DE2252585A1 - PHOTOGRAPHIC SILVER BROMIODIDE EMULSIONS WITH IMPROVED GREEN SENSITIVITY - Google Patents

Description

Photographic silver broin iodide emulsions with improved green sensitivity

The invention is concerned with silver bromoiodide emulsions, which contain crystalline grains, which mixed crystals of silver bromoiodide with iodide ions and contain one or more sensitizer dyes adsorbed on the surface thereof, and relates to in particular improved photographic silver bromine ο ο did emulsions, which are suitable for spectral sensitization to green light.

According to the invention is a photographic Silver boron iodide emulsion indicated that at least one green sensitxer dye and a phot ο graphic Silver bromoiodide emulsion contains, wherein at least

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0.01 hol % iodide ions, based on the silver halide, are adsorbed on the surface of the silver bromide iodide grains contained in the emulsion.

In the field of photographic emulsion production, it is known that spectral sensitivity a photographic emulsion having the spectral sensitivity inherent in silver halide, which mainly ranges from the near ultraviolet to the blue light range, to visible light from longer Wavelength or to the infrared range by adding cyanine series dyes to the photographic Emulsion can be expanded. This process is known as spectral sensitization.

The foregoing process has highlighted the utility of photographic art in the art Materials using silver halides as photosensitive elements increased. Especially from the point of view of practical use, the spectral sensitization to the silver halide gives one good parallelism with the spectral responsiveness of the human eye and this results in a good one Reproduction of the natural colors in a silver halide system. Furthermore, there has been the development of scientific uses such as infrared detectors and the like. Also made possible.

A variety of combinations of dyes and Photographic emulsions have been developed in which the above-mentioned spectral sensitization is used depending on the purpose of the particular photographic light-sensitive material. the Dye / emulsion combination is the main factor that determines in which spectral range the emulsion will sensitize and how high a sensitivity that is

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Has emulsion. It has also been part of some inventions the emulsions with regard to other favorable properties, such as suitability for rapid treatment, good storage suitability of the photosensitive material and the latent images on it, decreased color staining of the treated photosensitive materials and the like. By applying specific To improve dye / emulsion combinations. Despite extensive investigations, however, so far has still been not a fully satisfactory dye / emulsion combination suggested by all of the foregoing Factors for a specific emulsion are met.

For example, in the case of reproducing a green object, difficulties arise due to the fact on that the main spectral reflection range of the green of the leaves of natural plants usually around 55Q nro, while the main spectral reflection range of the artificial Greens, for example the green of artificial plants ^ for example Hong Kong flowers and that of different types of printed material ranges from 510 to 530 nm. In practice it is not always easy, a phot ο graphic emulsion with a spectral sensitivity necessary to achieve a good reproduction of the two green tones the same time is suitable.

Furthermore it is in the case of the formation of a light-sensitive Material often necessary for color prints, the spectral sensitivity or the light sensitivity of the photosensitive material for reproduction or printing within a range of about 5 to about 10 nm corresponding to the spectral absorption range of

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to adjust dyes used in the original color photographic image. However, this is not an easy one Task because if the spectral absorption range to the desired range by a small modification of the chemical structure of the spectral sensitizing dyes for the purpose of shifting the spectral sensitivity is shifted by only about 5 to 20 nm, simultaneous difficulties often occur, for example the Sensitivity is greatly changed, the extent of development is changed, the suitability for storage is influenced becomes, visually there is an increase in the color stains remaining on the treated material, and the like.

One object of the invention is photographic Silver halide emulsions which markedly improve the foregoing difficulties, and specific is one The object of the invention, the formation of a photographic emulsion in a photographic, photosensitive Gelatin silver bromoiodide material wherein the spectral sensitization in the green area in the desired spectral wave length range is achieved without that the secondary errors described above occur.

In the context of the invention it was found that in the case of spectral sensitization a photographic Silver bromodide emulsion in the green range a practically constant high green sensitivity can be obtained, even if a number of green, light absorbing and spectral sensitizing dyes, their spectral absorption ranges are slightly different from each other, used by adding iodide ions to the Silver bromoiodide grains are adsorbed and the amount of the adsorbed iodide ions are regulated according to the type of spectral sensitizing agent used will.

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Based on the "previous knowledge it could be ' do not expect that the spectral sensitivity range will be set exactly in the desired way can without the difficulties described above occur, for example changes in sensitivity and the like

It represents a significant technical advance shows that the present invention makes it extremely easy to match a photosensitive material the desired end use of the element.

In a silver bromoiodide emulsion, iodide ions are naturally contained in the grains as mixed crystals and therefore it would of course be assumed that a certain amount of iodide ions on the surface of the Grains present. It is therefore a surprising finding that despite the above facts a a certain amount of iodide ions added provides striking effects from the point of view of spectral sensitization.

It is known that iodide ions occasionally accidentally form a photographic emulsion together with the spectral Sensitizing dyes are added. That is, numerous of the often considered spectral sensitizing Dyes applied cyanine dyes are cationic dyes and when these dyes are considered an iodide ion Having counterion, the iodide ions become the photographic emulsion along with the dye cation are added without any intention, and they are sometimes adsorbed on the silver halide grains. However is the molar amount of iodide ions added in this case is equal to that of the dye added. I. E. usually this amount is very small in comparison to the amounts to be used according to the invention, so that

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the effect obtainable according to the invention in that the added Amount of iodide ions is set, is not achieved.

The spectral sensitizers which can be used in the context of the invention Dyes are known and are, for example, in Japanese Patent Publication 22884/68, the German Offenlegungsschrift 2 O3O 326 and other publications.

In Japanese Patent Publication 22884f £ 8 it is stated that the spectral sensitivity can be changed by changing the properties of the emulsion can be changed, in particular by changing the silver ion concentration. It is true that adsorption Of course, iodide ions cause a certain change in the silver ion concentration, however can be the effect through the adsorbed iodide ions in a silver bromiodide system from the known teachings do not foresee. In addition, due to the invention there is a tendency to reduce the silver ion concentration, which is completely opposite to the tendency of the above reference that the silver ion concentration is increased to increase the spectral sensitivity.

The process for the preparation of photographic emulsions according to the invention having a high green sensitivity is dealt with in detail below.

The photographic silver halide emulsion contains Silver bromoiodide mixed crystals, preferably about 0.5 to about 10 mol% contain iodide ions and are hydrophilic Protective colloid has a larger proportion of gelatin. Others commonly used in the field Protective colloids, for example phthalated gelatin, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone

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can of course be used ■ -in general is the ratio of silver «] odbromide to protective colloid about 3 * 1 to about 1: 3 by weight. However, that is not particularly critical and it higher and lower ratios can be used will.

The mean grain size of the silver bromoiodide is usually in the range from 0.2 to 2 to 3 μm in diameter, although finer or coarser grain sizes of the silver halide according to the invention can also be used, for which purpose e.g. B. Trivelli Smith "Empirical relations between sensitometric size frequency characterized in photographic series, Photographic Journal", Volume LXXIX, pages 330 to -338 (1939). These grains are usually subjected to various sensitization processes commonly referred to as chemical ripening such as sulfur sensitization, noble metal sensitization, reduction sensitization and the like.

The iodide ions are usually added to the system as water-soluble iodide ion compounds and are usually added to the silver bromoiodide photographic emulsion sol in the form of an aqueous solution. The water-soluble iodide ion compounds are preferably completely soluble or considerably soluble in water. For practical reasons, the term "water-soluble" means a solubility of at least 10% by weight. Examples of water-soluble iodide ion compounds are salts, for example alkali salts such as sodium iodide and potassium iodide, Co I2? Amine salts, such as ammonium iodide and alkaline earth salts, such as Zm ^ »CdJ ₂ J CaJ ₂ ί SrJo * & * ■ & BaJ ^. The ratio of added iodide ions, based on silver bromo'odide, is at least

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at least 0.01 mol% and preferably not more than 1.0 mol%, more preferably 0.05 to 0.3 mol%, which is more suitable Manner depending on the type of sensitizing · dye and the emulsion is adjusted.

On the other hand, an iodide ion compound and a bromide ion compound, the molar ratio Br / J ~ being applicable within a range of 1 to 30 are mixed to form an aqueous solution and become the silver bromoiodide emulsion in the sol state can be added. This concentration of iodide. And / or bromide is in addition to that in the grains as a mixed one Bromide or iodide present in silver halide. This method results in even more precisely controllable Results according to the invention than with the sole addition of the iodide.

The aqueous solution that contains the iodide ions will added to the emulsion and stirred sufficiently. It is believed that practically all of the added iodide ions instantly adsorbed on the silver bromoiodide grains will. This can easily be seen by an immediate change in the color of the grains.

To the obtained photographic silver bromoiodide emulsion, which is kept in the sol state to which the iodide ions have been added becomes an organic solution a spectral sensitizing dye added, which provides Gi-un sensitivity. General will be about 10 to about 2 χ 10 moles of the green sensitizing agent Dye or more such dyes added per mole of silver halide. The application is much less Iiengen produces weakened effects, while no sipificant increase occurs, if much greater

n can be used.

"i 0 9 8 18/1 Q 7

The term "green sensitizing dye" includes both anionic and cationic dyes Dyes with or without iodide ions as counterions.

As green sensitizing dyes according to Invention, cyanine dyes that have an oxacarbocyanine skeleton, for example benzoxacarbocyanine, naphthoxacarbocyanine and the like, contain (group I), Cyanine dyes that have a benzimidazole carbocyanine structure, a benzimidazole oxacarbocyanine skeleton or a benzimidazole indocarbocyanine skeleton, for example benzimidazole naphthoxacarbocyanine and the like. Contain (group II) preferably either independently of one another or 'in Combination of at least two dyes, one of which belongs to group I and the other to group II, can be used or at least two dyes belonging to group II can be used. The term "cyanine" denotes cyanine dyes and Includes merocyanine dyes, for example monomethine cyanine dyes and carbocyanin dyes. As from the publication by Mees and James ("The Theory of Photographic Process ". 3 Edition, 1966, p. 201 to 202) known, is a characteristic of the cyanine dyes, the amidinium ion as a chromophoric system, each nitrogen atom contained in a heterocyclic ring is.

To illustrate the above, preferred are the dyes corresponding to the following general Formula (I) used among the dyes belonging to group (I):

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R.
, -CH = C-CH

where A. and A ₇ a hydrogen atom or a halogen atom (for example chlorine, bromine, iodine or fluorine), Ap and A. a hydrogen atom, halogen atom, a hydroxyl group, alkoxy group (for example a methoxy, or itoxy group and the like) »amino group ( for example an amino,! ethylamino, dimethyl am in ο group and the like) »acylamido group (for example acetamido, propionamido group and the like), acyloxy group (for example acetoxy group and the like), alkoxycarbonyl group (for example methoxycarbonyl, ethoxycarbonyl , Propoxycarbonyl group, butoxycarbonyl group and the like), lower alkyl group (e.g. methyl, ethyl, isopropyl group and the like) or alkoxycarbonylamino group (e.g. ethoxycarbonylamino group and the like) or, taken together, A _x . and A2 and A ^ and A ^ the atoms necessary to form a benzene ring, in which case a heterocyclic ring results, for example an α-naphthoxazole ring, ß, ß * -naphthoxazole ring or ß-naphthoxazole ring, R a hydrogen atom, a lower alkyl group (e.g. methyl, ethyl, n-propyl group and the like), aryl group (e.g. phenyl, tolyl

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group and the like) »E ^ taid E ₀ an alkyl group (for example a methyl, ethyl, n-propyl group), hydroxyalkyl group (for example a 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group and the like), acetoxyalkyl group ( for example 2-acetoxyethyl, 3-acetoxypropyl, 4-acetoxybutyl group and the like), alkoxyalkyl group (for example 2-methoxyethyl, 3-methoxypropyl group and the like), an alkyl group with a carboxyl group (for example a carboxymethyl, 2-carboxyethyl) , 3- ^c arboxypropyl-, 4-carboxybutyl, 2- (2-Carboxyäthoxy) -äthylgruppe and the like.)? an alkyl group with a sulfo group (for example a 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2- (3-sulfopropoxy) ethyl, 2-acetoxy-3 -sulfopropyl-, 3-kethoxy-2- (3-sulfopropoxy) -propyl-, 2 ~ / 2- (3-sulfoporpoxy (-ethoxy_7-ethyl-, p-sulfobenayl-, p-sulfophenäthy1gruppe and the like.), BenEyl group, Phenethyl group, vinylmethyl group and similar groups, X ~ an acid anion (for example a chloride, bromide, iodide, thiocyanate, methyl sulfate, ethyl sulfate, perchlorate, p-toluenesulfonate ion and the like) and ir the numbers 1 or 2 In the above formulas, the radicals A ^, A. * · » ^A 7i - ^ 4.» E » R * and Ep can be the same or different from one another.

Of the dyes belonging to group (II) those corresponding to the following general formula (2) are preferably used:

303818/1 U7 E.

where B _x . a hydrogen atom or a halogen atom (e.g. chlorine, bromine, iodine fluorine), Β ~, B, and B ^, a hydrogen atom, a halogen atom, a lower alkyl group (e.g. a methyl, ethyl, trifluoromethyl group and the like) »amino group ( e.g. amino, methylamino, dimethylamino group and the like), acylamido group (e.g. acetamido, propionamido group and the like), acyloxy group (e.g. acetoxy group and the like), alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl group and the like. ), Carboxyl group, alkoxy group (e.g. methoxy, ethoxy group and the like), aryl group (e.g. phenyl, tolyl group and the like), cyano group, carbamoyl group (carbamoyl, methylcarbamoyl, phenylcarbamoyl, direthylcarbamoyl, diethylcarbamoyl, morpholine carbamoyl , Piperidinocarbamoyl group and the like) »alkylsulfonyl group (e.g. methylsulfonyl group and the like), alkylaminosulfonyl group (e.g. methylaminosulfonyl group (e.g. methylamino sulfonyl group, etc.) fonyl, ethylaminοsulphonyl, dimethylaminosulphonyl, morpholinosulphonyl, piperidinosulphonyl, pyrrolidinosulphonyl and the like) or aminosulphonyl or, taken together B ₅ , and B ^ the atoms necessary to form a benzene ring,

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Y the 'groups -O-ΛC, in which En and Eg are an alkyl

group (e.g. methyl, ethyl, vinylmethyl group and the like), the group ^ NE ₀ , wherein Eq represents an alkyl group (e.g. methyl, ethyl group), E ,, E ^ and En represent the same alkyl groups such as E. or E ^ represent, B, - represents a hydrogen atom or E ₁ - and Eg connected to one another through an alkylene group (e.g. dimethylene, trimethylene group and the like), Ec- often being an alkylene group in the benzimidazolindocarboayanine dyes represents, and m represent the numbers 1 or 2. In the above general formula (2), the best B ₁ , B £, B 1, B ^, E ^, E ^, E 1 - and E _{0 may be the} same as or different from each other.

Specific examples of those that can be used in the present invention Dyes are given below, without the invention being limited thereto

Examples of dyes corresponding to the above general formula (I) are as follows:

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Table I.

CD CO OO

dye

No.

Λ 2 3 4

6 7

H H H H H H

5 - Cl 5 -COOCH. 5 - F 5 - Br 5 - OCH ₃ 5 - CH,

5 -

H H H H H H

C ₂ H ₅

- Cl

5'-COOCH ₃ C ₂ H ₅ (CH ₂ ) SO ₃

C ₂ H ₅ (CH ₂ ) ₃ SO ₅

C ₂ H ₅ (CH ₂ ) ₃ SO ₅

- F

5 '- Br

- OCH ₅ C ₂ H ₅ (CH ₂ ) 3

5 · - CH

-

C ₂ H ₅ (CH ₂ ) ₃ SO ₃ -C ₂ H ₅ (CH ₂ ) ₃ SO ₃ -

(CH ₂ )

(CH ₂ )

(The numbers on the left-hand side of columns A ₂ and A ^ indicate the position of the substituents.)

cn 00 cn

Examples of dyes corresponding to the general formula (2) are as follows:

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SI X 1

HI

O I

HI

HI

frj

in

in

CM CXJ

ο ο

I I

ro i

W. W

ο ο

in I.

w ι

ro
O
CO

CVl

tr!

ro O CO

ro

CM

WHERE

ro O CO

ro

CU O

ro O

co

ro CJ

K O

ro O

co ro

CXJ

W ο

ro O CO

ro

CXJ

CXI

CXJ O

ro O

tn

CVl O

ro
PS

ro O

CO ro

CXJ O

ro O CO

ro

CXJ Ü

ΙΧΛ in CXJ CXJ O O

,

ro O CO

ro

CXJ

WHERE

in

ro O

approx

ro CXJ O

ro O

approx

ro CXJ

WHERE

ro O

approx

ro CXl

WHERE

CXl

CXI O

in in in in « W. W. OJ CXJ CXl CXl O O O O

tn

CXl O

in W

CXi O

ro O

approx

ro

CXJ

WHERE

in

CXJ

ro

CXJ

O H ro ro O O tn W. O I. O O O in O I. I. I. in in in

O · -PfH

co

tn

in

HO

in

p ~ { H W. H JT {- H H O O O O I. I. I. I. in in VO VO H H H H H H H O O O O O O O I. I. I. I. I. I. I. in vo in VO in in in H σ \ H H H H H O O H O O O I. I. I. I. I. VO VO VO VO VO DO O rxj ro * =! - H H H

'-Cl W. in VO '-Cl ro
G. vo in H
O H
O
I. in I.
in H
O
VO 6-Cl in
H VO
r-l

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The digits on the left side of columns B. B2, B, and B ^, indicate the position of the substituent.

As stated above, the iodide ion and the green sensitizing dyes become a photographic one Sol state emulsion for adsorption on the surface of the silver bromogodide grains contained therein added. The molar ratio of the water-soluble iodide to the added green-sensitizing dye is preferably within a range from more than 1 to about 6. The green sensitizing agent used Dye is preferably composed of a dye without an iodide counterion when the ratio is close to one. To further addition of other known additives for photographic emulsions to this emulsion, for example Stabilizers, hardeners, coating aids and the like., is the photographic emulsion in the sol state on a Carrier film made of cellulose triacetate, polyethylene terephthalate and the like., Applied to a uniform thickness, solidified with cold air and then dried by a large amount of air of low moisture content and blown over the film at a high temperature. In this way, the desired photographic, obtained light-sensitive materials.

example 1

A negative working photographic emulsion, the silver bromoiodide grains with an average grain diameter of 0.7 / U and 7 * 1 mol% iodide ions (based on the amount of silver ions) and gelatin (grains / gelatin = weight ratio 1.18) was in the sol state at Maintained 35 ° C. The solutions of potassium given in Table III below were added to this emulsion.

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iodide and the green sensitizing dye, respectively added in the amounts specified there for adsorption of the same on the grains.

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Table III

Sample no. Additives

_γΐ

_yiI

Potassium iodide *

mg 50 mg 100 mg

50 mg

Dye no. 1 ** 130 mg 200 mg 270 mg 200 mg 200 mg 200 mg 200 mg 200 mg

Dye no. 13 ** - -. _ _cn ^& _rn ^b

^J "- 50 mg 50 mg

(The amounts given are based on Λ mol of silver.)

co * Added as a 0.1% aqueous solution. 2l ** Added as 0.1% methanol solution.

cn 00 cn

The emulsions obtained (sol state) were applied to a cellulose triacetate film base in a coating amount of 15 mg silver / dm to a thickness of 5 a. (after drying) applied and then dried.

The materials thus obtained were exposed to light of 4600 ⁰ K (tungsten lamp with a prescribed Davis-Gibson filter) under an illumination of 100 lux at the exposure surface for 1/100 second through a yellow filter and a neutral, continuous wedge, wherein the gel filter allowed the blue light section and thus the determination of only the sensitivity of the spectrally sensitized area.

The exposed samples were developed in the following developer at 20 ° C. for 6 minutes.

Developer composition:

Monol (name of the Fuji Photo-Film Co., Ltd. for N-methyl p-aminophenyl sulfate) 4.5 g

Sodium sulfite (anhydrous) 50 g

Hydroquinone 4.5 g

Sodium carbonate (monohydrate) 35 g Potassium bromide 2g

The addition took place successively to 1 l of water. Immediately after developing the materials were treated in a stop bath (0.3% glacial acetic acid solution), then in a fixer bath (Kodak F-5 solution), washed and dried. The optical density of the formed silver images was determined and the sensitivity from the reciprocal value of the exposure required to obtain an optical density of 0 5 above fog, determined. The results are summarized in Table IV:

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Sample no.

Table IV

II III IV V. VI VII VIII

Sensitive- 100 * 145 160 160 200 225 200 320 speed

Peak wavelength OyO 550 550 550 550 550 550 565 565

* Taken as 100 as the standard for comparison.

By adding potassium iodide in an amount of more more than 100 mg, the sensitivity was no longer increased. Rather, the development was enhanced by this addition delayed ..

As can be seen from the table above »could in the area where a significant increase in sensitivity by increasing the amount of dye added (1) Could not expect a further increase in sensitivity by using potassium iodide together with the dye. In this case, the appropriate amount is still between 50 and 100 mg potassium iodide each Mole of silver.

It is also found that potassium iodide is equally effective for the combination of dyes (1) and (13) to raise awareness. This combination results in a green sensitivity of around 15 mia. longer sitting wavelength than is obtained when using the dye (1), however, the sensitivity between the both dyes kept the same by the addition of the appropriate amount of iodide according to the invention, as is evident from one Comparison of samples V and VII of Tables III and IV above gives. Such a combination of dyes provides represents a further embodiment according to the invention.

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Example 2

The dyes shown in Table V were made into the same silver bromoiodide photographic emulsion as in Example 1 added. In this example, the amount of potassium iodide added was fixed. the Sensitivity of each sample was determined in the same manner as in Example 1 and those listed in Table V. Get results.

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Table V

Sample No. IX X XE XII XIII XIV XT? XVI XVII XVIII

Added

Dye, Nrv (2) (2) (3) (3) (4) (4) (5) (5) (6) (6)

200 mg 200 mg 200 mg 200 mg 200 mg 200 mg 200 mg 200 mg 200 mg 200 mg Lot . '

Amount added
Potassium iodide

Sensitivity * 35

Q peak wave 540
to length (ma)

.85 mg wm 85 mg - 85 nrg 35 85 ai 12th 85 mg 45 50 100 35 40 545 140 535 32 540 525 525 550 550 545 535

^ (The amounts added are given per 1 mole)

* "* * The sensitivity of Sample I was taken to be 100.

Example 5

The following is an example of the application of the photographic emulsions according to the invention given the green-sensitive layer of a light-sensitive color material.

The same silver bromoiodide gelatin emulsion as in Example 1 was kept in a sol state at 35 ° C and Potassium iodide and the green sensitizing dyes were used as a 0.1% aqueous solution or 0.1% Methanol solution added in the amounts shown in Table VI. The emulsions obtained were then used Stirred for 30 minutes to make the iodide and dyes sufficient adsorb to the surface of the grains. Then the following additives (ge 1 mol of silver) were added thereto added successively: 60 ml of a 0.5% aqueous solution Solution of 5-methyl-7-hydroxy-1,3i4-triazaindolizine as a stabilizer, 70 g of 1- (2,4,6-trichloro) -phenyl-3-dodecylamido-5-pyrazolone (as a magenta coupler), dissolved in one Mixture of 70 g of tricresyl phosphate and 100 ml of ethyl acetate with heating and then dispersed in 700 g of an aqueous gelatin solution of 10% by weight in the presence from 84 ml of an aqueous 5% sodium dodecyl sulfate solution; 20 ml of a 2% strength aqueous solution of 2,6-dichloro-4-hydroxytriazine and 3 nil of a 4% aqueous Solution of saponin.

The obtained photographic emulsion was applied to the same carrier as in Example 1 to a thickness (after drying) of 5yu, so that there is an amount of silver of 18 mg / dm, applied, this carrier with an antihalation layer containing 1.4 mg / dm of colloidal silver particles, dispersed in 2.14 g / m gelatin, and a red-sensitive layer containing 0.8 g / m ^ H-n-dodecyl-

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1-hydroxy-2? -Naphthoic acid amide as a cyano coupler, 1.2 g / m Silver as silver bromide grains and the red sensitizing ones Dye contained as the main component of this layer had been applied.

A yellow filter layer of colloidal was successively applied to the green-sensitive layer obtained Silver, a blue-sensitive layer, the 4-dodecylbenzoyl-2-methoxyacetanilide contained as a yellow coupler, and applied a protective film layer and the photosensitive Color material received.

The sensitivity of the obtained photosensitive material was determined in the same manner as in Example 1 except the following method: the yellow filter was not applied during exposure and therefore, the photosensitive material was exposed directly to the light source of 4-800 ⁰ K. To the developer, 1.5 g (per liter) of potassium thiocyanate was further added, and development was carried out at 24 ° C. for 10 minutes. After development, the light-sensitive material έη was treated in a stop bath and then exposed to a highly diffuse, white light over the entire surface to form a fog on the material. Subsequently, color development was carried out at 24 ° C for 15 minutes in the following color developer and a color positive image was obtained.

Composition of the color developer:

Benzyl alcohol 5 * 0

Sodium sulfite (anhydrous) 5 »0. g

Trisodium phosphate (12-hydrate) 40 g

Sodium hydroxide 1.5 g

Potassium bromide. 0.5 g

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Ethylenediamine 5 »0

Citrazinic acid 1.5 g

p-Amino-N-ethyl-N-ß-methanesulfonamidoethyl-m-toluidinsulfonat 10.5 B The ingredients were added successively to 1 water.

Subsequently, washing, bleaching, fixing and washing were carried out to obtain the color image. The optical density of the magenta image in it was determined by a green filter, which is the reciprocal of the exposure, which has a density of 0.5 results, represents. The results obtained are shown in the table below.

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Table VI

Sample No. XIX

XX XXI XXII XXIII XXIV XXV XXVI XXVII XXVIII XXIX XXX XXXi XXXII

Dye"

'Lot

No.
lot

Amount of

didzüsa-

tzes
to

ο feeling inconsistent

_ * Peak wave * s, length

(1) (1) (2) (2) (4) (4) (6) (6) (8) (8) (10) (10) (12) (12) 200mg 200ms 200ms 200ms 200ms 200mg 200mg 200mg 200ms 200mg 200mg 200mg 200mg 200mg

(13) (13) (13) (13) (13) (13) (13) '(13) - - - -

50mg 50mg 50mg 50mg 50mg 50mg. 50mg 50mg

85mg -

85mg - 85mg

85mg -

85mg -

85mg -

100

565

150 565

135

55

64

540+ 565

540+ 565

565

55

535+ 570

65

535+ 570

(de 1 mol of silver) * 100, taken as the standard.

85mg

70 45 55 80 95 I.
do 560 555 555 560 560

CfI

ro αϊ co Cn

From the above Table VI, the excellent effect according to the invention results in the same way Heise as in the case of example 2.

Example 4

The same silver bromoiodide photographic emulsion as in Example 1, an aqueous solution of potassium iodide and a methanol solution were kept in the sol state at 35 ° C the color was added according to Table VII to make the color and iodide on the grains to adsorb. The obtained emulsions were applied and dried in the same manner as in Example and then the sensitometric determinations and thereby obtained the sensitivity values given in the table below. Even in the case using these dyes, the same effect of potassium iodide as in the previous examples was shown.

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Sample no.

Amount of potassium iodide added

Amount of dye added (16)

Amount of dye added (13)

Amount of dye added (1)

Sensitivity determination

Peak wavelength (nui)

Table VII

ZXXIII XXXIV XXXV - XXXVI XXXVII

50mg

200mg

100 '85mg

85mg

200mg 200mg 200mg 200mg

50mg 50mg

25 55 90

565 535 535 (added amounts per 1 mole of silver)

535+
565

535+ 565

* 100, taken as the standard.

In the foregoing, the invention has been described on the basis of preferred embodiments, without being subordinate to this is limited.

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Claims (20)

Claims 1. Silver bromoiodide photographic emulsion, the contains a photographic silver bromoiodide emulsion in addition to at least one green sensitizing dye, wherein at least 0.01 mol% of iodide ions, based on the Silver halide, are adsorbed on the surface of the silver bromoiodide grains contained in the emulsion. 2. Photographic emulsion according to claim 1, characterized in that bromide ions in an amount of 1 to 30 times the molar concentration of the added Iodide ions are also adsorbed on the surface of the silver bromoiodide grains contained in the emulsion are. 3 photographic emulsion according to claim 1 or 2, characterized in that the mixed silver bromoiodide crystals with about 0.5 to about 10 moles # iodide ions adsorbed on the surface thereof. 4. Photo graphic emulsion according to claim Λ to 3 »characterized in that the green-sensitizing dye consists of an anionic dye. 5 · Photographic emulsion according to claims 1 to 3i characterized in that the green sensitizing dye consists of a cationic dye without an iodide ion exists as a counter anion. 6. Photographic emulsion according to claim 1 to 5 » characterized in that the amount of iodide ions added is at least 0.05 mol%, based on silver halide, and the green sensitizing dye consists of a cationic dye with an iodide ion exists as a counter anion. 7- photographic emulsion according to claims 1 to 6, 309818/1075 characterized in that the amount of iodide ions added is in the range from O ₁ O ^ to 0.3 mol%, based on silver halide. 8. Photo graphic emulsion according to claim 1 to 7 » characterized in that at least one green-sensitizing The dye is in the form of one or more cyanine dyes. 9 · Photographic emulsion according to claim 8, characterized in that the cyanine * dye is a Contains oxacarbocyanine skeleton. 10. Photographic emulsion according to claim 8, characterized in that the cyanine dye is a Contains benzimidazole carbocyanine, benzimidazole oxacarbocyanine or benzimidazole indocarbocyanine skeleton. 11. Photo graphic emulsion according to claim 8, characterized characterized in that the cyanine dye used consists of a combination of at least one cyanine dye with an oxycarbocyynine skeleton and at least one cyanine dye with a benzimidazole carbocyanine, Benzimidazole oxacarbocyanine or benzimidazole indocarbocyanine skeleton consists. 12. Photographic emulsion according to claim 10, characterized in that at least two cyanine dyes from this group can be used in combination. 13. Photographic emulsion according to claim 8, characterized characterized in that the gyanine dye corresponds to the following general formula 30981 ^ / 1075 2 (X ~) n-1 wherein A. and A, a hydrogen or a halogen atom, Ap and A ^, a hydrogen atom, a halogen atom, a Hydroxyl group, alkoxy group, amino group, acylamido group, Acyloxy group, alkoxycarbonyl group, lower alkyl group or alkoxycarbonylamino group or A- and Ao and A ^, and A ^ together those necessary for the formation of a benzene ring Atoms, R a hydrogen atom, a lower alkyl group or an aryl group, R- and R2 an alkyl group, Hydroxyalkyl group, acetoxyalkyl group, alkoxyalkyl group, An alkyl group with a carboxyl group, an alkyl group with a sulfo group, a benzyl group, a phenethyl group or a vinylme thy! group "mean and / or (2) VCH = CH-C = / 2 ' 309818/1075 wherein B. is a hydrogen atom or halogen atom, I ^, B ₇ . and B ₂ , a hydrogen atom, halogen atom, a lower alkyl group, amino group, acylamido group, acyloxy group, alkoxycarbonyl group, carboxyl group, alkoxy group, aryl group, cyano group, carbamoyl group, alkylsulfonyl group, alkylaminosulfonyl group or amino sulfonyl group or together B ₇ . and B ₂ , which form a benzene ring necessary atoms, Y the groups -0-, / C <^, where B ₁ -, and Eg represent an alkyl group, the group where Eq represents an alkyl group, E _{1 , E 4} , and B 1 - the same alkyl groups as E _x . or B ^, while E ^ is a hydrogen atom or Br- and E _c are linked to one another by an alkylene group, and m is the number 1 or 2 mean. 14. Photographic emulsion according to claim 13i, characterized in that the halogen atom in the best Ay. , A ₅ , or B _x , consists of chlorine, bromine, iodine or fluorine, the alkoxy group from a methoxy or ethoxy group, the amino group from an amino, ethylamino or dimethylamino group, the acylamido group from an acetamido or propionami do group, the acyloxy group from an acetoxy group, the alkoxycarbonyl group from a methoxycarbonylf ^ i ethoxycarbonyl, propoxycarbonyl or butoxy carbonyl group in the best Ap »A ^ ,, B ^, B ^ or B ^, the lower alkyl group a methyl , Ethyl and isopropyl group in the best Ap or A ₂ , where the lower alkyl group consists of a methyl, ethyl or n-propyl group and the aryl group consists of a phenyl or tolyl group in the case of E ₂ , the alkyl group being methyl, ethyl - Or n-propyl group, the hydroxyalkyl group is a 2-hydroxyethyl, 3-hydroxypropyl or ε-hydroxybutyl group, the acetoxy alkyl group is a 309818/1075 2-Acetoxyäthyl-, 3-Acetoxypropyl- or 4-Acetöxybutylgruppe, the alkoxyalkyl group a 2-Methoxyäthyl- or 3-Methoxypropylgruppe, the alkyl group with a carboxy group a Carboxymethyl-, 2-CaPbOXyEtIIyI-, 3-Carboxypropyl-, 4-Carboxybutyl- or 2- (2-carboxyethoxy) ~ ethyl group, the alkyl group with a sulfo group from a 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2- (3-sulfopropoxy ) -ethyl-, 2-acetoxy-3-sulfopropyl-, 3-methoxy-2- (3-sulfopropoxy) -propyl- _f 2- ^ 2- (3-sulfopropoxy) -ethox2 / ^r -ätb.yl-, p -Sulfobenzyl-, pßulfobenzyl- or p-SuIfophenäthy1gruppe with the best E ^, Bp, B, t R ^ or Er means in which the lower alkyl group is a methyl, ethyl or trifluoromethyl group, the aryl group is a phenyl or tolyl group, the carbamoyl group a carbamoyl, methylcarbamoyl, phenylcarbamoyl, dimethylcarbamoyl, methylcarbamoyl, morpholinocarbamoyl or piperidinocarbamoyl group, the alkylsulfonyl group, a methylsulfonyl group, the alkylaminos Sulphonyl group is a methylaminosulphonyl, ethylaminosulphonyl, dimethylaminosulphonyl, morpholinoeulphonyl, piperidinosulphonyl or pyrrolidinosulphonyl group for the best B ^ »B, or B ^, in which the alkyl group for the best Br ₇ or Bg is a methyl, ethyl or vinylmethyl group means in which the alkyl group in Best Eg means a methyl or ethyl group and in which the alkylene group, formed from the best B ₁ - and E ^, means a dimethylene or trimethylene group. 15. Photographic emulsion according to claim 1 to 14, characterized in that the green-sensitizing. The dye consists of a cyanine dye of the following formulas: 309818/1075 L0 (CHg) ₃ SO ₃ H (C ₂ H ₄ O 309818/1 0 * 7 5 16. Photographic emulsion according to claim 1 to, characterized in that, if more than one green sensitizing dye is used that Dyes consist of one of the following combinations (CH ₂ J ₃ SO ₃ H CJß and 1 -CH = CH-CH = (CHg) ₃ SO ₃ H or 309818/1075 17 · Photographic emulsion after. Claims 1 to 16, characterized in that the amounts of the green sensitizing dye are within a range of 1Q "" ^ to 2 χ 1Q ~ ² mol per 1 mol of silver halide wearing. . 18 · Photographic emulsion after. Claim. 1 to 17 »characterized in that the emulsion is one of the hydrophilic colloids gelatine, phthalated gelatine, Polyacrylamide, polyvinyl alcohol or polyvinylpyrrolidone contains * ■ 19 · Photo graphic emulsion according to claims 1 to 18, characterized in that it further contains a coupler, 20. Phot ο graphic s, light-sensitive silver halide material, consisting of a support with at least one layer thereon which is a photographic Emulsion according to claim 1 to 19 contains. 21 · Procedure for the spectral sensitization of a photographic silver bromoiodide emulsion containing at least contains a green sensitizing dye, characterized in that at least 0.01 mol% of iodide ions the surface of the silver halide grains in the emulsion, adsorbed, so that the emulsion intensely for green with practically no deterioration of the photographic Properties is sensitized. 309818/1075