DE1597577A1 - Silver halide photographic emulsions - Google Patents

Description

PATENT ANWXLTE

1597S77

DR. E. WIEGAND DIPL-ING. W. NIEMANN. ■■ '' ' DR. M. KOHLER DIPL-ING. C. GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 555 476 8000 MO N CH EN 1 5, 30 · HUUt 1D67

TELEGRAMMEtKARPATENT NUSSBAUMSTRASSE 10 ''

■ ι ■. . ■

W. 13292/67

Shashin PiIm Kabushiki Kaisha Kanagawa (Japan)

Silver halide photographic emulsions

The invention relates to photographic silver halide emulsions, which contain a new sensitizing dye.

In the field of silver halide photographic emulsions it is known that the addition of a sensitizing dye to the silver halide emulsion increases the spectral, light-sensitive range of the silver halide emulsion, i.e. is optically sensitized.

However, generally occurs in photographic silver halide emulsions containing a sensitizing dye, the formation typically of larbflecken to ₉ caused by the after completion of the photographic processes such as development,! Fixing, stabilization and water washing, remaining sensitizing dye. Such color spots after processing reduce the brightness or whiteness of the finished printing paper in a photographic

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phic printing paper and deteriorate the tint of the. Image quality and continue to show bad effects color reproduction in color photographic films.

It is therefore an object of the invention to provide photographic silver halide emulsions in which by use of an improved sensitizing dye, the occurrence of color stains is markedly reduced.

Another object of the invention is photographic Silver halide emulsions with higher sensitivity than the usual silver halide emulsions.

The objects of the invention are achieved by in a silver halide photographic emulsion a novel sensitizing dye is incorporated according to the following general formula A:

(GH ₂ ) _n C00H

which is an asymmetrical benzimidazole carbocyanine dye with a sulfoalkyl group as a substituent on the nitrogen atom of one nucleus and a carboxyalkyl group on the nitrogen atom of the other nucleus, wherein V ₁ , V ₂ , W ₁ and W ₂ , which can be the same or different, hydrogen atoms or halogen atoms, such as chlorine -, bromine, iodine or fluorine atoms, R ₁ and

0098 * 4/0301

Rp, which can be the same or different, lower Alkyl groups, for example methyl groups, ethyl groups, n-propyl groups or n-butyl groups, A a polymethylene group, for example an ethylene group, a trimethylene group or a tetramethylene group, or an alkylpolymethylene group, for example a methyltrimethylene group, and η is an integer from 1 to 4.

The sensitizing dye, the asymmetric benzimidazole carbocyanine, can be produced by conventional condensation processes. This is followed by general procedures for the preparation of an intermediate for the sensitizing dye and for the preparation of the sensitizing dye it, which is used in the context of the invention, described.

A quaternary benzimidazolium salt which is an intermediate for the sensitizing dye according to the invention is, by reacting a benzimidazole with a-bromoacetic acid, ß-bromopropionic acid, ß ~ iodopropionic acid, γ-bromobutyric acid and the like can be obtained; However is used to produce the pure quaternary benzimidazolium salt a benzimidazole for reaction with an acid amide compound or a nitrile compound in good yield Brought carboxylic acids listed above, instead of that with the carboxylic acid to produce a quaternary salt is reacted, which is then with a mineral acid, such as hydrogen bromide acid, is hydrolyzed to give the quaternary benzimidazolite salt with a carboxyalkyl group. By

0098A4 / 0301 ~ _BAD ORIGINAL

Implementation of the quaternary salt listed above with Diphenylformamidine, is an anilinovinyl intermediate accordingly produced by the general formula B:

?1

-CH = CH-NH- ^ ^N \ B

(CH ₂ ) _n COOH X "

where ^ν · ι » ^v ? ' ¹¹ I ¹¹¹¹ ^ ⁿ ^ ^e have the meaning given above for formula A and X is an anion such as chloride, bromide, iodide or perchlorate.

The anilinovinyl intermediate B is used for reaction with acetic anhydride in a suitable solvent, for example Nitrobenzene, which is an acetanilidovinyl intermediate results and by reacting this intermediate product obtained in the presence of a suitable organic Base, such as triethylamine or N-alkylpiperidine, by adding of the quaternary salt of the present general formula C becomes the benzimidazole carbocyanine dye corresponding to the above Get Formula A:

Ϊ2 ■ '

H ₃ CG

^W 1

wherein W ^, Wp ₁ R ₂ and A have the meaning given above for formula A.

0098 ^ / 0301. "bad OR, G .. _NA L

As typical examples of the anilinovinyl intermediate according to the general formula B become the following two connections 1 and 2 specified:

C-CH = CH-NH - / ^%

Br "

O ₂ H ₅

C-CH = CH-NH - / ^

CH ₂ COOH Br "

The intermediate anilinovinyl represented by Formula 1 above can be made in the following ways: ™

A mixture of 4 g of 1-Y-carboxypropyl-5j6-dichloro-3-ethyl-2-methylbenzimidazolium bromide and 4 g of diphenylformamidine was added to I6O5; heated on an oil bath and, after the aniline formed was removed under reduced pressure, the reaction was continued for an additional hour. After the reaction, the resulting crystals were washed with acetone to give 3.7 g of light yellow crystals with a melting point of 22O ⁰ C.

009 8-44 / 03 01

BATH ORIGINAL

The intermediate anilinovinyl represented by Formula 2 can also be prepared by a method similar to that used for the preparation of Compound 1. The melting point of this is 215 ^° C.

Typical examples of sensitizing dyes used in the present invention are the following:

C = CH-CH = CH-C

CH ₂ COOH

(CH ₀ )

C = CH-CH = CH-C

^C 2 ^H 5

C = CH-CH = CH-C

Cl

(OHg) ₃ SO ₃ "

II

III

00984A / 0301

O ₂ H ₅

C = CH-CH = GH-C

CH ₂ COOH

CH ₂ -CH ₂ -CH-SO ₅ "CH,

The sensitizing dye represented by the formula I can be prepared in the following manner: 4.7 g of dta intermediate 2, ie 2- (β-anilinovinyl) -1-carboxymethyl-5,6-dichloro-3-ethylbenzimidazolium broniide, were refluxed for 15 minutes Heated for minutes in a mixture of 2 ml of acetic anhydride and 20 ml of nitrobenzene. The resulting solution was mixed with 3.8 g of anhydro-5,6-dichloro-1-ethyl-2-methyl-3- (3-sulfobutyl) -benzimidazoliuinhydroxyd and 2 ml of triethylamine and the mixture was heated under reflux for 10 minutes. After cooling, ether was added to the product to precipitate the dye. The precipitate was washed with water and recrystallized from a mixed solution of methanol and chloroform to give 1.2 g of crystals of Sensibilisierfarbstoffes were obtained with a melting point of 238 ⁰ C (dec.) I. The spectral absorption maximum of the dye in methanol was 518 m λΐ.

Sulfur analysis: calculated: 4.84 1>. _% found: 4.61 ^.

■ O0

/ 030 1

BATH ORIGINAL

Sensitizing dye II was also obtained by the same procedure as above. Of the Melting point of the dye was 27CW (dec.), And that the maximum spectral absorption of the dye in methanol was 513 m / U.

Sulfur analysis: calculated: 4.98 %, found: 4 »73 $.

Sensitizing dye III was also obtained by the same procedure. Its melting point was 284 ° C (decomp.) And the spectral absorption maximum of the dye in methanol was 518 m yes .

Sulfur Analysis: calculated: 4.73 #, found: 4.65 $>

Sensitizing dye IV was also obtained by the same procedure as for the preparation of dye I. Thereof The melting point was 236 ⁰ C (dec.), And the spectral absorption maximum of the dye in methanol was 518 m / rev.

Sulfur analysis: calculated: 4.84 #, found: 4.68 fi.

In the silver halide emulsions used in the context of the invention can use various silver salts, such as silver chloride, silver bromide, silver iodide, silver; iodobromide and the like, be used.

For preparing the sensitized silver halide photographic emulsions according to the invention, one can use one or more of the sensitizing dyes are incorporated into the silver halide photographic emulsion by conventional methods will. «

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00984470301

Since the concentration of the sensitizing dye in of the emulsion in the range from 1 to 150 mg per kg of the emulsion can be, the concentration thereof can be within a wide range according to the desired effect can be varied.

The sensitizing dye used in the context of the invention can be made into a silver halide photographic emulsion incorporated through physical maturation and / or chemical ripening has been sensitized.

In addition, in the preparation of the silver halide photographic emulsions, the emulsion can be added customary process additives, such as sensitizers, stabilizers, tinting agents, hardeners, wetting agents, Anti-opacifying agents, plasticizing development accelerators, Couplers and fluorescent brighteners or whiteners can be added.

The silver halide photographic emulsion according to the invention can be deposited on a suitable support, for example Glass plates, cellulose derivative films, synthetic resin films or baryta paper.

The new sensitizing dyes used in the context of the invention are very effective sensitizers because when they are incorporated into a photographic silver halide emulsion are incorporated that spectrally sensitize the silver halide emulsion, and especially in the range of gelatin silver halide emulsions increase the spectral

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Light sensitivity range of the emulsion. Furthermore, the Sensitizing dye also used as a sensitizer for photographic Silver halide emulsions are used which contain hydrophilic colloids other than gelatin, e.g. agar-agar, Collodion, water-soluble cellulose derivatives, polyvinyl alcohol and the like, or other hydrophilic synthetic or natural Contains resins.

When the photographic photosensitive silver halide

element, which is the silver halide emulsion layer, which is the new

has ^

Sensitizing dye according to the invention contains / photographic Processes such as development, fixation and water washing are subjected to the coloration of the image-bearing Layer due to the remaining dye is very low, and continues because the sensitizing dye has a low level Reactivity with compounds with anionic groups, for example surfactants, color couplers and the like, does not have the dye sensitizing property of the dye due to the presence of such anionic ones Affects connections.

example

A silver iodobromide emulsion (molar ratio of AgJ to AgBr 7:93) or a silver chlorobromide emulsion (molar ratio of AgBr to AgCl 40:60), each containing the sensitizing dye according to the invention, was coated on a base film and dried. The film thus prepared was exposed to the daylight of 64 lux (540O ⁰ K) through a Fuji No. 3 filter (manufactured by Fuji Photo-Film Co .; lets light

009844/0301 BATHROOM OP- /

with wavelengths greater than 500 m / u through) exposed and developed. As the developer, the composition listed in Table I for the silver iodobromide emulsion layer and the composition listed in Table II for the
Silver chlorobromide sulfide layer used. The results
are listed in Tables III and IV.

Table I. Table II Table III 20 g Sensation
opportunity N-methyl-p-aminophenol sulfate N-methyl-p-aminophenol sulfate Sensitizing ν
No. Dye Amount 'Emulsion 5.0 g 950
900
950 '
980
950
1160 Hydroquinone Hydroquinone I 0.09 AgGl-Br
II 0.08 »
III 0.04 "
I 0.09 AgBr-J
II 0.08 "
III 0.04 " 100 g Sodium sulfite ' Sodium sulfite ⁺ 'm-g mol / kg emulsion 20 g borax Sodium carbonate (anhydrous) 009844/0301 1000 ml Water too Potassium bromide Water too 20 g 40 g 40 g 24 g 1 g 1000 ml Awareness
Maximum (m ax) Verse. 575-580
574-578
575-580
577-580
576-578
576-584 1
2
2
4th
5
6th - · - ¹ - ^ *
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AIg sensitivity is the value when exposed to the
Silver iodobromide emulsion indicated by the Fuji Pilter No. 3, the sensitivity of the silver bromide emulsion,
which did not contain any new sensinilizing dye according to the invention when 100 was set.

Sensitizing
dye Table IV emulsion Density of
Parbfleoken Verse.
No. I. lot
(mgMol /
kg emulsion) AgBr-Cl 0.02 1 V ⁺⁾ 0.09 Il 0.08 CVJ II 0.04 Il 0.03 3 VI ⁺⁺ > 0.08 Il 0.05 4th III 0.04 It 0.04 5 y +) 0.04 ti 0.08 6th 0.04

Sensitizing dyes V and VI of the following structure have been used as ordinary sensitizing dyes used for comparison purposes:

C-CH = CH-CH-C

^C 2 ^H 5

Cl

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? 2 ^H 5

N.

C-CH = CH-CH-C

C ₂ H ₅ Eq

Cl

009844/0301

Claims (6)

- 14 - '■ Claims 1. Silver halide photographic emulsions, characterized by a content of a sensitizing dye of the general formula R ₁ R ₂ C = CH-CH = CH-C (CHg) _n COOH where V .., V ₂ , ^ i ^ ³³¹ ^ - ^ p * ^ ^e S ^ - ^e: * - ^cn ° ^ e ^r can be different, hydrogen atoms or halogen atoms, R ₁ and R ₂ , the same or may be different, lower alkyl groups, A is a polymethylene group or an alkylpolymethylene group and η is an integer from 1 to 4. 2. The silver halide photographic emulsion of claim 1, characterized by the content of the sensitizing dye CH ₂ COOH 3. Photographic silver halide emulsion according to claim 1, characterized by the content of the sensitizing dye SAD 009844 / 030-1 ? 2 ^H 5 (CH ₂ J ₃ COOH 4. The silver halide photographic emulsion of claim 1, characterized by the content of the sensitizing dye IH XXV> C1 _; . . . : (CH ₂ ) ₃ SO ₃ - .-. · .: _; 5. The silver halide photographic emulsion of claim 1, characterized by the content of the sensitizing dye ? 2 ^H 5 C = CH-CH = GH-C ^cl GH ₂ -CH ₂ -CH-SO ₃ " (CH ₀ COOH) 6. New benzimidazole carbocyanine compounds of the general formula _BA D 0098 £ A / Π30 C = CH-OH = CH-O (CHg) _n COOH where V ₁ , V ₂ * W ₁ and W ₂ , which may be the same or different, hydrogen atoms or halogen atoms, R ₁ and R ₂ , which may be the same or different, lower alkyl groups, A a polymethylene group or an alkylpolymethylene group and η a whole Number from 1 to 4 mean. 0098U / 0301