DE1572133C - Process for the preparation of color photographic silver halide emulsions - Google Patents

Description

At present, the color reversal method is the most popular method of subtractive color photography to watch. Multilayer color reversal films with couplers present in the layers usually exist from a substrate which is successively coated with a blue-green color coupler, a green-sensitive gelatin-silver halide layer containing a magenta coupler, a Yellow filter layer and a blue-sensitive gelatin-silver halide layer containing a yellow color coupler contains. Various types of chemical compounds have proven to be useful color couplers proven for these multilayer color reversal films. Stored color couplers have different requirements are sufficient, first and foremost they must be diffusion-resistant in the light-sensitive layers. Diffusions are characteristic of many of the known ones, present in their simplest molecular configuration Color coupler. Attempts have been made in various ways to prevent the couplers from diffusing. One of these methods is used to link larger residues, e.g. B. large fatty acid groups with the Color coupler or color former molecule. Another method is to have the coupler in embedded in a polymeric or high-boiling solvent that is insoluble in water, but in the hydrophilic Carriers for the silver halide, e.g. B. gelatin, is dispersible; another method is to that one has the color coupler molecule with the linear carbon chain of such a synthetic polymer linked, which is either compatible with the colloidal carrier for the halogen silver or in this is dispersible. The non-diffusible color couplers produced by one of these methods are classified as hydrophilic or lipophilic coloring agents. coupler differentiated.

Hydrophilic color couplers generally have one or more water-insolubilizing radicals, such as sulfonic groups or carboxyl groups in the molecule, while lipophilic color couplers such Leftovers not included. It is well known in the use of these two types of color couplers pointed out that the presence or absence of polar groups affects the physical Properties of the layers in which they have been incorporated exerts a significant influence. It are many examples that the hydrophilic or lipophilic properties affect the emulsion with regard to its sensitometric "behavior. For example, diffusion-resistant, hydrophilic, have Color couplers mentioned containing acid groups have a strong tendency to react with gelatin when they are resolved.

Such reactions increase the viscosity of the entire emulsion mixture and cause large ones Gelatin and water amounts, based on the amount of ^ color coupler, to make a suitable coating medium to be able to prepare. Conversely, however, such coating compositions tend to be slow dry and increase the thickness of the applied layer. As a result, the at decreases Achievable color density for a given layer thickness. The presence of hydrophilic color couplers also has one strong influence on the lowering of the pour point of the applied emulsion layer. Another significant one Disadvantage lies in the fragile wedge of the applied layer, especially when thin layers are desired which have one for the purpose of forming images with high color density and good resolution have a high proportion of color couplers. An attempt to create layers with good flexibility is to use polymeric latexes, such as. B. Polyäthylacrylat to disperse in the gelatin emulsion layers. The layer thickness is increased in the process. It could also found that the use of hydrophilic couplers to affect the Development speeds and either accelerated or decelerated development depending on which particular color coupler was used.

Problems also arise when using lipophilic color couplers. For example, effective incorporation of sufficient amounts of color couplers into a gelatin-silver halide emulsion requires complicated and time-consuming dispersion methods. In general, a high-boiling solvent is used for the color coupler together with a low-boiling solvent. The color coupler solutions are then dispersed in aqueous gelatin, the low-boiling solvent is removed and the dispersion obtained is added to the silver halide emulsion. As with the hydrophilic color couplers, large amounts of gelatin and high-boiling solvent, based on the amount of color coupler, are required to ensure uniform dispersion of the color couplers in the emulsion layers. The layers drawn on from such dispersions generally proved to be too thick for good resolution, and the layer hardness was also severely impaired by the presence of high-boiling solvents in an amount sufficient to dissolve the couplers. The multilayer films obtained are not too. brittle, they also do not tear when bent, like some films made with the aid of hydrophilic couplers, but they have extremely soft layers that are sensitive to surface abrasion. Decreasing the amount of high-boiling solvent to eliminate this disadvantage can reduce the reactivity of the color coupler during the development process. In addition, in the case of dispersions with a low solvent content, the color coupler can crystallize out. '. ■■■■'. . _:

The invention is based on the object of a process for the production of color photographic emulsions to develop with sufficient thickness, sufficient flexibility and good abrasion resistance the emulsion layers is guaranteed.

The invention is based on a process for the production of color photographic silver halide emulsions, by adding a hydrophilic color coupler to a gelatin-silver halide emulsion added in aqueous solution, characterized in that one of the silver halide emulsion adding a colloid-containing aqueous solution in which a lipophilic color coupler is dispersed, which has been dissolved in an organic solvent that is below the boiling point of the Water has boiling point, with 30 to 300 parts by weight of the hydrophilic color coupler 100 parts by weight of the lipophilic color coupler come and the two color couplers are selected so that that they give the same or approximately the same dye when developing and at least one the color coupler is a polymeric color coupler.

The invention achieves that the mixed hydrophilic and lipophilic color couplers make an extremely fine dispersion of the lipophilic color coupler superfluous, as this is only a part of the entire image-providing color coupler system. Accordingly, the need for the high-boiling solvent ethyl acetate as dispersion aid add, reduced, which because the operational hazard as well as the costs and the system components to remove the ethyl acetate are bypassed.

In addition, the mixed color couplers of the invention allow the formation of neutrally colored ones developed color images. They also allow control of relative color development speeds in the hydrophilic and lipophilic phases on the way of adjusting the amount of oil in the droplets and the solvent such as benzyl alcohol in the color developer.

The invention also makes it possible to achieve an optimal balance between emulsion dilution and to ensure flexibility without j; in the obtained color images, deteriorated Resolution is to be determined. The invention combines the dispersed oil droplet systems of storage lipophilic color coupler own flexibility with the high clarity of in compatible or continuous phase present hydrophilic color coupler systems, without the disadvantages of very strong Softness of the dispersed systems and the fragility of the systems present in continuous phase to have to accept. It was also found that the speeds of the Black and white development for each of the constituent layers of yellow, cyan and purple in color reversal films Can be made more uniform by changing the ratio of hydrophilic to lipophilic Coupler balances in each layer.

Those prepared by the above procedure

. Emulsions are suitable for the production of photographic color films with thin, hard layers with a Thickness of 0.013 mm or less. The films are pliable and can become colored with formation Images are developed that have good color density and

'Have high resolution.

The solvents which can be used for the process described are generally in the vicinity of the Boiling point of the water and preferably below this point volatile. Examples: methyl, ethyl, Propyl and butyl acetates, methyl propionate, ethyl and butyl formate, methylene chloride, nitromethane and Nitroethane. Other low-boiling solvents can also be used.

The amount of low-boiling solvent required depends on the solubility of the lipophilic color coupler in the solvent under normal conditions. The amount of solvent is usually not above the amount that is required to add the desired proportion of lipophilic color coupler to the Bringing aqueous silver halide emulsion and producing very fine dispersions.

The hydrophilic color couplers should be used in quantities from at least 30 to 300 and preferably 50 to 200 parts by weight based on 100 parts of the lipophilic Color coupler, are applied. The two color coupler genera can either be from the mono- ' molecular discomforting residue type or polymeric type.

Among the high-boiling solvents that can be used with the lipophilic color couplers, include those that have a double-bonded or semi-polar oxygen atom in their structure and boil above 200 ° C. They are particularly useful because of their plasticizing effects on gelatin and hydrophilic couplers. Esters have proven particularly useful in this context, such as phthalates, also N, N-dialkylamides, sulfones, phosphate esters, preferably tributyl phosphate, N-alkylated urethanes and their mixtures. The use of these high-boiling compounds is particularly useful because it has surprisingly been found that lipophüe Color couplers, especially those of the monomolecular type, which have large diffusion-preventing residues, exert a plasticizing effect on the gelatin-silver halide emulsion. So you just have necessary to use low-boiling solvents in order to dissolve and disperse the lipophilic color coupler in the emulsion.

The amount of high-boiling solvent can according to one embodiment of the invention from 0 to 100 parts by weight per 100 parts by weight of the lipophilic color coupler vary. It could be determined that the combination of the hydrophilic and the lipophilic color coupler determines the amount of the for the emulsion required color coupler not changed.

Unless otherwise stated, all quantitative data in the examples are to be regarded as weight data.

B e is ρ ie I 1

This example illustrates the improvement in flexibility for a typical gelatin layer containing cyan color couplers, according to which Invention a mixture of lipophilic and hydrophilic couplers is used, compared to one containing only a hydrophilic color coupler Layer. ;

To an aqueous gelatin solution containing 120 parts of gelatin, 60 parts of a hydrophilic blue-green color coupler were added with stirring. Mols "of the monomers with the following _formula: ■■ ■ <■■ ,. ■

CONHCH ₇ CH ₇ - Ο - CH == CH ₂

was obtained with 1 mole of maleic anhydride.

This gelatin solution was applied to a carrier film

. the base of polyethylene terephthalate drawn under Ausbildun g a 0.008 mm in the dry state thick layer.

Then a dispersion was made using

made of a lipophilic blue-green color coupler,

which had the following formula: :::

■■■■■ · ■■■ '-V- ^ ^ΐ:;

CONHC ₁₈ H ₃₇

6.5 g of the coupler were dissolved in 37.5 cm ^{3 of} ethyl acetate at 66 ° C. The solution was with the help of a mixer in 300 cm ^{3 of} a 5% aqueous gelatin

solution dispersed which contained 10 cm ^{3 of} a 10% strength aqueous solution of an alkylated sodium naphthalene sulfonate as a surface-active substance. The temperature was maintained at 66 ° C while mixing and then the ethyl acetate was removed by heating to 88 ° C. Sufficient amounts of this mixture and also of the hydrophilic copolymer blue-green color coupler were used, as described above, to prepare a dispersion with the following composition:

120 parts gelatin,

40 parts of the hydrophilic color coupler,
20 parts of the lipophilic color coupler.

The dispersion obtained was drawn onto the polyethylene terephthalate carrier film in such a way that a dry layer about 0.008 mm thick was present. Both coatings were deposited at room temperature for several weeks and then their brittleness was measured by the method for determining the wedge brittleness described in P. Z. A d e 1 stein in the Journal of Photografic Science and Engineering, Vol. 1, No. 2, October 1957, pp. 63-68 is (at 10% relative humidity). The crack diameter of the gelatin layer, which is only the hydrophilic cyan color coupler was 9.9 mm, while that of the mixture of hydrophilic and gelatin layer containing lipophilic couplers according to the invention has a crack diameter of only 5.8 mm. One containing 60 parts of the lipophilic coupler alone per 100 parts of gelatin Gelatin layer which is pulled up to form a coating 0.008 mm thick when dry showed a tendency for the color coupler particles to turn out strongly during color development Dimensions merge as evidenced by a graininess image projected on an 8mm color projection was seen.

■ ■ - ■ '■ ■) Example 2 ■ /. ·: ■, ■ ·.; _' .. ■

Example 1 was repeated, but with the gelatin containing the hydrophilic coupler alone 20 parts of tributyl phosphate dispersed. When making the coupler mixture, the lipophilic Coupler using 20 parts of tributyl phosphate in place of ethyl acetate for dissolution dispersed. In both cases, the dispersions were prepared using a mixer without heating. The crack diameter of the den hydrophilic coupler, gelatin and tributyl phosphate-containing layer was 6.4 mm, while that the gelatin layer containing both lipophilic and hydrophilic couplers and tributyl phosphate, was only 4.6mm. .

Eg I 3 ■

To an aqueous containing 120 parts of gelatin 60 parts of the hydrophilic purple color coupler were added to the solution while stirring Copolymerization of 1 mole of a color coupler monomer of the formula,

O CH ₃

- H ι

C-NH-CC = CH ₂

O = C - CH ₂
with 1.25 mol of acrylic acid and 0.75 mol of acrylic acid amide. The solution was drawn onto a colorless carrier film to form a layer about 0.01 mm thick when dry. "Then a dispersion was made using a lipophilic purple color coupler of the formula

Cl

-N-N-

CC ₁₇ H

17 ⁿ 35

manufactured. 7.5 g of the coupler were in 7.5 cm ² tributyl phosphate and 30 cm ³ of ethyl acetate dissolved at 66 ⁰ C. The solution was added to 300 cm ^{3 of} a 5% strength aqueous gelatin solution which contained 10 cm ^{3 of} a 10% strength aqueous solution of the surface-active agent according to Example 1. The temperature of the mixture became increasingly vigorous. Maintained thorough mixing with a mixer at 66 ° C. in order to form a fine dispersion of the lipophilic color coupler in gelatin. Sufficient amounts of this mixture and also of the mixed polymer of the hydrophilic purple color coupler described above. Art were used to prepare a dispersion with the following composition:

120 parts gelatin,
40 parts of the hydrophilic coupler, 20 parts of the lipophilic coupler, 20 parts of tributyl phosphate.

The resulting dispersion was about 0.01 mm thick to form a dry state Layer raised. The crack diameters measured according to Example 1 were 8.9 mm for the hydrophilic color coupler in the gelatin layer and 6.1 mm for the gelatin layer, according to the invention contained both hydrophilic couplers and lipophilic couplers.

Example 4.

This example illustrates a comparison of the flexibility of a conventional color reversal film, which did not contain any pliable substances, with a color reversal film, which contained polymeric latexes according to German patent specification 1 154 717 as pliable Y sam-making substances, and a color reversal film, the mixtures of lipophilic and had hydrophilic color couplers within the meaning of the invention . · ■:, · .v .. _. ·.:. . :; -.-. ; \ '.: ■ ·: - ^; .. "■: ■.. ■.

A. Color reversal film was made as follows:

• '. 1. A photographic carrier film based on Cellulose triacetate with the usual undercoat

. which was coated with a halo-free layer consisting of 7 mg / dm ² bone gelatin and 3.5 mg / dm ^{2 of} a colloidal silver dispersion that absorbed light of all visible wavelengths. 2. A gelatin-silver bromoiodide emulsion layer which was sensitive to blue and red light and comprised 3.4 mole percent silver iodide and 96.6 mole percent silver bromide and also contained a sufficient amount of the hydrophilic cyan copolymer color coupler of Example 1 to be a color-forming agent Layer with a layer weight of the color former of 9 mg / dm ² , the gelatin of 18 mg / dm ² and the silver

halide, calculated as silver bromide, of 20 mg / dm ² was present.

3. A separating layer, consisting of a solution of Knophen gelatine, which contained normal additives, saponin as surface-active substance and chrome alum hardener and which had been drawn up over the blue-green layer while maintaining a gelatine layer weight of 20 mg / dm ² . ^;

4. A blue and green sensitive gelatin silver bromoiodide layer containing 3.4 mole percent silver iodide and 96.6 mole percent silver bromide and containing the hydrophilic, copolymeric magenta color coupler of Example 3 in an amount equal to the weight of the coupler in the layer of 9.6 mg / dm ² , 17 mg / dm ² for gelatin and 32 mg / dm ² for silver halide.

· ■ posed. ■■ ·:. ■■■ ....-.

5. A gelatin-silver colloid intermediate layer for the absorption of blue light, containing 10 mg gelatin and Z mg of the yellow colloidal silver per square decimeter of the layer.

6. A gelatin silver bromoiodide emulsion layer sensitive to blue light and Contained 3.4 mole percent silver iodide and 96.6 mole percent silver bromide, plus a hydrophilic one Benzoylacetanilide yellow color former prepared by transacetalization of 100 parts of low-viscosity, 99% hydrolyzed poly vinyl alcohols with 120 parts of m-Benzoylacetamidobenzaldehydäthylenglykolacetal and 50 parts of o-sulfobenzaldehyde in a reaction medium consisting of ethanol and water that uses p-toluenesulfonic acid as the acetalization catalyst adjusted to a pH of 1.7 and following the US method.

Patent specification 2,513,190 was obtained and applied to form a color-forming coating (color-forming agent weight in the coating: 25 mg / dm ² ; gelatin weight: 10 mg / dm ² ; silver halide weight: 25 mg / dm ² ).

7. An anti-abrasion gelatin layer with a weight in the coating of 10 mg bone gelatin per square decimeter, 1.5 mg per square decimeter of an ultraviolet absorbent agent obtained from 2,2'-disulfo-4,4'-diaminostilbene. Calculated total thickness of the layers: 0.013 mm.

B. Color reversal film was then made as described above, except that mg of polyethyl acrylate added per square decimeter of the blue-green layer, 6 mg per square decimeter of the purple layer and 15 mg per square decimeter of the yellow emulsion layer. In all cases it was worked in accordance with Example 3 of German Patent 1,154,717. The total thickness of the Layers was calculated to be 0.017 mm.

G; A color reversal film was now produced as described under A, but in the red-sensitive layer on 120 parts of gelatin, 40 parts of the hydrophilic cyan color coupler, 20 parts of the lipophilic cyan color coupler and 20 parts of tributyl phosphate stored in accordance with the information in Example 2. In the green-sensitive layer 120 parts of gelatin were 40 parts of the hydrophilic purple color coupler, 20 parts of the lipophilic Purple color coupler and 20 parts of tributyl phosphate according to Example 3 incorporated. In the blue-sensitive one 20 parts of gelatine and 40 parts of the hydrophilic yellow-color coupler were stored in each layer, which is described above under 6, also 20 parts of a lipophilic yellow color coupler formula below

NHCOCH ₂ CO

NHCOCH ₇ CO

and finally 20 parts of tributyl phosphate. The coating weights of the combined color formers and the Gelatins in the emulsion were of the same order as in A, as was the total thickness of the layer.

The flexibilities of the three color films were determined by specifying their crack diameters according to the test method of Example 1 compared. Tear diameter of film A: 18.5 mm, tear diameter of the lower Polyethyl acrylate addition film obtained B: 8.4 mm.

Film C made using mixtures of lipophilic and hydrophilic couplers accordingly of the invention showed a crack diameter of 6.4 mm. When checking on their resolving power, which is carried out in accordance with the information in Example 5 below Films A and C showed 90 lines each Millimeters, while the thicker Emulsion B, which had the non-coupling latex, by resolving power of 75 lines per millimeter character-

was terized. :,

Example 5

This example illustrates the superior results obtained using lipophilic and hydrophilic polymeric color couplers can be obtained when compared with the application of hydrophilic polymeric color couplers as the only color coupling substance in the emulsion layer.

A. Reversal color film was produced as described in A of Example 4, except that a 1.0 mm thick carrier film was used, as in Example 4 of the USA patent 2,779,689. The final build of the film is through following Characterized data:

Silver halide As in USA patent
3 182 029 Coupler gelatin Abrasion. · 17 mg / dm ² 10 mg / dm ²
11 mg / dm ²
10 mg / dm ² Yellow, 15 mg / dm ²
Yellow filter layer

continuation

10

Silver halide . ■. . · ■ - · Coupler gelatin Purple, 13 mg / dm ² 3.9 mg / dm ^{2 of} the aluminum 7 mg / dm ² , 9 mg / dm ² Separating layer aurintricarbonic salts 12 mg / dm ² acid Blue-green, 21 mg / dm ² Antihalation layer 11 mg / dm ² 15 mg / dm ² carrier

Total thickness of the coatings: about 0.01 mm

B. Corresponding to A in Example 4, a color reversal film was made produced, but in the red-sensitive layer to 80 parts of gelatin 30 parts of the blue-green, hydrophilic polymeric color coupler described in Example 1 and incorporated 30 parts of a blue-green lipophilic polymeric color coupler, which by copolymerization of 1 mol of the color coupler monomer of the formula

CONH - CH ₇ CH, - O - CH = CH ₇

with 1.5 mol of ethyl acrylate had been obtained. The lipophilic color coupler was incorporated into the gelatin silver bromide ^{iodide emulsion by first dissolving 400 g of the copolymer in 4000 cm 3 of} ethyl acetate and 120 cm ^{3 of} diisobutyl phthalate, after which this solution was stirred into an aqueous gelatin solution containing 120 g of gelatin, 7000 cm ³ distilled water and 320 cm ^{3 of} a 10% aqueous solution of sodium lauryl sulfate. The ethyl acetate was removed by heating, after which a fine dispersion of the lipophilic polymer in aqueous gelatin remained. A sufficient amount of this dispersion was used to establish the ratio described above in the final gelatin-silver bromide iodide emulsion. In each of the green-sensitive emulsion layer, 80 parts of gelatin, 30 parts of the hydrophilic, copolymerized purple color coupler of Example 3 and 30 parts of the lipophilic, copolymerized purple color coupler, which was obtained by copolymerizing 1 mole of the purple - color coupler - monomers - of the formula below *

N - N 'O

C-NH-CC = CH ₂
I = C-CH ₂ CH ₃

with 3 moles of ethyl acrylate. The lipophilic, copolymeric purple color coupler formed was incorporated into the silver halide emulsion in the same manner as that described above lipophilic, blue-green color coupler polymers.

In the blue-sensitive emulsion layer, 20 parts of the hydrophilic, mixed polymeric yellow color coupler incorporated by copolymerization of 1 mole of the yellow Color coupler monomers of the formula below

Ο

// X

ο.

OCH ₃

C-CH ₇ -C -NH

= / "O CH ₃

NH-CC = CH ₃

with 1 mole of acrylic acid and 40 parts of the lipophilic yellow copolymerization color coupler obtained by copolymerizing 1.0 mole of the above monomer with 1.5 moles of 2-ethylhexyl acrylate had been made. The resulting lipophilic yellow color coupler mixed polymer became whole analogous to the incorporation of the lipophilic blue-green color coupler mixed polymer in the gelatin-silver halide emulsion stored.

The three silver halide emulsions were so composed and stacked that the amounts of silver halide based on S overbromide total lipophilic and hydrophilic present

45. Color coupler and gelatin about the coating weight of the color film A described above corresponded.

The films produced as indicated above were made according to the specifications with regard to their flexibility of Example 1, which showed that film A had a crack diameter of 14.8 mm, film B, one of 7.6 mm.

Samples of films 1 and 2 were tested for their resolving power by using white light were exposed on a resolvometer according to the information in »Proceedings of the Royal Photographic Society Centenary Conference, London (1953), p. 292. The films were then, as indicated below, further treated by the inverse procedure, with all solutions and washing liquids at 27 ° C were used:

step Black and white development
Short break;
Water time PH value 1
2
3 6 minutes
1 minute
5 minutes 10.45 to 10.55
3.8 to 4.2

continuation

step

time

PH value

Photo flood exposure

Color development.
Short break

Water

Bleaching

Water

Fixation

Water

Wetting hardening
Drying

The treatment solutions had the following composition:

1. Black and white developer

Sodium hydroxide 1.00 g

Sodium hexametaphosphate 1.00 g

Sodium sulfite (anhydrous) ........ 60.00 g

p-methylaminophenol sulfate 5.00 g

Hydroquinone 2.00 g

Sodium carbonate (mono) 50.00 g

Potassium iodide (0.1%) 10.00 g

Sodium bromide 2.00 g

Sodium thiocyanate 1.25 g

6-nitrobenzimidazole (0.5%) 7.00 g

Remainder: water at 1.01

2. Color developer

p-amino diethylaniline hydrochloride 5.00 g

Sodium sulfite (anhydrous) 5.00 g

Sodium hexamethaphosphate 1.00 g

Sodium bromide 0.50 g

Sodium hydroxide. 1.00 g

Sodium carbonate 10.00 g

Potassium iodide (0.1%) 10.00 g

; Benzyl alcohol .. 6.00 g

Remainder: water to 11

3. Stop bath

Chrome alum 30.00g

Remainder: water to 11

4. Bleach bath

Sodium bromide ................ 30.00 g

Sodium sulfate 45.00 g

Potassium ferrocyanide 123.00 g

Remainder: water to 11

5. Fixing bath

Sodium thiosulphate (anhydrous) .... 115.00 g

Sodium sulfite ........ ...... 9.00g

Remainder: water to 11

6. Hardening bath

Formalin 20.00 cm ³

Remainder: water to 11

'115 lines / mm could be resolved for both films.

15 seconds

every side

Distance: 76.2 cm
6 minutes

2 minutes

3 minutes

4 minutes

1 minute

2 minutes
6 minutes
2 minutes

10.9 to 11.1 3.8 to 4.2

8.0 to 8.6 7.6 to 8.0 8.0 to 8.8

B e i s ρ i e 1 6

This example illustrated the use of a hydrophilic cyan polymeric color coupler in connection with a lipophilic colored color coupler in a disperse phase for the Color negative films useful color correction.

A lipophilic colored color coupler became the following by dissolving 10 g of the color coupler formula

C-NH-C ₁₈ H

obtained in a solution containing 750 cm ^{3 of} ethyl alcohol, 250 cm ^{3 of} water and 100 cm ^{3 of} 3 sodium hydroxide. 20 g of the diazoniurh salt of the following formula were then added to 750 cm ^{3 of water}

OCH ₃

ZriClf

dissolved. . ■■. '■ .-.''- ..

The color coupler solution, composed as described above, was slowly added to the diazonium salt solution with stirring and the pH was lowered to 4.5 to 5.0 with acetic acid. A dye precipitated which, after separation, gave about 15 g of an orange colored coupler in the form of a UI. _;

^{6 cm 3 of} the orange colored coupler oil were dissolved in 17.5 cm ³ of - 2 parts of dibutyl phthalate and 1 part of tributyl phosphate. This solution was heated to 49 ° C. and added to 300 cm ^{3 of} a 5% strength aqueous gelatin solution which contained a surface-active substance, whereupon vigorous dispersion was carried out with the aid of a Waring mixer.

13 14

To the surface-active color coupler of the following Forstelite gelatin silver bromide iodide emulsion according to A (2) of Example 4, a solution containing the formulation was added,
sufficient amounts of the hydrophilic blue-green

given polymeric color coupler, which in Example 1 OH

is described. In addition, the above 5

characterized dispersion of the lipophilic orange-AA. q XjH q

dyed color coupler added to for every 120 parts ί ji J

Gelatin in the emulsion 30 parts of each deir

lipophilic and hydrophilic couplers together with,

80 parts of the above 2: 1 high-boiling solution SO ₃ Na -

set solvent. '

The emulsion was adjusted to a silver The solution (A) became the solution (B) at .38 bis

Halide layer weight of 20 mg / dm ^{2 added} to a 41 ° C and carefully using a mixer

Layer support pulled up. The layer was next dispersed at a high stirring speed. The other

an otherwise identically composed, but only 15 falling dispersion of three blue-green coupler types

the control plate containing the hydrophilic coupler was developed from a gelatin silver bromide iodide solution

sample exposed with a sensitometer, which is added and speaking with the above examples

was equipped with a brightness scale. Could be used to manufacture extremely thin, flexible,

became a filter which was developed for 5 minutes in photographic color films of high line definition

a color developer below can be used.

setting:. . , _o

^b examples

Ν, Ν-diethyl-p-phenylenediamine- This example illustrates the use of anio-

hydrochloride '... '. 5.0 g of niche surface-active coupler for the purpose

Sodium Sulphite (Anhydrous) 4.0 g 25 lipophilic polymeric couplers that work in solvents

Sodium carbonate (mono) 10.0 g as organic esters are highly soluble, in gelatine

To disperse sodium salt of ethylenediamine silver halide emulsions and

store tetraacetic acid 2.0 g. These uniformly soluble lipophilic poly-

6-Nitro-BenzimidazoI meren were by addition polymerization of a

(0.5% solution) 7.0 cm ^{3 of} 30 coupler of the formulation

Potassium bromide 0.5 g.

Borax '. 10.0 g R.

Potassium iodide (0.1% solution) .... 10.0 cm ³ 1

3N sodium hydroxide 23.0 cm ³ CH = CAO

Polyethylene oxide (average 35 ² ■.

average molecular weight 4000) 2.0 g

Remainder: water to 11. won. In this formula is the color dome

Q with a polymerizable vinyl group

After development, the films were given the linking divalent radical —A—, corresponding to steps 6 to 13 of Example 5, either —O— or
acts. After washing and drying it was

for the control film a y-value at 436 ηΐμ of V

+0.07 measured, while the y-value at 644 πΐμ Jl ₁

was +1.0. In contrast, the y-value of the
green image of which the mixed color coupler 45

containing element at 436 πΐμ at -0.10 (due to, associated with at least one equimolar masking), while the y value at 644 πΐμ amount of a non-coupling comonomer was set to +1.0. This made an ester of acrylic acid, methacrylic acid, and maleic acid easy overcorrection for external absorption. The purpose of this example is to show that the detection of the blue light of the color-developed blue-green indicates color. The low-melting, colored by different distribution of the coupling couplers of this example is suitable for the use function between the hydrophilic and the lipo with smaller amounts of permanent oil (solution philic emulsion phases can be controlled,
medium), so that the ratio of oil to total layers was 25 mg silver halide / dm ²

coupler is lower than that for the thin emulsions from emulsions of the following composition ion preferred value of 0.5. manufactured: :

■> ■ '>■■■■; : ■: ■■■■ '■■■: - Example 7. γ _{; |} A. 120 parts bone gelatin,

This example illustrates the incorporation of 160 parts of the hydrophilic, blue-green polymer

of lipophilic and hydrophilic color couplers in 60 'naphthol couplers of Example 1,

a gelatin-silver halide emulsion with the aid of a. 188 parts of silver bromoiodide (97 mole percent bromine

anionic surface-active color coupler. In one and 3% iodine).

Solution (A) of 250 cm ^{3 of} n-propyl acetate and 25 cm ^{3 of} B. 120 parts of bone gelatin,

Tributyl phosphate was 25 g of the lipophilic blue- 45 parts of the lipophilic, blue-green polymer

Grünkupnlers dissolved according to Example 1. For 65 naphthol couplers of Example 5, film B, dispersible

1000 cm ^{3 of} the aqueous solution (B), the 100 g of the yaws according to this example, but below

hydrophilic copolymers of Example 1 contained, use of 15 parts of the color coupler

250 cm ^{3 of} an aqueous 50 g of the anionic were used as an anionic surface-active substance

Place of the non-coupling surfactant of that example.

OH

C - NHCrH

18 "37

SO ₁ Na

188 parts of silver bromoiodide,
C. 120 parts of bone gelatin,
. "188 parts of silver bromoiodide.

Films A, B and C were made using a Sensitometer exposed and in the first or. ■ Black-and-white developer of Example 5 treated further. It was observed that the rate of development of silver in film A was relatively in with respect to the control film C was delayed, ver! ■ presumably due to the naphthol structure of the

f "? | j hydrophilic coupler. In film B, in which the largest

•; Zj part of the naphthol now in the lipophilic, dispersible

At this stage, the development delay was reduced.

Example 9

A color reversal film was produced as described under A of Example 4, except that the blue-sensitive emulsion (6) contained 120 parts of gelatin, 117 parts of benzoylacetanilide of the yellow color former corresponding to (6) and 68.5 parts of the yellow color former, the was prepared by polymerizing 1 mole of the monomeric p-methacrylamide-. benzoylacetanilide and 2 moles of ethyl acrylate. The lipophilic coupler was dispersed by dissolving it in a 168/140 mixture of ethanol and water at a pH value of 11.35 and the pH value was adjusted to 6.3 after admixing the color formers. The emulsion was drawn up with the formation of a total color former coating weight of about 24 mg / dm ² , of 20 mg of gelatin / dm ² and 28 mg of silver halide / dm ² . A comparative color reversal film was then produced according to A of Example 4, except that the coating weight of the color former was 27 mg / dm ² , the gelatin weight was 15 mg / dm ² and the silver halide weight was mg / dm ² . The flexibility tests resulted in a crack diameter above 22.9 mm for the comparison sample and only 11.2 mm for the film produced according to the above information, which had the combination of lipophilic and hydrophilic couplers in the yellow layer.

Claims (4)

Patent claims: 1. A process for the preparation of color photographic silver halide emulsions, in which a gelatin-silver halide emulsion hydrophilic color coupler in aqueous solution, added, characterized in that. an aqueous solution containing a colloid is added to the silver halide emulsion, in which a lipophilic color coupler is present in dispersed form, which is dissolved in an organic solvent was, the one below the boiling point of Water has boiling point, would be 30 to 300 parts by weight of the more hydrophilic Color coupler KX) parts by weight of the lipophilic color coupler come and the two dye couplers are selected so that they wind the same or approximately the same when finting Dye result and at least one of the color couplers is a polymeric color coupler. 2. The method according to claim I, characterized in that the colloid to be used Solution in which a lipophilic color coupler is dispersed is gelatin. 3. Process according to claims 1 and 2, characterized in that one is used to dissolve of the lipophilic color coupler in addition to the low-boiling organic solvent high-boiling organic solvent, especially tributyl phosphate, is used. • 4. The method according to claim 2, characterized in that a weight ratio up to 100 parts of the high boiling solvent applied to 100 parts of the lipophilic color coupler will. · 5; Process according to Claims 1 to 4. characterized in that a hydrophilic color coupler is selected which is anionically surface-active is. 109 649/16