JPH02184847A - Photographic inversion treatment - Google Patents

Abstract

PURPOSE: To form a copy image without mottling defects by preparing a photographic material in such a manner that an emulsion having a specified high chlorine content is used and a blue sensitive layer as a first layer is formed on a base body but a yellow filter layer is not formed, and then subjecting the obtd. photographic material to reversal development. CONSTITUTION: The reversal color photographic material to be used is produced by applying at least one blue sensitive silver halide emulsion layer, and then at least one green sensitive silver halide emulsion layer and at least one red sensitive silver halide emulsion layer on a reflection supporting body. The photosensitive emulsion layers are formed in such a manner that at least 80mol%, more preferably at least 95mol% of the silver halides is AgCl. After the photographic material is exposed, the material is subjected to standard reversal development. Thereby, especially, even when a base body having a smooth surface is not used, a copy image without mottling defects can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color reversal process using special color photographic materials in a color reversal process for producing positive color prints using transparent color positives as original documents. In photographic reversal processing, positive color images are produced by using a color positive to expose color reversal paper, which acts as a negative, and by a special reversal development process.

To summarize the invention, in a color reversal processing method for producing color positive prints using a positive image as an original original, the reversal color photographic material used is first coated with at least one blue-sensitive silver halide emulsion layer, then sequentially In either case, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer are coated on a reflective support, and the silver halide in the light-sensitive emulsion layer is The object of the present invention is to obtain a copy screen free from mottling and so-called 7 tor defects even when using a material in which at least 80 mol% of the support is AgC+ and is not particularly pretreated.

A color reversal photographic paper comprises a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer in that order on a support, typically It has a layered structure in which both sides of the paper are coated with polyethylene. The material also has an anti-halo layer, an intermediate layer and a protective layer.

The silver halide emulsion layer contains silver halide, primarily silver bromide.

Photographic materials of this type have the disadvantage of mottling, ie uneven colored areas. To eliminate this drawback, special supports with particularly smooth surfaces must be used. However, manufacturing this support is expensive. Furthermore, the support must be protected from dust.

The problem that the present invention seeks to solve is to produce color reversal paper using a support that requires simple processing for color negative paper that is free of 7 torr defects.

According to the invention, this problem is solved by using an emulsion with a high chlorine content, coating the blue-sensitive layer as a first layer on the support, removing the yellow filter layer and reversing developing the resulting material. do.

Therefore, the present invention provides a color reversal processing method for producing color positive prints using a positive image as an original document.
The reversal color photographic material used comprises first at least one blue-sensitive silver halide emulsion layer, then in any order at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide layer. an emulsion layer coated on a reflective support, and at least 80 mole % of the silver halide in the light-sensitive emulsion layer, preferably at least 9
5% of AgCl and is characterized in that after exposure the same material is subjected to standard reversal development.

In a preferred embodiment, at least one green-sensitive layer is first run over the blue-sensitive layer of the at least IN, followed by a red-sensitive layer.

Furthermore, it is possible to apply only one layer of each color sensitive layer,
This is preferable in order to simplify manufacturing.

The positive image from which a positive copy is made can be a print or a transparence.

The color reversal processing method preferably includes the following steps: first development=black and white negative development. The silver halide exposed according to the image during photographing is developed with a first developer to obtain a black and white negative image.

Optional intermediate cleaning = removes the first developer solution and prevents black and white development from occurring again in the color developer bath.

Diffuse second exposure or chemical capri--allows all silver halide not developed in the first developer to be developed.

Activated silver halide is converted into silver and dye by one-color development and second development or by chemical fogging.

- A corresponding amount of dye is formed from the colored coupler and the development oxidation product formed in proportion to the reduced silver halide in the color developer.

- Bleach and Fix or Bleach/Fix - Elutes all developed silver in the first and color development leaving a positive dye image.

- Final cleaning and stabilization bath = washes away chemicals and stabilizes the image dyes and image surface.

Typical black and white developers, such as methol-hydroquinone or phenidone-hydroquinone developers, are usually used in the first development step. In this case, intermediate cleaning is essential.

Under certain conditions, it is also possible to use color developers of the p-phenylenediamine derivative type used in color development in the first development step. In this case, intermediate cleaning is not necessary (German Patent (DE-A) No. 2,249.8
(See No. 57).

Advantageously, the method of the invention can be carried out in a shorter time than conventional methods.

In addition to silver chloride, the emulsion used contains 0 to 20 mol% AgBr and 0 to 5 mol% Agl, preferably 0
5 to 5 mol% AgBr and 0 to 1 mol% Ag
Contains l.

A preferred color developer corresponds to the following formula.

During the ceremony R3 and R2 are C1-, which may be substituted with H11 layer.

Alkyl%C6-1゜Aryl and C1-, alkoxy, R3 is C3-, alkyl which may be optionally substituted with H1,
C1-3° represents aryl, C1-, alkoxy, and halogen, and n is 1 or 2.

Particularly suitable first aromatic amine developers are N,N-dialkyl-p-phenylene diamines, substituted or unsubstituted in their alkyl and aromatic portions. Examples of such compounds include N,N-diethyl-p-phenylenediamine hydrochloride, 4-N,N-diethyl-2-methylphenylenediamine hydrochloride, and 4-(N-diethyl-p-phenylenediamine hydrochloride).
-ethyl-N-2-methanesulfonylamineethyl)-
2-methylphenylenediamine sesquisulfate monohydrate, 4-(N-ethyl-N-2-methylphenylenediamine sulfate and 4-N.

N-diethyl 2,2-methanesulfonylaminoethylphenylenediamine hydrochloride.

The concentration of the developer in the first developer bath, whether black and white or color developer, is in the range of 2 to 20 g/Q, preferably in the range of 4 to Log/Q.

Additionally, if the processing steps are carried out sequentially, a wetting agent and a complexing agent are added to the two developer solutions to facilitate penetration of the solution into the emulsion layer and to scavenge calcium ions from the gelatin and water in the solution. , it is advantageous to combine it with it.

Suitable complexing agents for complexing calcium ions are, for example, aminopolycarboxylic acids, which are well known per se. Typical examples of such aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), 1,3-diamino-2-hydroxypropyltetraacetic acid, diethylenetriaminepentaacetic acid, N,N-bis-( These include 2-hydroxybenzyl)-ethylenediamine-N,N'-diacetic acid, hydroxyethylethylenediaminetriacetic acid, cyclohexanediaminotetraacetic acid, and aminomalonic acid.

Other calcium complexing agents include polyphosphates, phosphonic acids, aminopolyphosphonic acids, and hydrolyzed polymaleic anhydrides such as sodium hexametaphosphate.
1-Hydroxyethane-1,1-diphosphonic acid (HED
P), aminotrimethylenephosphonic acid. (2)-Hydroxyethane-1,1-diphosphonic acid also acts as a complexing agent for iron.

Furthermore, it is advantageous to add an iron complexing agent to these two developer solutions.

Complex forming agents for iron include, for example, 4,5-dihydroxy-1°3-benzenedisulfonic acid, 5,6-dihydroxy-1
．． Mention may be made of 2.4-benzenetrisulfonic acid and 3.4.5-trihydroxybenzoic acid.

To complex calcium, add a calcium complexing agent,
It is preferred to use from about 0.02 to about 0.2 moles per mole of developer compound.

Additionally, it may be appropriate to add black-and-white couplers to the developer solution.

Other suitable components also include optical brighteners, lubricants such as polyalkylene glycols, surfactants, stabilizers such as heterocyclic mercapto compounds, or nitrobenzimidazole and desired pH-establishing agents. The developer solution can also contain up to 5 g/Q of benzyl alcohol.

However, preferably it does not contain benzyl alcohol.

Ready-to-use developer solutions can be prepared from the individual components or from so-called stock solutions in which the individual components are dissolved in a highly concentrated state. The stock solution is formulated in such a way that a so-called regenerant can be produced, that is, a solution in which the individual component concentrations are slightly higher than that of a ready-to-use developer, while a developer that can be further diluted and used by adding an initiator. Get the liquid or
Alternatively, highly concentrated solutions can be added continuously to the developer in use to replace chemicals consumed during development or to replace those displaced from the developer by overflow or developed material. To compensate. Since chloride ions are normally released from photographic materials during development, there is no need to add them to anything other than the initially prepared developer solution.

After color development, the photographic material is stopped, bleached, fixed, washed and dried in the usual manner. Bleaching and fixing can be combined into a single stage of bleach-fixing, while washing can be replaced by a stabilizing bath. Bleach bath or bleaching/
If the fixing bath is sufficiently acidic, a stop bath can be dispensed with.

Example 1 A color photographic recording material suitable for the processing method of the present invention was prepared by coating the layers shown below in the order shown below on a support layer of double-sided polyethylene coated paper. All quantities given below are per l m 2 . The amount of silver halide applied is
AgN0. It is shown in terms of conversion.

Combination layer 1: 1st layer (undercoat layer) 0.2g gelatin.

Second layer (blue sensitive layer) 1.38 g of gelatin 0.95 g of yellow coupling agent Y 0.2 g of white coupling agent W 0.29 g of tricresyl phosphate (TCP).
A blue-sensitive silver halide emulsion (consisting of 99.5 mol % chloride, 0.5 mol % bromide, average grain size 0.8 μm) corresponding to 63 g of AgNO3.

Third layer (protective layer) 1.1 g gelatin 0.06 g 2,5-dioctylhydroquinone 0.
06 g dibutyl 7-tarrate (DBP) 4th layer (green sensitive layer) 1.08 g gelatin 0.41 g magenta coupling agent M0.08 g
of 2,5-dioctylhydroquinone 0.5 g of DBP 0.5 g of TCP in a green-sensitive silver halide emulsion corresponding to 0.45 g of AgNO3 (99.5 mol% chloride, 0.5 mol% It consists of bromide and has an average particle size of 0.6 μm).

5th layer (UV-absorbing layer) 1.15 g of gelatin 0.6 g of UV-absorbing agent corresponding to the following formula: 0.045
g of 2.5-dioctylhydroquinone 0.04 g of TCP.

6th layer (red sensitive layer) 0.75 g gelatin 0.36 g cyan coupling agent C0, 36 g T
Red-sensitive silver halide emulsion (consisting of 99.5 mol% chloride, 0.5 mol% bromide, average grain size 0.5 μm) corresponding to 0.3 g AgNO3 containing CP.

7th layer (UV-absorbing layer) 0.35 g gelatin 0.15 g UV-absorbing agent same as the 5th layer 0.2 g T
CP 8th layer (protective layer) A coupling component using a hardening agent corresponding to the following formula for 0.9 g of gelatin and 0.3 g has the following formula.

A step-unige scale (a scale whose optical density is changed stepwise) was placed on the photographic recording material described above, exposed, and processed as follows.

1st development: 36°C, 160 seconds washing, 22°C, 120 seconds diffusion second exposure, 2nd development: 36°C, 30 seconds washing
22°C 130 seconds bleach/fix bath 36
°0190 seconds washing 22℃, 120 seconds drying 1st developer water 900
rtrQEDTA 2 gHE
DP, 60% by weight 0.5 mQ Sodium sulfite 7 g Sodium chloride 2 g Hydroquine sulfonic acid potassium salt 15 g l-phenyl-3-pyrazolidone 0.3 g (ph
(en 1done) Potassium carbonate 10 g The pH was adjusted to 9 with potassium hydroxide or sulfuric acid, and the whole was brought to la with water.

2nd developer water 900
mQEDTA 2 gHEDP
, 60% by weight 0.5 mQ sodium chloride 2g N,N-diethylhydroxylamine, 85% by weight
5 mQ4-(N-1 thyl-N-2-methane-3mQ sulfonylaminoethyl)-2-methylphenylenediamine sesquisulfur ml hydrated salt (CD 3) 50 g 1% potassium carbonate 10 g potassium hydroxide or sulfuric acid The pH was adjusted to 9 and the whole was brought to 1Q with water.

Bleach/fixing bath water 800
rmQEDTA 4 g ammonium thiosulfate 100 g sodium sulfite 15 g ammonium-iron-EDT
Complex A 60 g 3-Mercapto-1,2,4-) Riazole 2 g Adjust pH to 7.3 with ammonia or acetic acid and bring to 112 with water.

The resulting color print does not show any torsion, especially in the mid-gray region.

The main outline and aspects of the present invention are as follows.

1. In the color reversal processing method in which a positive image is used as the original original image to produce a color positive print, the reversal color photographic material used is first coated with at least one blue-sensitive silver halide emulsion layer, and then at least one blue-sensitive silver halide emulsion layer in any order. one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer coated on a reflective support, and at least 80 mole % of the silver halide in the light-sensitive emulsion layer. A color reversal processing method characterized in that is made of AgCl.

2. The following steps, viz. 1. First development 2. Intermediate cleaning as needed 3. Diffuse second exposure 4. Color development 5. Bleaching and fixing 6. Cleaning and stabilization 7.Drying The color reversal processing method according to item 1 above.

3. The color reversal processing method according to item 1 above, characterized in that a black and white developer is used in the first development.

4. The color reversal processing method as described in item 1 above, characterized in that a p-fuynylenediamine type developer is used in the first development.

5. The p-7-functional nylene diamine derivative is represented by the following formula % Formula % In the formula, R1 and R2 are H1, C+-a alkyl which may be optionally substituted, and Ca-+. represents aryl and C14 alkoxy, R1 is C1□alkyl which may be optionally substituted with H1;
, -1° aryl and C1-3 alkoxy, halogen, and n is 1 or 2.

5. The color reversal processing method according to item 4, wherein the 6,N,N-dialkyl-p-7-functional nylenediamine derivative corresponds to the following formula %.

7. The developer is present in the first developer in an amount of 4 to 10 g/Q.
5. The color reversal processing method according to item 4, characterized in that:

8. The color reversal processing method according to item 1 above, wherein the color developer substantially does not contain benzyl alcohol.

9. At least 95 mol% of the photosensitive silver halide emulsion layer
2. The color reversal processing method according to item 1 above, characterized in that: is made of AgCl.

Claims (1)

[Claims] 1. In the color reversal processing method in which a positive image is used as the original original image to produce a color positive print, the reversal color photographic material used is first coated with at least one blue-sensitive silver halide emulsion layer, and then at least one blue-sensitive silver halide emulsion layer in any order. one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer coated on a reflective support, and at least 80 mole % of the silver halide in the light-sensitive emulsion layer. A color reversal processing method characterized in that is made of AgCl.