JPH04330441A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain stable photographic performance high in gradation and small in fog and stable against the change of the concentration of a developing agent in a color developing solution. CONSTITUTION:The method for processing the imagewise exposed silver halide color photographic material is characterized by using the color developing solution containing bromine ions in the concentration of >=30millimol/l and substantially no sulfite.

Description

Detailed Description of the Invention [Field of Industrial Application] [0001] The present invention relates to a silver halide color photographic light-sensitive material.
(hereinafter referred to as color photosensitive materials)
In addition, it has high gradation, less fog, and
Stable photographic performance against changes in the concentration of the active ingredient in the color developer.
This relates to the processing method obtained. [Prior Art] Generally, a color developer contains a color developer.
Various preservatives are used to prevent deterioration of the main drug and prevent liquid discoloration.
It is used. Hydroxylua is a typical preservative.
There are minerals and sulfites, but these compounds affect photographic performance.
often have an impact. In particular, sulfites are
The main agent reacts with the coupler after silver development and becomes a dye.
Acts as a competitive compound for the puller, reducing the efficiency of color development
Ru. Removing sulfites from color developers reduces color development efficiency.
Generally speaking, sensitivity or gradation increases in terms of photographic performance.
To increase. For example, in Japanese Patent Application Laid-Open No. 61-73955,
2 for high-sensitivity, high-contrast color development, and shortened processing time.
A color photosensitive material containing an equivalent magenta coupler is treated with sulfite ion.
Color development with an on-concentration of 0.015 mol/liter or less
It describes how to treat with liquid. According to the document, sulfur
By reducing the concentration of acid ions, the oxidized form of the developing agent can be
This reduces competition with other couplers, and provides high sensitivity gradations.
It says that it can be done. However, if the sulfite ion concentration is reduced, turnip
This may cause oxidation to occur more easily, or the density of the color developing agent may change.
The accompanying changes in photographic properties will increase, and stable photographic performance will always be obtained.
It turned out that it would no longer be possible. Problems to be Solved by the Invention Therefore, the first aspect of the present invention
The purpose of this is to process color photosensitive materials with high gradation and low fog.
The objective is to provide a method of management. The second object of the present invention is to
Stable photographic performance against changes in main ingredient concentration in color developer
The purpose of this invention is to provide a processing method that can obtain the following. [Means for Solving the Problems] The objects of the present invention are as follows.
achieved by the method. That is, imagewise exposed halogen
silver chloride color photographic light-sensitive materials containing substantially sulfites.
and no more than 30 mmol/liter of bromide io
It is characterized by being processed with a color developer containing
Depending on the processing method of silver halide color photographic light-sensitive materials,
achieved. Furthermore, the effect of the present invention is that the above color developer is
2-Methyl-4-[N-ethyl-N-(β-hydroxy
ethyl)amino]aniline and/or its salts
-Contains at least 21 mmol/liter of developing agent
and the bromide ion to the color developing agent.
Optionally, the molar ratio present is in the range of 1.3 to 3.5.
Effectively demonstrated. The present invention will be explained in more detail below. Main departure
"Substantially sulfite-free" as defined in
The concentration of sulfite in the image solution is 1.6 x 10-3 mol/
It refers to less than a liter, preferably 0.8 x 10
-3 moles/liter or less, preferably no
It means that. As a sulfite, sodium sulfite
Thorium, potassium sulfite, ammonium sulfite, etc.
Sodium sulfite is particularly preferred. The bromide ion concentration in the present invention is 30 mmol/liter.
Torr or more, preferably 40 mmol/liter
be. These bromide ion concentrations are affected by the development inhibitory effect.
This is a concentration range that is normally considered undesirable.
be. However, the present invention does not contain substantially sulfites.
By not having it, the effect of suppressing development is small and good results can be obtained.
What was obtained is surprising even to those skilled in the art.
Ta. Bromide ion is optionally added to color developers as an additive.
Can be added. KBr is a typical additive.
, NaBr, NH4Br, and the like. Furthermore, the main
In order to maintain the specified bromide ion concentration, color exposure
Adjust the replenishment amount by taking elution from the material into consideration, and adjust the color appearance.
By adjusting the halogen composition of the optical material, a specified concentration can be achieved.
It can be done as follows. Color development that can be used in the present invention
The main component of the liquid is an aromatic primary amine color developing agent.
It is an alkaline aqueous solution containing Preferred color development
The main drug is a p-phenylenediamine derivative.
They are shown below, but are not limited to these. D-1 N,N-diethyl-p-phenylenediamine
D-2 2-methyl-N,N-diethyl-p-phenylene
Diamine D-3 4-[N-ethyl-N-(β-hydroxyethyl
thyl)amino]aniline D-4 2-methyl-4-[N-ethyl-N-(β-
hydroxyethyl)amino]aniline D-6 4-amino-3-methyl-N-ethyl-N-
[β-(methanesulfonamido)ethyl]aniline D-
7 4-amino-3-methyl-N-ethyl-N-meth
Xyethylaniline D-8 4-amino-3-methyl-N-ethyl-N-
(4-Hydroxybutyl)aniline Among the above p-phenylenediamine derivatives, particularly preferred is
Specifically, it is D-4. In addition, these p-phenylene
Diamine derivatives include sulfate, hydrochloride, sulfite, and p-tol.
It may also be a salt such as an ensulfonate. aromatic first
The amount of grade amine color developing agent used is 1 liter of color developing solution.
A concentration of 0.01 to 0.1 mol per torr is preferred, and more
Preferably the concentration is 0.021 mol or more. The present invention
For more effective implementation, the developer concentration should be
Concentration of approximately 0.016 mol/liter, which is the typical usage amount.
If the amount is 0.021 mol/liter or more, which is considerably higher than that of
and the bromide ion concentration is
It is best to adjust the ratio so that the ratio is in the range of 1.3 to 3.5.
preferable. That is, the bromide ion concentration is 0.027
So-called high activity equivalent to ~0.074 mol/liter
It is more effective in the case of color developers that tend to be
You can get results. The color developer of the present invention contains the aromatic
As a compound that directly preserves primary amine color developing agents.
JP-A-63-5341 and JP-A No. 63-106655
Various hydroxylamines (among them sulfo groups and
Compounds having a carboxy group are preferred. ), Japanese Patent Publication No. 6
Hydroxamic acids described in No. 3-43138, No. 63-
hydrazines and hydrazides described in No. 146041,
Described in No. 63-44657 and No. 63-58443
phenols described in No. 63-44656;
Droxyketones and α-aminoketones, 63-36
It can contain various saccharides described in No. 244. In addition, in combination with the above compounds, JP-A No. 63-4235
, No. 63-24254, No. 63-21647, No. 6
No. 3-146040, No. 63-27841 and No. 6
Monoamines described in No. 3-25654, etc., No. 63-3
No. 0845, No. 63-14640, No. 63-4313
Diamines described in No. 9, etc., No. 63-21647, No. 9, etc.
Described in No. 63-26655 and No. 63-44655
Polyamines, nitro as described in No. 63-53551
Xyradicals, No. 63-43140 and No. 63-5
Alcohols described in No. 3549, No. 63-56654
The oximes described in No. 63-239447 and the oximes described in No. 63-239447
The tertiary amines mentioned can be used. Other protection
As a constant agent, JP-A-57-44148 and JP-A-57-44148
Various metals described in No. 53749, No. 59-18058
Salicylic acids described in No. 8, described in No. 54-3582
alkanolamines, described in No. 56-94349
Polyethyleneimines of U.S. Pat. No. 3,746,54
Add the aromatic polyhydroxy compound described in No. 4 as necessary.
It may also be included. In particular, the sulfites that constitute the present invention
If the alkanolamines do not substantially contain
Addition is preferred. As alkanolamines, monoe
Tanolamine, diethanolamine, triethanol
Examples include amines, with triethanolamine being particularly preferred.
Delicious. 1 liter of alkanolamine color developer
Preferably 20 mmol to 140 mmol per 35
More preferably mmol to 100 mmol. The color developer used in the present invention is preferably
preferably pH 9 to 12, more preferably 9 to 11.0.
Ru. Various buffers are used to maintain the above pH.
is preferable. Specific examples of buffering agents include sodium carbonate.
potassium carbonate, sodium bicarbonate, potassium bicarbonate
, trisodium phosphate, tripotassium phosphate, dibasic phosphate
Thorium, dipotassium phosphate, sodium borate, boron
potassium acid, sodium tetraborate (borax), tetraboric acid
Potassium, sodium o-hydroxybenzoate (salici
sodium chlorate), potassium o-hydroxybenzoate,
Sodium 5-sulfo-2-hydroxybenzoate (5-
sodium sulfosalicylate), 5-sulfo-2-hydro
Potassium roxybenzoate (potassium 5-sulfosalicylate)
(m), etc. The amount of buffer added is
The amount should be 0.1 mol or more per liter of color developer.
Preferably, it is particularly preferably 0.1 to 0.4 mol.
Delicious. [0009] In addition, the color developer contains calcium and
As a magnesium precipitation inhibitor or for color development
Use various chelating agents to improve liquid stability
is preferred. Organic acid compounds are preferred as chelating agents.
For example, aminopolycarboxylic acids, organic phosphonic acids
, phosphonocarboxylic acids. these
Typical examples are diethylenetriaminepentaacetic acid and ethylene.
Ndiaminetetraacetic acid, N,N,N-trimethylenephosphone
acid, ethylenediamine-N,N,N',N'-tetramethane
tyrenephosphonic acid, transcyclohexanediaminetetra
Acetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyl
Tyliminodiacetic acid, glycol ether diamine tetraacetic acid
, ethylenediamine orthohydroxyphenylacetic acid, 2
-phosphonobutane-1,2,4-tricarboxylic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, N,N
'-Bis(2-hydroxybenzyl)ethylenediamine
-N,N'-diacetic acid and the like. these beautiful
Two or more of these agents may be used in combination, if necessary. Chelate
The amount of agent added is determined to sequester metal ions in the color developer.
For example, 1 liter of color developer
The amount is about 0.1g to 10g per bottle. [0010] The color developer may contain any developing agent as required.
Accelerators can be added. However, the present invention
Color developing solutions in
Contains virtually no benzyl alcohol in terms of prevention
The case is preferred. Here, "substantially" means color developer
Contains less than 2ml per liter, preferably not at all
It means that. Other development accelerators include
No. 37-16088, No. 37-5987, No. 38-7
No. 826, No. 44-12380, No. 45-9019
, U.S. Patent No. 3,818,247, etc.
Tel-based compounds, JP-A-52-49829 and JP-A-52-49829
p-phenylenediamine compound described in No.-15554
Product, JP-A No. 50-137726, JP-A No. 44-300
No. 74, JP-A-56-156826, JP-A No. 52-434
Quaternary ammonium salts described in No. 29 etc., U.S. Patent No. 2
, No. 494,903, No. 3,128,182, No. 494,903, No. 3,128,182, No.
No. 4,230,796, No. 3,253,919, Special
Publication No. 41-11431, U.S. Patent No. 2,482,54
No. 6, No. 2,596,926, No. 3,582,3
Amine compounds described in No. 46 etc., Japanese Patent Publication No. 37-160
No. 88, No. 42-25201, U.S. Patent No. 3,128
, No. 183, Special Publication No. 41-11431, No. 42-23
No. 883, U.S. Patent No. 3,532,501, etc.
Polyalkylene oxide, other 1-phenyl-3-
Add pyrazolidones, imidazoles, etc. as necessary
can do. The amount of development accelerator added depends on the color developer.
It is about 0.01g to 5g per liter. [0011] In the present invention, if necessary, furthermore,
Any antifoggant can be added. As an antifoggant
are alkali metals such as sodium chloride and potassium iodide.
Genus halides and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole.
, 6-nitrobenzimidazole, 5-nitroisoin
dazole, 5-methylbenzotriazole, 5-nitro
Benzotriazole, 5-chloro-benzotriazole
, 2-thiazolyl-benzimidazole, 2-thiazoli
methyl-benzimidazole, indazole, hydro
Nitrogen-containing heterozygotes such as xiazaindolizine and adenine
A typical example is a ring compound. Anti-fogging
The amount of inhibitor added is 0.001 per liter of color developer.
It is about 1 g to 1 g. Color developer used in the present invention
may contain an optical brightener. As an optical brightener
is 4,4'-diamino-2,2'-disulfostilbe
Preferred are ion-based compounds. The amount of optical brightener added depends on the color
0 to 5 g, preferably 0.1 g to 4 g per liter of image solution
It is g. In addition, alkyl sulfonic acid, alkyl sulfonic acid,
Lylsulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid
Various surfactants such as acids may be added. [0012] The color developer replenisher includes
Includes compounds that have. What is the role of color developer replenisher?
, due to deterioration over time during processing of photosensitive materials and in automatic processors.
replenishing the color developer with compounds that decrease due to
The concentration of compounds eluted from photosensitive materials can be controlled by
By rolling, the developing performance can be kept constant.
Ru. Therefore, the former compound is more effective than the color developer tank liquid.
in high concentrations, and the latter compounds in low concentrations. Examples of the former compounds include color developing agents and preservatives.
The replenisher contains 1.1 to 2 times the amount of tank fluid. In addition, the latter compounds include halides (e.g. bromide).
Development inhibitors such as potassium (potassium) are included in the replenisher.
contains 0 to 0.6 times the tank liquid. In addition, processing and
Compounds that are not prone to concentration changes are usually colored
Contained at approximately the same concentration as the developer tank liquid. As an example of this
Examples include chelating agents and buffering agents. Furthermore, color development
The pH of the replenisher prevents the pH of the tank liquid from decreasing due to processing.
Therefore, it should be about 0.05 to 1.5 higher than the tank liquid. child
The difference in pH of
. The replenishment amount of color developer is 3 per m2 of photosensitive material.
000ml or less, but 70ml to 1000ml
It is preferable that [0013] Processing temperature with color developer is 20 to 50°C.
is suitable, preferably 30 to 45°C. During processing
The appropriate time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes.
minutes and 20 seconds, more preferably 1 minute to 2 minutes and 30 seconds.
Ru. In addition, the color developing bath can be divided into two or more baths as necessary.
Then, replenish the color developer replenisher from the first bath or last bath.
However, even if you shorten the development time and further reduce the amount of replenishment,
good. The processing method of the present invention is also suitable for color reversal processing.
It can be used properly. Reversal processing is performed as necessary after black and white development.
After applying reversal processing, color development is performed. Koto
The black and white developer used for this process is a commonly known color developer.
- Called black and white first developer used for reversal processing of photosensitive materials.
It is used as a processing solution for black and white silver halide photosensitive materials.
A well-known additive used in black and white developers.
Various additives can be included. [0015] Typical additives include 1-phenyl-
such as 3-pyrazolidone, methol and hydroquinone.
developing agents, preservatives like sulfites, sodium hydroxide
From alkalis such as aluminum, sodium carbonate, potassium carbonate, etc.
Potassium bromide and 2-methylbenzimidazo
Inorganic or organic substances such as alcohol, methylbenzthiazole
water softeners such as polyphosphates, trace amounts of
Examples of development inhibitors include iodides and mercapto compounds.
can be done. [0016] Using the above black and white developer or color developer
When processing with an automatic processor, the developer (color developer and
The area where the black and white developer) comes in contact with air (opening area) is
It is preferable to make it as small as possible. For example, the opening area (cm
2) divided by the volume of developer (cm3) is the aperture ratio.
Then, the aperture ratio is preferably 0.01 (cm-1) or less.
more preferably 0.005 or less. The developer can be recycled and used. Recycling of developer means converting used developer into an anion exchange resin.
using fat, electrodialysis, or a process called a regenerating agent.
Increase the activity of the developer by adding chemical chemicals and process again.
It is used as a liquid. In this case, the reproduction rate (compensation
The ratio of overflow liquid in the filling liquid is preferably 50% or more.
Preferably, it is particularly preferably 70% or more. Using developer regeneration
As a process, after regenerating the developer overflow solution,
Use as a replenisher. As a method of regeneration, anion exchange resin
It is preferable to use Particularly preferred anion exchange resins
Regarding the composition and resin recycling method, please refer to Mitsubishi Chemical Industries, Ltd.
) published by Diaion Manual (I) (1986
14th edition). Also,
Among anion exchange resins, JP-A No. 2-952 and JP-A No.
Preferably, the resin has the composition described in No. 1-281152.
stomach. In the present invention, a color-developed photosensitive material
The gold is desilvered. The desilvering treatment mentioned here is basically
Basically, it consists of bleaching and fixing, but these can be done at the same time.
Bleach-fixing treatment and combinations of these treatments
be done. Typical desilvering treatment processes include the following:
Ru. ■ Bleach-Fix ■ Bleach-Bleach-Fix ■ Bleach-Water-Wash-Fix ■ Bleach-Bleach-Fix-Fix ■ Bleach-Fix ■ Fix-Bleach-Fix Among the above steps, steps ■, ■, and ■ are particularly preferred.
stomach. Regarding process
Disclosed in the issue. For process ■, see JP-A-61-1
43755 and Japanese Patent Application No. 2-216389.
There is. In addition, bleaching baths, fixing baths, etc. applied to the above processes
Even if the treatment bath has one tank configuration, it may have two or more tanks (for example, two or more tanks).
~4 tanks, in which case countercurrent replenishment method is preferred)
good. The above desilvering process is performed after color development using a rinse bath and water.
This may be done through a washing bath or a stop bath, but it is possible to
It is preferable to do this immediately after color development.
During reversal processing, it is performed through a conditioning bath after color development.
is preferred. The bleaching solution contains the compound of the present invention as described above.
It can contain things. The main components of the bleaching solution of the present invention and
Bleaching agents that can be contained include red blood salt, ferric chloride,
Inorganic compounds such as dichromates, persulfates, bromates and
Aminopolycarboxylic acid ferric complex salt, aminopolyphosphone
Some organic compounds of ferric acid complex salts can be mentioned.
. The present invention aims to improve environmental protection, handling safety, and metal corrosion.
Aminopolycarboxylic acid ferric complex salt is used from the viewpoint of edibility etc.
It is preferable to do so. [0020] Below, the aminopolycarboxylic acid used in the present invention will be described.
Specific examples of ferric acid complex salts are listed below, but are not limited to these.
It's not something you can do. In addition, the oxidation-reduction potential is recorded. No. Compound
　　　　　　　　　　　　　　　　　　　　　　　　　
redox potential
　　　　　　　　　　　　　　　　　　　　　　　　　
(mV vs.NHE
, pH=6)1. N-(2-acetamido)imino
Ferric diacetic acid complex salt 1802.
Methyliminodiacetic acid ferric complex salt
2003. stomach
Ferric minodiacetic acid complex salt
2104.
1,4-Butylenediaminetetraacetic acid ferric complex salt
2305. Diethylenethi
Oetherdiaminetetraacetic acid ferric complex salt
2306. Glycol ether diamine tetraacetic acid
Ferric complex salt 2407.
1,3-propylenediaminetetraacetic acid ferric complex salt
2508. Ethylenediami
Tetraacetic acid ferric complex salt
1109. diethylenetriamine
Ferric pentaacetic acid complex salt
8010. trans-1,2-cyclohex
Sandiaminetetraacetic acid ferric acid salt 800021
The redox potential of bleach in
Members of the Faraday Society (Tran
actions of the Faraday S
55 (1959), 1312-1
Obtained by measuring by the method described on page 313
Defined by redox potential. In the present invention, rapid processing
Oxidation from the viewpoint of effectively exhibiting the effects of the present invention
Bleaching agents with a reduction potential of 150 mV or more are preferred, and more preferred.
Preferably, the redox potential is 180 mV, most preferably 2
It is a bleaching agent with a voltage of 00 mV or more. Redox potential too high
The upper limit is 700 mV because this causes bleaching fog.
It is preferably 500 mV or less. Among these
However, particularly preferred is compound No. 7 no 1, 3-
It is a ferric complex salt of propylene diamine tetraacetic acid. [0022] Aminopolycarboxylic acid ferric complex salt is
It is used in salts of lium, potassium, ammonium, etc.
Ammonium salts are preferred because they bleach the fastest. [0023] The amount of bleach used in the bleaching solution is 1 liter of bleaching solution.
0.01 to 1 mol per liter is appropriate, preferably
is 0.17 to 0.7 mol, which speeds up the processing and speeds up the process over time.
0.25 to 0.7 mol is more preferable in terms of reducing tein.
stomach. Particularly preferred is 0.30 to 0.6 mol. Ma
The amount of bleach used in the bleach-fix solution is 1 liter of bleach-fix solution.
0.01 to 0.5 mol per mol, preferably 0.0 mol
It is 2 to 0.2 mol. In addition, in the present invention, an oxidizing agent
may be used alone or in combination of two or more, and two or more
When used together, ensure that the total concentration falls within the above range.
Bye. [0024] It should be noted that the bleaching solution is used to remove aminopolycarboxylic acid secondary
When using iron complex salts, add them in the form of complex salts as described above.
However, the complex-forming compound aminopolycal
Bonic acids and ferric salts (e.g. ferric sulfate, ferric chloride,
ferric nitrate, ferric ammonium sulfate, ferric phosphate) and
may coexist to form a complex salt in the treatment solution. this
If by complexation, the aminopolycarboxylic acid is
Added slightly in excess of the amount required for complex formation with ions.
When added in excess, it is usually 0.01 to 1.
Preferably, the amount is in excess of 0%. [0025] The above bleaching solution generally has a pH of 2 to
Used in 7.0. To speed up the process, bleaching
The pH of the liquid is preferably 2.5 to 5.0, more preferably
preferably 3.0 to 4.8, particularly preferably 3.5 to 4.5
The replenisher is usually 2.0 to 4.2.
Good to use. In the present invention, the pH is adjusted to the above range.
For binding, known acids can be used. This way
As the uric acid, an acid having a pKa of 2 to 5.5 is preferable. Book
In the invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant.
and was determined at an ionic strength of 0.1 mol/dm and 25°C.
Show value. The bleach solution has a pKa in the range of 2.0 to 5.5.
Containing 0.5 mol/liter or more of acid that causes bleaching
To prevent white fog and precipitation of replenisher due to aging at low temperatures.
This is preferable because it allows for This pKa2.0-5.5
Examples of acids include inorganic acids such as phosphoric acid, acetic acid, malonic acid,
It may be any organic acid such as citric acid, but the above
Acids with a pKa of 2.0 to 5.5 that exhibit effective effects through improvement
is an organic acid. Also, even in organic acids, carboxyl
Particularly preferred are organic acids having groups. pKa is 2.0-5
．． The organic acid in step 5 may be a monobasic acid or a polybasic acid.
It's okay. In the case of a polybasic acid, its pKa is 2.0 above.
~5.5, metal salts (e.g. sodium or carbonate)
It can be used as ammonium salt) or ammonium salt. Also p
Two or more types of organic acids with Ka2.0 to 5.5 can be used in combination.
Can also be done. However, the acid mentioned here includes aminopolycarbohydrate.
Excludes phosphoric acid, its salts and its Fe complex salts. pKa2. which can be used in the present invention.
Preferred specific examples of organic acids having a molecular weight of 0 to 5.5 include acetic acid.
, monochloroacetic acid, monobromoacetic acid, glycolic acid,
Ropionic acid, monochloropropionic acid, lactic acid, pyruvate
acid, acrylic acid, butyric acid, isobutyric acid, pivalic acid, aminobutyric acid
aliphatic monobasic acids such as valeric acid and isovaleric acid;
paragine, alanine, arginine, ethionine, glycine
glutamine, cysteine, serine, methionine,
Amino acid compounds such as isin; benzoic acid and chloro
, monosubstituted benzoic acids such as hydroxy, aromatic acids such as nicotinic acid, etc.
Aromatic monobasic acids; oxalic acid, malonic acid, succinic acid, alcoholic acid
Tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid
, aliphatic dibasic acids such as glutaric acid and adipic acid;
Amino acids such as spartic acid, glutamic acid, cystine, etc.
Dibasic acid; aromatic dibases such as phthalic acid and terephthalic acid
List of various organic acids such as polybasic acids such as citric acid
can do. Among these, hydroxyl groups and
Monobasic acids having a carboxyl group are preferred, especially
Licolic acid and lactic acid are preferred. Use of glycolic acid and lactic acid
The dosage is between 0.2 and 2 mol per liter of bleach solution, preferably
The amount is 0.5 to 1.5 mol. These acids are
More effective, no odor and eliminates bleaching fog
This is preferable because it suppresses Also, acetic acid and glycolic acid or
solves precipitation and bleaching fog at the same time by using lactic acid.
This is preferable because the effect of acetic acid and glyco
The preferred combination ratio of oleic acid or lactic acid is 1:2 to 2:1.
Delicious. The total amount of these acids used is
A suitable amount is 0.5 mol or more per liter. preferably
is 1.2 to 2.5 mol/liter. even more preferable
The ratio is 1.5 to 2.0 mol/liter. [0027] When adjusting the pH of the bleaching solution to the above range,
The acids and alkalis listed below (e.g. aqueous ammonia, KOH,
NaOH, imidazole, monoethanolamine, diene
(tanolamine) may be used in combination. Among them, ammonia
Water is preferred. [0028] Also, the starting solution of the bleach solution can be prepared from the replenisher solution.
As an alkaline agent to be used as a bleach starter when knotting,
Potassium carbonate, aqueous ammonia, imidazole, monoeta
Preference is given to using nolamine or diethanolamine.
Delicious. Also, use the replenisher as is without using a bleach starter.
It may also be used diluted. [0029] In the present invention, the bleaching solution or its pre-bath
Various bleach accelerators can be added. like this
For bleach accelerators, see, for example, U.S. Pat.
3,858, German Patent No. 1,290,821
Specification of British Patent No. 1,138,842, Patent Specification
Publication No. 53-95630, Research Scroll
The method described in Jiyar No. 17129 (July 1978 issue)
Compounds having lucapto or disulfide groups, JP-A
Thiazolidine induction described in Publication No. 50-140129
body, as described in U.S. Pat. No. 3,706,561.
Ourea derivatives, described in JP-A-58-16235
Iodide, as described in German Patent No. 2,748,430
Polyethylene oxides listed in Japanese Patent Publication No. 45-8836
Polyamine compounds described in the publication can be used.
Wear. Particularly preferably British Patent No. 1,138,842
Mercer as described in the specification and Japanese Patent Application No. 1-11256
Preferred are compound compounds. [0030] The bleaching solution in the present invention includes a bleaching agent and
In addition to the above compounds, bromides such as potassium bromide, bromide
Sodium, ammonium bromide or chloride, e.g. salt
Potassium chloride, sodium chloride, ammonium chloride, etc.
A rehalogenating agent may be included. rehalogenating agent
The concentration is 0.1 to 5 per liter in the treated liquid state.
．． 0 mol, preferably 0.5 to 3.0 mol. Also
, using ammonium nitrate as a metal corrosion inhibitor.
is preferable. [0031] In the present invention, a replenishment method is adopted.
is preferable, and the amount of replenishment of bleaching solution is per 1 m2 of photosensitive material.
, preferably 600 ml or less, more preferably 100 to
It is 500ml. In addition, the bleaching time is 120 seconds or less.
Preferably 50 seconds or less, more preferably 40 seconds or less
It's below. In addition, during treatment, aminopolycarboxylic acid
Bleach solutions using diiron complex salts should be aerated.
, oxidize the aminopolycarboxylic acid iron(II) complex salt produced.
It is preferable to do so. This regenerates the oxidizer and
True performance is maintained extremely stably. The drift in the present invention
For processing with white liquor, supply water equivalent to the evaporated content of the processing solution.
It is preferable to perform so-called evaporation correction. especially,
Odors from bleaching solutions containing color developers or high-potential bleaching agents
It is preferable. Specific methods for replenishing water in this way
Although there are no particular restrictions on the
No. 9, separate from the bleaching tank described in Publication No. 1-254960
A monitor aquarium is installed, and the amount of water evaporation in the monitor aquarium is measured.
From the amount of evaporation of water, calculate the amount of water evaporation in the bleaching tank.
Calculate the amount of evaporation and refill the bleach tank with water in proportion to this amount of evaporation.
Methods and patent applications No. 2-46743 and 2-47777,
2-47778, 2-47779, 2-11
Liquid level sensor and overflow described in 7972 specification
An evaporation correction method using a low sensor is preferred. After being treated with a bleaching solution in the present invention
The photosensitive material is processed with a processing liquid that has fixing ability. child
The processing liquid with fixing ability referred to here specifically refers to a fixing liquid.
and a bleach-fix solution. Processes that have bleaching ability are bleach-fixed.
When it is done with liquid deposition, it is
may also serve as a treatment having fixing ability. bleaching with bleach solution
In the above-mentioned steps ■ and ■, which involve processing with a bleach-fix solution after processing,
You can use different bleaching agents for the bleach solution and bleach-fix solution.
. When there is a washing process in between, as in the process of ■ above,
The liquid may also contain the compound of the present invention. [0033] The processing liquid having fixing ability contains a fixing agent.
It will be done. Sodium thiosulfate and thiosulfate are used as fixing agents.
ammonium, sodium ammonium thiosulfate, thiosulfate
thiosulfate like potassium acid, sodium thiocyanate
ammonium thiocyanate, potassium thiocyanate
Thiocyanates (Rhodan salts), thiourea, thio
Ether etc. can be given. Among them, thiosulfate
Preference is given to using ammonium. The amount of fixative is fixed.
0.3 to 3 mol per liter of processing solution with adhesion ability, preferably
Preferably it is 0.5 to 2 mol. Also, from the perspective of promoting retention
From the above ammonium thiocyanate (RO) to thiosulfate.
ammonium), thiourea, thioether (e.g.
(3,6-dithia-1,8-octanediol)
It is also preferable that Of these, thiosulfate and thiothia
Most preferably, it is used in combination with a phosphate salt. In particular, thiosulfur
The combination of ammonium acid and ammonium thiocyanate
preferable. The amount of these compounds used together has fixing ability.
0.01 to 1 mol per liter of processing solution, preferably
is preferably used at 0.1 to 0.5 mol, but in some cases
By using 1 to 3 moles, the effect of promoting fixation can be greatly increased.
It can also be increased. [0034] The processing liquid with fixing ability contains a preservative.
Sulfites (e.g. sodium sulfite, potassium sulfite,
ammonium sulfite), hydroxylamines, hydra
gins, bisulfite adducts of aldehyde compounds (e.g.
Acetaldehyde sodium bisulfite, particularly preferably
Compounds described in Japanese Patent Application No. 1-298935) or Japanese Patent Application Publication No. 1999-1
sulfinic acid compounds described in specification No.-231051, etc.
can be contained. In addition, various types of fluorescent whitening
agent, antifoaming agent or surfactant, polyvinylpyrrolidone
, an organic solvent such as methanol can be contained. Furthermore, the processing liquid having fixing ability has a
Various aminopolycarboxylic acids and organic phosphors are used for stabilization purposes.
Addition of chelating agents such as sulfonic acids is preferred. preferable
As a chelating agent, 1-hydroxyethylidene-1,
1-diphosphonic acid, ethylenediamine-N,N,N',
N'-tetramethylenephosphonic acid, nitrilotrimethylene
phosphonic acid, ethylenediaminetetraacetic acid, diethylenetetraacetic acid
lyaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,
2-propylenediaminetetraacetic acid can be mentioned. Among these, 1-hydroxyethylidene-1,1-diphon
Particularly preferred are sulfonic acid and ethylenediaminetetraacetic acid. The amount of chelating agent added is 0 per liter of processing liquid.
．． 01-0.3 mol, preferably 0.1-0.2 mol
be. The pH of the fixer is preferably 5 to 9.
, and more preferably 7 to 8. Also, the pH of the bleach-fix solution
is preferably 4 to 7, more preferably 5 to 6.5.
. Also, after being treated with a bleach solution or a first bleach-fix solution,
The pH of the bleach-fix solution is preferably 6 to 8, and more preferably
6.5 to 8.0 is preferred. [0037] A processing liquid having fixing ability has a pH range of
pKa of 6.0 or as a buffer.
It is preferable to contain a compound in the range of 9.0 to 9.0. Imidazole compounds are preferred as these compounds.
. The imidazole compound contains 0.01 mol/liter or more.
It is preferable to have it. Better than imidazole compounds
The preferable addition amount is 0.1 to 10 mol/liter, and
It is preferably 0.2 to 3 mol/liter. Imida
Zole compound refers to imidazole and its derivatives.
, as a preferable substituent of imidazole, an alkyl group
, alkenyl group, alkynyl group, amino group, nitro group,
Examples include halogen atoms. Also, alkyl
group, alkenyl group, alkynyl group can further include amino group, nitrogen group,
It may be substituted with a tro group, a halogen atom, etc. Imi
The preferred total carbon number of the substituents of dazole is 1 to 6,
The most preferred substituent is the methyl group. Specific examples of imidazole compounds are listed below.
However, it is not limited to these. imidazole 1-methylimidazole 2-methylimidazole 4-methylimidazole 4-(2-hydroxyethyl)-imidazole 2-ethyl
Imidazole 2-vinylimidazole 4-propylimidazole 4-(2-aminoethyl)imidazole 2,4-dimethy
Imidazole 2-chloroimidazole Among these, preferred compounds are imidazole and 2-methymidazole.
Ru-imidazole, 4-methyl-imidazole,
The most preferred compound is imidazole. [0039] In addition, the bleach-fix solution contains the above-mentioned bleach solution.
It can contain compounds that can have. In the present invention, the bleach-fix solution at the start of processing
(Start solution) is the chemical used in the bleach-fix solution mentioned above.
Bleach prepared by dissolving the compound in water, but prepared separately
It may also be prepared by mixing appropriate amounts of the liquid and the fixer. [0041] When using the replenishment method, the fixing solution or bleaching
The replenishment amount of white fixer is 10 per m2 of photosensitive material.
0 to 3000ml is preferred, more preferably 300ml
~1800ml. To replenish the bleach-fix solution, use the bleach-fix supplement.
It may be replenished as a filling liquid, or
No. 5 and Japanese Patent Application No. 2-216389, bleaching solution and
This may be carried out using an overflow solution of the fixer. [0042] Also, as in the bleaching process described above, processing solution replenishment and
Both are bleach-fixed while replenishing water equivalent to evaporated water.
It is preferable to do this. [0043] Furthermore, in the present invention, a treatment having a fixing ability
The total processing time is 0.5 to 4 minutes, preferably 0.5 to 2 minutes.
minutes, particularly preferably 0.5 to 1 minute. Smell of the present invention
The entire desilvering process consists of a combination of bleaching, bleach-fixing, and fixing.
The total processing time is preferably 45 seconds to 4 minutes, more preferably
Preferably it is 1 minute to 2 minutes. In addition, the processing temperature is 25 to 5
0°C, preferably 35-45°C. The processing liquid having the fixing ability of the present invention may be a known one.
Silver can be recovered by law, and if such silver recovery is carried out,
A regenerated liquid can be used. The silver recovery method is
Electrolysis method (described in French Patent No. 2,299,667),
Precipitation method (JP-A-52-73037, German Patent Nos. 2 and 3)
31,220), ion exchange method (Japanese Unexamined Patent Publication No. 1983-1
7114, German Patent No. 2,548,237) and
and metal replacement method (described in British Patent No. 1,353,805)
etc. are valid. These silver recovery methods recover silver from tank liquid.
It is preferable to carry out the process in-line, as the suitability for rapid processing is even better.
Delicious. After the fixing process, usually
Perform the water washing process. After processing with a processing liquid that has fixing ability,
Stabilization treatment using a stabilizing solution is performed without actually washing with water.
A simpler treatment method can also be used. Used for washing process
The washing water used and the stabilizing liquid used in the stabilization process include
To prevent uneven water droplets when drying photosensitive materials after processing,
It can contain various surfactants. these realms
As a surfactant, polyethylene glycol type nonionic
surfactant, polyhydric alcohol type nonionic surfactant
, alkylbenzenesulfonate type anionic surfactant
agent, higher alcohol sulfate ester salt type anionic surfactant
sexual agent, alkylnaphthalene sulfonate type anionic field
Surfactant, quaternary ammonium salt type cationic surfactant
, amine salt type cationic surfactant, amino salt type amphoteric surfactant
There are surfactants and betaine type amphoteric surfactants, but noniodine
It is preferable to use surfactants, especially alkyl surfactants.
Preferred are phenolic ethylene oxide adducts. Archi
In particular, phenols include octyl, nonyl, and dodecyl.
, dinonylphenol is preferred, and ethylene oxa
The number of moles of ide added is particularly preferably 8 to 14. Furthermore, using a silicone surfactant with a high antifoaming effect
Both are preferable. [0046] Also, the washing water and stabilizing solution contain water stains.
To prevent mold from forming on raw and processed photosensitive materials,
It can also contain various antibacterial and antifungal agents.
Wear. Examples of these antibacterial and antifungal agents are
JP-A-57-157244 and JP-A No. 58-105145
Thiazolylbenzimidazole system as shown in No.
Compounds, isothiol compounds as shown in JP-A No. 57-8542
Typical are azolone compounds and trichlorophenol
Chlorophenolic compounds such as bromophenols
compounds, organotin and organozinc compounds, acid amide compounds
, diazine and triazine compounds, thiourea compounds
, benzotriazole compounds, alkylguanidination
compound, as typified by benzalkonium chloride
Quaternary ammonium salts, such as penicillin
Antibiotics, etc., Journal Antibacteria and
・Antifungus Agent (J. Antib
act. Antifung. Agents) V
ol 1. No. 5, p. 207-223 (1983
There are two types of general-purpose anti-bacterial agents listed in ).
The above may be used in combination. Also, JP-A-48-83820
The various fungicides described can also be used. [0047] In addition, various types of cleaners are contained in the washing water and stabilizing solution.
It is preferable to include an agent. Preferred chelating agent
as ethylenediaminetetraacetic acid, diethylenetriacetic acid,
Aminopolycarboxylic acids such as aminepentaacetic acid and 1-hydroxy
Thiechylidene-1,1-diphosphonic acid, ethylenediamine
-tetraacetic acid, diethylenetriamine-N,N,N',N'
- organic phosphonic acids such as tetramethylene phosphonic acid;
Rui is anhydrous Malay as described in European Patent 345172A1
Examples include hydrolysates of phosphoric acid polymers. It can also be included in the fixer or bleach-fixer mentioned above.
It is also preferable to include a preservative in the washing water and stabilizing solution.
stomach. [0048] As the stabilizing liquid used in the stabilization step, the dye
Processing liquid that stabilizes images, such as organic acids and pH 3~
6 buffering capacity, aldehydes (e.g. formalin),
Do not use liquids containing chlorine or glutaraldehyde.
I can do it. The stabilizer contains compounds that can be added to the washing water.
It can contain all of the above, and if necessary, it can also contain
Ammonium compounds such as ammonium and ammonium sulfite
metal compounds such as Bi and Al, optical brighteners, hardeners
, alkanolamide described in U.S. Pat. No. 4,786,583.
You can use the following methods. [0049] In the present invention, the stabilizing liquid substantially contains
Preferably, it does not contain lumaldehyde. substantially
Free formaldehyde means free formaldehyde.
Total amount of dehyde and its hydrate is 0 per liter of stabilizer
．． 003 moles or less. Use such a stabilizing solution
This reduces the scattering of formaldehyde vapor during processing.
Wear. In this case, for the purpose of stabilizing the magenta dye,
Stabilizing solution or bleaching solution containing maldehyde-releasing compounds
Alternatively, it is preferable to have it present in the pre-bath (e.g. preparation bath).
Yes. Preferred as formaldehyde releasing compound
The compound is hexamethylenetetramine and its derivatives.
, formaldehyde bisulfite adduct, and N-methyl
It is a chemical compound. These preferred compounds are magenta
In addition to stabilizing the pigment, it also prevents the development of yellow stain over time.
suppress life. Hexamethylenetetramine and its derivatives
As for ``Beilstein's Handbook der...
"Organischen Hemy" (Beilsteins)
Handbuch der Organishen C
hemie) Volume II Expanded Edition Volume 26 P. 200-P.
Compounds described in 212 can be used, but in particular,
Hexamethylenetetramine is preferred. Also, Holmua
Formaldehyde bisulfite adduct is formaldehyde bisulfite.
Sodium sulfate is preferred. [0052] As the N-methylol compound, in particular, pyra
N-methylol compounds of sol and its derivatives, tri-
N-methylol compounds of azoles and their derivatives,
N-methylol compounds of lazole and its derivatives are preferred.
Delicious. Among the above formaldehyde-releasing compounds, especially
Preferred are hexamethylenetetramine and formamine.
rudehyde sodium bisulfite, and the preferred
It is an N-methylol compound. Among them, pyrazo
N-methylol compounds and triazol compounds and their derivatives
N-methylol compounds of alcohol and its derivatives, urazo
N-methylol compounds of alcohol and its derivatives are preferred.
stomach. Specific examples of these N-methylol compounds are:
, 1-hydroxymethylpyrazole 1-hydroxymethyl-2-methylpyrazole 1-hydro
roxymethyl-2,4-dimethylpyrazole 1-hydro
oxymethyltriazole 1-hydroxymethylurazole Among these, the most preferred is 1-hydroxymethyl
It is a pyrazole. The above N-methylol compound is
Amine compounds without tyrol groups and formalde
by reacting with hyde or paraformaldehyde.
Therefore, it can be easily synthesized. The above N-methylol compound
When using methylol groups in the processing solution,
It is preferable to coexist with an amine compound, and N-methyl
Preferably, the coexistence is 0.2 to 10 times the molar concentration of the alcohol compound.
. The preferred amount of the above formaldehyde-releasing compound is
0.003 to 0.2 mol per liter of treatment liquid, preferably
The amount is 0.005 to 0.05 mol. these holms
Aldehyde-releasing compounds can be used in combination of two or more in the bath.
You can stay there. [0053] The pH of the stabilizing solution is preferably 6 to 9.
, 6.5 to 8 are more preferable. The washing process and stabilization process
, a multistage countercurrent system is preferred, and the number of stages is preferably 2 to 4.
Delicious. The replenishment amount is the amount brought in from the previous bath per unit area.
1 to 50 times, preferably 2 to 30 times, more preferably
It is 2 to 15 times. [0054] Used in these water washing steps and stabilization steps.
Tap water can be used, but ion exchange resin
The Ca and Mg ion concentration was adjusted to 5 mg/liter by
Deionized water, halogen, ultraviolet germicidal lamp, etc.
It is preferable to use more sterilized water. Also, various places
Even if you use tap water to correct the evaporation of the physical solution,
Good, but deionized preferably used in the above water washing step
It is best to use treated or sterilized water. Also, wash with water
The overflow liquid of a process or stabilization step is a prebath
By using a method of flowing into a bath having fixing ability
, is preferable because the amount of waste liquid can be reduced. process
In addition to bleaching solution, bleach-fixing solution, and fixing solution,
Other processing solutions (e.g. color developer, wash water, stabilizer)
However, to compensate for the concentration due to evaporation, an appropriate amount of water or
It is preferable to replenish the correction liquid or processing replenishment liquid. [0055] In the present invention, the drying process after the bleaching process is started.
The total treatment time with the treatment solution is 1 minute to 3 minutes, preferably
The effect is particularly effective between 1 minute and 20 seconds to 2 minutes.
. In the present invention, the drying temperature is preferably 50 to 65°C.
The temperature is particularly preferably 50 to 60°C. Drying time is 30
Seconds to 2 minutes are preferred, particularly 40 seconds to 80 seconds are more preferred.
stomach. The photosensitive material of the present invention has a small amount on the support.
At least halogen in the blue-sensitive layer, green-sensitive layer, and red-sensitive layer
It is sufficient if at least one silver emulsion layer is provided.
, the number and layers of silver halide emulsion layers and non-photosensitive layers
There are no particular restrictions on the order. Typically, on a support
, multiple colors with substantially the same color sensitivity but different sensitivities
Halogen with a photosensitive layer consisting of a silver halide emulsion layer
It is a silver oxide color photographic material, and the photosensitive layer is blue light and green light sensitive.
Unit sensitivity that is sensitive to either colored light or red light
It is a multilayer silver halide color photographic material.
In general, the unit photosensitive layers are arranged sequentially from the support side.
A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order.
Ru. However, even if the above installation order is reversed depending on the purpose,
Also, when different color-sensitive layers are sandwiched within the same color-sensitive layer,
The installation order can also be determined. Between the silver halide photosensitive layer above,
and non-photosensitive layers such as various intermediate layers on the top and bottom layers.
It may be provided. For the middle class, JP-A No. 61-43748
, No. 59-113438, No. 59-113440,
In the specifications of No. 61-20037 and No. 61-20038
Coupler etc. as described may be included and commonly used.
Color mixing prevention agents, ultraviolet absorbers and stays are commonly used.
It may also contain an inhibitor. A plurality of halogens constituting each unit photosensitive layer
The silver emulsion layer is manufactured by West German Patent No. 1,121,470 or
High sensitivity as described in British Patent No. 923,045
Preferably use a two-layer structure of an emulsion layer and a low-sensitivity emulsion layer.
Can be done. Usually, the sensitivity decreases gradually toward the support.
It is preferable that each halogen emulsion layer
A non-photosensitive layer may be provided between them. Also, special
Kaisho No. 57-112751, Kaisho No. 62-200350,
No. 62-206541, No. 62-206543, etc.
Low speed emulsion on the side away from the support as described
A high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, low sensitivity blue light
Color layer (BL) / High-sensitivity blue-sensitive layer (BH) / High-sensitivity green sensitivity
Photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red
The order of photosensitive layer (RH)/low sensitivity red sensitive layer (RL)/,
Or in the order of BH/BL/GL/GH/RH/RL, or
are installed in the order of BH/BL/GH/GL/RL/RH etc.
can be done. Also, in Special Publication No. 55-34932
Blue color from the side farthest from the support as described
The photosensitive layer/GH/RH/GL/RL can be arranged in this order.
can. Also, JP-A-56-25738 and JP-A No. 62-63
As described in the '936 specification,
From the farthest side, the blue-sensitive layer/GL/RL/GH/RH.
It can also be arranged in Also, special public service 15495/1973
As stated in the publication, the upper layer has the highest sensitivity.
The silver halide emulsion layer, the middle layer has a lower sensitivity than the middle layer.
Silver halide emulsion layer with higher sensitivity than the middle layer
A low silver halide emulsion layer is placed and exposed towards the support.
It is composed of three layers with different photosensitivity, each with a sequentially lowered luminous intensity.
An example of this is the array. Three layers with different photosensitivity like this?
Even if it is composed of
The support in the same color-sensitive layer as described
From the farthest side: medium-speed emulsion layer/high-speed emulsion layer/low-speed emulsion layer
The emulsion layers may be arranged in this order. respectively as above
Various layer configurations and arrangements can be selected depending on the purpose of the photosensitive material.
can be done. Support of photosensitive material and undercoat layer of the support
The dry film thickness of all constituent layers except the back layer is based on bleach fog.
, 12.0 to 20.0μ from the viewpoint of staining over time, etc.
It is preferable that More preferably 12.0 to 18.0
μ. The film thickness of the photosensitive material is 2.
Stored under conditions of 5°C and 50% RH for 7 days after photosensitive material preparation
First, measure the total thickness of this photosensitive material, and then
After removing the coating layer on the support, measure the thickness again.
With that difference, the entire coating excluding the support of the above photosensitive material
The thickness of the cloth layer. This thickness measurement can be performed using, for example, a contact type
Film thickness measuring device using a thick electrical conversion element (Anritus El
etric Co. Ltd. , K-402BSta
nd. ) can be measured using In addition, support
To remove the coating layer on the support, use a sodium hypochlorite aqueous solution.
It can be done using: In addition, scanning electron microscopy
to take a cross-sectional photograph of the above photosensitive material (magnification: 3,
000 times or more) and actually measure the total thickness on the support.
You can also. Swelling rate of the photosensitive material in the present invention [(25
°C, equilibrium swelling film thickness in H2O -25 °C, 55% RH
Dry total film thickness at 25°C, 55% RH)
×100] is preferably 50 to 200%, and 70 to 150%
% is more preferable. If the swelling rate deviates from the above values, it will cause damage.
The remaining amount of color developing agent increases, and the photographic performance and desilvering
It may adversely affect the image quality, such as film properties, and the film properties, such as film strength.
It becomes. Furthermore, film swelling of the photosensitive material in the present invention
Processing speed is in color developer (38℃, 3 minutes 15 seconds)
Swelling film saturates 90% of the maximum swelling film thickness reached when processed.
thickness, and expand the time it takes to reach 1/2 of this thickness.
When T1/2 is defined as 15
Preferably it is less than a second. More preferably within 9 seconds
be. Photographic emulsion layer of the light-sensitive material used in the present invention
The silver halides contained in are silver iodobromide and iodochlorobromide.
It may be silver, silver chlorobromide, or silver bromide. preferred
Silver halide contains about 0.1 to 30 mol% silver iodide.
silver iodobromide, silver iodochloride or silver iodochlorobromide.
Ru. Particularly preferred contains 2 to 25 mol% silver iodide.
It is silver iodobromide. The silver halide grains of the photographic emulsion are cubic,
Those with regular crystals such as octahedrons and tetradecahedrons,
Those with irregular crystal shapes such as spherical or plate-like, twin crystals
Those with crystal defects such as planes, or a combination thereof
It can also be a shape. [0064] The grain size of silver halide is approximately 0.2 microns.
Even the following fine particles have a projected area diameter of approximately 10 microns.
Large-sized particles up to
It may also be a drug. Silver halide photographic emulsion that can be used in the present invention
For example, Research Disclosure (RD) No.
．． 17643 (December 1978), pp. 22-23,
“I. Emulsion preparation
ion and types)” and No. 187
16 (November 1979), p. 648, by Grafkide, “
"Physics and Chemistry of Photography", published by Paul Montell (P.Gla.
fkides, Chimie et Physi
que Photographique Paul
Montel, 1967), Duffin, “Photographic Breasts”
"Reagent Chemistry", published by Focal Press (G.F. Duffi)
n, Photographic Emulsion
Chemistry (Focal Press, 19
66)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
Published by Focal Press (V.L.Zelikman)
et alMakingand Coating
Photographic Emulsion
, Focal Press, 1964), etc.
It can be prepared using the method described above. US Patent No. 3
, No. 574,628, No. 3,655,394 and English
Monodisperse as described in National Patent No. 1,413,748 etc.
Emulsions are also preferred. Also, the aspect ratio is about 5 or more.
Eel tabular grains can also be used in the present invention. Tabular grains are
Gatoff, Photographic Science &
Engineering (Gutoff, Photography
ic Science and Engineering
ng), Vol. 14, pp. 248-257 (1970);
U.S. Patent No. 4,434,226, U.S. Patent No. 4,414,
No. 310, No. 4,430,048, No. 4,439
, 520 and British Patent No. 2,112,157, etc.
It can be prepared by the method described in . Even if the crystal structure is uniform, there are internal and external parts.
may consist of a different halogen composition, and the phase structure
It may also be Also, due to epitaxial bonding,
Silver halides of different compositions may be bonded together,
In addition, other than silver halides, such as Rodan silver and lead oxide,
It may be conjugated with a compound. Also, grains of various crystal shapes
Mixtures of children may also be used. Silver halide emulsions are usually subjected to physical ripening, chemical
Use those that have been subjected to chemical ripening and spectral sensitization. This way
The additives used in the eel process are
-Jiya No. 17643 (December 1978), same
No. 18716 (November 1979) and the same No.
．． 307105 (November 1989)
The relevant sections are summarized in the table below. Used in this invention
Known photographic additives that can be used are also based on the above three research studies.
It is listed in the IS Closure (RD) and includes information regarding the following:
The relevant sections are shown below. Type of additive [RD17643] [
RD18716] [RD307105] 1.
Chemical sensitizer page 23 6
Page 48, right column, page 866 2. sensitivity
elevating agent
Page 648, right column 3. spectral sensitizer, 23
〜24 pages 648 pages right column
Pages 866-868 Supersensitizer
~649 page right column
4. Brightener page 24
Page 647 Right column Page 868
5. Anti-fogging pages 24-25
649 page right column 868-87
Page 0 Agents, stabilizers 6. Light absorber, pages 25-26
Page 649 Right column Page 873
filter
~Page 650 Left column Dyes, UV absorbers 7. Stain page 25 right column
650 pages left column 872 pages
inhibitor
~Right column 8. dye image
Page 25 650 Page left column
Page 872 Stabilizers 9. Hardener page 26
651 page left column 874-87
5 page 10. Binder 26 pages
651 page left column 873 ~8
74 page 11. Plasticizer, page 27
650 page right column 8
Page 76 Lubricants 12. Application aids, pages 26-27
650 page right column 875-876
Page Surfactant 13. Statistic 27 pages
650 page right column 876-877
Page Inhibitor 14. matte agent
87
Pages 8 to 879 [0068] The present invention has various colors.
Couplers can be used together, typical examples are
, the aforementioned RD No. 17643, VII-CG and
RDNo. 307105, VII-C to G
It is described in the patent that was published. Examples of yellow couplers include US special
Permit No. 3,933,501, No. 4,022,620,
Same No. 4,326,024, Same No. 4,401,752
, No. 4,248,961, Special Publication No. 58-10739
British Patent No. 1,425,020, British Patent No. 1,476
, 760, U.S. Patent No. 3,973,968, U.S. Patent No. 4
, No. 314,023, No. 4,511,649, Europe
Preferred are those described in Patent No. 249,473A and the like. As a magenta coupler, 2 equivalents and/or
is 4 equivalents of 5-pyrazolones and pyrazoloazoles.
Preferred compounds are U.S. Pat. No. 4,310,619;
No. 4,351,897, European Patent No. 73,636
, U.S. Patent No. 3,061,432, U.S. Patent No. 3,725,
No. 064, RD No. 24220 (June 1984)
, JP-A No. 60-33552, RD No. 24230
(June 1984), JP-A No. 60-43659, No. 6
No. 1-72238, No. 60-35730, No. 55-1
No. 18034, No. 60-185951, U.S. Patent No. 4
, No. 500,630, No. 4,540,654, No. 4,540,654, No.
No. 4,556,630, WO (PCT) 88/0479
Those described in No. 5 and the like are more preferred. As the cyan coupler, phenolic or
and naphthol couplers, and U.S. Patent No. 4,
No. 052,212, No. 4,146,396, No. 4
, No. 228,233, No. 4,296,200, No. 4,296,200, No.
No. 2,369,929, No. 2,801,171, No. 2,801,171, No. 2,801,171, No.
No. 2,772,162, No. 2,895,826,
Same No. 3,772,002, Same No. 3,758,308
, No. 4,334,011, No. 4,327,173
No., West German Patent Publication No. 3,329,729, European Patent No.
No. 121,365A, No. 249,453A, U.S. Pat.
Permit No. 3,446,622, No. 4,333,999
, No. 4,753,871, No. 4,451,559
No. 4,427,767, No. 4,690,88
No. 9, No. 4,254,212, No. 4,296,1
No. 99, JP-A No. 61-42658, etc. are preferred.
Delicious. [0072] A colorant for correcting unnecessary absorption of color dyes.
Lard coupler is RD No. VII of 17643
- Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 5
No. 7-39413, U.S. Patent No. 4,004,929,
No. 4,138,258, British Patent No. 1,146,3
No. 68 and those described in Japanese Patent Application No. 2-50137 are preferred.
stomach. Also, the cup described in U.S. Pat. No. 4,774,181
No need for color dye due to fluorescent dye released during ringing
Couplers that correct for absorption and U.S. Pat. No. 4,777,1
Colors that can react with developing agents to form dyes as described in No. 20
Using a coupler with an elementary precursor group as a leaving group
It is also preferable that Couplers whose color dyes have appropriate diffusivity
- U.S. Patent No. 4,366,237, British Patent No.
Patent No. 2,125,570, European Patent No. 96,570
, as described in West German Patent (Publication) No. 3,234,533.
is preferable. Typical of polymerized dye-forming couplers
Examples are U.S. Patent Nos. 3,451,820 and 4,08
No. 0,211, No. 4,367,282, No. 4,4
No. 09,320, No. 4,576,910, British Patent
No. 2,102,173, etc. Photographically useful residues associated with coupling
Couplers that emit . image during development.
A coupler that releases a nucleating agent or a development accelerator in an imagewise manner.
British Patent No. 2,097,140, British Patent No. 2,1
No. 31,188, JP-A-59-157638, JP-A No. 59
-170840 is preferred. Other materials that can be used in the photosensitive material of the present invention
A possible coupler is U.S. Patent No. 4,130,42.
Competitive coupler described in No. 7 etc., European Patent No. 173,30
Couplers that release dyes that recover color after separation as described in No. 2A
, RD No. 11449, same No. 24241, special
Bleach accelerator release mechanism described in Kaisho 61-201247 etc.
puller, the link described in U.S. Patent No. 4,553,477, etc.
Gund emission coupler, described in JP-A-63-75747
Leuco dye-releasing coupler, U.S. Pat. No. 4,77
Couplers that emit fluorescent dyes described in No. 4,181, etc.
Can be mentioned. The couplers used in the present invention include various known couplers.
It can be introduced into photosensitive materials by a dispersion method. Oil droplet dispersion method
Examples of high boiling point solvents used in
No. 027, etc., and used in the oil-in-water dispersion method.
High-boiling organic solvents with a boiling point of 175°C or higher at normal pressure
A specific example is phthalate esters (dibutyl phthalate).
dicyclohexyl phthalate, di-2-ethyl
Xyl phthalate, decyl phthalate, bis(2,4-
di-t-amyl phenyl) phthalate, bis(2,4-
di-t-amyl phenyl) isophthalate, bis(1,
(1-diethylpropyl) phthalate, etc.), phosphoric acid or
is an ester of phosphonic acid (triphenyl phosphate
, tricresyl phosphate, 2-ethylhexyl diphthate
enyl phosphate, tricyclohexyl phosphate
, tri-2-ethylhexyl phosphate, tridodecy
tributoxyethyl phosphate, tributoxyethyl phosphate,
Lichloropropyl phosphate, di-2-ethylhexy
ruphenylphosphonate, etc.), benzoic acid esters (
2-Ethylhexylbenzoate, dodecylbenzoate
2-ethylhexyl-p-hydroxybenzoate
), amides (N,N-diethyldodecanamide,
N,N-diethyl laurylamide, N-tetradecylpi
lolidone), alcohols or phenols (e.g. lolidone), alcohols or phenols (e.g.
sostearyl alcohol, 2,4-di-tert-amino
ruphenol, etc.), aliphatic carboxylic acid esters (bi-ruphenol, etc.),
(2-ethylhexyl) sebacate, dioctylase
rate, glycerol tributyrate, isostearyl
lactate, trioctyl citrate, etc.), aniline
Derivative (N,N-dibutyl-2-butoxy-5-ter
t-octylaniline, etc.), hydrocarbons (paraffin,
dodecylbenzene, diisopropylnaphthalene, etc.)
Which can be mentioned. In addition, as an auxiliary solvent, the boiling point is approximately 30
℃ or higher, preferably 50℃ or higher and about 160℃ or lower
Typical examples include ethyl acetate and butyl acetate.
Chil, ethyl propionate, methyl ethyl ketone,
lohexanone, 2-ethoxyethyl acetate, dimethy
Examples include ruformamide. Processes, effects and impregnation of latex dispersion method
Specific examples of latexes for use in
No. 63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230, etc. [0079] These couplers also have the above-mentioned high boiling point.
Loadable latex in the presence or absence of organic solvents
Polymers (e.g., U.S. Pat. No. 4,203,716)
or water-insoluble and organic solvent-soluble porous.
Dissolve in reamer and emulsify and disperse in hydrophilic colloid aqueous solution.
can be done. Preferably, International Publication No. WO88/
Homopolymerization described on pages 12 to 30 of Specification No. 00723
Polymers or copolymers are used. Especially acrylamide type
It is preferable to use a polymer in terms of color image stabilization and the like. Suitable supports that can be used in the present invention include, for example
For example, the above-mentioned RD No. 17643, page 28 and the same No.
18716, from the right column on page 647 to the left column on page 648.
It is. The present invention can be applied to various photosensitive materials.
can. Color negative film especially for general use or movies
For use in reversing film for films, slides or televisions.
It is preferable to [Example] The present invention will be explained in detail with reference to the following example.
However, the present invention is not limited thereto. Example-1 On a subbed cellulose triacetate film support,
Multilayer coating of each layer with the composition shown below and color negative
A film sample 101 was produced. (Photosensitive layer composition) The numbers corresponding to each component are in g/m2 unit.
For silver halides, the coating amount is expressed in degrees.
Shows the converted coating amount. However, the sensitizing dye is the same.
Indicates the coating amount in moles per mole of silver halide of the layer.
vinegar. First layer (antihalation layer) Black colloidal silver Silver
0.18 gelatin
1.40 2nd layer (middle layer
) 2,5-di-t-pentadecylhydroquinone
0.18EX-1
0.18EX-3
0
．． 020EX-12
2.0×10-3U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.060U-2
0.080U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10HBS-1
0.10HBS-2
0.02
0 gelatin
1.04 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion A Silver
0.25 silver iodobromide emulsion B
Silver 0.25 Sensitizing Dye I
6.9×10-5
Sensitizing dye II
1.8x10-5 sensitizing dye III
3.1×10-4E
X-2
0.17EX-10
0.020EX
-14
0.17U-1
0.070U-
2
0.050U-3
0.070H
BS-1
0.060 gelatin
0.87 008
4] Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion G Silver
1.00 Sensitizing dye I
5.1×10-5 sensitizing dye II
1.4
×10-5 sensitizing dye III
2.3×10-4EX-2
0
．． 20EX-3
0.050EX-10
0.
015EX-14
0.20U-1
0.
070U-2
0.050U-3
0
．． 070 gelatin
1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion D Silver
1.60 Sensitizing dye I
5.4×10-5 sensitizing dye II
1.4
×10-5 sensitizing dye III
2.4×10-4EX-2
0
．． 097EX-3
0.010EX-4
0.
080HBS-1
0.22HBS-2
0.10 Zera
Chin
1.63 6th layer (middle layer) EX-5
0.040HBS-1
0.020 Zera
Chin
0.80 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion A Silver
0.15 silver iodobromide emulsion B
Silver 0.15 sensitizing dye IV
3.0×10-
5 Sensitizing dye V
1.0x10-4 sensitizing dye VI
3.8×10-4E
X-1
0.021EX-6
0.26EX-
7
0.030EX-8
0.025HBS-
1
0.10HBS-3
0.010 gelatin
0
．． 63 Layer 8 (Second green-sensitive emulsion layer) Silver iodobromide emulsion C Silver
0.45 sensitizing dye IV
2.1×10-5 sensitizing dye V
7.0
×10-5 sensitizing dye VI
2.6×10-4EX-6
0
．． 094EX-7
0.026EX-8
0.
018HBS-1
0.16HBS-3
8.0×10-3ze
latin
0.50 9th layer (3rd green-sensitive emulsion layer) Silver iodobromide emulsion E Silver
1.20 Sensitizing dye IV
3.5×10-5 sensitizing dye V
8.0
×10-5 sensitizing dye VI
3.0×10-4EX-1
0
．． 013EX-11
0.065EX-13
　　　　　　　　　　　　　　　　　　　　　　　　　
0.019HBS-1
0.25HBS-2
0.10
gelatin
1.54 10th layer (yellow filter layer) Yellow colloidal silver Silver
0.050EX-5
0.080HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.030 gelatin
0.95 11th layer (1st blue
Sensitive emulsion layer) Silver iodobromide emulsion A Silver
0.080 silver iodobromide emulsion B
Silver 0.070 silver iodobromide emulsion F
Silver 0.070 increase
Sensitive dye VII
3.5×10-4EX-8
0.042
EX-9
0.72HBS-1
0.28 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.10 12th layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion G Silver
0.45 sensitizing dye VII
2.1×10-4EX-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15EX-10
7.0×10-3HBS-1
0
．． 050 gelatin
0.78 13th layer (3rd blue milk)
silver iodobromide emulsion H silver
0.77 sensitizing dye VII
2.2×10-4EX-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20HBS-1
0.070 gelatin
0.6
9 14th layer (first protective layer) Silver iodobromide emulsion I Silver
0.20U-4
0.11U-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17HBS-1
5.0x10-2 gelatin
1
．． 00 15th layer (second protective layer) H-1
0.40B-1 (diameter 1.7μ
m) 5.0 x 10-2B-2 (diameter
1.7 μm) 0.10
B-3
0.10S-1
0.20ze
latin
1.20 [0091] In addition, all layers have preservability
, processability, pressure resistance, anti-mold and anti-bacterial properties, anti-static properties and coating properties.
In order to improve cloth properties, W-1, W-2, W-3, B-
4, B-5, F-1, F-2, F-3, F-4, F-5
, F-6, F-7, F-8, F-9, F-10, F-1
1, F-12, F-13 and iron salt, lead salt, gold salt, platinum
Contains salts, iridium salts, and rhodium salts. use
The silver iodobromide emulsion and compound used are as follows. [Table 1] [Formula 1] [Formula 1] [Formula 2] [Formula 2] [Formula 2] [Formula 3] [Formula 4] [Formula 4] [Formula 4] [Formula 5] [Formula 6] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] [Chemical formula 14] [Chemical formula 15] Sample 101 prepared as above was subjected to 3
Cut into 5mm width and in three colors: yellow, magenta, and cyan.
Apply decomposition wedge exposure to the following processing steps and treatment prescriptions.
Processing was performed. Processing process Processing time Processing temperature
Color development 3 minutes 15 seconds 38℃ floating
White 45 seconds 38℃
Fixation (1) 45 seconds
Fixation at 38℃ (2) 45 seconds
Stable at 38℃ (1) 20 seconds
Stable at 38℃ (2)
Stable at 38℃ for 20 seconds (3)
Dry at 38℃ for 20 seconds
1 minute Temperature the processing solution below 60℃
The composition of (Color developer)
Unit (g)
diethylenetriaminepentaacetic acid
2.0 1-hydroxy
Ethylidene-1,1- 3.3
Diphosphonic acid Sodium sulfite
(See Table 1) Charcoal
acid potassium
37.5 Potassium bromide
Mu
(See Table 1) Potassium iodide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.3mg hydroxylamine sulfur
Acid acid 2
．． 4 2-Methyl-4-[N-ethyl-N-
(β-hydroxyethyl)amino]
Aniline sulfate
(See Table 1) Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter p
H
10.05 011
0] (Bleach solution)
Unit (g)
1,3-diaminopropanetetraacetic acid
130 Ferric Anmo
Ammonium bromide
80
ammonium nitrate
15 Hido
Roxyacetic acid
50 Acetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
40 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter pH [
Adjust with ammonia water]
4.2 (Fixer)
Unit (g)
ammonium sulfite
19 Thiosulfur
ammonium acid solution
280ml (700g/liter) Ethylenediaminetetraacetic acid
15 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter pH [
Adjusted with ammonia water and acetic acid]
6.5 (Stabilizer)
Unit (g)
p-toluenesulfinic acid
0.1 Natori
Polyoxyethylene-p-monononyl
0.2 Phenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt
0.05 Pyrazole
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0 1-hydroxymethylpyra
Sol 1.5
add water
1.0 liter
pH [adjusted with aqueous ammonia and hydrochloric acid]
7.5 After each treatment, the house
Measure the raw dye concentration, KBr=1.4g/liter and
and sodium sulfite = 5.0g/liter color pigment.
Minimum yellow density (Dmin) when processed with image solution,
and the sensitivity (S) of yellow dye as the standard, and from that value
The difference was calculated. Sensitivity here is the concentration Dmin +0
．． It refers to the logE value at point 2. Furthermore, the gradation (γ) and
Then, the density (S0) at the point of the above sensitivity (S) and its logE
The density (S1.5) at the point where 1.5 in logE is added to the value
The slope of the straight line connecting them was measured. γ=(S1.5 −S0)/1.5 The results are shown in Table 1. [Table 2] [0115] As is clear from Table 1, potassium bromide
If the amount of sodium sulfite is small, the current
There is a strong dependence on the image agent concentration, especially for sodium sulfite.
It can be seen that when the amount is small, the increase in Dmin is large.
. (No. 1 to No. 6) On the other hand, the concentration of potassium bromide is
4.3g/liter and 6.5g/liter, which are within the scope of the invention.
liter, the amount of sodium sulfite is within the range of the present invention.
If there is, the dependence on developer concentration is small and good results can be obtained.
I know that it will happen. (No. 10 to No. 15)
Furthermore, when the developing agent is 21 mmol/liter or more,
and the KBr concentration is in the range of 1.3 to 3.5 times the amount of the developing agent.
(Nos. 13 to 15), particularly good results were obtained.
I know that it will happen. [0116] Example-2 [0117] Sample 101 prepared in Example-1 was
After cutting into m-width pieces and applying imagewise exposure, use an automatic developing machine.
The treatment was carried out under the following conditions. Treatment process and treatment liquid set
The composition is shown below. [0118]
Processing process Process
Processing time Processing temperature Refill amount* Tan
capacity
(℃) (ml) (Li
color development 3 minutes 5 seconds
38.0 80 5
Bleach 45 seconds 38.0
140 5 Fixation (1
) 45 seconds 38.0 ─
── 5 Fixation (2)
45 seconds 38.0 420
5 Stable (1) 2
0 seconds 38.0 ────
3 Stable (2) 20 seconds
38.0 --- 3
Stable (3) 20 seconds 38.0
900 3 dry
Drying 1 minute 60 *Supplementary
The amount of stabilizer to be filled is (3) per 1 m2 of photosensitive material.
(2) and (2) to (1) in a countercurrent manner.
The fixer is a countercurrent method from (2) to (1).
Ru. In addition, the amount of developer brought into the bleaching process, the fixing process of bleaching solution
Amount brought into the process and amount of fixer brought into the washing process
are 65ml and 50ml respectively per 1m2 of photosensitive material.
, 50ml. Also, crossover time yes
The deviation is also 6 seconds, and this time is included in the processing time of the previous process.
be done. The composition of the treatment liquid is shown below. (Color developer)
Tank fluid (g) Replenishment fluid (g) Diethyl
Lentriamine pentaacetic acid 2.0
2.0 1-hydroxyethylidene
　　　　　　　　　　　　　　　　　　　　　　　　　
-1,1-diphosphonic acid
3.3 3.3 Sulfur
acid sodium
(See Table 2) Potassium carbonate
37.5
39.0 Potassium Bromide
6.3
− Potassium iodide
1.5 mg
- Hydroxylamine sulfate
2.4 3.3 Trietano
amine 10.0
11.0 4-[N-ethyl-N-
β-hydroxyethylamino]-2-methylaniline sulfate
(See Table 2) Add water
1.0 liter
1.0 liter pH
10.60
10.95 (Bleach solution)
Tank fluid (g) Refill fluid (g) 1,3
-Diaminopropanetetraacetic acid ferric ammonium monohydrate 1
30.0 195.0 Ammonium bromide
Umu 80.0
120.0 Ammonium nitrate
15.0
25.0 Hydroxyacetic acid
50.0
75.0 Acetic acid
40.0
60.0 Add water
1.0 liter
1.0 liter pH
4.3
4.00121 (Fixer replenisher)
(g) Ammonium sulfite
55 Ammonium thiosulfate aqueous solution (700g/liter) 8
40.0 ml imidazole
50 ethylenediaminetetraacetic acid
40 Add water
1.0
liter pH
7.450122](
Fixer tank liquid) Fixer replenisher diluted 3 times with tap water.
(pH 7.4) (Stable liquid)
Common for tank fluid and refill fluid (g) Pyrazo
rule
3.0 1-Hydroxymethylpyrazo
1.5 p-toluene
Sodium sulfinate 0.1 por
Lyoxyethylene-p-monononyl
phenyl ether
0.2 (average degree of polymerization
10) Ethylenediaminetetraacetic acid disodium salt
0.05 Add water
1.0 liter p
H
7.5 0124 Color image
Continuous processing until the replenishment amount of image solution reaches twice the tank capacity.
At the end of continuous processing, attach an optical wedge to sample 101.
Processed with 50 lux and 0.01 second exposure through
did. The concentration of the sample after each treatment was measured, and the same as in Example-1.
Sensitivity and gradation were evaluated. However, the sensitivity standard is sodium sulfite = 0g/liter,
In the case of developing agent = 6.5g/liter (tank liquid)
Ta. The results are shown in Table 2. [Table 3] [0126] As is clear from Table 2, sodium sulfite
If um is present, regardless of the bromide ion concentration.
, Sensitivity and gradation vary greatly depending on the amount of developing agent added.
However, if sodium sulfite is not present, bromide i
The on-concentration is within the range of the present invention, depending on the amount of developing agent added.
It can be seen that the changes in sensitivity and gradation are small and good.
. Example 3 A similar model to that described in Example 2 of JP-A No. 61-73955 was used.
A color-sensitive material was prepared and subjected to wedge exposure in the same manner as shown below.
The treatment was performed according to the treatment process and treatment recipe. Processing process Color development time: 3 minutes 15 seconds
The following steps were the same as in Example 2 of the above patent. Processing recipe Color developer of Example-2 of the above patent
In the composition of 4-(N-ethyl-N-β-hydroxy
(ethylamino)-2-methylaniline sulfate, sulfite
Sodium and potassium bromide as shown in Table 3 below
The same procedure was followed except that the bleach solution was changed to
. After each treatment, the yellow dye density was measured, KBr = 1.4
g/liter and sodium sulfite = 5.0g/liter
The minimum density of yellow when processed with a color developer of
Based on the sensitivity (Dmin) and the sensitivity (S) of yellow dye
The difference from that value was calculated. Sensitivity here means concentration
This refers to the logE value at the point of Dmin +0.2. Furthermore, as the gradation (γ), the density (S0
) and its logE value plus 1.5 in logE.
The slope of the straight line connecting the angle (S1.5) was measured. γ=(S1.5 −S0)/1.5 The results are shown in Table 3. [Table 4] [0129] As is clear from Table 3, potassium bromide
If the amount of sodium sulfite is small, the current
There is a strong dependence on the image agent concentration, especially for sodium sulfite.
It can be seen that when the amount is small, the increase in Dmin is large.
. (No. 1 to No. 6) On the other hand, the concentration of potassium bromide is
5g/liter and 7g/liter, which are within the scope of the invention.
In this case, if the amount of sodium sulfite is within the range of the present invention,
Good results can be obtained with little dependence on image agent concentration.
I understand. (No. 10 to No. 15) Example 4 Samples 2 and 4 described in Example 1 of Japanese Patent Publication No. 3-15734
A color photosensitive material similar to Sample-3 was prepared and
Provides three-color separation wedge exposure of low, magenta, and cyan.
The treatment was carried out using the following treatment steps and treatment recipe. Processing process Color development time: 3 minutes 30 seconds
The following steps were the same as in Example 1 of the above patent. Processing prescription Color developer of Example-1 of the above patent
in the composition of 4-amino-3-methyl-N-ethyl-
N-(β-hydroxyethyl)-aniline sulfate, anhydrous
Sodium sulfite and potassium bromide are shown in Table 4 below.
Same procedure except for changing the bleach solution and the bleach solution.
And so. [0131] After each process, yellow, magenta, cyan
Measure the concentration of each dye, and sample-2 with KBr=9 mmol/
Minimum yellow when processed with liters of color developer
Based on the density (Dmin) and the sensitivity (S) of each dye
, the difference from that value was calculated. Sensitivity here is the concentration D
It refers to the logE value at the point of min +0.2. Furthermore
As the gradation (γ), the density (S0) at the point of the sensitivity (S) above is
The density at the point where 1.5 in logE is added to the logE value (
The slope of the straight line connecting S1.5) was measured. γ=(S1.5 −S0)/1.5 The results are shown in Table 4. [Table 5] [Table 6] [0134] As is clear from Table 4, sodium sulfite
If potassium bromide is present, the concentration of potassium bromide is 9 mm.
Both mol/liter and 35 mmol/liter
However, sensitivity and gradation changes are large due to changes in developer concentration.
, and regardless of the halogen composition of the color photosensitive material.
I understand. (No. 1 to No. 12) On the other hand, sulfite sodium
In the absence of thorium, the concentration of potassium bromide
35 mmol/liter and 50 mmol/liter, which is the range of the present invention.
Dependency on developer concentration is limited to mol/liter.
You can see that it's small. (No. 16 to No. 18,
No. 25~No. 27) [Effect of the invention] By implementing the present invention, high gradation
Less fog, effective against changes in main ingredient concentration in color developer
stable photographic performance.

Claims (2)

[Claims] Claim 1: An imagewise exposed silver halide color photographic light-sensitive material substantially free of sulfites and containing 30%
1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer containing bromide ions in an amount of millimoles/liter or more. 2. The color developer contains 2-methyl-4-
[N-ethyl-N-(β-hydroxyethyl)amino]
It contains at least 21 mmol/liter of a color developing agent that is aniline and/or a salt thereof, and the molar ratio of the bromide ion to the color developing agent is 1.
A method for processing a silver halide color photographic material, characterized in that the silver halide color is in the range of 3 to 3.5.