DE1282456B - Photographic diffusion process for the production of positive color images - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY Int. Cl .:

GERMAN

PATENT OFFICE

EDITORIAL

G03c

■ German class: 57 b -5/54

Number: 1282456

File number: P 12 82 456.5-51 (E 27782)

Filing date: September 16, 1964

Open date: November 7, 1968

• The invention relates to a photographic diffusion process for producing positive color images using a color photographic material with a support, optionally with one on the emulsion side of the photographic material provided hydrophilic colloid layer, at least one hydrophilic silver halide emulsion layer preferably gelatin as a binder, which forms latent inner grain images, and at least one does not diffusing color coupler that diffuses dyes with oxidized aromatic, primary amines forms, imagewise exposed, in the presence of a nucleating agent with an alkaline developer solution is developed and in which the or those diffused to the surface of the material during the development Dyes are transferred to an image-receiving sheet. It is known to have positive color images to produce photographic diffusion processes. Such photographic diffusion processes are in British Patents 840,731 and 904,364. In this process, a photographic Recording material with preferably direct-positive silver halide emulsions used, which form internal latent grain images as described in U.S. Patent 2,592,250. That Photographic recording material contains non-diffusing color couplers which act upon coupling diffusing with oxidized primary aromatic amines as they occur in the development process Form dyes. The exposed recording material is developed in an alkaline Developer made and takes place in the unexposed image parts of the emulsion layers. the The oxidized primary aromatic amines formed are in this part of the picture with the color couplers um, and form a positive dye image which then diffuses onto an image-receiving sheet.

It is also known to facilitate the reverse effect that occurs with silver halide emulsions, which provide latent internal grain images is obtained, in addition hydrazines, such as those in the United States patents 2,563,785 and 2,588,982 to be used as nucleating agents.

The disadvantage of using these hydrazines as nucleating agents is that they are unstable and cause skin allergies can evoke. The developer solutions used for color development are also unstable contained primary aromatic amines, which can also cause skin allergies.

As a result of the instability of the known hydrazine nucleating agents and the primary aromatic amines used as color developers, color density photographic diffusion processes can be used
Production of positive color images

Applicant:

Eastman Kodak Company,

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

Representative:

Dr.-Ing. W. Wolff, H. Bartels

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

8000 Munich 22, Thierschstr. 8th

Named as inventor:
Wilho Mathias Salminen,
Rochester, NY (V. St. A.)

Claimed priority:
V. St. v. America September 20, 1963
(310424)

Losses in those obtained on the image receiving sheets Images occur.

The object of the invention is, in a photographic diffusion process for the production of positive color images with thin silver halide emulsion layers high color densities through the use of more stable, but at the same time non-allergic Obtain nucleating agents.

Thin layers are required to reduce image transfer time. On the other hand must the emulsion layers are of sufficient thickness to accommodate sufficient color couplers to be able to form high color density transfer images.

The invention relates to a photographic diffusion process for manufacture of positive color images, in which a color photographic material with a support, optionally with a hydrophilic one provided on the emulsion side of the photographic material Silver halide layer, at least one hydrophilic silver halide emulsion layer, preferably with gelatin as a binder, which forms latent internal grain images, and at least one non-diffusing

809 630/937

3 4

Color coupler, which with oxidized aromatic, pri-.

mary amines forms diffusing dyes, HatwicMer ΰ

imagewise exposed, in the presence of a nucleating agent N-methyl-p-aminophenol sulfate 2.0 g

Sodium sulfite is developed with an alkaline developer solution, 90.0 g dehydrated

and in which the one or more hydroquinone 8.0 g during development

Coloring sodium carbonate, monobydrate 52 * 5 g diffused onto the surface of the material

substances transferred to an image receiving sheet, potassium bromide 5.0 g

and is characterized in that the dye sodium thiosulfate 10.0 g

development with an aminohexose _{reductone or with water Züm L} ; _te ^ _padded .

Anhydroammohexose reductone as a nucleating agent through io
whose amino radical has the formula

That used in the method of the invention

R ² photographic material has the

I usual construction. For the production of the silver halide

Ri - N - 15 emulsion for that to be processed according to the invention

A wide variety of protective colloids can be used as the material

has, wherein R ¹ and R ^{2 are the} same as alkyl groups or binders such as gelatin, koHodial.es albumin, preferably 1 to 8 carbon atoms or atoms of cellulose derivatives, synthetic resins ad. The like, yer or atomic groups, which are used together with the, whereby gelatin is preferred, amino nitrogen atom and optionally a wide- «ο Pie silver halide emulsions can. verren heteroatom, preferably nitrogen or acid contain the most diverse known additives, such as. B. material atom, a five- or six-membered, z. B. gelatin hardeners, gelatin plasticizers, impaired, heterocyclic ring form, are, layering aids, chemical and optical sensi-

The photographic diffusion process, sub-bilisers, etc.

accordingly differs from corresponding known »5 The emulsions can be on the most varied Process arranged through the use of a new and conventional photographic support as has been shown to be surprisingly effective germination.

bildners. The in which according to the method of the invention too

The photographic processing material suitable for carrying out the process contains silver-color couplers which contain ballast groups and are halide emulsions which are familiar with silver halide grains. They diffuse in the silver halide emulsions, which are produced to a considerable extent and do not have sion layers. In the development with arovorzugsweise predominantly in the interior of the matic, primary amines (color developer for the relevant grain are sensitive. The after silver halide such as, for example, p-phenylenediamine) forming method of the invention, processable recording 35 they diffusible in a known manner dyes ,
The material can be silver halides, such as silver chloride, which are used as nucleating agents in the process of the invention

Silver bromide, silver bromide iodide, silver chloride iodide, used aminohexose reductones and anhydroaminO 'silver chloride bromide iodide, etc. Emulsions, hexose reductones are derived from sugars, especially those that form latent inner grain images, are z. B. in d-glucose, although other reducing US Pat. No. 2,592,250 and in the book 40 hexoses are suitable "such. B, d-galactose, d-man "by Glafkides," Photographic Chemistry ", vol. 1, nose, d-fructose, 1-sorbose, etc.
Pp. 31/32, Fountain Press, London. Characteristic for such emulsions is that they, if reductones consists in the sugar in practically they are examined according to the normal photographic test anhydrous medium with an aliphatic medium or by taking a sample of the 45 cyclic secondary Amine in the presence of an emulsion on a transparent support on a suitable acid, such as, for example, phosphoric acid, boric acid, and the photographic acetic acid, succinic acid or the like thus obtained, as a catalyst material of a light intensity scale with a solid for formation of the aminohexose reductone exposed for a given time of 1 · 10 ~ ^e to 1 second, heat, whereby 3 molecules of water are split off. 5 minutes in a 0.3% potassium ferricyanide contained- 5 ° In order to get bleached from the aminohexose reductones to anhydrode solution and about 5 minutes in about aminohexose reductones, the 18 ° C in the developer B given below are ent-hydrochloride of the aminohexose reductones in It is developed to show a sensitivity, measured in an entity of strong acids such as sulfuric acid, vinegar 'density of 0.1 above fog, which is greater than acid anhydride, zinc chloride and the like, heated further until than the sensitivity of a same sample, which in 55 still has a fourth molecule of water split off.
exposed in the same way and 6 minutes at 20 ⁰ C As suitable aminohexose reductones and anhydrous

has been developed in the following developer A. aminohexose reductones have been shown to:

Developer A ^ dimethylaminohexose reductone,

N-methyl-p-aminopheno-sulfate 0.31 g diallylaminohexose reductone,

Krochinlfn ' ^dehydrated % q ^g di-n-butylaminohexose reductone,

Sodium Sibonate ':.''.'.'.'.'.'.'.'.'.'.'.'.'.'. IS ,? I di-n-hexylaminohexose reductone,

Potassium bromide 0.86 g ₆ - morpho-hexose reductone,

Citric acid 0.68 g piperazinohexose reductone,

Potassium metabisulfite 1.5 g pyrrolinohexose reductone,

Filled up to the liter with water. Piperidinohexose reductone ,.

Piperidino-di- (hexose reductone),

AnhydrodimethylaminohexQseredukton,

Anhydrodiallylaminohexose reductone,

Anhydrodi-n-hexylaminohexose reductone,

Anhydromorpholinohexose reductone,

Anhydropiperazinohexose reductone,

Anhydropyrrolinohexose reductone and

Anhydropiperidinohexose reductone.

According to one embodiment of the invention, the aminohexose reductone or the anhydroaminohexose reductone is used Piperidinohexose reductone, diallylaminohexose reductone, Piperazinohexose reductone, morpho-jinohexose reductone, dimethylaminohexose reductone or anhydropiperidinohexose reductone is used.

The nucleating agents described can either be in the developer solution, in the recording material or can be used in the image receiving sheet. The amount of aminohexose reductone to be used or Anhydroaminohexose reductone can be very different. When the compounds used in the developer it preferably contains about 0.1 to 10 g / l. The compounds in photosensitive Silver halide emulsion layers or used in layers or receiving layers adjoining them, expediently contain them about 1 to 100 mg of the compounds, based on 1 mol of silver halide in the emulsion layers of the used photographic material. The layers in which the nucleating agents of the invention are applied represent hydrophilic colloid layers.

According to a further embodiment of the invention, the aminohexose reductone is used in the alkaline developer solution added in an amount between 0.1 and 10 g per liter of solution.

According to a further embodiment of the invention, the aminohexose reductone or the anhydroaminohexose reductone is used in the hydrophilic one provided on the emulsion side of the photographic material Colloid layer, preferably in a gelatin layer, in a concentration of 1 to 100 mg on 1 mole of silver halide, used in the emulsion layers.

The development takes place in a manner known per se with aqueous alkaline solutions in the presence an aromatic, primary amine, p-phenylenediamine developers being particularly suitable. The amine can either be an aqueous-alkaline mixture which is applied during development on the photosensitive material is applied, added or incorporated into the recording material.

The image-receiving sheet can either consist of a special sheet that is pressed onto the photosensitive sheet Material is brought into contact, exist or one with the light-sensitive material Form unity.

The image-receiving sheets can contain the known mordants customary for acidic dyes.

The photographic recording materials to be developed according to the process of the invention preferably consist of at least three emulsion layers which are applied to the selected support and which are superposed in the usual manner and which are sensitive to different regions of the visible spectrum. A filter layer of colloidal silver is usually provided between the blue- and green-sensitive emulsion layers. The red-, green- and blue-light-sensitive silver halide layers contain adjacent to the silver halide, that is, either in the emulsion itself or in adjacent, special layers, blue-green, magenta or yellow dye-forming color couplers, so that dyes are produced during color development, the color of which corresponds to the color sensitivity values of the corresponding emulsions is essentially complementary. Such photographic recording materials can also have other intermediate or sublayers.
The invention achieves that, despite the use of thin silver halide emulsion layers, high color densities are obtained in the positive color images produced on the image receiving sheets.
Furthermore, by adding the reductones, a

ao stabilization of those used as color developers primary aromatic amines.

example 1

A multilayer photographic material suitable for multicolor transfer images was prepared by successively laying the following layers on a cellulose acetate support were applied:

1. A red sensitive layer made as follows:

To 1 mole of a liquid, direct positive silver bromide iodide emulsion, which had been red-sensitized became 108 g of the cyan coupler 1-Oxy-4 - (3 - octadecylcarbamylphenylthio) - N - ethyl-3 ', 5'-dicarboxy-2-naphthanilide in 2500 ml of water and so much gelatin that a total of 139 g of it accounted for 1 mol of silver halide. The mixture was applied to the substrate in such a way that on 0.09 square meters of substrate surface 150 mg of silver, 193 mg of gelatine and 150 mg of color coupler were omitted.

2. An intermediate layer made as follows:

To 4540 g of a 10 weight percent photographic gelatin solution, 250 g of the Antioxidant 2-octadecyl-4-sulfohydroquinone, potassium salt, in 5000 ml of hot water added. The mixture was applied over the red-sensitive layer in such a way that 0.09 square meters of the 50 mg antioxidant and 91 mg gelatine layer were used.

3. A green sensitive layer prepared as follows:

To 1 mole of a liquid, direct positive silver bromide iodide emulsion, who was green-sensitized, 81 g of the purple coupler 1 - (4 - sulfophenyl) - 3 - (4- SuIf oanilino) -4 - (2 - oxy-4 - pentadecylphenylazo) -5-pyrazolone, Dipotassium salt, in 3000 ml of water and so much gelatin added that a total of 162 g of it per 1 mole of silver halide accounted for. The solution was applied over the intermediate layer in such a way that 0.09 m² of the layer, 120 mg silver, 90 mg color coupler and 180 mg gelatine were omitted.

ϊ 262456

'4. An intermediate layer made as follows: "; 4540 g of 10 weight percent photographic

; shear gelatin solution were 250g of the first intermediate layer used antioxidant

^{1 ] i} means in 5000 ml of hot water and 4.0 g of yellow colloidal silver in the form of a dispersion. This mixture was applied over the green-sensitive layer in such a way that 8 mg of colloidal silver, 50 mg of antioxidant and 91 mg of gelatin were used on 0.09 m² of the layer.

5. A blue sensitive layer prepared as follows: '' To 1 mole of a liquid, direct positive silver

'-' bromide iodide emulsion, which is already blue in itself - "" - sensitive was, 144 g of the color coupler dissolved in 750 ml of ethyl alcohol and 3000 ml of water α - pivalyl - α - (3 - qctadecylcarbamyl- • phenylthio) -4-sulfoacetaniiid, potassium salt, and so much gelatin added that of it in total 118 g per mole of silver halide accounted for. The mixture was like this over the last interlayer applied so that 150 mg of silver, 200 mg of color coupler and 161 mg Gelatine was omitted.

6. A top layer made as follows:

4540 g of a 10 weight percent photo

'■ graphic gelatin solution were 250 g of the ultraviolet absorbing compound, 5- (4-methoxy-3 - suhO) - benzylidene-2-phenylimino - 3 - octyl-

^: · Thiazolidone, sodium salt, added in 5000 ml of water. This solution was like this via the

: blue-sensitive layer applied so that 50 mg of ultraviolet-absorbing material is applied to 0.09 m² of the layer Compound and 91 mg gelatin were omitted.

The ones used to make layers 1, 3 and 5. Silver bromide iodide emulsions. corresponded Emulsions such as those described in U.S. Patent 2592250 be described, d. i.e., their silver halide grains

'5 had' high internal and low surface sensitivity. "

Test samples of the photographic recording material produced as described were then _{exposed in an intensity scale sensitometer Y for 10} seconds with a 500 watt lamp through a blue, 4.08 mm thick, red radiation absorbing filter, then immersed in a color developer solution for 10 seconds and finally 5 Pressed for minutes at 24 ° C on image receiving sheets containing a cationic mordant. The image-receiving sheets were then stripped from the exposed recording material, and the color densities of the positive images transferred to the image-receiving sheets were then measured.

A part of the recording material became as follows in a color developing solution (developing stock solution) Composition developed:

Sodium sulfite, dehydrated 2 g

Sodium hydroxide 20 g

4-Amino-N-ethyl-N-dÖ-oxyäthyl) -

anilih .-. 20 g

Filled up to the liter with water.

Other parts of the material were in developer solutions which had the same composition as the developer stock solution, additionally per liter, however, 2.0 g of the in the Aminohexosereduktonverbindungen listed below contained.

The positive images obtained using the various developing solutions had those shown in FIG the following table I compiled color densities.

Table I.

Color developing solution used

j
Red J n% Qj ^ VV CJL Lv
green blue J
Red 3 _m / _B values
green blue 0.75 0.38 0.35 0.17 0.20 0.30 1.14
0.95 0.55
0.54 0.40
0.41 0.20
0.17 0.20
0.17 0.26
0.17 1.37 0.74 0.62 0.15 0.16 0.27

Developer stock solution

Developer stock solution with the addition of dimethyl- · - aminohexose reductone

Stock developer solution

Developer stock solution with the addition of piperidinohexose reductone

As can be seen from the values for the maximum The densities in the table are determined by the reductone used in the color developer according to the invention the reverse effect in each case facilitates what is expressed in particular in the fact that the images obtained therewith have higher color densities.

example 1

The procedure described in Example 1 was carried out with the same photographic material repeated, but this time a developer stock solution of the following composition was used for development used:

Benzyl alcohol 5.0 ml

Sodium sulfite, dehydrated 2.0 g

6-nitrobenzimidazole 0.15 g

Potassium bromide 0.5 g

Sodium hydroxide 10.0 g

Oxyethyl cellulose (1%) 500 ml

Sodium hydroxide (2.5 normal) 40.0 ml

4-Amino-N-ethyl-N-OS-oxyethyl) aniline 20.0 g
Water 400 ml

to which in each case 0.2 g of one of the reductones indicated in the table below were added.

The D _max and £>",*" values obtained for the transferred dye images are compiled in Table II below.

Table II

Reductones in the developer

Red ZW values
green

blue

Am-n values
Red j green blue

1. Piperidine hexose reduction

2. Diallylaminohexose reductone

3. Piperazindi (hexose reductone) ...

4. Anhydropiperidine hexose reductone

5. Morpholine hexose reductone

2.38
2.35
2.32
2.22
2.30

2.38
2.30
2.14
2.06
2.22

2.41
2.32
1.84
2.16
2.24

0.17
0.18
0.18
0.16
0.18

0.18
0.20
0.18
0.18
0.17

0.24
0.26
0.24
0.26
0.22

Example 3

A multilayer photographic material was prepared as described in Example 1, however, the top layer contained the primary aromatic amine and a reductone. After exposure the photographic recording material was developed by treating it with an aqueous alkaline Activator solution was soaked, with the positive dye images, as described, on image receiving sheets were transferred.

The top layer was created from a mixture of the following composition:

10 ° / ₀ gelatin solution 4540 g

10% developer-reductone solution,

consisting of 4-amino-N-ethyl-

N- (jS-oxyethyl) aniline 100 g

Piperidine hexose reductone Ig

Sodium sulfite, dehydrated 2 g

Sodium hydroxide, cookies 20 g

Water 750 ml

To 11 water with a pH of 6.5, adjusted by adding

2 η-sulfuric acid 9080 g

15% saponin solution 1000 ml

2.72 ° / ₀ sodium mucochloric 45 ml

It was made up to a total weight of 59,000 kg with water.

The mixture was applied over the blue light-sensitive layer so that on 0.09 square meters the layer 200 mg of 4-amino-N-ethyl-N - (/? - oxyethyl) -aniline accounted for.

The obtained with this color photographic material positive images showed for all three colors high D _ma x and low £>"""- values.

Example 4

The reductones used as nucleating agents according to the invention have the further advantage that they also Represent stabilizers for aromatic primary amine developing agents. Ascorbic acid ζ. Β. is also a stabilizer for color developing agents. However, ascorbic acid has the Disadvantage that they reduce the sensitivity, especially of the blue-green image in the sagging area of the blackening curve changed in an undesirable manner. Those used according to the invention exert this disadvantageous effect Reductones not off.

To demonstrate this, several strips of the photographic material described in Example 1 were used developed with a developer which was made from the developer solution (developer stock solution) of Example 1 consisted of ascorbic acid in varying amounts and piperidinehexose reductone on the other was added. The relative sensitivities obtained with the various color developers in the sagging area of the blackening curve are in

ao of the following Table III.

Table III

Piperidino Relative hexose reductone Sensitivity in Developer additives (g / l) 0 Passage area 0.4 the blackening curve 0.8 (Blue-green scale, .0 = 0.6) rt.bL U Γ DU 1 α Λ LU C 1.6 100 0 0 100 0 0 100 0 0 100 0 63 0.05 59 0.10 45 0.20

Claims (4)

Patent claims: 1. Diffusion photographic process for the production of positive color images, in which a color photographic material with a support, optionally with one on the Emulsion side of the photographic material provided hydrophilic colloid layer, at least a hydrophilic silver halide emulsion layer with preferably gelatin as a binder, which forms latent inner grain images, as well as at least one non-diffusing Color coupler that forms diffusing dyes with oxidized aromatic primary amines, imagewise exposed, in the presence of a nucleating agent with an alkaline developer solution is developed and in which the or the during the development to the surface of the material diffused dyes are transferred to an image-receiving sheet, characterized in that that the color development with an aminohexose reductone or anhydroaminohexose reductone is carried out as a nucleating agent, the amino radical of which has the formula R ² R ¹ —N - has, wherein R ¹ and R ^{2 are} equal to alkyl groups with preferably 1 to 8 carbon atoms or atoms or atomic groups, which together with the amino nitrogen atom and optionally a further hetero atom, preferably nitrogen or 809 630/937 Oxygen atom, form a five- or six-membered heterocyclic ring, are. 2. The method according to claim 1, characterized in that the aminohexose reductone or anhydroaminohexose reductone Piperidinohexose reductone, diallylaminohexose reductone, piperazinohexose reductone, morpholinohexose reductone, dimethylaminohexose reductone or anhydropiperidinohexose reductone is used. 3. The method according to claim 1, characterized in that the aminohexose reductone of the al- potash developer solution in an amount between 0.1 and 10 g per liter of solution is added. 4. The method according to claim 1, characterized in that the aminohexose reductone or anhydroaminohexose reductone in the hydrophilic colloid layer provided on the emulsion side of the photographic material, preferably in a gelatin layer, in a concentration of 1 to 100 mg, based on 1 mol Silver halide, is used in the emulsion layers. 209 630/937 10.68 O Bundesdruckelei Berlin