JP2681758B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] FIELD OF THE INVENTION The present invention relates to silver halide color copying.
True photosensitive materialHow to processFor more details on the
A preservative that replaces the harmful and deadly poison, hydroxylamine
UsingDirect positive image formation Silver halide color photographic light-sensitive
Internal latent image type silver halide emulsion layer by color developer for materials
HavingSilver halide color photographic materialsHow to processTo
Related. [0002] BACKGROUND OF THE INVENTION In color development, exposed halogens
Silver halide is reduced to silver and at the same time oxidized aromatic group
Primary amine developing agent reacts with coupler to form dye
You. During this process, the haf
Rogen ions are eluted and accumulated in the developer. Another way
Heavy metal compounds contained in other processing solutions such as white liquor and bleach-fix solution.
Components such as on are also called back contamination.
It is brought into the color developer and accumulated. In a color developing solution used for such color developing
Are usually sulphites or sulphites to increase their homeostasis.
The water-soluble salts of acid salts and hydroxylamine are preservatives (antioxidant
It is added as a (stopper). Of these, like the former,
Fogging occurs over time when using sulfite alone
Therefore, as with the latter, sulfite and hydroxyl
Preservation of developer by using water-soluble salt of min
Of the fogging caused by the aged developer.
Occurrence is being reduced. However, hydroxylamine has the following
Such defects or inconveniences are observed. [0005] That is, first, hydroxylamine is affected by the human body.
Reported to be harmful [eg P. G. Steche
r, `` The Merck Index An Encyclopedia of Chemical an
d Drugs "(The Merck Index En Ensai
(Cropedia of Chemicals and Drugs)
8th.Ed. (1953)]. Secondly, in the Poisonous and Deleterious Substances Control Law
To sell and sell hydroxylamine salt
Registration of general sales business of goods and establishment of a person in charge of handling are required
It is extremely inconvenient to handle. Thirdly, hydroxylamine is a kind of black and white.
It is a developer and has silver developability for silver halide.
I have. Therefore, the silver halide color photographic light-sensitive material
The utilization efficiency of silver rogenide is poor, and it is necessary to obtain the target dye concentration.
Uses more silver halide and couplers in photosensitive materials
There is an inevitable necessity, and it is extremely economically disadvantageous
It is a profitable existence. [0008] Fourth, hydroxylamine is formed.
Heavy metal ions (e.g. iron or copper) in the color developer.
(E.g. on) decomposes into ammonia.
May cause fog on the color light-sensitive material and adversely affect photographic performance.
It has the drawback of being affected. The color developer is
From the viewpoint of economic efficiency and pollution, in recent years there has been a trend toward low replenishment
In addition, for the purpose of further cost reduction, such as potassium carbonate
As the grade of raw materials is being reduced, these
The amount of the heavy metal ions accumulated in the color developer is
It is increasing more and more. Therefore, the amount of hydroxylamine
The fourth problem that is caused by the solution is the occurrence of fogging.
The situation is becoming more severe. Therefore, in-house processing and color development at stores will be performed in the future.
When performing color copying with the method,
Preservatives to replace hydroxylamine due to pollution problems
Is strongly desired. As a preservative to replace hydroxylamine
2-anilinoethanol and dihydroxyalkene
However, in U.S. Pat.Nos. 3,823,017 and 3,615,503 respectively
Is being planned. However, these are all compounds
The body is unstable and the preservative effect in the color developer is extremely high.
Very weak. On the other hand, hydroquinone or N-alkyl
-Developer containing p-aminophenol as a developing agent (black
Sucrose is used as a preservative in
It is known that sucrose is an aromatic primary amine
As a preservative, the color developer containing
There is no effect. Ascorbic acid and its derivatives are black.
Known as a preservative for white photographic developers and color original image solutions
However, these impede color development and cause a significant decrease in color density.
However, the color developer has a
Inferior to Further, α-hydro described in JP-A-52-7779
Xy aromatic alcohol, hydr described in JP-A-52-27638
Loxamic acid compounds, α-aminoca described in No. 52-143020
Lubonyl compounds and monosaccharides described in No. 52-102727, No. 52
The amino acid derivative described in -140324 is disclosed. However, a large amount of monosaccharides and amino acid derivatives
When used, shows considerable preservation at room temperature
Is easily decomposed by heat and is not desirable for pollution
have. The substitution of the α-aminocarbonyl compound
D-glucosamine hydrochloride is known as a representative compound
However, this compound is more preservative than hydroxylamine
Is inferior. The hydroxamic acid compound is a hydroxyl group.
It has the same preservative properties as amines, but the cost is high.
Disadvantage. Japanese Patent Publication No. 61-48698 discloses a preservative for color developing solution.
As hydroxylamine or its derivative and aldehyde
The technique of using the bisulfite adduct of
-48699 uses diethanolamine in addition to the above structure
Techniques for doing so are disclosed. According to the study by the present inventors
For example, even with the above configuration, the preservation ability is insufficient.
You. Therefore, in order to enhance the preservative ability, sulfite is added.
Coexistence is easy, but coexistence of sulfite
It was found that there were the following problems when they were allowed to do so. Primarily
This is a problem that the density of the coloring pigment decreases. Amount of sulfite added
The density of the coloring pigment decreases when
Is known, but according to the study by the present inventors, it contains silver chloride.
The higher the rate of light-sensitive materials, the easier the concentration of color-forming dye decreases.
It has been found. Second, color development for direct positive image formation
Solution, for example, color developing solution represented by photofogging development
When used as an additive, increasing the amount of sulfite causes a yellow stain.
Problem has also been found that is likely to occur and the image quality is greatly impaired
did. Third, in the case of rapid processing development, sulfite ion
Concentration and presence of hydroxylamine greatly affect speed
To reduce the sulfite ion concentration as much as possible, and
The requirement is not to use hydroxylamine
However, on the contrary, there is a problem that the homeostasis tends to deteriorate. Therefore, to reduce the sulfite ion concentration
However, according to the study by the present inventors, the sulfite concentration
Even if the degree is low, the homeostasis does not deteriorate significantly.
In fact, it is better to allow some sulfite to coexist.
It turned out to be sufficient as an ability. However
In addition, as a result of further study by the present inventors,
I knew there was a problem. First is high-speed rapid processing and pollution
If low replenishment processing is performed due to the measures of
Insufficient preserving ability of color developer
When using dehydrated bisulfite, suspended solids are
Occurs, clogs the filter, and circulation is poor.
That is, the processing characteristics become unstable. [0021] OBJECTS OF THE INVENTION The object of the invention is therefore to overcome the above-mentioned drawbacks.
It contains a preservative that is harmless to the human body and easy to handle.
Preservation is improved compared to color developer and photographic characteristics
Providing a color developing solution that can be processed quickly without significantly affecting
Is to do. [0022] The above object of the present invention is to:Internal latent image type halogen
Silver halide color photographic light-sensitive material having silver halide emulsion layer
ToHydroxylamine derivative represented by the following general formula [1]
1.0 x 10 per liter of body and color developer^-Four~ 1.5 × 10^-2Mole of
Containing concentration of sulfite ion and chelating agentDirect positive
Image forming silver halide color developer for color photographic light-sensitive materials
Method for processing silver halide color photographic light-sensitive material
Achieved by [0023] Embedded image Where R₁And R_TwoIs a hydrogen atom or
It represents an alkyl group which may be substituted. Where R₁as well as
R_TwoAre not hydrogen atoms at the same time. The bisulfite addition compound of aldehyde is sulfurized
To be used in combination with acid salts, JP-B-61-48698 and 61-48699
The above-mentioned compounds are disclosed in the publication, from the viewpoint of homeostasis.
It is easy to infer that sufficient preservative is obtained by using a large amount of
However, due to the photographic characteristics, the density of the coloring pigment decreases, for example.
There are problems and the addition amount is highly dependent, so the optimum addition amount is
The limitation is also described in the above publication. According to the study by the present inventors, it is necessary for quick processing.
The higher the content of silver chloride in a photosensitive material, the more it depends on the sulfite ion concentration.
It is highly positive, and it is possible to directly use positive photosensitive materials containing high silver bromide.
In light-sensitive materials, the degree of yellow stain depends on the amount of sulfurous acid.
It turned out that there is a notable difference. Also from the perspective of homeostasis
As mentioned above, the higher the sulfite ion concentration, the higher the preservative capacity.
However, according to the study by the present inventors,
If the sulfuric acid concentration is increased, it is possible to improve homeostasis to some extent.
There is an advantage that the number of days of tarring is shortened
On the contrary, the deterioration rate of sulfite depends on the residual concentration of sulfite.
Therefore, the deterioration rate becomes faster, and as a result, remarkable preserving ability
It turns out that I can't hope for a rise. However, al
Sulfite concentration when combined with bisulfite adduct of dehydrate
It does not mean that the homeostasis is significantly deteriorated even if the value is lowered.
Rather, the coexistence of a certain amount of sulfite
It turned out to be sufficient as an ability. However, as described above, the present inventors
As a result of examination, it was found that there are the following two problems.
Was. The first is low replenishment processing due to high-temperature rapid processing and pollution control measures.
Unexpectedly, the preservative ability of the color developer is unexpectedly
Second, aldehyde bisulfite
If used, suspended solids will be generated on the surface of the treatment liquid and
It causes clogging, poor circulation, and unstable processing characteristics.
It means that [0028] This fact has never been known.
That was unexpected for the present inventors. Hydroxyl contained in the color developing solution of the present invention
In the above general formula [1] representing a silamine derivative, R
₁And R_TwoThe substituent of the alkyl group represented by is sulfone
Acid group, hydroxyl group, alkoxy group (methoxy group,
(Toxy group, propyloxy group, etc.), carboxyl group,
Mino group and the like can be mentioned, for example, these are US patents
No. 3,287,125, No. 3,293,034, No. 3,287,124, etc.
And hydroxylamines described in. Hydroxylamine represented by the general formula [1]
Among the derivatives, especially R₁And R_TwoHas 2 or more carbon atoms
Ethyl group, methoxyethyl group, ethoxyethyl group, etc.
Are most preferred. Preferred embodiments represented by the following general formula [1]
Specific examples of compounds are shown below. (1) CH_Three-NH-OH (2) C_TwoH_Five-NH-OH (3) iso-C_ThreeH₇-NH-OH (4) C_ThreeH₇-NH-OH (5) HO-CH_Two-NH-OH (6) CH_Three−O−C_TwoH_Four-NH-OH (7) HO-C_TwoH_Four-NH-OH (8) HOOC-C_TwoH_Four-NH-OH (9) HO_ThreeS-C_TwoH_Four-NH-OH (10) N_TwoH-C_ThreeH₆-NH-OH (11) C_TwoH_Five−O−C_TwoH_Four-NH-OH (12) HO-C_TwoH_Four−O−C_TwoH_Four-NH-OH [0033] Embedded image [0034] Embedded image [0035] Embedded imageThese compounds are usually hydrochlorides, sulphates,
p-toluenesulfonate, oxalate, phosphate, acetate, etc.
Used in the form of salt. Shown by the above general formula [1] in the color developer.
The concentration of the compound to be used is usually preferably 0.1 to 50 g / l.
It is more preferably 0.3 to 30 g / l, and particularly preferably
It is preferably 0.5 to 20 g / l. The above compounds may be used in combination of two or more kinds.
May be used. In the color developing solution of the present invention, sulfite ion
1.0 x 10 per liter of color developer^-Four~ 1.5 × 10^-2Mole Lee
A water-soluble sulfite, such as
Sodium sulfate, potassium sulfite, etc. may be added. The color developer of the present invention has a sulfite ion concentration.
Is 1.0 x 10^-Four~ 1.5 × 10^-2Mol / l
1.5 × 10^-2Higher silver chloride sensitizer when the amount exceeds mol / l
Concentration decrease becomes large with respect to food, 1.0 × 10^-FourMol / l
If it is lower, the deterioration of homeostasis becomes a problem. The color developer of the present invention contains a chelating agent.
Due to the contamination of heavy metal ions
Deterioration of the color developing solution is prevented and preservability is improved. Like
Amino polycarboxylic acid, organic phos
Examples include phosphonic acid and Tyrone derivatives. Especially Tyrone
The derivative does not precipitate with Ca or Mg in the color developer.
It is preferably used because it is difficult. The above aminopolycarboxylic acid has the following general formula
In [2], the organic phosphonic acid is represented by the following general formula [3] or
It is represented by [4]. [0043] Embedded image In the formula, E is an alkylene group or cycloalkyl group.
Group, phenylene group, -B_Five-OB_Five-, -B_Five-O-
B_Five-OB_Five-Or-B_Five-Z-B_FiveRepresents-. [0045] Embedded image B₁~ B₆Each represents an alkylene group
You. A₁′ 〜A_Three′ Is −COOM ′ or −PO, respectively_ThreeM_Two′
Represent, A_Four'And A_Five'Is a hydrogen atom, a hydroxyl group,
-COOM 'or -PO_ThreeM_TwoRepresents ′. M 'is a hydrogen atom or
Represents an alkali metal atom. General formula [3] B₇−N− (CH_TwoPO_ThreeM ′_Two)_Two In the general formula [3], B₇Is an alkyl or aryl group
Alternatively, it represents a nitrogen-containing 6-membered ring group. M'is a hydrogen atom or ar
Represents a potassium metal atom. [0048] Embedded imageIn the general formula [4], B₈, B₉And B_Ten
Are hydrogen atom, hydroxyl group, -COOM ', -PO_ThreeM ′_Twoor
Represents an alkyl group, L₁, L_TwoAnd L_ThreeIs water
Elementary atom, hydroxyl group, -COOM ', -PO_ThreeM ′_TwoOr −N− (J)_TwoTo
Express. J is a hydrogen atom, an alkyl group, -C_TwoH_FourOH or −PO
_ThreeM ′_TwoRepresents M'is a hydrogen atom or an alkali metal atom
And n and m each represent 0 or 1. In the following general formula [2], [3] or [4]
Some of the specific examples of the represented chelating agents are shown. In the present invention
The chelating agent used is limited to the following specific examples.
There is no. [0051] Embedded image [0052] Embedded image[0053] Embedded image[0054] Embedded image[0055] Embedded image[0056] Embedded imageRepresented by the above general formulas [2] to [4]
The chelating agent is 0.01 to 1
It is preferable to use 100 g, more preferably 0.05 to 5
It is 0 g, particularly preferably 0.1 to 20 g. The Tyrone derivative is represented by the following general formula [5]
It is a compound represented by [8]. [0059] Embedded image In the general formulas [5] and [6], R_Fifteen,
R₁₆, R₁₇And R₁₈Are hydrogen atom, halogen atom, and
Rufonic acid group, substituted or unsubstituted, having 1 to 7 carbon atoms
Alkyl group, -OR₁₉, -COOR₂₀, -CON (R_{twenty one}) (R_{twenty two}) Or
It represents a substituted or unsubstituted phenyl group. R₁₉, R₂₀,
R_{twenty one}And R_{twenty two}Is a hydrogen atom or an atom having 1 to 18 carbon atoms.
Represents a alkyl group. n represents an integer of 1 to 3. R_FifteenAre the same
But it may be different. R_FifteenIs preferably a sulfonic acid group
is there. [0061] Embedded image In the general formula [8], R₂₉And R₃₀Is each
Hydrogen atom, phosphoric acid group, carboxylic acid group, -CH_TwoCOOH, −C
H_TwoPO_ThreeH_TwoOr a salt thereof, X_ThreeIs a hydroxyl group or its salt
Represents W₁, Z₁And Y₁Are hydrogen atom and halogen
Atom, hydroxyl group, cyano group, carboxylic acid group, phosphoric acid group,
Sulfonic acid groups or their salts, alkoxy groups or
Represents a alkyl group. Also m_ThreeIs 0 or 1, n_ThreeIs an integer from 1 to 4
Number, l₁Is 1 or 2, p_TwoIs an integer from 0 to 3, q₁Is an integer from 0 to 2
Represents a number. The cracks represented by the above general formulas [5] to [8]
The following may be mentioned as specific examples of the coating agent. [0064] Embedded image [0065] Embedded image[0066] Embedded image[0067] Embedded image[0068] Embedded image Chelates represented by the general formulas [5] to [8]
Among the agents, the chelating agent represented by [5] or [8] is used
Is more effective, and more preferably the general formula
That is, the chelating agent represented by [8] is used. Especially
Preferred chelating agents (45), (49), or (54)
Is to use a chelating agent represented by. These keys
Two or more rate agents may be used in combination. The above-mentioned general formula [5] used in the present invention:
The chelating agent represented by any one of [8] is the color developer 1
1 x 10 per liter^-FourIt is preferable to add it in the range of 1 mol to 1 mol.
Better, more preferably 2 × 10^-Four~ 1 × 10^-1Molar range
It is possible to add by, more preferably 5 × 10^-Four~ 5x
Ten^-2It can be added in a molar range. Color development used in the color developing solution of the present invention
As the main drug, p-phenylenediamine having a water-soluble group
The system compounds are preferable from the viewpoint of obtaining the effects of the present invention. P-Phenylenediamine System Having Water-Soluble Group
The compound is water such as N, N-diethyl-p-phenylenediamine.
Compared to p-phenylenediamine compounds that do not have a soluble group
In addition, there is no contamination of the photosensitive material and the skin
It has the advantage of being less susceptible to rash. The water-soluble group is a p-phenylenediamine type
At least one on the amino group or benzene nucleus of the compound
Specific examples of water-soluble groups include: − (CH_Two) n-CH_TwoOH, − (CH_Two) m-NHSO_Two− (CH_Two) n-CH_Three, − (CH_Two) m−O− (CH_Two) n-CH_Two, − (CH_TwoCH_TwoO) nCmH_Twom₁ (m and n are each an integer of 0 or more
Represents ), -COOH group, −SO_ThreeH groups and the like are mentioned as preferable ones. Color developing agent preferably used in the present invention
Specific examples of the compound are shown below. [0075] Embedded image [0076] Embedded image[0077] Embedded image[0078] Embedded image[0079] Embedded image[0080] Embedded image The above color developing agent is usually a hydrochloride or a sulfuric acid.
Used in the form of salt such as salt and p-toluene sulfonate
1 x 10 per liter of normal color developer^-3~ 2 × 10^-1Mole of
It is preferable to use it within the range, but from the viewpoint of rapid processing
1.5 × 10 per liter of color developer^-3~ 2 × 10^-1Mole range
More preferred. In addition to the above components, the color developing solution of the present invention comprises
The following developer components can be included. As the alkaline agent, for example, sodium carbonate
Mu, potassium carbonate, sodium hydroxide, potassium hydroxide
System, silicate, sodium metaborate, potassium metaborate
Um, trisodium phosphate, tripotassium phosphate, boric acid
Etc. can be used alone or in combination. Further adjustment
To meet your needs or to increase ionic strength
Disodium hydrogen phosphate, dihydrogen phosphate
Lithium, sodium bicarbonate, potassium bicarbonate, borate
It is possible to use various salts such as. If necessary, inorganic and organic turnips may be used.
An anti-static agent can be added. If necessary, a development accelerator may also be used.
Can be. US Pat. No. 2,64 as a development accelerator
No.8,604, No. 3,671,247, Japanese Patent Publication No.44-9503
Representative pyridinium compounds and other
Cationic colors like on-type compounds, phenosafuran
Elemental, neutral salts such as thallium nitrate, U.S. Patent No. 2,533,990
No. 2,531,832, No. 2,950,970, No. 2,577,12
Polyethylene grease described in No. 7 and Japanese Patent Publication No. 44-9504
Nonionics such as kohl, its derivatives, and polythioethers
Compounds and organic solvents described in JP-B-44-9509 are included.
I will. Also described in US Pat. No. 2,304,925
Benzyl alcohol, phenethyl alcohol and this
Or acetylene glycol, methyl ethyl ketone, shiku
Rohexanone, thioethers, pyridine, ammonium
A, hydrazine, amines and the like. However, the color developing solution of the present invention is harmful to humans.
Can give good development performance without benzyl alcohol
So it is preferable not to contain benzyl alcohol
No. Further, the color developing solution of the present invention is required to
Depending on ethylene glycol, methyl cellosolve, meta
Nole, acetone, dimethylformamide, β-cyclo
Dextrin, other Japanese Patent Publication Nos. 47-33378 and 44-9509
Organic solvents for increasing the solubility of developing agents
Agents can be used. Further, an auxiliary developing agent is used together with the developing agent.
You can also. As these auxiliary developers, for example,
For example, N-methyl-p-aminophenol hexaulfate (
Tall), phenidone, N, N′-diethyl-p-aminophen
Nol hydrochloride, N, N, N ', N'-tetramethyl-p-phenyl
Diamine amine hydrochloride, etc. are known.
In general, 0.01 to 10 g / l is preferable. Besides this, it is necessary
Competitive coupler, fogging agent, colored coupler according to
-Development inhibitor release type coupler (so-called DIR coupler
-), And development inhibitor releasing compounds can be added.
Wear. Furthermore, other anti-staining agents and suds
Use various additives such as ludge inhibitors and layering effect promoters.
Can be. Each component of the above color developing solution is dissolved in a certain amount of water.
It can be prepared by subsequent addition and stirring. In this case water
Low solubility components before triethanolamine
It can be added by mixing with the organic solvent and the like. Again
In general, multiple components that can coexist stably
Was prepared in a small container in a concentrated aqueous solution or solid state.
Can be obtained by adding and stirring in water. The color developer of the present invention can be used in any pH range.
However, from the viewpoint of rapid processing, the pH should be 9.5 to 13.0.
It is preferably used at a pH of 9.8 to 12.0. Color development using the color developer of the present invention
The processing temperature is 30 ℃ or more and 50 ℃ or less, and the higher the temperature, the shorter the time.
It is preferable because it enables rapid processing, but on the contrary, the preservative property deteriorates.
There is also a problem that it is easy to do, more preferably 30 ° C
It should be below ℃. Color development processing using the color developing solution of the present invention
After that, it is processed with a processing solution having fixing ability.
If the processing solution that has the ability is a fixing solution, bleach it before
Is performed. Bleaching solution or bleaching used in the bleaching process
Bleaching agents used in fixers include metals of organic acids
A complex salt is preferably used, and the metal complex is developed by development.
Simultaneously when the metallic silver produced is oxidized and converted to silver halide
Has a function of coloring the uncolored part of the color developing agent,
Its structure is aminopolycarboxylic acid or oxalic acid, citric acid, etc.
Coordinated metal ions such as iron, cobalt, and copper with organic acids
Things. To form metal complex salts of such organic acids.
The most preferred organic acids used for
Examples thereof include boric acid and aminopolycarboxylic acid. these
The polycarboxylic acid or aminopolycarboxylic acid of is an alkali
Metal salt, ammonium salt or water-soluble amine salt
You may. The bleaching solution used is an organic acid as described above.
Various additives as well as containing a metal complex salt as a bleaching agent
Can be included. Especially as an additive
Halides or ammonium halides such as potassium bromide
, Sodium bromide, sodium chloride, ammonium bromide
Rehalogenating agents such as aluminum, metal salts, chelating agents
Is desirable. Also borate, oxalate, carbonate, phosphoric acid
PH buffers such as salts, alkylamines, polyethylene oxide
It is known to be added to normal bleaching liquids such as sides
Can be appropriately added. Further, the fixing solution and the bleach-fixing solution are sulphites.
Ammonium, potassium sulfite, sodium bisulfite,
Ammonium bisulfite, potassium metabisulfite, meta
Sulfite such as sodium bisulfite, boric acid, borax, and hydroxide
Sodium, potassium hydroxide, sodium carbonate, carbonate
Lium, sodium bicarbonate, potassium bicarbonate, acetic acid, vinegar
Consists of various salts such as sodium acidate and ammonium hydroxide
These pH buffers may be used alone or in combination of two or more. Replenish the bleach-fixing solution (bath) with a bleach-fixing replenisher.
When performing processing while performing bleach-fixing solution (bath)
Acid salt, thiocyanate or sulfite
OK, make sure that the bleach-fix replenisher contains these salts
The treatment bath may be replenished. To increase the activity of the bleaching solution and the bleach-fixing solution
Desired in bleach-fix bath and storage tank for bleach-fix replenisher
To blow air or blow oxygen
Good or suitable oxidizing agents such as hydrogen peroxide, bromine
Acid salts, persulfates and the like may be added as appropriate. The pH of the bleach-fixing solution is preferably 3.0 to 9.0,
More preferably, it is in the range of 4.0 to 8.0. Color development processing using the color developing solution of the present invention
After bleaching and fixing (or bleach-fixing), wash with water.
It is possible to perform a stable treatment without performing
It may be post-stabilized. In addition to the above steps, dura, neutralization,
Known methods such as black and white development, reversal, small amount water washing process
An auxiliary process may be added. Alternative to preferred treatment methods
The following steps are included as specific examples. (1) Color development → bleach-fixing → washing with water (2) Color development → bleach-fixing → washing with a small amount of water → washing with water (3) Color development → bleach-fixing → washing → stable (4) Color development → bleach-fixing → stable (5) Color development → bleach-fixing → 1st stability → 2nd stability (6) Color development → washing (or stable) → bleach-fixing → washing
(Or stable) (7) Color development → Stop → Bleach-fix → Wash with water (or stable) (8) Color development → Bleaching → Washing → Fixing → Washing → Stable (9) Color development → bleaching → fixing → washing → stable (10) Color development → bleaching → washing with a small amount of water → fixing → 1st stability → 1st
2 stable (11) Color development → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → water
Wash → stable (12) Color development phenomenon → bleaching → fixing → stable (13) Color development → stop → bleaching → washing with a small amount of water → fixing → a small amount of water
Washing → water washing → stable The color developing solution of the present invention is a color paper or a color filter.
System, color positive film, color positive paper, slide
Color reversal film for movie, color reversal film for movie,
Color reversal film for TV, reversal color paper, etc.
Applicable to photographic materials. Sensitivity to be processed by the color developing solution of the present invention
There are no special restrictions on the optical material. For example silver halide composition
Is silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, chloroiodo
It is used for ordinary silver halide such as silver bromide and silver chloride.
It can be anything you like. In the silver halide composition, chloride
For emulsion layers with silver content of 85 mol% or more, especially 90 mol% or more
On the other hand, the color developing solution of the present invention can be used for preservability, developability and rapid processing.
It is particularly advantageous in reason. The crystals of silver halide grains may be normal crystals or twin crystals.
It may be crystal or other, and the ratio of {100} plane to {111} plane is arbitrary.
You can use whatever you want. Furthermore, these silver halide grains
The crystal structure of the child is uniform from the inside to the outside.
Also has a layered structure with different inside and outside (core / shell type)
May be done. Also, these silver halides
Is a type that forms a latent image mainly on the surface,
It may be a mold formed on the part. Further flat halogen
Silver halide grains (see Japanese Patent Application Laid-Open No. 58-113934, Japanese Patent Application No. 59-170070).
It may be used. The silver halide grains are substantially monodisperse.
Are preferred, which may be acidic, neutral, or
It may be obtained by any method such as the monia method.
No. The particle size distribution of the monodisperse emulsion is almost normal.
Since it is made of cloth, the standard deviation can be easily obtained. Seki from now on
Ceremony (Standard deviation / average particle size) x 100 = breadth of distribution (%) If the breadth (%) of the distribution is defined by, the breadth of the distribution is
Those with monodispersity of 20% or less are preferable, and more preferable.
Or less than 10%. The grain size is spherical silver halide grains.
If it is a child, it is its diameter. If it is not a sphere, it has the same area.
Converted to. The above silver halide forms seed grains by an acidic method.
In addition, it is grown by the ammonia method, which has a fast growth rate.
However, it may be grown to a predetermined size. Halogen
When growing silver halide grains, adjust the pH, pAg, etc. in the reaction kettle.
Control, and is described in, for example, JP-A-54-48521.
Amount corresponding to the growth rate of silver halide grains
Sequential simultaneous injection and mixing of silver and halide ions
Is preferred. These silver halide emulsions contain activated gelatin.
Sulfur sensitizers such as allylthiocarbamide, thiourine
Sulfur sensitizers such as iodine and cystine; Selenium sensitizers; Reduction sensitizers
Sensitizers such as stannous salt, thiourea dioxide, polyamines, etc.
 Noble metal sensitizers such as gold sensitizers, specifically potassium
-Lithiocyanate, potassium chloroaurate, 2-
Ortho-thio-3-methylbenzothiazolium chloride, etc.
Or, for example, ruthenium, palladium, platinum, rhodium
And sensitizers of water-soluble salts such as iridium,
Monium chloroparadate, potassium chloroplatinum
And sodium chloroparadate (some of these
Sensitizers or antifoggants depending on the amount
Act as ) Etc. alone or in combination
(For example, a combination of gold sensitizer and sulfur sensitizer, gold sensitizer and
It may be chemically sensitized). To the silver halide emulsion, a sulfur-containing compound is added.
And chemically ripen it before, during, or during this chemical ripening.
After formation, at least one hydroxytetrazaindene and
Fewer nitrogen-containing heterocyclic compounds containing mercapto
Both of them may be included. Silver halides are used in the respective desired photosensitizing wavelength ranges.
In order to impart photosensitivity, a sensitizing dye is added to the silver halide 1 mol.
5 × 10 for Le^-8~ 3 × 10^-3Optical sensitization by adding moles
May be. Various sensitizing dyes should be used.
And a combination of one or more sensitizing dyes
Can be used. Further, the light-sensitive material to which the present invention can be applied is red-sensitive.
-Sensitive silver halide emulsion layer, blue-sensitive silver halide emulsion layer and
In the green-sensitive silver halide emulsion layer, a coupler, that is,
A compound capable of forming a dye by reacting with an oxidized product of a color developing agent.
The thing containing the thing is preferable. A yellow coupler which can be used is a closed coupler.
Chain ketomethylene compounds and so-called 2-equivalent couplers
Active-point-o-aryl substituted couplers, referred to as active-point-o-
Acyl-substituted coupler, active-point hydantoin compound-substituted coupler
Puller, active site urazole compound substitution coupler and activity
Point succinimide compound substitution coupler, active point fluorine unit
Replacement coupler, active site chlorine or bromine substituted coupler, active
The yellow pigments for which -o-sulfonyl substituted couplers are effective
It can be used as a puller. Available yellow mosquitoes
Specific examples of pullers include U.S. Pat.
No. 3,265,506, No. 3,408,194, No. 3,551,155,
No. 3,582,322, No. 3,725,072, No. 3,891,445
No., West German Patent No. 1,547,868, West German Application Publication No. 2,219,917
No. 2,261,361, No. 2,414,006, British Patent No. 1,
425,020, Japanese Patent Publication No. 51-10783, JP-A No. 47-26133,
48-73147, 51-102636, 50-6341, 50
-123342, 50-130442, 51-21827, 50-8
7650, 52-82424, 52-115219, 58-95346
Nos. And the like can be mentioned. As magenta couplers that can be used,
Razolone, pyrazolotriazole, pyrazolinoben
List of imidazole and indazolone compounds
Can be. These magenta couplers are yellow caps
As with Ra, it is not only a 4-equivalent coupler but also a 2-equivalent cap.
It may be Ra. Magenta couplers that can be used
As a body example, U.S. Patent Nos. 2,600,788 and 2,983,608
No. 3,062,653, No. 3,127,269, No. 3,311,47
No. 6, No. 3,419,391, No. 3,519,429, No. 3,558,3
No. 19, No. 3,582,322, No. 3,615,506, No. 3,834,
908, 3,891,445, West German Patent 1,810,464, West
German Patent Application (OLS) Nos. 2,408,665 and 2,417,945,
No. 2,418,959, No. 2,424,467, Japanese Patent Publication No. 406031
No. 5, JP-A-51-20826, No. 52-58922, and No. 49-129538
No. 49-74027, No. 50-159336, No. 52-42121,
No. 49-74028. 50-60233, 51-26541, 53
-55122, Japanese Patent Application No. 55-110943, etc.
Can be mentioned. Examples of cyan couplers that can be used include
Examples include phenol-based and naphthol-based couplers.
Can be. And these cyan couplers are yellow
Like the puller, it is not only a 4-equivalent coupler but also a 2-equivalent coupler.
It may be a puller. Cyan coupler tool that can be used
As a body example, U.S. Patent Nos. 2,369,929 and 2,434,272
No. 2, No. 2,474,293, No. 2,521,908, No. 2,895,82
No. 6, No. 3,034,892, No. 3,311,476, No. 3,458,3
No. 15, No. 3,476,563, No. 3,583,971, No. 3,591,
No. 383, No. 3,767,411, No. 3,772,002, No. 3,93
No. 3,494, No. 4,004,929, West German patent application (OLS) No. 2,4
No. 14,830, No. 2,454,329, JP-A-48-5983, No. 51
-26034, 48-5055, 51-146827, 52-696
No. 24, No. 52-90932, No. 58-95346, Japanese Patent Publication No. 49-1157
No. 2 etc. can be mentioned. Silver halide emulsion layer and other photographic constituent layers
Colored magenta or colored cyan coupler,
You may use together couplers, such as a polymer coupler. Kara
Book for Red Magenta or Colored Cyan Couplers
Applicant described in Japanese Patent Application No. 59-193611
Regarding the coupler, Japanese Patent Application No. 59-172151 by the present applicant
The description of each issue can be referred to. Although the amount of the above coupler added is not limited,
1 x 10 per mole of silver^-3~ 5 mol is preferred and more preferred
1x10^-2~ 5 × 10^-1Is a mole. There are various other photosensitive materials to which the present invention can be applied.
The above photographic additives can be incorporated. For example
Search Disclosure magazine 176
No. 43, antifoggant, stabilizer, UV absorber
Aqueous agent, anti-staining agent, fluorescent whitening agent, anti-fading agent for color image,
Antistatic agents, hardeners, surfactants, plasticizers, wetting agents, etc.
Can be used. In the light-sensitive material to which the present invention is applied, the emulsion
The hydrophilic colloid used to prepare
Chin, derivative gelatin, and gelatin and other polymers
Proteins such as futopolymer, albumin, casein, and hydr
Roxyethyl cellulose derivative, carboxymethyl cell
Cellulose derivatives such as loin, starch derivatives, polyvinyl
Alcohol, polyvinyl imidazole, polyacrylic
Synthetic hydrophilic polymer such as single or copolymer such as amide
Any are included. As a support for a light-sensitive material to which the present invention is applied
Is a reflective support such as baryta paper or polyethylene coated paper,
Transparent supports are mentioned, and these supports are used for the photosensitive material.
It is appropriately selected according to the purpose of use. In a light-sensitive material to which the present invention can be applied,
It is optional to provide an intermediate layer having an appropriate thickness depending on the purpose.
In addition, filter layer, anti-curl layer, protective layer, anti
Various layers such as a halation layer are appropriately combined as constituent layers
Can be used. As a binder for these constituent layers
A hydrophilic roller that can be used in the emulsion layer as described above.
Ids can be used as well, and the
Various photographs that can be contained in the emulsion layer such as
Additives can be included. Even if the photographic material contains a DIR compound
Well, in addition to DIR compounds, develop with development
It may also contain compounds that release inhibitors, for example
For example, U.S. Patent Nos. 3,297,445 and 3,379,529, West German Patent
Application (OLS) No. 2,417,914, JP-A Nos. 52-15271, 53
-9116, 59-123838, 59-127038, etc.
Things. The above-mentioned DIR compounds are oxidants of color developing agents.
Reacts with and releases a development inhibitor or development inhibitor precursor.
A non-diffusible DIR compound that can be released
Or a diffusible DIR compound. As typical examples of such DIR compounds,
Has a development inhibitory effect when it leaves the active site
Introduce a group capable of forming a compound into the active site of the coupler.
There are DIR couplers, such as British Patent No. 935,454, US
National Patent Nos. 3,227,554, 4,095,954, 4,149,88
It is described in No. 6 etc. The above-mentioned DIR coupler is an acid of a color developing agent.
When the coupling reaction with the compound
It has the property of forming, while releasing a development inhibitor. Ma
In the present invention, U.S. Pat.Nos. 3,652,345 and 3,928,041
No. 3, No. 3,958,993, No. 3,961,959, No. 4,052,21
3, JP-A-53-110529, JP-A-54-1333, and JP-A-55-1612
Oxides of color developing agents as described in No. 37 etc.
Releases the development inhibitor when the coupling reaction occurs,
Also included are compounds that do not form pigments. Furthermore, JP-A-54-145135 and JP-A-56-145135.
Color development as described in 114946 and 57-154234.
When reacted with the oxidized form of the main drug, the mother nucleus becomes
Form a colored compound, while the released timing group is
Development inhibitor via intranucleophilic nucleophilic substitution reaction or elimination reaction
Even so-called timing DIR compounds that are compounds that release
Good. Further, JP-A-58-160954 and JP-A-58-162949
When it reacts with the oxidant of the color developing agent described in
In addition, the coupler nucleus that forms a completely diffusible dye
A timing DIR compound with a timing group such as
It may be a thing. These DIR compounds are generally used in silver in the emulsion layer.
2 x 10 per mole^-Five~ 5 × 10^-1Mol is preferred and more preferred
Preferably 1 × 10^-Four~ 1 × 10^-1The use of moles. [0126] The following effects (a) to (e) are obtained by the present invention.
be able to. (A) As a preservative of the color developing solution, it is a poisonous substance.
Without using hydroxylamine, which has some drawbacks
Also has sufficient homeostasis. (B) As described above, in the color developer
Improves one of the homeostasis, color density and rapid processing
It is unavoidable that if the measures are taken, the other will deteriorate.
According to the invention, preservative and color density and quicker than conventional
Processability (especially photosensitive material with emulsion layer having high silver chloride content)
This relationship with (for fees) is improved. That is,
For example, in terms of color density and rapid processing property,
It is possible to improve the stability of the color developer while maintaining the level.
Can be. In addition, even in the case of low replenishment
It can give homeostasis. (C) According to the anti-irradiation dye
Inferred stains are prevented. (D) By the improvement of the preservative described in (c),
Silver halide color photographic light-sensitive material having internal latent image type emulsion
When light-fog developing the material,
The filter effect is reduced and stable photographic characteristics are obtained.
You. (E) Aldehyde bisulfite as a homeostasis
Table of color developers, which is a drawback when using salt addition compounds
No floating matter on the surface. [0132] The present invention will be described below in more detail with reference to examples.
However, the embodiment of the present invention is not limited to these.
There is no. [0133]referenceExample 1 A color developer having the following composition was prepared. [0134] (Color developer) Potassium sulfite Amount to obtain sulfite ion concentration in Table 1   0.3 g of sodium chloride   Potassium carbonate 25.0g   Preservative (listed in Table 1)   Chelating agent (listed in Table 1)   Color developing agent [Exemplified compound 1)] 5.0 g   The following fluorescent whitening agent 2.0g Potassium hydroxide and water were added to make 1 liter. The pH is 10.1.
0 was set. Optical brightener [0136] Embedded image Each color developing solution contained 4 ppm of ferric ion and copper
On 2ppm and calcium ion 100ppm (FeC
l_Three, CuSO_Four・ 6H_TwoO and CaCl_Two(Dissolve and add)
Opening ratio 30 cm at ℃^Two/ L (for 1 liter developer, air
30 cm contact area^Two) The glass container was stored. The appearance (coloring degree) of the color developing solution after 10 days was observed.
I thought. However, the appearance of the liquid was divided into the following four stages. ++ Generation of a large amount of tar ++ Blackening + Browning (discoloration) -Almost unchanged Table 1 shows the results. Separately, the polyethylene-coated paper support was coated on the bottom.
Each layer described above is sequentially coated from the side of the support to prepare a light-sensitive material.
did. As for polyethylene coated paper, the average molecule
200 parts by weight of polyethylene with an amount of 100,000 and a density of 0.95 and the average content
20 parts by weight of polyethylene having a molecular weight of 2000 and a density of 0.80 was mixed.
6.8% by weight of anatase-type titanium oxide
Weight 170g / m by extrusion coating method^TwoHigh quality paper
A coating layer with a thickness of 0.035 mm is formed on the front surface, and
A coating layer with a thickness of 0.040 mm made only of styrene
Was used. The core is coated on the polyethylene-coated surface of the support.
After pretreatment with Rona discharge, the following layers are applied in sequence.
Clothed. First layer: Silver chlorobromide milk containing 4 mol% of silver bromide
A blue-sensitive silver halide emulsion layer composed of an agent
Silver halide containing 350 g of gelatin per mol of silver halide
Sensitizing dye (1) of the following structure per mole: 2.5 × 10^-FourMole
Sensitized using isopropyl alcohol as solvent
Used), 2,5 dissolved and dispersed in dibutyl phthalate
-Di-t-butyl hydroquinone 200mg / m^TwoAnd yellow mosquito
As a puller, [Y-1] having the following structure is used as a silver halide
2.0 × 10 per le^-1Containing mol, silver amount 300mg / m^TwoTo be
It has been applied. Second layer: dissolved in cibutyl phthalate
Dispersed di-t-octylhydroquinone 300mg / m^Two,ultraviolet
2- (2'-hydroxy-3 ', 5'-di-t-butyl as a radiation absorber
Ruphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3'-t-butyl-5'methylphenyl) -5-chloro
Ro-benzotriazole, 2- (2'-hydroxy-3 ', 5'-
Di-t-butylphenyl) -5-chloro-benzotriazole
Mixture of (1: 1: 1: 1) 200mg / m^TwoContaining gelatin
Gelatin 1900mg / m in layers^TwoIt is applied so that it becomes. Third layer: silver chlorobromide milk containing 2 mol% of silver bromide
A green-sensitive silver halide emulsion layer composed of an agent
Silver halide containing 450 g of gelatin per mol of silver halide
Sensitizing dye (2) of the following structure per mole: 2.5 × 10^-FourMole
Sensitized with dibutyl phthalate and tricresylpho
Sulfate 2: dissolved in a solvent consisting of 1, 2,5-di-t
-Butyl hydroquinone and magenta coupler as below
[M-1] of the above structure is 1.5 × 10 5 per mol of silver halide.
^-1Molar content, silver amount 230mg / m^Two, AI dye 50mg / m^TwoIn
Is applied as. As an antioxidant, 2,
2,4-Trimethyl-6-lauryloxy-7-t-octyl
Chroman was added in an amount of 0.30 mol per mol of the coupler. Fourth layer: Dissolved in dioctyl phthalate
Dispersed di-t-octylhydroquinone 30 mg / m^TwoAnd purple
2- (2'-hydroxy-3 ', 5'-di-t-
Butylphenyl) benzotriazole, 2- (2′-hydro)
(Xy-5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-
5-chloro-benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chloro-benzotri
Mixture of azoles (2: 1.5: 1.5: 2) 500mg / m^TwoTo
Contains gelatin layer, gelatin 1900mg / m^Twobecome
Is applied as. Fifth layer: silver chlorobromide milk containing 3 mol% of silver bromide
A red-sensitive silver halide emulsion layer composed of an agent
Silver halide containing 500 g of gelatin per mol of silver halide
Sensitizing dye (3) having the following structure per mol: 2.5 × 10^-FiveMole
Sensitized using, dissolved in dibutyl phthalate and dispersed
2,5-di-t-butylhydroquinone 150mg / m^TwoAnd Shi
Halogenated [C-1] having the following structure as an uncoupler
3.5 × 10 per mol of silver^-1Molar content, silver amount 280mg / m^Two, AI
40 mg / m dye^TwoIt is applied so that it becomes. Sixth layer: a gelatin layer containing 90% gelatin.
0 mg / m^TwoIt is applied so that Used for each photosensitive emulsion layer (first, third, fifth layers)
Other silver halide emulsions are described in Japanese Patent Publication No. 467772.
Prepared by the method described above, and each of them is sodium thiosulfate 5 water
Chemically sensitized with a Japanese-style product, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene (halogen
2.5 g per mol of silver halide, bis (vinyls) as a hardener
Rufonylmethyl) ether (10 mg / g gelatin) and
And saponin as a coating aid. [0149] Embedded image[0150] Embedded imageThe color paper produced by the above method is exposed.
After the light irradiation, the treatment was performed using the following treatment steps and treatment liquids. [0152]   Processing steps   (1) Color development 35 ℃ 45 seconds   (2) Bleach fixing 35 ℃ 45 seconds   (3) Stabilization treatment as an alternative to washing with water                       30 ℃ 90 seconds   (4) Dry 60 ℃ -80 ℃ 1 minute 30 seconds Treatment liquid composition [Color development tank liquid] The above color developer [Bleaching and fixing tank fluid]   Ferric ethylenediaminetetraacetic acid   Ammonium dihydrate 60.0g   Ethylenediaminetetraacetic acid 3.0g   Ammonium thiosulfate (70% solution) 100.0 ml   Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 5.50 with aqueous ammonia or glacial acetic acid and add water.
To make a total volume of 1 l. [0153] [Stable tank liquid alternative to washing]   Orthophenylphenol 0.2g   2.0 g of 1-hydroxyethylidene-1,1-diphosphonic acid (60% solution)   Ammonia water 3.0g Adjust to 1 liter with water and adjust to pH 7.8 with aqueous ammonia and sulfuric acid. The above-mentioned color developing tank solution and the floating
Fill the white fixing tank liquid and the stabilizing tank liquid, and
Samples were processed to determine the maximum yellow density.
Table 1 shows the results. However, the above-mentioned maximum density is the developer No. 1-6.
It was shown as a relative value with the concentration when 100 was used as 100. [0156] [Table 1] From Table 1, the color developer is represented by the general formula [1].
Contains hydroxylamine derivative and chelating agent
And the sulfite ion concentration is 1.0 × 10^-FourMore than 1.0 ×
Ten^-2By the following, color development by conventional technology
Compared to liquids, without deteriorating the preservability of color developer
Silver chloride is a bad side effect on the photographic properties of preservatives
When the photosensitive material with a high content rate is processed rapidly,
It turns out that it decreases. [0158]referenceExample 2 Change the color developing agent from 1) to 3) and exemplify the general formula [1]
Compound (17) to (13), (18), (20) and (24)
Other than changed toreferenceThe same experiment as in Example 1 was performed. The result
As a result, (13) above is slightly inferior to (17) above in terms of homeostasis.
ButreferenceResults similar to those of Example 1 were obtained. Example1 On a paper support laminated with polyethylene,
Layers are sequentially applied from the support side to produce an internal latent image type photosensitive material.
Made. First layer: cyan-forming red-sensitive silver halide milk
Agent layer 2,4-Dichloro-3-methyl-6- [α- as cyan coupler
(2,4-di-tert-amylphenoxy) butyramide] pheno
90 g, 2,5-di-tert-octylhydroquinone 2 g,
50 g of tricresyl phosphate, 200 g of paraffin and
50 g of ethyl acetate is mixed and dissolved, and dodecylbenzene sulfo
Gelatin solution containing sodium acidate was added, and the average particle size was 0.
Dispersed to 6 μm (described in US Pat.
Was prepared by the conversion method according to Example 1 of
Add internal latent image type silver halide emulsion (AgBr: AgCl = 70: 30)
And silver amount 400mg / m^Two, AI dye 20mg / m^Two, Coupler amount 360mg
/ M^TwoWas applied. Second layer: intermediate layer Dispersed in 5 g of gray colloidal silver and dibutyl phthalate
Containing 10 g of 2,5-di-tert-octylhydroquinone prepared 2.
100 ml of 5% gelatin solution is 400 mg / m of colloidal silver.^TwoWill be
Was applied. Third layer: magenta-forming green-sensitive silver halide
Emulsion layer 1- (2,4,6-trichlorophenyl) as magenta coupler
-3- (2-chloro-5-octadecylsuccinimidoanilino)
-5-Pyrazolone 100g, 2,5-di-tert-octylhydroxy
Non 5g, Sumilizer MDP (Sumitomo Chemical Co., Ltd.) 50g, PA
200 g of raffin, 100 g of dibutyl phthalate and ethyl acetate
50 g of dodecylbenzene sulfonic acid sodium salt
Add gelatin solution containing strontium to obtain an average particle size of 0.6 μm.
Internal dispersion prepared in the same way as the first layer
Add image type silver halide emulsion (AgBr: AgCl = 60: 40)
Amount 400mg / m^Two, AI dye 20mg / m^Two, Coupler amount 400mg / m^TwoTo
It was applied so that Fourth layer: yellow filter layer 5 g of yellow colloidal silver and dibutyl phthalate
Containing 5 g of 2,5-di-tert-octylhydroquinone dispersed
Mu 2.5% gelatin solution contains 200 mg / m of colloidal silver.^TwoTo be
Was applied. Fifth layer: yellow-forming blue-sensitive silver halide
Emulsion layer Α- [4- (1-benzyl-2-phenyl) as a yellow coupler
L-3,5-dioxo-1,2,4-triazolidinyl)]-α-viva
Ryl-2-chloro-5- [γ- (2,4-di-tert-amylphenoki
Si) Butyramide] acetanilide 120 g, 2,5-di-tert-
Octyl hydroquinone 3.5g, paraffin 200g, chinu
Bottle (manufactured by Ciba Geigy) 100 g, dibutyl phthalate 100
g and 70 ml of ethyl acetate are mixed and dissolved, and dodecylbenzene
Add a gelatin solution containing sodium sulfonate and add
Dispersed to have a diameter of 0.9 μm, the same as for the first layer
Made internal latent image type silver halide emulsion (AgBr: AgCl = 80: 2
0) is added, and the amount of silver is 400 mg / m^Two, Coupler amount 400mg / m^TwoIn
So that it was applied. Sixth layer: protective layer The amount of zetillane is 200 mg / m^TwoWas applied. [0166] All of the above layers are supported as a coating aid.
It contained nin. As a hardening agent, 2,4-dichloro-6-
Hydroxy-s-triazine sodium layers 2, 4 and 6
Add 0.02 g per 1 g of gelatin.
Added. The above internal latent image type light-sensitive material sample was subjected to an optical wetting
After exposing through a die, it was processed in the next step. Treatment process (38 ° C) Immersion (color developer) 8 seconds Color development 120 seconds (For the first 10 seconds, the entire surface is uniformly exposed with 1 lux of light) Bleach fixing 60 seconds 60 seconds Dry 60-80 ℃ 120 seconds The composition of each processing solution is as follows. [0169] (Color developer)   Benzyl alcohol 15ml   Ethylene glycol 10ml   Potassium sulfite Amount to obtain sulfite ion concentration in Table 2   Potassium bromide 1.0g   0.3 g of sodium chloride   Potassium carbonate 25.0g   Preservative (listed in Table 2)   Chelating agent (listed in Table 2)   Color-developing agent (exemplified compound (1) / (3) = molar ratio 1/1) 7.5 g   Optical brightener (same as in Example 1) 2.0 g Potassium hydroxide and water were added to make 1 liter. The pH is 10.2
0 was set. [0170] (Bleaching fixer)   Pure water 550 ml   Ethylenediaminetetraacetic acid iron (III)   65g ammonium salt   Ammonium thiosulfate (70% aqueous solution) 85 g   Sodium hydrogen sulfite 10g   Sodium metabisulfite 2g   Ethylenediaminetetraacetic acid-2 sodium 20 g Add pure water to make 1 liter, pH with ammonia water or dilute sulfuric acid
Adjust to = 7.0. The light-sensitive material is subjected to stepwise exposure by a conventional method.
By the method described above, the minimum reflection density (blue
Degree) was measured. Also, as in Example 1, the colorability of the color developing solution
Was evaluated. The results are shown in Table 2. [0173] [Table 2] From Table 2, the color developing solution according to the present invention is
For partial latent image type photosensitive materials, there is a desire for preservative photographic characteristics.
Blue Dmin, which is a bad influence, that is, yellow stay
And the relationship between increased homeostasis and homeostasis is improved, and
Color developer in light fog development due to improved stability
Stabilization of photographic characteristics by reducing the filter effect due to coloring
It is presumed that the effects such as the conversion can be obtained. Furthermore, the above effect
Fruit has a sulfite ion concentration of 1.0 × 10^-Four~ 1.5 × 10^-2Mol / l
It turns out that it is particularly large in the range. Example2 Chelating agents from (43) to (2), (3), (4),
Example except for changing to (5), (14), (15) and (16)
1As a result of performing the same experiment as in Example1Results similar to
was gotten.

Claims (1)

(57) [Claims] Halogenation with an internal latent image type silver halide emulsion layer
A silver color photographic light-sensitive material is prepared by using a hydroxylamine derivative represented by the following general formula [1] and 1.0 × 1 per liter of color developer.
Direct positive imaging silver halide color transfer containing sulphite ions at a concentration of 0 ^{-4 to} 1.5 x 10 ^-2 molar and a chelating agent.
A method of processing a silver halide color photographic light-sensitive material , which comprises processing with a color developing solution for a true light-sensitive material . Embedded image [In the formula, R ₁ and R ₂ each represent a hydrogen atom or an optionally substituted alkyl group. However, R ₁ and R ₂ are not hydrogen atoms at the same time. ]