
0
500 e Teirazaindcn.
Mol Ag 347
100
389 100
447 0.03
0.03
0.13 0
100
100 2
2
Ί

From the results, shown in Table VI, it can be seen that silver halide photographic emulsions are obtained advantageously by using an enamine tricarbocyanine dye, a sulfonated one super-sensitize polynuclear aromatic compound, a silver halide reducing agent and an azaindene permit.

Claims (10)

Patent claims: 1. Supersensitized light-sensitive silver halide photographic emulsion containing a Content of a spectrally sensitizing tricarbocyanine dye as well as at least one supersensitizing compound, characterized in that that it contains (A) as a sensitizing dye at least one tricarbocyanine dye the formula N - (CH = CH) _n -C = CH - CH = CC = C A. V _Q y in which m and π each denote 1 or 2, R ₁ and R each represent an optionally substituted alkyl or aryl radical, Q the atoms required to complete an optionally substituted ethylene, trimethylene or o-phenylene radical. R ₃ and R ₄ individually each represent an optionally substituted alkyl or aryl radical or together the atoms required to complete a heterocyclic ring containing 5 or 6 ring atoms, Z ₁ and Z ₂ each represent the typical heterocyclic ring required to complete a cyanine dyes and X is an acid anion and (B) as a supersensitizing compound at least (a) a polynuclear aromatic compound known per se as a supersensitization component and having at least one sulfonic acid or sulfonic acid salt residue, (b) an azaindene and / or (c) a silver halide reducing agent. 2. A supersensitized photosensitive silver halide photographic emulsion according to claim 1, characterized in that it contains (B, a) as the supersensitizing compound a water soluble organic compound of the formula CH = CH - D ₂ SO ₃ M 45 in which D ₁ denotes a 1,3,5-triazin-6-ylamino radical, D ₂ an optionally substituted benzene radical and M a hydrogen atom or a cation. 3. A supersensitized photosensitive silver halide photographic emulsion according to claim 1, characterized as being super-sensitizing Compound (B, b) contains a triazaindene, tetrazaindene or penta / .undum substituted by a hydroxy or amino radical. 4. Supersensitized, photosensitive, photographic Silver halide emulsion according to Claim 1, characterized in that it is used as a supersensitizing agent Compound (B, c) contains a benzene, lactone, tetronimide, pyronimide, furan or pyrrole each with at least two hydroxyl radicals or an aminohexose reductone. 5. Supersensitized, light-sensitive, photographic silver halide emulsion according to claim 1, characterized in that it contains as (A) a tricarbocyanine dye of the formula given in which m and η each mean 1, = CH-C = (CH-CH) = T = N * X ^e R ₁ and R ₂ each represent a short-chain alkyl radical having 1 to 4 carbon atoms. Q is an ethylene radical. R ₃ and R ₄ individually each represent an optionally substituted alkyl or aryl radical or together those to complete an optionally substituted morpholino. Thiomorpholino, piperidino. Piperazinyl, pyrrolidinyl, indolinyl. Tetnihydrochinoyl or Decahydrochinoylringes required atoms. Z ₁ and Z ₂ each represent the atoms required to complete an optionally substituted benzoxazole or benzothiazole ring, and X is an acid anion. 6. Supersensitized, photosensitive, photographic Silver halide emulsion according to Claims 1, 2, 3 and 5, characterized in that it is used as the supersensitizing component (B) a polynuclear aromatic compound with at least one sulfonic acid or sulfonic acid salt residue and an azaindene and optionally also a silver halide reducing agent. 7. Supersensitized, photosensitive, photographic Silver halide emulsion according to Claims 1 to 6, characterized in that it as a supersensitizing compound (B. c) contains: Ascorbic acid,
Piperidinohexose reduction, hydroquinone and / or
S-phenyl-S-hydroxytetronimide monobenzoate. 8. A supersensitized, photosensitive, silver halide photographic emulsion according to claims 1 to 6, characterized in that it contains 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as the supersensitizing compound (B, b) contains. 9. A supersensitized, photosensitive, silver halide photographic emulsion according to claims 1 to 8, characterized in that the silver halide grains of the emulsion have a cubic « Have shape, 10. Supersensitized, photosensitive, photo Graphic silver halide emulsion according to Proverbs 1 to 9, characterized in that si < contains as (A) an anhydro-11- (4-ethoxycarbonyl-1-piperazinyl) -10.12-ethylene-3,3 '-di (3-sulfo propyOthiatricarbocyanine salt or the disodium salt of a bis [s-triazin-2-ylamino] stilbene-2,2'-di sulfonic acid and 4-hydroxy-6-methyl-1.3.3a.7-te trazainden.