JP2670667B2 - Color developer for silver halide color photographic light-sensitive material with improved safety and preservative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a silver halide color
-For more details on color developers for photographic light-sensitive materials, see
Replaces hydroxylamine, which is harmful and harmful to humans
Color development for silver halide color photographic materials using preservatives
Regarding the developer. [0002] 2. Description of the Related Art In color development, exposed halogen
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. In addition to others
The components such as heavy metal ions contained in the treatment liquid of
Accumulated by being brought into the color developing solution by Kukonami
It is. 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.
Harm has been reported [see, for example, G. FIG. St
echer, "The Merck Index An
  Encyclopedia of Chemical
  and Drugs "(The Merck Index
Ann Encyclopedia of Chemical and
・ Drags) 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 (such as iron ions or copper ions) in the color developer.
When it is mixed in, it decomposes and becomes 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, “occurrence of fogging”, caused by the solution is further
The situation is becoming 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, U.S. Pat. Nos. 3,823,017 and 3,61
No. 5,503, respectively. But these yes
The compound itself is unstable, and the color developer
There is no preservation effect in. On the other hand, hydroquinone or N-alkyne
Developer containing ru-p-aminophenol as a developing agent
Saccharose (sucrose) is a preservative
Also known as sucrose, sucrose is an aromatic primary
As a preservative for color developers containing min as a developing agent
Little effect. Ascorbic acid and its derivatives are black.
Known as a preservative for white photographic developers and color developers
However, these impede color development and cause a significant decrease in color density.
However, the color developer has a
Inferior to Further, α-described in JP-A-52-7779
Hydroxy aromatic alcohol, JP-A-52-27638
Hydroxamic acid compounds described in No. 52-143020
Α-Aminocarbonyl compound and the same 52-10
No. 2727, monosaccharides, No. 52-140324,
Amino acid derivatives of are 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 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. Also, Japanese Patent Publication No. 61-48698 and
No. 61-48699 discloses a bisulfite of aldehyde.
A method of using an addition compound in a color developer is disclosed.
You. Aldehyde bisulfite addition compounds can be used alone.
Even though it shows some degree of stability,
Not enough. As a method of increasing the preservative ability, sulfurous iodite
It is easily conceivable that co-existence of sulfur
The coexistence of the dye
In addition, the following problems are clarified by the study of the present inventors.
It was clear. That is, bisulfite addition of aldehyde
When a compound is used, the liquid itself is less colored but floats on the surface.
It was also found that there was a problem that playable things were generated. [0019] SUMMARY OF THE INVENTION Therefore, the object of the present invention.
Solves the above-mentioned drawbacks and is harmless to the human body and easy to handle.
Color development using conventional hydroxylamine containing a preservative
Preservation is improved compared to image liquid, and no floating matter is generated.
A processing solution that does not affect the photographic characteristics and can be processed quickly
To provide. [0020] [MEANS FOR SOLVING THE PROBLEMS]
Bright silver halide color photographic light-sensitive material color developer
Hydroxylamine derivative represented by the following general formula [1]
And a fluorescent whitening agent represented by the following general formula [2]And
Sulfite ion concentration is 2.5 × 10 ^-2 At mol / l or less,
Contains no benzyl alcoholIt is characterized by the following. [0021] 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. [0023] Embedded image Where X₁₁, X₁₂, Y₁₁And Y₁₂Is water
Acid group, halogen atom, morpholino group, alkoxy group,
Reeloxy group, alkyl group, aryl group, amino group,
It represents an alkylamino group or an arylamino group. M is water
Elemental atom, sodium atom, potassium atom, ammonium
Represents a group or a lithium atom. Hydrobisulfite adduct of aldehyde
Derivatives of xylamine or hydroxylamine are used together
Things are Japanese Patent Publication No. 61-48698 and 61-4869.
No. 9 gazette, the inventions described therein are
Hydroxylamine and aldehyde bisulfite
It is true that the combination with an addition compound is recognized as the best.
It is clear from the examples. According to the study by the present inventors, the above general formula
And a hydroxylamine derivative represented by [1]
By using together with the optical brightener represented by the general formula [2],
It turned out that the following points were greatly improved. Firstly color
Secondly, the stability of the developer is greatly improved.
Occurs over time when using a bisulfite addition compound of hydr
And no third matter is generated
Processing For example, when processing a light-sensitive material having a high silver chloride content.
Hydroxylamine causes a large concentration loss,
On the other hand, the color developer using the hydroxylamine derivative is
Suitable for rapid processing because almost no decrease in concentration occurs
Fourth, use a hydroxylamine derivative together
And suspected to be due to anti-irradiation dye
Thetain is prevented, and in addition, a light fog with a direct positive image is used.
In the redevelopment, the filter effect due to the coloring of the color developer
The number of fruits is reduced and stable photographic performance is obtained.
(5) Use of the above-mentioned fluorescent whitening agent prevents tar generation
It became clear that it will be done. Therefore, according to the present invention, the homeostasis is hydroxy.
Improved over color developer using silamine
Provides a stable color developer without impairing photographic performance.
It became possible to do. Furthermore, rapid processing and light fog development
It was possible to provide a suitable color developer. In the general formula [1], R₁And R_TwoBut
Examples of the substituent of the alkyl group represented include a sulfonic acid group and a hydrido group.
Roxyl group, alkoxy group (methoxy group, ethoxy group,
Propyloxy group, etc.), carboxyl group, amino group, etc.
Which may be mentioned, for example, in US Pat.
No. 7,125, No. 3,293,034, No. 3,2
87,124 etc. described in hydroxylamines
No. Hydroxylamine represented by the general formula [1]
R₁And R_TwoA compound in which both are not hydrogen atoms
The object is preferably used for improving the homeostasis, and particularly
R₁, R_TwoC number of 2 or more ethyl group, methoxyethyl
Most preferred are compounds such as groups, ethoxyethyl groups. 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-OC_TwoH_Four-NH-OH (7) HO-C_TwoH_Four-NH-OH (8) HOOC-C_TwoH_Four-NH-OH (9) HO_ThreeSC_TwoH_Four-NH-OH (10) N_TwoHC_ThreeH₆-NH-OH (11) C_TwoH_Five-OC_TwoH_Four-NH-OH (12) HO-C_TwoH_Four-OC_TwoH_Four-NH-OH [0032] Embedded image [0033] Embedded imageThese compounds are usually hydrochlorides, sulphates,
p-toluenesulfonate, oxalate, phosphate, acetate
It is used in the form of salt. Shown by the above general formula [1] in the color developer.
The concentration of the compound to be administered is usually, for example, 0.1 g / l to 50
g / l is preferable, and more preferably 0.3 g / l to 30
g / l, particularly preferably 0.5 g / l to 20 g /
It is l. The above compounds may be used alone or in combination of two or more.
May be used. The color developing solution of the present invention contains triazyl stylus.
Use of Ruben optical brightener prevents tar generation
It is preferable that the triazyl stilbene-based fluorescence is increased.
As the whitening agent, the compound represented by the general formula [2] is preferable.
It is used well. In the general formula [2], X₁₁, X₁₂, Y₁₁
And Y₁₂Is hydroxyl group, halogen such as chlorine or bromine
Atoms, morpholino groups, alkoxy groups (eg methoxy,
Ethoxy, methoxyethoxy, etc.), aryloxy groups
(Eg, phenoxy, p-sulfophenoxy, etc.), al
Kill group (eg, methyl, ethyl, etc.), aryl group (eg,
Phenyl, methoxyphenyl, etc.), amino groups, alkyl groups
Ruamino groups (eg methylamino, ethylamino, pro-amino
Pyramino, dimethylamino, cyclohexylamino,
β-hydroxyethylamino, di (β-hydroxyethyl
) Amino, β-sulfoethylamino, N- (β-sulfur
Foethyl) -N-methylamino, N- (β-hydroxy
Ethyl-N-methylamino, etc.), arylamino groups (eg,
For example, anilino, o-, m-, p-sulfoanilino, o-,
m-, p-chloroanilino, o-, m-, p-toluigi
No, o-, m-, p-carboxyanilino, o-, m
-, P-hydroxyanilino, sulfonaphthylamino,
o-, m-, p-aminoanilino, o-, m-, p-a
Nidino, etc.) M is hydrogen atom, sodium, cariu
Represents ammonium, ammonium or lithium. Specifically, the following compounds may be mentioned.
It is possible, but not limited to these. [0040] Embedded image[0041] Embedded image[0042] Embedded image [0043] Embedded image[0044] Embedded image[0045] Embedded imageThe above-mentioned triazyl stilbene whitening agent is
For example, "Fluorescent whitening agent" edited by the Chemical Industry Association (8 August 1976)
Issued monthly) Synthesize by the usual method described on page 8.
Can be. These triazylstilbene-based brighteners are
A preferred range is 0.2 to 20 g per liter of the color developing solution of the present invention.
Preferably used, particularly preferably in the range of 0.4 to 10 g
It is. The color developing solution of the present invention contains bisulfite of aldehyde.
It is an object of the present invention to contain an acid salt adduct.
It is preferable because it can be achieved at a high level. Alde preferably used in the present invention
The bisulfite addition compound of a hydride is represented by the following general formula [3] or
It is a compound represented by [4]. [0050] Embedded image In the general formulas [3] and [4], A₁,
A_Two, A_ThreeAnd A_FourIs a hydrogen atom or an alkane having 1 to 6 carbon atoms.
Represents a kill group, a formyl group, an acyl group or an alkenyl group.
M represents an alkali metal atom, and n represents an integer of 0 to 4
Represent. As the alkyl group having 1 to 6 carbon atoms, a linear
Alternatively, it includes branched ones, for example, methyl group, ethyl
Group, propyl group, isopropyl group, butyl group, pentyl
Group, isopentyl group, hexyl group, isohexyl group, etc.
And may be substituted.
(E.g., formylmethyl, 2-formylethyl, etc.)
Each group), amino group (eg aminomethyl, aminoethyl)
Each group), hydroxyl group (eg hydroxymethyi)
2-hydroxyethyl, 2-hydroxypropyl, etc.
Groups), alkoxy groups (eg methoxy, ethoxy, etc.)
Each group), a halogen atom (eg chloromethyl, trike
Substituents such as loromethyl and dibromomethyl).
I can do it. Examples of the acyl group include an acetyl group and a propyl group.
Ropionyl group, butyryl group, valeryl group and the like can be mentioned.
You. The alkenyl group is a substituted or unsubstituted group.
And the unsubstituted group is vinyl, 2-propenyl, etc.
And each of them is substituted with, for example, 1,2-
Dichloro-2-carboxyvinyl, 2-phenylvinyl
And the like. Examples of the alkali metal atom represented by M are
Examples are sodium and potassium. Of the addition compounds represented by the above general formula
A specific example of the aldehyde moiety will be described, but the present invention is not limited to this.
It is not limited by this. [Exemplified Compound] I-1 formaldehyde I-2 acetaldehyde I-3 Propionaldehyde I-4 Isobutyraldehyde I-5 n-butyraldehyde I-6 n-valeraldehyde I-7 Isovaleraldehyde I-8 Methylethylacetaldehyde I-9 Trimethylacetaldehyde I-10 n-Hexaldehyde I-11 Methyl-n-propylacetaldehyde I-12 Isohexaaldehyde I-13 Glyoxal I-14 Malonaldehyde I-15 Succinic aldehyde I-16 Glutaraldehyde I-17 Adipine aldehyde I-18 Methylglyoxal I-19 Acetoacetaldehyde I-20 glycol aldehyde I-21 ethoxyacetaldehyde I-22 Aminoacetaldehyde I-23 Betaine aldehyde I-24 Chloral I-25 Chloroacetaldehyde I-26 dichloroacetaldehyde I-27 Bromar I-28 dibromoacetaldehyde I-29 Iodoacetaldehyde I-30 α-chloropropionacetaldehyde I-31 α-Bromopropionacetaldehyde I-32 Mucochloric acid Among these compounds, with formaldehyde bisulfite
Additives and acetaldehyde bisulfite adducts are effective
Greatly preferred. Color development of bisulfite adducts of aldehydes
The appropriate amount of addition to the liquid is 0.1 to 30 g / l.
It is preferably 0.7 to 10 g / l. In the color developing solution of the present invention, sulfite ion
Concentration is 2.5 × 10^-2Mol / l or less, especially 1.5 × 10
^-2It is preferably mol / l or less. Sulfite ion
In order to contain the above-mentioned concentration,
In addition to addition of acid salt adducts, water-soluble sulfites such as sulfite
Sodium acid, potassium sulfite, etc. may be added. Sulfite ion concentration is 2.5 × 10^-2Mol /
If it exceeds 1, there is a large decrease in density with respect to high silver chloride light-sensitive materials.
It becomes. Sulfite ion concentration is 1.0 x 10^-FourMol / l
It is preferable that it is not too low from the viewpoint of homeostasis. The color developer of the present invention contains a chelating agent.
Is that the above-mentioned object of the present invention can be achieved to a higher degree.
Are preferred. That is, due to the contamination of heavy metal ions
This is because deterioration of the color developing solution is prevented and preservability is improved.
You. Aminopolycarboxylic acid as a preferred chelating agent,
Examples include organic phosphonic acids and tyrone derivatives. Especially
The Tyrone derivative precipitates with Ca and Mg in the color developer.
It is preferably used in the sense that it hardly causes starch formation. The above aminopolycarboxylic acid has the following general formula
In [5], the organic phosphonic acid is represented by the following general formula [6] or
It is represented by [7]. [0062] Embedded image In the general formula [5], E is alkylene
Group, cycloalkylene group, phenylene group, -B_Five-O-
B_Five-, -B_Five-OB_Five-OB_Five-Or-B_Five-Z-B_Five
Represents-. [0064] Embedded image B₁~ B₆Each represents an alkylene group
You. A₁′ 〜A_Three'Is -COOM' or -PO, respectively_Three
M_TwoRepresents'_Four'And A_Five'Is a hydrogen atom,
Hydroxyl group, -COOM 'or -PO_Three(M ')_TwoRepresents
M'represents a hydrogen atom or an alkali metal atom. [0066] Embedded imageIn the general formula [6], B₇Is alkyl
Represents a group, an aryl group or a nitrogen-containing 6-membered ring group. M'is water
Represents an elementary atom or an alkali metal atom. [0068] Embedded image In the general formula [7], B₈, B₉And B_Ten
Is a hydrogen atom, a hydroxyl group, -COOM ', -PO, respectively._Three
(M ')_TwoOr represents an alkyl group, L₁, L_TwoAnd L_ThreeIs
Hydrogen atom, hydroxyl group, -COOM ', -PO
_Three(M ')_TwoOr -N (J)_TwoRepresents J is a hydrogen atom,
Alkyl group, -C_TwoH_FourOH or -PO_Three(M ')_TwoRepresents
You. M'represents a hydrogen atom or an alkali metal atom, n
And m each represent 0 or 1. The following is represented by the general formula [5], [6] or [7]
A part of the specific examples of the chelating agent represented will be shown. For use in the present invention
The chelating agents that can be used are not limited to the following specific examples.
Absent. [0071] Embedded image[0072] Embedded image[0073] Embedded image[0074] Embedded image[0075] Embedded image[0076] Embedded imageRepresented by the above general formulas [5] to [7]
The chelating agent is 0.0 per 1 liter of the color developing solution of the present invention.
It is preferable to use 1 to 100 g, more preferably
0.05 to 50 g, particularly preferably 0.1 to 20
g. The Tyrone derivative is represented by the following general formula [8]
It is a compound represented by [11]. [0079] Embedded imageIn the general formulas [8] and [9], 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 a substituted or unsubstituted phenyl group
Represents R₁₉, R₂₀, R_{twenty one}And R_{twenty two}Are hydrogen atoms or
It represents an alkyl group having 1 to 18 carbon atoms. n is 1-3
Represents an integer. R_FifteenMay be the same or different. R_FifteenIs good
Preferred is a sulfonic acid group. [0081] Embedded image In the general formula [10], R_{twenty three}And R_{twenty four}Is
It represents a hydrogen atom, a halogen atom or a sulfo group. [0083] Embedded image In the general formula [11], R₂₉And R₃₀Is
Hydrogen atom, phosphoric acid group, carboxylic acid group, -CH_TwoCO
OH, -CH_TwoPO_ThreeH_TwoOr a salt thereof, X_ThreeIs water
Represents an acid group or a salt thereof, W₁, Z₁And Y₁Is water
Elemental atom, halogen atom, hydroxyl group, cyano group, carboxylic acid
Groups, phosphoric acid groups, sulfonic acid groups or their salts,
Represents a coroxy group or an alkyl group. Also m_ThreeIs 0 or 1,
n_ThreeIs an integer from 1 to 4, l₁Is 1 or 2, p_TwoIs an integer from 0 to 3
Number, q₁Represents an integer of 0 to 2. Keys represented by the above general formulas [8] to [11]
Specific examples of the rate agent include the following. [0086] Embedded image [0087] Embedded image[0088] Embedded image[0089] Embedded imageKiret represented by the general formulas [8] to [11]
Chelating agents represented by [8] or [11]
It is more effective to use
That is, the chelating agent represented by the formula [11] is used.
Particularly preferred chelating agents (45), (49), or
Is to use the chelating agent represented by (54).
It is possible to use two or more of these chelating agents in combination.
Wear. The above-mentioned general formula [8] used in the present invention:
The chelating agent represented by any one of [11] is a color developing solution.
1 × 10 per liter^-FourAdd in the range of 1 mol to 1 mol
Is preferred, and more preferably 2 × 10^-Four~ 1 × 10^-1Mo
Can be added within the range of 5 to 1 and more preferably 5 x 1
0^-Four~ 5 × 10^-2It can be added in a molar range. Color development used in the color developing solution of the present invention
As a main drug, p-phenylenediamine having a water-soluble group
Compounds are preferable from the viewpoint of obtaining the effects of the present invention. P-Phenylenediamine Having Water-Soluble Group
The compound is N, N-diethyl-p-phenylenediamine
P-Phenylenediamine system that does not have water-soluble groups such as amine
Compared to compound, there is no contamination of the light-sensitive material and the skin
Also has the advantage that the skin is less likely to get rash. The water-soluble group is p-phenylenediamine.
At least one on the amino group or benzene nucleus of the compounds
Specific examples of the water-soluble group include those having: -(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 respectively
Represents an integer of 0 or more. ), -COOH group, -SO_ThreeH group
And the like are preferred. Color developing agents preferably used in the present invention
Specific examples of the compound are shown below. [0096] Embedded image[0097] Embedded image[0098] Embedded image[0099] Embedded image[0100] Embedded image[0101] Embedded image The above color developing agent is usually a hydrochloride or a sulfuric acid.
Salt, p-toluenesulfonate, etc.
1 × 10 per liter of color developing solution^-3~ 2 x 10^-1Mo
It is preferable to use within the range of
To 1.5 × 10 per liter of color developer^-3~ 2 x 10^-1Mo
Is more preferable. In addition to the above components, the color developing solution of the present invention comprises
The following developer components can be included. As an 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. In addition, if necessary, an inorganic or organic turnip may be used.
An anti-static agent can be added. If necessary, a development accelerator may also be used.
Can be put. U.S. Patent No. 1 as a development accelerator
No. 2,648,604, No. 3,671,247, special
Various types of pyridis represented by the official gazette of Kosho 44-9503
Nium compounds and other cationic compounds, phenosa
Medium such as furan-like cationic dye, thallium nitrate
Salt, US Pat. Nos. 2,533,990 and 2,53
1,832, 2,950,970, 2,5
77, 127 and JP-B-44-9504.
Polyethylene glycol and its derivatives, polythioether
Nonionic compounds such as rutiles, Japanese Patent Publication No. Sho 44-9509
The organic solvents described in the report are included. Also, US Pat.
Benzyl alcohol described in No. 04,925,
Phenethyl alcohol and acetylene glyco
, Methyl ethyl ketone, cyclohexanone, thioe
Ethers, pyridine, ammonia, 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
Nol, acetone, dimethylformamide, β-cyclo
Dextrin and other Japanese Patent Publication Nos. 47-33378 and 4
The solubilities of the developing agents described in JP-A-4-9509 are listed.
Organic solvents for 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
(Meth), phenidone, N, N'-diethyl-p-
Aminophenol hydrochloride, N, N, N ', N'-tetra
Methyl-p-phenylenediamine hydrochloride and the like are known.
The addition amount is usually 0.01 g to 10 g / l.
preferable. In addition to this, competing couplers, or
Blurring agents, colored couplers, development inhibitor releasing caps
Ra (so-called DIR coupler), and development inhibitor release
A compound or the like can be added. 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 developing solution of the present invention can be used in any pH range.
It is possible, but from pH 9.5 to 13.0 from the viewpoint of rapid processing
Preferably, it is more preferably pH 9.8 to 1
Used in 2.0. Color development processing using the color developing solution of the present invention
The theoretical temperature is 30 ° C or higher and 50 ° C or lower, and the higher the temperature, the shorter
This is preferable because it enables rapid processing in time, but conversely
There is also a problem of easy deterioration, more preferably 30 ° C.
The temperature is preferably 45 ° C or lower. Color development processing using the color developer 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.
Simultaneous oxidation of the formed metallic silver 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. Specific examples of these are as follows.
Things can be mentioned. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or sake
Lithic acid) [9] Ethyl ether diamine tetraacetic acid [10] glycol ether amine tetraacetic acid [11] ethylenediaminetetrapropionic acid [12] phenylenediamine tetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt
    salt [14] Ethylenediaminetetraacetic acid tetra (trime
Chill ammonium salt [15] Ethylenediaminetetraacetic acid tetranatriu
Salt [16] pentanate diethylenetriaminepentaacetate
Lium salt [17] Ethylenediamine-N- (β-oxyethyl
) -NN ′, N′-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt
Salt The bleaching solution used contains the metal complex salt of an organic acid as described above.
In addition to being contained as a whitening agent, it may contain various additives.
it can. As the additive, particularly an alkali halide or
Ammonium halides such as potassium bromide, sodium bromide
Re-halogenation of lithium, sodium chloride, ammonium bromide, etc.
It is desirable to include a genating agent, a metal salt, and a chelating agent.
New The pH of borate, oxalate, carbonate, phosphate, etc.
Propellants, alkylamines, polyethylene oxides, etc.
What is known to be added to the normal bleaching solution
Can be 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
PH buffering agents may be used alone or in combination of two or more.
You. Replenishing bleach-fixing solution (bath) with bleach-fixing replenisher
When performing the treatment while doing so, the bleach-fix solution (bath) should be treated with thiosulfuric acid.
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 bleach-fixing solution preferably used in the present invention
The pH is preferably 3.0 to 9.0, more preferably 4.
It is in the range of 0 to 8.0. Washing solution after bleach-fixing treatment or stabilizing solution alternative to washing with water
Fixing solution and bleach-fixing solution
From the processing solution containing the soluble silver complex salt of
May be collected. For example, electrolysis method (French Patent No. 2,29
9,667), precipitation method (JP-A-52-73037,
German Patent 2,331,220), ion exchange method (JP
Sho 51-17114, German Patent No. 2,548,237
No. 1) and a metal substitution method (British Patent No. 1,353,805).
No.) etc. can be effectively used. Color development using the color developer 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 stabilizing) → bleach-fixing → washing
(Or stable) (7) Color development → stop → bleach-fix → washing with water (or stable) (8) Color development → bleaching → washing → fixing → washing → stable (9) Color development → bleaching → fixing → washing with water → stable (10) Color development → bleaching → washing with a small amount of water → fixing → 1st stability
→ 2nd stability (11) Color development → bleaching → washing with a small amount of water → fixing → washing with a small amount of water
→ Washing → Stable (12) Phenomenon → Bleaching → Fixing → Stable (13) Color development → stop → bleaching → washing with a small amount of water → fixing → low
Amount Washing → 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.
It can be applied to photographic materials. The feeling of being processed by the color developing solution of the present invention.
There is no special limitation on the light-sensitive material,
Has a silver chloride content of 85 mol% or more, and further 90 mol% or more
In the case of, the effect of the present invention, the speed is achieved, preferably
Used. The crystals of silver halide grains are
It may be crystal or other, and the {100} plane and {111} plane
Any ratio can be used. In addition, these halogens
The crystal structure of silver halide grains is uniform from the inside to the outside.
However, even if it is a
It may be of a rectangular shape. Also these halos
Silver genide is a type that mainly forms a latent image on the surface.
May also be of the type formed inside the particles. More flat
Silver halide grains (JP-A-58-113934,
Japanese Patent Application No. 59-170070).
Is also good. 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 you define the width (%) of the distribution by
Those having a monodispersity of 20% or less are preferable, and more preferable.
It is preferably 10% or less. The particle size is spherical halogenated
In the case of silver particles, this is the diameter; in the case of non-spheres, the area is the same
It is calculated in terms of spheres. 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, the pH and pAg in the reaction kettle
And the like, for example, JP-A-54-48521.
Growth rate of silver halide grains as described in
Sequential and simultaneous injection of appropriate amounts of silver and halide ions
It is preferable to mix and mix. These silver halide emulsions were prepared from active gelatin
Sulfur sensitizers such as allylthiocarbamide, thiourine
Sulfur sensitizers such as elemental and cystine; Selenium sensitizers; Reduction sensitizers
For example, stannous salt, thiourea dioxide, polyamine, etc .;
Metal sensitizers, such as gold sensitizers, specifically potassium auriti
Ocyanate, potassium chloroaurate, 2-uro
Thio-3-methylbenzothiazolium chloride, etc.
Or ruthenium, palladium, platinum, rhodium,
Sensitizers for water-soluble salts such as iridium, specifically ammonium
Umchloroparadate, potassium chloroplatinate and
And sodium chloroparadate (some of these
Is a sensitizer or antifoggant depending on the amount.
Act. ) Alone or in combination as appropriate (eg
Combination of gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer
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 have a wavelength in the desired photosensitivity range.
In order to impart photosensitivity, a sensitizing dye is added to the silver halide 1 mol.
5 × 10 for Le^-8~ 3 x 10^-3Optical by adding a mole
You may sensitize. Various sensitizing dyes are used
And one or more sensitizing dyes
It can be used together. Further, the light-sensitive material to which the present invention can be applied is a red-sensitive material.
-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 type.
Chain ketomethylene compounds and so-called 2-equivalent couplers
Active point-O-aryl substituted coupler, active point
-O-acyl-substituted coupler, active-point hydantoin compound
Substitution coupler, active point urazole compound substitution coupler and
Active site succinimide compound substituted coupler, active site
Fluorine substitution coupler. Active site chlorine or bromine substituted coupler
Active sites, o-sulfonyl-substituted couplers, etc.
It can be used as an yellow coupler. I can use
Specific examples of the yellow coupler include U.S. Pat. No. 2,872.
No. 5,057, No. 3,265,506, No. 3,4
08,194, 3,555,155, 3,
No. 582,322, No. 3,725,072, No.
3,891,445, West German Patent No. 1,547,868
No. 2, West German Application Publication No. 2,219,917, No. 2,2
61,361, 2,414,006, British patent
No. 1,425,020, Japanese Patent Publication No. 51-10783,
JP-A-47-26133, 48-73147, and
No. 51-102636, No. 50-6341, No. 50-
No. 123342, No. 50-130442, No. 51-2
No. 1827, No. 50-87650, No. 52-8242
No. 4, No. 52-115219, No. 58-95346.
And the like. 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 examples, US Pat. No. 2,600,788,
No. 2,983,608, No. 3,062,653, No.
No. 3,127,269, No. 3,311,476,
No. 3,419,391, No. 3,519,429
Issue No. 3,558,319 Issue No. 3,582,32
No. 2, No. 3,615, 506, No. 3, 834, 9
08, No. 3,891,445, West German Patent No. 1,8
No. 10,464, West German Patent Application (OLS) No. 2,40
No. 8,665, No. 2,417,945, No. 2,4
No. 18,959, No. 2,424,467, Japanese Patent Publication No. 4
No. 0-6031, JP-A Nos. 51-20826 and 52-
58922, 49-129538, 49-74.
027, 50-159336, 52-4212.
No. 1 and 49-74028. No. 50-60233,
No. 51-26541, No. 53-55122, Japanese Patent Application No.
Listed in No. 55-110943 etc.
Can be. 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 examples, US Pat. No. 2,369,929,
No. 2,434,272, No. 2,474,293, No.
No. 2,521,908, No. 2,895,826,
No. 3,034,892, No. 3,311,476
No. 3, No. 3,458,315, No. 3,476,56
No. 3, No. 3,583,971, No. 3,591,3
No. 83, No. 3,767, 411, No. 3,772,
No. 002, No. 3,933,494, No. 4,000
No. 4,929, West German Patent Application (OLS) No. 2,414,
No. 830, No. 2,454,329 and JP-A-48-5.
No. 983, No. 51-26034, No. 48-5055.
No. 51-146827, No. 52-69624,
No. 52-90932, No. 58-95346, Japanese Patent Publication Sho
49-11572 etc. can be mentioned.
You. 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
The applicant's description of Japanese Patent Application No. 59-193611 is
Regarding the polymer coupler, Japanese Patent Application No.
The description of No. 9-172151 can be referred to. The addition amount of the above coupler is not limited, but
1 x 10 per mole of silver^-3~ 5 mol is preferred and more preferred
Or 1 × 10^-2~ 5 × 10^-1Is a mole. Silver halide color copying to which the present invention can be applied
In addition to various photographic additives in the true light-sensitive material
be able to. For example, Research Disclosure Magazine 1
Antifoggant, stabilizer, purple described in No. 7643
Outside line absorbent, color stain preventive, fluorescent whitening agent, color image fading prevention
Antistatic agent, antistatic agent, hardener, surfactant, plasticizer, wetting
Agents and the like can be used. In the light-sensitive material to which the present invention can be applied, milk
The hydrophilic colloids used to prepare the agent include
Latin, derivative gelatin, and gelatin and other macromolecules
Proteins such as raft polymer, albumin, and casein
Droxyethylcellulose derivative, carboxymethylse
Cellulose derivatives such as lulose, starch derivatives, polyvinyl chloride
Alcohol, polyvinyl imidazole, polyacryl
Single or copolymer synthetic hydrophilic polymer such as amide
Any of are included. Support for photographic light-sensitive material to which the present invention can be applied
As a reflective support such as baryta paper or polyethylene coated paper
A holding body and a transparent support are mentioned, and these supports are photosensitive materials.
It is appropriately selected according to the purpose of use of the fee. 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 light-sensitive material contains a DIR compound,
Well, in addition to the DIR compound, the
It may also contain compounds which release image inhibitors, eg
For example, US Pat. Nos. 3,297,445 and 3,37.
9,529, West German Patent Application (OLS) No. 2,417,
914, JP-A-52-15271 and JP-A-53-911.
No. 6, No. 59-123838, No. 59-127038.
And the like. The above-mentioned DIR compound is an oxidation of the color developing agent.
React with the body to develop a development inhibitor or a development inhibitor precursor
A non-diffusible DIR compound that is a compound that can be released
It may be a compound or a diffusible DIR compound. Representative examples of such DIR compounds
Has the effect of suppressing development when it leaves the active site.
By introducing a group capable of forming a compound at the active site of the coupler.
DIR couplers, such as British Patent No. 935,
454, U.S. Pat. Nos. 3,227,554 and 4,
095,954, 4,149,886, etc.
Have been. The above DIR coupler is a color developing agent.
Upon coupling reaction with the oxidant, the coupler nucleus is a dye
And has the property of releasing the development inhibitor.
In the present invention, U.S. Pat. Nos. 3,652,345 and
No. 3,928,041, No. 3,958,993, No.
No. 3,961,959, No. 4,052,213,
JP-A-53-110529, JP-A-54-13333,
Coloring as described in No. 55-161237
When a coupling reaction occurs with the oxidant of the developing agent, the development is suppressed.
Includes compounds that release an inhibitor but do not form a pigment
You. Furthermore, JP-A-54-145135
No. 56-114946 and No. 57-154234.
Reaction with an oxidant of a color developing agent as described in No.
The mother nucleus forms a pigment or a colorless compound,
Or the detached timing group is an intramolecular nucleophilic substitution reaction or
Is a compound that releases a development inhibitor by an elimination reaction
A so-called timing DIR compound may be used. Further, JP-A-58-160954 and JP-A-58-160954.
Oxidation of color developing agents described in US Pat.
When it reacts with the body, it produces a completely diffusible pigment.
The timing group as described above is bound to the puller nucleus.
It may be an iming DIR compound. These DIR compounds are generally used in emulsion layers.
2 x 10 per mole of silver^-Five~ 5 × 10^-1Mole is preferred,
More preferably 1 × 10^-Four~ 1 × 10^-1Use moles
And [0148] 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. Example 1 A color developer having the following composition was prepared. [0150] (Color developing solution)   Potassium sulfite 3.0 × 10^-3Mole   Sodium chloride 0.3g   25.0 g potassium carbonate   Preservative (listed in Table 1)   No fluorescent whitening agent (listed in Table 1) or 2.0 g   Color developing agent [exemplary compound (1)] 5.0 g Potassium hydroxide and water were added to make 1 liter. The pH is 1
It was set to 0.10. Second in color developing solution (No. 1 to No. 7)
Iron ion 4ppm, copper ion 2ppm and calcium ion
On 100ppm (each FeCl_Three, CuSO_Four・ 6
H_TwoO and CaCl_TwoDissolved and added) to 50 ℃
Opening ratio 30cm^Two/ L (for 1 liter developer, air
Contact area is 30 cm^Two) In a glass container. The appearance (coloring degree) of the color developing solution after 7 days and
The floating material was observed. However, the appearance of the liquid was divided into the following four stages. [0154] +++ Large amount of tar generation ++ Blackening + Browning (quite discolored) -Almost unchanged Table 1 shows the results. [0155] [Table 1] From Table 1, as a preservative, the formula [1]
A hydroxylamine derivative represented by the formula [2]
By using the optical brighteners represented, conventional preservatives
In comparison with the case of using
It can be seen that there are no floating substances. Example 2 Change the color developing agent from the exemplified compound (1) to (3),
An example is a hydroxylamine derivative represented by the general formula [1]
To the compounds (13), (18), (21) and (24)
Even if changed, the same results as in Example 1 could be obtained. Example 3 The following layers were formed on a polyethylene-coated paper support.
A photosensitive material was prepared by sequentially coating from the side. As the polyethylene-coated paper, a flat paper is used.
Polyethylene with an average molecular weight of 100,000 and a density of 0.95
200 parts by weight, an average molecular weight of 2000 and a density of 0.80
Anatase-type acid mixed with 20 parts by weight of polyethylene
Extrusion coating by adding 6.8% by weight of titanium oxide
170g / m by method^TwoThickness of 0.
A coating layer of 035 mm is formed and polyethylene
If a coating layer with a thickness of 0.040 mm is provided,
Using. Roll over the polyethylene coated surface of this support
After the pre-treatment by na discharge, the following layers are sequentially applied.
did. First layer: silver chlorobromide milk containing 4 mol% of silver bromide
A blue-sensitive silver halide emulsion layer composed of an agent
Halogenated containing 350 g of gelatin per mol of silver halide
Sensitizing dye (I) having the following structure: 2.5 × 10 per mol of silver^-Four
Sensitized with mol (isopropyl alcohol as solvent
), Dissolve in dibutyl phthalate and disperse
2,5-di-t-butylhydroquinone 200 mg /
m^TwoAnd [Y-1] having the following structure as a yellow coupler
2.0 × 10 per mol of silver halide^-1Including moles, silver
Amount 300mg / m^TwoIt is applied so that it becomes. Second layer: dissolved in cibutyl phthalate
Dispersed di-t-octylhydroquinone 300 mg /
m^Two, 2- (2'-hydroxy- as UV absorber
3 ', 5'-di-t-butylphenyl) benzotriazo
2- (2'-hydroxy-5'-t-butylphene
Nyl) benzotriazole, 2- (2'-hydroxy-
3'-t-butyl-5'methylphenyl) -5-chloro
-Benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chloro-
Mixture of benzotriazoles (1: 1: 1: 1) 200
mg / m^TwoGelatin layer containing 1900m gelatin
g / m^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
Halogenated containing 450 g of gelatin per mol of silver halide
Sensitizing dye (II) of the following structure 2.5 × 10 per mol of silver^-Four
Sensitized with moles of dibutyl phthalate and tricle.
2,5 dissolved in a solvent of dil phosphate 2: 1
-Di-t-butyl hydroquinone and magenta coupler
[M-1] of the following structure per mol of silver halide
1.5 × 10^-1Mol content, silver amount 230mg / m^Two, A
50 mg / m of I dye^TwoIt is applied so that it becomes.
As the antioxidant, 2,2,4-trimethyl-6-
Coupling lauryloxy-7-t-octyl chroman
0.30 mol was added per mol. Fourth layer: Dissolved in dioctyl phthalate
30 mg / m of di-t-octylhydroquinone dispersed
^TwoAnd 2- (2'-hydroxy- as an ultraviolet absorber
3 ', 5'-di-t-butylphenyl) benzotriazo
2- (2'-hydroxy-5'-t-butylphene
Nyl) benzotriazole, 2- (2'-hydroxy-
3'-t-butyl-5'-methylphenyl) -5-chloro
Lo-benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chloro-
A mixture of benzotriazoles (2: 1.5: 1.5:
2) 500 mg / m^TwoIs a gelatin layer containing
Latin 1900mg / m^TwoIs applied so that
You. Fifth layer: silver chlorobromide milk containing 3 mol% of silver bromide
A red-sensitive silver halide emulsion layer composed of an agent
Halogenated containing 500 g of gelatin per mol of silver halide
2.5 × 10 sensitizing dye (III) having the following structure per mol of silver
^-FiveSensitized with mol and dissolved in dibutyl phthalate
2,5-di-t-butylhydroquinone 15 dispersed
0mg / m^TwoAnd a cyan coupler having the following structure [C
-1] to 3.5 × 10 per mol of silver halide^-1Including mole
Having, silver amount 280 mg / m^Two, AI dye 40mg / m^Two
It is applied so that it becomes. Sixth layer: This is a gelatin layer.
00 mg / m^TwoIt is applied so that Used for each photosensitive emulsion layer (first, third, fifth layers)
The silver halide emulsion is described in JP-B-46-7772.
Prepared by the method listed, and use sodium thiosulfate
Chemically sensitized with sodium pentahydrate and used as a stabilizer
Roxy-6-methyl-1,3,3a, 7-tetrazaine
Den (2.5g per mol of silver halide) as a hardener
Bis (vinylsulfonylmethyl) ether (gelatin
Containing 10mg per 1g) and saponin as coating aid
I was sorry. [0167] Embedded image[0168] [Chemical 38]The 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. [0170]   Processing steps   (1) Color development 35 ° C 45 seconds   (2) Bleach-fixing 35 ℃ 45 seconds   (3) Washing alternative stabilization treatment 30 ° C 90 seconds   (4) Drying 60 ℃ -80 ℃ 1 minute 30 seconds Treatment liquid composition [Color developer tank solution] Color developer solution N used in Example 1
o. 1-1 to No. 1-13 [Bleach-fix tank liquid]   Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0 g   Ethylenediaminetetraacetic acid 3.0g   Ammonium thiosulfate (70% solution) 100.0 ml   Ammonium sulfite (40% solution) 27.5ml When the pH is adjusted to 5.50 with aqueous ammonia or glacial acetic acid,
Then, add water to make the total volume 1 liter. [0171] [Stable tank substitute for washing]   Orthophenylphenol 0.2g   1-hydroxyethylidene-1,1-diphosphonic acid   (60% solution) 2.0 g   Ammonia water 3.0g Adjust to 1 liter with water and adjust pH to 7.8 with aqueous ammonia and sulfuric acid.
You. The above-mentioned color developing tank solution and a floating
Fill the white fixing tank liquid and the stabilizing tank liquid, and
The super sample was processed. Table 2 shows the results. However, the maximum concentration is the same as that of developer No. 1-11
It was shown as a relative value with the concentration when 100 was used as 100. [0174] [Table 2] From Table 2, the photographic characteristics with preservatives are shown.
The adverse effect is that the compound represented by the general formula [1] is used as a preservative.
And a fluorescent whitening agent represented by the general formula [2]
At least equivalent to conventional preservatives
It turns out that it is less than that. Therefore, the results shown in Table 1
Together with the preservative and optical brightener according to the present invention,
Traditional preservatives can have undesired effects on photographic properties.
To be equal to or less than that of
It turns out that it can be improved. Example 4 Developer No. 1 of Example 1. Table 3 is described in 1-1 developer composition.
Developing solution (No. 2-1 to No. 2-
5) was used and storage conditions were changed to 50 ° C-14 days.
The same experiment as in Example 1 was conducted. The results are the developer of Example 1.
No. It is shown in Table 3 together with the data of 1-1. [0177] Further, the amount of the yellow ink measured by the same method as in Example 3 was used.
The maximum color density of the rho is set to No. Relative with 1-1 as 100
The values are shown in Table 3. [0178] [Table 3] From Table 3, in the color developer, the general formula
A preservative represented by [1] and a firefly represented by general formula [2]
In addition to (a) sulfite ion concentration
2.5 x 10^-2(B) the sharpness
The purpose of the present invention is further enhanced by the inclusion of a glaze agent.
It turns out that it can be achieved every time. Example 5 Illustrative compounds (4) of the optical brighteners are (2), (5),
(7), (9), (11) and (14)
Is the same as Example 4 as a result of performing the same experiment as Example 4.
Was obtained. Example 6 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 Cyan coupler, 2,4-dichloro-3-methyl-6-
[Α- (2,4-di-tert-amylphenoxy) bu
Cylamide] phenol 90 g, 2,5-di-tert
-Octylhydroquinone 2g, tricresylphosphine
50 g, paraffin 200 g and ethyl acetate 50 g
Mixed and dissolved in sodium dodecylbenzenesulfonate
The average particle size becomes 0.6μm by adding the gelatin solution containing
(As described in US Pat. No. 2,592,250)
Prepared by the conversion method according to Example 1 of
Internal latent image type silver halide emulsion (AgBr: AgCl)
= 70: 30), and the amount of silver is 400 mg / m^Two, AI
Dye 20 mg / m^Two, Coupler amount 360mg / m^Twobecome
As applied. Second layer: intermediate layer Dispersed in 5 g of gray colloidal silver and dibutyl phthalate
2,5-di-tert-octylhydroquinone 1
100 ml of 2.5% gelatin solution containing 0 g of colloidal silver
Amount 400mg / m^TwoWas applied. Third layer: magenta-forming green-sensitive silver halide
Emulsion layer Magenta coupler, 1- (2,4,6-trichlorophene
Nyl) -3- (2-chloro-5-octadecylsuccine
Imidoanilino) -5-pyrazolone 100 g, 2,5-
Di-tert-octyl hydroquinone 5 g, Sumirai
ZD MDP (Sumitomo Chemical Co., Ltd.) 50 g, paraffin 2
00 g, dibutyl phthalate 100 g and ethyl acetate 5
Mix and dissolve 0 g of sodium dodecylbenzene sulfonate
And a gelatin solution containing
An inner part prepared in the same manner as the first layer, dispersed so that
Latent image type silver halide emulsion (AgBr: AgCl = 60:
40) was added, and the amount of silver was 400 mg / m 2.^Two, AI dye 20
mg / m^Two, Coupler amount 400mg / m^TwoPainted to be
Clothed. Fourth layer: yellow filter layer 5 g of yellow colloidal silver and dibutyl phthalate
Dispersed 2,5-di-tert-octylhydroquinone
Colloidal silver is 200m in 2.5% gelatin solution containing 5g
g / m^TwoWas applied. Fifth layer: yellow-forming blue-sensitive silver halide
Emulsion layer Yellow coupler, α- [4- (1-benzyl-2-f
Phenyl-3,5-dioxo-1,2,4-triazolide
Nyl)]-α-bivalyl-2-chloro-5- [γ-
(2,4-di-tert-amylphenoxy) butyla
Mido] acetanilide 120 g, 2,5-di-tert-
Octyl hydroquinone 3.5 g, paraffin 200
g, Tinuvin (Ciba-Geigy) 100 g, dibutyl
Mix and dissolve 100g of phthalate and 70ml of ethyl acetate
And Zera containing sodium dodecylbenzene sulfonate
Add tin solution and disperse so that the average particle size becomes 0.9μm.
Internal latent image type halogen made in the same manner as the first layer
Add silver halide emulsion (AgBr: AgCl = 80: 20)
And silver amount 400mg / m^Two, Coupler amount 400mg / m^Two
Was applied. Sixth layer: protective layer The amount of zetillan is 200 mg / m^TwoWas applied. In all the above layers, a support as a coating aid is used.
It contained nin. Also, as a hardening agent, 2,4-dichloro
-6-hydroxy-s-triazine sodium layer 2,
0.04g per 1g gelatin in 4 and 6 respectively
It was added so that it might become. The above-mentioned internal latent image type light-sensitive material sample
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, 1 Lux of light is used to uniformly expose the entire surface.
light) Bleach fixing 60 seconds Water wash 60 seconds Dry 60-80 ℃ 120 seconds The composition of each processing solution is as follows. [0191] (Color developing solution)   Benzyl alcohol 15ml   Ethylene glycol 10ml   Potassium bromide 1.0g   Sodium chloride 0.3g   25.0 g potassium carbonate   Preservative (listed in Table 4)   Fluorescent brightener (described in Table 4) not added or 2.0 g   Chelating agent (Exemplary compound 43) 0.6 g   Color developing agent (exemplary compound (1) / (3) = molar ratio 1/1) 5.0 g Potassium hydroxide and water were added to make 1 liter. The pH is 1
It was set to 0.20. As preservatives, those described in Table 4 were used.
In addition to the
Potassium sulfate was added. [0193] (Bleaching fixer)   Pure water 550 ml   Iron (III) ammonium ethylenediaminetetraacetate 65g   85 g of ammonium thiosulfate (70% aqueous solution)   Sodium hydrogen sulfite 10g   Sodium metabisulfite 2g   Ethylenediaminetetraacetic acid-2 sodium 20 g Add 1 liter of pure water and pour with ammonia water or dilute sulfuric acid.
Adjust to H = 7.0. The above light-sensitive material is subjected to stepwise exposure by a conventional method.
By the method described above, the minimum reflection density (blue
Was measured. Also, as in Example 1, coloring of the color developing solution
The sex was evaluated. Table 4 shows the results. [0196] [Table 4]From Table 4, for the internal latent image type photosensitive material
Also, by the preservative and optical brightener according to the present invention,The present invention
The color developing solution of contains benzyl alcoholPhoto
The increase in Dmin, which is an undesirable effect on sex, is obeyed.
Color development at or below the level of conventional preservatives
It is possible to improve the homeostasis of the liquid, and
By improving the homeostasis, it is
The filter effect due to coloring is reduced and the photographic characteristics are reduced.
It can be seen that effects such as standardization can be obtained. Further, the color developing solution according to the present invention isBenji
Even if it contains alcoholSulfite ion concentration is 1.0 ×
10^-FourMol / l or more 2.5 × 10^-2Mol / l or less, especially
1.0 x 10^-FourMol / l or more, 1.5 × 10^-2Mol / l
It turns out that the following is preferable. [0199] According to the present invention, the following effects (a) to (d) are obtained.
Can be obtained. (A) As a preservative of the color developing solution, it is a poisonous substance.
It is not necessary to use a hydroxylamine, and
Preservation of the color developer is improved compared to the conventional one, especially tar
Is prevented from occurring. (B) Silver halide color suitable for rapid processing
ー As a photographic light-sensitive material, it has little adverse effect on photographic characteristics.
A color developing solution that does not exist and has good homeostasis is provided. (C) According to the anti-irradiation dye,
Inferred stains are prevented. (D) Halogenation having an internal latent image type emulsion
When light-fog developing a silver color photographic light-sensitive material, color development
The filter effect due to the coloring of the image liquid is reduced and stable.
Excellent photographic characteristics can be obtained.

   ────────────────────────────────────────────────── ─── Continuation of front page    (56) References Japanese Patent Laid-Open No. 54-3532 (JP, A)                 JP-A-57-150847 (JP, A)                 Japanese Patent Publication 7-11696 (JP, B2)                 Patent 2544608 (JP, B2)                 US Patent 4906554 (US, A)                 European Patent Application Publication 278003 (EP, A)

Claims (1)

(57) [Claims] Contains a hydroxylamine derivative represented by the following general formula [1] and a fluorescent bleaching agent represented by the following general formula [2]
And the sulfite ion concentration is 2.5 × 10 ^-2 mol / l or less
And a color developer for silver halide color photographic light-sensitive materials, characterized in that it does not contain benzyl alcohol . 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. [Chemical formula 2] [Wherein, X ₁₁ , X ₁₂ , Y ₁₁ and Y ₁₂ each represent a hydroxyl group, a halogen atom, a morpholino group, an alkoxy group, an aryloxy group, an alkyl group, an aryl group, an amino group, an alkylamino group or an arylamino group. . M represents a hydrogen atom, a sodium atom, a potassium atom, an ammonium group or a lithium atom. ]