DE1009023B - Process for the preparation of a mixed color photographic emulsion - Google Patents

Description

GERMAN

The invention relates to a method for producing a color photographic mixed emulsion.

There have been several methods of preparing mixed color photographic emulsions; H. for photographic systems in which differently sensitized halogen silver grains are incorporated into a single photographic emulsion layer are incorporated, especially for color photographic systems are therefore used to produce different colored photographic images in a single layer, has become known. Mixed-grain systems have a number of advantages. One of these advantages is, for example, that a single layer of emulsion is much easier to cast with the required accuracy leaves as multiple emulsion layers. Another advantage is, for example, that you that the differently sensitized particles are arranged side by side in a single emulsion layer, can achieve a much better image sharpness and image reproduction. In addition, the Treatment of the photographic material, especially its color development, etc., is greatly simplified will.

There is also known a process for the preparation of a photographic mixed emulsion whose light-sensitive, color-developable portion consists of colloid units or colloid "packets" which are in a uniform phase or a carrier material made of gelatin or another hydrophilic, water-permeable Colloid are suspended or dispersed. The term "packages" for the colloid units was chosen because these represent self-contained structures that make up those in them contained parts cannot escape. The colloid units are made by both a Halosilver gelatin emulsion and dye-forming compounds sensitized to a spectral range, that is, couplers, with a polymeric material referred to below as a packet former in Presence of another polymerisation product or modifier that facilitates the package formation, be treated. Then another gelatin mass or another carrier of the emulsion can be used be admitted. In a similar way, further colloid units are then produced, in which one lets develop another color. The "package" emulsions are then mixed and the mix as one shed single layer. A separate package former is used to produce the known mixed emulsion and a coupler is needed. This is a disadvantage in some cases.

The invention is based on the object of the process for the production of photographic mixed emulsions of the type mentioned, so that

Method of making a
color photographic mixed emulsion

Applicant:

Eastman Kodak Company,
Rochester, NY (V. St. A.)

Representative: Dr.-Ing. W. Wolff, patent attorney,
Stuttgart N, Lange Str. 51

Claimed priority:
V. St. v. America March 30, 1953

Leopold Godowsky, Westport, Conn.,

and Louis Morton Minsk, Rochester, N.Y. (V. St. A.),

have been named as inventors

in particular the image reproduction and the resolution of such emulsions can be increased.

This object is achieved in that a diffusion-resistant synthetic resin coupler connection formula

R "R"

-CH ₂ / -CH \ -Ct-

R J _x COOH CONHR '

in which R denotes a hydrogen, a phenyl group, a carboxyalkyl group, an alkyl -COO- group (C _n H _{2n + 1} COO—), an alkyl group or an alkoxy group, χ and y are each 0 or 1, R 'a color-forming group inclusive an aryl group which can be reacted with the oxidation product of a primary aromatic amino developer during development, and R "denotes a hydrogen or an alkyl radical, is dissolved in a gelatin-halosilver emulsion and that the solution with a packet-forming compound, and with a copolymerization product of methyl methacrylate-methacrylic acid or with an alkali salt of polymeric d-mannuronic acid (algin) or carboxymethyl cellulose or cellulose sulfate or alkaline earth salts, so that a dispersion of the gelatin particles of halogen silver and synthetic

709 510/359

resin coupler compound is formed in a gelatin phase, and that similarly at least one further dispersion of gelatin particles, sensitive to a wider range of the visible spectrum Halogen silver and a synthetic resin coupler compound containing another color forming group is formed in a gelatin phase, further that the gelatin dispersions with a solution of a hydrophilic colloid, preferably mixed with a gelatin solution. - '

Resin coupler compounds are known per se. They are in photosensitive halogen silver emulsions multilayer photographic material used, for example, the diffusion of the To avoid couplers and their detrimental effect on the sensitivity of the halogen silver emulsions and to make the couplers compatible with the gelatin binders. However, it is not known that synthetic resin coupler compounds are suitable for the preparation of photographic mixed emulsions could be. The known synthetic resin coupler compounds also have no carboxyl groups of the polymeric chain, as provided in the method according to the invention.

The process steps described are shown in the drawing according to the invention compiled schematically.

A solution can now be used to prepare the photographic mixed emulsion according to the invention a sodium salt or other water-soluble salt of the synthetic resin coupler first Halogen silver emulsion, preferably a silver chlorobromide gelatin emulsion, be added, as indicated by the top three fields of the drawing.

Packets or discrete particles of the emulsion and the resin coupler are now formed by the combination of the emulsion and the resin coupler either

1. a water-soluble polymerization product or a water-soluble salt of a polymerization product which contains salt-forming acidic groups, for example methyl - α - methacrylate methacrylic acid, as indicated on the left side of the drawing, or

2. a solution of a precipitant for the synthetic resin coupler, preferably an alkaline earth salt, for example Calcium acetate, as indicated in the drawing (right side), is added.

In the process specified under 1, the formation of the packets is caused by the fact that the liquid Halogen silver emulsion and the solution of the synthetic resin coupler an aqueous solution of a water-soluble one Polymerization product or a water-soluble salt of a polymerization product, the contains salt-forming acidic groups, such as, for example, a copolymerization product of methacrylic acid and methyl α-methacrylate (U.S. Patent 2,391,181) or an alkali salt of the polymers d-manmironic acid, or carboxymethyl cellulose (U.S. Patent 2278612) or cellulose sulfate (Belgian patent 448 249) is added. The synthetic resin coupler can also vice versa of a liquid emulsion and the solution of the water-soluble polymerisation product or the salt of the polymerization product can be added.

In the process specified under 2, the liquid halide silver emulsion and the solution of the Resin coupler and a solution of a polyvalent metal salt, a polyamine or a High molecular weight amine or a higher molecular weight quaternary salt, in particular a solution of an alkaline earth salt, for example calcium, strontium or magnesium, slowly and simultaneously added to a second solution of an alkaline earth salt. The alkaline earth ion forms with the acidic group of the resin coupler a salt, so that packets or particles of the resin coupler salt the gelatin and halogen silver. In general, gelatine is also added, to complete the emulsion or dispersion of the photosensitive dye-forming particles.

The formation of the package emulsions is described in more detail in the following examples.

example 1

4.4 g of a red-sensitive bromochlorosilver emulsion, which contains 80 percent by weight of silver chloride and has a gelatin content of 21.6 g per mole of halogen silver, are mixed with 44 ecm of water and stirred for 10 minutes at 40 °. The emulsion is then 14 cc of a 5% aqueous solution of the sodium salt of the compound described in Example 7 resin coupler _(pH-value about 7) was added. The mixture is stirred for 20 minutes with 3 cc of a solution of the lOVoigen Mischpolymerisationsproduktes of the methyl-a-methacrylate and methacrylic acid at a _pH value added from the 8th The solution is mixed for 25 minutes and then 6 ecm of a 10% magnesium sulfate solution are added and the mixture is stirred for a further 5 minutes. Then 25 ecm of a 20% gelatin solution are added.

Example 2

3.2 g of a chlorobromide silver emulsion containing 2 percent by weight of chlorosilver and 21 g of gelatin per mole of halosilver are mixed with 22 ecm of water and stirred for 10 minutes at 40 °. Of the emulsion are 14 cc of a 5% solution of the sodium salt of the compound described in Example 8 resin coupler (p _H value of about 8) was added.

The mixture is stirred for 10 minutes and the pjj value is brought to 7 with 28% acetic acid. Thereafter, the mixture 2 are ecm a lO ° / o solution of the copolymer of the methyl-a-methacrylate and methacrylic acid at a _pH value of 8 was added and the mixture stirred for 25 minutes. The mixture is then mixed with 6 ecm of a 10% magnesium sulfate solution and stirred for 5 minutes. Then 25 ecm of a 20% gelatin solution are added.

Example 3

4 g of a green-sensitive chlorobromosilver gelatin emulsion containing 80 percent by weight of chlorosilver and 8.7 g of gelatin per mole of halosilver with 40 ecm of water and 3.3 g of 20% phthalic anhydride gelatin added by reacting 20 g of phthalic anhydride with 100 g of gelatin according to Example 1 of U.S. Patent 2,525,753. The emulsion is 7 ecm of a 5% aqueous solution of the sodium salt of the synthetic resin coupler specified in Example 9 was added. To 20 minutes of stirring are 2 ecm of a 10% solution of the copolymerization product of the Methyl-a-methacrylate and methacrylic acid introduced into the emulsion. If a good dispersion of the Forming packets is reached, 3 ecm of a 10% magnesium sulfate solution and then

15 ecm of a 20% gelatin solution was added which consists of equal parts bone gelatine and phthalic anhydride gelatine.

Example 4

A two-color mixed photographic emulsion is now prepared as follows:

1 part of the emulsion prepared as described in Example 2 is mixed with 2 parts according to Example 1 prepared emulsion mixed with the addition of the usual distributing agents and hardening agents. The emulsion mixture is poured onto glass plates that are placed under a photographic step wedge exposed and developed into a negative color image in the following developer solution:

2-Amino-5-diethylamino-toluene · H Cl 2 g

Sodium sulfite 2 g

Sodium carbonate 20 g

Potassium bromide 2 g

Water on 1 1.

A photographic mixed emulsion can also be prepared using the synthetic resin couplers according to FIG Invention can be made by using the synthetic resin coupler and the halosilver gelatin package a heavy metal salt are precipitated without water-soluble polymerization products such as for example, the copolymerization product of methyl a-methaorylate and methacrylic acid is used will. This is illustrated in the following examples.

Example 5

35

30 ecm of a 4% solution of the as described in Example 12, by reaction of the vinyl acetate-maleic anhydride - copolymerization product and. of 1 - oxy - 4 - chloro - 2 - ^ -aminoäthylnaphtharnids resin coupler produced are mixed with as much dilute acetic acid that the _pH value of the solution is 7 to 7.5. At 40 °, 3.5 g of a red-sensitive chlorobromosilver gelatin emulsion containing 80 percent by weight of chlorosilver are then stirred into the solution. The solution of the halogen silver emulsion and of the coupler as well as 32 ecm of a 10% calcium acetate solution are slowly poured into 56 ecm of a 0.1% calcium acetate solution within two and a half hours. During the pouring, packets of the emulsion and the coupler are formed, the size and dispersion of which depends in part on the stirring speed during the addition. Finally, the red-sensitive emulsion is completed by adding 30 g of a 20% bone gelatin solution.

Example 6

60

In a manner similar to that described in Example 5, a dispersion of a green-sensitive, a Purple image-producing emulsion produced by using 15 ecm of a 4% solution as a synthetic resin coupler as described in Example 14 by reacting the copolymerization product styrene-maleic anhydride and l-p-aminophenol-3-butyramido-5-benzoxypyrazole produced synthetic resin coupler and 2 g of a 80 percent by weight chlorosilver containing green-sensitive silver chlorobromide gelatin emulsion can be used. This solution and 16 ecm, one 2% calcium acetate solution is slowly added in 28 ecm to form the green-sensitive package emulsion an O, 2% calcium acetate solution stirred in. "'

To form the mixed emulsion to be 7.5 g of the red-sensitive and green-sensitive emulsion 7.5 g of a lOVoigen bone gelatin ge ¹ - 'mixed, which was treated with a 100 mg D iocty hydroquinone corresponding Dioctylhydrochinondispersion!. Each 12 ecm of the mixed emulsion are poured onto a plate ^{each having an area of 88.9 cm 2.} After drying, the plates are exposed to light under a color table, developed with the developer specified in Example 4 and bleached and fixed in the usual way.

The package emulsions according to the invention can not only be used for the production of a photographic m Mixed packages can be used. Any of the package emulsions can also be used as a single layer on a conventional photographic support will. Of course, one or more package emulsions can also be used together as one layer multilayer photographic material, for example a superimposed red-sensitive, multilayer photographic material containing green-sensitive and blue-sensitive hemogenous silver emulsions, be used.

The synthetic resin couplers can also be used directly in the manner described in US Pat. No. 1,102,028 can be incorporated into a hemogenous overemulsion without the formation of packets.

Polymerization products which are used to form the resin couplers according to FIG Invention have proven to be particularly suitable, and described processes for their preparation.

A. Polyacrylic anhydride
- CH ₈ - CH - CH ₂ - CH -

CO

CO

CO

CO

CH ₂ - CH - CH ₂ - CH - CH ₂ - CH -

CO

CO

- CH-CH ₈ -

In a completely made of glass, protected against moisture by means of a calcium chloride tube The reflux device is 292 g of acrylic anhydride, 2920 ecm of anhydrous 1,4-dioxane and 1.46 g of benzoyl peroxide heated on a steam bath for 4 hours, the reaction mixture having a white, thick sentence. The precipitated product is filtered off on a Buchner funnel, quickly with 1,4-Dioxane and washed in a vacuum dryer under constant vacuum over calcium chloride dried.

B. copolymerization product of vinyl acetate and maleic anhydride

-CH ₂ -CH-CH-CH preparation of suitable polymeric couplers is described below.

Example 7

—CH ₂ -CH-CH-CH-

CO

CH,

CO CO

CO CO

OHCl

CO OH NH-

CH,

V- CH,

In an all-glass reflux device protected against moisture by means of a calcium chloride pipe a mixture of 196 g of maleic anhydride, 172 g of vinyl acetate, 7.4 g of benzoyl peroxide, 4456 g anhydrous benzene and 44 g xylene on a steam bath heated to form a slurry. The heating continues for IV2 hours after the opacification the reaction mixture continued. The precipitated product is filtered off, twice with 2 l each of dry Stirred toluene and filtered off after each extraction. The product is in a vacuum dryer dried under constant negative pressure over calcium chloride and then in an oven Maintained at 100 ° for 20 hours. The yield is 310 g. The intrinsic toughness of the product is 0.23 after the in »J. Colloid Science ", Vol. 1, p. 261 (1946), specified measuring methods.

C. Styrene-maleic anhydride interpolymerization product

- CH ₂ - CH - CH "- CH - CH - Cl

CO CO 0

This styrene-maleic anhydride copolymerization product is produced according to Examples 2 and 3 of German patent application E 3591 IVa / 57b. The intrinsic toughness of the product is about 0.2.

The synthetic resin couplers used in the process according to the invention are prepared by reacting these or similar polymerization products with couplers containing an amino radical. The 50 g of a vinyl acetate-maleic anhydride copolymerization product (intrinsic viscosity of the product = 0.21 when using 0.25 g of the product in 100 ecm of acetone) are equipped with a stirrer and a reflux condenser by stirring in a tube protected from moisture by means of a calcium chloride tube All-glass device dispersed in 750 ecm anhydrous acetone. 100 g of 2-amino-4,6-dichloro-5-methylphenol are added to the paint. The reaction mixture is stirred on a steam bath for 1 ¹ U hours. The red-brown solution is then stirred into 8 l of distilled water to which 200 ecm of concentrated hydrochloric acid have been added. The precipitated product is filtered off on a Buchner funnel, washed in the funnel with distilled water and then stirred up twice with 3 liters of distilled water and filtered off after each stirring. The product is reprecipitated twice from 600 ecm of an aqueous hydrochloric acid-acetone solution and washed each time with distilled water. Finally, the product is washed free of chlorine with distilled water and dried over calcium chloride in a vacuum dryer under constant water pump pressure. The yield is 88 g.

Analysis: N = 3.25%; Cl = 15.55%.

Other synthetic resin couplers useful in forming blue-green images in color development can be made from 2-aminophenol and polyacrylic anhydride, 2-aminophenol and styrene-maleic anhydride polymerization products, 2-amino-4,6-dichloro-5-methylphenol and styrene-maleic anhydride copolymerization products as well as from 5-amino-1-naphthol and vinyl acetate-maleic anhydride copolymerization products getting produced.

Example 8

- CH, - CH - CH - CH -

I I co co

OH NH- -NHCOCH ₉ CO-:

In a facility as described above, g of the styrene-maleic anhydride interpolymerization product (Intrinsic viscosity 0.18) dispersed in 700 ecm anhydrous acetone. 200 g in 100 ecm p-amino-a-benzoylacetanilide washed with dry acetone are introduced into the reaction mixture and then on a steam bath for 1 hour touched. After this time, a second, highly viscous phase has separated out. The reaction mixture is poured into 16 l of distilled water containing 500 ecm of concentrated hydrochloric acid while stirring vigorously. The gummy precipitate that forms is stirred until it becomes crumbly. After that, that will Product filtered off on a Buchner funnel, washed with water and made twice from acetone in 16 l with ecm concentrated hydrochloric acid added distilled water reprecipitated. After the second precipitation the product is washed free of chlorine and overnight in a vacuum dryer over calcium chloride dried under constant water pump vacuum. Then the product is dissolved in 900 ecm acetone, boiled with 150 g of active charcoal and filtered. The filtrate is 400 ecm of a solution of 9 parts Acetone and 1 part distilled water and diluted

precipitated in 8 l of distilled water. The precipitated product is washed with distilled water and dried in a vacuum dryer over calcium chloride under constant water pump vacuum. The yield is 120 g.
Analysis: N = 6.2%.

Example 9

- CH ₂ - CH - CH - CH

There are 32 g of the styrene-maleic anhydride copolymerization product (Viscosity = 0.21) dispersed in 250 ecm anhydrous acetone. The paint 62 g of l-p-aminophenyl ~ 3-methyl-5-pyrazolone, which has been washed in 70 ecm of anhydrous acetone was admitted. The reaction mixture is stirred on a steam bath for 35 minutes. The clear, orange one The paint becomes cloudy and the polymerisation product settles as a soft cake. To Add 200 ecm of distilled water, stir it up and pour off the supernatant liquid and further addition of 200 ecm of distilled water is the acetone from the reaction mixture on a Steam bath distilled off. Thereafter, the reaction mixture with 300 ecm 10% aqueous sodium hydroxide added and heated with stirring on a steam bath until the remaining acetone distilled over is. After a total heating time of 3 hours, the gelatin mass is slowly dispersed, until a gelatinous, reddish-brown smooth varnish results. The paint is in a hot state through a Filtered glass cloth. The filtrate is made up to 3 liters with distilled water and with concentrated hydrochloric acid acidified on Congo red paper. A copious precipitate forms in the process. The precipitation is filtered under its weight on paper and washed on paper with distilled water. The precipitate is again dissolved in 3 l of distilled water by adding 10% aqueous Dissolved sodium hydroxide. By acidifying Congo red paper using concentrated hydrochloric acid, the Product, in turn, is liked. The precipitate is filtered and washed as indicated above until the filtrate is chloride free. Dissolve in dilute sodium hydroxide and precipitate as indicated above are repeated. The filtrate is also washed once more free of chloride. The product will then dried over calcium chloride in a dryer under constant negative pressure from the water pump. The yield is 58 g.

55

60

Example 10
-CH ₂ -CH-CH ₂ -CH- OH

I I

CO CONH-

OH

In one with an inlet tube for nitrogen, a mechanical stirrer and a reflux condenser equipped, three-necked, protected against moisture by means of a calcium chloride pipe = C-CH *

CO-CH,

6.3 g of polyacrylic anhydride, 20 g of 2-amino-4, o-dichloro-S-methylphenol and 100 ecm anhydrous acetone stirred on a steam bath, the air in the flask passing through anhydrous nitrogen is displaced. An orange-brownish varnish is obtained after a short time. To After heating for one hour, the lacquer is poured into 21 distilled water in a fine stream, the 50 ecm contain concentrated hydrochloric acid. The resulting crumbly precipitate is mixed with distilled water and washed twice from 150 ecm acetone in 2 l of distilled water, the 50 ecm concentrated hydrochloric acid included, fell over. The precipitated product is then washed free of chloride with distilled water and dried in a vacuum dryer under constant water pump vacuum. The yield is 11.2 g.

OH

Example 11

■ CH, - CH - CH - CH -

CO CONH-

OH

In one with a mechanical stirrer and a reflux condenser and an inlet tube for Three-necked ones equipped with nitrogen and protected against moisture by means of a calcium chloride pipe 20 g of the styrene-maleic anhydride copolymerization product are placed in the reaction flask anhydrous nitrogen dispersed in 200 ecm anhydrous acetone. The paint is made with 25 g of o-aminophenol added and heated on a steam bath under anhydrous nitrogen. After 20 minutes will be a further 100 ecm of acetone were added. After a total heating time of 1 hour, the reaction mixture is taken up with acetone and distilled in 3 liters Water containing 75 ecm of concentrated hydrochloric acid is poured in. The resulting precipitate is washed with water and reprecipitated twice from acetone as indicated above. The product will then washed free of chloride and in a vacuum dryer under constant water pump vacuum dried. -The yield is 25 g.

In the above manufacturing process, the intermediate coupler is used in excess, so that it combines with the carboxyl groups formed during the course of the reaction. Around reduce the required amount of the intermediate coupler from the calculated molar ratio the manufacturing process changed slightly. The following examples relate to such modified ones Procedure.

709 510/359

example

-CH ₉ -CH-CH-CH-OH

O CO CONH - CH ₂ CH ₂ NHCO -
CO OH

CH ₃

In one equipped with a reflux condenser and a mechanical stirrer, against moisture by means of a calcium chloride tube protected three-necked reaction flask, 322 g of the vinyl acetate-maleic anhydride copolymerization pro- dispersed in 2100 ecm anhydrous acetone. When the lacquer formation is complete, 470 g of l-oxy-4-chloro-2 - (^ - aminoethyl) naphthamide and then 1120 ecm anhydrous aoetone and 150 ecm anhydrous pyridine were added. The reaction mixture is stirred on a steam bath, becoming cloudy after 5 minutes. After 10 minutes a second phase separates, after 20 minutes a soft cake is present. After 35 minutes of heating 320 ecm of distilled water are added and the cake is dissolved again by stirring. Of the Lacquer is mixed with 1500 ecm of a solution of acetone and distilled water (ratio of the volumes = 10: 1) diluted and 37.8 l of distilled water containing 1500 ecm of concentrated hydrochloric acid, stirred in. Which The precipitate that forms is filtered off using a Buchner funnel, distilled on the funnel Cl

Washed water and stirred up again with 37.8 l of distilled water. The solid then becomes dissolved in 5000 ecm acetone. There are 320 g of active charcoal added, and after the mixture to Has been brought to the boil, the solution is smooched through a filter paper covered with a fuller's earth. The filtrate is dissolved in 37.8 l of distilled water, which contained 750 ecm of concentrated hydrochloric acid, poured in. After stirring for 15 minutes, the precipitate becomes friable, the solid is filtered off, washed on a funnel with distilled water and stirred again for 30 minutes in 37.81 of distilled water. The product is on a funnel filtered off, washed again with distilled water and placed in a vacuum drying device dried over calcium chloride under constant negative pressure from the water pump. The yield is 581 g.

Analysis: N = 5.850 / 0, Cl = 7.05%, acetyl = 9.2%.

A portion of the moist product specified above is dried in an air oven at 40 °, whereby a satisfactory product is obtained.

example

-CH ₂ -CH-CH-CH-

CO CONH-

OH

160 g of the styrene-maleic anhydride copolymerization product are in a equipped with a mechanical stirrer and a reflux condenser, All-glass return flow device protected against moisture by means of a calcium chloride pipe dispersed in 1600 ecm anhydrous acetone. 220 g of benzoylaceto-p-aminoanilide are added to the paint and then 400 ecm of anhydrous pyridine was added. The varnish is on a steam bath for 2 hours stirred, with a soft second phase occurring. By adding 100 ecm of distilled water and Continued stirring gives again a smooth varnish. This is distilled with 3 l of an acetone Water mixture (ratio of volumes = 9: 1) and diluted in 18.9 l of distilled water, which contains 1 1 concentrated hydrochloric acid, poured. The resulting precipitate is stirred until it becomes crumbly, and then filtered off on a Buchner funnel, on which it continues to be distilled NHCOCHXO-

Water is washed. The precipitate is then dispersed in 2500 ecm of acetone and the dispersion 300 g of active charcoal are then added.

After the mixture is brought to the boil, it is covered with a fulling earth Filter paper sucked off. The acetone lost through the suction is replaced again and then the filtrate is precipitated in 18.91 of distilled water containing 500 ecm of concentrated hydrochloric acid. The precipitate is filtered off on a funnel and washed on the funnel with distilled water and then stirred for V2 hours in 18.9 l of distilled water. The product is in a vacuum dryer dried over calcium chloride under constant negative pressure from the water pump. The yield is 227 g, the product contains 5.25% nitrogen.

Part of the moist product is air-dried in an oven at 40 °. The product showed satisfactory 'results.

example

CH, -CH- CH-CH-

CO CONH-

/ OH, N = N-CONHC ₄ H ₉

XO-

In one equipped with a reflux condenser, a me-nitrogen, against moisture means mechanical stirrer and an insertion tube for 70 of a calcium chloride tube protected all-glass

The reflux device is 90 g of the copolymerization product of styrene - maleic anhydride (intrinsic viscosity = 0.21) in 800 ecm of dry pyridine stirred up to a varnish, the reaction mixture under a stream of anhydrous stick- substance is set. 163.8 g of l-p-aminophenol-3-butyramido-5-benzoxypyrazole are added to the paint, which had been washed in 100 ecm anhydrous pyridine. The reaction mixture will Stirred for 75 minutes on a steam bath under anhydrous nitrogen. Then the paint is 450 ecm anhydrous pyridine and precipitated in 18 liters of ether. The precipitated product is placed on a Buchner funnel sucked off, washed on the funnel with 21 ether and then slurried in 4 liters of ether. After that, will the precipitated product washed again on the funnel with 2 liters of ether to evaporate the ether on the Air-dried and twice for 20 minutes with 8 liters of distilled water each time, which each concentrated 200 ecm Containing hydrochloric acid, slurried. After suction ao and washing on the funnel with distilled Water, the product is stirred up for 10 minutes with 8 l of distilled water, filtered, and continued on the funnel washed with distilled water and air dried in an oven at 40 °. the The yield is 173 g, the product contains 8.35% nitrogen.

This coupler polymerization product dissolves in dilute potassium carbonate solution when heated, the benzoxyl group being hydrolyzed.

Other synthetic resin couplers which produce a purple image when coupling are, for example, pyrazolyl styrene Maleic acid copolymerization products as described in US Pat. No. 2,646,421 are.

The examples serve only to explain the process. The skilled person can depending on the given Modify the invention easily within the scope of the inventive concept.

40

Claims (6)

PATENT CLAIMS: 1. A process for the production of a color photographic mixed emulsion, characterized in that that a diffusion-resistant synthetic resin coupler compound of the formula R " R " -CH ₂ / -CH \ - C (-CH ₂ J ₁₁ -C- COOH CONHR ' 55 in which R denotes a hydrogen, a phenyl group, a carboxyalkyl group, an alkyl-C O O group, an alkyl group or an alkoxy group, χ and y are each 0 or 1, R 'denotes a color-forming group including an aryl group, which upon development with the oxidation product of a primary aromatic amino developer can be reacted, and R "denotes a hydrogen or an alkyl radical, is dissolved in a gelatin-halosilver emulsion and that the solution with a packet-forming compound, namely with a copolymerization product of methyl methacrylate-methacrylic acid or with a Alkali salt of polymeric d-mannuronic acid (algin) or carboxymethyl cellulose or cellulose sulfate or alkaline earth salts are added so that a dispersion of the gelatin particles of the halogen silver and the resin coupler compound is formed in a gelatin phase, and that in the like Way at least one further dispersion of gelatin particles, for a wider range of the halogen silver sensitive to the visible spectrum and one containing another color-forming group Resin coupler compound is formed in a gelatin phase, further that the gelatin dispersions with a solution of a hydrophilic colloid, preferably with a gelatin solution, be mixed. 2. The method according to claim 1, characterized in that a synthetic resin coupler compound Compound of formula - CH ₂ / - CH \ - CH (CHj), - CH - CO OH NHR ' R /, CO 'is used in which R denotes a phenyl group, a carboxyalkyl or an alkyl-C O O group, χ and y are each 0 or 1 and R' denotes a color-forming group including an aryl group, which upon development with the oxidation product of a primary aromatic amino developer can be converted, and that a water-soluble salt of the copolymerization product of methyl methacrylate-methacrylic acid is used as the packet-forming compound. 3. The method according to claim 1, characterized in that a salt is a non-diffusing Resin coupler compound of the formula R "R" ch ₂ / - ch \ - c (-ch ₂ ) ^ - c- A cooh conhr ' is used, where R is a phenyl group, a carboxyalkyl or an alkyl-C O O group. 4. Process according to Claims 1 and 2, characterized in that the sodium salt of the synthetic resin coupler compound the formula - CH ₂ - CH - CH - CH O CO CO CO OH NHR CH ₃ in the R one in the ortho position with a hydroxyl group substituted phenyl radical, with a preferably red-sensitive gelatin-halosilver emulsion is mixed so that a solution of the resin coupler compound is formed in the emulsion and that this solution with a solution of a water-soluble salt of the copolymerization product of methyl methacrylate-methaoryl acid is mixed so that a dispersion of the gelatin particles, the red-sensitive halogen silver and the synthetic resin coupler compound is formed in a gelatin phase, and that in a similar manner another dispersion from gelatin particles, preferably blue-sensitive halogen silver and a synthetic resin coupler compound the formula -CH ₂ -CH-CH-CH λ " -CH ₂ / - CH \ - CH (-CH ₂ ) ^ - CH— CO OH CO NHR ' 10 CO CO OH NH- -NHR ' in which R 'denotes the remainder of a benzoylacetyl group, is prepared in a gelatin phase and that the dispersions of the particles are mixed, ao 5. The method according to claims 1 and 2, characterized in that a water-soluble salt is a Resin coupler compound of the formula -CH ₁ -CH-CH-CH-is mixed with a gelatin-halosilver emulsion and that this mixture together with a solution of a calcium salt is slowly stirred into a further solution of the calcium salt so that a dispersion of gelatin particles, halosilver and the calcium salt the resin coupler compound is formed in a gelatin phase, and similarly at least one further dispersion of gelatin particles, halosilver and the calcium salt of the resin coupler compound is prepared in a gelatin phase, and that the dispersions are mixed with a solution of a hydrophilic colloid. 6. The method according to claims 1 and 2, characterized in that a water-soluble salt is a Resin coupler compound of the formula OH CO CONHCh ₂ CH ₂ NHCO -ι CO OH CH ₃ is mixed with a red-sensitive gelatin-halosilver emulsion so that a solution of the Resin coupler compound is formed in the emulsion and that this solution and a Calcium acetate solution is slowly stirred into a second calcium acetate solution so that a dispersion of the gelatin particles, the red -CH ₉ -CH-CH-CH- CO CONH OH is prepared in a gelatin phase and that the dispersions of the particles are mixed with one another will. sensitive halogen silver and the resin coupler compound in a gelatin phase will, further, that in a similar manner another dispersion of gelatin particles, green-sensitive Halogen silver and a synthetic resin coupler compound of the formula _/ N == N-CONHC ₄ H ₉ CO - CH, Considered publications:
U.S. Patent Nos. 2,422,680, 2,463,794. 1 sheet of drawings © 709 510/359 5.57