DE1597581C3 - A photographic recording material having a spectrally sensitized silver halide emulsion layer - Google Patents

Description

Ν — SO

R,

(CH = CH) _n ,

NO,

CH-CH = C- -C = O

contains the sensitizing dye represented, wherein R ₁ , R ₂ and R _{3 are} an optionally substituted alkyl group or an aryl group R ₄ or R ₅ , which may be the same or different, each a hydrogen atom, a lower alkyl group or an atomic group necessary to form a ring, Y is an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, X is an anion, U ₁ and n _{2 are} each O or 1, and Z is an atomic group necessary to form a heterocyclic ketomethylene ring.

The invention relates to a photographic recording material having a dye provided by a benzimidazole cyanine spectrally sensitized silver halide emulsion layer.

It is known to add benzimidazole trimethine cyanines or benzimidazole merocyanines to the emulsions for the spectral sensitization of silver halide emulsions, in particular for increasing the sensitivity to the green spectral range. It is also known that such benzimidazole cyanine dyes can be used to sensitize photographic silver halide emulsions in such a way that the sensitized materials are free from residual coloration or color stains after processing. This is necessary so that copies can be obtained with a high degree of whiteness in black-and-white photography and with good color reproduction in color photography. (British Patent 975 504, German Auslegeschrift 1 180 241).
However, the disadvantage of the known sensitizers which produce residual color-free recordings is that they often do not impart the required spectral sensitivity.

The object of the invention is to provide recording materials with improved spectrally sensitized photographic silver halide emulsions which, after conventional photographic treatment,; such as development and fixing, residual staining-free ^: provide photographic images, whereby sensitizers should be used, which give the spectrally sensitized emulsions an increased green sensitivity.

The object of the invention is based on a photographic recording material with a at least one silver halide emulsion layer spectrally sensitized by a benzimidazole cyanine dye and is characterized in that the emulsion layer has at least one of the the following general formulas

N-SO ₂

/ - ■ ^γ - \

(CH = CH) ,, - CH = "/ NR ₃

(CH = CH) _n ,

X "

(A)

N-SO.

(B)

CH-CH = C-

The sensitizing dyes shown contain in which R ₁ , R ₂ and R _{3 are} an optionally substituted alkyl group or an aryl group R ₄ or R ₅ , which may be the same or different, each a hydrogen atom, a lower alkyl group or an atomic group necessary to form a ring, Y a group of atoms required to form a 5- or 6-membered nitrogen-containing heterocyclic ring, X is an anion, H ₁ and n _{2 are} each O or 1, and Z is a group of atoms required to form a heterocyclic ketomethylene ring.

R ₁ , R ₂ and R ₃ can each be an alkyl group such as methyl, ethyl or propyl, a substituted alkyl group, e.g. B. / 3-hydroxyethyl, ß-acetoxyethyl, γ-acetoxypropyl, carboxymethyl, / S-carboxyethyl, γ-carboxypropyl, / 3-sulfoethyl, γ-sulfopropyl, (5-sulfobutyl or ethyl sulfate group , an allyl group, an aryl group or aralkyl group, and R ₄ and R ₅ , which may be the same or different, each represent a hydrogen atom, a lower alkyl group or an atomic group required to form a ring, for example of pyrrolidine, piperidine or morpholine, X an anion and Y an atomic group which forms a heterocyclic ring, such as thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, selenazole, benzoselenazole, naphthoselenazole, thiazoline, oxazoline, selenazoline, 2-quinidazole, 4-quinidazole, imidazole Z is an atomic group required for the formation of a heterocyclic ketomethylene ring, for example a pyrazolone, 2,4,6-triketohexahydropyrimidine, diketohydroindene, rhodanine, hydantoin, thiohydantoi n-, or a 2-thio-2,4-oxazolidone ring.

The invention achieves spectrally sensitized photographic recording materials, which have an increased sensitivity to green and after processing are free of residual discoloration and stains are.

Examples of the preparation of the intermediate compounds of the dyes according to FIG Invention and the preparation of the dyes indicated. The specified manufacturing instructions are not the subject of the invention.

Synthesis of the intermediate compound (I)

. 6-chloro-1-ethyl ^ -methyl-S-morpholinosulfonylbenzimidazole

C ₂ H ₅

Ice chilled. Thereafter, a solution of 35 g of morpholine in 300 ml of acetone was added dropwise to the solution thus cooled while stirring. After stirring for 1 hour, 1 liter of water was added to the resulting solution, and the crystals formed were collected by filtration. The crystals were washed with water and recrystallized from methanol, 45 g of 5-dichloro-4-morpholinosulfonyl-2-nitrobenzene with a melting point of 163 ^° C. being obtained. The compound thus prepared was refluxed for 30 minutes with 17 g of an aqueous 70% strength monoethylamine solution in 500 ml of ethanol. The obtained crystals were collected, washed with water and recrystallized from methanol to give 40 g of N-ethyl-5-chloro-4-morpholinosulfonyl-2-nitroaniline. The compound obtained in this way was dissolved in 290 ml of acetic acid, and after 58 g of acetic anhydride had been added, 56 g of zinc dust were gradually added in small amounts with stirring and heating to 100 ^° C. After further continuing the reaction for 2 hours under reflux by heating, the product was filtered while the system was hot, the filtrate was concentrated under reduced pressure, and after adding an aqueous sodium hydroxide solution to the residue formed to make the product alkaline, this was then extracted by chloroform. When the crude crystals obtained by the extraction were recrystallized from methanol, 26 g of the intermediate compound (I) were obtained with a melting agent; point of 206 ° C. ■ · '

Synthesis of the intermediate compound (II)

6-chloro-1-ethyl ^ -methyl-S-piperidinosulfonylbenzimidazole

N — SO

-L-CH ₃

58 g of 2,4-dichloro-5-nitrobenzenesulfonyl chloride were dissolved in 500 ml of acetone and then with the same procedure as described above for the preparation of intermediate compound (I), with the modification that piperidine was used instead of morpholine, the intermediate compound (II) with a melting point of 142 ^° C. was obtained. The melting points of 1,5-dichloro-2 - nitro - 4 - piperidinosulfonylbenzene and N-ethyl-5 - chloro - 2 - nitro - 4 - piperidinosulfonylaniline formed during the preparation of intermediate (II) were 134 and 173, respectively ⁰ C.

Synthesis of intermediate compound (III)

o-chloro-1-ethyl-S-N-ethylsulfamyl - ^ - methylbenzimidazole

C ₂ H ₅ -N

10 35 g of 6-chloro-1-ethyl-2-methyl-5-morpholinosulfonylbenzimidazole (intermediate compound I) were reacted with 30 g of sodium iodopropanesulfonate at 170 ^° C. for 6 hours. The product was thoroughly washed with acetone and dried, whereby the crude crystals of the intermediate compound (V) having a melting point above 250 ° C. and a hygroscopic behavior were obtained. The raw crystals were used in situ for the preparation of the sensitizing dye.

Following the same procedure as indicated for the preparation of the intermediate compound (I) with the modification to use monoethylamine in place of morpholine became the intermediate (III) obtained with a melting point of 200 ° C. The melting points of 1,5-dichloro-4 - N - ethylsulfamyl - 2 - nitrobenzene and N - ethyl-5-chloro-4-N-ethylsulfamyl-2-nitroaniline, generated during the preparation of intermediate (III) were 146 and 179 ° C, respectively.

Synthesis of the intermediate compound (IV)

■ 6-chloro-1,3-diethyl-2-methyl-5-morpholinosulfonylbenzimidazolium-p-toluenesulfonate

30th

35

7 g of the intermediate compound (I), 6-chloro-1-ethyl-2-methyl-5-morpholinosulfonylbenzimidazole, were to react with 5 g of ethyl p-toluenesulfonate during Brought 6 hours at 160 ° C. By treating the reaction product with acetone after cooling 5 g of the crystals of the intermediate

40

manure (IV)
receive.

with a melting point of 190 ° C

Synthesis of the intermediate compound (V)

Sodium salt of 6-chloro-1-ethyl-2-methyl-5-morpholinosulfonyl-3- (3-sulfopropyl) -

benzimidazolium iodide

C,

N-SO-

CH ₃

SO ₃ Na Γ

Synthesis of intermediate compound (VI)

The sodium salt of 6-chloro-1-ethyl-2-methyl-

5-piperidinosulfonyl-3- (3-sulfopropyl) -

benzimidazolium iodide

CH,

C ₃ H ₆ SO ₃ Na Γ

Following the same procedure as in the preparation of the intermediate compound (V) 6 - chlorine -1 - ethyl - 2 - methyl - 5 - piperidinosulfonylbenzimidazole (Intermediate compound II) brought to react with sodium iodopropanesulfonate, the Intermediate compound (VI) with a melting point of above 250 ° C and a hygroscopic Behavior was obtained.

Synthesis of the intermediate compound (VII)

Sodium salt of o-chloro-1-ethyl-S-N-ethylsulfamyl-2-methyl-3- (3-sulfopropyl) -benzimidazolium iodide

C ₂ H ₅

45

50 C ₂ H ₅ -N-SO ₂

H _n S 0, Na

According to the same procedure as indicated for the preparation of the intermediate compound (V) with the modification that the intermediate compound (III) was used in place of the intermediate compound (I), became the intermediate compound (VII) with a melting point above 250 ° C and a hygroscopic Behavior established.

Synthesis of sensitizing dye (I) of the following structure C ₂ H ₅

CH = CH-CH = C

N-SO

C ₃ H ₆ SO ₃ -

3.2 g of the intermediate compound (VI) described above were reacted with 2.2 g of 2 - {ß - acetovinyl) - 3 - ethylbenzoxazolium iodide in a solvent mixture of 20 ml of nitrobenzene, 1 ml of acetic anhydride and 2 ml of triethylamine for 15 minutes by heating brought under reflux. After cooling the product, ether was added to the system to precipitate the product, whereupon the product was washed with ether and mixed with water to precipitate the crystals of the product. The crystals were collected by filtration, washed with water, and recrystallized from a mixed solvent of methanol and chloroform, whereby 1.3 g of the sensitizing dye having a melting point of 291 ^° C. was obtained. The spectral absorption maximum of the product in methanol was 492 ΐημ.

Synthesis of sensitizing dye (II) of the following structure

/ Nn

C ₂ H ₅ -N-SO ₂
H

/O
CH = CH-CH = C '

CH,

C ₃ H ₆ SO ₃

C ₂ H ₅

2 g of 2- ( β-anilinovinyl) -3-ethyl-5-methylbenzoxazolium iodide were refluxed for 10 minutes in a solvent mixture of 20 ml nitrobenzene and 2 ml acetic anhydride. 2.8 g of the intermediate compound (VII) prepared above and 2 ml of triethylamine were added to the solution thus obtained, and the reaction was 25

carried out by refluxing for 10 minutes. By treating the product like given above in the preparation of the sensitizing dye (I), 1 g of the sensitizing dye was used (II) obtained with a melting point of 284 ° C. The spectral absorption maximum of the dye in methanol was ηΐμ at 496.

Synthesis of sensitizing dye (III) of the following structure

CH = CH-CH = C

N-SO ₂

CH ₆ SO,

(III)

In a solvent mixture of 25 ml of nitrobenzene and 2 ml of acetic anhydride, 2.6 g of 2- {ß- anilinovinyl) -3-ethyl-5-phenylbenzoxazolium iodide were refluxed for 10 minutes. To the solution were added 3.2 g of the intermediate compound (V) and 2 ml of triethylamine, and the reaction of the system was carried out under reflux for 10 minutes. By treating the product as in the preparation of sensitizing dye (I), 1.2 g of sensitizing dye (III) having a melting point above 300 ° C was obtained. The spectral absorption maximum of the dye in methanol was ηαμ at 499.

Synthesis of sensitizing dye (IV) of the following structure

N — SO,

\ ^ ^{CH = CH} ~ ^{CH = C}

C ₃ H ₆ SO ₃ "

C ₂ H ₅

(IV)

3.2 g of intermediate compound (V) were reacted with 2 g of 2 - (ß - acetanilinovinyl) - 3 - ethylthiazolium iodide in a mixture of 20 ml of nitrobenzene, 1 ml of acetic anhydride and 2 ml of triethylamine by heating under reflux for 10 minutes. The product was treated in the same manner as in the preparation of the sensitizing dye (I), and the product was recrystallized from ethanol to obtain 1.1 g of the sensitizing ^{dye (IV) having a melting point of 246 °} C., the maximum absorption spectrum of the dye in methanol was at 477 πΐμ ..

309 647/170

9 10

Synthesis of sensitizing dye (V) of the following structure

CH ₃ CH ₃

CH = CH-CH = C |

N-SO

C ₃ H ₆ SO ₃ CH,

3.2 g of the intermediate compound (VI) were reacted with 2.3 g of 2 - (/ 3-acetanilinovinyl) -1, 3,3-trimethylindolenium iodide in a mixture of 20 ml of nitrobenzene, 1 ml of acetic anhydride and 2 ml of triethylamine reacted by refluxing for 10 minutes. The product was like making the sensitization

15 treated with dye (I), and the crystals thus obtained were recrystallized from a mixed solvent of ethanol and isopropanol to obtain 0.8 g of sensitizing dye (V) having a melting point of 223 ° C. The spectral absorption maximum of the dye in methanol was πΐμ at 510.

Synthesis of sensitizing dye (VI) of the following structure

CH = CH-CH = C

C ₃ H ₆ SO ₃ -

C ₂ H ₅ -N-SO ₂
H

(VI)

Cl

In a mixture of 20 ml of nitrobenzene and 2 ml of acetic anhydride, 2.5 g of 2- (/ 9-anilinovinyl) -S.o-dichloro-l ^ -diethylbenzimidazolium iodide were added heated under reflux for 15 minutes. The solution 3 g of the intermediate compound (VII) and 2 ml of triethylamine were added and the system became reacted for 15 minutes by refluxing. By treating the product in the in the manner described in the preparation of the sensitizing dye (I), 0.7 g of the sensitizing dye was obtained (VI) with a melting point of 288 ° C. The spectral absorption maximum of the product in methanol was πΐμ at 519.

Synthesis of sensitizing dye (VII) of the following structure

N — SO

CH = CH-CH = C
C ₃ H ₆ SO ₃ "■ C ₂ H ₅

(VII)

In a mixture of 20 ml of nitrobenzene and 2 ml of acetic anhydride, 2.5 g of 2 - (/? - anilinovinyl) -5,6-dichloro-1,3-diethylbenzimidazolium iodide were added heated under reflux for 15 minutes. The solution was then mixed with 3.2 g of the intermediate compound (V) and 2 ml of triethylamine, and the system was reacted by refluxing for 15 minutes. By treating the product following the procedure described in the preparation of sensitizing dye (I), 0.9 g Sensitizing dye (VII) having a melting point of 233 ° C was obtained. The spectral absorption maximum of the dye in methanol was ηΐμ at 519.

Synthesis of sensitizing dye (VIII) of the following structure

N — SO

CH = CH-CH = C

(VIII)

SO, —N

4.5 g of the intermediate compound (IV) were to be reacted with 15 ml of ethyl orthoformate in a Mixture of 30 ml of nitrobenzene and 3 ml of triethylamine for 15 minutes by heating under Brought to reflux. After cooling, the reaction mixture became ether to precipitate the product

added, which was washed with ether., The product was dissolved in a small amount of methanol dissolved, and after adding a methanol solution containing an excess amount of sodium iodide 'The solvent was removed to form crystals which were washed with water and off

were recrystallized from a mixed solvent of methanol and chloroform. 1.8 g of the sensitizing dye with a melting point of 263 ^° C. were obtained. The spectral absorption maximum of the dye in methanol was πΐμ at 518.

Synthesis of sensitizing dye (IX) of the following structure C ₂ H ₅

O N SO

C = S

(IX)

1.8 g of the intermediate compound (IV) were reacted with 0.6 g of S-ethyl-S-acetanilidomethylidenrhodanine in a mixture of 50 ml of ethanol and 2 ml of triethylamine for 30 minutes by refluxing. After cooling the reaction mixture, the deposited crystals were collected by filtration and recrystallized from a mixed solvent of methanol and chloroform, whereby 0.6 g of the sensitizing dye (IX) having a melting point of 272 ^° C. was obtained. The spectral absorption maximum of the dye in methanol was πΐμ at 523.

Synthesis of sensitizing dye (X) of the following structure

3.2 g of the intermediate compound (VI) were reacted with 1.2 g of 1-ethyl-2-ethylmercapto-6-methylquinolium methyl sulfate refluxed by heating in a mixture of 50 ml of ethanol and 1 ml of triethylamine for 20 minutes. Ether was added to the product solution to precipitate the dye. The dye was then purified by recrystallization from a mixed solvent of ethanol and methanol. The spectral absorption maximum of the dye in methanol was ΐημ at 452.

The sensitizing properties of the dyes in the silver halide photographic emulsion are determined not reduced if other common emulsion additives such. B. surfactants, couplers or other compounds with anionic groups are also present in the emulsion, since the interaction of the sensitizers with such compounds is low. .

In preparing the silver halide photographic emulsions of the present invention, chemical Sensitizers, stabilizers, coloring agents, hardeners, wetting agents, antifoggants, Plasticizers, development promoters, couplers and fluorescent brighteners are added will.

The silver halide photographic emulsions sensitized according to the present invention can be used in conventional manner Way can be applied to a suitable conventional substrate.

example 1

A photographic emulsion was prepared by adding the sensitizing dye according to the invention to an iodobromide silver emulsion (AgI: AgBr = 7:93 in molar ratio) or a chlorobromide silver emulsion (AgBr: AgCl = 40:60 in molar ratio). The photographic emulsion was applied to a film base made of triacetyl cellulose and dried. The photosensitive film was exposed through a filter, the light having a wavelength longer than 500 transmits πΐμ, namely ⁽⁰ 5400 K) and then developed with natural light of 64 lux. In the development, a developer having the composition shown in Table I below for the iodobromide silver emulsion and a developer having the composition given in Table II below for the silver chlorobromo emulsion were used. The results are compiled in Tables III and IV below.

Table I.

N-methyl-p-aminophenol sulfate 20 g

Hydroquinone 5.0 g

Sodium sulfite 100 g

Borax 20 g

Water, rest to 1000 ml

Table II

N-methyl-p-aminophenol sulfate 20 g

Hydroquinone 4.0 g

Sodium sulfite 40 g

Sodium carbonate (anhydrous) 40 g

Potassium bromide 24 g

Water, rest to 1000 ml

Table III

attempt
No.' Color
material (A) Type of
emulsion Sensitive
ization
maximum Relative
Sensation
opportunity 1 I. 0.08 AgBr / I 530-535 362 2 II 0.08 AgBr / I 540-545 450 3 III 0.06 AgBr / I 542 388 4th IV 0.06 AgBr / I 514 246. 5 V 0.08 AgBr / I 548-550 670 6th VI 0.08 AgBr / I 564-568 950 7th VII 0.08 AgBr / I 560-568 900 8th VIII 0.08 AgBr / I 570 720 9 I. 0.08 AgCl / Br 510-520 370 10 II 0.08 AgCl / Br 510-530 300 11th III 0.08 AgCl / Br 535-540 324 12th IV 0.08 AgCl / Br 510 105 13th V 0.08 AgCl / Br 550 175 14th VI 0.08 AgCl / Br 570 350 15th VII 0.08 AgCl / Br 570 335 16 LX 0.08 AgCl / Br 560-570 290

attempt
No. dye mg-mol / kg
emulsion Type of
emulsion rest
coloring
density 1 πι 0.06 AgBr / I Ö, Ö4 ~ 2: • XI *) 0.06 AgBr / I 0.14 3 ■ VII 0.08 AgBr / I 0.04 4 .. XII *) 0.08 AgBr / I 0.08 5 LX 0.08 AgCl / Br 0.05 6th XIII *) 0.08 AgCl / Br 0.08

IO which had been developed in the unexposed state, fixed for 10 minutes, ^{washed with water for 29 minutes at 10 °} C. and dried. The value of the residual color density given in the table gives the density on exposure through a filter with a maximum permeability of 525 πΐμ. again.

The common sensitizing dyes used as the control dye are those identified by the the following structural formulas:

Sensitizing Dye XI

C ₂ H ₅

N _n

h ~ CH = CH-CH = C

W ^N N

(CH ₂ ) ₃ SO ₃ -

(CH ₂ ) ₃ SO ₃ Na
Sensitizing Dye XII

The relative speed was calculated by taking the speed of a silver halide emulsion containing no dye as 100. For the AgCl / Br emulsions the sensitivity value obtained without using a filter was given, while for the AgBr / I emulsion the sensitivity behind a filter, permeable to light with wavelengths longer than 500 πΐμ is given. _{Tabdk IV}

C ₂ H ₅

C ₂ H ₅

C ₂ H ₅

CH = CH-CH = C

/ N-

C ₇ H,

35

Sensitizing Dye XIII
QH ₅

C ₂ H ₅

CH-CH = C

40

45 S-C = S

C-N

OC ₂ H ₅

*) The comparative sensitizing dyes have those below specified structures.

The test results listed in Table IV were carried out using the samples

Example 2

The sensitizers Nos. II, III and VIII used according to the invention with regard to the Effect compared with the structurally closest comparable sensitizers No. 13, 14 and 9 of Table 3 of British Patent 975 504.

Assuming that the spectral sensitivity of the photographic emulsion containing a dye according to British Patent Specification 975 504, is 100 for each attempt, the obtained spectral sensitivities given in the table below.

table

Attempt no. Dye no. mg · mol / kg
emulsion emulsion blue
sensitive
ability *) green
sensitive
ability **) C.
^u max
(Γημ) veil Residual color 1 II
13th 0.08
0.08 AgCl / Br
AgCl / Br 120
100 165
100 530
510 0.05
0.05 0.04
0.04 2 III
14th 0.08
0.08 AgCl / Br
AgCl / Br 110
100 130
100 540
530 0.05
0.05 0.04
0.04 3 VIII
9 0.08
0.08 AgCl / Br
AgCl / Br 150
100 150
100 555
550 0.05
0.05 0.04
0.04

*) Sensitivity when exposed through a filter, permeable to light with a wavelength greater than 500 ηΐμ. **) Sensitivity when exposed through a filter, permeable to light with a wavelength greater than 520 πΐμ.

Claims (1)

Claim:,. Photographic recording material comprising, at least one, benzimidazole cyanine dye spectrally sensitized silver halide emulsion layer, characterized in that the Emulsion layer at least one of the following general formulas and , N-SO ₂