DE1797199A1 - Photographic silver halide emulsion - Google Patents

Description

PATENTANWXLTI _, _Ä

DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPL-ING. C. GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 55547 «800OMoNCHENIS ^. AUGUST 1968

TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

W. 13th 835/68 Loe / 13

Fuji Shashin Movie Kabushiki Kaisha Kanagawa (Japan).

Photographic silver halide emulsion.

This invention relates generally to a silver halide photographic emulsion containing a novel sensitizing dye and, more particularly, to a silver halide photographic emulsion containing an unsymmetrical benzimidazole carbonyanine dye in which the substituents on the nitrogen atoms in the i

both heterocyclic rings are sulfo-alkyl groups.

It is well known in the art of making photographic silver halide emulsions that by adding a sensitizing dye to a halogen emulsion of the light-sensitive wavelength range this emulsion is enlarged. However, when adding a SensLbiLLsLsLerungnfarerstoffes to a ü

0 0 9 H 5 o / 0 9 S 4

Silver emulsions generally have a tendency to concomitantly increase photographic haze due to the presence of the dye. Accordingly, the sensitizing dye to be selected under such severe limitations, namely that the sensitivity of the desired spectral nsibilisierungsbereiches S _e, which is sensitized by the addition of the F _a rbstoffs, bJach and the formation of fog is low.

A benzimidazole carbocyanine dye can be a halide silver emulsion give a high spectral sensitivity, but has the disadvantage that the fogging by the addition of which is increased.

It is known that when the nitrogen atoms of the two heterocyclisdbene rings of the benzimidazole carbocyanine dye Sulphalkyl groups have the above-described fogging can be remarkably reduced. However, the known such are benzimidazole carbocyanine dyes with sulfalkyl groups on the nitrogen atoms of both heterocyclic rings, a total of symmetrical dyes. For example, although some unsymmetrical benzimidazole carbocyanine dyes are described in the Belgian patents 659 415, 659 853 and 66o 65o, SuLfalkyl group on the nitrogen atom of one

\ j.id voe.V € rW «vi Sinti

der heterocyolLachen Rin ^ e a-leee-

50/0 964 "

symmetrical benzimidazolecarbooyanine dyes with sulfalkyl groups on the nitrogen atoms in both heterocyclic channels are described in US Pat. No. 2,912,329 and in Belgian Patents 648,981 and 669,3o8. But were unbalanced Benz imidazo-1 carbonyani ι, ϊ arbstoffe previously bdannt like with Sulfalkylgruppen on the nitrogen atoms in the two heterocyclic rings.

The object of the invention is to provide a photographic Halopensi lberemulsi on with a high sensitivity over the range of spectral sensitization wavelengths by using a novel sensitizing dye without increasing the sensitizing dye caused photographic fog.

The above-described purposes according to the invention can be achieved in that one r

photographic halo silver emulsion a novel '

Sensitizing dye of the following general Formula (I)

\ + L CH = CH - CH =

A - SO, " ^B -

009850/0964

incorporated, in which Z and Z ¹ each have the non-metallic atoms required to complete the benzimidazole nuclei, the radicals A and B, which can be the same or different, each a polymethylene group, e.g. ethylene, trimethylene or tetramethylene group or an alkylpolymethylene group e.g. a methyltrimethylene group and H is a hydrogen cation, a metal ion which is required to form a salt of sulfonic acid, for example potassium, sodium or the like ion or a cation of an organic amine, for example a triethylamminium ion, I ^ yridinium ion, S-benzylthiaronium ion or the like. represent.

As can be seen from the formula given above, the sensitizing dye used in the invention is an unsymmetrical benzimidazole carbocyanine dye with sulfalky groups as substituents on the nitrogen atoms in both heterocyclic rings.

Examples of the benzimidazole nucleus formed by the atomic group Z or Z ¹ given above are 1-ethylbenzimidazole, 1-phenylbenzimidazole, 1-methyl ~ 5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl-5,6-dichlorobenzimidaz oil, 1-ity1-5,6-dichlorobenzimidazole, 1- (ß-hydroxyethyl) -5,6-dichlorobenzimidazole, 1- (γ-acetoxypropyl) -5,6-dichlorobenzimidazole, 1-ethyl-5,6-dibromobenzimidazole, 1- Ethyl-5-chloro-6-bromobenzimidazole, 1-ethyl-5-phenylbenzimidazole,

009850/0964

, 1 ~ -Lthyl-5, G-dif

y, 1- (C-Ace tox ^ üt inidaaol, 1-iithyl-5-chloro-6-cyanobenzridazole, 1-ethyl

bcnzinidazol _t 1 -Il

carbü.ülio: ^ ybenzinidw> 2ol, i-JLtliyl-p- ^ ca ^ lbenzinidazole,

1-2Ltliyl-5 ~ 3ulf affiylbciizinidazol1 ~ ltii7l-5-H-ethylsul £ a ^ yl- ™

bonziiiiidazole,

5-iaethylsulfonylbenziiaidazole, i-ii
iüiidazol or the like.

'As described above, dor approx. 3 is the inventor Sensitizing substance an unsyru-etrical one Benzimidazole carbocyanine dye with sulphide alkyl group on the Nitrogen atoms on its two heterocyclic pendants, where the desired substituents are both hetero- |

cyclic rings are expediently chosen and tiit such Sensitizing dye can increase the sensitivity of the desired spectral wavelength range photographic silver emulsion by adding the Sensitizing dye to & this without substantial increase the formation of fog can be increased.

BATH ORIGINAL

009860/09 * 4

In addition, the method used in the invention has Sensitizing dye forms such that the alkyl groups of the nitrogen atoms in the two hetero cyclic rings of the dyestuff and the alkylene dyes Sulfalkyl groups can be selected in the desired manner *

The novel by the above all * sensitizing dyes shown in general formula (I) can be prepared by adding an anllinovinyl intermediate with a sulfalkyl group as a sub * substituent of the nitrogen atom in the heterocyclic ring, as indicated below by the general formula (Ii) i

+ «# ■ - VyJl s» \ j Ά - Ji - * · -jjf t

H
A - SO ₅ "

wherein Z and A have the meaning given above in connection with the general formula (I), with Acetic anhydride converts in nitrate benzene to form an acetoanilido-vinyl intermediate to obtain, and the intermediate in the presence of an organic base, for example Triethylamine, with an intermediate of the general formula (III)

/ (HD

B -

009850/0964

wherein Z and B are those given in connection with the above General formula I have given meaning, condensed.

General examples of the preparation of the intermediate products and the dyes used in accordance with the invention are listed below.

Intermediate 1:

CH-OH -KH

2 g of anhydro-1-a'thyl-methyl-I-O-sulfopropyl-benzimidazolium hydroxide and 2.8 g of diphenylformamidine were melted and reacted with heating for 20 minutes. The reaction product thus obtained was waxed with acetone and then with water and recrystallized from an alcohol, 1 g of intermediate 1 having a melting point of ⁰ C being obtained.

Intermediate 2;

= CH - NH

009850/0964

3 g of anhydro-5-chloro-1-ethyl-2-methyl-3- (3-6Ulfopropyl) -benzimidazolium hydroxide and 3.7 g of phenylformaemidine were melted and reacted with heating for 20 minutes. The reaction product was washed with acetone and then with water and then recrystallized from a mixed solvent of methanol and dimethylformamide, 1.3 g of intermediate 2 having a melting point of 304 ° C. being obtained. '■' · ■ '■

Intermediate 3:

? 2 ^H 5

CH - CH - NH

3 g of anhydro ^ 5-dichloro-1-ethyl-2-methyl-3- (3-sulfopropyl) benzimidazolium hydroxide and 3.2 g of diphenylformamidine were melted with heating for 20 minutes, and the reacted reaction product was washed with acetone and then with water and then recrystallized from methanol, intermediate product 3 having a melting point of 288 ^° C. being obtained.

009850/0964

Intermediate product 4t

= CH - NH

2 g of anhydro-1-ethyl-2-methyl-3- (j5-sulfopropyl) -5-trichlorobenzimidazolium hydroxide and 4 g of phenylformamidine were stirred while heating. merged and implemented. The reaction product was washed with acetone and then with water and then recrystallized from methanol, 2.3 g of the intermediate product having a melting point of above 300 ° C. being obtained.

Dye 1;

CH = CH-CH

In a mixture of 15 ml of nitrobenzene and 2 ml of acetic acid 1.5 g of anhydro-2- (ß-anilino vinyl) -l-ethyl-5- (3-sulfopropyl) -benzimidazolium hydroxide were anhydrfl with heating Refluxed for 5 min. The solution prepared in this way was treated with 1.5 g of anhydro-sio-dichloro-l-ethyl - ^ - methyl-3- (3-sulfoputyl) -benzimldazolium hydroxide and 2 ml

009850/0964

Triethylamine mixed and the resulting mixture was reacted under reflux by heating. After the end of the reaction, ether was added to the reaction product mixture to precipitate the dye, which was collected by filtration and treated with an aqueous solution of potassium acetate to give dye 1. ^The spectral absorption maximum of the dye in methanol was at

dye 2: / ^Äv W
-CH = CH-CH = · \ I ^ J • egg ? 2 ^H 5
+ // O ₃ "" C ₃ H ₆ SO ₃ Na cr ^^ I.

In a mixture of JO ml of nitrobenzene, 1.5 ml of acetic anhydride and 0.2 ml of triethylamine were 4.2 g of anhydro-2- (ß-anilinovinyl) -5-chloro-1-ethyl-3- (3-sulfopropyl) benzimidazolium hydroxide refluxed by heating for 10 minutes; The solution thus prepared was with 4 g of anhydro-l-O-aeetoxypropylJ ^ o-dichloro ^ -methyl -;? - (j5-sulfopropyl) -benzimidazolium hydroxide and 2 ml triethyjomin mixed and the mixture was reacted by heating under reflux for 10 minutes.

009850/0964

- li -

After the completion of the reaction, ether was added to the reaction product to precipitate the dye, which was recovered, washed with ether and mixed with water to be crystallized. The obtained dye was dissolved in ethanol, and an aqueous sodium iodide solution was added to the obtained solution to convert the dye into its sodium salt. In the recrystallization g sodium salt of the dye from a solvent mixture of methanol and isopropanol was added 0.8 g of dye 2 in the form of crystals having a melting point of 260 ° C obtained. The spectral absorption maximum of the dye in methanol was at 515 nyu.

Dye 3:

= CH - CH _v . _ C ₃ H ₆ SO ₃ Na

In a mixture of 15 ml of nitrobenzene and 2 ml of acetic anhydride 2 g of anhydro-2-0i-anilinovinyl) -5,6-dichloro-1-ethyl-3- (3-sulfopropyl) benzimidazolium hydroxide reacted for 5 min. Under reflux by heating. The solution prepared in this way was treated with 2 g of anhydro-5-chloro-1-ethyl-2-methyl-3- (3-sulfopropyl) benzimidazolium hydroxide,

009850/0964

1.5 ml of triethylamine and 0.1 ml of acetic acid were mixed, and the resulting mixture was reacted for 5 minutes under reflux by heating. After completion of the reaction, ether was added to the reaction product to precipitate the dye, which was recovered by filtration, washed with ether and treated with an aqueous sodium iodide solution to convert the dye into the sodium salt of the dye. When the sodium salt of the dye was recrystallized from methanol 0.5 g of the dye ^ in the form of crystals having a melting point of 277 ⁰ C obtained. the spectral absorption maximum of the dye in. methanol was nyu at 5I5.

Dye 4;

-CH = CH - CH =

ei ■

__ + C ₄ H ₃ SO ₃ NH (C ₂ H ₅ ) ₃

In a mixture of 20 ml of nitrobenzene and 2.5 ml of acetic anhydride, J5 g of anhydro-2- (0-anilinovinyl) -5,6-dichloro-1-ethyl-3- (3-sulfopropyl) benzimidazolium hydroxide were added Reacted for 5 min. Under ^ üreflux by heating. The solution thus obtained was treated with 3 g of anhydro-5,6-dichloro-1-ethyl-2-methyl-3- (4-sulfobutyl) -benzimidazoliuinhydroxyd and 1.5 ml of triethylamine mixed and the obtained

009850/0964 BATH ORIGINAL

The mixture was reacted for 10 minutes under reflux by heating. After completion of the reaction, the reaction product ether was added to precipitate the dye which was recovered by filtration, washed with ether and was recrystallized from Athani ^ to give 1.2 g of the dye 4 having a melting point of 235 ⁰ C were obtained. The spectral absorption maximum of the dye "

in ^ ethanol was at 519 m / rev.

Dye 5;

-GH = GH-CiI =

In a mixture of 25 ml of nitrobenzene and 4 ml of acetic anhydride, j> g of anhydro-2- (β-aniLinovinyl) -5,6-dichloro-ethyl-3- (3-sulfopropyl) benzimidazolium hydroxide were refluxed for 5 minutes by heating implemented. The solution thus obtained was mixed with 3 g of anhydro-o-chloro-1-ethy.l ^ - methyl-5-morphoiinosulforiy.L-3-O-sulfopropyl) benzimidazollum hydroxide and 2 ml of TflüthylaraLn and the mixture obtained was for 15 min Reacted under reflux by heating.After completion of the reaction, the reaction was converted into ether to precipitate the dye

SAD ORIGINAL 009850/0964

-u-

added, which was obtained by filtration, washed with ether and treated with an aqueous solution of potassium acetate to convert the dye to its potassium salt. The potassium salt of the dye was mixed in a solvent mixture of water / water and a small amount of ethanol and an aqueous solution of S-benzylthiuronium chloride was added to the prepared solution. That so precipitated S-benzylthiuroniura salt of the dye recrystallized from a solvent mixture of methanol and ethanol and chlorine form, v / obei 1.2 g of the dye in the form of crystals having a melting point of 213 ° C. The spectral absorption maximum of the The dye in methanol was 522 nyu.

Dye 6:

3 ο 3

In a mixture of 30 ml of nitrobenzene, 4 ml of acetic anhydride In 0.1 ml of triethylamine, 2 g of anhydro-2- (β-anilinovinyl) -l-ethyl-3- (3-sulfopropyl) -5-trifluoromethylbenzimidazolium hydroxide were added reacted for 5 min. Under reflux by heating. The solution thus prepared was with

BAD ORIQiNAt 009850/0964

^; g anhydro - ^, o-dichloro-l-ethyJ -2-methyl -;> - (3-sulfopropyl) - •. "ni: iniii - ::.: cliumli5 ^T drox3'd and 4 ml triethylunine genii see and. .. i'j mixture was wührend 1 $ min reflux uureh Krki ^ s implemented Küch completion of the reaction was ae r Reaicti: ^ product ether conces- to precipitate the dye ^T just that by winning Filteticn with. ether and washed a .-. vr with "-i'ner wäirigen solution of K liumaoetat to Umwand- J development the dye in its Kaliumsais treated. With "•! ■ crystallization of the potassium salt from a LÜGur.gsmittelger.isch of I - '. Ethancl and isopropsnol 0.7 g of the dye

ii. For: n of crystals with a melting point of above .-, 0 ° - he obtains .. The spectral absorption maximum of the dye in methanol was 512%

The fenli .: the invention applied new: -. Rtii-e 'e :: sensitizing dyes *; off can ^ lalogensilberemulsicnei: spectral sensitizers and in particular the f dye is very effective with regard to the enlargement of the spectrally sensitive area of gelatin - Halogen silver emulsion. In addition, the sensitizing dye can effectively and sufficiently sensitize photographic silver halide emulsions containing other hydrophilic colloids, such as gelatin, such as agar agar, collodium, etc., soluble cellulose derivatives, polyvinyl alcohol and their natural or synthetic hydrophilic resins. In the photographic :: Kaloge :: -

P.Q9850 / 096A BADORIOtMAL

Silberemulsinn according to the invention such silver salts, such as silver chloride, silver bromide, silver iodobromide, Silver chlorobromide and silver chloroiodobromide can be used.

For preparing the silver halide photographic emulsion according to the invention, one or more of the The above-mentioned novel sensitizing dyes of a photographic silver halide emulsion are in common use Way to be incorporated. In the practical

Emulsion As a guide, the dye is usually a photographic /

in the form of a solution in a solvent such as methanol and ethanol are added. The amount of the sensitizing dye to be incorporated into a photographic emulsion can vary in a wide range from 5 mg to 150 mg / kg of the emulsion in accordance with the desired effect.
k The photographic halosilver emulsification according to the

Invention can further include supersensitization and hyper-sensitization be subjected, moreover, köaöen at the photographic silver halide emulsians according to the invention customary additives, for example a chemical sensitizing agent, a stabilizing agent Anti-bronzing agent, a hardening agent, a surface active agent Agents, an anti-fogging agent, a plasticizer, a development accelerator, a color coupler and

_; _ 009850/0964

a fluorescent whitening agent, can be added in a customary manner.

The photographic silver halide emulsion according to the invention can be applied to a support such as a glass plate, a cellulose derivative film, a synthetic resin film or a baryta paper according to the usual procedure can be applied to obtain the photographic photosensitive element.

The invention is explained in more detail below with the aid of the following example.

example

! Ine ^E photographic halogen lb ^ remulsion was, with addition of the sensitizing dye according to the invention, as stated above to a Jodbroms jBoer emulsion (AgI: 7 mol AgBr = 92 mole). The photographic | Emulsim was applied to a triacetyl cellulose film and then dried. The photographic photosensitive film was exposed to a lamp (color temperature 2660 ° K) and, after development, the spectral sensitivity properties were measured with the aid of a diffraction grating spectrometer.

0 0 9 8 5 0 / C 9 6 A ORIGINAL INSPECTED

The composition of the developer used above was as follows:

N-methyl-p-aminophenol sulfate 20 g

Hydroquinone 5.0 g

Sodium sulfite 100 g

Borax 20 g.

P water rest to 1 liter

Table I below shows the S sensitization maxima obtained when various sensitizing dyes according to the invention are used. Were Further, the fog densities of the photographic light-sensitive ^E are ELEMENTS, the using of the photographic silver halide emulsions according to the invention zucammen with those of comparable light-sensitive elements, the other using photogzqphischer silver halide emulsions, the conventional control sensitizing dyes, shown below, unfold, prepared in the following Table II listed.

009850/0964

Table I.

Sensitization
coloring dye mg-mol / kg
emulsion Type of
emulsion Awareness raising
maximum (m / u) 1 0.08 AgBr / J 560 2 π η 570 /. It It 50 ¹ O 4th π It 5Ö2 η Il 565 ο η It 575 Table II Sensitization
rungs dye mg-mol / kg
emulsion Type of
emulsion veil 1 0.0ö AgBr / J 0.04 T ⁺ η Il 0.11 4th π It 0.04 S ⁺ η If 0.27 O π Il 0.04 9 ⁺ N π 0.09 1O ⁺ It π 0.06 Annotation: : Common Sensitizing dyes

for comparison purposes, represented by the formulas below.

009850/0964

Ol \

- 20 -

ι ·

= CH - OH '= \

° 2 ^H 5

• ^C 2 ^H 6 ·

OH = OH - OH ■■ J

- OH = £

Λ ^1;.

»Ci

c "H _e sor ··

. ₂ -CH = OH ^ ₂

Cl

+ /> - 'CH = CH - CH

· ... C ₃ H ₆ SO ₃

92H5

= CH-CH = / '

x -, ■

009850/0964

Claims (1)

Claims A photographic silver halide emulsion, characterized in that it contains at least one unsymmetrical benzimidazole carbocyanine sensitizing dye of the general formula C - CH = CH - CH = C \ \ ι ¹ - »- A-SO ^ B-SO ₃ M included, in which Z and Z ¹ are each required to complete a benzimidazole nucleus of the non-metallic atomic group, A and B 'r.'. ls a Pclymethylen- or Alkylpolymethylengruppe and M ei / '^ lat. -i da.ov ^ .. " ⁵ .1, 2. Photographic silver halide emulsion according to claim 1, characterized in that the benzimidazole nuclei from the group of 1-ethylbenzimidazole, l-ethyl-5-chlorobenzimidazole, l-ethyl-sio-dlchlorobenzimidazole,! - (γ-acetoxypropyl) -5,6-dichlorobenzimidazole, 1-Ethyl-5-fluorobenzimidazole and l-ethyl-S-morpholinosulfonpl-o-chlorobenzimidaseol is chosen are, 3. Halogen photographic emulsion according to claim 1, characterized in that the polymethylene group consists of an ethylene group, a trimethylene group or a tetramethylene group Du SS 50/0 δ 6 A ■■■ ■■ - ■■ ■ ■■ ■ ■ ■ ■ ■ ■■■■ χ - 22 - 4. Photographic silver halide ion according to claim 1, characterized in that the alkylpolymethylene group is a methyltr! methylene group. 3 «Photographic silver halide ion according to claim 1, characterized in that the cation consists of one or hydrogen ion, potassium! on, sodium ion / dam! cation of a Cation of the organic amine, where the / organic amine? Is triethylammonium, pyridinium or S-benzylthiuronium. 6. Photographic silver halide emulsion according to any one of claims 1 to 5, characterized in that the Sensitizing dye in an amount from 5'Bg to 150 rag per 1 kg of the emulsion is contained. 7. Photographieches photosensitive element with a layer of the silver halide photographic emuleion according to claim 1. 009850/0964 ., ir -