DE1123913B - Process for the diffusion-proof incorporation of organic compounds in photographic layers containing gelatin - Google Patents

Description

The invention relates to a method for determining organic, monomeric compounds in gelatin-containing photographic layers, especially in photographic silver halide emulsion layers.

There are various methods of color photography with diffusion-proof intercalated couplers Ways have been suggested to the color coupler in terms of the theoretical requirement to be stored in the individual layers in such a way that they are neither during the casting nor during the Processing penetrate into the neighboring layers. So you can z. B. work in a heterogeneous phase and thereby the solution of hydrophobic color couplers in a non-volatile hydrophobic crystalloid in emulsify in a gelatin solution. Or you can work in a homogeneous phase and the couplers, which are made alkali-soluble by sulfo- or carboxyl groups and with diffusion-inhibiting, long-chain, aliphatic residues have been added to the halide silver emulsion.

In addition to these two methods mentioned, numerous proposals have been made for the Structure of color photographic multilayer materials the diffusion resistance of the individual Layers to be incorporated by linking these with higher polymer compounds to reach. So is z. B. has been proposed, synthetic high molecular weight compounds, z. B. polyvinyl alcohol to bind acetal-like to color couplers and add these polymers to the emulsion. Also links via carbonamide bridges between couplers and copolymers have been described. So z. B. in U.S. Patent 2,297,732 a reaction product a copolymer of styrene and maleic anhydride with 6-amino-1-naphthol-3-sulfonic acid mentioned. As synthetic polymers for establishing monomeric couplers are also z. B. from the USA.-Patent 2 307 399 Polyäthylenimine known which with couplable acid chlorides implemented.

The synthetic polymer chained couplers described above show various in practice Disadvantage. The nitrogen-containing z. B. tend to fog with different emulsions. Other cannot be added to the emulsion in the required concentration, because presumably due to the lack of constitutional relationship to gelatine, only limited miscibility is available. As a result, the color intensity is too low. Other synthetic polymers, e.g. B.

Process for the diffusion-proof storage of organic compounds in gelatine-containing photographic layers

Applicant:

Agfa Aktiengesellschaft,

Leverkusen-Bayerwerk,

Kaiser Wilhelm Allee

Dr. Josef Nogradi, Dr. Hans Ulrich,

Cologne-Stammheim,

Dr. Willibald Pelz, Opladen,

Dr. Walter Püschel, Cologne-Stammheim,

and Dr. Hans Schellenberger, Leverkusen,

have been named as inventors

based on copolymers of styrene and maleic anhydride to which the couplers are linked, have the property that, after addition to the molten emulsion, their viscosity increase in an unacceptable manner, making the casting technique difficult. By adding water you can easily reduce the viscosity to the correct value, but the energy expenditure is for Evaporation of the added water considerably when the applied layer dries. A The above-described color couplers with long-chain diffusion-preventing agents also show similar behavior Leftovers.

It has now been found that one can overcome the difficulties outlined in diffusion-resistant storage of organic compounds in gelatin-containing photographic layers, if the organic compounds to be stored are ester-like or amide-like with copolymers of N-vinylpyrrolidone and polymerizable unsaturated acid derivatives linked and these polymeric Introduces reaction products into the photographic layers.

The polymeric reaction products are hydrophilic and contain pyrrolidone groups

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react organic compound and then polymerize this product together with N-vinylpyrrolidone subject.

The following first describes the production of some within the scope of the process according to the invention usable copolymers and their implementation with color couplers and dyes described.

soluble in water and form homogeneous phases with gelatin solutions.

If one of the reactants is a color coupler to be incorporated and this is the reaction product When added to a photographic silver halide emulsion, the viscosity of the coating solution changes hardly after addition of the polymeric coupler. After exposure and color development of such an emulsion layer strong color gradations with exceptionally low haze values are obtained.

Copolymers of N-vinylpyrrolidone with polymerizable unsaturated acid chlorides are preferred, such as B. methacrylic acid chloride, acrylic acid chloride, fumaric acid dichloride, crotonic acid

chloride, or polymerizable acid anhydrides, _i5 . under nitrogen at 75 ° C after 10 hours such as maleic anhydride, use. completed. A sample is dried in a high vacuum,

The ratio of N-vinylpyrrolidone to acid derivative can be varied. Is preferred the ratio of 20 to 80 mole percent N-vinylpyrrolidone to 80 to 20 mole percent acid derivative.

The copolymers are advantageously prepared in an inert solvent, such as. B. cyclic ethers such as dioxane, tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene

or dialkylamides such as dimethylformamide. 50 g of maleic anhydride and 1 g of polymerization catalyst can be used as a mixture to dissolve azo-bis-isobutyric acid nitrile. The air above the borrowed peroxide, furthermore azo-diisobutyric acid dinitrile approach, is displaced with nitrogen and the like. The polymerization reaction vessel is heated ^{to 70 ° C.} At this temperature depends on the decomposition temperature, the temperature is stirred for 8 hours. After a certain amount of time and the polymerization catalyst used, the polymer begins to precipitate, the batch is preferably at 50 to 100 ° C. thickens 2x1 to a paste that can still be stirred.

This is filtered off with suction, washed with dioxane and dried at 50 ° C. in vacuo. The yield at Polymer is 105 g = 95% of theory.

Representation of copolymers

1. In a 1-1 three-necked flask, 500 ecm submitted dry dioxane and add 110 g of methacrylic chloride, 100 g of N-vinylpyrrolidone and 2 g of azodiisobutyric acid dinitrile are added. The polymerization

the polymerization conversion is 96%. The nitrogen analysis shows 47 percent by weight of N-vinylpyrrolidone.

2. As described under 1, 140 g of methacrylic chloride and 160 g of N-vinylpyrrolidone are added in 500 ecm polymerized with dry dimethylformamide.

3. 200 ecm of dioxane are added to a 1-1 stirred vessel and submitted 60 g of N-vinylpyrrolidone. In this

Manufacture of diffusion-proof couplers

1. Yellow coupler a) 14 g (3-aminobenzoyl) -acet-o-anisidide are in

The copolymers obtained can be used with all monomeric organic compounds that are resistant to diffusion to be incorporated into photographic gelatin-containing layers. as such are the color couplers used in color photography, Coupling components as described in Belgian patent 560 907, dyes,

such as B. filter dyes, UV-absorbing sub- 40 of the solution of 8.5 g of sodium acetate in 100 ecm punch, organic developer substances, stabilized glacial acetic acid suspended, 72 g of one at room temperature Sators and the like in question. 30% dioxane solution of the acid chloride, as in

The resulting polymeric couplers, filter dyes, the representation of the copolymers under 1 on developers, stabilizers, etc. can be added, added dropwise, stirred until dissolved, stirred into the combination with corresponding monomeric volumes of water, with water, compounds Photographic layers added then washed with methanol, dried, off. Their use is general in both black and white photographic materials and in
multilayer color photographic materials
possible, with the polymeric products both of the 5 °
Halogen silver emulsion layer as well as one of the
photographic auxiliary layers are added
can.

Implementation of the copolymers with the in question

Coming monomeric organic compounds 55 5-hydrochloride are suspended in the solution of 20 g by known methods and based on sodium acetate in 150 ecm of glacial acetic acid. It according to whether for the production of the copolymers
Acid chlorides or acid anhydrides were used
and whether the monomeric organic compound is a

free hydroxyl or a primary or secondary 60 of the acid chloride, as in the preparation of the mixed amino group. The reaction can be polymerizate indicated under 1, added dropwise. Quantitatively with equimolecular amounts of the reaction is then carried out 2 ¹ I ₂ hours at 35 to 40 ° C and ion partner, or only partially then stirred at 70 ° C for 1 hour. It is stirred into 1000 ecm of the acid chloride or acid anhydride groups for 2N hydrochloric acid, filtered off with suction, the acylation used with dilute solvents and the remainder washed with 65 hydrochloric acid and then with water and converted into carboxyl groups by hydrolysis. One dries.

but can also use the monomeric unsaturated acid b) In an analogous manner, l- (4'-aminophenyl) -

derivative reacted directly with the monomeric 3-methylpyrazolone-5-hydrochloride to be stored.

Dissolved methanol.
Be in an analogous way

b) Benzoylacet-S-amino ^ -methoxyanilid,

c) Benzoylacet ^ -amino ^ -methoxyanilid,

d) 4-aminobenzoylacet-p-abusidide implemented. ₂ p _ur p _Urku ppi _er

a) 22.6 g of l- (3'-aminophenyl) -3-methylpyrazolone-

is heated with stirring to 60 to 70 ° C for 1 hour "; cooled to room temperature and at this temperature 72 g of a 30% dioxane solution

c) reaction of l-phenyW-aminopyrazolone-S
with poly- (maleic anhydride-vinylpyrrolidone)

17.5 g l-phenyl-3-aminopyrazolon- (5), 21.5 g polymaleic anhydride vinylpyrrolidone) and 150 ecm of glacial acetic acid are heated to 60 ° C. for 2 hours with stirring, then to 100 ° C. for 1 hour and then chilled. The whole thing is introduced into 600 ecm of water with stirring, filtered off with suction, with 200 ecm 2 N HCl mixed up and sucked off again. The filter cake is washed with water on the suction filter until the draining filtrate is acid-free. After drying, the product is briefly treated with 300 ecm isopropanol Boil heated, cooled and sucked off. 33.5 g of the condensation product from 1-phenyl-3-aminopyrazolone- (5) are obtained and poly (maleic anhydride vinyl pyrrolidone).

d) reaction of 6-aminoindazolone with polymaleic anhydride vinylpyrrolidone)

14.9 g of 6-Aminoindazolon (free base) 21.5 g of polymaleic anhydride-vinyl pyrrolidone) and 150 cc of glacial acetic acid are heated for 2 ¹ I ₂ hours at 70 ° to 80 ° C under stirring, then for 1 hour at 100 ° C and 1 hour heated to boiling. After cooling, the mixture is poured into 600 ecm of water with stirring, filtered off with suction, washed with 200 ecm 2 N HCl, then with water until the filtrate running off is acid-free. After drying, the condensation product is briefly boiled twice with 150 ecm of isopropanol each time and filtered off with suction after cooling. 33 g of white condensation product are obtained.

3. Cyan couplers

a) 45 g of l-naphthol-2-carbonic acid (N-3'-aminobenzyl-N-3 ", 5" -dicarboxyphenyl) amide are suspended in a solution of 8.5 g of sodium acetate in 100 ecm of glacial acetic acid and at room temperature 72 g of a 30% strength dioxane solution of the copolymer, as indicated under 1 for the preparation of the polymers, are added. The mixture is stirred ¹ I ₂ hour at room temperature and then ¹ I ₂ hour at 60 ° C after carrying in the tenfold volume of a water, filtered off with suction, washed with water, dried and then triggers methanol.

In an analogous manner, for. B. 3-aminophenol or 2-chloro-5-aminophenol implemented.

b) 11 g 55 of a copolymer of N-vinylpyrrolidone, maleic anhydride (molar ratio: as noted in Preparation Procedure 3 with 45) _7, and 1/2 hour 12 g of 6-chloro-3-aminophenol refluxed in 100 cc of glacial acetic acid. It is allowed to cool to room temperature, suctioned off and the residue rubbed twice with 75 ecm glacial acetic acid each time and suctioned off again. It is then triturated again with 75 ecm of methanol, suction filtered and dried in vacuo. Yield 15g.

4. White couplers

20 g of l- (3'-aminophenyl) -3,4-dimethylpyrazolone-5 are suspended in a Lpsung of 8.5 g of sodium acetate in 100 cc of glacial acetic acid and at room temperature with 50 of a 30 _<0 y dimethylformamide strength g of the copolymer as specified under 2 in the preparation of the polymers, added. The mixture is stirred for 1/2 hour at room temperature and then for 1/2 hour at 60.degree. The mixture is stirred into ten times the volume of water, filtered off with suction, washed with water, dried and then redissolved from methanol.

Production of a diffusion-resistant yellow dye

a) 10 g of 4-aminoazobenzene are added to the solution of 13.5 g of sodium acetate in 100 ecm of glacial acetic acid. To this end, 36 g of a 30% strength dioxane solution of the acid chloride according to Example 1 are added dropwise at room temperature. It is then heated 3 ¹ I for ₂ hours at 35 to 40 ° C and ¹ I ₄ hour in boiling water bath, to 500 cc of 2 N hydrochloric acid discharged, suction filtered, first with dilute hydrochloric acid, then washed with water and dried.

Be in an analogous way

b) 4-amino-2 ', 3-dimethyl-azobenzene,

c) 2-phenyl- (1-azo) -4-naphthylamine-1
implemented.

1.5 g of the diffusion-resistant yellow coupler described under 1, a) are dissolved in 20 ecm of methanol and Dissolved 20 ecm of 4% sodium hydroxide solution and mixed with 100 ecm of a conventional silver halide gelatin emulsion applied to a support, dried, exposed and subjected to a color development process. When using N, N-diethylaminoaniline as the color developer, a yellow dye image is obtained.

Example 2

1.5 g of the method described above for the manufacture of diffusion-resistant color couplers under 2, a) polymeric purple coupler are dissolved in 20 ecm methanol and 20 ecm 4% sodium hydroxide solution and mixed with 100 ecm of a conventional halosilver gelatin emulsion, applied to a carrier, dried, exposed and subjected to color development. You get when using of N, N-diethylaminoaniline as a color developer, a purple dye image.

Example 3

1.5 g of that described above in the production of the diffusion-resistant color couplers under 3, a) polymeric blue-green coupler are dissolved in 20 ecm methanol and 20 ecm 4% sodium hydroxide solution and with 100 ecm of a conventional hooked silver gelatin emulsion mixed, applied to a support, dried, exposed and a color development subject. If Ν, Ν-diethylaminoaniline is used as a color developer, this is obtained a cyan dye image.

Example 4

A red-sensitive halogen silver layer is located on a substrate made of barite base paper, the 15 g per kilogram of emulsion used in the manufacture of the diffusion-resistant color couplers contains the blue-green coupler described under 3, a).

There is a green-sensitive layer on top. This layer contains 15 g per kilogram of emulsion a purple coupler in accordance with representation specification 2, a). There is a yellow filter layer on top, consisting of colloidal silver. Over these layers is a blue-sensitive halogen silver layer arranged the 15 g per kilogram of emulsion in the manufacture of the diffusion-resistant Color coupler of the polymer described under 1, a)

Contains yellow coupler. This material is exposed behind a colored template and then developed in a known manner with N-ethyl-N-oxäthylaminoaniline as a color developer, one obtains a multicolored · image.

Example 5

In a color photographic material according to Example 4, between the red and green-sensitive layer attached a separating layer of the following composition: 15 g of the The preparation instructions described under 4 are the colorless coupling compound in 50 ecm of methanol and 20 ecm of 4% sodium hydroxide solution and mixed with 1000 ecm of a 5% gelatin solution. The color separation of this material is much better than with a material that does not have this separation layer or whose corresponding layers have only been separated by an empty gelatin layer.

20th

Claims (4)

PATENT CLAIMS: 1. A process for the non-diffusible incorporation of organic compounds in gelatin- containing photographic layers, characterized in that the compounds to be incorporated are those which are linked in ester or amide-like fashion with copolymers of N-vinylpyrrolidone and polymerizable unsaturated acid derivatives. 2. The method according to claim 1, characterized in that copolymers of N-vinylpyrrolidone and unsaturated acid chlorides or acid anhydrides can be used. 3. The method according to claim 1 and 2, characterized in that copolymers are used made up of 20 to 80 mole percent N-vinylpyrrolidone and 80 to 20 mole percent unsaturated Acid derivative exist. 4. The method according to claim 1 to 3, characterized in that one known per se Coupling components, filter dyes, UV absorbers, organic developer substances or Stabilizers that have an ester or amide bond with a copolymer of N-Viny.1-pyrrolidone and unsaturated acid derivatives are linked into a gelatin-containing photographic Layer. © 209 509/314 2.62