DE1246406B - Color photographic direct positive process - Google Patents

Description

GERMAN WJWWp PATENT OFFICE

EDITORIAL

German class: 57 b-18/13

Number: 1 246 406

File number: E 28059IX a / 57 b

J 246406 filing date: November 4, 1964

Opened on August 3, 1967

The invention relates to a new color photographic direct positive process and a color photographic one Material for performing this procedure.

Direct positive color photographic processes are known. These procedures consist of several Process steps such as black-and-white development, in which a negative image is produced, a reversal exposure, development with a color developer and treatment in a bleach bath and a fixation. There are also known color photographic processes in which the positive Color images are transferred to receiving layers by diffusion of the color images. These too Processes consist of several process stages, with several treatment baths with relatively large ones Volumes are used. Furthermore, direct positive emulsions are used in the known diffusion transfer process as well as special color compounds with developing properties are used

In a known diffusion transfer method, as e.g. B. in the German Auslegeschrift 1101 954 discloses a photographic material having at least one silver halide emulsion layer used, which 'contains any black and white developing agent and color coupler. The production of color positives takes place in in such a way that the imagewise exposed emulsion layer passes through after black-and-white development Exposure is fogged and then color developed.

For the production of color reversal images, it is also known, e.g. B. from the U.S. Patent 2,937,086, a photographic material having several differently sensitized silver halide emulsion layers to use the non-diffusing color coupler, development nuclei and a non-diffusing, reducing compound or an acceptor for the oxidized. Contains developer compound. The production of color images from this material takes place in such a way that the image-properly exposed material initially in one Black and white developer developed, placed in a break bath, washed, color developed, in an interruption bath is brought, washed, bleached, washed and fixed.

The present invention is based on the object of a new color photographic direct positive process to create, which simplifies the known color photographic process is and according to which direct-positive color images without the use of direct-positive silver color graphics Direct positive process

Applicant:

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

Representative:

Dr.W. Wolff, Η. Bartels

and Dipl.-Chem. J. Brandes, patent attorneys,

Munich 22, Thierschstr. 8th

Named as inventor:
Charles Robert Barr,

Rochester, N. Y. (V. St. A.)

Claimed priority:
V. St. v. America 6 November 1963
(321925)

Have halide emulsions produced. In particular, a color photographic process is to be developed without the usual reversal exposures. Ultimately, you want direct positive color images can be obtained by diffusion on a receiving layer, and to carry out the new Transfer process should only be required one liquid treatment stage.

The task at hand was achieved by developing a color photographic direct positive process, in which a color photographic material having at least one high-sensitivity silver halide emulsion layer has, which non-diffusing color couplers with the oxidation products of primary aromatic amino developer compounds react to form dyes, and contains a black-and-white developer substance, is exposed in accordance with the image and then developed, solved by the fact that a color photographic material is used according to the invention, the except a non-diffusing color coupler and a black and white developer substance, consisting of a diffusible hydroquinone with at least one amino-substituted, short-chain alkyl radical or a diffusible catechol with at least one amino-substituted, short-chain Alkyl radical or the combination of a diffusible 3-pyrazolidone and a hydroquinone with

709 619/609

a ballast group preventing diffusion, contains physical development nuclei, and that the photographic material after imagewise exposure in the presence of a primary aromatic Amino color developing agent is treated with an aqueous alkaline solution containing an Contains silver halide solvents.

In the process of the invention, the developed in the silver halide emulsion layer or in the Black and white developing agent present in the presence of the silver halide emulsion layer Color developer and, upon exposure to aqueous alkali, the latent image to form an off metallic silver by chemical development without the formation of a color image. Subsequently, unexposed and undeveloped silver halide corresponding to the positive Image areas physically developed by the color developer to form a positive color image. When the color coupler in the color photographic material forms a diffusing dye image forms, this can be transferred to a receiving layer by diffusion, which either may consist of a layer which is an integral part of the photographic material or which represents a separate receiving layer. The color coupler does not turn on diffusing dyes, so the color photographic material can then with treated with a bleaching solution and fixed, whereby metallic silver is removed and a positive dye image remains.

The silver halide emulsions used in making the color photographic material consist of conventional developable silver halide photographic emulsions of the negative type.

The physical development nuclei added to the silver halide emulsions can consist, for example, of noble metals in colloidal form, 4c such as silver and gold, colloidal metal sulfides, selenides and tellurides, such as, for example, lead sulfide, nickel sulfide, cadmium sulfide, silver sulfide, silver selenide, silver telluride, copper sulfide, metal silver sulfide, and such as silver proteinates, sodium sulfite, colloidal sulfur and such organic sulfur compounds as thiourea and xanthates.

The black and white silver halide developers incorporated in the emulsion layers are preferably colorless. You have the task of developing the latent image formed by exposure before the Color developer physically developed the undeveloped silver halide in the unexposed areas. A compound is referred to as a black-and-white developer substance which is capable of is to chemically develop exposed silver halide to metallic silver and which does not have development oxidation products supplies that can react with the color couplers to form dyes.

Black and white developing agents suitable for carrying out the method of the invention are for example:

65

1. Diffusible hydroquinones with at least one amino-substituted short-chain alkyl group, including those hydroquinones produced by the action of aqueous alkali Have masking carbonyl groups which can be split off by hydrolysis;

2. diffusible catechols with at least one amino-substituted, short-chain alkyl group, including those catechols which are produced by the action of aqueous alkali masking sulfonyl or carbonyl groups which can be split off by hydrolysis to protect the Have hydroxyl groups;

3. Combinations of

a) diffusible 3-pyrazolidones and

b) non-diffusing hydroquinones, which have a photographically inert ballast group have, or

4. Mixtures of these black and white developing agents.

Suitable diffusible hydroquinones with at least one amino-substituted, short-chain Alkyl radicals have the following formula:

OR ²

OR ³

where R denotes an amino-substituted, short-chain alkyl radical in which the alkyl part preferably consists of a methyl group and in which the amino part can be substituted, for example by short-chain alkyl groups, substituted, short-chain alkyl groups, such as short-chain alkanol groups and halogenated, short-chain alkyl groups, cyclic groups, the consist of the carbon, hydrogen and oxygen atoms which, including the nitrogen atom, are required to form a morpholino group, as well as quaternary salts of such amino groups; R ^{1 is} an amino-substituted lower alkyl radical, as described for R, a hydrogen atom, a short-chain alkyl radical which may optionally be substituted, or a short-chain alkoxy radical; R ² and R ^{3 are} hydrogen atoms or a masking or blocking carbonyl radical which is hydrolyzed or split off upon exposure to the aqueous alkaline treatment solution.

Suitable masking or blocking radicals have, for example, the following formulas:
O

- C - O - short-chain alkyl radical;
OO

- C - CO - short-chain alkyl radical;
O

- C - (halogenated, short-chain alkyl radical),
such as B.

O O

II II

-C-CF ₃ , C - CH2CI,

ο ο

C-CHCl _2j -C-CCl ₃

Suitable hydroquinones are, for example:

2,5-bis- [N, N-bis - (^ - hydroxyethyl) -amino-

methylj-hydroquinone;
2,5-bis (N, N-dimethylaminomethyl) -

hydroquinone;
2- (N, N-dimethylaminomethyl) -5-methyl-

hydroquinone;
2- [N, N-bis (/ S-hydroxyethyl) aminomethyl] -

5-methylhydroquinone;
2- [N, N-bis - (^ - hydroxyethyl) aminomethyl] -

5-methylhydroquinone metho-methanesulfonate; 2,5-bis- (N-morpholinomethyl) -hydroquinone-

bis (α-chloroacetate);
2- {y- [bis - (^ - hydroxyethyl) amino] propyl} -5-methylhydroquinone.

Suitable diffusing catechol black and white silver halide developers with at least one amino-substituted short-chain alkyl radical can be represented by the following formula:

-R ⁶

Suitable 3-pyrazolidones have the following formulas:

R ⁷

where R ⁴ and R ^{5 represent} a substituent corresponding to R and R ¹ as in the hydroquinones, R ⁶ and R ^{7 are} hydrogen atoms or separately or together represent the necessary atoms which represent masking sulfonyl or carbonyl radicals which hydrolyze on exposure to aqueous, alkaline solutions.

These masking residues consist, for example, of the following groups:

S = O, C = O,

- C - O - short-chain alkyl radical; O O

II II

- C - C - O - short-chain alkyl radical; O

. II

- C - • O - (halogenated, short-chain alkyl radical), such as. B.

O O

C-CF ₃ , -C-CH ₂ Cl, OO

- C - CHCI2,

C-CCl ₃ and the like.

and

Suitable pyrocatechins are, for example:

4- [N, N-bis (ß-hydroxyethyl) -ammomethyl] -

5-methylcatechol;
4-TN, N-bis ( _l ö-hydroxyethyl) aminomethyl] -

5-methylcatechol carboxylic acid ester; 4-pST, N-bis (/ 3-hydroxyethyl) aminomethyl] -5-methylpyrocatechol sulfuric acid ester.

Suitable 3-pyrazolidone black and white developers are, for example, in the USA patents 289 367, 2 685 516, 2 751 297 and 2 772 282 and in Journal of Organic Chemistry, 26, p. 2803 (1961), described.

R ¹¹
I. RIO - I.
C.
I. -C =
I. 0 · R ⁹ - I.
C. I.
N-
/ Ria Rl ₉ / \ _N / I.
R ⁸ Ru RIO - I.
c -c -
II O - R ⁹ - I.
C. N
/ Rl ₉ /

RIB

R ⁸

wherein R ⁸ , R ⁹ , R ¹⁰ _5, R ¹¹ and R ^{19 are} optionally substituted, short-chain alkyl radicals, such as, for example, short-chain alkyl radicals substituted by chlorine atoms, hydrogen atoms and optionally substituted aryl radicals, such as phenyl, chlorophenyl, p-tolyl and j3-hydroxyethylphenyl radicals; R ^{12 is} a hydrogen atom or a masking carbonyl radical which hydrolyzes off on exposure to aqueous alkali, as indicated ^{for R 2} and R ^3; R ^{18 is} a masking radical as indicated ^{for R 2} and R ^3.

Suitable, non-diffusing hydroquinones containing a ballast group, which serve as auxiliary developers can be used together with the 3-pyrazolidones described, can be through the the following formula is given:

OH

R13

R14

OH

Herein, R ^{13 means} a photographically inert organic diffusion-preventing ballast group. Such a ballast group consists, for example, of a long-chain alkyl group with 8 to 22 carbon atoms; R ^{14 is} a ballast group which is structured as for R ⁱ³ , or a solubilizing group, such as, for example, a sulfo group or an alkali metal salt of such a group. Such solubilizing groups facilitate the introduction of the hydroquinone into the silver halide emulsion in an aqueous medium without the hydroquinone becoming diffusible.

Suitable hydroquinones with such ballast groups are, for example:

2-n-octadecyl-5-sulfohydroquinone;
2-n-octyl-5-sulfohydroquinone;
2-n-pentadecyl-5-sulfohydroquinone;
2,5-diisooctyl hydroquinone.

The term "short-chain" alkyl radical means that the alkyl radical has 1 to 6 carbon atoms.

1

The amount of black-and-white developing agents used, which should be present in the emulsion layers, can vary widely. However, the amounts should be sufficient to ensure that complete chemical development of the negative latent images takes place. It has proven to be expedient to use the diffusing hydroquinones and pyrocatechols in concentrations of at least mol per mol of silver halide in the corresponding emulsions. If a diffusing 3-pyrazolidone is used, it has been found to be expedient to use at least 1 mole of the 3-pyrazolidone per mole of silver halide. In addition, in the latter case, about ¹ 1/2 moles of the non-diffusing, ballasted hydroquinone are used with the diffusing 3-pyrazolidone.

The black and white developer substances used are at least as strong as silver halide reducing compounds are like color developing agents and are generally stronger Reducing agent. The presence of the color developing agents appears to be the black and white development without the formation of dyes in the negative image areas.

In the silver halide emulsion layers of the invention for carrying out the process The color photographic material used is at least one non-diffusing photographic color coupler, which with the oxidation products of the primary, aromatic Amines existing color developing agents reacts to form a dye. Such couplers are known and generally consist of 5-pyrazolones, phenolic compounds or open-chain ketomethylene compounds. Non-diffusing ones are particularly suitable Couplers which form diffusing dyes upon color development. Such couplers are used when the developed dye image is applied to an image-receiving layer under a Diffusion transfer method is to be transferred. Do not want the developed dye images to appear are transferred to an image receiving layer, non-diffusing couplers are used which are not form diffusing dyes.

Suitable diffusing dye forming couplers can be represented by the following two formulas reproduce:

F-Bi- (K-Ba) _ra

Ba - Bi - (K - L) »

55

Herein means

1. F is a dye residue with a solubilizing acid residue;

2. Bi is a link, consisting of residues such as: an azo residue (- N = N -), an azo residue

-N = N-

- a mercury residue (—Hg—), an oxy residue

406

(—O—), an alkylidene radical, including the groups

R R

i I

^ C- and = C-

wherein R is a hydrogen atom or an alkyl radical with generally 1 to Has 4 carbon atoms, a monothio group (- S -) or a dithio group (- S - S -);

3. K is a coupler radical, such as a 5-pyrazolone coupler radical, a phenolic coupler radical or open-chain ketomethylene coupler radical, with the coupler radical in the coupling position at the link Bi is bound;

4. Ba is a photographically inert organic ballast group of such a molecular size and configuration that the coupler in the photographic material during the treatment with the alkaline Treatment solution does not diffuse;

5. L represents a hydrogen atom or a solubilizing acid group if the color developing agent contains a solubilizing acid group or a solubilizing acid group if the Color developing agent does not contain a solubilizing acid group; and

6. η is an integer from 1 to 2 if Bi is an alkylidene radical, and 1 if Bi is an azo, oxy, monothio, dithio, azoxy or mercury radical.

The solubilizing acid residues of the couplers can consist of such solubilizing residues, when they become part of the coupler or developer residue of a dye, the Dye diffuses in photographic material when treated with an alkaline solution do. Suitable radicals are, for example, carboxylic acid, sulfonic acid, ionizable sulfonamido or radicals substituted by hydroxyl groups, which give the dyes negative charges.

Suitable radicals F of the couplers forming diffusing dyes are, for example, azo, azomethine, Indoaniline, indophenol and anthraquinone residues as well as other known residues which are in the visible Absorb part of the spectrum.

When implementing this coupler with the formula

F-Bi - (K-Ba) _ra

The link Bi is split off with the oxidation products of color developing agents, thereby forming a diffusible acidic dye which image-wise onto a receiving layer can diffuse. A solubilizing acid group in the dye makes it diffusing and causes the dye to be retained on the image-receiving layer. The coupling one Part of coupler K couples with the color developer oxidation product to form a dye, which is not diffusing because it has a ballast group Ba in the non-coupling position. Using this type of diffusing dye forming coupler, the color becomes of the diffusing dye determined by the color of the pre-formed dye residue F, wherein the color of the reaction product of the color developer oxidation product with the coupler residue K has no effect on the color of the diffusing image.

These couplers own the formula

Ba-Bi- (KL) _n

and if they are reacted with oxidized color developing agents, the link Bi 5 is split, whereby a diffusing dye is formed from the color developer oxidation product and the coupling part K of the coupler, which can diffuse imagewise onto a receiving layer. The diffusibility of the dye is brought about by an acidic, solubilizing group which is in the non-coupling position of the coupling part K of the coupler or of the color developing agent. The ballast group of the coupler remains immobile. When using such couplers, the color of the diffusible dye is determined by the color of the reaction product of the color developer oxidation product and the coupler residue K.

If couplers are used in which the coupler radical K consists of a 5-pyrazolone radical, it is It is advantageous to use those couplers which have an AniHno or in the 3-position of the pyrazolone radical have an alkoxy group. If the coupler residue K of the coupler consists of a blue-green one Dye-forming phenolic coupler radical, so it is advantageous to use such radicals as in ortho- or 2-position of the phenolic radical is a fully substituted amido group (for example a group

- CON -R

wherein R consists of an alkyl group or a phenyl group).

If the link Bi is in the couplers of the formula

Ba-Bi- (KL) _n

40

from an azo radical, it is advantageous if the ballast group Ba consists of a phenyl radical with either a hydroxyl group or an amino group, which is in the ortho or 2-position of the phenyl radical is located.

In the method of the invention, it is preferred to use color developing agents which consist of p-phenylenediamine developer compounds. The color developing agents can either in the alkaline developer solution or added to the color photographic material will.

When the color developer is added to the photographic material, it is advantageous to use such forms of the color developer that are stable in emulsions, e.g. B. Schiff bases of primary Amines. Such Schiff bases have, for example, the formula

R15 _ _N = CH - Ri ⁶

60

in which R ¹⁵ denotes an aryl radical, such as, for example, a phenyl radical, which is substituted in the ortho or para position by a hydroxyl or amino group, for example an —OH—, —NH2—, NHR ¹⁷ - or N (R ¹⁷ ) 2- Group in which R ^{17 has} the meaning of a short-chain alkyl radical having 1 to 6 carbon atoms; and R ^{16 is} an aryl radical, such as, for example, a phenyl or naphthyl radical, which can be substituted by an acidic group, such as, for example, a carboxyl, sulfo or lower alkyl group with a hydroxyl group.

Such color developer compounds consisting of Schiff's bases can be prepared, for example, by reacting 2-amino-5-diethylaminotoluene and o-sulfobenzaldehyde. Other suitable Schiff bases are, for example, N-ethyl-N - (ß - hydroxyethyl) -4 - (o - sulfobenzylideneamino) aniline sodium salt; N, N-diethyl-4- (2,4-dihydroxybenzylideneamino) -3-methylaniline and N-ethyl-3-methyl-N- (/ 5-methylsulfonamidoethyl) -4- (2-sulfobenzylideneamino) aniline sodium salt.

The color developing agents can be incorporated in all layers of the photographic material in which the developer compounds after activation with aqueous alkaline Solutions for development are available. It has proven to be useful to use the color developer compounds to be accommodated in layers corresponding to the photosensitive silver halide emulsion layers are adjacent, although the color developers are also in the silver halide emulsion layers can be accommodated by yourself.

The aqueous alkaline solutions used in carrying out the process of the invention represent activating solutions containing a silver halide solvent. Suitable Silver halide solvents are, for example, the ammonium and alkali metal thiosulfates, thiocyanates, Sulfites and also N, N-diethyl-l, 3-propanediamine, triethanolamine, ammonium hydroxide, ammonium sulfate, Ammonium nitrate, ammonium chloride and aminoethanol.

If a diffusion transfer process is carried out, the image receiving layer can consist of a separate Consist of a receiving layer which is brought into contact with the photographic material, or a photographic material in which the image-receiving layer can be used forms an integral part of the photographic material.

If a special image-receiving layer is used, development and transfer either by bathing the exposed photographic material and the pickled image receiving layer or by bathing any of these ingredients in the developer solution before rolling the both components are effected. On the other hand, it is also possible to use a viscous developer solution between the elements, which is then distributed between the two surfaces. In this In case the viscous developer solution can be accommodated in one or more containers, which form an integral part of the photographic material or the image-receiving layer and which can be easily destroyed during development, so that the developing solution is based on the pours material to be developed. Such development methods are, for example, in the United States patents 2543181,2559643,2647049,2647056, 2 661293, 2 698 244, 2 698 798 and 2 774 668.

A color photographic material in which the image receiving layer is an integral part of the material, consists for example of a carrier on which a pickled colloid layer is applied on which the various

709 619/609

1 246

406

11

12th

Emulsion layers are located. If easy solutions F i g. 1 can be developed

Emulsions are used, d. H. for example with the exception that the aqueous alkaline

those made from polyvinyl alcohol or an alkali treatment solution have no color developer added to them

soluble cellulose ether phthalate.

contain agents, or if a dry or 5 The in F i g. The color photographic wet strippable layer shown in Fig. 3 with such a binding material has a plurality of silver halide emulsifiers between the emulsion layers and the layers. A three-color image-receiving layer can be provided from this material and the direct-positive image can be produced. The silver developed emulsion layers are easily separated from the halide emulsion layers of this color photographic image-receiving layer. The io phic material contains color couplers, the color image receiving layer remains the dye image. Forming further substances whose color is complementary to the spekhin, it is also possible for the image-receiving layer to be applied to the outer emulsion layer for the sensitivity of the silver halide layers. are. The material consists of a carrier 30, in this case it is usually advantageous on to expose therethrough a red-sensitive, containing cores by the carrier when the silver halide emulsion layer 15 is applied 31, image-receiving layer is not itself transparent. which further contains a cyan dye. Such photographic materials can be developed into forming couplers and black-and-white dye in the same manner as those containing developing agents. Over the layer 31 there is no integral image receiving layer. there is an intermediate layer 32, which

The image-receiving layers can contain the usual 20 different additives, such as

Have mordants for dyes. Reducing compounds containing suitable pickling ballast groups

medium are, for example, in the USA. patent fertilizers, which a migration of oxidized

Documents 2,882,156 and 2,484,430. Color developing agents can prevent and

In the drawings, in FIGS. 1, 2 and 3 which can also contain filter dyes, such as a

to carry out the method of the invention 25 magenta filter dye, which, for example, the

suitable color photographic materials are shown. Green sensitivity of the red sensitizing color

The in Fig. 1 is intended to compensate for the color photographic substance shown in the layer 31. About material consists of a carrier 10 on which the layer 32 is a green-sensitive, a physical development nuclei, a non-containing cores silver halide emulsion layer diffusible color coupler and a black 30 33, which further material contains a magenta color-white developer containing Silberhalogenidemul- forming coupler and a black and white ion layer 11 is applied. That contains photosensitive developer. Material from FIG. 1 is located above layer 33. 1 may be a positive color in turn, an intermediate layer 34, which are entbild developed when speaking of the intermediate layer is dipped 32 a reducing in an aqueous alkaline solution after exposure, may contain 35 connection with ballasting groups, an aromatic primary Aminofarbentwickler- to prevent the migration of oxidized color developing agent and a silver halide solvent compound, and which further contains one. Contains the layer 11 a may include a diffundie- yellow filter, such as a Governing dye-solubilizing coupler as yellow dye or colloidal silver by Carey, the obtained positive color image on a Bildemp- 40 Lea. A blue-sensitive capture layer is disposed over layer 34 to form a positive color silver halide emulsion layer 35 which is copy transferred. If the layer 11 contains physical nuclei and a yellow color, a coupler which forms a substance-forming coupler during color development and a black-and-white non-diffusing dye, the developer may contain. Schutzdas a photographic material is then applied to a 45 layer 36 to the layer 35, which are brought to the color developer, bleaching bath, comprising a metallic one ultraviolet light absorbing compound is silver oxidizing compound, such as a can contain. The color couplers of layers 31, alkali metal ferricyanide, permanganate, dichromate 33 and 35 can be made from non-diffusing Farbod. Like., Contains to consist of the developed silver in the couplers, including those that convert negative and positive image areas in silver 5 ° of the reaction with oxidized color developer connector halide, whereupon the material is fertilized by non-diffusing dyes as well as treatment with a Bath containing a silver-diffusing dyes form. Are Farbhalogenidlösungsmittel such as an alkali used couplers which diffusing dyes metal thiosulphate, a thiocyanate, etc., forming the purpose, so that is, the layers 30 to 36 comprising removal of the silver halide obtained fixed 55 color photographic material together with a will. Image receiving layer 39 used, which on a

In Fig. 2 is a color photographic material carrier 40 is seated. Layer 39 consists of one illustrated in accordance with the invention which contains a color mordant layer that contains the light developing compound as it develops. The material consists of sensitive color photographic material consisting of a support 20 on which a silver halide 60- formed color image is received. Between the light emulsion layer 21 is applied, the developer-sensitive material and the image-receiving layer, a color coupler and a black, a breakable container 38 is arranged, which contains white developer substance. On the layer 21 of developer liquid 37, for example in the form of a color developer layer 23 , which contains a viscous solution, is applied. This developer liquid, a primary, aromatic amino color developer, contains a color developer if the color developer compound in a hydrophilic binder does not stop in the color photographic material itself. The in Fig. 2 and a silver halide solvent. Material can be used in the same way as that in After exposure of the color photographic

1

Material in a camera, the frangible container 38 is broken by feeding the material into two rollers in a camera or other device, the processing liquid pouring uniformly over the color photographic light-sensitive material. The treatment liquid penetrates the layers 36 to 31, the latent image developing to form a silver image without any color development occurring in the light-sensitive layers 31, 33 and 35 by chemical development. This is followed by physical color development in the unexposed and undeveloped areas that correspond to the positive image areas in the photosensitive layers 31, 33 and 35 , diffusing dyes being formed by reaction of the color couplers in the photosensitive layers with the oxidized color developer compounds, whereupon the in The dyes formed in the positive image areas diffuse image-wise onto the pickled image-receiving layer 39 and form a positive, colored transfer image there.

The following examples are intended to further illustrate the process of the invention.

example 1

A color photographic material of the type shown in FIG. 3 with the layers 30 to 36 is produced by coating a cellulose acetate film carrier provided with a base layer in the following way:

1. Red-sensitive layer, accordingly
layer 31 of FIG. 3

35

The layer consists of a developable, negative gelatin-silver bromoiodide emulsion with 98% bromide and 2% iodide, which is sensitized to red light and contains 0.15 mg colloidal silver, 250 mg gelatin, 90 mg l ^{per 0.09 m 2 of support surface} -Hydroxy-4- (3-n-octadecylcarbamylphenylthio) -N-ethyl-3 ', 5'-dicarboxy-2-naphthanilide, 63 mg of 2- [N, N-bis - (^ - hydroxyethyl) aminomethyl] -5 - methylhydroquinone metho - methanesulfonate and 45 mg silver in the form of silver halide.

2nd intermediate layer, corresponding to layer 32 in FIG. 3

This layer consists of a gelatin layer with per 0.09 m ^{2 of support} surface, 100 g gelatin, 3 mg 2-n-octadecyl-5-sulfohydroquinone, sodium salt and 22 mg l-hydroxy-4 '- (4-tert.-butylphenoxy) -4-phenylazo-2-naphthanilide.

55

3. Green-sensitive layer, accordingly
layer 33 of FIG. 3

This layer consists of a developable, negative gelatine - silver bromoiodide emulsion with 98% bromide and 2% iodide, which is sensitized to green light and contains per 0.09 m ^{2 of support area} : 400 mg gelatine, 90 mg l-phenyl-3- (3, 5-disulfobenzamido) -4 - (2-hydroxy-4-pentadecylphenylazo) -5-pyrazolone, 0.24 mg colloidal silver, 126 mg 2- [N, N-bis (/ S-hydroxyethyl) aminomethyl] -5 -methylhydroquinone metho -methane sulfonate and 45 mg silver in the form of the silver halide.

406

4. Intermediate layer, corresponding to layer 34 in FIG. 3

This layer consists of a gelatin layer with per 0.09 m ^{2 of support} surface, 100 mg gelatin, 30 mg 2-n-octadecyl-5-sulfohydroquinone, sodium salt and 60 mg yellow Carey Lea silver.

5. Blue-sensitive layer, accordingly
layer 35 of FIG. 3

This layer consists of a negative ausentwickelbaren gelatin silver bromoiodide emulsion with 98% bromide and 2% iodide with its own sensitivity to blue light with pto 0.09 m ² support surface, 250 mg of gelatin, 150 mg of a-benzoyl Ot - (3 - η - octadecylcarbamylphenyl thio) -3,5- dicarboxyacetanilide, disodium salt, 0.15 mg colloidal silver, 31.5 mg 2- [N, N-bis - (^ - hydroxyethyl) aminomethyl] -5 - methylhydroquinone - metho - methanesulfonate and 45 mg of silver in the form of silver halide.

6. Protective layer, corresponding to layer 36
the F i g. 3

This layer consists of a gelatin layer with 75 mg gelatin per 0.09 m ^{2 support} surface.

The photographic film is then in a sensitometer through a multicolored, transparent Original exposed. The exposed color film is then placed in an aqueous color developer at 24 ° C. for 1 minute immersed and then for 4 minutes at 24 ° C on a recording material with a stained image receiving layer pressed. The recording material is then removed from the film deducted. The material consists of a cellulose acetate carrier with a white pigment and a pickled image-receiving layer made of gelatin with N, N-dimethyl-N- (jS-hydroxyethyl) -N- (j'-stearamidopropyl) ammonium dihydrogen phosphate as a pickling agent. The color developer used has the following composition:

4-amino-N-ethyl-N- (j9-hydroxy-

ethyl) aniline 7.5 g

Sodium metaborate, octahydrate ... 10.0 g

Sodium sulfite (anhydrous) 1.0 g

Ascorbic acid 0.1 g

Potassium bromide ....; 4.0 g

Potassium iodide 0.04 g

Aminoethanol 5.0 ml

N, N-diethyl-1,3-propanediamine .... 5.0 ml

Benzyl alcohol 5.0 ml

Sodium hydroxide 2.75 g

made up to 11 with water.

A color image with saturated colors and good color separation is transferred to the image-receiving layer. The transferred cyan image has a Dmin-WQTt of 0.2 and a D _m0 X value of 1.2. The transferred yellow image has a Dmin value of 0.2 and a D _max value of 1.4. _{The transmitted purple image} has an i) _m i _ra value of 0.26 and a D mff ^ value of 1.82.

Equally good results are obtained using the following diffusing black-and-white developers in equal molar proportions in the red, green and blue sensitive layers instead of 2- [N, N-bis (^ - hydroxyethyl) aminomethyl] -5-methylhydroquinone methomethanesulfonate be used:

1. 2,5-bis- (N, N-dimethylaminomethyl) -hydroquinone-bis- (metho-p-toluenesulfonate),

2. 2,5-bis (N-morpholinomethyl) hydroquinone bis (metho-p-toluenesulfonate),

3. 4- [N, N-bis (/ 9-hydroxyethyl) aminomethyl] -5-methylcatechol sulfuric acid ester and

4. 4-N, N-bis (/ 3-hydroxyethyl) aminomethyl-5-methylpyrocatechol carboxylic acid ester ethane sulfonate.

Furthermore, equally good results were obtained when instead of 2- [N, N-bis (ß-hydroxyethyl) - aminomethyl] - 5 - methylhydroquinone - methomethanesulfonate a combination of I-phenyl-3-pyrazolidone and 2-n- Octadecyl-5-sulfohydroquinone, sodium salt can be used as black-and-white developer in each of the light-sensitive silver halide emulsion layers in amounts of 80 and 18 mg per 0.09 m ^{2 of support area.}

Example 2

A series of color films can be produced with a single emulsion layer as shown in FIG. 1, prepared by coated with a base layer cellulose acetate film support with various developable, negative gelatin silver halide emulsions with 0.15 mg of colloidal silver as physical development cores, 300 mg of gelatin and 45 mg of silver in the form of silver halide per 0.09 m ^{2 of support} area . The emulsions are not sensitized, but have an inherent sensitivity to blue light. Various black-and-white developer substances and auxiliary black-and-white developers containing ballast groups can be added to the various emulsion batches. The composition of the individual colored coatings is shown in the following table:

Film no. Coupler
mg / U »uy Ixi ⁱⁱ Black and white developer
mg / 0.09 m ² Black and white auxiliary developer
mg / 0.09 m ² Emulsion type 1 I, 90 0 0 AgClBr (2/98) 2 I, 90 0 a, 18 AgClBr (2/98) 3 I, 90 A, 100 a, 18 AgClBr (2/98) 4th I, 90 A, 100 0 AgClBr (2/98) 5 I, 90 B, 88 0 AgClBr (2/98) 6th I ₅ 90 C, 65 0 AgClBr (2/98) 7th I, 90 D, 100 0 'AgBrI (98/2) 8th I, 90 D, 100 a, 18 AgBrI (98/2) 9 I, 90 D, 200 0 AgBrI '(98/2) 10 I, 90 E, 80 a, 18 AgClBr (2/98) 11 I, 90 F, 80 a, 18 AgClBr (2/98) 12th I, 90 G, 80 a, 18 AgClBr (2/98) 13th I, 90 H, 80 a, 18 AgClBr (2/98) 14th I, 90 I, 80 a, 18 AgClBr (2/98) 15th I, 90 J, 80 a, 18 AgClBr (2/98) 16 II, 90 A, 150 a, 24 AgClBr (2/98) 17th II, 90 A, 150 a, 30 AgClBr (2/98) 18th II, 90 A, 200 a, 18 AgClBr (2/98) 19 * I, 90 A, 100 0 AgClBr (2/98) 20 * I, 90 D, 100 0 AgClBr (2/98)

* 0.36 mg of zinc sulfide per 0.09 m ^{2 of support} surface is used as physical development nuclei instead of colloidal silver.

In the table means:

I = l-hydroxy-4- (3-n-octadecylcarbamyl-

phenylthio) -N-ethyl-3 ', 5'-carboxy-2-naphthanilide;

II = l-phenyl-3- (3,5-disulfobenzamido) -

4- (2-hydroxy-4-pentadecylphenylazo) -

5-pyrazolone;

A = 2,5-bis-N, N-bis (jS-hydroxyethyl) -aminomethyl-hydroquinone;

B = 2- (N, N-dimethylammomethyl) -5-methylhydroquinone;

C = 2-pST, N-bis (/ 3-hydroxyethyl) aminomethyl] -5-methylhydroquinone;

D = 2,5-bis- (N, N-dimethylaminomethyl) -

hydroquinone bis (metho-p-toluenesutfonate);

E = 1-phenyl-3-pyrazolidone;

F = 1-phenyl-4-methyl-3-pyrazolidone;

G = 1-phenyl-4,4-dimethyl-3-pyrazolidone;

H = 1-phenyl-2-acetyl-3-pyrazolidone;

I = 1-phenyl-3-acetoxy-4-methyl-pyrazolidone
and

J = 1-phenyl-2-chloroacetyl-3-pyrazolidone.

The black and white auxiliary developer substance "a" consists of the sodium salt of 2-n-octadecyl-5-sulfohydroquinone. The films described can be saved in

17 18

A sensitometer can be brought through a neutral density. The recording material with

Step tray to be exposed. The exposed films of the image-receiving layer are then removed from

are then developed by peeling off 30 seconds of film.

The long at 24 ° C in an aqueous color developer The activator solution has the following submerged and then with a pickled 5 settlement:

Absorption material as described in the example Sodium carbonate (anhydrous) 20 g

Sodium thiosulphate 4 ε brought into contact for 3 minutes at 24 C m

will. Then the sodium sulfite (anhydrous) '.' ::. '.':. '.' ::: 2g

and carrier consisting of image receiving material of kahumthiocyanate 3 g

peeled off the feet. The color to be used io ^ _{water liters to füUt}

developer has the following composition: ^b

... j- A positive is placed on the image receiving layer

^ ίίΓ "Transfer blue-green Büd. Corresponding results

a ι m · ■■■ "£ nisse are obtained when a color photographic

Sodium carbonate (anhydrous) 20 g * · ι j * · j l · j j- j ■ l *

_λΤ . ,. _lf ^ν · '. ⁶ is material is used in which the color scheme

mtrium miosuitat. . · .... 4g winder · containing layer (layer no. 2) under-

Natrmrnsulfit (anhydrous), 2 g _{of the} ^ J ^ _{eights nndlichen chicht ^(Schich; t # 1}.}

Kahumthiocyanat 3 g is _arranged t. .

filled up to the liter with water. ^ö

Of all films except Films I and 2, 20 Example 4
reverse color images are obtained. Films 1 will contain multiple films with a single and 2 no diffusing black layer with the one shown in FIG. 1 structure shown in white developer. When using films, produced, the individual layers corresponding to films 10 and 15, which, however, do not contain a non-diffusing color coupler, non-diffusing black-and-white auxiliary developer, 25 which deals with the oxidation products of the color separators only for the 3- Pyrazolidone developers contain, developing compounds to a non-diffusing one, no reversal images are obtained. Furthermore, the dye converts. No reversal images can then be obtained as carrier materials, cellulose acetate films are used which are made with from hydroquinone or N-methyl-p-aminophenol wound gelatin silver chlorobromide emulsions as black and white developer substance in the 30 with 2% chloride and 98% bromide from negative emulsion layer can be used. Type to be coated. The emulsion layers ent . . 1 hold 300 mg of gelatin per 0.09 m ^{2 of} _{support surface, Example 3 015 mg of} colloidal silver, 70 mg of 5- [a- (2,4-di-t.-amyl-

A color film of the in FIG. 2 shown structure phenoxy) - butyramido] - 2 - butyramidophenol as well as

is prepared by putting on a base 35 70 mg di-n-butyl phthalate in which the color coupler

layered cellulose acetate film carrier is subsequently dissolved, and finally 45 mg of silver in the form of the

the following layers are applied to each other: silver halide and various black and white

_<T ., »· J, -, ο, ·, _AA 1 j developer in various amounts. The emul

1. L ₁ sensitive layer, corresponding _{ions are unsensitized but have a}

Layer 21 of the F 1 g. 2, _4Q intrinsic sensitivity to blue light. the

The layer consists of a developable, black and white developer substances consist of

negative gelatin silver chlorobromide emulsion with 2,5-bis [N, N-bis - (/ S-hydroxyethyl) aminomethyl] -

2% chloride and 98% bromide and hydroquinone per 0.09 m ² , applied in amounts of 100 mg

Support area 0.15 mg colloidal silver, 300 mg per 0.09 m ^{2 support area} as well. 2- [N, N-Bis - (/ S-hy-

Gelatin, 90 mg 1 - hydroxy - 4 - (3 - η - octadecyl- 45 hydroxyethyl) - aminomethyl] - 5 - methylhydroquinone-

carbamylphenylthio) - N - ethyl - 3 ', 5' - dicarboxy methomethanesulfonate in amounts of 50, 84 and

2-naphthanide, 100 mg 2,5-bis- [N, N-bis- (ß-hy- 100 mg per 0.09 m ^{2 support area} . The produced

hydroxyethyl) aminomethyl] hydroquinone and 45 mg of films are then replaced by a neutral

Silver in the form of silver halide. The step wedge emulsion exposed in a sensitometer and

is unsensitized, but has an inherent sensitivity- 50 then for 4 minutes at 22 ° C in a tank

openness to blue light. - developed, which contains a color developer. the

"^ ₁ . ,,,. ,, jo, -, -, -. Development is activated by a 1 minute

2. Color developer layer, corresponding to layer 23 _{, dip the films} . _{in a 5} % acetic acid _{stop bath}

the t 1 g. 2. interrupted what the films. For 3 minutes in The layer contains 55 ^{water per 0.09 m 2 of support area,} washed for 3 minutes, bleached for 3 minutes, again 300 mg of gelatine and a sulfur dioxide salt which are washed in water for 30 seconds and color developer compound 4- {3- [(4 - tert. - Amyl fixed and then washed again and ge x - sulfophenoxy) - benzamido] - benzylidehamino} - dried. Positive, blue-green N-ethyl - (^ - hydroxyethyl) -aniline, sodium salt are obtained in one picture. The color developer used is 28 mg of sulfur dioxide and 140 mg of color 60 and has the following composition:
developer compound per 0.09 m ^{2 support area} .
The two-layer color film can be 4-amino-N-ethyl-N - ((S-hydroxy-

then in a sensitometer through a new (ethyl) aniline 5.0 g

tral density step tablet are exposed and sodium sulfite (anhydrous) ......... 2.0 g

then for 30 seconds at 22 ⁰ C in a 65 wäß- sodium metaborate, octahydrate 20.0 g

dipped alkaline activator solution and final potassium thiocyanate 4.0 g

borrowed for 3 minutes at 22 ⁰ C with an image recording potassium bromide 4.0 g

material as described in Example 1, in contact ascorbic acid 0.2 g

1

Benzyl alcohol °. 10.0 cm ³

N, N-diethyl-1,3-propanediamine 10.0 cm ³

Sodium hydroxide. 2.75 g

filled up to the liter with water.

The bleaching bath to be used has the following composition:

Sodium hexametaphosphate 1.0 g

Potassium ferricyanide 100.0 g

Sodium bromide ... 34.4 g

filled up to the liter with water.

The fixer has the following composition:

Sodium thiosulfate 240.0 g

Sodium sulfite (anhydrous) 15.0 g

Acetic acid (28%) 48.0 cm ³

Boric acid, 7.5 g

Aluminum chewing sulfate 15.0 g

filled up to the liter with water.

Example 5

Several color films of the in FIG. 1, the black-and-white developer is dissolved in a high-boiling solvent and droplets of this solution are finely dispersed in the emulsion. The emulsions are coated on basecoated cellulose acetate film backing. Developable gelatine - silver chlorobromide emulsions with 2% chloride and 98% bromide are used, which ^{contain per 0.09m 2} support surface: 350 mg gelatine, 0.15 mg colloidal silver, 90 mg l-hydroxy-4- (3-noctadecylcarbamylphenylthio) -N- ethyl 3 ', 5' - dicarboxy-2-naphthanilide, 45 mg of silver in the form of the silver halide and 54 mg of 2,5-bis- (N, N-dimethylaminomethyl) -hydroquinone, dissolved in a high-boiling, organic solvent in a ratio from 1 part by weight of black and white developer substance to 3 parts by weight of solvent. The emulsions were unsensitized, but had an inherent sensitivity to blue light. The following high-boiling organic solvents are used to dissolve the couplers: di-n-octyl phthalate, tetrahydrofurfuryl phthalate and N-amyl succinimide. The films are exposed in a sensitometer through a neutral density step tablet, immersed for 30 seconds at 22 ° C. in the color developer described in example 2 and then brought into contact with the image-receiving layer of the image-receiving material described in example 1 at 22 ° C. for 3 minutes. After the image-receiving material has been stripped off, blue-green positive images of excellent quality are obtained in the image-receiving layer.

The color developer compound used in the color photographic material of Example 3 is produced according to the following process:

Stage 1: 2- (m-nitrophenyl) -l, 3-dioxolane

A mixture consisting of 680 g of m-nitrobenzaldehyde, 307 g of ethylene glycol and 1.2 ml of 85% strength Phosphoric acid in 600 ml of xylene is refluxed for 4 hours, with 64 ml of water from the Mixture are distilled off. The xylene is then distilled off in vacuo. The residue

406

is in a mixture consisting of 1200 ml of ethyl alcohol, 5 g of sodium carbonate and 50 ml of water, given. The clear solution obtained is cooled to 0 ° C. with stirring, whereupon Sich. 818 g of 2- (m-nitrophenyl) -1,3-dioxolane deposit.

Stage 2: 2- (m-aminophenyl) -l, 3-dioxolane

A solution of the product from stage 1 in 150 ml of ethyl acetate is shaken for 1 hour in a Parr hydrogenation device in the presence of Raney nickel at a hydrogen pressure of 3.15 kg / cm ² . The mixture is then filtered and the clear ethyl acetate solution is concentrated in vacuo. The remaining liquid is distilled. 22.5 g, corresponding to a yield of 76%, of 2- (m-aminophenyl) -l, 3-dioxolane with a boiling point of 163 to 167 ° C. at a pressure of 5 to 6 mm Hg are obtained.

Step 3: 3- [3- (4-t.-Amyl-X-chlorosulfonylphenoxy) -benzamidoj-benzaldehyde

To a solution consisting of 20 g of anhydrous sodium acetate and 20 g of that obtained in step 2 Intermediate product in 200 ml of acetic acid, 50 g of 3 - (4 -1. - Amyl -X-chlorosulfonylphenoxy) - benzoyl chloride given with stirring at a temperature of 27 ° C. The reaction mixture is 30 minutes stirred for a long time, after which the mixture is diluted with 450 ml of water. It separates an oily one Precipitate, which is separated off. The oily precipitate crystallizes out on standing and becomes recrystallized from 350 ml of acetonitrile. There are 42 g of the desired product with a melting point obtained from 188 to 190 ° C.

Step 4: 3- [3- (4-t.-Amyl-X-sulphophenoxy) -benzamidoj-benzaldehyde, sodium salt

A solution of 159 g of the intermediate obtained in step 3 in 2 l of methyl alcohol is refluxed for 2 hours, after which the solution is concentrated in vacuo. The solid residue is then dissolved in a solution of 14 g of sodium hydroxide in 200 ml of water. A saturated sodium chloride solution is added to this solution. The solid mass that separates out is separated off and recrystallized from a mixture consisting of ethyl ether and absolute ethyl alcohol. 83 g of the desired product, which has a melting point of 244 to 245 ^° C., are obtained.

Manufacture of the developer salt

To a solution of 105 g of the intermediate product obtained in step 4 in a mixture of -60 ml. Water and 400 ml of ethyl alcohol, a solution consisting of 46 g of 4-amino-N-ethyl-N - (jS -hydroxyethyl ) - aniline sulfate in 160 ml of water and 33 g of sodium carbonate in 260 ml of water, added with stirring. The solution obtained is stirred for 1 hour at room temperature, after which it is diluted with 500 ml of absolute ethyl alcohol. It is then filtered and the clear filtrate concentrated in vacuo. The dark red residue obtained is then recrystallized from absolute alcohol, 90 g of the desired product being obtained. To a solution of

1 g of the product obtained in 5 ml of ethanol

2 moles of sulfur dioxide gas were added. The solution obtained is incorporated into gelatin and without

Claims (9)

1 Isolation of the resulting salt coated onto the photographic element. The diffusing hydroquinones and pyrocatechols with amino-substituted, short-chain alkyl groups to be used as black-and-white developer substances can be prepared in a known manner. For example, they can be produced by the Mannich reaction from a hydroquinone or a pyrocatechol, formaldehyde and an amine by alkylation. Such methods are described in Photographic Science and Engineering, Vol. 4, No. 2, March-April 1960, pp. 101-109; Hellmann and Opitz, a-aminoalkylation, Verlag Chemie GmbH., Weinheim / Bergstrasse, 1960; Reichert, The Mannich reaction, Springer-Verlag OHG, Berlin, Göttingen and Heidelberg. Patent claims: 1. Color photographic direct positive process in which a color photographic material, which has at least one photosensitive silver halide emulsion layer which is not diffusing color couplers that interact with the oxidation products of primary aromatic Amino developer compounds react to form dyes, and a black and white developer substance contains, is exposed image-wise and then developed, characterized in that a color photographic -Material is used that consists of a non-diffusing color coupler and a black-and-white developer substance from a diffusible hydroquinone with at least one amino-substituted, short-chain Alkyl radical or a diffusible pyrocatechol with at least one amino-substituted, short-chain alkyl radical or the combination of a diffusible 3-pyrazolidone and a hydroquinone having a ballast group preventing diffusion, physical development nuclei and that the photographic material after imagewise exposure in the presence of a primary aromatic Amine color developing agent is treated with an aqueous alkaline solution containing the contains a silver halide solvent. 2. The method according to claim 1, characterized in that the primary aromatic amino color developer compound is added to the aqueous alkaline solution. 3. The method according to claim 1, characterized in that the primary aromatic amino color developer compound is disposed in a layer of the photographic material. . 4. The method according to claims 1 to 3, characterized in that a photographic material is used which has a plurality of light-sensitive Having silver halide emulsion layers containing color couplers which the spectral sensitivity of the layers form complementary dyes. • 5. The method according to claims 1 to 4, characterized in that the diffusible from Dyes existing dye image is transferred to an image-receiving layer. 6. The method according to claims 1 to 4, characterized in that after the ent- winding of a dye image consisting of non-diffusible dyes that bleaches the silver and is fixed. 7. A method according to claim 4, characterized ge _r indicates that a color photographic material is used, the red-, green- and blue-sensitive silver halide emulsion having a cyan, magenta and yellow dye-forming, containing non-diffusing couplers by reaction with the oxidation products of the amino developer compounds form diffusing dyes and have the following formulas: F-Bi- (K-Ba) _7l or Ba-Bi- (KL) _n where means F a dye residue absorbing in the visible range of the spectrum with a solubilizing agent Acid residue; Bi a link, consisting of an azo, oxy, alkylidene, monothio, dithio, azooxy or mercury residue; K is a coupler radical of a 5-pyrazolone, phenolic, or open-chain ketomethylene coupler, which are bound to the link Bi in the coupler position; Ba is a photographically inert organic ballast group; L represents a hydrogen atom or a solubilizing acid group, if the color developing agent contains a solubilizing acid group, or a solubilizing acid group, if the color developing agent does not contain a solubilizing acid group; η is a number from 1 to 2 if Bi is an alkylidene radical, and 1 if Bi is an azo, oxy, monothio, dithio, azoxy or mercury radical. 8. The method according to claims 1 to 7, characterized in that a color photograph " phical material is used, which is a compound of the black and white developing agent contains the following formula: OR ² OR ³ wherein R denotes an amino-substituted, short-chain aryl radical; R ^{1 is} an amino-substituted, short-chain alkyl radical, a hydrogen atom, a short-chain alkyl radical or a short-chain alkoxy radical, and R ² and R ^{3 are} hydrogen atoms or masking carbonyl radicals which are split off under alkaline conditions. 9. The method according to claims 1 to 7, characterized in that a color photographic Material used as a