DE2046687A1 - Supersensitized, photosensitive, silver halide photographic emulsions - Google Patents

Description

Registration number. 122

Eastman Kodak Company, 343 State Street, Rochester, New York State, United States of America

Supersensitized light-sensitive silver halide photographic emulsion

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

It is known e.g. B. from the book by Mees and James: "The Theory of the Photographic Process, "3rd Edition, The MacMillan Company, 1966, pp. 198 and 199, photographic To spectrally sensitize silver halide emulsions to the infrared region of the spectrum.

Disadvantages of the previously known silver halide emulsions sensitized to the infrared region of the spectrum 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 when stored.

The object of the invention is therefore to provide a light-sensitive, photographic Indicate silver halide emulsion, which by a

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is characterized by excellent infrared sensitivity, retains it even when stored, and also has excellent blue sensitivity.

The invention was based on the knowledge that one to such Silver halide emulsions are obtained when they are made by adding certain tricarbocyanine dyes and certain supersensitizing agents acting compounds are supersensitized. It has been found that they can be used to prepare silver halide emulsions Tricarbocyanine dyes, whose meso carbon atom of the methine chain is attached to the Nitrogen atom of an amino radical is bonded, which forms an enamine with the methine chain of the Tr! Carbocyanine dye. Be there the emulsion as supersensitizing compounds as supersensitizing components known per se polynuclear aromatic compounds with at least one sulfonic acid or sulfonic acid salt residue, azaindenes and / or silver halide reducing agents added.

The invention is therefore a supersensitized, light-sensitive silver halide photographic emulsion having a Content of a dye sensitizing the silver halide and at least one dye which is supersensitizing the emulsion Compound which is characterized in that it contains:

(A) at least one tricarbocyanine dye as the sensitizing dye the formula:

N- (CH-CH) _{n- 1} -C-CH-CH-CCC-CH-CH-C

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m and η ^R 2 ^R 1 and Q ^R 4 ^R 3 and

where mean:

each »1 or 2;

each an optionally substituted alkyl or aryl radical;

those to complete an optionally substituted ethylene, trimethylene or o-phenyl radical required atoms;

individually each an optionally substituted one Alkyl or aryl radical or in total those containing 5 or 6 ring atoms to complete a 5- or 6-ring atom heterocyclic ring required atoms;

Ζ., And Z _{2 are} each the atoms required to complete a heterocyclic ring typical of cyanine dyes and

θ
X is an acid anion and

(B) as a supersensitizing compound at least (a) a polynuclear aromatic compound known per se as a supersensitizing component and having at least one sulfonic acid or sulfone f acid salt residue, (b) an azaindene and / or (c) a silver halide reducing agent.

The present invention provides supersensitized silver halide photographic emulsions which have excellent properties Have sensitivity to the infrared region of the spectrum, at the same time a high sensitivity to the have the blue region of the spectrum and also the sensitivity compared to the infrared and blue range of the spectrum, even when stored.

BATH ORIGINAL

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The term "tricarbocyanine dyes" is used here to refer to such dyes understood, which have a chromophoric amidinium ion system (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 ones heterocyclic rings linked by a straight methine chain with 7 methine residues. 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-N understood. Reference is made to the book by

Raphael, Taylor and Wynberg "Advances in Organic Chemistry, Methods and Results", Volume 4, 1963, Interscience Verlag, page and the book by Fieser and Fieser, "Advances Organic Chemistry", Reinhold Publishing Corporation, 1961, pages 494-499.

_{If R 1} and R- in the given structural formula have the meanings of optionally substituted alkyl radicals, then these preferably have 1-12, in particular 1-4, carbon atoms. The alkyl radicals can be aliphatic and cycloaliphatic in nature. This means that R and R _{2 can,} for example, have the meaning of methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, decyl or dodecyl radicals. If RJ and R ₂ represent substituted alkyl radicals with preferably 1-12, in particular 1-4, carbon atoms, these alkyl radicals can for example consist of hydroxyalkyl radicals, e.g. B. ß-hydroxyethyl or cJ-hydroxybutyl, alkoxyalkyl, z. B. ß-Methoxyäthyl- or c * r-Butoxybutylresten or carboxyalkyl, z. B. ß-carboxyethyl or cJ-carboxybutyl, sulfoalkyl, z. B. ß-sulfoethyl or <^ - sulfo-

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butyl radicals or sulfatoalkyl radicals, e.g. B. ß-sulfatoethyl or ω-sulfatobutyl radicals or acyloxyalkyl radicals, e.g. B. ß-acetoxyethyl, γ-acetoxypropyl or ω-butyryloxybutyl radicals or alkoxycarbonylalkyl radicals, z. B. ß-Methoxycarbonyläthyl- or ω Äthoxycarbonylbutylresten or aralkyl radicals, ζ. Β. Benzyl or Phenethyl residues.

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

X can be an acid anion of the type customary for cyanine dyes, z. 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 Rj or R ", for example when Rj and / or R _{2 have} the meaning of sulfoalkyl or carboxyalkyl radicals.

Zj and Z ₂ preferably represent the atoms required for the formation of 5- or 6-membered heterocyclic rings, as are typical for cyanine dyes. B. may have an oxygen, sulfur, selenium or nitrogen atom.

Z- and Z ₂ preferably stand for the atoms which are necessary to complete the optionally substituted heterocyclic rings indicated below, namely:

a thiazole ring, e.g. B-. of a thiazole, 4-methylthiazole, 4-

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Phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-diinethylthiazole, 4,5-diphenylthiazole, 4- (2-thienyl) thiazole, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, S-bromobenzothiazole, 6-bromobenzothiazole, 5-phenylbenzothiazole, 6-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-hydroxybenzothiazole, 5,6-hydroxybenzothiazole -, 6-Hydroxybenzothiazole, naphthol, 1-d7thiazole, naphtho- / T, 2-d7thiazole, 5-methoxynaphtho, 2,3-d7thiazole, 5-ethoxynaphtho- / 2,3-d7thiazole, 8-methoxynaphtho / 2,3-d7thiazole, 7-methoxynaphtho- ^ 2,3-d7thiazole or a 4'-methoxythianaphtheno-7 ¹ , 6 * -4,5-thiazole ring;

an oxazole ring, e.g. B. a 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyloxazole, benzoxazole, S-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, naphthol, 1-d7oxazole or naphtho / 7,2-d7-oxazole ring;

a selenazole ring, e.g. B. 4-Methylselenazol-, 4-Phenylselenazol-, benzoselenazole, 5-Chlorobenzoselenazol-, 5-Methoxybenzoselenazol-, 5-Hydroxybenzoselenazol-, Tetrahydrobenzoselenazol-, naphtho / 5,1-d 7 ~ selenazole or naphtho / 1 _t 2 -d7selenazole ring;

a thiazoline ring, e.g. B. a thiazoline or 4-methylthiazoline ring;

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a pyridine ring, e.g. a 2-pyridine, 5-methyl-Z-pyridine, 4-pyridine or a 3-methyl-4-pyridine ring;

a quinoline ring, e.g. a 2-quinoline, 3-methyl-Z-quinoline, 5-ethyl-Z-quinoline-, o-chloro-Z-quinoline-, S-chloro-Z-quinoline-, 6-methoxy-Z-quinoline-, 8-ethoxy-Z-quinoline-, 8-hydroxy-Z-quinoline-, 4-quinoline, 6-methoxy-4-quinoline, 7-methyl ~ 4-quinoline, 8-chloro-4-quinoline, 1-isoquinoline, 3 ^ -dihydro-i-isoquinoline, or one 3-isoquinoline ring;

a 3,3-dialkylindolenine ring, e.g. a 3,3-dimethylindolenine or a 3,3,5-trimethylindolenine ring;

an imidazole ring, e.g. an imidazole, 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-alkyl-4,5-diraethylimidazole, benzimldazole, 1-alkylbenzimidazole, i-aryl-S ^ -dichlorobenzimidazole-, 1-alkyl-1H-naphth £ "i , Z-d / imidazole-, 1-aryl-3H-naphth / "* 1, Z-d / imidazole- or an i-alkyl-5-methoxy-IH-naphth / 1, Z-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 radicals may be substituted with 1-4 carbon atoms. j

If R, and R- are optionally substituted alkyl radicals, these preferably have 1 to 12 carbon atoms. They can be substituted by the substituents indicated for Rj and R-. For example, R ₃ and R can be: methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl or dodecyl radicals or alkoxycarbonylalkyl radicals, for example methoxycarbonylmethyl, ethoxycarbonylmethyl or ethoxycarbonylethyl radicals. If Rj and R2 have the meaning of aryl radicals, these preferably consist of optionally substituted aryl radicals of the phenyl or naphthyl series, for example phenyl, naphthyl, tolyl-j / chlorophenyl or alkoxyphenyl radicals, the alkoxy groups of which preferably have 1-4 carbon atoms.

/ Hydroquinolyl,

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If R, and R. together represent the heterocyclic ring containing 5- or 6-ring atoms, then exists this preferably from an optionally substituted morpholino, thiomorpholino, piperidino, piperazinyl, pyrrolidinyl, Indolinyl, tetrahydrochinoyl or decahydrochinoyl ring.

If R ₃ and R are the atoms required to complete a piperazinyl ring, this preferably consists of a 4-alkyl-i-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, Ätfyl, 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 ₉ represent the atoms required to complete benzoxazole, naphthothiazole or benzothiazole rings, when Q is also an ethylene radical and when R and R. together are those needed to complete a piperazinyl radical, in particular represent a 4-Äthoxycarbonyl-1-piperazinylrestes required atoms.

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

Table A.

I 11- (4-ethoxycarbonyl-i-piperazinyl) -3,3'-diethyl-1O, 12-ethylene oxatricarbocyanine perchlorate,

II 3,3-diethyl-10,12-ethylene-11 - (4-methyl-i-piperazinyl) -oxatricarbocyanine perchlorate,

1 0 9 B 1 5 / U ü 8

2 U 4 6 6 8 7

III 3.3 ^t -diethyl-1O, 12-ethylene-11- (4-methyl-1-piperazinyl) thiatricarbocyanine perchlorate,

IV 11- (4-ethoxycarbonyl-1-piperazinyl) -3,3'-diethyl

10,12-ethylene-5,5-diphenyloxatricarbocyanine perchlorate,

V anhydro-11- (4-ethoxycarbonyl-1-piperazinyl) -10,12-ethylene-3,3'-di (3-sulfopropyl) thiatricarbocyanine hydroxide,

VI anhydro-10,12-ethylene-11- (4-methyl-1-piperazinyl) -3,3'-di (3-sulfopropyl) oxatricarbocyanine hydroxide,

VII anhydro-10,12-ethylene-11- (4-methyl-1-piperazinyl) -3,3'-di (3-sulfopropyl) thiatricarbocyanine hydroxide,

VIII 11- (4-ethoxycarbonyl-1-piperazinyl) -3,3'-diethyl-10,12-ethylthiatricarbocyanine perchlorate,

IX 11- (4-phenyl-1-piperazinyl) -3.3 ^l -diethyl-1O, 12-orthophenylenethiatricarbocyanine-p-toluenesulfonate,

X anhydro-11-dibutylamino-10,12-ethylene-3,3-di (3-sulfopropyl) thiatricarbocyanine hydroxide, Sodium salt,

XI 3,3 · -Diethyl-10,12-ethylene-11- (1-pyrrolidinyl) -thiatricarbocyanine odid,

XII 1O, 12-ethylene-1,1 ', 3,3,3', 3-hexamethyl-11- (1 -pyrrolidinyl) indotricarbocyanine iodide,

XIII 3,3'-diethyl-10,12-ethylene-11-piperidinothiatricarbocyanin iodide,

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XIV 3,3 ^f -diethyl-10,12-ethylene-11-morpholinothiatricarbocyaninjodid,

XV 3,3'-diethyl-11-piperidino-10,12-trimethylene thiatricarbocyanine iodide,

XVI 3,3-diethyl-10,12-ethylene-11- (i-indolinyl) oxatricarbocyanine perchlorate,

XVII S ^ '- diethyl-IOJZ-äthylen-H- ^ i-CI, 2,3,4-tetrahydroquinolyl ^ oxatricarbocyanine perchlorate,

IVI11 11-diethylamino-3,3 ^f -diethyl-10,12-ethylthiatricarbocyanine perchlorate,

XIX 11-diethylamino-10,12-ethylene-i, 11,3,3,3 », 3'-hexamethylindotricarbocyanine perchlorate,

XX 3,3'-diethyl-10,12-ethylene-11- £ T- (1,2,3,4-tetrahydroquinolyl74.5; 4 ', 5'-dibenzothiatricarbocyanine perchlorate,

XXI 1i-diphenylamino-3,3'-diethyl-10,12-ethylene oxatricarbocyanine perchlorate,

XXII H-dimethylamino-S ^ '- diethyl-IO.n-ethylthiatricarbocyanine perchlorate,

XXIII 3,3'-diethyl-10,12-trimethylene-ii-thiomorpholinooxathiatricarbocyanine perchlorate,

XXIV 3,3'-diethyl-10,12-ethylene-l1- (1-decahydroquinolyl) -4,4'-tricarbocyanine perchlorate,

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XXV anhydro-11- (4-äthoxycarbonylpiperazin-1-y1) -10,12-ethylene-3,3'-bis (3-sul £ opropyl) -5,6, 5 ^1, 6'-dibenzothiatricarbocyaninhydroxyd, Triäthylaminsalζ.

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

^IX * ^ -z; - o

<'· ¹ ^ n ii

N - (CH-CH) == C-CH = CH-NC-CH ₃ Χ ^θ R ₁ C ₆ H ₅

with one mole of an enamine salt of the formula III ¹¹¹ * ^R 3 \

H-C-C-CH-

² IJ ²

whereby a compound of the following formula IV is obtained: IV. ^R 3 _V / ^R 4

'«S.

NX (CH-CH) = T = C-CH-CH-CC-CH, i η-ι ι ι ι

C ^e R, LqJ

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 given formulas

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Ü A 6 6 8 7

X, η, m, Z ₁ , Z ₂ , Q, R ₁ , R ₂ , R ₃ and R _{4 have} the meaning given.

O
Il ^ N-CH-CH-C- (CH-CH) m-1 \
ι CH ₃ Il
"Cs I.
R. C ₆ H 5

_χ θ

The reactions are preferably carried out in a suitable solvent, z. B. acetone or acetic anhydride, preferably in the presence of a conventional basic condensing agent, z. B. triethylamine and at elevated temperatures, e.g. B. reflux tempera door of the reaction mixture. In detail you can Methods are used, such as those in French patent 1 410 864, the Belgian patent 674 800, Belgian patent specification 702 840 and USA patent application with serial no. 860 395 of Sept. 23, 1969 and the associated cip application with serial no. 22 708 of March 25, 1970 to be described in more detail.

Under "polynuclear aromatic compounds with at least a sulfonic acid or sulfonic acid salt residue "are those aromatic compounds to consist of which two or more condensed Have benzene rings, e.g. B. naphthalene or pyrene compounds and also compounds containing at least two benzene rings or have other aromatic rings directly linked to one another, e.g. B. diphenyl, terphenyl and quaterphenyl compounds and finally also such connections,

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in which at least two benzene rings or other aromatic Rings are connected to one another via an aliphatic chain or an aliphatic radical. Such polynuclear aromatic Compounds can be represented by the following general formula:

IVa D-SO ₃ M

where mean:

D is a polynuclear aromatic radical as indicated above and

M is a hydrogen atom or a water-soluble cation salt residue, z. B. a metal atom, e.g. B. an alkali metal atom, for example a sodium or potassium atom or an ammonium radical or a triethylammonium, Triethanolammonium or pyridinium radical.

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

_ i

-CH-CH-D ₂

Herein mean: ^S0

D.J a 1,3,5-triazin-6-ylamino radical and D- an aromatic Remainder, e.g. B. an optionally substituted benzene radical. M has the meaning already given.

Typical compounds falling under the formula V in which D.

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is 1,3,5-triazin-f-ylamino; d. H. a 1, S.S-Tri Z-ylaminorest, are compounds of the following general Formula Vb:

CH-CH

wherein M has the meaning already given and R., R ^, Ry and R _{11 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 xthoxy radical or a halogen atom, e.g. B, 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, ß-hydroxyethylamino, di-hydroxyäthylamino- or ß-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-toludino 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 p-acetamidoanilino radical.

To produce a supersensitized, photosensitive,

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Photographic silver halide emulsions are furthermore, for example, compounds of the formula Vb in which R ₁₁ , Rr, _Rft and / or R _{7 represent} heterocyclic amino radicals, e.g. B. 2-benzothiazolamino or 2-pyridylamino radicals.

Another class of polynuclear aromatic compounds having at least one sulfonic acid or sulfonic acid salt residue, the suitable for the preparation of a supersensitized silver halide photographic emulsion of the invention can be obtained by the reproduce the following structural formula VIa:

Herein mean:

Rg is an acylamido radical, e.g. B. an acetamido, sulfobenzamido, 4-methoxy-3-sulfobenzamido, 2-ethoxybenzamido, 2,4-diethoxybenzamido, p-tolylamido, 4-methyl-2-methoxybenzamido, 1-naphthoxylamino, 2-naphthoylamino, 2,4-dimethoxybenzamido, 2-phenylbenzamido or 2-thienylbenzamido radical or one Sulforest;

an acylamido radical, as _{indicated for R g} , or a sulfoaryl radical, e.g. B. a sulfophenyl or p'-sulfodiphenyl radical and

a hydrogen atom or a Sulforest, with the proviso that the compound is at least one Sulforest, d. H. a sulfonic acid or sulfonic acid salt residue.

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Compounds of formula Vb, which are advantageous for the preparation of a supersensitized silver halide photographic emulsion according to the invention are, for example 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 in the textile industry used.

The preparation of the dibenzothiophene dioxide compounds of the formula VIa is described, for example, in US Patents 2,573,652; 2,580,234 and 2,563,493 and also 2,937,089 are known.

For preparing a light-sensitive silver halide photographic emulsion Compounds of the formula IVa which are suitable according to the invention are also known from the USA patent 2937089 and the USA patent 2 950 196 (cf. in particular the formulas II, III and IV of this patent specification).

Compounds of the formula Va, in which D- is a benzotriazolyl radical represents, for example, according to US Patents 2,713,057; 2,684,966; 2,784,197 and 2,784,183 known Process are produced. Further similar compounds with a 2-benzotriazolyl radical which are used according to the invention are described in U.S. Patent 2,733,165. Such compounds fall under the formula IVa given above

Typical polynuclear aromatic compounds with at least

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a sulfonic acid or sulfonic acid salt residue, which comes under the formulas IVa, Va and VIa are, for example:

1. Triazolostilbene compounds containing sulfonic acid residues, e.g. B. of the type known from U.S. Patent 2,713,057;

4.4 ^t -Di (4 ", 6" -dihydroxy-2 "-s-triazinylamino) stilbene-2.2 ^l -disulfonic acid,

3. 4,4'-Bis ^ 4- (3 ^l -sulfoanilino) -6-amino-s-triazin-2-ylamino7-stilbene,

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

5. Sulfonated triazinyl stilbene, e.g. B. that from the United States patent documents 2,595,030 and British Patent 595,065,

6. 4,4'-Bis ^ 2- (4-sulfoanilino-2-β-hydroxyethylamino) -1,3,5-triazine 6-ylaming7stilbene-2,2'-disulfonic acid,

7. 4,4'-bis (2,4-dihydroxy-1,3,5-triazin-6-ylamino) dibenzyl-2.2 ^l disulfonic acid,

^{8.4 l} -bis (2-ß-hydroxyethylamino-4-anilino-1,3,5-t * iazin-6-ylamino) -1,4-distyrylbenz-2,2'-disulfonic acid,

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

10.

^C 6 ^H 5 ^ 3,7-bis (2-phenylbenzamido) - 2,8-disulfodibenzothiophene-5,5-dioxide,

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

12. 3- / 4- (4-Methoxy-3-sul £ topzamido) phenyl7-7- (4-methoxy-3-sul £ topzamido) cp #ibenzothiophendioxyd, 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-i-sulfonic acid, sodium salt,

17 4/5-phenoxy-6- (.beta.-hydroxyethylamino ^T> s-triazine-2-ylamino7-4 "- ^ 3-chloro-6-di (.beta.-hydroxyethyl) amino-s-triazine-2-ylamino7 -stilbene-2,2'-disulfonic acid,

18. 2,8-Bis ^ 4- (4-sul £ oanilino) -6-hydroxy-s-triazin-2-ylaming7-carbazole,

19. 4,4'-Bis (4,6-di (β-hydroxyethylamino) -s-triazin-2-yl) benzidine 2,2'-disulfonic acid,

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20. 2-Laurylamino-4,6-di (4-sulfoanilino) -s-triazine,

21. 4,4'-Bis [4- ^ 4 ^l - (N ^t , 4 "-sulfobenzyl-N'-ethyl) aminoanilino7-6-hydroxy-s-triazin-2-ylamino] stilbene-2,2'- disulfonic acid,

22. 5-Acetamido-2- (4-styryl-3-sulfo) phenyl-1,2,3-benzotriazole, Sodium salt,

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

24. 4-sulfo-o-terphenyl, sodium salt (Lour. Organ. Chem., Vol. 14 (1949), page 163,

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

26. 3,7-bis (4-methyl-2-methoxybenzamido) -2 _> 8-disulodibenzothiophene-5,5-dioxide, sodium salt.

As can be seen from the foregoing listing of the preparation of a supersensitized light-sensitive photographic Silver halide emulsion according to the invention suitable polynuclea- f ren aromatic compounds with at least one sulfonic acid or sulfonic acid salt residue, these compounds can, for example in the form of their water-soluble alkali metal salts, e.g. B. in the form of their sodium and potassium salts or ammonium salts or Amine salts, e.g. B. triethylamine, triethanolamine, pyridine and Aniline salts can be used. You can use the emulsions in practically neutral aqueous solutions without affecting the pH of the emulsions to change, are added.

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Particularly useful silver halide reducing agents; H. Compounds that are able to reduce silver halide are reducing dihydroxy compounds / äü3 * of the group of Benzenes, V-lactones, pyronimides, tetronimides, furans and pyrroles, which have at least two hydroxyl groups.

Typical dihydroxy compounds that act as supersensitizing agents Compounds for preparing a supersensitized light-sensitive silver halide photographic emulsion according to Hydroquinone, resorcinol, pyrocatechol, 3-methylpyrocatechol, toluhydroquinone, naphthalenediols and the like, also Y ~ -lactones, z. B. ascorbic acid, isoascorbic acid and the like., Also 3-hydroxytetronimides; 3,4,5-trihydroxy-5,6-dihydro-pyronimide, also Aminohexosereductone, z. B. those in which the KiiSstteRrest by the following formula can be reproduced:

R ²
R ¹ -N-

where mean:

R and R each represent an alkyl radical preferably having 1 to 8 carbon atoms or together the necessary to complete a heterocyclic ring with preferably 5 to 6 ring atoms

i ο

chen atoms, with the proviso that the heterocyclic formed by R and R In addition to the nitrogen atom present, rings may also have a second nitrogen atom or an oxygen atom can. For example, R and R can represent the atoms that are required to complete a morpholino, piperazino, pyrrolino, pyridino, pyrimidino or piperidino ring.

Typical ones used for making a photosensitive photographic

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Silver halide emulsion according to the invention as a supersensitizing agent Compound suitable tetronimides, pyronimides and aminohexose reductones are compiled in the following table B:

Table B.

5-phenyl-3-hydroxytetronimide HO-C = C-OH

C, H ..- C C = NH

6 S i \ /

5- (4-carboxyphenyl) -3-hydroxytetronimide, 5- (3,4-dimethoxyphenyl) -3-hydroxytetronimide, 5- (η-butyl) -3-hydroxytetronimide, 5- (2-furyl) -3-hydroxytetronimide, (5- -Furyl-S ^ -dihydroxy ^ -imino ^ .S-dihydrofuran), 5,6-diphenyl-3,4,5-trihydroxy-5,6-dihydro-pyronimide

OH

C.Hv-CH C-OH

6 5,,

C, H _C -CH C »NH

5,6-di-n-butyl-3,4,5-trihydroxy-5,6-dihydro-pyronimide, 5,6-di-morpholino-3,4,5-trihydroxy-5,6-dihydro-pyronimide, 5,6- (2-sulfophenyl) -3,4,5-trihydroxy-5,6-dihydro-pyronimide, Dimethylaminohexose reductone, di-n-butylaminohexose reductone,

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Di-n-hexylaminohexose reductone,
Morpholinohexose reductone,
Piperazinohexose reductone,
Pyrrolinohexose reductone,
Piperidinohexose reductone.

For preparing a light-sensitive silver halide photographic emulsion Tetronimides and pyronimides suitable according to the invention can be produced, for example, by processes as described in British patent 782 304 and Swiss patent 322 985 and the journal HeIv. Chim. Acta, £ 3, (1956) page 1780. the specified and other 3-hydroxytetronimides and also suitable 3,4,5-trihydroxy-5,6-dihydro-pyronimides, which are used for the production a photographic silver halide emulsion of the invention are also disclosed in U.S. Patent 3 330 655.

The aminohexose reductones useful in preparing a light-sensitive silver halide photographic emulsion according to the invention are derived from sugars, in particular from D-glucose and also from other six carbon atoms reducing hexose sugars, e.g. B. D-galactose, D-mannose, D-fructose and L-sorbose.

A typical process for making those useful in the present invention Reductone consists in a reducing medium practically free of water and a reducing hexose sugar aliphatic or cyclic secondary amine in the presence of an acidic, reductone-forming catalyst, e.g. B. phosphoric acid, Boric acid, acetic acid or succinic acid to heat. When the aminohexose reductone is formed, three molecules of water become

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free. To produce a supersensitized, photosensitive, Reductones suitable for the photographic silver halide emulsion of the invention and processes for their preparation are known from US Pat. No. 2,936,308, for example.

If azaindenes are used as supersensitizing compounds, so these z. B. consist of triazaindenes, tetraazaindenes or pentaazaindenes. Azaindenes are particularly advantageous those substituted by a hydroxy and / or amino radical " are. Azaindenes which can be used according to the invention are, for example from the following U.S. Patents 2,735,769; 2,743,181; 2,835,581; 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 magazine for scientific photographic £ 7 (1952), pages 2 - 28 known.

Particularly advantageous tetraazaindenes for producing a light-sensitive photographic silver halide emulsions according to the invention are those of the following structural formula:

OH

wherein R * has the meaning of an alkyl radical, e.g. B; one Methyl, ethyl, propyl or butyl radical.

Typical, particularly advantageous azaindenes are, for example:

4-Hydroxy-2-ß-hydroxy-ethyl-6-methyl-1,3,3a, 7-tetrazaindene, 5-carbethoxy-4-hydroxy-1,3,3a, 7-tetrazaindene, 7-hydroxy-t _t 2,3,4,6-pentazainden,
2,4-dihydroxy-6-methyl-1,3a, 7-triazaindene,

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4-Hydroxy-Z-oC-hydroxypropyl-ö-methyl-1,3,3a, 7-tetrazaindene, 4-Hydroxy-2 (4-pyridyl) -6-methyl-1,3,3a, 7-tetrazaindene, 4-Hydroxy-6-methyIr 1,2,3,3a, 7-pentazaindene, 5-amino-2- (p-carboxyphenyl) -7-hydroxy-1,3,4,6-pentazaindene, 2,4-dihydroxy-6-methyl-1,3a, 7-triazaindene, 2,5-dimethyl-7-hydroxy-1,4,7a-triazaindene, 5-amino-7-hydroxy-2-methyl-1,4,7a-triazaindene, 5-carboxy-4-hydroxy-1,3,3a, 7-tetrazaindene, 1,2-bis (4-hydroxy-6-methyl-1,3,3a, 7-tetrazainden-5-yl) ethane, 1,2,3,4-tetrakis (4-hydroxy-6-methyl-1,3,3a, 7-tetraazainden-2-yl) butane,

2-amino-5-carboxy-4-hydroxy-1,3,3a, 7-tetrazaindene, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene.

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

Furthermore, particularly advantageous results can often be achieved then achieve when a polynuclear aromatic compound with at least one sulfonic acid or sulfonic acid salt residue and one Silver halide reducing agent is used. In some cases it can be particularly advantageous for both supersensitization a polynuclear aromatic compound with a sulfonic acid or sulfonic acid salt residue, an azaindene and 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 photosensitive silver halide emulsion.

The most favorable concentration of enamine tricarbocyanine dye in the individual case and supersensitizing compounds can be determined in a known manner by a series of tests.

It has proven to be useful to add about 0.01 to 1 g of dye and about 25-2000 mg, preferably 50-1000 mg, per mole of silver the polynuclear aromatic compound with at least one sulfonic acid or sulfonic acid salt residue or reducing agent and about 1 - 8 g, preferably 2 - 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, 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 emulsions of medium grain size or mixed emulsions with silver halides of different grain sizes act. You can do this by customary known methods are produced, d. H. it can be, for example, so-called single-nozzle emulsions or double-nozzle emulsions. Further the supersensitized emulsions according to the invention can consist of so-called Lippmann emulsions, ammoniacal emulsions or from emulsions ripened in the presence of thiocyanates or thioethers, such as those from the USA patents 2,222,264; 3,320,069 and 3,271,157 are known. Furthermore, the emulsions can be those having cubic silver halide grains be, for example, from the Journal of Photo-

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- 26 -

graphic Science, Volume 12, pages 242 ff. or the Journal of Photographic Science, Volume 13, 1965 / bath of the British Patent 1 156 193 are known.

The silver halide emulsions of the present invention can be used for the purposes of Removal of the soluble salts can be washed emulsions, but also unwashed emulsions. This means that the soluble Salts can be removed, for example, by quenching and leaching the emulsion or else that the emulsion is a Can be subjected to coagulation washing, as described, for example, in U.S. Patents 2,618,556; 2,614,928; 2,565,418; 3 241 969 and 2 489 341 is known.

The emulsions according to the invention can furthermore be prepared with the aid of conventional chemical sensitizers, e.g. B. reducing active compounds, sulfur, selenium or tellurium compounds or gold, platinum or palladium compounds or combinations be sensitized to these compounds. Typical chemical sensitization processes, after which the photographic silver halide emulsions of the present invention are chemically sensitized are, for example, from the USA patents

1,623,499, 2,399,083; 3,297,447 and 3,297,446 are known.

Advantageously, the supersensitized according to the invention Silver halide emulsions also contain speed increasing compounds, e.g. B. polyalkylene glycols, cationic surface-active substances and thioethers or combinations thereof, such as those from the USA patents

2,886,437; 3,046,134; 2,944,900 and 3,294,540 are known.

The silver halide emulsions of the present invention can also protected from the appearance of veils and opposed to

/ "Pages 85 to 89

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2U46687

a loss of sensitivity during storage the emulsion. For example, known antifoggants and stabilizers and conventionally known to the emulsions be added alone or in the form of combinations, e.g. B. those from US Pat. No. 2,131,038 and US Pat 2,694,716 known thiazolium salts, those known from U.S. Patents 2,886,437 and 2,444,605 Azaindenes, the mercury salts known from US Pat. No. 2,728,663, which are known from US Pat. No. 3,287,135 known urazole; the sulfocatechols known from US Pat. No. 3,236,652; those from the British patent specification 623 448 known oximes, also nitrone and nitroindazole and also those from US patents 2,403,927; 3,266,897 and 3,397,987 known mercaptotetrazoles, as well as the polyvalent ones described in US Pat. No. 2,839,405 Metal salts; also the thiuronium salts known from US Pat. No. 3,220,839 and finally those from palladium, platinum and gold salts known in U.S. Patents 2,566,263 and 2,597,915.

Optionally, the supersensitized silver halide photographic emulsions of the present invention can also contain developing agents incorporated, e.g. B. Hydroquinones, catechols, aminophenols, 3-PyrazoIidone, ascorbic acid and its Derivatives, reductones and phenylenediamines or combinations thereof. Optionally, the developing agents can be added to another layer of one using a supersensitized one light-sensitive, photographic silver halide emulsion according to the invention is incorporated into the recording material will.

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2U46687

The developer compounds can be in the form of solutions or in the form of dispersions, as described, for example, in the USA patent 2,592,368 and French patent 1,505,778, can be added.

For hardening the supersensitized photographic materials of the present invention Silver halide emulsions can contain the customary known organic and inorganic hardeners as well as combinations Functions thereof 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, carbodiimics as well as hardening agents with two: various hardening radicals, e.g. an epoxy and an aldehyde radical or a halogen and an aldehyde radical as well as curing agents consisting of polymers, e.g. B. oxidized polysaccharides, e.g. B. dialdehyde starch, oxyguargum and the like.

For the preparation of the silver halide photographic emulsions of the present invention The customary known colloids can also be used as carriers or binders. To Her-P position of the emulsions suitable hydrophilic binders can consist of naturally occurring substances such. B. off Proteins, for example gelatin, gelatin derivatives, cellulose derivatives, polysaccharides, e.g. B. dextran, gum arabic and the like or from synthetic polymers, e.g. B. of water-soluble polyvinyl compounds, e.g. B. poly (vinyl pyrrolidone), also Acrylamide polymers and other synthetic polymeric compounds, e.g. B. dispersed polyvinyl compounds in latex form, namely especially those which are used to increase the dimensional stability of the prepared using the silver halide emulsion contributing photographic material. To produce the emul-

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Synthetic polymers suitable for ionization are described, for example, in U.S. Patents 3,142,568; 3,193,386; 3,062,674; 3,220,844 and 3,287,289 and also 3,411,911. Those which are insoluble in water have proven to be particularly effective Polymers of alkyl acrylates and alkyl methacrylates, acrylic acid, Sulfoalkyl acrylates or sulfoalkyl methacrylates proven, in particular those which have groups suitable for cross-linking that facilitate curing, and those which, such as the polymers disclosed in Canadian Patent 774 054, have sulfobetainic repeating units exhibit.

The silver halide emulsions according to the invention can be used for production of the most varied of recording materials are used, which are advantageously antistatic or effective have conductive layers, e.g. B. layers with soluble salts, e.g. B. chlorides or nitrates or the vapor-deposited metal layers or layers of ionic polymers, such as those from U.S. Patents 2,861,056 and 3,206 or layers with insoluble inorganic salts, such as those known from US Pat. No. 3,428,451, for example are.

The silver halide emulsions of the invention can be based on the a wide variety of customary known substrates are applied, for. B. on films made of cellulose nitrate, cellulose esters, polyvinyl acetal, Polystyrene, polyesters, e.g. B. polyethylene terephthalate, polycarbonates and the like. As well as on glass substrates, Paper and metal. A typical flexible layer support consists, for example, of a layer support made of paper, which optionally can be partially acetylated. Furthermore, the paper layer carrier can, for example, be a barite layer or a Have a layer of a t ^ -olefin polymer, in particular from

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a polymer of an o ( -olefin with 2-10 carbon atoms, e.g. a layer of polyethylene, polypropylene, an ethylene-butene copolymer and the like.

The emulsions according to the invention can advantageously also plasticizers or plasticizers and lubricants, e.g. B. polyalcohols, e.g. B. glycerine and diols from the US patent 2,960,404, and also fatty acids or esters such as those described in US Pat. No. 2,588 and US Pat. No. 3,121,060 or silicone resins, as known, for example, from British patent specification 955 061.

Finally, the emulsions according to the invention can also be surface-active Contain compounds, e.g. B. saponin and / or anionic compounds, such as alkylarylsulfonates, as they are known, for example, from US Pat. No. 2,600,831 and / or amphoteric compounds, such as, for example in U.S. Patent 3,133,816.

Finally, those using a supersensitized photographic silver halide emulsion recording materials prepared according to the invention also include matting agents included, e.g. B. from starch, titanium dioxide, zinc oxide, silica, polymer particles, such as those in the USA patents 2,992,101 and 2,701,245; and the like.

The silver halide emulsions according to the invention can also be used also for the production of photographic recording materials can be used which contain optical brighteners, for example based on stilbene, triazine, oxazole and coumarin. For the production of the recording materials can also be water-

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Soluble brighteners can be used, as for example in the German patent specification 972 067 and the USA patent specification

2 933 390 or further dispersions of whitening agents, as known, for example, from German patent specification 1,150,274 and US patent specification 3,406,070 are.

The silver halide emulsions according to the invention may further be used for producing such recording materials are% which contain light absorbing materials and / or filter dyes such as, for example, from the US Patents 3,253,921; 2,274,782; 2,527,583 and 2,956,879 are known. If necessary, such dyes can be fixed with the aid of mordants such as are known, for example, from US Pat. No. 3,282,699.

The dyes used for sensitization and the other emulsion additives can be the emulsions from aqueous solutions or from solutions of organic solvents are added, for example by methods such as those described in U.S. Patents 2,912,343;

3,342,605; 2,996,287 and 3,425,835 are known. If several dyes are used, these can be used separately or together in one ' Solvents are dissolved and added. If necessary, it is also possible to use one made from a silver halide emulsion Layer to bathe in the solution of the dye or dyes.

For the production of photographic recording materials under Use of a supersensitized, photosensitive, Various conventionally known coating methods can be used for silver halide photographic emulsions including dip coating, coating with an air coating knife, curtain coating, extruder

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2Ü46687

coating using a coating funnel such as that known from US Pat. No. 2,681,294 is and the like. If necessary, two or more layers can also be applied at the same time, as is the case, for example US Pat. No. 2,761,791 and British Pat. No. 837,095.

The emulsions according to the invention can also be used for the production of Recording materials for the colloid transfer process can be used, for example as described in the USA 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;

2,543,181; 3,020,155 and 2,861,885. Finally you can the emulsions can also be used in the production of recording materials which are used for carrying out the color image transfer process can be used as described, for example, 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 is known and also for the production of recording materials for the suction transfer method, as is known, for example, from US Pat. No. 2,882,156.

The photosensitive substances according to the invention can advantageously be used Use silver halide emulsions for the production of color photographic recording materials, d. H. for example such recording materials which contain color couplers, as described, for example, in U.S. Patents 2,376,679; 2,322,027; 2,801,171; 2,698,794; 3,227,554 and 3,046,129 are known are. On the other hand, the emulsions can also be used advantageously for the production of such color photographic recording materials are used, the solution containing color couplers

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2Ü46687

Solutions can be developed, for example from the USA patents 2,252,718; 2 592 243 and 2 950 970 is known.

Exposed photographic silver halide emulsions according to the invention can be developed by the known customary developing processes, in particular using the customary known alkaline developer solutions whose developer compounds consist of hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid derivatives, hydroxylamines, hydrazines and the like . To develop the silver halide emulsions, the customary known ribbon development processes can also be used, such as those described, for example, in US Pat. B. from US Pat. No. 3,179,517, and also the so-called stabilization development processes, such as those known from the "PSA Journal", Volume 16B, August 1950, for example. Finally, they can also be developed with so-called monobaths, as are known, for example, from the magazine "Phot., Sei. And Eng.", Volume 2, No. 3, October 1958 and US Pat. No. 3,392,019. If desired, the emulsions can also be developed using so-called hardening developer as they like, for example, are known from US Patent 3,232,761. Finally, the development can 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 light-sensitive silver halide photographic emulsions of the present invention can also be used

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are also used for the production of recording materials that are used for the production of planographic printing plates, as known from U.S. Patents 3,402,045 and 3,271,150, for example.

It has proven to be particularly advantageous to use the supersensitized emulsions for the production of color films for aerial photography with high resolution use. Such color films can consist, for example, of a film substrate on which the following reference sequence 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 gelatine-silver bromoiodide emulsion layer, which form a non-diffusing, non-diffusing yellow dye detfn dC-pivalyl-eC-phenoxyacetanilide couplers as is known, for example, from column 6 of US Pat. No. 3,408,194;

3. a gelatin layer containing 2,5-dioctylhydroquinone;

4. one containing a bleachable, blue-green colored dye Gelatin layer;

5. a slightly reddish-sensitive gelatin-silver bromoiodide emulsion ^, their silver halide grains from a silver broniodide core with a shell made of silver bromide, which is practically free of silver iodide

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where the emulsion contains a nondiffusible 1-hydroxynaphtharaide color coupler which is capable of forming a nondiffusible, blue-green dye, as described, for example, in column 2 of US Pat. contains phenolic couplers substituted in the 2- and 5-positions, which are capable of forming a non-diffusing blue-green dye and may, for example, have the constitution of a color coupler, as is known from column 3 of US Pat. No. 2,895,826;

6. a gelatin layer containing 2,5-dioctylhydroquinone;

7. one containing a bleachable, magenta colored dye Gelatin tight;

8. a low green-sensitive gelatin silver bromoiodide emulsion layer, the silver halide grains of which consist of a core of silver bromoiodide and a shell of silver bromide which is practically free of silver iodide, the emulsion layer containing a non-diffusing 3-benzamido-i-phenyl-S-pyrazolone color coupler, which is capable of forming a non-diffusing magenta dye, the non-diffusing color coupler λ being, for example, a color coupler of the type known from column 3 of US Pat. No. 2,908,573;

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

10. A gelatin layer in which a UV absorber is dispersed, as is known, for example, from Table A in column 4 of US Pat. No. 3,250,617 and which also contains a mordant of the type known from US Pat. No. 2,882,156 , which consists of the reaction product of aminoguanidine and a polymeric oxo compound.

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The silver halide emulsions consisting of a core and a shell silver halide grains can advantageously be prepared by generating iodide-rich cores of silver bromoiodide during the first 15% of the precipitation, after which an iodide-free silver halide shell is precipitated, the pAg- Value is kept constant in order to achieve the desired grain size. Preferably, the procedure is such that the diameter of the silver halide grains is less than about 0.75 microns, preferably less than 0.5 microns.

Such a recording material can e.g. B. used in a camera used for aerial reconnaissance, with which Earth photographs are made, whereupon the exposed material is developed as part of a color development process, as it is for example from US Pat. No. 3,046,129, column 23, line 34 to column 24, line 27 is known. That in the development The resulting color image has an improved resolution compared to the resolution of an image which has been obtained using a corresponding recording material of the prior art.

It has been found that sensitization of a silver halide emulsion compared to the infrared region of the spectrum is generally higher when the silver halide grains Emulsion consist of cubic silver halide grains rather than octahedral silver halide grains.

As a result, exist according to a particularly advantageous embodiment of the invention, the silver halide grains of the supersensitized light-sensitive silver halide photographic emulsion of cubic silver halide grains.

1 0 9 8 I 5 / U U 8

Particularly advantageous antifoggants for infrared-sensitized silver halide emulsions with cubic silicon halide grains are 3,3'-alkylene-bis (benzothiazolium salts) ζ. B. 3,3'-decamethylene bis (benzothiazolium bromide ¹ ) or an antifoggant consisting of a diselenide, ζ. Β. ο, ο ¹ -Diseleno-bis (N-methylacetanilide) 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

NHCOC ₃ F ₇ -Ii

0-CH-CONH

CONH- (CH ₉ ) ^ O

these dissolved in a coupler solvent, e.g. B. in dibutyl phthalate or dissolved in tricresyl phosphate can be dispersed in the emulsion, or if the emulsion is a so-called Contains anti-stain agent (antistain agent), such as dioctylhydroquinone, which is also advantageously in one suitable solvent, e.g. B. tricresyl phosphate dissolved in the emulsion can be dispersed.

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The following examples are intended to illustrate the invention in more detail. The dyes listed in the following tables have been described in more detail in Table A.

example 1

Different proportions of one and the same by means of a sulfur and a gold compound sensitized gelatin-silver bromoiodide emulsion, the silver halide grains of which are about 2.1 mol consisted of iodide, the dyes T-8 in the The concentrations given in Table I below were added.

For supersensitization of the individual emulsions this, either the sodium salt was the bis ^ s-triazin-2-vlaming7stilben-2,2-disulfonic acid * at concentrations of 200 ml per mole of silver (in Table I, referred to as "stilbene ¹¹⁾ or the combination of this Stilbene and 4-hydroxy-6-methyl-1 _f 3,3a, 7-tetrazaindene (referred to as "azaindene" 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 support in such a way that that on a carrier Gelatine was omitted.

that on a support surface of 0.0929 RA ² 600 mg of silver and 1342 mg

The recording materials obtained were then passed through filters (Kodak Wratten filters No. 35 and 38A) in a conventional sensitometer (type Eastman IB) and a filter which absorbed infrared radiation, ie radiation above about 700 nm (for example a Chance Glass CG Filter) and a Kodak Wratten filter 89B exposed to a tungsten light source, whereupon the test specimens were developed for four minutes at 20 ^° C. in a developer with the following composition:

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Water, about 50 C.

p-methylaminophenol sulfate Sodium sulfite, dehydrated hydroquinone, sodium carbonate, monohydrate Potassium bromide Top up with cold water

500 ml

2.0 g 90.0 g

8.0 g 52.5 g 5.0 g 1.0 liter

The recording materials were then fixed, washed and dried in the usual way. In the following table The relative speeds obtained when the recording materials were exposed are given using the filters: Wratten 35 + 38A + CG on the one hand and the Wratten 89B filter on the other. The used Wratten filters are further described in the company's publication "Kodak Wratten Filters for Scientific and Technical Use, Editor, Eastman Kodak Company, 22nd Edition, 1966.

Table I.

Color Conc additions Azainden - Azainden Relati Relati veil material tration ve blue ve Infra in g / mol Sensation red sens Ag Azainden opportunity opportunity I. 0.02 100 100 0.40 I. 0.02 Stilbene 151 166 0.59 I. 0.02 "+ Azainden 191 132 0.12 II 0.04 —— 100 100 0.45 II 0.04 Stilbene 316 295 0.13 II 0.04 ·· + 331 159 0.04 III 0.04 —— 100 100 0.23 III 0.04 Stilbene 871 3720 0.15 III 0.04 ¹¹ + 832 1450 0.03 IV 0.02 - 100 100 0.14 IV 0.02 Stilbene 832 159 0.16 IV 0.02 209 182 0.04

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V.
V.
V. 0.02
0.02
0.02 Stilbene
¹¹ + Azainden 100
132
145 100
617
575 0.15
0.22
0.09 VI
VI
VI 0.02
0.02
0.02 Stilbene
"+ Azainden 100
1320
2090 100
479
240 0.80
0.50
0.04 VII
VII
VII 0.02
0.02
0.02 Stilbene
"+ Azainden 100
200
550 100
1000
575 0.69
0.29
0.06 VIII
VIII
VIII 0.02
0.02
0.02 Stilbene
"+ Azainden 100
15 OK
2000 100
11000
11000 2.20
0.72
0.30

The effective supersensitization can be seen from the results obtained of the tricarbocyanine dyes used according to the invention using polynuclear aromatic compounds with at least one sulfonic acid or sulfonic acid salt residue. The table also shows that in such fog, which appears to be caused by an enamine dye The veil produced can be reduced by using an azaind.

The activity of silver halide reducing compounds as supersensitizers for an enamine tricarbocyanine dye emulsions containing emulsions result from the following example 2.

Example 2

Various proportions of a gelatin silver bromoiodide emulsion with 0.77 mol-t iodide of the in the journal Phot. Journal, 79i, (1939), page 330, the dyes listed in the table below were added. The various emulsion-

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share the sodium salt of bis ^ i-triazin-2-ylamino7stilbene-2,2 ^f disulfonic acid, a silver halide reducing compound in concentrations of 200 ml per mole of silver or the combination 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 single emulsion portions were 10 minutes digested at 52 ⁰ C, were coated and the emulsion samples Celluloseacetatfilmschichtträger in a concentration corresponding to 432 mg of silver per 0.09 m support surface.

Samples of the recording materials obtained were then exposed in a sensitometer (Eastman IB) through a Wratten No. 89B filter, whereupon the test specimens were ^{developed, fixed, washed and dried for three minutes at 20 °} C. in the developer described in Example 1.

The results obtained are shown in the table below. The fog values for the emulsions according to the invention were all below 0.08. ,

Table II

Dye Additives Relative

Infrared sensitivity

X - 100

X ascorbic acid 120

X stilbene 330

X stilbene + ascorbic acid 400

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20,6687

XI
XI
XI
XI

XII XII XII XII

XIII XIII XIII XIII

XIV XIV XIV XIV

XV XV XV XV

XVI XVI XVI XVI

XVII XVII XVII XVII

XVIII XVIII XVIII XVIII

XIX XIX XIX XIX

XX XX XX XX

_ M mm 100 Stilbene 262 PHR ⁺ 132 Stilbene + PHR 416 _{- -} ^ 100 Stilbene
HO ** 242
200 Stilbene + HQ 416 ■ »_ M 100 Stilbene 208 PHTB ⁺⁺⁺ 142 Stilbene + PHTB 316 mm m »mm 100 Stilbene 195 PHR 110 Stilbene + PHR 230 a »ι— ma 100 Stilbene 250 PÄ 160 Stilbene + PHl 416 . »_._ 100 Stilbene 230 Ascorbic acid 160 St practice + ascorbic acid 272 100 Stilbene 156 Ascorbic acid 170 Stub-em + ascorbic acid 210 --- 100 Stilbene 190 Ascorbic acid 170 Stilbene + ascorbic acid 200 -__ 100 Stilbene 220 Ascorbic acid 170 Stilbene + ascorbic acid 416 100 Stilbene 220 Ascorbic acid 200 Stilhene + ascorbic acid 470

109815 / U08

XXI Stilbene 100 XXI Ascorbic acid 795 XXI Stilbene + ascorbic acid 316 XXI ___ 891 XXII Stilbene 100 XXII Ascorbic acid 501 XXII Stilbene + ascorbic acid 126 XXII 631

Piperidinohexose reductone

Hydroquinone

S-phenyl-3-hydroxy-tetronimide

The results, shown in Table II, show that silver halide photographic emulsions containing an enamine tricarbocyanine dye excellent due to the addition of a polynuclear aromatic compound with at least one sulfonic acid or a sulfonic acid salt residue on the one hand or a silver halide reducing agent to be supersensitized. From the The data compiled in Table II also shows that when a polynuclear aromatic A synergistic compound having at least one sulfonic acid or sulfonic acid salt residue and a silver halide reducing agent or superadditive effect is achieved.

Correspondingly favorable results were obtained when instead of the specified silver halide reducing agents other reducing agents with at least two hydroxyl groups are used became.

1098 16 / UU8

Example 3

Various proportions of a silver halide emulsion of the type described in Example 2, which can be spectrally produced by the addition of the Dye II had been sensitized, the sulfonated, polynuclear, aromatic compounds added in concentrations of 200 mg per mole of silver. Those using these emulsions The recording materials produced were then tested according to the method described in Example 2. It became the get the following results:

Table III

Stilbene without

Commercially available sulfonated triazinyl stilbene (Calcofluor White MR)

4,4 ^l -bis / (4-amino-6-anilino-s-triazin-2-yl) aming7-2,2'-stilbene sulfonic acid, disodium salt, 4,4'-bis ^ T4-amino-6-phenoxy- s-triazin-2-yl) aming7-2,2'-stilbene disulfonic acid, disodium salt,

4,4'-bis (3-phenylureido) 2,2'-stilbene disulfonic acid, Disodium salt,

4,4'-Bis ^ 5,6-bis (p-sulfoanilino) -s-triazin-2-yl7-amino-2,2-stilbenedisulfonic acid, Hexasodium salt, 4,4'-bis ^ (4-anilino-6-hydroxy-s-triazin-2-yl) aming7-2,2'-stilbene disulfonic acid, Disodium salt,

4,4'-bis / T4-hydroxy-6-phenoxy-s-triazin-2-yl) amino7-2,2'-stilbene disulfonic acid, Disodium salt,

4,4 ^l -bis £ 1,4,6-bisanilino-s-triazin-2-yl) amino72,2 ^l stilbene disulfonic acid, disodium salt.

Relative

Infrared-

Sensitivity

100 166

115 166 120 126 151 151 151

109815 / U08

i'F !!: Ι! Ί !! Ι! 'ϊ » ¹¹¹¹ SI ¹ :? ¹¹¹¹ : ¹ ! ; :: ■:

- 45 -

From the results obtained, it can be seen that the most diverse sulfonated polynuclear aromatic organic compounds for the supersensitization of photographic silver halide emulsions with an enamine tricarbocyanine dye are suitable.

The following example 4 describes the supersensitization of emulsions described with an enamine tricarbocyanine dye with an azaindene. The following example 4 also shows that that it is particularly advantageous to use a combination of an azaindene for the supersensitization of an enamine tricarbocyanine dye and a sulfonated organic compound.

Example 4

Several recording materials were made starting from a gelatin-silver bromoiodide emulsion sensitized with fine sulfur and a gold, their silver halide to about 2.5 mole-t consisted of iodide. The emulsions were in a layer thickness corresponding to 250 mg silver and 574 mg gelatin applied per 0.0929 m on cellulose acetate film backing. The silver halide grains of the emulsion consisted of cubic grains an average size of about 0.3 microns. It was produced in detail according to the method known from British patent specification 1,156,193.

The dyes tested in detail are shown in the following Tables IV and V. Compounds having a supersensitizing effect were tested in detail:

A ■ sodium salt of bis ^ s-triazin-2-ylamino7stilbene-2,2'-disulfonic acid;

1Q9815 / UU8

B »sodium salt of bis / i-triazine - ^ - ylamiiu ^ stilbene- ^, 2-disulfonic acid;

(Two different commercial products A and B were used)

C ■ disodium salt of 4,4 ^f -Bis ^ 3-phenoxy-4- (2-hydroxyethylamino) -1,3,5-triazin-6-ylaming7stilbene-2,2'-disulfonic acid;

D ■ the sodium salt of 3,7-bis (4-methoxy-3-sul £ topzamido) -dibenzothiophendioxides;

E »sodium salt of chrysene-6-sulfonic acid;

F - disodium salt of 4,4'-bis / 5,6-bis (o-chloroanilino) -2-triazinyl amino7stilbene-2,2-disulfonic acid;

Z »4-Hydroxy-6-methyl-1, S ^ a ^ -tetrazaindene.

Table IV

Mg Dy- g Super- g Tetra Blue Light Exposure Infrared Exposure lfli ^S Usato ^b r '/ deÄl ^ Veil Relati- Veil

^MolA " ^A * SENSITIVITY?"

k V ik

___ ___ opportunity 3.8 0.06 opportunity -__ ___ without 229 4.3 0.08 5.5 0.08 1 (40) 2.0 100 4.1 0.14 100 4.9 0.14 1 (40) A (300) 2.0 363 4.3 0.08 269 4.7 0.08 1 (40) B (300) 2.0 240 4.0 0.10 309 4.8 0.10 I (40) C (300) 2.0 302 4.4 0.10 380 5.2 0.11 '1 (40) 324 3.66 0.38 417 4.2 0.38 Π (40) 2.0 100 3.74 0.22 100 4.1 0.22 11 (40) A (300) 2.0 398 4.5 0.10 141 4.8 0.10 11 (40) 251 398

109815 / U08

11 (40) B (300) 2.0 316 4.1 0.10 289 5.0 0.10 5.50 0.08 123 5 , 90 0.11 11 (40) C (300) 2.0 316 4.2 0.10 389 6.8 0.10 4.90 0.14 224 5 , 25 0.15 _ — _ 295 3.70 0.04 —_ _— 0.04 4.70 0.08 339 5 , 40 0.09 XXV (IOO) 123 1.60 0.04 17 4.25 0.04 4.80 0.10 372 5 , 35 0.10 XXV (IOO) F (IOOO) 346 4.35 0.04 794 3.50 0.03 5.20 0.11 457 5 , 15 0.09 XXV (IOO) 2.0 282 3.27 0.04 23 4.30 0.04 4.70 0.38 89 4th , 30 0.48 XXV (IOO) F (IOOO) 2.0 468 4.15 0.04 1024 2.80 0.05 4.10 0.22 91 4th , 70 0.28 Table V 4.80 0.10 550 5 , 35 0.26 Color
material
(40 mg /
Mol Ag) mg super
sensitive
lizer /
Mol Ag 4.60 0.14 331 5 , 20 0.25 I. - M> - 5.40 0.13 479 5 , 20 0.13 I. Z (2000) I. Z (2000)
+ A (300) I. Z (2000)
+ B (300) I. Z (2000)
+ C (300) II II Z (2000) II Z (2000)
+ A (300) Fresh material Incubated material
Relati- veil Relati- veil
ve Infra- ve Infra-
rotemp- rotemp
sensitive- sensitive-
ity r ity Y II Z (2000)
+ B (300) 100 II Z (2000)
+ C (300) 269 309 380 417 100 141 436 331 417

109815 / UU8

I. Z (2000)
+ D (2000) 234 5 , 60 0 , 08 209 6th , 10 0 , 07 II Z (2000)
+ D (300) 138 4th , 20 0 , 22 100 4th , 90 0 , 22 II Z (2000)
+ E (300) 276 4th , 30 0 , 26 107 4th , 40 0 , 31

"One week at a temperature of 49 ⁰ C and a relative humidity of 50 I-incubated material.

The results compiled in Tables IV and V show that azaindenes excellently those described Able to supersensitize tricarbocyanine dyes and that, furthermore, particularly good results are obtained when when a sulfonated polynuclear aromatic compound is used together with an azaindene for supersensitization.

Corresponding favorable results were obtained when the azainden used in Example 4 by appropriate concentrations to 7-hydroxy-1,2,3,4,6-pentazaindene or 2,4-dihydroxy-6-methyl-1,3a, 7-triazaindene or other azaindenes was replaced.

The following Example 5 illustrates the supersensitization of a silver halide photographic emulsion with a tricarbocyanine amine dye by sulfonated, polynuclear, aromatic compounds, silver halide reducing agents and an azaindene.

Example 5

Following the procedure described in Example 4, three recording materials were prepared based on a gelatin silver halide

10 9 8 l!) / Hü8

emulsion with cubic silver halide grains and cellulose acetate film supports. The emulsion layers each contained 2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per mole of silver. Two of the three emulsion layers contained 100 mg of dye II and 1000 mg of the disodium salt of the 4,4 ^f- bis / i4,6-bis-o-chloroanilino-s-triazin-2-yl) aming7-2,2'- stilbene disulfonic acid (stilbene F) per mole of silver. One of the emulsion layers contained the dye II, the stilbene F and also 500 mg ascorbic acid per mole of silver.

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

Table VI

mg dye mg stilstoff II / ben F /
Mole ag mole ag

mg Ascor- g Tet- Relati- Relati- Schleier binsäure / razain-ve Blau- ve Rot-Mol Ag den / Mol sensitivity-sensitivity-Ag sensitivity

0 0 0 2 347 - _— 0.03 100 1000 0 2 100 100 0.03 100 1000 500 2 389 447 0.13

From the results shown in Table VI, it can be seen that silver halide photographic emulsions are more advantageous Way by using an enamine tricarbocyanine dye, a sulfonated polynuclear aromatic compound, a Supersensitize silver halide reducing agent and an azaindene.

10981S / U08

Claims (1)

Claims y Supersensitized, light-sensitive, photographic silver halide emulsion containing a dye sensitizing the silver halide and at least one compound which is supersensitizing the emulsion, characterized in that it contains: (A) as a sensitizing dye at least one tr! Carbocyanine dye of the formula: N- (CH = CH) _Λ HC-CH-CH-CC = C-CH = CH-C- (CH-CH) _t «N In-ι ι ι m-ι ι ν J 'θ K ₁ q R ₂ X where mean: m and η each * 1 or 2; Rl and R2 each represent an optionally substituted alkyl or aryl radical; Q the completion of a possibly substituted ethylene, trimethylene or o-phenylene radicals required atoms; R, and R ^ individually in each case an optionally substituted alkyl or aryl radical or together the for Completion of a heterocyclic ring containing 5 or 6 ring atoms Atoms; 109815 / UQ8 Z ₁ and Z ₂ each represent the atoms required to complete a heterocyclic ring typical of cyanine dyes, and X is an acid anion and (B) at least (a) fonsäuresalzrest as supersensitizing compound is known as a supersensitizing component per se * polynuclear aromatic compound having at least one sulfonic acid or sulfonic ä, (b) an azaindene and / or (c) a Silberhalogenidreduktionsmittel. 2. Supersensitized photosensitive silver halide photographic emulsion according to claim 1, characterized in that it contains as supersensitizing compound (B, a): a water-soluble organic compound of the formula: CH = CH-D ₂ where mean: DJ is a 1 ^, S-triazin-o-ylamino radical, D _{2 is} an optionally substituted benzene radical and M is a hydrogen atom or a cation. .1 3. Supersensitized photosensitive silver halide photographic emulsion according to claim 1, characterized in that it is used as a supersensitizing compound (B, b) by a 1 0 9 8 1 egg / U U 8 Hydroxy or amino radical substituted triazaindene, tetrazaindene or pentazaindene. Supersensitized light-sensitive silver halide photographic emulsion according to claim 1, characterized in that it contains as supersensitizing compound (B, c): a benzene, lactone, tetronimide, pyronimide, furan or pyrrole each with at least two hydroxyl radicals or an aminohexose reductone. Supersensitized light-sensitive silver halide photographic emulsion according to claim 1, characterized in that it is a tricarbocyanine dye of the formula given as (A) contains, in which mean: m and η each «1; R. 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 ^ individually, each an optionally substituted alkyl or aryl radical or together those to complete an optionally substituted morpholino,
Thiomorpholino,
Piperidino,
Piperazinyl,
Pyrrolidinyl,
Indolinyl, Tetrahydroquinoyl or
Decahydrochinoylringes required atoms; 109815 / 1Aü8 046687 - 53 - Z ₁ and Ζ2 each have the atoms required to complete an optionally substituted benzoxazole or benzothiazole ring, and X is an acid anion. 6. Supersensitized photosensitive silver halide photographic emulsion according to claims 1, 2, 3 and 5, characterized in that it has a "supersensitizing component (B)" polynuclear aromatic compound with at least one sulfonic acid or sulfonic acid salt residue and an azaindene and optionally also contains a silver halide reducing agent. 7. Supersensitized photosensitive silver halide photographic emulsion according to claims 1 to 6, characterized in that it contains as supersensitizing compound (B, c): Ascorbic acid, Piperidinohexose reductone, Hydroquinone and / or S-phenyl-S-hydroxytetronimide monobenzoate. 8. Supersensitized photosensitive silver halide photographic emulsion according to claims 1 to 6, characterized in that as the supersensitizing compound (B, b): 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene contains. 9. Supersensitized photosensitive silver halide photographic emulsion according to claims 1 to 8, characterized in that the silver halide grains of the emulsion are cubic in shape own. 109815 / UÜ8 10. Supersensitized photosensitive silver halide photographic emulsion according to claims 1 to 9, characterized in that it contains as (A) an anhydro-11- (4-ethoxycarbonyl-1-piperazinyl) -10,12-ethylene-3,3 ^l -di (3-sulfopropyl) thiatricarbocyanine salt or the disodium salt of a bis ^ s-rtriazin-2-ylamino7stilbene 2.2 ^l -disulfonic acid and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. 109815/1408