DE2609993A1 - SUPERSENSITIZED PHOTOGRAPHIC SILVER HALOGENIDE EMULSION - Google Patents

Description

FATENTAN W ^ lTF

DR. E. WIEGAND DIPL-: NG. W. MItAMNN DR. AA. KÖHLER DIPL-ING. C GERNHARDT

MÖNCHEN HAMBURG 2609993

TELEPHONE: 555 476 8000 M 0 N CH E N 2,

TELEGRAMS: KARPATENT MATHI LDENSTRASSE 12 TELEX: 5290 (58 KARP D

V. 42507/76 - KoAe March 10, 1976

Fuji Photo Film Co., Ltd. Minami Ashigara-Shi, Kanagawa (Japan)

Supersensitized silver halide photographic emulsion

The invention relates to silver halide photographic emulsions and more particularly to sensitization improved photographic emulsions containing a carbocyanine dye and silver halide grains.

According to the invention there is provided a silver halide photographic emulsion specified, which in combination contains:

(1) (a) Silver halide grains practically having a (1 1 1) face and / of the b) silver halide grains practically with a (10 O) face and with a grain size distribution scale greater than about 0.7 microns,

(2) a sensitizing amount of a carbocyanine sensi-

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bilizing dye, wherein two 5- and / or 6-membered nitrogen-containing hetero rings with one
aliphatic group or aryl group on the nitrogen atom, whereby these nuclei can be the same or different from one another, are connected to one another via a trimethine chain and which have an -Ered-Etr value of greater than about -1.25, where Ered is the polarographic reduction potential of the dye, given as the value of V against SCE and Etr the transition energy of the dye, determined in
a methanol solution and given as a value of eV, and

(3) a hydroxytetrazaindene compound corresponding to the following general formulas (A) or (B) in an amount of more than Λ g per 1 mol of silver halide:

(A)

or

(B)

wherein R 1 and R _{2 can be the} same or different from one another and represent a hydrogen atom, an aliphatic group, a carboxy group, an alkoxycarbonyl group

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or an aryl group and η denotes the numbers 1 or 2.

Furthermore, there is also provided a method of sensitizing such a silver halide photographic emulsion specified.

In the art of preparing photographic emulsions, it is desirable to take measures to increase the high the sensitivity of an emulsion while controlling the fog.

The term "supersensitization" is used herein the phenomenon that at least d 3 spectral sensitization in a super additive way through the combined use of a sensitizing dye and another organic compound (supersensitizer) is increased. Supersensitization effects have been known for a long time and compounds having a super-sensitizing effect on carbocyanine dye e, as used in the context of the invention, are known, including the US patent 3,397,060, German patent 2 O3O 326, US patents 3,522,052, 3,526,641 and the British Patent specification 1 216 203 and the like. Reference is made.

In many cases, however, the supersensitizing dyes have them itself a spectral sensitizing effect and provide photographic sensitivity in a wavelength range different from that the sensitizing dye is what happens in some cases is not favorable from the viewpoint of the spectral properties of the photosensitive materials. That's why is the development of a new super-sensitizing combination with sanding of a compound that absorbs practically no light in the visible range and as a result itself has no spectral sensitizing effect, favorable.

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260999a

Hydroxytetrazaindenverbindungen are so far as Stabilizers for photographic emulsions known and are added in emulsions for the purpose of reducing haze. Of these connections, however, is also known to often show the effect of reducing photographic speed, including e.g. B. on the publication of V.C. Chambers' "A Correlation of the Chemical Structures of Some Triazolopyrimidines with Their Photographic Effects, "Photographic Science and Engineering, Volume 6, No. 2 is referenced.

However, it has already been found that the sensitivity of a silver halide emulsion can be markedly increased by incorporating a sulfur-containing compound and a hydroxytetrazaindene compound in combination into a monodisperse cubic silver halide grain emulsion containing 80% or more of silver bromide, as disclosed in Japanese Patent Application No. 46 398/73 and the German OLS 2 419 798 is referred to.

It is known that the incorporation of a substituted tetrazaindene compound in a silver halide material, 'which Contains 20 mol% or more of silver chloride in the silver halide, causes contrast sensitization (Japanese OPI 11 122/74).

It is also known that color-sensitized silver halide grains have a substantially (10 O) face and an emulsion containing a grain size distribution of less than 0.7 microns sensitized with azaindenes can be, for which reference is made to the German OLS 2 418 278.

It is also known that a silver halide light-sensitive material containing $ 0 mol% or more silver chloride through the combined use of

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Sulfocatechol and tetrazaindene is sensitized (US Pat. No. 3,671,258).

It is also known - that one with a dye, a hetero ring compound or with a heavy metal salt desensitized emulsion by immersion in a solution, containing a triazaind or tetrazaind is resensitized (see U.S. Patent 3,563,754)

It is also known to obtain the Gamma-Vert or the graduation by adding both 4-Hydroxytetrazainden as also to increase N - / (dialkylamino) -alkyl7-carbamate, for which purpose See U.S. Patent 3,190,752.

It is known that the coverage ratio can be increased by adding at least 0.5 mg / mol of silver halide Azaindene compound in the preparation of a silver halide emulsion containing 50 mol% or more of silver chloride to the silver halide emulsion is increased within 4 minutes of the first flocculation (including the See U.S. Patent 3,519,426.

It is also known that azaindenes have a supersensitizing effect on an emulsion which spectrally to the infrared region with a tricarbocyanine dye (Cyanine in which 7 methine groups connect the hetero rings) in which one carbon atom is in the meso position is linked to a nitrogen atom to form an enamine with respect to the methine chain,

reference is made to U.S. Patent 3,695,888.

It is also known that when a silver halide emulsion is chemically treated with a sulfur compound and a Gold compound is sensitized and then with an azainden The inherent sensitivity of the silver halide is stabilized by adding a monovalent gold compound and an azainden in a greater quantity than that

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amount commonly used as a stabilizer; H. no more than about 0.15 g 3 molar silver halide the sulfur sensitization can be increased, for which on British Patent 1,315,755 is referenced.

In the context of the present invention, however, it was unexpectedly found that with an emulsion, which contains silver bromide in a predominant amount; and (a) silver halide grains practically having a (111) face and / or (b) silver halide grains practically with a (10 0) face and with a grain size distribution value greater than about 0.7 microns, photographic speed is markedly increased when in Combination of a particular type of carbocyanine sensitizing dye (one or more) and a particular one Kind of a hydroxytetrazaindene compound (one or more) in considerably larger quantities than the usual ones stabilizing amounts are added.

This particular phenomenon was not known and is completely surprising.

It is an object of the invention to provide a photographic silver halide emulsion having a markedly increased photographic sensitivity to control fogging.

Another object of the invention is a method of making the above photographic emulsion.

Another object of the invention is a method of increasing the photographic sensitivity of a photographic emulsion containing a carbocyanine dye while controlling fog.

The above objects of the invention are achieved by a photographic emulsion which

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contains

(1) a silver halide, preferably with a content of about 80 % or more silver bromide, consisting of (a) silver halide grains practically with a (1 1 1) face and / or (b) silver halide grains practically with a (10 0) face and having a grain size distribution value greater than about 0.7 microns;

(2) a sensitizing amount of a carbocyanine sensitizing dye, wherein two 5- and / or 6-membered nitrogen-containing hetero rings with an aliphatic group or aryl group on the nitrogen atom, these Nuclei can be the same or different from one another and the preferred aliphatic groups have 1 to 8 carbon atoms and the preferred aryl groups are monoaryl groups having up to 10 carbon atoms are linked to each other through a trimethine group (chain) and the one -Ered-Etr-Vert, as it is defined below, of great than about -1.25 (Ered: ρölarographic reduction potential of the dye, given as the value of V versus SCE; Etr: transition energy of the dye, determined in methanol solution and given as a value of eV) and

(3) A hydroxytetrazaindene compound represented by the following general formula (A) or (B) in one greater than about 1 g per mole of silver halide

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wherein R ^ and Ε «, which are the same or different from one another, represent a hydrogen atom, an aliphatic group, the preferred aliphatic groups having 1 to 8 carbon atoms, more preferably Λ to 4 carbon atoms and which term includes both substituted and unsubstituted alkyl groups , for example those with a hydroxyl group, a carboxy group, a sulfo group, a halogen atom such as chlorine or bromine, an alkoxy group, most preferably with 1 to 4 carbon atoms, an alkoxycarbonyl group, in which the alkoxy moiety most preferably has 1 to 4 carbon atoms, for example a methyl group, an ethyl group, a propyl group, a butyl group such as a group substituted with a hydroxy, carboxy, alkoxy group or the like group and the like, a carboxy group, an alkoxycarbonyl group, most preferably where the alkoxy portion thereof is 1 to Contains 4 carbon atoms, for example one e ethoxycarbonyl group and the like, or an aryl group, most preferably a monoaryl group having up to 10 carbon atoms, for example a phenyl group, a phenyl group substituted with an alkyl group, a halogen atom, a hydroxyl group and the like.

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group, the most preferred substituents being alkyl groups with 1 to M carbon atoms, halogen atoms such as chlorine, bromine or iodine, hydroxyl groups, alkoxy groups with 1 to M carbon atoms, alkoxycarbonyl groups in which the alkoxy moiety contains 1 to M carbon atoms, a sulfo group, a Amino group, a mono- or dialkylamino group, in which the alkyl moiety contains 1 to M carbon atoms, and η denotes the numbers 1 or 2.

The term "value" denotes the value of a variable that corresponds to the maximum frequency among various "variables, which are capable of assuming different values occurs, in this case the grain size. If the variables are continuous Assume values, this is taken as the value of a variable corresponding to the maximum position of the distribution curve Are defined.

For a more detailed explanation of preferred embodiments the term "value" is explained in detail, assuming that the total number of silver halide grains with a particle size of 0.25 to 2.25 microns in one Batch is 1000 and that the number of silver halide grains with a particle size of (a) 0.25 to 0.75 microns, (b)> 0.75 to 1.25 microns, (c)> 1.25 microns to 1.75 microns, and (d)> 1.75 microns to 2.25 microns is 100, 500, 300 and 100, respectively, so the frequency as (a) 100,

(b) 500, (c) 300 and (d) 100 is defined. If it is further assumed that the particle size of (a), (b),

(c) and (d) 0.5 micron, 1.0 micron, 1.5 micron and, respectively Is 2.0 microns is from the particle size distribution curve in this case the "value" is the particle size corresponding to the maximum frequency, d. H. 1.0 micron. In Thus, in the specification, the term "value" is used to have virtually the same meaning as mean or average diameter.

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As nitrogen-containing hetero rings of the carbocyanine dyes, those can be listed as examples, which as hetero atoms have a sulfur atom, oxygen atom or selenium atom in addition to the nitrogen atom. Of course, these dyes containing a sulfur atom or an oxygen atom are only preferred.

Among the numerous known carbocyanine sensitizing dyes the carbocyanine sensitizing dyes used in the context of the invention are specifically those which has an-Ered-Etr value, as explained below, greater than about -1.25 and more preferably more than about -1.25 and less than about -0.50.

The term "Etr" as used herein denotes the value the transition energy of the dye in methanol in electron volts (eV), which is calculated according to the formula

Etr = hc / λ max

is determined by determining the maximum absorption wavelength (Xmax) of the absorption spectrum of a solution of the dye in methanol in the visible range. The determination is carried out using a dye solution of 10 to 10 "mol / l, preferably about 10 ^J mol / l, whereby it should be noted that the λ max of the dye does not depend on the concentration of the dye in methanol. In the formula h means the Planck constant and c means the speed of light.

Ered represents the reduction potential of the dye in a water-ethanol mixed solvent with a saturated calomel electrode is determined as a reference electrode.

The value of the reduction potential (Ered) as it is here is applied, denotes the electrical potential, at

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where a dye accepts an electron at the cathode to be reduced in voltammetry. Ered can be measured precisely voltametrically. This means that a pH buffer is prepared with a solution of the dye in methanol of 10 "^ to 10""mol / l (volume ratio 1: 1 of the pH buffer to ethanol) for the preparation of a sample solution (with the various ions in the pH -Buffer act as a transport electrolyte, ie ions that show no oxidation-reduction at -2 to 0 volts compared to SCE in a mercury electrode system can be used, for example Na ⁺ , K ⁺ , NH ₄ ⁺ , Cl ", NO ~ SO ^, CH, COO "and the like) and the volt-ampere curve at 25 C is obtained using a mercury drip electrode with a saturated calomel electrode (SCE) as a reference electrode and Ered is determined from the curve as the half-wave potential Description of this is in a publication by Tadaaki, Tani, Kenichi-Honda and Shinichi Kukuchi, entitled "Studies on the Relation between Polarographic Half-Wave Potentials and Electronic Energy Levels of Dyes", Journal of Electrochemical Society of Ja pan, J5Z, 16 (1969).

More detailed treatises on this voltammetric Methods are in P. Delahay, New Instrumental Methods in Electrochemistry (Interscience Publishers, 1954-) and in L. Meites, Polarographic Techniques (Interscience Publishers, 1965) 2nd Edition and the like.

A series of Ered values allows a maximum of one deviation of 100 mV, i.e. H. the maximum error is 100 mV, due to the influence of differences between the liquid contact potentials (liquid connection potential), Incomplete calibration of the liquid resistance of the sample solution or the like, the influence the dye concentration and similar factors.

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However, the reproducibility of the measured potential values by correcting any errors using 3i3'-diethylthiacarbocyanine bromide as the standard sample be ensured.

If a combination of a sensitizing dye and another sensitizing dye or one If the compound is practically colorless, it can be checked by the experts using customary measures whether this combination shows a supersensitizing effect or not-

The carbocyanine dyes used in the context of the invention can, for example, correspond to those of the following general formula (I) can be selected, the following structural formula of course also Resonance structure can assume:

R.
N - ^ - CH = CHt-YC = CH-C = CH-C = tCH- CH η ^ ~

t CH ^ ~

In the above general formula, 1, m and η each denote the numbers 1 or 2, R ^ denotes a hydrogen atom, an alkyl group, for example a methyl group, an ethyl group, propyl group, butyl group and the like, an aralkyl group such as a benzyl group, Phenethyl group and the like. Or an aryl group having a benzene ring, d. H. a monocyclic ring with up to 10

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Carbon atoms, for example one in the meta or para position with a hydroxy group, an alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, a halogen atom such as chlorine or bromine, and the like. Substituted phenyl group in which all alkyl or Most preferably, alkoxy units have 1 to 4 carbon atoms have, for example, a phenyl group, a carboxyphenyl group and the like., X "is an inorganic or organic acid anion capable of forming a salt with the dye, for example a chloride ion, bromide ion, Perchlorate ion, p-toluenesulfonate ion and the like, and if so

1 has the value 1, the dye forms an intramolecular salt.

E ^ and Er can each be from aliphatic groups including saturated aliphatic groups and unsaturated aliphatic groups such as unsubstituted alkyl groups having 1 to 8 carbon atoms, more preferred

2 to 4 carbon atoms, for example methyl groups, Ethyl groups, n-propyl groups, hexyl groups and the like, substituted alkyl groups (the alkyl moiety being preferred Has 1 to 4 carbon atoms, such as a vinylmethyl group, an aralkyl group, most preferably a monoaryl group of up to 10 carbon atoms, for example a benzyl group, a phenethyl group and the like., a hydroxyalkyl group, for example a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group and the like, a carbamoylalkyl group, for example a carbamoylethyl group and the like, an acetoxyalkyl group, for example a 2-acetoxyethyl group, a 5-acetoxypropyl group and the like, an alkoxyalkyl group, most preferred where the alkoxy moiety has 1 to 4 carbon atoms, for example a 2-methoxyethyl group,

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a 4-methoxybutyl group and the like, a sulfoxyalkyl group, · for example, a 3-sulfoxypropyl group, a 4-sulfoxybutyl group and the like, a carboxy group-containing one Alkyl group, for example a 2-carboxyethyl group, a 3-carboxypropyl group, a 2- (2-carboxyethoxy) ethyl group, a p-carboxybenzyl group and the like, a sulfo group-containing Alkyl group, for example a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, a 2-hydroxy-3-sulfopropyl group, a 2- (3-sulfopropoxy) ethyl group, a 2-ethoxy-3-sulfopropyl group, a 3-methoxy-2- (3-sulfopropoxy) propyl group, a 2- / 2- (3-sulfopropoxyethoxy) ethyl group, a 2-Hydrox3r-3- (3'-sulfopropoxy) propyl group, a p-sulfophenethyl group, a p-sulfobenzyl group and the like) or an aryl group, most preferably a monoaryl group with up to 10 carbon atoms, for example, a phenyl group and the like., can be selected.

Ίιλ and Zp each mean the non-metal atoms necessary to complete a 5- or 6-membered nitrogen-containing hetero ring. The hetero ring nuclei can by an atom or a grouping, such as an alkyl group with 1 to 4 carbon atoms, a monoaryl group, a halogen atom, an alkoxy group with 1 to 4 carbon atoms, a carboxy group, a monoaralkyl group, where the aralkyl moiety most preferably contains up to 10 carbon atoms , a hydroxy group, an alkoxycarbonyl group, all of the alkyl moieties having 1 to 4 carbon atoms, or similar groups being substituted. Or else a saturated or unsaturated aliphatic ^ hydrocarbon group can form, for example, a 6-membered ring, a. B. 4,5-tetra

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ethylene benzothiazole, 5> 6-tetramethylene benzoxazole, 6,7-tetraethylene benzoselenazole and the like., be condensed.

The hetero ring cores can, for example, consist of a benzothiazole nucleus (e.g. benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzotb-iazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, Bromobenzothiazole, 5-iodobenzothiazole, fj-pkenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-Ätb.oxycarbonylbenzothiazole, 5-phenethyl-6-benzothiazole, 5-phenethyl-6-benzothiazole, 5-phenethyl-6-benzothiazole, 5-phenethyl-6-dimethylbenzothiazole, 5-phenethyl-6-benzothiazole 5 5-hydroxy-6-meth.ylbenzothiazole, tetraliydrobenzothiazole, 4-phenylbenzotb.iazole, 5-pb.enylbenzothiazole and the like), a naphthothiazole nucleus (for example naphthoic, 1-a7thiazole, naphthol, 2-d7thiazole, d7-thiazole, 5-methoxynaphtho / i, 2-d / thiazole, 8-methoxynaphtho-Z2,1-4 / thiazole, ^ methoxynaphtho / ^ :, 3-d7thiazole and the like, a benzoxazole nucleus (e.g. benzoxazole, 5-chlorobenzoxazole , · 5- ^ ethylbenzoxazole, 5-bromobenzoxazole, 5- ^ ¹ IuOrbenzoxazole, 5-Ph.enylbenzoxaz ol, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4-, 6-dimeth.ylbenzoxazole and dgl .), a naphthoxazole nucleus (e.g. B. ITaphtho- / 2i 1-7oxazole, naphtho / Ϊ, 2-ci7oxazole, naphthol, 3-d7oxazole and the like the like,) a naphthoselenazole nucleus (e.g. naphthol »1-d7selenazole, naphtho / i, 2-d7selenazole and the like), a« m 3,3-dialkylindolenine nucleus (for example 3,3-dimethylindolenine, 3,3- Diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,

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methyl-5-methoxyindolenine, 3, 3-dimethyl-5-methylindolenine, 3i3-diQethyl-5-chloroindolenine and the like), a benzimidazole nucleus (for example I-methylbenzimidazole, 1-ethylbenzimidazole, i-methyl-fj-chlorobenzimidazole, i- ethyl-5-chlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-methoxybenzimidazole, 1-allyl-5i6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, I-phenylimidazole, 1-phenylbenzimidazole, 1-phenyl ~ 5-chlorobenzimidazole, i-phenyl ^^ - dichlorobenzimidazole, 1-phenyl-5-methoxybenzimidazole, and the like) »an efaphthoimidazole nucleus (for example i-phenylnaphtho ^^ 1- Ethylnaphtho / i, 2-d / dimidazole and the like a pyridine nucleus (for example pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine and the like.) A quinoline nucleus (for example quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 8-PIuOr-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, e-ethoxy -4-quinoline, e-chloro - ^ - quinoline, 8-fluoro-4-ch inoline, 8-methyl-4-quinoline, e-methoxy - ^ - quinoline, isoquinoline, 3,4-dihydro-1-isoquinoline and the like.) and similar groups.

An example of an embodiment of the preparation of the photographic emulsion according to the invention is given given below, which, however, in no way limit the invention.

For example, the photographic emulsion can be formed by forming silver halide grains through reaction between a water-soluble silver salt and a water-soluble halide in an aqueous solution of a hydrophilic colloid, optionally with the addition of a sulfur sensitizer and / or a gold sensitizer to that obtained thereby Emulsion for the purpose of chemical ripening, addition of the carbocyanine dye described above

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and further adding the above hydroxytetrazaindene compound getting produced. The step of adding the hydroxytetrazaindene compound can be before, during or after the chemical ripening described above and can be before or at the same time as the addition of the carbocyanine dye take place. The addition of a water-soluble iodide, for example an alkali iodide such as potassium iodide, sodium iodide and the like, or an iodide of the formula: N (E ^ E2ßz) J, where E ^, E2 and R, each a hydrogen atom, denote a methyl group, an ethyl group, a propyl group, a butyl group or an amyl group, before or during chemical ripening or before drawing, serves to increase the effect according to the invention. Most preferred results will be obtained with the addition of such iodide in an amount of about 0.001 to about 10 millimoles / mol silver halide, stronger preferably from 0.01 to 1 millimole / mole of silver halide.

The silver halide grains incorporated in the emulsion according to the invention preferably have no more than about 5 microns, more preferably less than about 2 microns medium grain size. The mean grain size, i.e. H. the average particle size as arithmetic mean average of the silver halide particles can be calculated in a conventional manner using, for example, a Photograph of the silver halide grains by means of an electron microscope or according to the method described in A.P.H. Trivelli, W.F. Smith, Empirical Eelations between Sensitometric and Siis-Frequency Characteristics in Photographic Emulsion Series should be determined.

Examples of silver halides to be used in the emulsions according to the invention are silver bromide, silver

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chlorobromide, silver bromoiodide and silver chlorobromide. In terms of the halogen composition, it is preferred that the silver bromide content exceeds about 80 Mo 1%. The content of silver iodide is preferably no more than about 10 Mo 1%, and more preferably no more than 1.5 mol%. With regard to the crystal form, the silver halide grains used in the emulsions according to the invention can either (a) practically a (1 1 1) surface, d. H. plate-like or octahedral grains, and / or (b) practically a (10 Oj area at a grain size distribution value greater than about 0.7 microns, i.e. H. cubic, tetradecahedral or potato-shaped (irregularly spherical) Grains included. The shapes and methods of making octahedron, cubic and tetradecahedron Grains are well known. For a detailed description, see The Theory of the Photographic Process, 3rd edition, C.E.K. Mees, T.H. James, Chapter 2 referenced. For the Manufacturing process is for example on the publication Precipitation of Twinned Silver Bromide Crystals by CR. Berry and D.O. Skillman, in Photographic Science and Engineering, Volume 6, ITr. 2 referenced.

In the context of the present description, terms like "with practically a (1 1 1) area" or with practically mean a (1 0 O) surface "or equivalent designations, that the sum of the total surface areas of all (1 0 O) surfaces and / or (111) surfaces is no less than about 80%, based on the total surface area of all grain areas in the silver halide.

In the context of the invention, chemically sensitized or chemically unsensitized silver L: -logenide emulsions be used. For chemical sensitization you can the usual gold sensitization, sensitization

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tion with precious metals, except gold, sulfur sensitization and reduction sensitization can be applied. In particular, sulfur sensitization gives good results. For example, the use of gold compounds, * such as chloroaurate, gold chloride and the like according to US patents 2 399 083, 2 540 085, 2 597 866, 2 597 915, the salts of precious metals such as platinum, palladium, iridium, Rhodium, ruthenium and the like corresponding to US Patents 2,448,060, 2,540,086, 2,566,245, 2,566,253,

2,598,079, of sulfur compounds which lead to the formation of
Silver sulfide are capable of reacting with silver salt, according to US Patents 1,574,944, 2,410,689,

3,189,458, 3,501,313, tin salts, amines or other reducing agents Substances according to US patents 2 487 850, 2 518 698, 2 521 925, 2 521 926, 2 69 ^ 637,

2,983,610, 3,201,254 and the like given as examples
will.

Various organic and inorganic sensitizers known as sulfur-containing sensitizers can be added to the silver halide emulsion used in the present invention
Connections are added. For example, thiosulfate, aryl thiocarbamide, thiourea, allyl isothiocyanate, cysteine, p-toluene thiosulfonate, rhodanine and the like are preferred. In addition, sulfur sensitizers can be used
U.S. Patents 1,574,944, 2,278,947, 2,440,206, 2,410,689, 3,187,458, 3,415,649, and the like. The sulfur-containing compound is used in an amount effective to increase the sensitivity of the emulsion
increase, added. This amount varies within one
considerably wide range under various conditions, however, an amount of about

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- 5 - 1

10 ^ moles to about 10 moles per mole of silver are preferred.

As more specific examples of carbocyanine dyes within the scope of the invention corresponding to the general formula (I) are those of the following general formula (II) listed:

X ⁹ (II)

wherein E, and X ~ have the same meaning as in the general formula (I), n> | and m ^ each an integer from 1 to 5> V ^ and Vp each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a monoaryl group, for example a phenyl, hydroxyphenyl, chlorophenyl, methylphenyl, methoxyphenyl, carboxyphenyl group and the like., a halogen atom, e.g. B. Cl or Br, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, a monoaralkyl group, most preferably if the aryl portion thereof contains up to 10 carbon atoms, a hydroxy group or an alkoxycarbonyl group in which the alkyl portion has 1 to 4 carbon atoms, and I _x and Ip each represent an integer from 1 to 4.

Specific examples of compounds represented by general formula (II) include 3 »3'-diethylthiacarbo cyaninjo did, 3,3'-diethyl-9-methylthiacarbo cyanine-

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iodide, 3.3 ^l -methyl-9-ethylthiacarbocyanine iodide, 5,5'-dichloro-3 »3 ^l -diethyl-9-ethylthiacarbocyaninoodide, 5,5'-dimethyl-3,3'-diethyl-9-ethylthiacarbocyanine odide, 5 »5'-dimethoxy-3,3'-diethyl-9-äthylthiacarbocyaninoodid, 5,5'-diphenyl-3,3'-dietliyl-9-ätliylthiacarbocyaninjodid and the like. Although the above list is given with reference to iodides, can also the chlorides, bromides, perchlorates, p-toluenesulfonates and the like can be used.

As other specific examples of carbocyanine dyes corresponding to the general formula (I), those corresponding to the following general formula (III) can be used will:

C ₂ H ₅

where W ^, Wp * I ^ and Io have the same meaning as in the general formula (II) and n ^ ¹ ^ ^m 2 each represent an integer from 2 to 4.

More specific examples of compounds of general formula (III) include 3 ^'3'-I) isulfopropyl-9-äthylthiacarbocyanin, _i 5 ^{5'-dichloro-3,3-9-l} -disilfopropyl äthylthiacarbocyanin, 5 »5'-Diniethyl-3 »3 ^l -clisulfopropyl-9-ethylthiacarbocyanine, 5,5 * -Dimethoxy-3,3'-disulfopropyl-9-ethyl-

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thiacarbocyanine, 5 * 5'-diphenyl-3,3'-disulfopropyl-9-ethylthiacarbocyanide and similar.

As other specific examples of carbocyanine dyes According to the general formula (I), those of the following general formula (IV) can be used:

(IV)

where VLj, W ^, I ^ and I2 have the same meaning as in the general formula (II), η ^ is an integer from 1 to 5 ¹ JHd m ^ is an integer from 2 to 4-.

More specific examples of compounds corresponding to the general formula (IV) include 3 - ethyl-3'-sulfopropyl-9-ethylthiacarbocyanine, 5i5'-dichloro-3-ethyl-3'-sulfopropyl-9-ethylthiacarbocyanine, 5> 5 '-Dimethyl-3-ethyl-3'-sulfopropyl-9-ethylthiacarbocyanine, 5 * 5 ¹ -Dimethoxy-3-ethyl-3'-sulfopropyl-9-ethylthiacarbocyanine, 5 ₅ 5'-diphenyl-3-ethyl-3'- sulfopropyl-9-ethylthiacarbocyanine and the like.

Other specific examples of carbocyanine dyes According to the general formula (I), those of the general formula (V) include:

609840/0974

(Wi)

C2H5

CH = C-CH

- (W ₂ ),

(V)

where W ^, V ^ ^ -λ ^{un <} i ^ p ^ " ^e 6l ^e i ^{cne have the same} meaning as in the general formula (II) and n ^, and nu each mean an integer from 2 to 4.

Specific examples of compounds corresponding to the general formula (V) include 3 »3'-disulfopropyl-9-ethyloxacarbocyanine, 5> 5 '-dichloro-3- > 3'-disulfopropyl-9-ethyloxacarbocyanine, 5 ^ 5'-dimethyl-3i3 '-disulfopropyl-9-ethyloxacarbocyanine, 5 »5 ¹ -dimethoxy-3,3'-disulfopropyl-9-ethyloxacarbocyanine, 5» 5'-diphenyl-3 »3'-disulfopropyl-9-ethyloxacarbocyanine and the like.

More specific examples of carbocyanine dyes according to the general formula (I) are those according to the following general formula (VI):

OH

- (VJ ₂ ),

X ⁰

(VI)

609 8 40/0974

2603993

where V ,,, Vp, X, l ^, and Ip have the same meaning as in the general formula · (II) and nc and m, - each mean an integer from 2 to 4-.

Specific examples of compounds of the general formula (VI) include 3 * 3'-dihydroxyethyl-9-ethylthiacarbocyanine, 5,5'-dichloro-3,3'-dihydroxyethyl-9-ethylthiacarbocyanine, 5 * 5'-dimethyl-3, 3'-dihydroxyethyl-9-ethylthiacarbocyanine, 5 , 5'-dimethoxy-3,3'-dihydroxyethyl-9-ethylthiacarbocyanine, 5 * 5'-diphenyl-3 »3'-dihydroxyethyl-9-ethylthiacarbocyanine and the like.

Further examples of carbocyanine dyes accordingly of the general formula (I) include those of the following general formula (VII):

(Wi)

C2H5

.0.

CH = C-CH = (j Hj

(CH ₂ ),

Lh

ν-

(VIl)

wherein

Vp, X,

and

the same meaning as in

and

respectively

of the general formula (II) and ^ ^ represent an integer from 2 to 4.

Specific examples of compounds corresponding to the general formula (VII) include 3'-dihydroxyethyl-9-ethyloxacarbocyanine, 5i5'-dichloro ~ 3i5'-dihydroxyethyl-9-ethyloxacarbocyanine, 515'-dimethyl-3,3'-dihydroxyethyl-9-

6 09840/0974

äthyloxacarbo cyanine, 515'-dimethoxy-3,3 * -dihydroxyethyl-9-äthyloxacarbo cyanine, 5 »5'-diphenyl-3,3'-dihydroxyethyl-9-ethyloxacarbocyanine and the like

More specific examples of carbocyanine dyes according to the general formula (I) are those of the following general formula (VIII):

N '

SO ₃ H

where W ^, ¥ 2, l / | and I2 have the same meaning as in the general formula (II) and n ^ and m ^ each have one an integer from 2 to 4.

Specific examples of compounds of the general Formula (VIII) include 3,3'-disulfopropyl-9-ethylthiaoxacarbocyanine, 5 »5'-dichloro-3,3'-disulfopropyl-9-ethylthiaoxacarbo cyanine, 515'-dimethyl-313'-disulfopropyl-9-ethylthiaoxacarbocyanine, 5 »■ 5'-dimethoxy-3,3'-disulfopropyl-9-ethylthiaoxacarbo cyanine, 5,5'-diphenyl-3 »3'-disulfopropyl-9-ethylthiaoxacarbocyanine and the like

Specific examples of carbocyanine dyes represented by general formula (I) also include those according to the following general formula (IX):

609840/0974

(W ₁ )

CH = CH-CH =;

SO ₃ H

C ₂ H ₅

(IX)

where W ^, I ^ and 1 ~ have the same meaning as in general Formula (II) have and ng and mg each have one an integer from 2 to 4-.

Specific examples of compounds corresponding to the general formula (IX) include 3-sulfopropylthia-4- ¹ _i 5 ^l -dichloro-1-ethyl-3 ^l -sulfopropylbenzimidacarbocyanine, 5-methoxy-3-sulfopropylthia-4 ', 5'-dichloro 1'-ethyl-3 ¹ -sulfopropylbenzimidacarbocyanine, 5-methyl-3-sulfopropylthia-4 ¹ ^ '- dichloro-i'-ethyl-3'-sulfopropylbenzimidacarbocyanine, 5-chloro-3-sulfopropylthia- ^ ^l , 5'-dichloro -1'-ethyl-3'-sulfopropylbenzimidacarbocyanine, 5-phenyl-3-sulfopropylthia-4 ¹ , 5'-dichloro-1'-ethyl-3 ¹ -sulfopropylbenzimidacarbocyanine and the like.

Further carbocyanine dyes according to the general Formula (II) include compounds corresponding to the following general formula (X):

609840/0974

wherein R ^, R ^, R, -, X ~ "and 1 have the same meaning as in the general formula (I), Rg and R ₁ -, can be the same or different from one another and each is an alkyl group, most preferably one An alkyl group having 1 to 4 carbon atoms, e.g., a methyl group, an ethyl group, propyl group, butyl group and the like, an allyl group, a hydroxyalkyl group in which the alkyl portion most preferably contains 1 to 4 carbon atoms, an acyloxyalkyl group, in which most preferably the acyl and alkyl moieties each have 1 to 4 carbon atoms, for example an acetoxyalkyl group and the like., or an aryl group, most preferably a methylaryl group of up to 10 carbon atoms, and V ^, and Vp or U ^ and Up may be the same or different can and each represent a halogen atom, for example chlorine, bromine and the like, a carboxyl group, an alkoxycarbonyl group, most preferably where the alkoxy moiety has 1 to 4 carbon atoms, For example, a methoxycarbonyl group, an ethoxycarbonyl group and the like, a cyano group, a trifluoromethyl group, a group -SC ^ Rq (Rg: alkyl group, most preferably an alkyl group having 1 to 4 carbon atoms) or a radical -SC ^ NRqRiq, where Rq and R ^ ₀ each represent an alkyl group, most preferably an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom.

Specific examples of compounds corresponding to the general formula (X) are the 'following compounds: anhydro-5,5 ¹ , 6-trichloro-1,1', 5'-triethyl-3- (4-sulfobutyl) benzimidazolocarbocyanine hydroxide, anhydro ^ »!? ¹ _t 6,6'-tetrachlor-1,1 ', 3-triethyl-3' - (4-sulfobutyl) -benzimidazolocarbocyanine hydroxide, 5i5 ', 6,6'-tetrachlor-1,1'-diethyl-3,3' -di (3-sulfopropyl) -benzimidazolocarbocyanine, 5i5 '»6.6 * -

609840/0974

Tetrachloro-1,1'-diethyl-3,3'-di- {2-Z2- (3-sulfopropoxy) -ethoxy / ¹ -ethylbenzimidazolocarbocyanine, anhydro-3- (2-carbamoylattiyl) -5i5 1, 6,6 ' -tetrachloro-1,1 ^l -diethyl-3 ^l - (3-sulfopropyl) -benzimidazolocarbocyanine, 1- (2-acetoxyethyl) -5,5'16,6'-tetrachloro-1'-ethyl-3,3'- di- (3-sulfopropyl-benzimidazole-carbocyanine, 5,5 ', e-e'-tetrachloro-i-ethyl-i' - (2-hydroxyethyl) -3,3'-di- (3-sulfopropyl) -benzimidazolocarbocyanine , 5 »6-dichloro-1,1'-diethyl-5'-trifluoromethyl-3,3'-cLi- (3-sulfopropyl) benzimidazole carbocyanine and the like.

The carbocyanine dyes listed above are added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies within a wide range depending on the emulsion conditions, however, they are preferred in one Amount from about 10 "to about 10" moles, especially 10 "to 10 "^ moles, per mole of silver halide added. Most powerful It is preferred that the emulsions according to the invention have an increased sensitivity in the sensitivity range from about 500 to about 700 mu (nm).

Specific examples of hydroxytetrazaindene compounds within the scope of the invention are listed below, but the list is not limited. Compound (I) 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene Compound (II) 4-Hydroxy-1,3,3a, 7-tetrazaindene Compound (III) 4-Hydroxy-6-methyl- 1,2,3a, 7-tetrazaindene compound (IV) 4-hydroxy-6-phenyl-1,3,3a, 7-tetrazaindene compound (V) 4-methyl-6-hydroxy-1,3,3a, 7- tetrazaindene compound (VI) 2,6-dimethyl-4-hydroxy-1,3,3a, 7-tetrazaindene
Compound (VII) 4-hydroxy-5-ethyl-6-methyl-1,3,3a, 7-

tetrazainden

Compound (VIII) 2,6-dimethyl-4-hydroxy-5-ethyl-1,3,3a, 7-

tetrazainden

609840/0974

Compound (IX)

azainden
Compound (X) 2,5,6-trimethyl-4-hydroxy-1,3,3a, 7-

tetrazainden
Compound (XI) 2-methyl-4-hydroxy-6-phenyl-1,3,3a, 7-

tetrazainden

Compound (XII) 4-hydroxy-6-ethyl-1,2,3a, 7-tetrazaindene Compound (XIII) ^ -Hydroxy-S-phenyl-i, 2,3a, 7-tetrazaindene Compound (XIV) 4-Hydroxy-1,2,3a, 7-tetrazaindene Compound (XV) 4-methyl-6-hydroxy-1,2,3a, 7-tetrazaindene

In order to effectively increase the sensitivity of an emulsion according to the invention, it is necessary to be more than about 1 g, preferably 3 g to 10 g, of the hydroxytetrazaindene add per mole of silver halide. The molar ratio from hydroxytetrazaindene linkage to the carbocyanine dye The scope of the invention is not particularly limited, but it is about 1 to about 2000 as a standard.

The addition of the hydroxytetrazaindene and the carbocyanine sensitizing dye to the emulsion can be made according to the usual methods for adding photographic Additives to emulsions are carried out. For example, they can be used as a solution by dissolving them into one suitable solvent which has no adverse effect on the photosensitive product obtained as the end product Material exerts, for example water, methanol or aqueous alkaline solution, are added.

The usual materials are used as the hydrophilic colloid (carrier for the silver halide), for example Gelatin, colloidal albumin, casein, cellulose derivatives, e.g. B. carboxymethyl cellulose, hydroxyethyl cellulose and Like., sugar derivatives, e.g. B. agar-agar, sodium alginate, Starch derivatives and the like, synthetic hydrophilic colloids,

609840/0974

for example polyvinyl alcohol, poly-N-vinylpyrrolidone, Polyacrylic acid copolymers, polyacrylamide, derivatives thereof and the like. If necessary or desired, a mixture of two or more such colloids can be used will.

Of these, the most commonly used consists of gelatin. The gelatin can be partially or fully by a synthetic substance of high molecular weight produced by a so-called gelatin derivative Treatment of gelatin with a reagent with a reagent for reaction with functional components contained in the gelatin molecule Groups, d. H. Amino groups, imino groups, hydroxyl groups or carboxy groups suitable groups or by a Graft polymer made by grafting a molecular chain a further high molecular weight substance on gelatin was replaced.

Without being restricted in any way, from about 10 to about 500 g, more preferably from 50 to 300 g, of the hydrophilic colloid are usually used as a binder for Λ mol of silver halide.

If desired, the emulsions can be hardened in a customary manner. Specific examples of hardeners are aldehyde compounds such as formaldehyde, glutaraldehyde and the like, ketone compounds such as diacetyl, cyclopentanedione and the like, compounds with a reactive hologue such as bis (2-chloroethylurea), 2-hydroxy-4-, 6- dichloro-1,3,5-triazine and in the US-patents 3,288,775, 2,732,303, British patents 974,723, 1,167,207, and the like. vbeschriebenen compounds, compounds wi th a reactive olefin such as divinylsulfone, 5 -Acetyl-1,3-diacryloylhexahydro-1,3 »5-triazine, which is disclosed in U.S. Patents 3,635,718, 3,232,763, the

609840/0974

British Patent 994-869 and the like. Described compounds, IT-Methylolverbindungen such as N-hydroxymethylphthalimide and the compounds described in U.S. Patents 2,732,316 and 2,586,168 and the like, isocyanates according to US Pat. No. 3,103,437, aziridine compounds corresponding to U.S. Patents 3,017,280 and 2,983,611 and the like; acid derivatives corresponding to U.S. Patents No. 3,017,280; U.S. Patents 2,725,294, 2,725,295, and the like, carbodiimide compounds according to US Pat. No. 3,100,704 and the like, epoxy compounds according to US Pat U.S. Patent 3,091,537 and the like, isoxazole compounds corresponding to U.S. Patents 3,321,313 and 3,54-3,292, Halocarboxyaldehydes such as mucochloric acid and the like, dioxane derivatives such as dihydroxydioxane, dichlorodioxane and the like, and inorganic hardening agents such as chrome alum, zirconium sulfate and the like. Also precursors of the compounds described above, such as alkali bisulfite-aldehyde adducts, hydantoinmethylol compounds, primary aliphatic nitro alcohols, and the like, may be used in place of those described above Connections are used.

The photosensitive layer of the photosensitive materials used in the present invention can, if desired in addition to the compounds described above, various gold compounds, e.g. B. potassium chloroaurate, Gold trichloride and the like described in U.S. Patents 2,540,085, 2,597,856, and 2,597,915 Gold (I) dithiocyanate complex salt, a gold (I) dithiosulfate complex salt and the like, corresponding to J. ' Pouradier, M.G. Gadet, and H. Chateau, Electrochemistry des SeIs Dr I. Acides auro et aurichlorhydriques et sels correspondents "in J. Chim. Phys., 62 (2), 203-216 (1965), various palladium compounds such as palladium chloride according to the US patent 2 540 086, potassium chloropalladate according to

6 0 9840/0974

U.S. Patent 2,598,079 or mixtures of these sensitizers to increase the sensitivity of the photosensitive material, its stabilization or for Reduction of the haze can be added.

In the case of using the silver halide photographic emulsions according to the invention as color photographic light-sensitive materials, the compounds to react with an oxidation product of a developing agent to form a dye, the commonly referred to as couplers, are incorporated into the light-sensitive photographic emulsion layers. These couplers have such a structure that they do not move into another layer during manufacture or diffuse processing.

Open-chain diketomethylene compounds are used as yellow couplers generally used widely. Useful examples are e.g. B. in U.S. patents 3 341 331, 2 875 057, 3 551 155, of the German OLS 1 54-7 868, U.S. Patents 3,265,506, 3,582,322, 3,715,072, German OLS 2,162,899, US Patents 3,369,895, 3,408,194 and German OLS 2,057,941, 2 213 461 \ 2 219 9.17, 2 261 361, 2 263 875 and the like.

5-Pyrs. Zolone compounds are mainly used as magenta couplers Used- In addition, indazolone compounds and cyanoacetyl compounds are also used. Useful Examples of these are, for example, in U.S. Patents 2,439,098, 2,600,788, 3,062,653, 3,558,319, British Patent 956,261, U.S. Patent Nos. 3,582,322, 5,615,506, 3,519 4-29, 3,311 4-76, 3 4-19,391, Japanese Patent Applications 21 4-54 / 73, $ 6 050/73, of German patent specification 1 810 464, the Japanese patent

609840/0974

Publications 2016/69, 45 971/73 and U.S. Patent 2,983,608 and the like.

Phenol or naphthol derivatives are used as cyan couplers mainly used. Useful examples of this are, for example, in US Patents 2,369,929,

2,474,293, 2,698,79 ^ ·, 2,895,826, 3,311,476, 3,458,315,

3 560 212, 3 582 322, 3 591 383, 3 386 301, 2 434-272, 2 706 684, 3 034 892, 3 583 971, the German OLS

2 163 811, Japanese Patent Publication 28 836/70, and Japanese Patent Application 33 238/73 and the like. described.

In addition, compounds that release a development-inhibiting compound during the color reaction can be used are capable of so-called DIR couplers, or compounds that capable of releasing a developmental inhibitor compound can be added. Examples are in the US patents 3 148 062, 3 227 554, 3 253 924, 3 61? 291

3 622 328, 3 705 201, British Patent 1 201 110, U.S. Patents 3,297,445, 3,379,529, 3,639,417, and the like.

In order to meet various requirements for photosensitive materials, two or more of the above can be used described couplers and the like. Be used in the same layer. It is also possible to do the same To use couplers or the same compound in two or more different layers.

Surfactants can be added to the above-mentioned photographic emulsions alone or in combination can be added. These are used as coating aids, but in some cases they are too to improve emulsion dispersion, sensitization and photographic properties, for antistatic Purposes and used for the prevention of liability.

609840/0974

These surface active agents can be classified into natural surface active agents such as saponin, nonionic surface active agents such as those alkylene oxide series, glycerin series, glycidol series and the like, cationic surfactants such as higher ones Alkylamines, quaternary ammonium salts, heterocyclic "compounds, for example pyridine and the like, phosphonium compounds, Sulfonium compounds and the like, anionic surfactants having an acidic group such as Carboxylic acid group, sulfonic acid group, phosphoric acid group, sulfuric acid ester group, phosphoric acid ester group and like., amphoteric surfactants such as amino acids, Aminosulfonic acids, amino alcohol sulfuric acid or phosphoric acid esters and the like. Subdivide.

Examples of useful surfactants are given in some patents such as U.S. patents

2 271 623, 2 240 4-72, 2 888 226, 2 739 891, 3 068 101,

3 158 484, 3 201 253, 3 210 191, 3 294-540, 3 4-15 649, 3 44-1 413, 3 44-2 654-, 3 4-75 174-, 3 54-5 974-, 3 666 478, 3,507,660 and British Patent 1,198 4-50 and in books such as Hhohei Oda et al., Synthesis and Application of Surface Active Agents (Maki Shoten, 1964), J.W. Perry, Surface Active Agents (Interscience Publication Inc. 1958), J.P. Sisley, Encyclopedia of Surface Active Agents, Volume 2, (Chemical Publish Co., 1964) and the like.

The hardening of the emulsion can be carried out according to conventional methods. As examples of hardeners are for example, aldehyde compounds such as formaldehyde, glutaraldehyde and the like, ketone compounds such as diacetyl cyclopentanedione and the like., Compounds with a reactive halogen, such as bis (2-chloroethylurea), 2-

609840/0974

and the compounds according to U.S. Patents 3,288,775, 2,732,303, 3 125 44-9, 1 167 207, compounds with a reactive olefin, such as divinyl sulfone, 5-acetyl-1,3-diacrylolhexahydro-1,3,5-triazine, Compounds according to U.S. Patents 3,635,718, 3,232,763, British Patent 994-869 and the like, N-methylol compounds such as N-hydroxymethylphthalimide and those in U.S. Patents 2,732,316 and 2,586 compounds described, isocyanates, corresponding to US Pat. No. 3,103-437, aziridine compounds correspondingly U.S. Patents 3,017,280 and 2,983,611 and the like, acid derivatives corresponding to U.S. Patents 2 725 294, 2 725 295 and the like, Garbo diimide connections accordingly U.S. Patent 3,100,704 and the like, epoxy compounds corresponding to US Pat. No. 3,091,537 and the like; isoxazole compounds corresponding to US Patents 3,321,313 and 3,543,292, halocarboxyaldehydes, such as mucochloric acid and the like, dioxane derivatives such as dihydroxydioxane, Dichlorodioxane and the like, and inorganic hardening agents such as chrome alum, zirconium sulfate and the like. Also precursors of the compounds described above, such as alkali bisulfite aldehyde adducts, hydantoirimethylol compounds, primary aliphatic ^ nitro alcohols and the like., Instead of the above listed compounds are used.

The photographic emulsion layers can also be used and others to be used if necessary within the scope of the invention Layers of synthetic polymer compounds, for example a latex such as one dispersed in water Vinyl compound polymer, especially compounds for increasing the dimensional stability of p.iotographic Materials and the like, alone or in combination of different Polymers or ". In combination with a hydro-

609840/0374

2609893

phile, water-permeable colloids are incorporated. as Examples of such polymers are numerous compounds, for example in US Patents 2,376,005, • 2 739 137, 2 853 4-57, 3 062 674-, 3 4-11 911, 3 488 708, 3,525,620, 3,635,715, 3,607,290, 3 74-5,740, British Patents 1,186,699, 1,307,373 and the like. Of these, copolymers or homopolymers of monomers from the group of alkyl acrylates, alkyl methacrylates, acrylic acid, Methacrylic acid, sulfoalkyl acrylates, sulfoalkyl methacrylates, Glycidyl acrylates, glycidyl methacrylates, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, alkoxyalkyl acrylates, alkoxyalkyl methacrylates, styrene, butadiene, Vinyl chloride, vinylidene chloride, maleic anhydride and Itaconic anhydride is generally used. In some cases, a so-called graft emulsion polymerization latex, by performing an emulsion polymerization in the presence of a hydrophilic protective colloid in Form of a Koehpoiymeren can also be used.

To the above-mentioned photographic emulsion various compounds commonly used in the art can be used to prevent the Reduction in sensitivity and training Fog is added during manufacture, storage or treatment of the light-sensitive material will. As such compounds, there have long been various compounds such as heterocyclic compounds including 3-methylbenzothiazole and 1-phenyl-5-mercaptotetrazole, Mercury-containing compounds, mercapto compounds, metal salts and the like are known.

Examples of useful compounds are given in C.E.K. Mees, The Theory of the Photographic Process 3rd edition 1966, pages 344 to 34-9, quoting the original literature

60 9.840 / 0974

and also in the following US patents 1,758,576, 2,110,178, 2,131,038, 2,173,628, 2,697,040, 2,304,962, 2,324,123, 2,394,198, 2,566,245, 2,694,716, 2,697,099-2 708 162, 2 728 663 to '665, 2 476 536, 2 824 001,

2,843,491, 3,052,544, 3,137,577, 3,220,839, 3,226,231,

3,236,652, 3,251,691, 3,252,799, 3,287,135, 3,326,681, 3,420,668, 3,622,339, 2,933,388, 3,567 W, 3,595,662 and British Patent 403,789.

The photographic emulsion according to the invention is on a conventional support, such as a rigid support, such as glass, metal, porcelain and the like., Or on a flexible support to form a photosensitive material applied. The silver halide is often applied to such a support in an amount of from about 0.1 to about

ρ
Applied 1 mg per 1 cm depending on the end use, although this range is not limiting. Typical flexible supports include cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, polycarbonate films, laminates thereof, thin glass films, paper and the like, which are commonly used for photographic light-sensitive materials. With barite or α-olefin polymers, in particular polymers of an α-01efin with 2 to 10 carbon atoms, such as polyethylene, polypropylene, ethylene-butene copolymers and the like. Coated or coated papers, plastic films, their surface to improve the adhesion properties to other polymer substances and for Increasing printability has been roughened as described in Japanese Patent Publication 19 068/72, and similar supports also give good results.

Transparent or opaque supports are used as supports

609840/0974

Depending on the end use of the photosensitive Materials selected. Not only colorless transparent carriers, but also transparent supports colored by the addition of dyes or pigments can be used. Opaque supports include from consist of opaque supports such as paper and additionally those made by adding dyes or figments such as titanium oxide made into a transparent film, plastic ilmoberf laughs treated according to that in Japanese Patent Publication 19 068/72, Papers or plastic films, including slip, dyes or Like. Added to make them completely light-blocking and similar materials.

If the adhesion between the support and the photographic emulsion layer is insufficient, it is possible an adhesion layer with an adhesion to both To form the carrier and the photographic emulsion layer as a primer layer. In order to further improve the adhesive properties, the surface of the carrier also prior treatment such as corona discharge, irradiation with ultraviolet rays, flame treatment, and Like. Have been subjected.

The present invention can be applied to a wide range of silver halide photographic emulsions will. For example, highly sensitive ITegative emulsions, positive emulsions, highly sensitive ones are listed here Reverse emulsions, indirect x-ray emulsions, high resolution emulsions, lithographic emulsions and the like, but are not limitative. As a result, the present invention to a wide range of silver halide photographic light-sensitive materials can be applied. Examples are light-

609840/0974

sensitive color negative materials and black and white negative materials for ordinary use, color and black-Veiss reversal photosensitive materials for ordinary Use, color and black and white paper, photosensitive lithographic materials, indirect X-ray sensitive materials, light sensitive materials for microfilms, light-sensitive color and black Veiss diffusion transfer materials and the like, without the invention being limited thereto.

The invention is explained in detail below with the aid of non-limiting examples of preferred embodiments Invention explained.

example 1

A photographic emulsion comprising AgBr octahedral silver halide grains (111) surface with an average grain size (distribution value) of 0.7 microns manufactured according to the usual double nozzle process. That that is, an aqueous silver nitrate solution and an aqueous potassium bromide solution became an aqueous one at the same time Gelatin solution added with stirring while the pAg in the solution was kept at 9.6. This emulsion contained about 0.35 mol of silver bromide and about 40 g of gelatin per kg. 2100 g portions of the emulsion thus prepared were removed and 5 ml of an aqueous sodium thiosulfate solution (Pentahydrate) at 0.1 wt% would be added, followed by 1 hour at 50 ° C for sulfur sensitization has matured.

Furthermore, 50 g portions of the in this way Sulfur sensitized emulsion removed, a solution with 2.2 10 "^ mol / l of the following sensitizing dye

B09840 / 0974

added in methanol and then an aqueous solution with

5 x 10 "mol / l of the compound (I) was added. Each part was then coated onto a transparent cellulose acetate film provided with a gelatin primer to a dry thickness of about 4 microns for the preparation of photographic light-sensitive materials and dried in the usual manner (emulsion layers in Examples 2 to 10 and Comparative example 1 also. amounted to 4 microns (dry thickness), unless otherwise indicated) Each sample was for 10 seconds through a continuous wedge (optical wedge) and a minus blue filter (using a tungsten lamp Färbtemperatur 2854- ⁰ K As the minus blue filter, the color glass filter V052 made by Tokyo Shibaura Electric Co., Ltd., which absorbs the total light of about 490 nm or more wavelength, about 10% of the light of 500 nm, 73 % of the light of 520 nm and 80 to 90% of the light transmitted longer than 54-0 nm was used The tungsten lamp used was a 1 KW lamp at a distance of 109 cm from the The element and the intensity at the element was 1000 lux. The exposure conditions in Examples 2 to 10 and Comparative Example 1 were identical, unless otherwise stated.

After exposure, each sample was left for 10 minutes at 20 ° C using a Metol ascorbic acid developer developed. The Metol Ascorbic Acid Desiccator was made prepared by adding 2.5 g Metol, 10 g ascorbic acid, 1.0 g potassium bromide and 35 10 g Kodalk (or Nabox) to water, so that a total of 1 liter was obtained (pH 9i8).

The photographic density was determined using a recording densitometer made by Fuji Photo Film ^- Co., Ltd.. The photographic speed is shown in Table I as the reciprocal number of the required exposure

BO9840 / 0974

amount to a photographic density of the veil + 0.1 to get specified. The minus blue sensitivity is given as the relative sensitivity that when applied of the minus blue filter was obtained. Table I also shows the -Ered, Etr and -Ered-Etr values of the dyes. the Experiments were carried out with the following dyes: Dye 1: 3> 3'-diethyl-9-methylthiacarbocyanine bromide Dye 2: 3,3'-diethyl-5,5'-dichloro-9-ethylthiacarbo-

cyanine-o-toluenesulfonate dye 3: 3,3'-disulfopropyl-5,5'-dichloro-9-ethylthia-

carbocyanine
Dye 4: 3.3 ^l -diethyl-5.5 ^l -diphenyl _? 9-ethyloxa-

carbocyanin iodide
Dye 5: 1,1'-diethyl-3,3'-disulfopropyl-5,6,5 ', 6'-

tetrachlorobenzimidacarbocyanine dye 6: 3 »3'-diethylthiacarbocyanine bromide

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2 1.04 2.23 -1.19 0.24 2 1.04 2.23 -1.19 0.12 2 1.04 2.23 -1.19 0.24 2 1.04 2.23 -1.19 0.12 2 1.04 2.23 '-1.19 0.24

3 1.36 2.24 -0.88 0.24 3 1.36 2.24 -0.88 0.12 3 1.36 2.24 -0.88 0.24 3 1.36 2,? 4 -0.88 0.12

Table I.

(Sulfur-sensitized emulsion with 0.7 micron octa-

edrisches silver bromide)

Ver »color« -Ered Etr -Ersd- Amount of added relative

such stoff (V) (eV) Etr sugesetz- amount of sensation-

No. th colour- connection

fabric (I)

(ibMoI / MoI (g / mol AgBr) IgBr)

1 1 1.17 2.28 -1.11 0.12 0 85

1 1.17 2.28 -1.11 0.24 0 100

(Standard)

1 1.17 2.28 -1.11 0.12 1.7 347

1 1.17 2.28 -1.11 0.24 1.7 288

1 1.17 2.28 -1.11 0.12 3.4 400

1 1.17 2.28 -1.11 0.24 3.4 331

2 2 1.04 2.23 -1.19 0.12 0 100

(Default)

0 68

1.7 257

1.7 265

3.4 224

3.4 34-7

1.36 2.24 -0.88 0.12 0 100

(Standard)

0 93

1.7 234

1.7 288

3Λ 230

1.36 2.24 -0.88 0.24 3.4-309

609840/0374

2609983

Table I (continued)

Discoloration -Ered Etr such stoff (V) (eV) No.

-Ered-Etr

Amount of added

additional amount of

th coloring compound

fabric (I)

(mmol / mol (g / mol AgBr) AgBr)

Relative sensitivity

4th 1.33 2.46 -1.13 0.12 4th 1.33 2.46 -1.13 0.24 4th 1.33 2.46 -1.13 0.24 4th 1.33 2.46 -1.13 0.24 VJl 1.62 2.39 -0.77 0.12 5 1.62 2.39 -0.77 0.24 VJl 1.62 2.39 -0.77 0.12 VJl 1.62 2.39 -0.77 0.24 5 1.62 2.39 -0.77 0.12 5 1.62 2.39 -0.77 0.24 6th 1.13 2.21 -1.08 0.12 6th 1.13 2.21 -1.08 0.24 6th 1.13 2.21 -1.08 0.12 6th 1.13 2.21 -1.08 0.24 6th 1.13 2.21 -1.08 0.12 6th 1.13 2.21 -1.08 0.24

0 81 0 100
(Stan
dard) 1.7 132 3.4 126 0 83 0 100
(Stan
dard) 1.7 295 1.7 209 3.4 363 3Λ 302 0 74 0 100
(Stan
dard) 1.7 324 1.7 380 3Λ 380 3.4 331

It is clear from the sensitivity values listed in Table I that the minus blue sensitivity of the octahedral silver bromide emulsion made with carbocyaninene-S-J.bilizing dyes are sensitized with an -Ered-Etr value of greater than 1.25, which is marked with the addition of the

609840/0974

bond (I) in the relatively large amount of more than 1 per mole of silver bromide was increased.

The same results as in Table I were obtained when exposure was carried out for 1/1000 of a second using of the emulsions described above. Similar results as in Table I were also obtained if the same experiments as in Example 1 were carried out and for 10 minutes at 20 ° C using the Developer D76 was developed.

Ye r Example 1

The sensitivity values obtained by operating the same procedure as in Example 1 except that the following sensitizing dyes were used in place of the dyes used in Example 1 are shown in Table II.
Dye 7 '· 3'3'-Eiäthyl ^{l-5,5-dichloro-9-äthyloxacarbocyanin-}

iodide

3,3'-diethyl-S-ethyloxacarboxyanine qodide

3,3'-diethyloxacarbocyanine iodide

1,1'-diethyl-2,2'-quinocyanine iodide

Dye 8: Dye 9: Dye 10, Dye 11: Erythrosine

Table II

Ver Color -Ered Etr -Ered- Added Added Relative search material (V) (eV) Etr dye Amount of Sensation No. lot link opportunity (mmol / mol AgBr) (g / mol AgBr)

1.08 1.08

1.08 1.08 1.08 1.08

2.50 2.50

2.50 2.50 2.50 2

1.42 1.42

1.42 1.42 1.42

0.12 0.24

0.12 0.24 0.12

2.4

74

100 (standard)

33 89 38 76

Table II (continued)

Ver
search
No. Color
material -Ered
(T) Etr
(eV) -Ered-
Etr Added
dye
lot
(mmol / hol
AgBr) Added relative
Amount of sensation
Connection loan
(D
(g / mol AgBr) 89 8th 8th 1.21 2.53 -1.32 0.12 0 100
(Stan
dard) 8th 1.21 2.53 -1.32 0.24 0 49 8th 1.21 2.53 -1.32 0.12 1.7 102 8th 1.21 2.53 -1.32 0.24- 1.7 44 8th 1.21 2.53 -1.32 0.12 3.4 71 8th 1.21 2.53 -1.32 0.24 3.4 35 9 9 1.16 2.56 -1.40 0.12 0 100
(Was standing-
dard) 9 1.16 2.56 -1.40 0.24- , 0 22nd 9 1.16 2.56 -1.40 0.12 1.7 62 9 1.16 2.56 -1.40 - 0.24 1.7 33 9 1.16 2.56 -1.40 0.12 3.4 57 9 1.16 2.56 -1.40 0.24- 3.4 100
(Default) 10 10 1.10 2.37 -1.27 0.12 0 95 10 1.10 2.37 -1.27 0.12 3.4 81 11 11 1.05 2.31 -1.26 0.12 0 100
(Default) 11 1.05 2.31 -1.26 0.24 0 51 11 1.05 2.31 -1.26 0.12 1.7 78 11 1.05 2.31 -1.26 0.24- '1.7 51 11 1.05 2.31 -1.26 0.12 3.4 63 11 1.05 2.31 -1.26 0.24 3.4

609 8 4 0/0974

As can be clearly seen from the sensitivity values listed in Table II, the minus blue sensitivity of the emulsions produced with carbocyanine dyes having an -Ered-Etr value, as defined above, of less than -1.25 and. color-sensitized with sensitizing dyes other than carbocyanine dyes, is not increased, but is, in contrast, decreased when compound (I) is added in an amount of more than 1 g per hol of silver bromide.

Example 2

In a procedure according to the same as in Example 1, except that the compounds (II), (IV) and (XII) were used in place of the compound (I) used in Example 1, sensitivity values obtained are listed in Table III.

Ur. dye Table III Tetrazainds Relative Ver 1 Added
lot
(mmol / mol
AgX) Added
lot
(g / mol AgX) sensitivity search
No. 1 0.12 No. 0 83 12th 1 0.24 II 0 100
(Default) 1 0.12 II 1.7 282 1 0.24 II 1.7 347 1 0.12 H 5.4 309 2 0.24 II 3.4 389 2 0.12 II 0 100
(Default) 2 0.24 II 0 89 2 0.12 II 1.7 200 0.24 II 1.7 309 II

609840/0974

26099S3

Table III (continued)

Ver gate. dye Mr. Tetrazainds Relative search
No. 2 Added
lot
(mmol / mol
AgX) II Added
lot
(g / mol AgX) sensitivity 13th 2 0.12 II 3.4 126 1 0.24 IV 3.4 276 14th 1 0.12 IV 0 100
(Default) 1 0.24 IV 0 83 1 0.12 IV 1.7 178 1 0.24 IV 1.7 209 1 0.12 IV 3.4 174 2 0.24 IV 3.4 214 15th 2 0.12 IV 0 100
(Default) 2 ■ 0.24 IV 0 74 2 0.12 IV 1.7 346 2 0.24 IV 1.7 224 2 0.12 IV 3.4 263 1 0.24 XII 3.4 275 16 1 0.12 XII 0 83 1 0.24 XII 0 100
(Default) 1 0.12 XII 1.7 302 1 0.24 XII 1.7 263 1 0.12 XII 3.4 302 0.24 3.4 288

609 8 4 0/0974

26099S3

Table III (continued)

attempt
No.

Ear stuff No. Tetrazainds Relative No. Added
lot
(mmol / mol
AgX) XII Added
lot
(gMol AgX) sensitivity 2 0.12 XII 0 100
(Default) 2 0.24 XII 0 89 2 0.12 XII 1.7 309 2 0.24 XII 1.7 339 2 0.12 XII 3.4 281 2 0.24 3.4 347

As is clear from the sensitivity values shown in Table III, the minus blue sensitivity becomes an octahedral silver bromide emulsion layer, those with carbocyanine dyes with an -Ered-Etr value, as defined above, were sensitized by more than -1.25, marked when the hydroxytetrazaindene compounds were added in the relatively large amount of more than 1 g per mole of silver bromide increased.

The same results as in Table III were obtained when exposure was carried out for 1/1000 of a second using the emulsions listed above. Similar results as in-Table III were also obtained by the same procedure as in Example 1 and a developing for 10 minutes at 20 ° C using the Developer D76.

Example 5

A photographic emulsion, the cubic silver bromide surface / with an average grain size

609840/0974

(Grain size distribution value) of 1 micron prepared by the same double nozzle process as in Example 1, the pAg of the reaction solution being kept at 7.9 became. This emulsion contained about 0.35 moles of silver bromide and about 40 g gelatin per kg.

Shares of 2100 g of the emulsion prepared in this way were removed and sodium thiosulfate (pentahydrate) added as an aqueous solution with 1 wt.% in the amounts listed in the following • Table IV, whereupon during 1 hour at 50 ° C to carry out sulfur sensitization has matured.

The upon addition of the dye 1 or the dye 2 and then the compound (I) to these emulsion fractions and the subsequent same process as in The sensitivity values obtained in Example 1 are shown in Table IV.

(Emulsion with Table IV Added amount
the conn
manure (I)
(g / mol AgBr) Micron) sodium
thio sulfate
(Pentahydrate)
(mg / mole AgBr) Color
material 0 Relative
Feel
opportunity Ver
search
No. 0 1 cubic silver bromide of 1 0 100
(Default) 18th 1 Added amount
of the color
fabric
(mmol / Iiol
AgBr) 0 66 1 0.06 1.7 - 1 0.12 129 1 0.24 3.4 129 1 0.06 3.4 145 1 0.12 120 0.06 0.12

609840/0974

Table IY (continued)

Ver
search
No. Sodium-
thiοsulfate
(Pentahydrate)
(mg / mole AgBr) ü'arb-
material Added amount
of the color
fabric
(mmol / hol
AgBr) Added amount
the conn
manure (I)
(g / mol AgBr) Relative
Sensation
opportunity 56 44 1 0.06 0 458 33 0.12 0 602 126 1 0.24 0 575 354 1 0.06 1.7 812 174 1 0.12 1.7 1150 110 1 0.24 1.7 1150 380 1 0.06 3.4 976 363 1 0.12 3.4 1410 1 0.24 3.4 1590 89 1 0.06 0 955 1 0.12 0 1100 1 0.24 0 1200 1 0.06 1.7 1740 1 0.12 1.7 2400 1 0.24 1.7 25IO 1 0.06 3.4- 2240 1 0.12 3.4 2950 1 0.24 3.4- 3390 19th O 2 0.06 0 100
(Default) 2 0.12 0 2 0.24 0 2 0.06 3.4 44 2 0.06 0 2 0.12 0 2 0.24 O 2 0.06 1.7 2 0.06 3.4

609840/0974

26Q9993

Table IV (continued)

Ver
search.
No. Sodium-
thiosulfate
(Pentahydrate)
(mg / mole AgBr) Color
material Added amount
of the color
fabric
(mmol / mol
AgBr) Added amount
mder conn
manure (I)
(g / Hol AgBr) Relative
Sensation
opportunity 204 89 2 0.06 0 427 324 2 0.12 0 676 224 2 0.24 0 446 407 2 0.06 1.7 840 2 0.12 1.7 1590 2 0.24 1.7 1050 2 0.06 3.4 910 2 0.12 3.4 I9OO 2 0.24 3.4 155O 20th 89 5 0.06 0 100
(Default) 5 0.12 0 93 5 0.24 0 83 5 0.06 1.7 182 5 0.12 1.7 257 5 0.24 1.7 214 5 · 0.06 3.4 580 5 0.12 3.4 282 5 0.24 3.4 324 21 89 6th 0.12 0 63 6th 0.24 0 100
(Default) 6th 0.12 1.7 6th 0.24 1.7 6th 0.12 3Λ 6th 0.24 3.4

6098 4 0/0974

As can be clearly seen from the sensitivity values listed in Table IV above, the minus blue sensitivity of the cubic silver bromide emulsion with an -Ered-Etr value, as defined above, of more than -1.25 and with a grain size distribution value of above 0 .7 microns significantly increased when compound (I) is added in the relatively large amount of more than 1 g per mole of silver bromide. It is also seen that the super sensitization with the carbocyanine dyes and the Hydroxytetraazaindenverbindung particularly is at sulfur sensitized emulsions remarkable although the supersensitization is independently determine thereof, ⁰ ^ sulfur sensitization was carried out or not.

Example 4-

A photographic emulsion containing cubic silver bromoiodide grains β ^ Λ 0 0 ^ surface area / having a size distribution value and a silver iodide content as shown in Table V below was prepared by the same double nozzle procedure as in Example 1. This emulsion contained about 0.35 mol of silver bromide and about 40 g of gelatin per kg.

Shares of 2100 g of the emulsion prepared in this way were removed and sodium thiosulfate (pentahydrate) Was added as an aqueous solution of 1% by weight in the amounts listed in Table V, whereupon during Was ripened at 50 ° C for 1 hour to carry out sulfur sensitization.

The with the addition of the dye 1 and then the Compound (I) to each emulsion portion according to the same Procedures as obtained in Example 1, sensitivity values are shown in Table V.

609840/0974

26099S3

Table V (Cubic Silver Bromiodide Emulsion)

Ver AgJ-Korngrössuch content senvertei no. (Mol%) value
(Micron)

0.03

1.1

Sodium-

thiosulfj

(Penta-

hydrate)

(.mg / mol

AgBrJ)

0.1

0.9

0.3

0.9

160

Additional addition
amount d. amount d
j? arb- connect-
fabric 1 dung (I.
(nmol / mol (g / mol
AgBrJ) AgBr) 0 Relative
. Sensation
opportunity
J 0.06 0 69 0.12 0 100
(Default) 0.24 1.7 66 0.06 1.7 190 0.12 1.7 219 0.24 3.4 263 0.06 3.4 263 0.12 3Λ 229 0.24 0 355 0.06 0 65 0.12 0 100
(Default) 0.24 1.7 83 0.06 1.7 162 0.12 1.7 214 0.24 3.4 288 0.06 3.4 229 0.12 3.4 263 0.24 0 339 0.06 0 58 0.12 0 100
(Default) 0.24 1.7 79 0.06 1.7 129 0.12 1.7 145 0.24 224

609840/0974

Table 7 (port setting)

Comparable AgJ- Eorngrössuch servertei no salary. (Mo 1%) value (microns)

0.8

0.8

Additive sodium thiosulphate amount d. (Pentahyr. Ifarbdrat) substance (mpr / mol (mmol / mol AgBrJ) AgBrJ)

160

80

0.06 0.12 0.24

0.12 0.24 0.43

0.24 0.24 0.48

0.12 0.24 0.48

0.48

Amount to be added to compound (I) (g / mol AgBr)

Relative sensitivity

3.4

3.4

3.4

0

0

0

(Default)

1.7

3.4

3.4

O

0

0

(Default)

3.4

As is clear from the sensitivity values listed in Table V, the minus blue sensitivity of the cubic silver bromoiodide emulsions produced with carbocyanine sensitizing dyes with an -Ered-Etr value, as defined above, of more than -1.25 and with a grain size ~ distribution value of above 0.7 microns were color sensitization, markedly increased when the "compound (I) was added in the relatively high amount of more than 1 g per mole of silver bromoiodide. The extent of the increase in minus blue sensitivity was particularly remarkable.

609840/097 4

useful when the silver iodide content was low. However was the increase in sensitivity even with emulsions found where the silver iodide content was high.

Example 5

A photographic emulsion containing irregular spherical silver bromide grains £ {Λ OO) -surface / with an average grain size (grain size distribution value) of 1 micron was prepared by an ordinary single nozzle method using an aqueous ammoniacal silver nitrate solution containing ammonia in an amount of 2 moles per mole Containing silver nitrate, which is hereinafter referred to as ammonical silver bromide emulsion. This emulsion contained 0.28 mol of silver bromide and about 40 g of gelatin per kg.

Portions of 2100 g of the emulsion prepared in this way were removed and 6 ml of an aqueous solution with 0.1% by weight of sodium thiosulfate (pentahydrate) were added, whereupon for 1 hour at 50 ° C for sulfur sensitization has matured.

To each emulsion, Dye 1 and then Compound (I) were added and the same procedure as in Example 1 was followed. The sensitivity values obtained are shown in Table VI.

609840/0974

- 56 - 2609893

Table VI

(Irregular spherical silver bromide emulsion)

attempt
No.

Addition amount of
Dye 1
(mmol / mol AgBr) Amount of the
Connection (I)
(g / mol AgBr) Relative
sensitivity 0.16 0 100
(Default) 0.16 2.1 200 0.16 4.3 246 0.31 0 47 0.31 2.1 145 0.31 4.3 195

As can be seen clearly from the sensitivity values listed in Table VI shows, the minus blue sensitivity of a silver bromide emulsion became the irregular spherical Silver bromide grains with a grain size distribution value of 1.0 micron and containing carbocyanine dyes with an -Ered-Etr-rVert, as defined above, of more than -1.25 were color-sensitized, markedly when the compound (i) was added in the relatively large amount of increased by more than 1 g per mole of silver bromide.

Example 6

A sulfur-sensitized silver bromide emulsion containing octahedral silver bromide grains / ti 1 1) surface / having an average grain size of 0.7 microns (distribution value) was prepared in the same manner as in Example 1. manufactured. To this emulsion were dye 1 or 2 and compound (I) with different orders of

609840/0974

Addition was added and the same procedure as in Example 1 was followed. The sensitivity values obtained are listed in Table VII.

Table VII Color
material Added amount
of the color
fabric
(mmol / Wol AgBr) link
(D
(m / Hol AgBr) Relative
Sensation
opportunity i 1 0.06 0 60 (Octahedral silver bromide emulsion) 1 0.12 0 93 In series
search for the
No addition 1 0.24 0 100
(Default) 28 (comparison) 1 0.06 1.7 234 1 0.12 1.7 309 1 0; 24 1.7 186 dye 1 0.06 3.4 177 I. 1 0.12 3.4 355 Connect
manure (I) 1 0.24 3.4 209 1 0.06 1.7 155 1 0.12 1.7 309 1 0.24 1.7 426 Connect
manure (I) 1 0.06 3.4 204 1 0.12 3.4 275 dye 1 0.24 3.4 537 2 0.12 0 100
(Default) 2 0.24 0 81 2 0.12 1.7 234 (Comparison) 2 0.24 1.7 427 2 0.12 3.4 209 29 dye Y link
(D

609840 / 097-4

Table YII (continued)

Sequential search follow the
No addition

link
(D

dye

Color addition amount

substance of the dye
(mmol / mol AgBr)

2 0.24

2 0.12

2 0.24

2 0.12

2 0.24

link

(D

(g / mol AgBr)

Relative sensitivity

3.4

1.7
1.7
3.4

316

145

219 126 132

As is clear from the sensitivity values shown in Table VII, the minus blue sensitivity became the octahedral silver bromide emulsion, those with carbocyanine dyes with an -Ered-Etr-Vert, as defined above, color sensitized from above -1.25 was striking when the compound (I) was added in the relatively large amount of above 1 g per mole Silver bromide increased regardless of the order of addition of dye and compound (I).

Example 7

A sulfur- sensitized octahedral silver bromide sulfone β, Λ 1 1) surface 7 with an average grain size of 0.7 microns (distribution value) was prepared in the same manner as in Example 1. To this emulsion, Dye 1 or 2 and then Compound (I) were added and the same procedure as in Example 1 was followed. The sensitivity values obtained are shown in Table VIII.

609840/0974

Color
material Table VIII Added amount
the conn
manure (I)
(g / mol AgBr) 2609993 1 (Octahedral silver bromide emulsion) 0 1 Added amount
of the dye
(mmol / mol AgBr) 1.7 Ver
search.
No. 1 0.24 3.4 Relative
sensitivity 30th 1 0.24 6.7 100
(Default) 1 0.24 13.4 275 2 0.24 0 389 2 0.24 1.7 417 2 0.24 3.4 467 31 2 0.24 6.7 100
(Default) 2 0.24 13.4 224 0.24 324 0.24 347 467

As is clear from the sensitivity values shown in Table VIII, the minus blue sensitivity became the octahedral silver bromide emulsion made with carbocyanine sensitizing dyes with an -Ered-Etr value, as defined above, were color-sensitized by more than -1.25, marked when the compound (I) was added increased in the large amount of more than 1 g, more preferably above 3 g, per mole of silver bromide.

Example 8

A sulfur sensitized octahedral silver bromide emulsion / ti 1 1) surface7 with a medium grain size

609840/0974

of 0.7 microns (distribution value) was prepared in the same manner as in Example 1. The dye 1 and 4,5,4 ', 5 ^l -dibenzo ~ 3.3 ^! -disulfopropyl-9-ethylthiacarbocyanine (dye 12: -Ered = 1.62 V; Etr »2.11 eV, -Ered-Etr = 0.49), then the compound (I) is added and the same procedure as in Example 1 is added it was accomplished. The sensitivity values obtained are listed in Table IX below.

Table IX 0.02 Encore
amount of
link
(D
(g / mol AgBr) Relative
Sensation
opportunity 0.05 O 100
(Default) Ver
search
No. (Octahedral silver bromide emulsion) 0.02 O 56 32 Addition- addition
amount of amount of
Dye 1 dye 12
(mmol / mol AgBr) (mmol / mol AgBr) 0.05 1.7 234 0.12 0.02 1.7 186 0.24 0.05 3.4 234 0.12 3.4 251 0.24 0.12 0.24

As is clear from the sensitivity values shown in Table IX, the minus blue sensitivity became the octahedral silver bromide emulsion, which is made with two carbocyanine sensitizing dyes with an -Ered-Etr value, as defined above, was color-sensitized from above -1.25, also upon addition of the compound (I) in the relatively large amount above 1 g increased per mole of silver bromide.

6098 4 0/0974

Example 9

A photographic emulsion containing tabular silver bromoiodide grains (Silver iodide content 4 mol%, (1 1 1 ^ surface) with a mean grain size (distribution value) of 0.9 microns was made by a conventional single nozzle method - This emulsion contained 0.28 91 silver bromoiodide and about 40 g gelatin per kg.

Portions of 2100 g of the emulsion prepared in this way were removed and 4 ml of an aqueous thiosulfate solution with 0.1% by weight were added, followed by maturing for 1 hour at 50 ° C. for sulfur sensitization.

To the emulsion, Dye 1, then Compound (I) were added and the same procedure as in Example 1 was carried out. The sensitivity values obtained are listed in Table X.

Table X

(Tabular silver bromoiodide emulsion) Relative amount added
the connection (I)
(g / mole AgBr) 100 (standard ^ Ver
search
No. Added amount
of the dye 1
(mmol / mol AgBr) 0 21 33 0.24 0 204 0.48 1.7 174 0.24 3.4 0.24

As is clear from the sensitivity values given in Table X above, the minus blue sensitivity of the emulsion with the tabular silver bromoiodide of an average grain size of 0.9 microns, that with a carbocyanine dye with an -Ered Etr value, such as

609840/0974

defined above, color sensitized from above -1.23 was when adding the compound (I) in the proportionate large amount of more than 1 g per KoI silver bromoiodide increased.

Example 10

A photographic emulsion, tabular silver bromine j ο did grain he (silver iodide content 7.2 mol%, (1 1 ^ surface) of a mean eorn size of 0.8 microns (distribution value) was produced according to the usual single-nozzle process. This emulsion contained 0.28 moles Silver halide and about 85 g gelatin ge kg.

2000 g portions of this emulsion were removed and 53i3 ml of an aqueous solution of sodium thiosulfate pentahydrate with 0.01 wt.%, 4-, 7 ml of an aqueous solution of chloroauric acid with 0.1 wt.% and 16 ml of an aqueous 1% by weight solution of potassium thiocyanate was added to this and then for 60 minutes at 51 ° G to carry out both the sulfur sensitization and matured of gold sensitization.

Dyes were added to the emulsion obtained in the amount indicated in Table XI below, followed by the Compound (I) was added and the same procedure as in Example 1 followed. The received Sensitivity values are listed in Table XI.

609840/0974

Color
material Table XI Added amount
the conn
manure (I)
(g / mol AgBr) 2609993 1 (Silver bromoiodide emulsion) 0 1 Added amount
of the dye
(mmol / mol AgBr) 0 Ver
search
Mr. 1 0.16 4.2 Relative
sensitivity 34 3 0.31 0 100
(Default) 3 0.51 0 49 3 0.51 0 135 35 3 0.47 4.2 89 3
12th 0.62 0 100
(Default) 5
12th 0.47 0 42 5
12th 0.16
0.05 0 195 36 5
12th 0.51
0.06 4.2 74 5
12th 0.47
0.09 4.2 100
(Default) 3
12th 0.16
0.03 4.2 26th 0.51
0.06 220 0.47
0.09 220 220

As is clear from the sensitivity values shown in Table XI above, the minus blue sensitivity became the sulfur and gold sensitized emulsion with tabular silver bromoiodide of a medium Grain size of 0.8 microns associated with the carbocyanine dye with an -Ered-Etr value (as defined above) of above -1.25 was color-sensitized when the

609840/0974

Compound (I) in the large amount of more than 1 g per mole Silver bromoiodide increased.

Example 11

A silver bromoiodide emulsion (silver iodide content 10 mol%, (1 1 1) surface area) with grains of 1.8 microns mean grain size (distribution value) was made by adding an aqueous ammoniacal silver nitrate solution with a content of 2 mol ammonia per mol silver to an aqueous solution, which contained potassium bromide, potassium iodide and gelatin, and then added an aqueous silver nitrate solution. This emulsion contained 0.87 mol of silver halide and about 90 g of gelatin per kg. 0.1 mol / l of an aqueous potassium iodide solution in the amounts given in Table XII, 0.1% by weight of an aqueous sodium thiosulfate pentahydrate solution, 4.7 mol of an aqueous chloroauric acid solution at 0.01% by weight and was 1.9 ^m l of an aqueous Ο, ΐη-potassium thiocyanate solution was added and ripened for 80 minutes at 51 ° C for sulfur sensitization and gold sensitization.

The dyes 3 and 12 in added to the amounts listed in Table XII below and then the compound (I) and 24 g of des The following coupler was added, which was then drawn up and dried so that a dry thickness of about 10 microns was obtained (the same thickness was used for the emulsion layer in Example 12).

609840/0974

OCH ₂ CONH-

C ₅ Hi ι CONH-C CH ₂

■ κ · ι

The films coated with the emulsion were passed through a continuous wedge and a V052 glass filter from Tokyo Shibaura Electric Co., Ltd., (light with a wavelength greater than about 54-0 nm, 25 % of the light 560 nm, 70% of the light with 570 nm and 85 to 90% light with a wavelength longer than 590 nm through) using a tungsten lamp (coloring temperature 4800 ⁰ E) exposed. The tungsten lamp was a 500 watt lamp located 57 cm from the surface of the element; the intensity of the exposure at the element surface was 400 lux. The exposure conditions in Example 12 were identical.

The films exposed in this way were developed using a color developer containing the following developing agent (37.8 ° C., 2 minutes, 34 seconds).

60 9840/0974

-66- 260999

\ zz / ^ C ₂ H ^ OH CH ₃

The composition of the color developer was as follows

Water (27 to 32 ° C) 800 ml

Nitrilotriacetic acid 0 * 72 g

Potassium metabisulphite 3 »38 g

Sodium sulfate 0.15 g

Potassium carbonate 31 »9 g

Sodium bicarbonate 3 * 82 g

Potassium hydroxide 1.60 g

Sodium bromide 1.21 g

Potassium chloride 0.32 g

Developing agent 4-, 33 g

Hydroxylamine sulfate 2.43 g

Water to 1 1 (pH 10.07)

The sensitivity values obtained are in Table XII listed.

609840/0974

Table XII
(Silver bromoiodide emulsion)

Ver Addition Addition Addition Addition Relative search amount of KJ amount d. amount d. amount d. More sensitive. (mmol / mol dye-dye compound
AgX) fabric $ fabric 12 dung (I)

(mmol / mol (mmol / mol (g / mol AgX)

AgX) AgX)

O 0.11 0.015 0.6 100

(Default)

0 0.11 0.015 3.4- 129

0 0.11 0.015 6.9 110

0.30 0.11 0.015 0.6 120

0.30 0.11 0.015 3.4 155

0.30 0.11 0.015 6.9 151 0.57 0.11 0.015 0.6 120 0.57 0.11 0.015 3.4-155 0.57 0.11 0.015 6.9 204-

As is clear from the sensitivity values shown in Table XII, the minus blue sensitivity became the sulfur and gold sensitized silver bromoiodide emulsion with an average grain size of 1.8 microns (Silver iodide content 10 mol%) with a carbocyanine dye with an -Ered-Etr-r value, as defined above, was sensitized above -1.25, markedly when the compound (I) was added in the large amount of more than 3 g increased per mole of silver bromoiodide. Also the addition of potassium iodide in the case of chemical ripening, it served to increase the mirus blue sensitivity more effectively.

60 98-0 / 09 7Α

Example 12

An emulsion with tabular silver bromoiodide (silver iodide content 8.5 mol%, (1 1 1) surface) with an average grain size of 1.8 microns (distribution value) was after customary single nozzle processes. This emulsion contained 0.83 mol of silver halide per kg and gelatin in one Quantity of 90 g ^ e kg of emulsion. This emulsion became chemical sensitized in the same manner as in Example 11. An appropriate amount of potassium iodide was added according to the chemical Sensitization added.

Dye 3 and then dye 13 and then compound (I) were added to the emulsion, and the same procedure as in Example 11 was followed. The sensitivity values obtained are listed in Table XIII.
Dye 13: 3-sulfopropyl-5-m ~ ethoxy-thia-1 ^I -ethyl-3 '~

sulfopropyl-5i6-dichlorobenzimidacarbocyanine (-Ered = 1.56 V versus SCE, Etr = 2.33 eV; -Ered-Etr = -0.77).

609840/0974

Table XIII

(Silver bromoiodide emulsion)

Ver
search
No. Encore-.
Amount of
KJ
(mmol / mol
AgX) Encore
Amount of
Color
fabric 3
(mmol / mol
AgX) Encore
Amount of
Color
fabric 13
(mmol / mol
AGX) Encore
Amount of
Connect
manure (I)
(g / mol AgX) Relative
Sensation
opportunity 38 O 0.08 0.16 0.6 '100
(Default) 0.04 0.08 0.16 0.6 98 0.11 0.08 0.16 0.6 123 0.37 0.08 0.16 0.6 107 0 0.08 0.16 3.6 115 0.04 0.08 0.16 3.6 120 0.11 0.08 0.16 3.6 126 0.37 0.08 0.16 3.6 129

As can be clearly seen from the sensitivity values listed in Table XIII, the minus blue sensitivity of the silver bromoiodide concentration with an average grain size of 1.8 microns (silver iodide content 8.5 mol%), which was obtained with the carbocyanine dye with an -Ered-Etr value, as defined above, was sensitized from above -1.25 and had been subjected to sulfur sensitization and gold sensitization, markedly increased when the compound (I) was added in the large amount of more than 3 S ü ^{e M} ° l of silver bromoiodide. The addition of potassium iodide after the chemical Keifung served to more effectively increase the minus blue sensitivity.

The invention has been described in detail above on the basis of preferred embodiments without affecting the invention is limited to this.

609840/0974

Claims (32)

Patent claims 'Λ /' Photo graph.! s before silver halide emulsion containing in combination (1) (a) silver halide grains practically with a (1 Λ 1) face and / or (b) silver halide grains practically with a (1 0 O) face and with a grain size distribution value greater than about 0.7 microns, (2) a sensitizing amount of a carbocyanine sensitizing dye, wherein two 5- and / or 6-membered nitrogen-containing hetero ring cores with an aliphatic Group or an aryl group on the nitrogen atom, the nuclei being the same or different from one another can, connected to each other via a trimethine chain and the one -Ered-Etr value of greater than about -1.25, where Ered has the polarographic reduction spot en ti al of the dye indicated as value V versus SCE and Etr indicates the transition energy of the Dye, determined in methanol solution and indicated as the value of eV, and (3) a hydroxytetrazaind compound according to the following general formulas (A) or (B) in an amount of more than about 1 g ge mol of silver halide: OH 609840/0974 or (B) where R ^ and Rp are the same or different from one another and each represent a hydrogen atom, an aliphatic group, a carboxy group, an alkoxycarbonyl group or an aryl group and n _Q denotes the numbers 1 or 2. 2. The silver halide photographic emulsion of claim 1 further comprising a Contains water-soluble iodide, which for this purpose before, during or after the chemical ripening, but before the growing was added regardless of the iodide in the silver halide. 3. Photographic emulsion according to claim 1 or 2, characterized in that the content of the hydroxytetrazaindene compound not less than 3 g per mole of silver halide amounts to. 4-. Photographic emulsion according to claims 1 to 3 »characterized in that the aliphatic group is in the general formula (A) or (B) from an unsubstituted Alkyl group or one having a hydroxy group, a carboxy group or an alkoxy group substituted alkyl group. 5- Phot ο graphic emulsion according to claim 1 to 4-, characterized in that the carbocyanine sensitizing dye is composed of a dye of the general formula: Ri, -N -4CH = CH ) . C = CH-C = CH-C = £ CH-CH £ = ~; ϊΡ_ n-1 m-i Jl-I 609840/0974 consists, in which 1, m and η each have the numbers Λ or 2, IU is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group with a benzene nucleus, X ~ "is an inorganic or organic acid anion which is due to form a salt with the dye, where, if 1 is 1, the dye is an intermolecular salt, R ^ and Rn each represent an aliphatic group or an aryl group and Zyj and Z2 represent the non-metal atoms necessary to complete a 5- or 5-membered nitrogen-containing heterocyclic ring. 6. Photographic emulsion according to claim 5 »thereby characterized in that the carbocyanine sensitizing dye from dyes corresponding to the general formulas (II) to (X) consists of: ⁰ Ii ₁ ^ n ₁ +! wherein R, and X ~ have the same meaning as in the general formula (I), n ^ and m ^ each an integer from 1 to 5 »W ^ and W ~ each a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, a monoaryl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, a monoaralkyl group, a hydroxy group or an alkoxycarbonyl group in which the alkyl moiety has 1 to 4 carbon atoms, and I ^ and 1 _P 609840/0974 Each is an integer from 1 to 4 so. (W ₂ ) where V ^, W \ - ,, I ^ and L · have the same meaning as in the general formula (II) and np is an integer
is from 2 to 4-; where W ,,, W ", I ^ and Ip have the same meaning as in the Formula (II) have n ^ an integer from 1 to 5 and m; represents an integer from 2 to 4-; 609840 / 097A (W ₁ ) C ₂ H ₅ CH = C-CH = SO ₃ H (V) wherein W ^, W ^, l ^ and I _{2 have} the same meaning as in the general formula (II) and n ^ and m ^ each represent an integer from 2 to 4; x ° CVD where W ^, "Wp, X, I ^ and I ^ have the same meaning as in the Formula (II) and n ^ and mc each have an integer are from 2 to 4; C ₂ H ₅ CH = C-CH = * T-I = S (CH ₂ ) GK r-χττΎ ·· ■ 60984Π / 097Α , X, I ^ and 1 ~ have the same meaning as in the have general formula (II) and ng and m ^ respectively represent an integer from 2 to 4-; (W ₁ ) SO ₃ H (W ₂ ), (VIII) wherein W ^, Wp, I ^ and ± £ have the same meaning as in the general formula (II) and n ^ and mn each represent an integer from 2 to 4; (Wi) CH = CH-CH = (CH ₂ ) SO ₃ H n ₈ (IX) where W ^, I ^ and I2 have the same meaning as in general Formula (II) have and ng and mg each have one an integer from 1 to 4, and 609840/0974 R ₇ - (X) wherein R ^, R ^, R ₁ -, X and 1 have the same meaning as in the general formula (I), Rg and Rr _{7 are the} same or different from one another and each represents an alkyl group, an allyl group, a hydroxyalkyl group, an acyloxyalkyl group or an aryl group and V ^ and Vp or TL · and Up, which can be the same or different, each represent a halogen atom, a carboxyl group, an alkoxycarbonyl group, a cyano group, a trifluoromethyl group, a group -SO2Rg, in which Rg is an alkyl group, or -SOpNRqR / iQ, where Rq and R ^ q are each an alkyl group or a hydrogen atom. 7. Photographic emulsion according to Claims 1 to 6, characterized in that the silver halide consists of Silver bromide, silver chlorobromide, silver bromoiodide or Silver chlorobromoiodide consists. 8. Photographic emulsion according to claims 1 to 7> characterized in that the silver halide contains no more than 10 mol% silver iodide. 9- Photographic emulsion according to Claims 1 to 8, characterized in that the silver halide is no longer contains than 1.5 Mo1% silver iodide. 10. A photographic emulsion according to claim 1 to 9 _t characterized in that the silver halide is chemically sensitized. 609840/0974 11. Photographic emulsion according to claim 9 or 10, characterized in that the chemical sensitization includes at least one sulfur sensitization. 12. Photographic emulsion according to claim 11, characterized characterized in that the chemical sensitization comprises a sulfur sensitization and a gold sensitization. 13- photographic emulsion according to claims 1 to 12, characterized in that the photographic emulsion further comprises a sufficient amount of a water-soluble one Contains iodide to increase the photographic sensitivity of the emulsion, the iodide ion and the amount thereof are independent of what may be contained in the silver halide. 14. Photographic emulsion according to claim 13 »thereby characterized that the iodide consists of potassium iodide. 15 photographic emulsion according to claims 1 to 14, characterized in that the carbocyanine dye has an -Ered-Etr value of less than about -0.5> 0. 16. Photographic emulsion according to claim 1 to 15, characterized in that the mean grain size of the Silver halide does not exceed 5 microns. 17 · Photographic emulsion according to Claims 1 to 16, characterized in that the mean grain size of the Silver halide is less than 2 microns. 18. Process for increasing at least the spectral sensitivity of a photographic silver halide emulsion, characterized in that (1) (a) Silver halide grains practically with a (1 1 1) surface and / or (b) Silver shark ο genid grains practically with a (1 0 O) surface and with a grain size distribution value of more than about 0.7 microns, 609840/0974 (2) a sensitizing amount of a carbocyanine sensitizing dye, wherein two 5- and / or 6-membered nitrogen-containing hetero ring cores with an aliphatic Group or aryl group on the nitrogen atom, these . Cores can be the same or different from each other can, connected to each other via a trinethine chain and the one -Ered-Etr value of greater than about -1.25, where Ered is the polarographic reduction potential of the dye, given as Vert V versus SCE and Etr is the transition energy of the dye, determined in methanol solution and indicated as value eV, indicates and (3) a hydroxytetrazaindene compound represented by "the following general formula (A) or (B) in an amount greater than about 1 gram per mole of silver halide CA) or 609840/0974 where R ^ and IL · are the same or different from one another and each represent a hydrogen atom, an aliphatic group, a carboxy group, an alkoxycarbonyl group or an aryl group and n _Q denotes the numbers 1 or 2, be used. 19- The method according to claim 18, characterized in that that uses a chemically sensitized silver halide 20. The method according to claim 19 *, characterized in that that at least one sulfur sensitization is used as chemical sensitization. 21. The method according to claim 19 »characterized in that that combined as a chemical sensitization a sulfur sensitization and gold sensitization is applied. 22. The method according to claim 19 to 21, characterized in that that the carbocyanine dye and the hydroxytetrazaindene compound can be incorporated into the photographic emulsion after sulfur sensitization. 23. The method according to claim 20, characterized in that that the hydroxytetrazaindene compound to the photographic Emulsion that has at least one sulfur sensitization has undergone extensive chemical sensitization, together with the carbocyanine sensitizing dye or before or is added after the addition of the carbocyanine dye. 24-, method according to claim 19 to -23, characterized in that that uses a chemically sensitized silver halide in the presence of a water-soluble iodide will. 25. Verification according to claim 19 to 24, characterized in that that the emulsion is drawn onto a carrier, and furthermore a water-soluble iodide to the chemically sensitized emulsion is added before the emulsion is drawn onto the support. 609840/0 9 7 k 26. The method according to claim 19 to 24, characterized in that that the emulsion is applied to a carrier and furthermore a water-soluble iodide to the emulsion added before drawing up, the emulsion undergoing a chemical sensitization and a spectral sensitization with the carbocyanine dye. 27. The method according to claim 24 to 26, characterized in that that potassium iodide is used as iodide. 28. The method according to claim 19 to 27, characterized in that a carbocyanine sensitizing dye the general formulas (II) to (X) is used n-, 2n, + 1 wherein IU and X ~ have the same meaning as in the general formula (I), n ^ and m ^ each an integer from 1 to 5i W ^ ₁ and W2 each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a Monoaryl group, a halogen atom, an alkoxy group with 1 to 4 carbon atoms, a carboxy group, a monoaralkyl group, a hydroxy group or an alkoxycarbonyl group in which the alkyl portion has 1 to 4 carbon atoms, and I ^ and I2 each have an integer of 1 to 4- mean ;. 0-9 840/0974 SO ₃ H (W ₂ ), (ITI) wherein W ^, Vp, I ^ and 1 ~ have the same meaning as in the general formula (II) and n ^ and nL · are an integer from 2 to 4; (IV) where W ^, W2, I ^ and I2 have the same meaning as in the general formula (II), n? is an integer from 1 to 5 and m is an integer from 2 to 4 ·; C ₂ H ₅ CH = C-CR, (CH ₂ ) SO ₃ (V) 6098-0 / 0974 wherein W ^, W ₂ , I ^ and I _{2 have} the same meaning as in the general formula (II) and n ^ and m ^ each represent an integer from 2 to 4-; C ₂ H ₅ H = C-CH = < (CH ₂ ) OH n ₅ Wed
(CH ₂ ) OH TCb (VI) wherein V ^ ,, V ₂ , X, I ^ and 1 _{Λ have} the same meaning as in the general formula (II) and nc and m, - each represent an integer from 2 to 4-; C ₂ H ₅ Ho) _i EO (VII) wherein W ^, V ₂ , X, I ^ and I _{2 have} the same meaning as in the general formula (II) and n ^ and m ^ each represent an integer from 2 to 4; 609840/0974 (Wi) i— (W ₂ ), (VIII) wherein V ^, W ₂ , I ^ and I ^ have the same meaning as in the general formula (II) and n ^ and Dn each represent an integer from 2 to 4; (W ₁ ) CH = CH-CIi = SO ₃ H C ₂ H SO ₃ (IX) where W ^ ₁ , I ^ and I ^ have the same meaning as in the general formula (II) and ng and m ^ each represent an integer from 2 to 4, 609840/0974 (X) wherein R ^, R ^, Er, X ~ and 1 have the same meaning as in the general formula (I), Rg and Rr _{7 are the} same or different from one another and each represents an alkyl group, an allyl group, a hydroxyalkyl group, an acyloxyalkyl group or a Aryl group and V ^ and "V ^ or TJ ^ and IU, which can be the same or different, each a halogen atom, a carboxyl group, an alkoxycarbonyl group, a cyano group, a trifluoromethyl group, a group , wherein Rg is an alkyl group, or -SOpNRqR ^ Q, wherein and R ^ q each represent an alkyl group or a hydrogen atom are, mean. 29 · The method according to claim 19 to 28, characterized in that a silver halide with a content of no more than 1.5 mole percent silver iodide is used. 30. The method according to claim 19 to 29, characterized in that a content of the hydroxytetrazaindene compound of not less than 3 grams per mole of silver halide is used will. 31. The method according to claim 19 to 30, characterized in that that a silver halide containing not less than about 80 mol% silver bromide is used. 32. Photographic emulsion according to claims 1 to 18, characterized in that the silver halide is not less contains than about 80 mole percent silver bromide. 33 · Photographic emulsion according to claim 2 to 18, characterized in that the water-soluble iodide is before or has been added during chemical ripening. 6098 4 0/0974