DE2164249A1 - Color development process - Google Patents

Description

FATfNVANWXLTE

DR. E. WIEGAND DIPL-ING. W. NIEMANN 2164249 DR. M. KÖHLER DIPL-ING. C GERNHARDT

MDNCHEN HAMBURG

phone: 55547 «8000 monks 15.23. December 1971

TELEGRAMMERICARPATENT NUSSBAÜMSTRASSE 10

W 40 881/71

Ji Photo Film Co., Ltd. Ashigara-Kamigun, Kanagawa (Japan)

Color development process

The invention relates to a color development process for multilayer, reversal color photographic light-sensitive materials; in particular, it relates to a method of increasing the color density of Reversal color images.

As multilayered light-sensitive color photographic material with a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer Materials of the so-called "coupler-in-emulsion" type are known, in which the photographic emulsion layers each contain a silver halide and a coupler which is produced by reaction with the Oxidation product of a photographic aromatic amine developing agent form a dye. There are also already known materials of the so-called "coupler-in-the-developer" type in which the photographic emulsion layers do not contain couplers (the Couplers are contained in the color developing liquids).

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The present invention now relates to a novel photographic material Process for improving the dye density in reversal color images, the developers containing color couplers have been color developed.

The light-sensitive color photographic materials from "Coupler the developer "type are usually developed in the following ways:

After exposure, the element undergoes a black and white development subjected from the back of the photographic material with exposed to red light, in one a cyan coupler and a photographic one cyan color developer containing aromatic amine developing agent developed, exposed to magenta light from the photographic emulsion layer side, in a yellow coupler and a yellow color developing agent containing a photographic aromatic amine developing agent and then developed in a Developed magenta color developing liquid containing magenta couplers and a photographic aromatic amine developing agent.

The present invention is now a new method for Improving the density of reversal color images in cyan color development, yellow color development and magenta color development, particularly a new method for improving the color density of the magenta color image.

If the density of reversal color images can be increased, a more efficient dye production system can be produced. In one in such a case, the thickness of the emulsion layers can be reduced, which leads to the advantage that the sharpness of the color images and the amount of that incorporated into the emulsion layers Silver halide can be reduced.

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According to the new inventive method to improve the Density of reversal color images becomes one as described below Gelatin-silver halide emulsion layer containing polymer as a binder developed by a color developer containing a color coupler. That according to the invention for the above purposes Polymer used xveist the following polymeric components on:

-f CH _O - CH -f-, --f CH - CH-J- and -f- CH ₀ -ClI -) - II I

COOR CONH ₀ - COOH

where the molar ratio -f CH ₀ -CH ■) -: -f CH ₀ -CH -γ : - ^ CH ₀ -CH -) -

² L ² I ² I.

COOR CONH ₂ . COOII

wherein R is an alkyl group having 1 to 4 carbon atoms and'x, y and ζ mean numbers that satisfy the following conditions:

40 = χ = 90 10 = y = 60

0 = ζ = 40 and
χ + y + ζ = 100.

Among the polymers that meet the above conditions, Particularly preferred polymers have an average molecular weight within the range from about 5,000 to about 500,000.

Practical examples of such polymers are given below, but the present invention is not limited to them Limited polymers. The term "polymer" used here _

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includes "copolymers" and also so-called "block copolymers ¹ ·.

Polymer 1

COOC ₂ H ₅

Polymer 2

^CH 2 ~ 9 ^Κ ~ * Ϊ5Ο ~ COOC ₂ H ₅

CONH

(average molecular weight: 20,000)

CH ₉ - CH

- ^ CH ₉ -

CONIL

COOH

(average molecular weight: 10,000)

Polymer 3

COOC ₇ H ₁ - CONH ₀ COOH

(average molecular weight: 20,000)

Polymer 4

CH

^ 5 CCiI ₂ -cn

COOC ₂ Il ₅

f CH ₇ - CH

CONH.

COOII

(average molecular weight: 100,000)

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Polymer 5

~ CH

'40

COOC ₂ H ₅

Polymer 6

COOCH.

Polymer 7

^cn 2-

COOC ₄ H ₉

CII ₂ -

CH ₂ -

CONH.

COOH

(average molecular weight: 10,000)

CH ₂ -

CONH

COOH

(average molecular weight: 70,000)

CH ₂ - CH

CONH

QIi COOH

(average molecular weight: 20,000)

The polymers used according to the invention are not water-soluble, however, they are in alcohols, such as. B. methanol, ethanol and water / alcohol mixtures soluble. The polymer becomes ordinary added in the form of a solution in an alcohol or a water / alcohol mixture to a photographic emulsion.

The polymers used according to the invention can be a photographic one Gelatin emulsion can be added or part of the Replace gelatin. The polymers can be added at any stage before coating, but they are preferably added between added to post-ripening and coating. A suitable one

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The amount of polymer is within the range from 1 to about 90% by weight, based on the total amount of gelatin and polymer in the gelatin-silver halide emulsion.

Particularly preferred results are obtained when the invention is applied to a gelatin-silver iodobromide emulsion, but the present invention can also be applied to various gelatin-silver halide emulsions. The silver halide emulsions used in accordance with the invention can be produced by a compound with labile sulfur, such as. B. sodium thiosulfate or allyl thiourea, by a complex gold (III) salt (auris salt) and thiocyanic acid, by a reduction sensitizer, such as. An amino compound or stannous chloride (see "The Theory of the Photographic Process", 3rd Edition, 113-116, (1966), published by McMillan Company), be sensitized by a polyalkylene oxide derivative or combinations thereof. In order to achieve a green sensitivity or a red sensitivity of the silver halide emulsion, dyes can be added which are capable of sensitizing in the wavelength range from 500 to 700 mp, such as e.g. B. 1,1'-diethyl-2,2 ¹ -cyanine iodide, S ^ '- diethyl-g-methylcarbocyanine iodide, etc. (cf. ibid., Pp. 199-232). The silver halide emulsion can also contain a stabilizer such as e.g. B. 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene (cf. ibid., Pages 344-346), a hardening agent, such as. B. formaldehyde or mucobromic acid (see. Ibid., Pages 54-60) and a wetting agent such. B, saponin or sodium alkylbenzenesulfonate. Such materials are known and can be added because of their known function.

A multilayer color photographic material containing a gelatin-silver halide emulsion layer, containing the polymer of the present invention is made by an ordinary color photographic developing process of the "coupler-in-the-developer" type.

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Here, each of the cyan, magenta and yellow color developers contains at least one a color developing agent and the diffusible couplers which are coupled to form cyan, magenta and yellow, respectively. As a color developing agent can the known p-phenylenediamine derivatives, such as. B. 4-amino-N, N-diethylaniline, 4-amino-N, N-diethyl-3-methylaniline, 4-amino-3-methyl-N-methyl-N- (ß-methylsulfonamidoethyl) aniline, 4-Amino-3-methyl-N-ethyl-N- (ß-hydroxyethyl) aniline, etc. (cf. ibid., P 387), can be used.

According to the invention, the known diffusible cyan couplers can be used phenolic couplers, e.g. B. 2-chloro-1-naphthol, 2,4-dichloro-1-naphthol, 2- (o-Acetamido-β-phenetyl) -1-hydroxynaphthamide, etc. (cf. ibid., Page 387), can be used.

The known methylene couplers can be used as diffusible magenta couplers be used with closed chains, such as B. acylacetonitrile, 2-cyanoethylbenzofuran and benzylacetonitrile, or cyclic methylene couplers, such as. B. 1-phenyl-3- (4-chlorobenzamido) -5-pyrazolone, 1-phenyl-3- (3-nitrobenzoylamino) -5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3- (4-nitroanilino) -5-pyrazolone etc..

The known methylene couplers can be used as diffusible yellow couplers with a closed acylamide chain can be used, e.g. B. 2-acetanilide, 2-aceto-2 ', 4' -dichloroacetanilide, 2-benzoylacetanilide, 2-benzo "yl-2 '-methoxyacetanilide, 2-methyl-4r (methylsulfoamidoethyl) ethylaniline, etc. (see ibid., P. 389 and G. H. Brown et al, "Journal of the American Chemical Society ", Vol. 79, pp. 2919-2927 (1957)).

The. The following examples are intended to be preferred embodiments of the invention explain in more detail, but without restricting them to them.

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example 1

A highly sensitive color photographic gelatin silver iodobromide reversal emulsion (Silver iodide content 3.5 mol%) subjected to sulfur and gold sensitization was obtained by heating melted and placed on a cellulose triacetate film support in a men-

ge of about 15 mg / 100 cm (as silver halide). The binder for the silver iodobromide in the emulsion thus applied was gelatin, which contained the polymer 2 described above in various proportions. The emulsion layer was under Using a sensitometer of the NSG II type exposed and the subjected to the following treatment procedures:

1. Pre-hardening

2. Wash with water

3. Negative development

4. Wash with water

5. Reverse exposure with white light

6. Magenta development

7. Wash with water

8. Fixate

9. Drying (samples used for the

Silver analyzes were used)

10. Silver bleaching "5 min.

11. Fix "3 min.

12. Washing with water and drying (samples necessary for the determination the dye density were used)

The compositions of the treating powders used in the above process steps were as follows:

27 ⁰ C 1 min. Il 1 min. Il 4 min. Il 3 min. Il 5 min. It 2 min. Il 3 min.

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Pre-hardener

Sulfuric acid (concentrated). 1.7 ml

Borax (10.H ₂ O) 20 g

Potassium bromide 2.3 g

Sodium sulfate 200 g

37 * formaldehyde 10 ml

Sodium bisulfite 1 g

Water to 1000 ml

Negative developer

N-methyl-p-aminophenol sulfate 5 g

anhydrous sodium sulfite 79 g

Hydro quinone 2 g

Sodium carbonate (monohydrate) 40 g

Potassium bromide 3.5g

Potassium thiocyanate 2.0 g

0.1 liter potassium iodide 12.5 ml

Sodium hydroxide 1.0 g

Water to 1000 ml

Massenta color developer

Sodium sulfite 5.0 g

• 4-Amino-3-methyl-N, N-diethyl

aniline hydrochloride 2.0 g

1-phenyl-3- (3 ~ nitrobenzoyl-

amino) -5-pyrazolone 1.4 g

Sodium hydroxide 2.5 g

n-butylamine 5 ml

Water to 1000 ml

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- to -

Silver bleach

Ferricyanide x 60 g

Potassium bromide 20 g

Water to 1000 ml

fixer

Sodium thiosulphate 100 g

Sodium sulfite 15 g

Water to 1000 ml

The ratio of binder (100% by weight gelatin) to silver iodobromide in the gelatin-silver halide emulsion was 5/11 by weight. The results thereby obtained are as follows Table I given.

Table I.

Ratio of
Polymer in
the gelatin /
Polymer
Mixture in wt. -I magenta
Max Amount of through
the color developer
developed Ag
(mg / 100cm ² ) . W ^A * 0 2.51 8.1 0.310 Polymer 1 10 3.12 8.2 0.358 Polymer 2 10 3.98 10.7 0.372 Polymer 3 10 2.92 7.4 0.395 Polymer 4 10 - - 3.93 9.9 0.397 Polymer 5 10 3.70 10.0 0.370 From the above Results it appears that then , if that according to the invention Polymer was added, the value ^{of D} max ^{/ Ag}

increased by about 201 »

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Example 2

The same procedure as in Example 1 was followed, wherein however, the polymer 2 was used in varying proportions as the polymer to be mixed with gelatin. The received Results are given in Table II below.

Table II

magenta
Max Amount of
developed Ag
f ms / 100 cm ² 1 T ^ / A ο *
Tu el X 2.48 8.2 0.302 3.00 7.9 0.380 3.23 8.6 0.375 3.32 9.1 0.365 3.56 9.9 0.360

Ratio of the polymer in the gelatine / polymer mixture in weight-3

Polymer 2 5 Polymer 2 10 Polymer 2 20 Polymer 2 30

It can be seen from the above results that the D / Ag value increased by about 201 when the polymer 2 was added.

Example 3

The same procedure as in Example 1 was followed, wherein this time the polymer 2, the polymer 6 or the polymer 7 was used as the polymer to be mixed with the gelatin. The results thereby obtained are as follows Table III given.

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Table III

Ratio of

Polymer in

of gelatine / _{Ma (jpntfl} amount of

Polymer magenta developed Ag _n,.

Mixture in weight -I max C mg / 100 cm ^z ) max ' ^g

0.2.60 8.2 0.317

Polymer 6 10 3.50 9.8 0.357

Polymer 2 10 3.80 10.5 0.362

Polymer 7 10 3.65 10.0 0.365

From the above results, it can be seen that the relationship D / Ag when adding the polymers according to the invention by about 20% increased.

Example 4

Using the same treatment procedures as in Example 1 a cyan color development process (27 ° C, 5 min.) was carried out instead of the magenta color development using the same color photographic film as prepared in Example 1. In addition, the same process was used in place of the magenta color development a yellow color development (27 ° C., 5 min.) was carried out. The results of these two cases are shown in Tables IV below and V indicated.

The compositions for cyan color developers and yellow color developers used are given below:

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Cy color developer

Potassium bromide

0.1% potassium iodide

Potassium thiocyanate

anhydrous sodium sulfite

Sodium carbonate (monohydrate) 30

Sodium hydroxide

5-nitrobenzimidazole nitrate

2,4-dichloro-1-naphthol

.4-Amino-3-methyl-N, N'-diethylaniline hydrochloride

Water ad

20th G 20th ml 3.0 G 10 G 30th G 2.0 G 0.5 G 2.0 G 3.0 G 1.0 liter

Yellow color developer

Sodium sulfite. 5.0 g

N, N'-diethyl-p-phenylene-

diamine hydrochloride 1.2 g

Sodium carbonate (monohydrate) 20.0 g

Potassium bromide 0.1 * potassium iodide

2-Benzoyl- (4-p-toluenesulfonamido) acetanilide

N at r iumhy d ro xy d

Water ad

0.3 g 20 ml

1.0 g 4.0 g 1.0 liter

Table IV

Ratio of
Polymerisatsin
the gelatin /
Polymer mixture in parts by weight

Polymer 2 10
Polymer 4 10

Cyan max

1.3 1.5 1.6 amount of
developed Ag
(mg / 100 cm2)

8.5
9.2
8.7

0.153 0.163 0.184

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Table V

Ratio of -I yellow Amount of D / Ag Polymer in 0 developed Ag Max the gelatin / 10 Max (mg / 100 cm ² ) 0.17 Polymer 10 1.51 8.7. 0.19 Mixture in wt. 1.86 9.8 0.20 2.10 10.5 Polymer 2 Polymer 4

From the above results, it can be seen that the values of D / Ag in the cyan-developed image and in the yellow-developed Image increased considerably on addition of the polymers according to the invention.

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Claims (5)

Godfather η ta η s ρ rü che Method of increasing the color density of a photosensitive color photographic material consisting of a support having at least one red-sensitive gelatin-silver halide emulsion layer, a green-sensitive gelatin-silver halide emulsion layer or a blue-sensitive gelatin-silver halide emulsion layer consists, characterized in that at least one of the gelatin-silver halide emulsion layers incorporates a polymer with components of the following formulas: -E-CH, -CH-3, -f-CH, -CH-) - and -f CH-CH-f |. I I COOR CONH ₂ COOH where the ratio of the components
-E CH ₉ - CH -) -: -eCH ₇ -CH -> -: - {- CH ₇ -CH -) - = χ: y: ζ I I I COOR CONH ₂ COOH wherein R is an alkyl group having 1 to 4 carbon atoms and x, y and ζ denote numbers such that they meet the following conditions suffice: 40 = x = 90 10 = y = 60 O = Z = 40 χ + y + ζ = 100 and then exposing the silver halide emulsion layer and with one containing a diffusible coupler 209828/1000 Color coupler developed. 2. The method according to claim 1, characterized in that the Polymer in an amount of 1 to 90% by weight, based on the total weight of gelatin and polymer, in the silver halide emulsion, used. 3. The method according to claim 1, characterized in that the silver halide emulsion to which the polymer is added is
a silver iodobromide emulsion is used. 4. The method according to claim 1, characterized in that a polymer having an average molecular weight of about 5,000 used to about 500,000. 5. The method according to claim 1, characterized in that the gelatin-silver halide emulsion layer which is the polymer
is added, a magenta color former emulsion layer is used. 2098? 8/1000