JPH04362945A - Processing method of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stabilize magenta color picture images by incorporating a kind of specified org. solvent having high boiling point into one layer of silver halide emulsion and incorporating a specified compd. thereinto after color development. CONSTITUTION:At least one layer of silver halide emulsion contains at least one kind of org. solvent having high boiling point expressed by formula I and/or II, and a specified compd. expressed by formula III and/or TV is incorporated thereinto after color development. In formulae, Ra, Rb and Re are independently alkyl groups, cycloalkyl groups or aryl groups, Rf is a halogen atom, alkyl group, etc., a is an integer 0-3, X0 is a group of nonmetal necessary to form a nitrogen-contg. heteroaromatic ring, and Rn and Ri are alkyl or alkenyl groups.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to silver halide color photography.
Processing of photosensitive materials (hereinafter referred to simply as photosensitive materials)
It relates to the method and also the staining over time after treatment.
This relates to a processing method that suppresses the increase. [Prior Art] Internal mold silver halide collars, which are currently the mainstream
- The principle of forming dye images in photographic materials is well known.
In the color development process, the exposed silver halide is
It is reduced by the image agent to produce silver, and is also oxidized.
The color developing agent reacts with the color former (coupler) to form a dye image.
give. In addition, the desilvering process that follows this color development process
In this case, due to the action of bleaching agent, which is an oxidizing agent, the color development process is
The silver produced in is oxidized, and then complex ionic forms of silver ions
Only the dye image is formed by being dissolved by the fixing agent.
will be accomplished. However, couplers in color films
- All of it is converted into pigment through color development processing.
It is very unlikely that unreacted coupler will be removed after processing.
Generally, it remains. The shadow of this remaining coupler
In some cases, the storage quality of the image after processing may deteriorate, especially when
Magenta dye stability can be problematic. this
Formalin is included in the final bath for treatment, and
Improvements in the image stability of zenta dyes have long been attempted.
It is well known and is used in the final processing bath of today's color films.
It has become common sense to use formalin. [0004] However, formalin is easily volatile.
For safety reasons, it is not recommended to use it.
The development of alternative compounds is desired. formalin substitute
For example, in Japanese Patent Application Laid-open No. 63-244036,
describes hexamethylenetetramine compounds.
Ru. By using this compound you can certainly avoid formaldehyde
The concentration of formaldehyde in the air decreases due to the volatilization of
However, fading of magenta dye occurs even at room temperature, and there is no sufficient fading prevention.
I can't say that I have the power to stop it. Also with other formalin substitutes
N-methylol compounds are known. For example, the United States
Urea
, guanidine, melamine, etc. are listed. But he
As with xamethylenetetramine compounds, the
Not only will image stability not be obtained, but the image stability will not be achieved at high temperatures and high humidity.
It has been found that a new problem arises in that
I made it clear. Problems to be Solved by the Invention Therefore, the first problem of the present invention is
The purpose is to reduce the occurrence of stains over time after processing the above-mentioned photosensitive materials.
To provide a method for processing photosensitive materials that significantly reduces
be. The second object of the present invention is to vaporize formaldehyde.
The image stability after processing of photosensitive materials is low, especially magenta.
Our goal is to provide a processing method with excellent stability for dyes.
. [Means for Solving the Problems] The above objects of the present invention are as follows.
Achieved by the method below. That is, imagewise exposed ha
Those who carry out color development processing of silver halide color photographic light-sensitive materials
In the law, if the photosensitive material is red-sensitive or blue-sensitive,
At least one silver halide emulsion layer has the following general formula (I) and
and/or a high boiling point organic solvent represented by general formula (II).
containing at least one of
The compound represented by the following general formula (A) and/or general formula (X)
treatment with a treatment solution containing at least one type of compound;
Processing method for silver halide color photographic material characterized by
achieved by law. General formula (I) [0008] (wherein Ra, Rb and Rc are
Each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
Represents a group. ) General formula (II) [Chemical formula 6] (wherein, Rd and Re each independently represent
represents an alkyl group, cycloalkyl group or aryl group
, Rf is a halogen atom, an alkyl group, an alkoxy group,
represents an aryloxy group or an alkoxycarbonyl group
, a represents an integer of 0 to 3. When a is 2 or more, multiple R
f may be the same or different. ) General formula (A) [Chemical formula 7] [0012] (wherein,
It is an important group of nonmetallic atoms. However, each nitrogen atom and
The bonding atom is a carbon atom, an oxygen atom, or a sulfur atom.
is the selected atom. ) General formula (X) [0014] (wherein, X0 represents a nitrogen-containing heteroaromatic ring)
Represents a group of nonmetallic atoms necessary to form a metal. Rh and
Ri may be the same or different, and each represents an alkyl group
Or represents an alkenyl group. Rh and Ri are each other
They may be combined to form a 4- to 8-membered ring. ) General formula (A) and/or general formula (
The compound represented by
interaction with the magenta coupler in the remaining photosensitive material.
and improves the stability of magenta dye over time.
It is thought that such an effect is caused by the general formula (A) of the present invention.
and/or the compound represented by general formula (X) is a photosensitive material
in a high-boiling organic solvent of general formula (I) and/or (II) of
This is thought to be because it remains in the Aging stains mentioned above
The problem seems to be caused by the influence of this remaining compound itself.
Therefore, depending on the type of high boiling point organic solvent in the photosensitive material,
It can be assumed that the stain level changes over time.
. The compounds of the present invention will be explained in detail below.
do. First, we will explain in detail the high boiling point organic solvent of the present invention.
I will clarify. In the compound represented by general formula (I), in the formula
Ra, Rb and Rc are each independently an alkyl group
, represents a cycloalkyl group or an aryl group. General formula (
In the compound represented by II), in the formula, Rd , Re
each independently represents an alkyl group, a cycloalkyl group, or
Represents an aryl group, Rf is a halogen atom, an alkyl group
, alkoxy group, aryloxy group or alkoxy group
It represents a carbonyl group, and a represents an integer of 0 to 3. a is 2 or more
In the above plural cases, the plural Rfs may be the same or different.
. In general formula (I) and general formula (II), Ra ~
Whether the alkyl group of Rf is linear or branched,
It is common to have substituents even if it contains unsaturated bonds.
You can. Examples of substituents include halogen atoms, aryl
group, alkoxy group, aryloxy group, alkoxycal
Bonyl group, hydroxyl group, acyloxy group, epoxy
There are bases etc. The cycloalkyl group of Ra to Rf is 3 to
The 8-membered ring may contain unsaturated bonds, and may contain substituents and bridges.
It may have a bridge group. Halogen atoms as examples of substituents
child, hydroxyl group, acyl group, aryl group, alkoxy
Examples of crosslinking groups include cy group, epoxy group, alkyl group, etc.
Examples include methylene, ethylene, and isopropylidene. The aryl group of Ra to Rf is a halogen atom or an alkyl group.
group, aryl group, alkoxy group, aryloxy group, a
May be substituted with a substituent such as alkoxycarbonyl group.
stomach. As the halogen atom of Rf, chlorine atom, fluorine atom
, bromine atom, and iodine atom. [0018] Ra, Rb and Rc will be explained in more detail.
To clarify, each independently represents the total number of carbon atoms (hereinafter abbreviated as the number of C).
) 1 to 24 (preferably 4 to 18) alkyl groups (e.g.
For example, n-butyl, 2-ethylhexyl, 3,3,5-t
Limethylhexyl, n-dodecyl, n-octadecyl,
benzyl, oleyl, 2-chloroethyl, 2,3-dichloride
lolopropyl, 2-butoxyethyl, 2-phenoxyethyl
chill), C5-24 (preferably 6-18) cyclo
Alkyl groups (e.g. cyclopentyl, cyclohexyl,
4-t-butylcyclohexyl, 4-methylcyclohexyl
Cyl) or C number 6 to 24 (preferably 6 to 18)
lyl groups (e.g. phenyl, cresyl, p-nonylphenyl)
nyl, xycle, cumenyl, p-methoxyphenyl, p
-methoxycarbonylphenyl). To explain Rd and Re in more detail:
, each having a carbon number of 1 to 24 (preferably 4 to 18)
Kyl group (for example, the alkyl group mentioned above for Ra)
Same group, ethoxycarbonylmethyl, 1,1-diethyl
Propyl, 2-ethyl-1-methylhexyl, cyclohexyl
xylmethyl, 1-ethyl-1,5-dimethylhexyl
), C5-24 (preferably 6-18) cycloal
Kyl group (for example, the alkyl group mentioned above for Ra)
Same group, 3,5,5-trimethylcyclohexyl, men
methyl, bornyl, 1-methylcyclohexyl) or C
Aryl groups of number 6 to 24 (preferably 6 to 18) (e.g.
For example, the aryl group mentioned above for Ra, 4-t-buty
Ruphenyl, 4-t-octylphenyl, 1,3,5-
Trimethylphenyl, 2,4-di-t-butylphenyl
, 2,4-di-t-pentylphenyl). Rf is a halogen atom (preferably a chlorine atom)
), C1-18 alkyl groups (e.g. methyl, iso
propyl, t-butyl, n-dodecyl), C number 1-18
alkoxy groups (e.g. methoxy, n-butoxy, n-
octyloxy, methoxyethoxy, benzyloxy)
, C6-18 aryloxy group (e.g. phenoxy
, p-tolyloxy, 4-methoxyphenoxy, 4-t
-butylphenoxy) or C2-19 alkoxy
Carbonyl groups (e.g. methoxycarbonyl, n-butoxy
cycarbonyl, 2-ethylhexyloxycarbonyl)
and a is preferably 0 or 1. Represented by general formula (I) or (II) below:
Specific examples of compounds that can be used are shown below. [Formula 9] [Formula 10] [Formula 10] [Formula 11] [Formula 12] [Formula 12] [Formula 13] [Formula 13] [Formula 14] Among the above-mentioned high boiling point organic solvents, general formula (II)
A compound represented by is preferably used. Furthermore, the general formula
Among the compounds represented by (II), especially Rd and Re are
Compounds that are substituted alkyl groups or alkyl groups with side chains
S-24, S-25, S-
Particularly preferred are No. 34, S-37, and S-39. These high boiling point organic solvents have red sensitivity or blue sensitivity.
green color must be present in the silver halide emulsion layer.
It doesn't matter whether it exists or not in the gender layer. This is maze
In the green-sensitive layer containing the intercoupler, the general formula (
A) and/or the compound represented by general formula (X) is mazene
Because it reacts with tacoupler and substantially decreases its abundance,
The generation of stains over time after treatment with compounds with high boiling points
It is not necessarily necessary to suppress it by using organic solvents.
It is thought that. [0031] The high boiling point organic solvent is applied to the photosensitive material in a single layer.
It can contain 0.1 to 10 mmol per 1 m2 of the material.
Preferably, 0.1 to 5 mmol is more preferable, 0.1
-2 mmol is more preferred. High boiling point organic solvent of the present invention
When looking at the amount of addition of couplers in the same layer, the amount of
It can be contained in an amount of 0.01 to 10% by weight based on the puller.
Preferably, 0.01 to 5% by weight is more preferable. Next, the compound represented by the general formula (A) of the present invention
Regarding the compound (hereinafter referred to as the N-methylol compound of the present invention)
explain. The N-methylol compound of the present invention is a water-soluble
Compounds with a total number of carbon atoms of 12 or less
is preferable, more preferably 10 or less, even more preferably
Or less than 6. -N(CH2OH) by X
Even if the 4- to 8-membered ring formed with -N- is saturated,
May be unsaturated, preferably 5- to 6-membered ring, 5-membered ring
is more preferable. Among them, pyrazole ring, 1,2,4-to
Riazole rings and urazole rings are preferred, and pyrazole rings are preferred.
and 1,2,4-triazole rings are particularly preferred. -N
formed by X together with (CH2OH)-N-
Carbon atoms and nitrogen atoms on the ring may be unsubstituted or substituted.
It may be These substituents include alkyl groups (
For example, methyl, ethyl, n-propyl, butyl,
lopropyl, hydroxymethyl, methoxymethyl),
alkenyl group (e.g. allyl), aryl group (e.g.
phenyl, 4-tert-butylphenyl), heterocycle
groups (e.g. 5-pyrazole, 4-pyrazole), halo
Gen atoms (e.g. chlorine, bromine, fluorine), nitro groups,
Ano group, sulfo group, carboxyl group, phosphor group, acyl
groups (e.g. acetyl, benzoyl, propanoyl),
Sulfonyl groups (e.g. methanesulfonyl, octane
sulfonyl, toluenesulfonyl), sulfinyl group (e.g.
(e.g. dodecanesulfinyl), acyloxy group (e.g.
(e.g., acetoxy), alkoxycarbonyl groups (e.g.,
methoxycarbonyl, butoxycarbonyl), carbamo
yl group (e.g. carbamoyl, N-ethylcarbamoy
), sulfamoyl groups (e.g. sulfamoyl, N
-ethylsulfamoyl), amino groups (e.g. amino
, diethylamino, acetylamino, methanesulfona
mino, methylureido, N-methylsulfamoylamide
methoxycarbonylamino), alkoxy groups (e.g.
(e.g., methoxy, ethoxy), alkylthio groups (e.g.,
methylthio, octylthio), aryloxy groups (e.g.
(e.g. phenoxy), arylthio groups (e.g. phenyl
thio), heterocyclic oxy groups (e.g. 1-phenyltet)
razol-5-oxy), heterocyclic thio groups ((e.g.
Examples include benzothiazolylthio). less again
If both have two or more substituents, mutual
A substituent at the ortho position is bonded to the ring to form a 5- to 7-membered aromatic ring.
May be fused with rings, alicycles or heterocycles, spiro rings and
It's okay to be. Among these, compounds with fused benzene rings
Because the solubility decreases, the benzene ring is not fused.
A compound is preferred. The N-methylol compound of the present invention is added to water.
When dissolved, the following reactions occur and equilibrium is reached. ##EQU00001## In the present invention, the equilibrium constant is defined as the equilibrium constant for the above reaction.
It refers to the K who runs. Also, the release rate constant of formaldehyde
refers to Kr in the above reaction. In addition, in the present invention, underwater
In addition to normal water, it also includes heavy water. How to measure these values
As, the equilibrium constant K is the N-methylol compound of the present invention.
A heavy aqueous solution containing a substance or an equimolar amount of amine compound
Lumaldehyde (37% formalin aqueous solution) coexisted.
A heavy aqueous solution is measured by nuclear magnetic resonance absorption (NMR), and NM
Components generated in the solution when the R peak change disappears
can be calculated from the proton ratio. In addition, the formaldehyde release rate constant K
r is formaldehyde and amine compound mixed with water at room temperature.
Or add it to heavy water and N-methylo produced in this reaction.
level out the amounts of amine compounds, formaldehyde and amine compounds.
N-methylolation by chasing until equilibrium is reached.
The formation rate constant Kf of the compound is determined, and the N
- Formation rate constant Kf of methylol compound and the above equilibrium constant
It can be obtained by multiplying it with K. These chemical species
Detection methods include nuclear magnetic resonance absorption, ultraviolet or
Visual spectroscopy, high performance liquid chromatography, colorimetry
Depending on the degree of reaction rate, these detection means are
Just choose. The equilibrium constant K is 2×10−2 mol/liter
preferably less than 1 x 10-2 mol/liter, and less than 1 x 10-2 mol/liter.
More preferred. The release rate constant Kr of formaldehyde is
, 2×10-5 sec-1 or more is preferable, and 1×10
-4 sec-1 or more is more preferable, and 1
More preferably, the compound is ×10−3 sec−1 or more.
Compounds with 1×10-2 sec-1 or more are the most
preferable. In the present invention, the released amine
Preferably, the compound has a pKa of 8 or less in water at room temperature.
preferably, more preferably 7 or less, even more preferably 6 or less
It is. On the other hand, the lower limit is 0.01 or more, which is preferable.
preferably 0.1 or more, more preferably 0.5 or more, most preferably
Preferably it is 1 or more. Particularly preferred N in the present invention
-The methylol compound is represented by the following general formula (A-1)
Ru. General formula (A-1) ##STR16## In the formula, Za is -C(R2)= or -N
=, and R1, R2 and R3 are the same or different
may be a hydrogen atom, an alkyl group, or an alkenyl group, respectively.
group, aryl group, heterocyclic group, halogen atom, nitro group
, cyano group, sulfo group, carboxyl group, phosphor group, a
Syl group, sulfonyl group, sulfinyl group, acyloxy
group, alkoxycarbonyl group, carbamoyl group, sulfur
Represents an amoyl group, an amino group or -YRj. here
-Y represents -O- or -S-, Rj is alkyl
represents a group, an alkenyl group, an aryl group or a heterocyclic group.
vinegar. These groups may be further substituted. Also R1
and R2 or R2 and R3 are bonded to each other and 5 to 7
It may also form a membered ring. More specifically, R1, R2 and R3 are
hydrogen atom, alkyl group (e.g. methyl, ether), respectively.
chill, n-propyl, butyl, cyclopropyl, hydro
oxymethyl, methoxymethyl), alkenyl groups (e.g.
, allyl), aryl groups (e.g. phenyl, 4-te
rt-butylphenyl), heterocyclic groups (e.g. 5-pylphenyl),
razole, 4-pyrazole), halogen atoms (e.g.
chlorine, bromine, fluorine), nitro group, cyano group, sulfo group,
Carboxyl groups, phospho groups, acyl groups (e.g. acetyl groups)
benzoyl, propanoyl), sulfonyl groups (e.g.
For example, methanesulfonyl, octanesulfonyl, toluene
sulfonyl), sulfinyl group (e.g. dodecane sulfonate)
finyl), acyloxy groups (e.g. acetoxy),
Alkoxycarbonyl groups (e.g. methoxycarbonyl
, butoxycarbonyl), carbamoyl groups (e.g.
Rubamoyl, N-ethylcarbamoyl), Sulfamoy
group (e.g. sulfamoyl, N-ethylsulfamoyl)
), amino groups (e.g., amino, diethylamino,
Acetylamino, methanesulfonamino, methylurei
Do, N-methylsulfamoylamino, methoxycarbo
nylamino), alkoxy groups (e.g. methoxy, ethoxy
xy), alkylthio groups (e.g. methylthio, octyl
ruthio), aryloxy groups (e.g. phenoxy),
Arylthio groups (e.g. phenylthio), heterocyclic groups
xy group (e.g. 1-phenyltetrazol-5-oxy
), heterocyclic oxy groups (e.g. benzothiazolylti
e). In general formula (A-1), R1, R
2 and R3 are hydrogen atoms or electron donating among the above
The group is preferably a hydrogen atom or an unsubstituted atom having 1 to 3 carbon atoms.
More preferred is alkyl group. More preferably, R1, R
At most one of 2 and R3 is a methyl group, and the others are
A compound of hydrogen atoms, particularly preferably all hydrogen atoms
It is a compound of atoms. [0042] Below, the N-methylol compound of the present invention will be described.
Although specific examples are shown, the present invention is not limited to these.
do not have. [Table 1] [Table 2] [Chemical 17] [Chemical 18] [Chemical 18] The N-methylol compound of the present invention
Amine compounds without a metal group and formaldehyde
or by reacting with paraformaldehyde
, can be easily synthesized. Those amine compounds and the present invention
As a method for synthesizing a compound, for example, European Published Patent No. 6
No. 0,222 and Khim. Geterotsikl.
Soedin. , (2), 251 ('80) [Cem
ical Abstracts, 93:46530W]
, U.S. Pat. No. 2,883,392 and Chem. be
r. , 85, 820 ('52), J. Org. Che
m. , 15, 1285 ('50), The Chem
istry ofHeterocyclic Comp
Volume 22 of R.ounds. H. Wiley”
Pyrazoles, Pyrazolines, Pyr
azolines, Indazoles and C
ondensed Ring”, INTERSCIE
Method described in NCE PUBLISHERS ('67)
Alternatively, it can be synthesized by a similar method. The following is a synthesis of the N-methylol compound of the present invention.
An example is shown. Synthesis Example 1 Synthesis of Compound (A-1) 500ml three-necked flask equipped with a stirrer, thermometer, and cooling tube
Co, pyrazole (68.1g), sodium hydroxide (
0.14g) and methanol (80ml), and heated to 50°C.
After heating to 90% paraformaldehyde (3
3 g) was added little by little and stirred at the same temperature for 1 hour. reaction
After completion, filtration was performed, and the filtrate was concentrated under reduced pressure at below 40°C.
. The obtained concentrate was crystallized from ethyl acetate (300 ml).
Ta. Compound (A-1) was obtained as colorless crystals. (yield
72g, melting point: 79-84℃) The chemical structure is
It was confirmed by analysis and various spectra. equilibrium constant of this compound
K was 5.6 x 10-3 mol/liter. In addition
, the measurement of this equilibrium constant is based on 25 mmol/kg of this compound.
Measuring liters of heavy water solution using nuclear magnetic resonance absorption (NMR)
When there is no change in the NMR peak, add it to the solution.
The resulting components were calculated from the proton ratio. Also, this
The formaldehyde release rate constant kr of the compound is 8
．． It was 7×10-2 sec-1. In addition, this form
The release rate constant kr of aldehyde is measured at room temperature.
Mialdehyde and pyrazole are added to water and the reaction produces
Amounts of diruco compounds, formaldehyde and pyrazole
This compound is first determined by tracking it over time until it reaches equilibrium.
The production rate constant kf of the substance was determined. I found it like this
The formation rate constant kf of this compound and the above equilibrium constant K
Calculated by the product. As a means of detecting this chemical species,
, performed by ultraviolet spectroscopy. This compound also releases
The pKa of the pyrazole produced in water at room temperature is 2.
It was 5. Synthesis Example 2 Synthesis of Compound (A-5) A 300ml three-necked flask equipped with a stirrer, a thermometer, and a cooling tube.
3,5-dimethylpyrazole (48.1g), water
Sodium oxide (0.07g), methanol (50ml
) and warm it to 50℃, then add 90% parahol.
Add maldehyde (16.5g) little by little and at the same temperature.
Stirred for 1 hour. After the reaction is completed, filter the filtrate to 40%
Concentrate under reduced pressure below ℃. The obtained concentrate was diluted with ethyl acetate (
150 ml). Compound (A) as colorless crystals
-5) was obtained. (Yield 28g, melting point: 108-111℃
) The chemical structure was confirmed by elemental analysis and various spectra. Note that the equilibrium constant K of this compound is 3.3 x 10-3 mo
per liter. Also released from this compound
The resulting 3,5-dimethylpyrazole in water at room temperature
pKa was 4.1. Below is compound (A-1)
Representative N-methylol compounds of the present invention determined according to the method
Indicates the equilibrium constant K of a substance. [Table 3] [0051] The following is obtained according to the method for compound (A-1).
The formaldehyde of representative N-methylol compounds of the present invention
The release rate constant kr of aldehyde is shown. [Table 4] [0053] The compound of the present invention can be prepared by the above-mentioned synthesis method etc.
The compound obtained by isolation may be used, or the compound obtained by isolating
without formaldehyde and methylol groups.
obtained by adding an equimolar amount of an amine compound
An aqueous solution containing the N-methylol compound of the present invention as it is
May be used. Furthermore, formaldehyde and medicinal
An amine compound without a tyrol group can be directly
of the present invention obtained in this treatment bath by adding it to the treatment bath.
N-methylol compounds may also be used. Next, the compound represented by the general formula (X) of the present invention
Describe something in detail. General formula (X) [Chemical formula 19] [0056] (wherein, X0 represents a nitrogen-containing heteroaromatic ring
Represents a group of nonmetallic atoms necessary to form a metal. Rh and
Ri may be the same or different, and each represents an alkyl group
Or represents an alkenyl group. Rh and Ri are each other
They may be combined to form a 4- to 8-membered ring. ) In the general formula (X), X0 is nitrogen-containing hetero
B represents a group of nonmetallic atoms necessary to form an aromatic ring,
As the nitrogen-containing heteroaromatic ring obtained as a result, for example,
, pyrrole ring, pyrazole ring, imidazole ring, tria
Zole ring, tetrazole ring, benzene fused to these rings
Cyclic rings (e.g. indazole ring, indole ring iso
Indole ring, benzimidazole ring, benztriazo
ring), a ring in which heterocycles are condensed (e.g., purine ring)
, a condensed alicyclic ring (e.g., 4,5,6,7-tetra
hydroindazole ring), etc. These inclusions
The nitrogen heteroaromatic ring may have substituents, and these
Examples of substituents include alkyl groups (e.g., methyl,
Ethyl, n-propyl, butyl, cyclopropyl, hydride
roxymethyl, methoxymethyl), alkenyl groups (e.g.
(e.g., allyl), aryl groups (e.g., phenyl, 4-t
ert-butylphenyl), heterocyclic groups (e.g. 5-
pyrazole, 4-pyrazole), halogen atoms (e.g.
, chlorine, bromine, fluorine), nitro group, cyano group, sulfo group
, carboxyl group, phosphor group, acyl group (e.g. acetic acid)
thyl, benzoyl, propanoyl) or sulfonyl group (
For example, methanesulfonyl, octanesulfonyl, benzene
zenesulfonyl, toluenesulfonyl), sulfinyl
groups (e.g. dodecanesulfinyl), acyloxy (
For example, acetoxy), alkoxycarbonyl group (e.g.
(e.g., methoxycarbonyl, butoxycarbonyl), carbonyl
Bamoyl group (e.g. carbamoyl, N-ethylcarba
moyl), sulfamoyl groups (e.g. sulfamoyl
, N-ethylsulfamoyl), amino group, alkyl group
amino groups (e.g. methylamino, dimethylamino),
Cylamino groups (e.g. acetylamide, benzoylua)
), sulfonamide groups (e.g., methanesulfonate),
(mido), imide group (e.g. succinimide), urei
group (e.g. methylureido), sulfamoylamide
group (e.g. N-methylsulfamoylamino),
Rhethane groups (e.g. methoxycarbonylamino), alkaline
Koxy groups (e.g. methoxy, ethoxy), alkyl groups
o group (e.g. methylthio, octylthio), aryl
Oxy groups (e.g. phenoxy), arylthio groups (e.g.
(e.g., phenylthio), heterocyclic thio groups (e.g., benylthio),
(zothiazolylthio), heterocyclic oxy group (1-phenyl
tetrazol-5-oxy). Rh and Ri may be the same or different
Often each alkyl group (e.g. methyl, ethyl,
n-propyl, butyl, cyclopropyl, hydroxyethyl
methyl, methoxyethyl) and alkenyl groups (e.g.
allyl). These groups are substituted with substituents.
For example, it may be placed in the ring formed by X0 above.
Substituents listed as groups that may be substituted, and further hydroxy
Examples include sil group and trialkylsilyl group. Rh
and Ri may be combined with each other to form a 4- to 8-membered ring
. Rh and Ri combine with each other to form a 4- to 8-membered ring.
When Rh and Ri are alkyl groups, alkyl groups
Nyl group may be directly bonded, or oxygen atom, nitrogen atom,
They may also be bonded via a sulfur atom or the like. As a representative example,
Pyrrolidine ring, piperidine ring, morpholine ring, piperazine
ring, pyrroline ring, pyrrole ring, imidazole ring, imidazole ring,
Dazoline ring, imidazolidine ring, 1,4-oxazine ring
, 1,4-thiazine ring, azetidine ring, etc.
. These rings may also be substituted with the above Rh group.
may be substituted with the substituents listed above. Among the compounds represented by the general formula (X),
The nitrogen-containing heteroaromatic ring formed by 0 is a non-fused
A monocyclic ring is preferable, and a pyrazole ring and a tria ring are more preferable.
It is a sol ring. If it is a triazole ring, 1, 2,
A 4-triazole ring is preferred. These inclusions
The nitrogen heteroaromatic ring is unsubstituted or an alkyl group,
Alkenyl group, alkoxy group, alkylthio group, halogen
Substituted with a group selected from a carbon atom and an amide group.
preferable. Particularly preferred are those without substitution. on the other hand
, Rh and Ri are -N(Rh)(Ri)
Of the secondary amines represented by the corresponding general formula (Y) below, acids
The dissociation constant pKa (value in water at room temperature (approximately 25°C)) is
Rh and Ri in secondary amines such that 8 or more
It is preferable that there be. General formula (Y) ##STR20## Below, the compounds represented by the general formula (Y) are
Specific examples and their pKa are shown, but are not limited to these.
It's not. [Chemical 21] [Chemical 22] [Chemical 22] [Chemical 23] [Chemical 24] [Chemical 24] More preferred among Rh and Ri
Rh and Ri combine to form a 5- to 6-membered ring.
A more preferred case is a 5- to 6-membered saturated ring.
is formed, and this formed ring is pyrrolidine
ring, piperidine ring, morpholine ring, piperazine ring
It is particularly preferable to form a piperazine ring.
is also preferable. Among the compounds represented by general formula (X), this
The following general formula (X-I) is superior in terms of the effects of the invention.
can be expressed. General formula (X-I) [Image Omitted] In the above general formula (X-I), X0 is
Represents X0 defined by general formula (X), and X0' is X0
has the same meaning as The compound represented by general formula (X) is
, preferably water-soluble, with a total carbon number of 30 or less
is preferable, more preferably 20 or less, especially
Preferably it is 16 or less. Below, the general formula of the present invention (
Specific examples of the compound represented by
It is not limited to these. [Formula 26] [Formula 27] [Formula 27] [Formula 28] [Formula 29] [Formula 29] [Formula 30] [Formula 32] [Chemical formula 33] [Chemical 34] [Chemical 34] [Chemical 35] [Chemical 36] [Chemical 36] [Chemical 36]
, J. Org. Chem. , vol. 35, P88
3 (1970), Chem. Ber. , vol. 8
5, P820 (1952), U.S. Pat. No. 4,599.
, No. 427, etc., or a method similar thereto.
It can be synthesized with Also, represented by the general formula (X)
The compound represented by the general formula (Y), one of the compounds described below,
A compound represented by the general formula (Z) and formaldehyde (A
or a compound that releases formaldehyde) in solution.
Easily produced by just mixing. The content of the compound represented by general formula (X) is
, 1.0 x 10-4 to 0.5 mol per liter of processing solution
is preferable, more preferably 0.001 to 0.1 mol.
Yes, more preferably 0.001 to 0.03 mol
. In the present invention, a compound represented by general formula (X)
Using a compound represented by the following general formula (Z) together with the compound
It is preferable that In this case, formaldehyde vapor
The pressure can be further reduced, and the effects of the present invention are also improved.
becomes more noticeable. General formula (Z) [Chemical formula (Z)] In the general formula (Z), X1 is a nitrogen-containing group.
Represents a group of nonmetallic atoms necessary to form a teloaromatic ring.
, the nitrogen-containing heteroaromatic ring obtained as a result is as described above.
listed as a nitrogen-containing heteroaromatic ring formed by
The following can be mentioned. These nitrogen-containing heteroaromatic rings also
It may have a substituent, and these substituents also include X0
Substitutions that the nitrogen-containing heteroaromatic ring formed by may have
Examples include those listed as bases. Among the compounds represented by the general formula (Z), carbon
Preferably, the sum of prime numbers is 20 or less, more preferably
is 15 or less, more preferably 10 or less. Also, X
The nitrogen-containing heteroaromatic ring formed by 1 is a non-fused
A monocyclic ring is preferable, and a pyrazole ring and a tria ring are more preferable.
It is a sol ring. If it is a triazole ring, 1, 2,
A 4-triazole ring is preferred. these rings
is unsubstituted, or an alkyl group, alkenyl group, alkyl group,
Rukoxy group, alkylthio group, halogen atom, amide group
Those substituted with a group selected from are preferred. Especially good
Preferably, it is unsubstituted. Below, the general aspects of the present invention will be explained.
Specific examples of the compound represented by formula (Z) will be shown, but the present invention
It is not limited to these. embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image
can be obtained. The content of the compound represented by the general formula (Z) is
, 0.0 per mol of the compound represented by general formula (X)
1 to 100 mol is preferable, more preferably 0.1 to 2 mol
0 moles, most preferably 1 to 10 moles. of the present invention
In an aqueous solution, the compound represented by general formula (X) is partially
May cause hydrolysis. In the processing liquid of the present invention,
contains these hydrolysates and even condensates, etc.
You may have one. [0093] Also, the compound of general formula (Y) is
In the case where there are two secondary amines, i.e. 2 equivalents,
In this case, compared to the case of 1 equivalent, the compound of general formula (Y) is
Half the number of moles is sufficient; for example, when using Y-22,
is formaldehyde, Y-22, and Z-4 are each 2
Mol, 1 mol, 2 mol reaction, ratio of X-35 to 1 mol
Generate with . Therefore, in a preferred embodiment of the present invention,
, at least for formaldehyde in the general formula (Z)
Add the represented compound in excess (1.01 to 100 times the mole)
Just add it. In addition, the compound represented by the general formula (Y) is
, preferably 1/2 mole or more relative to formaldehyde
It is preferable to add, therefore, it is represented by the general formula (Z).
The compound represented by general formula (Y) is 2
．． It may be added in an amount of 0.2 to 200 times by mole. General formula (A) and/or general formula (
The treatment liquid containing the compound represented by
Compounds represented by general formula (A) and/or general formula (X)
By containing the dye image formed by color development.
Image stabilizing effect (especially for magenta dye over time)
This treatment liquid has the effect of preventing color fading. Therefore
, a processing solution after color development, specifically a stabilizing solution, a preparation solution, etc.
These are liquid conditioning solution, bleach solution, bleach-fix solution and stop solution, and are more preferred.
or stabilizing liquids, conditioning liquids and bleaching liquids. particularly preferred
is a stabilizing liquid. [0095] The above stabilizer is a conventional color negative film.
It is used in the final processing process of films and color reversal films.
It is a stabilizing liquid that can be used as a substitute for water washing, and the final process is a washing process.
It is used in the stabilization process of the pre-bath in the case of the rinsing process.
It also includes stabilizers used in the final process.
It is preferable to do so. Conventionally, it is used in the final treatment process.
The stabilizing solution used is a treatment containing formalin etc. as mentioned above.
This formalin etc. has an image stabilizing effect.
However, in the present invention, instead of formalin,
By using the N-methylol compound of the present invention,
Reduces formalin vapor pressure without staining
The image was stabilized and the image was stabilized.
The processing solution of the invention does not substantially contain formalin.
It is. Here, it means that it does not substantially contain formalin.
, may be included as long as the effects of the present invention are achieved.
It means something. Specifically, formaldehyde and form
Total amount of aldehyde hydrate is 0.005 mol/liter
This refers to the following cases. To lower formalin vapor pressure,
The above formaldehyde and formaldehyde hydrate
The lower the total, the better, 0.003 mol/liter or less
is particularly preferred. In addition, the N-methylol of the present invention mentioned above
Formaldehyde and methylol depending on how the compound is used
Ungrouped amine compounds directly in the same treatment bath
Even when used in combination with
, the processing solution of the present invention does not substantially contain formalin.
range. General formula (A) and/or general formula (
The processing liquid containing the compound represented by
In general formula (A) and/or general formula (X) of the present invention,
Preferably, it is refilled with a replenisher containing the compound represented.
Indeed, the replenisher is used in the processing of photosensitive materials and in automatic processing machines.
The amount of compounds in the processing solution that decreases due to deterioration over time
Compounds eluted from photosensitive materials by replenishment and, conversely, by processing.
By controlling the concentration of
adjusted accordingly. Therefore, the compounds that decrease are
and the latter compound at a lower concentration. In addition, compounds that do not easily change in concentration due to processing or aging
is contained in approximately the same concentration as the normal processing solution. General formula (A) and/or general formula (
The preferred amount of the compound represented by X) is
0.003 to 0.30 mol per liter, which is more preferable.
Preferably, it is 0.005 to 0.10 mol, and 0.01
-0.05 mol is particularly preferred. Processing liquid of the present invention
Therefore, in the general formula (A), the methylol group is substituted.
It is preferable to contain an excess amount of an amine compound. child
These are contained in an amount of 10 times or less by mole relative to the compound of the present invention.
It is preferable to increase the amount by 0.2 to 5 times, and more preferably 0.2 to 5 times. Hereinafter, general formula (A) and/or one of the present invention will be described.
Treatment to which the compound represented by general formula (X) can be added
The physical solution and other processing solutions will be explained. In addition, stable
When using the compound of the present invention in a stabilizing solution,
may not contain the compound of the present invention, in which case
The processing liquid itself has no stabilizing effect on color images.
It is inappropriate to call it stabilizer liquid, but for convenience, we will refer to it the same way below.
to be called. First, general formula (A) and/or one of the present invention
Preferred compounds containing the compound represented by formula (X)
The constant solution and adjustment solution will be explained. Conditioning solution accelerates bleaching
It is a processing liquid that is sometimes called a bath. The stabilizer contains
It can contain all the compounds that can be added to the washing water mentioned above.
Wear. Particularly prevents uneven water droplets when drying photosensitive materials after processing.
Various surfactants are used to prevent water stains and after treatment.
Various antibacterial products to prevent mold from forming on photosensitive materials
Preferably contains a disinfectant, a fungicide, a fungicide, and a chelating agent.
have Moreover, the general formula (A) and/or the general formula of the present invention
Stabilizes the dye image in addition to the compound represented by (X)
compounds, e.g. hexamethylenetetramine, hexame
Tylenetetramine derivatives, hexahydrotriazine, hexahydrotriazine
Xahydrotriazine derivative, dimethylol urea, organic
It may also contain an acid or a pH buffer. Also, other necessary
Ammonium chloride, ammonium sulfite, etc.
monium compounds, metal compounds such as Bi and Al, and fluorescence enhancement.
Whitening agents, hardeners, alkaline agents described in U.S. Pat. No. 4,786,583
Canolamine and the like can be used. As a stabilizing liquid
In this case, the pH is usually used in the range of 4 to 9, but the pH range is 6 to 8.
is preferred. The replenishment amount of the stabilizing solution of the present invention is determined by the amount of the stabilizer to be processed.
Preferably 200 to 1500 ml per m2 of material, especially 3
00 to 600 ml is more preferable. With the stabilizer of the present invention
The treatment temperature is preferably 30 to 45°C. Also during processing
The time period is preferably 10 seconds to 2 minutes, particularly preferably 15 to 30 seconds.
Yes. [0100] As the conditioning bath, other than the compound of the present invention,
, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid
acid, 1,3-diaminopropanetetraacetic acid, cyclohexane
Aminopolycarboxylic acid chelates such as diaminetetraacetic acid
Acids; acid salts such as sodium sulfite and ammonium sulfite.
Sulfate and Thioglycerin, Aminoethanethiol, Sulphate
Various types explained in the bleaching solution section, such as lefoethanethiol.
Bleach accelerators may be included. Also prevents scum
For the purpose of
Sorbitan esters of fatty acids substituted with ren oxide
U.S. Pat. No. 4,059,446 and Research D.
In Scrooger Magazine, Volume 191, 19104 (1980)
Containing the listed polyoxyethylene compounds, etc.
is preferable. These compounds are
It can be used in the range of 0.1g to 20g.
, preferably in the range of 1 g to 5 g. The pH of the adjustment bath is
, usually used in the range of 3 to 11, preferably 4 to 11.
9, more preferably 4.5-7. Treatment in conditioning bath
The time is preferably 30 seconds to 5 minutes. Also, the tone
The amount of bath replenishment is 30ml to 30ml per 1m2 of photosensitive material.
00ml is preferred, but especially 50ml to 1500ml
It is preferable that there be. The processing temperature of the adjustment bath is 20℃~50℃
℃ is preferable, and 30℃ to 40℃ is particularly preferable.
Yes. [0101] Normally, photosensitive materials are subjected to imagewise exposure and then
G-type and direct positive-type photosensitive materials undergo color development and reaction.
Transfer positive photosensitive materials undergo black and white development, reversal processing, etc.
Perform color development. Color development that can be used in the present invention
The main component of the developer is an aromatic primary amine color developing agent.
It is an alkaline aqueous solution containing as. preferred color
The developing agent is a p-phenylenediamine derivative, and the representative
Examples are shown below, but are not limited thereto. 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 Particularly preferred among the above p-phenylenediamine derivatives
Examples are D-4 and D-6. In addition, these p-fe
Nylenediamine derivatives include sulfate, hydrochloride, sulfite, p
- It may be a salt such as toluenesulfonate. aroma
The amount of primary amine color developing agent used in the color developing solution is
A concentration of 0.001 to 0.1 mol per liter is preferred.
more preferably at a concentration of 0.01 to 0.06 molar.
Ru. [0102] The color developing solution also contains sulfite as a preservative.
Sodium, potassium sulfite, sodium bisulfite,
Potassium sulfite, sodium metasulfite, potassium metasulfite
Requires sulfites such as lithium or carbonyl sulfite adducts.
It can be added depending on the situation. Preferences for these preservatives
The correct amount to add is 10g or less per liter of color developer.
More preferably, it is 5 g or less. [0103] Also, the aromatic primary amine color development
As a compound that directly preserves the main drug, JP-A-63-53
Various hydroxides described in No. 41 and No. 63-106655
Sylamines (among others, those with sulfo and carboxyl groups)
Compounds are preferred. ), described in JP-A No. 63-43138.
Hydroxamic acids described in No. 63-146041
hydrazines and hydrazides, 63-44657 and
and phenols described in No. 63-58443, No. 63-58443;
α-hydroxyketones and α described in No. 3-44656
-Aminoketones, various sugars described in No. 63-36244
There are many types. Also, in combination with the above compounds
JP-A-63-4235 and JP-A-63-24254
, No. 63-21647, No. 63-146040, No. 63-146040, No. 63-21647, No. 63-146040, No.
No. 63-27841 and No. 63-25654, etc.
Monoamines listed in No. 63-30845, No. 63-1
Diamines described in No. 4640, No. 63-43139, etc.
63-21647, 63-26655 and
and polyamines described in No. 63-44655, No. 63
-Nitroxy radicals described in No. 53551, No. 63
-43140 and 63-53549
Coles, oximes and the like described in No. 63-56654
and tertiary amines described in No. 63-239447.
can be used. As other preservatives, JP-A-57
-44148 and 57-53749
Salicylic acid as described in Metals No. 59-180588
alkanolamines described in No. 54-3582
, polyethyleneimines described in No. 56-94349
, the aromatic polyester described in U.S. Pat. No. 3,746,544.
A hydroxy compound or the like may be included if necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound. [0104] The color developing solution used in the present invention is preferably
preferably pH 9 to 12, more preferably 9 to 11.0.
. In order to maintain the above pH, various buffering agents are used.
is preferred. Specific examples of buffering agents include sodium carbonate
, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Trisodium phosphate, tripotassium phosphate, disodium phosphate
Lium, dipotassium phosphate, sodium borate, boric acid
Potassium, Sodium Tetraborate (Borax), Potassium Tetraborate
sodium o-hydroxybenzoate (salicyl)
(sodium acid), potassium o-hydroxybenzoate, 5
-Sodium sulfo-2-hydroxybenzoate (5-sulfo-2-hydroxybenzoate)
sodium sulfosalicylate), 5-sulfo-2-hydro
Potassium xybenzoate (potassium 5-sulfosalicylate)
), etc. The amount of buffer added depends on the color development.
The amount is preferably 0.1 mol or more per liter of developer.
and particularly preferably 0.1 to 0.4 mol.
stomach. [0105] In addition, calcium and magenta are contained in the color developing solution.
Used as an anti-precipitation agent for gnesium or in color developing solutions.
It is preferable to use various chelating agents to improve stability.
Delicious. As the chelating agent, organic acid compounds are preferred;
For example, aminopolycarboxylic acids, organic phosphonic acids,
Examples include sulfonocarboxylic acids. These generations
Table examples include diethylenetriaminepentaacetic acid, ethylenediethylenediaminepentaacetic acid,
aminetetraacetic acid, N,N,N-trimethylenephosphonic acid,
Ethylenediamine-N,N,N',N'-tetramethylene
transphosphonic acid, transcyclohexanediaminetetraacetic acid
, 1,2-diaminopropanetetraacetic acid, hydroxyethyl
iminodiacetic acid, glycol ether diamine tetraacetic acid,
ethylene diamine orthohydroxyphenylacetic acid, 2-pho
Sphonobutane-1,2,4-tricarboxylic acid, 1-hydro
Roxyethylidene-1,1-diphosphonic acid, N,N'-
Bis(2-hydroxybenzyl)ethylenediamine-N
, N'-diacetic acid, etc. These chelating agents
may be used in combination of two or more types if necessary. chelating agent
The amount added is sufficient to sequester metal ions in the color developer.
For example, 0 per liter of color developer.
．． It is about 1 g to 10 g. [0106] The color developing solution may contain any development accelerator if necessary.
A promoter can be added. However, the present invention
The color developing solution used in
If it does not substantially contain benzyl alcohol in terms of
is preferred. Here, "substantially" means 1 liter of color developer.
Contains no more than 2 ml per torle, preferably no at all.
means. Other development accelerators include:
No. 16088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019, United States
Thioether type described in Patent No. 3,818,247 etc.
Compound, JP-A-52-49829 and JP-A-50-15
p-phenylenediamine compounds described in No. 554, especially
1977-137726, Special Publication No. 44-30074
, JP-A-56-156826, JP-A No. 52-43429
Quaternary ammonium salts described in et al., U.S. Pat. No. 2,49
No. 4,903, No. 3,128,182, No. 4,2
No. 30,796, No. 3,253,919, Special Publication No. 4
No. 1-11431, U.S. Patent No. 2,482,546,
Same No. 2,596,926, Same No. 3,582,346
Amine compounds described in Japanese Patent Publication No. 37-16088
, No. 42-25201, U.S. Patent No. 3,128,18
No. 3, Special Publication No. 41-11431, No. 42-23883
No. 3,532,501, etc.
Lukylene oxide, other 1-phenyl-3-pyrazo
Addition of lydones, imidazoles, etc. as necessary.
I can do it. The amount of development accelerator added is 1 liter of color developer.
The amount is about 0.01g to 5g per bottle. [0107] In the present invention, further, if necessary,
Any antifoggant can be added. As an antifoggant
, such as sodium chloride, potassium bromide, and potassium iodide.
Alkali metal halides and organic antifoggants
can be used. Examples of organic antifoggants include benzene.
Zotriazole, 6-nitrobenzimidazole, 5-
Nitroisoindazole, 5-methylbenzotriazole
5-nitrobenzotriazole, 5-chloroben
Zotriazole, 2-thiazolyl-benzimidazole
, 2-thiazolylmethyl-benzimidazole, inda
sol, hydroxyazaindolizine, adenine-like
A typical example is a nitrogen-containing heterocyclic compound.
Wear. The amount of antifoggant added is per liter of color developer.
The amount is about 0.01g to 1g. [0108] The color developing solution used in the present invention includes fluorescent
It may also contain a brightener. As a fluorescent whitening agent, 4,4
'-Diamino-2,2'-disulfostilbene compounds
is preferred. The amount of optical brightener added is 1 liter of color developer.
0 to 5 g, preferably 0.1 g to 4 g per bottle. [0109] Also, if necessary, alkyl sulfonic acid,
Aryl sulfonic acid, aliphatic carunic acid, aromatic carvone
Various surfactants such as acids may be added. [0110] The color developer replenisher contains the components contained in the color developer.
Contains compounds that are The role of color developer replenisher is to
Decreased due to material processing and deterioration over time in automatic processors.
Replenishment of a small amount of compound to the color developing solution and conversely, processing
to control the concentration of compounds eluted from photosensitive materials.
By doing so, the developing performance is kept constant. follow
Therefore, the former compound is concentrated at a higher concentration than the color developing tank solution.
The latter compound is also found in lower concentrations. The former compound
These are color developing agents and preservatives, and the replenisher contains tar.
Contains 1.1 to 2 times the amount of liquid. Also, the latter compound
Representative examples include halides (e.g. potassium bromide).
The replenisher contains a development inhibitor that contains 0 to 0 of the tank solution.
．． Contains 6 times more. The halide concentration in the replenisher is
Usually less than 0.006 mol/liter, but low replenishment
It is necessary to reduce the concentration as much as possible, and if there is no
There are also cases. In addition, it does not cause concentration changes due to processing or aging.
The compound is contained at approximately the same concentration as the normal color developing tank solution.
be possessed. Examples of this are chelating agents and buffering agents. Furthermore, the pH of the color developer replenisher varies depending on the tank solution due to processing.
To prevent pH drop, approximately 0.05 to 0.5 higher than the tank liquid.
Make it higher. This difference in pH also increases as the amount of replenishment decreases.
There is a need to. The replenishment amount of color developer is 1 m of photosensitive material.
100 to 1500 although it is done with less than 3000ml per 2
ml is preferred. [0111] The processing temperature with the color developer is 20 to 50°C.
The temperature is suitable, preferably 30 to 45°C. processing time
20 seconds to 5 minutes is appropriate, preferably 30 seconds to 3 minutes.
20 seconds, more preferably 1 minute to 2 minutes 30 seconds
. [0112] Two or more color developing baths may be used as necessary.
Add color developer replenisher from the first bath or the last bath.
refill, shorten development time, and further reduce replenishment amount.
You can. 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. [0114] 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. [0115] Using the above black and white developer or color developer
When processing with an automatic processor, the developer (color developer and black developer)
The area where the white developer) contacts the air (opening area) can be
The smaller the size, the better. For example, the opening area (cm2
) divided by the volume of developer (cm3) is the aperture ratio.
Then, the aperture ratio is preferably 0.01 (cm-1) or less.
, 0.005 or less is more preferable. [0116] 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 resin
Regarding the composition and resin regeneration method, please refer to Mitsubishi Chemical Corporation (
Diaion Manual (I) (198
6th edition, 14th edition). Ma
Among the anion exchange resins, Japanese Patent Application Laid-Open No. 2-952 and
A resin having the composition described in JP-A No. 1-281152 is preferred.
Delicious. [0117] In the present invention, a color-developed photosensitive material
is desilvered. The desilvering process mentioned here is basically
consists of a bleaching process and a fixing process, but these processes cannot be performed at the same time.
Bleach-fixing treatment and combinations of these treatments
It will be done. Typical desilvering treatment processes include the following:
. ■ 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.
For example, regarding the process
It is disclosed in No. 52. Regarding process ■, please refer to JP-A-61
-143755 and Japanese Patent Application No. 2-216389.
It is. In addition, bleach baths and fixing baths applied to the above steps
The tank composition of treatment baths such as baths may be one tank or two or more (for example,
2 to 4 tanks, in which case countercurrent replenishment method is preferable).
You can. [0118] The above desilvering step is performed using a rinsing bath after color development.
, it may be carried out through a water washing bath or a stop bath, but it may be carried out with a negative type effect.
For optical materials, it is preferable to carry out immediately after color development.
, during reversal processing, it is carried out 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, aminopolystyrene
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. [0120] The aminopolycarboxylic acid used in the present invention will be described below.
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)iminodi
Ferric acetate complex salt 1802. Mail
Tyliminodiacetic acid ferric complex salt
2003. Imi
Ferric acid complex salt
2104.
1,4-Butylenediaminetetraacetic acid ferric complex salt
2305. diethylenethio
Etherdiaminetetraacetic acid ferric complex salt
2306. glycol ether diamine tetraacetic acid
Diiron complex salt 2407.
1,3-propylenediaminetetraacetic acid ferric complex salt
2508. ethylenediamine
Ferric tetraacetic acid complex salt
1109. diethylenetriamine5
Ferric acetate complex salt
8010. trans-1,2-cyclohe
Xanediaminetetraacetic acid ferric complex salt 80 012
1] The redox potential of the bleach mentioned above is
Actions of the Faraday Society (T
transactions of the Farada
y Society), Volume 55 (1959), 131
Obtained by measuring by the method described on pages 2 to 1313.
It is defined by the redox potential. [0122] In the present invention, from the viewpoint of rapid processing and from the present invention,
From the viewpoint of effectively demonstrating the brightening effect, the redox potential is 15.
A bleaching agent with a voltage of 0 mV or more is preferable, and more preferably a bleaching agent with a
The original potential is 180 mV, most preferably 200 mV or more.
It's bleach. If the redox potential is too high, it will cause bleaching fog.
The upper limit is 700 mV or less, preferably
is 500mV or less. Among these, particularly preferred
What is new is Compound No. 7 1,3-propylenedia
It is a ferric complex salt of mintetraacetic acid. [0123] 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. [0124] The amount of bleach used in the bleach solution is 1 liter of bleach solution.
It is preferably 0.17 to 0.7 mol per liter, and
0.25-0.
7 mol is preferred. Particularly preferred is 0.30 to 0.6
It is a mole. Also, the amount of bleach used in the bleach-fix solution is
The amount is preferably 0.01 to 0.5 mol per liter of fixer.
Preferably it is 0.02 to 0.2 mol. In addition, the present invention
The oxidizing agent can be used alone or in combination of two or more.
When using two or more types together, the total concentration should be within the above range.
All you have to do is make it happen. [0125] In addition, if bleaching solution is used, 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 acid and ferric complex salts (e.g. ferric sulfate, ferric chloride)
, ferric nitrate, ferric ammonium sulfate, ferric phosphate)
may coexist to form a complex salt in the treatment solution. child
If by complexation of the aminopolycarboxylic acid, the second
Add slightly more than the amount required for complex formation with iron ions.
When added in excess, it is usually 0.01~
Preferably, the amount is in excess of 10%. [0126] The above bleaching solution generally has a pH of 2 to
Used in 7.0. To speed up processing, 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,
Any organic acid such as citric acid may be used, 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.
You can. 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,
Use a mixture of two or more organic acids with a pKa of 2.0 to 5.5.
You can also do that. However, the acid mentioned here includes aminopolycal.
Bonic acid, its salts and its Fe complex salts are excluded. 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; schonic 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. [0128] 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. [0129] Also, the starting solution for 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. [0130] 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 Disclosure
The method described in Jar No. 17129 (July 1978 issue)
Compounds having a lucapto group or a disulfide group, 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. [0131] 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. [0132] In the present invention, a replenishment method may be adopted.
is preferable, and the amount of replenishment of bleaching solution is per 1 m2 of photosensitive material,
600ml or less is preferable, more preferably 100-5
00ml. The bleaching time is preferably 120 seconds or less.
Preferably 50 seconds or less, more preferably 40 seconds or less
It is. [0133] During the treatment, aminopolycarboxylic acid
Bleach solutions using ferric complex salts should be aerated.
The resulting aminopolycarboxylic acid iron (II) complex salt is treated with an acid.
It is preferable to This regenerates the oxidizer,
Photographic performance is maintained extremely stably. [0134] The treatment with the bleaching solution in the present invention includes the treatment
So-called evaporation compensation, which supplies water equivalent to the evaporated content of the liquid
It is preferable to do this. In particular, color developers and high-potential bleaching
Preferred in bleaching solutions containing whitening agents. water like this
There are no particular restrictions on the specific method of replenishing the
Among them, JP-A-1-254959 and JP-A-1-254960.
Install a monitor tank separate from the bleach tank as described in the publication,
Determine the amount of evaporation of water in the monitor tank, and calculate whether this water evaporates or not.
Calculate the amount of water evaporated in the bleach tank from
For example, how to replenish water in a bleaching tank and patent application No. 2-4674.
No. 3, No. 2-47777, No. 2-47778, No. 2
-47779, the liquid described in the specification of 2-117972
Evaporation using level and overflow sensors
A correction method 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.
. [0136] 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 mentioned. 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. [0137] Also, from the viewpoint of promoting fixation, thiosulfate
Ammonium thiocyanate (Rhodan ammonium)
, thiourea, thioether (e.g. 3,6-dithia-1
, 8-octanediol) is also preferably used in combination. Among these, thiosulfate and thiocyanate are used together.
is most preferable. In particular, ammonium thiosulfate and
Preferably, it is used in combination with ammonium ocyanate. Combined
The amount of these compounds is 1 liter of processing solution with fixing ability.
0.01 to 1 mol per mol, preferably 0.1 to 0.5 mol per mol
It is best to use moles, but in some cases, 1 to 3 moles may be used.
The retention promotion effect can be greatly enhanced by using
. [0138] 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. [0139] Furthermore, processing liquids having fixing ability include
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. [0140] The pH of the fixer is preferably 5 to 9.
, more preferably 7 to 8. Also, the smell of bleach-fixer
is preferably 4.0 to 7.0, more preferably 5
．． It is 0 to 6.5. Also, bleach solution or first bleach-fix
The pH of the bleach-fix solution after processing in the bath is 6 to 8.
．． 5 is preferable, and 6.5 to 8.0 are more preferable. Adjusting a processing solution with fixing ability to such a pH range
and as a buffering agent, the pKa range is from 6.0 to 9.0.
Preferably, the compound contains the following compounds. these compounds
As imidazole, 2-methyl-imidazole
Imidazoles such as are preferred. These compounds are preferred
Preferably, 0.1 to 10 mol per liter of treatment liquid.
Preferably it is 0.2 mol to 3 mol. [0141] In addition, the bleach-fix solution contains the above-mentioned bleach solution.
It can contain compounds that can have. Book
In the invention, the bleach-fix solution (start solution) at the start of processing
The above-mentioned compound used in the bleach-fix solution is dissolved in water.
However, it is prepared by applying separately prepared bleach and fixing solutions.
It may be prepared by mixing the amounts. [0142] Fixer or bleach when using the replenishment method
The replenishment amount of white fixer is 100 per m2 of photosensitive material.
~3000ml is preferred, but more preferably 300~
It is 1800ml. To replenish bleach-fix solution, use bleach-fix replenishment.
It may be replenished as a liquid, or
No. 2-216389 and Japanese Patent Application No. 2-216389.
This may be carried out using the overflow liquid of the deposited liquid. Also
As with the bleaching process mentioned above, as well as replenishing the processing solution, the evaporation
It is preferable to carry out the bleach-fixing process while replenishing the corresponding amount of water.
Yes. [0143] 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. [0144] The processing liquid having 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.
If done online, the suitability for rapid processing will be even better.
preferable. [0145] After the processing step with fixing ability, usually
Perform the water washing process. After processing with a processing liquid that has fixing ability,
Stabilization treatment using the stabilizing solution of the present invention without substantial washing with water
It is also possible to use a simple processing method that performs the process. Washing machine
The rinsing water used during drying of photosensitive materials after processing is
Contains various surfactants to prevent uneven water droplets
be able to. These surfactants include polyethylene
Len glycol type nonionic surfactant, polyhydric alcohol
type nonionic surfactant, alkylbenzene sulfone
Acid type anionic surfactant, higher alcohol sulfate ester
Ter salt type anionic surfactant, alkylnaphthalene
Sulfonate type anionic surfactant, quaternary ammonium
Salt type cationic surfactant, amine salt type cationic interface
Active agent, amino salt type amphoteric surfactant, betaine type amphoteric surfactant
There are surfactants, but it is best to use nonionic surfactants.
Preferably, especially alkylphenol ethylene oxide
Adducts are preferred. As an alkylphenol, especially
Cutyl, nonyl, dodecyl, dinonylphenol are preferred.
Moreover, the number of added moles of ethylene oxide is
8 to 14 are preferred. Silicone with even higher antifoaming effect
It is also preferable to use a surfactant. [0146] In addition, water stains may occur in the washing water, and water stains may be present after treatment.
To prevent mold from forming on photosensitive materials, various anti-bacterial products are used.
It can also contain a bacterial agent and a fungicide. this
Examples of antibacterial and antifungal agents include JP-A-57
-157244 and 58-105145
Thiazolylbenzimidazole compounds such as
Isothiazolone series as shown in No. 57-8542
chemical compounds, such as trichlorophenol.
Bromophenol compounds, bromophenol compounds,
Machine tin, organozinc compounds, acid amide compounds, diazide
compounds, triazine-based compounds, thiourea-based compounds, and benzoate.
Riazole compounds, alkylguanidine compounds, benzene
Quaternary anhydrides such as zalkonium chloride
Antibiotics such as monium salts and penicillin
, Journal of Antibacteria and Antibiotics
Fungus Agent (J. Antibact.A
ntifung. Agents) Vol 1. No.
5, p. 207-223 (1983)
These include anti-bacterial agents, etc. Two or more of these may be used in combination.
stomach. In addition, various sterilization methods described in JP-A No. 48-83820
Agents can also be used. [0147] The washing water also contains various chelating agents.
It is preferable to let Preferred chelating agents include:
Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid
aminopolycarboxylic acids such as 1-hydroxyethylide
-1,1-diphosphonic acid, ethylenediaminetetraacetic acid,
Diethylenetriamine-N,N,N',N'-tetrame
Organic phosphonic acids such as tyrenephosphonic acid, or
Maleic anhydride polymer described in State Patent 345172A1
Examples include hydrolysates of Also, the above
A preservative that can be included in the fixer or bleach-fixer.
It is preferable to include it in the washing water. [0148] A multistage countercurrent method is used for the water washing process and stabilization process.
Preferably, the number of stages is preferably 2 to 4 stages. Refill amount and
1 to 50 times the amount brought in from the front bath per unit area, preferably
Preferably 2 to 30 times, more preferably 2 to 15 times
. Tap water is the water used in these washing processes.
Can be used, but Ca, Mg
Deionized to reduce ion concentration to 5mg/liter or less
Uses water that has been sterilized using halogen, ultraviolet germicidal lamps, etc.
It is preferable to do so. Also, correct the evaporation content of each processing liquid.
Tap water may be used for the water, but the washing process described above
Deionized water, preferably used for sterilized
It is better to use water. In addition, the water washing process or stabilization process
The overflow liquid flows into the pre-bath, which has fixing ability.
The amount of waste liquid can be reduced by using a method that
It is preferable because it can be done. In processing, bleach solution, bleach
In addition to white fixer and fixer, other processing solutions (e.g.
Corrects concentration due to evaporation even in color developer, washing water, stabilizer)
Add an appropriate amount of water or correction solution or processing replenishment solution to
It is preferable to supplement. [0149] In the present invention, the drying process after bleaching
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. [0150] 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 photosensitive 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. [0151] Plural 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
The order of red-sensitive 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. [0152] Support of photosensitive material and undercoat layer of the support.
The dry film thickness of all constituent layers except the back layer is bleached fog,
It is 12.0 to 20.0 μ from the viewpoint of aging stain etc.
It is preferable. More preferably 12.0 to 18.0μ
It is. The film thickness of the photosensitive material is measured at 25°C.
, stored under conditions of 50% RH for 7 days after producing the photosensitive material,
First, measure the total thickness of this photosensitive material and then
After removing the coating layer on the support, measure the thickness again,
Based on the difference, the entire coating layer of the above photosensitive material excluding the support
The film thickness shall be . This thickness can be measured using, for example, a contact-type thick electrical
Film thickness measuring device using conversion element (Anritus Elec)
tric Co. Ltd. , K-402BStand
．． ) can be measured using In addition, the support
To remove the upper coating layer, use a sodium hypochlorite aqueous solution.
You can do it by doing this. Additionally, using a scanning electron microscope
Then, a cross-sectional photograph of the above photosensitive material was taken (magnification: 3,000
(preferably more than double) and measure the total thickness on the support.
Can also be done. [0153] 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)
The saturated swelling film thickness is 90% of the maximum swelling film thickness reached when
The swelling time required to reach 1/2 of this film thickness is
When the speed is defined as T1/2, T1/2 is 15 seconds.
It is preferable that it is below. More preferably 9 seconds or less
Ru. 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, silver bromide, or silver chloride. Preferred silver halide has about 0.1 to 30 mole percent iodide.
Silver iodobromide, silver iodochloride or iodochlorobromide containing silver
It is silver. Particularly preferred is 2 to 25 mol% silver iodide.
It is silver iodobromide containing. 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. [0157] 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
ation and types)” and the same No.
18716 (November 1979), 648 pages, Graffki
"Physics and Chemistry of Photography" by De, published by Paul Montell (P.
Glafkides, Chimie et Phys
ique Photographique Paul
Montel, 1967), Duffin, Photographic Emulsion
"G.F. Duffin", published by Focal Press (G.F. Duffin
, Photographic Emulsion Ch
emistry (Focal Press, 196
6)), “Production and Coating of Photographic Emulsions” by Zelikman et al.
Published by Local Press (V. L. Zelikman
et al. ,Makingand Coating
Photographic Emulsion, Fo
cal Press, 1664) etc.
It can be prepared using a method. U.S. Patent No. 3,57
No. 4,628, No. 3,655,394 and British Patent
Monodisperse emulsions described in No. 1,413,748 etc.
preferable. Also, flat surfaces with an aspect ratio of approximately 5 or more
Platy particles can also be used in the present invention. Tabular grains are Gatoff
Author, Photographic Science and Engineering
Alling (Gutoff, Photographic
Science and Engineering)
, Vol. 14, pp. 248-257 (1970);
Permit No. 4,434,226, No. 4,414,310
, No. 4,430,048, No. 4,439,520
and British Patent No. 2,112,157, etc.
It can be prepared by a method. [0159] Even if the crystal structure is uniform, there are internal and external parts.
may be composed of different halogen compositions, and have a layered structure.
It may also be formed by 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. [0160] 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 process are listed in Research Disc.
- Jar No. 17643 (December 1978), same
No. 18716 (November 1979) and the same No.
．． 307105 (November 1989)
The relevant sections are summarized below. Can be used in this invention
Known photographic additives also meet the above three research questions.
closure (RD) and related to the following:
The locations where the information is written are shown. Additive type RD17643
RD18716 RD30
7105 1. Chemical sensitizer page 23
Page 648 right column
866 pages 2. Sensitivity enhancer
Page 648, right column 3.
Spectral sensitizers, pages 23-24
Page 648 right column 866-868
Page Supersensitizer
~ Page 649, right column 4. Masuhaku
agent page 24
Page 647 right column Page 868 5.
Anti-fogging pages 24-25
Page 649 right column 868-870
Page agent, stabilizer 6. Light absorber, pages 25-26
Page 649 right column 8
Page 73 Filter
~ Page 650 left column Dyes
, UV absorber 7. Stain page 25 right column
Page 650 left column 8
Page 72 Inhibitor
~Right column 8. color
Raw image 25 pages
Page 650 left column Page 872
Stabilizer 9. Hardener page 26
Page 651 left column 87
4-875 pages 10. binder 2
Page 6 Page 651 left column
873-874 pages 11. plasticizer,
Page 27 Page 650 Right column
Page 876 Lubricants
12. Coating aids, pages 26-27
Page 650 right column 875
~page 876 Surfactant 13. Statistic 27 pages
Page 650 right column 876~
Page 877 Inhibitor 14. matte agent
　　　　　　　　　　　　　　　　　　　　　　　　　
Pages 878-879 [0161] The present invention includes various
color couplers can be used, the typical
A specific example is the above-mentioned RD No. 17643, VII-
C to G, and RD No. 307105, VII-C~
It is described in the patent described in G. Yellow used in blue-sensitive silver halide emulsions
As a low coupler, for example, U.S. Pat. No. 3,933,
No. 501, No. 4,022,620, No. 4,326,
No. 024, No. 4,401,752, No. 4,248
, No. 961, Special Publication No. 58-10739, British Patent No. 1
, No. 425,020, No. 1,476,760, United States
Patent No. 3,973,968, Patent No. 4,314,023
No. 4,511,649, European Patent No. 249,4
Those described in No. 73A etc. are preferred. [0163] Matrix used in green-sensitive silver halide emulsion layer
Zenta couplers include 5-pyrazolone and pyrazolo
Azole compounds are preferred, US Pat. No. 4,310
, No. 619, No. 4,351,897, European Patent No. 7
No. 3,636, U.S. Patent No. 3,061,423, U.S. Pat.
No. 3,725,064, RD No. 24220 (19
June 1984), JP-A No. 60-33552, RD No.
24230 (June 1984), JP-A-60-436
No. 59, No. 61-72238, No. 60-35730
, No. 55-118034, No. 60-185951,
U.S. Patent No. 4,500,630, U.S. Patent No. 4,540,6
No. 54, No. 4,556,630, WO (PCT) 8
More preferred are those described in No. 8/04795 and the like. In the present invention, 4 equivalents of the following general formula (M), 5-
Particularly effective when using pyrazolone magenta couplers
effective. embedded image In the formula, R4 is an alkyl group, an aryl group,
Represents an acyl group or a carbamoyl group. Ar is Fe
Nyl group or one or more halogen development, alkyl group,
Ano group, alkoxy group, alkoxycarbonyl group, or
represents a phenyl group substituted with an acylamino group. still,
Either R4 or Ar is divalent or more polyvalent
may form a multimer such as a dimer.
A polymer cap is formed by connecting the molecular main chain and the coupling core.
It is also possible to form a lar. [0167] The alkyl group of R4 is a straight alkyl group having 1 to 42 carbon atoms.
Chain or branched alkyl, aralkyl, alkenyl
group, alkynyl group, cycloalkyl group or cycloalkyl group
It represents a kenyl group, and the aryl group is an aryl group having 6 to 46 carbon atoms.
The acyl group represents an aliphatic aryl group having 2 to 32 carbon atoms.
Represents a sil group or an aromatic acyl group having 7 to 46 carbon atoms,
The carbamoyl group is an aliphatic carbamoyl group having 2 to 32 carbon atoms.
represents a group or an aromatic carbamoyl group having 7 to 46 carbon atoms
. These groups may have substituents, such as carbon
Connected by elementary atoms, oxygen atoms, nitrogen atoms, or sulfur atoms
It is an organic substituent or a halogen atom. More specifically, R4 is an alkyl group (for example,
Methyl, ethyl, butyl, propyl, octadecyl, i
Sopropyl, t-butyl, cyclopentyl, cyclohexyl
sil, methoxyethyl, ethoxyethyl, t-butoxy
ethyl, phenoxyethyl, methanesulfonylethyl,
2-(2,4-di-tert-amylphenoxy)ethyl
), aryl groups (e.g. phenyl, 2-chlorophenyl),
2-methoxyphenyl, 2-chloro-5-tetrade
Canamidophenyl, 2-chloro-5-(3-octade
Cenyl-1-succinimido)phenyl, 2-chloro-
5-octadecylsulfonamidophenyl, 2-chloro
-5-[2-(4-hydroxy-3-tert-butyl
phenoxy)tetradecanamidophenyl]), acyl
groups (e.g. acetyl, pivaloyl, tetradecanoyl,
2-(2,4-di-tert-pentylphenoxy)a
Cetyl, 2-(2,4-di-tert-pentylphenol)
xy)butanoyl, benzoyl, 3-(2,4-di-t)
ert-amylphenoxyacetamido)benzoyl)
, carbamoyl group (e.g. N-methylcarbamoyl, N
, N-dimethylcarbamoyl, N-hexadecylcarba
Moyl, N-methyl-N-phenylcarbamoyl, N-
[3-{1-(2,4-di-tert-pentylphenol)
xy)butyramide}]phenylcarbamoyl)
vinegar. Describe in detail the substituents that these groups may further have.
For example, alkyl groups, aryl groups, heterocyclic groups, sia
- group, hydroxy group, nitro group, carboxy group, amino group
group, acyl group, aryloxycarbonyl group, alkoxy
Cycarbonyl group, carbamoyl group, alkoxy group, ali
hydroxy group, heterocyclic oxy group, acyloxy group, carbon
Rubamoyloxy group, silyloxy group, aryloxy group
carbonylamino group, acylamino group, alkylamino group
group, anilino group, ureido group, sulfamoylamino group
, alkoxycarbonylamino group, sulfonamide group,
Aryloxycarbonylamino group, imide group, alkyl
ruthio group, arylthio group, heterocyclic thio group, sulfa group
Moyl group, sulfonyl group, sulfinyl group, azo group,
Sulfonyl group, azolyl group, fluorine atom, chlorine atom, bromine
It is an atom. R4 is preferably an aryl group or an acyl group
It is. [0169] Ar is a phenyl group or one or more halogen groups.
atom, alkyl group, cyano group, alkoxy group, alco
Phyl substituted with oxycarbonyl group or acylamino group
Although it represents a phenyl group, to be more specific, Ar is, for example, a phenyl group.
phenyl group, 2,4,6-trichlorophenyl group, 2,5
-dichlorophenyl group, 2,4-dimethyl-6-methoxy
Cyphenyl group, 2,6-dichloro-4-methoxyphenylene
group, 2,6-dichloro-4-ethoxycarbonylphenyl group
Nyl group, 2,6-dichloro-4-cyanophenyl group or
is 4-[2-(2,4-di-tert-amylphenoxy)
c) butylamide] phenyl group. Preferably one
Phenyl atoms substituted with the above halogen atoms (especially chlorine atoms)
The case of 2,4,6-trichlorochloro group is preferable, especially
phenyl group or 2,5-dichlorophenyl group is preferred
. Specific examples of preferred couplers are listed below. [Formula 44] [Formula 45] [Formula 45] [Formula 45] [Formula 46] [Formula 47] [Formula 47] In the present invention, represented by the general formula (M)
The amount of 4-equivalent magenta coupler applied is 1 m2 of photosensitive material.
It should be 0.4 x 10-3 to 3.5 x 10-3 mol per
is preferable. [0178] Silica used in the red-sensitive silver halide emulsion layer
As uncouplers, phenolic and naphthol
U.S. Patent No. 4,052,212
No. 4,146,396, No. 4,228,23
No. 3, No. 4,296,200, No. 2,369,9
No. 29, No. 2,801,171, No. 2,772,
No. 162, No. 2,895,826, No. 3,772
, No. 002, No. 3,758,308, No. 4,33
No. 4,011, No. 4,327,173, West German Patent Publication
Patent No. 3,329,729, European Patent No. 121,365
No. A, No. 249,453A, U.S. Patent No. 3,446
, No. 622, No. 4,333,999, No. 4,75
No. 3,871, No. 4,451,559, No. 4,4
No. 27,767, No. 4,690,889, No. 4,
No. 254,212, No. 4,296,199, JP-A-Sho
Those described in No. 61-42658 and the like are preferred. [0179] Color for correcting unnecessary absorption of coloring dye
The code coupler is RD No. VII of 17643
- Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929,
No. 4,138,258, British Patent No. 1,146,36
The one described in No. 8 is preferred. Also, U.S. Patent Nos. 4 and 7
74,181, released upon coupling.
Couplers that use photopigments to correct unnecessary absorption of coloring pigments
, and the developing agent described in U.S. Pat. No. 4,771,120.
A dye precursor group that can react to form a dye is a leaving group.
It is also preferable to use a coupler having as . [0180] Couplers whose coloring dyes have appropriate diffusivity
As U.S. Patent No. 4,366,237, British Patent No.
No. 2,125,570, European Patent No. 96,570,
As described in West German Patent (Publication) No. 3,234,533
is preferred. 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. [0184] 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
As the high boiling point solvent used in the present invention, general formula (I)
or a compound represented by (II) is required;
Other examples that may be used in combination include U.S. Patent No. 2,322,
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-amylphenyl) phthalate, bis(2,4-
di-t-amylphenyl)isophthalate, bis(1,
(1-diethylpropyl) phthalate, etc.), phosphoric acid or
is an ester of phosphonic acid (triphenyl phosphate
, tricresyl phosphate, 2-ethylhexyl diphthate
phenyl 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
etc.), amides (N,N-diethyldodecanamide
, N,N-diethyl laurylamide, N-tetradecyl
pyrrolidone, etc.), alcohols or phenols
(isostearyl alcohol, 2,4-di-tert-
amylphenol, etc.), aliphatic carboxylic acid esters
(bis(2-ethylhexyl) sebacate, dioctyl
Azelate, glycerol tributyrate, isostear
lyllactate, trioctyl citrate, etc.),
Phosphorus derivative (N,N-dibutyl-2-butoxy-5-t
ert-octylaniline, etc.), hydrocarbons (parafluorocarbons, etc.),
quinine, dodecylbenzene, diisopropylnaphthalene, etc.
etc.). In addition, as an auxiliary solvent,
About 30℃ or higher, preferably 50℃ or higher and about 160℃ or lower
Organic solvents can be used; typical examples include ethyl acetate,
Butyl acetate, ethyl propionate, methyl ethyl ketone
, cyclohexanone, 2-ethoxyethyl acetate,
Examples include dimethylformamide. [0185] 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. [0186] 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)
impregnated with water-insoluble and organic solvent-soluble polyester
Dissolve in mer and emulsify and disperse in hydrophilic colloid aqueous solution.
be able to. Preferably, International Publication No. WO88/0
Homopolymer described on pages 12 to 30 of Specification No. 0723
Alternatively, a copolymer is used. In particular, acrylamide-based
It is preferable to use a reamer 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,
A multilayer color photosensitive material consisting of each layer with the composition shown below.
Samples 101 to 107 were prepared. (Composition of photosensitive layer) The coating amount is silver halide and colloid.
For silver, the amount expressed in g/m2 of silver, also in caps.
in g/m2 for fillers, additives and gelatin.
For sensitizing dyes, halogen in the same layer.
It is expressed as the number of moles per mole of silveride. 1st layer (antihalation layer) Black colloidal silver
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.90
ExM-1
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-3 2nd layer (middle layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
2.10 UV-1
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-
2 UV-2
　　　　　　　　　　　　　　　　　　　　　　　　　
6.0×10-2 UV-3
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-2
ExF-1
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0×10-3 Solv-2
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-2 019
1] Third layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high A
gI type, equivalent sphere diameter 0.3μm, equivalent sphere diameter
Coefficient of variation 29%, normal crystal, mixed twin grain, diameter/thickness ratio
2.5)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount 0.50 gelatin
hmm
　　　　　　　　　　　　　　　　　　　　　　　　　
1.50 ExS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4 ExS
-2
3.0×
10-4 ExS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-5 ExC-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0
．． 11 ExC-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.11 ExC-4
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10
-2 ExC-7
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-2 High boiling point organic solvent (
(See Table A)
7.0×10-3 4th layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal height A
gI type, equivalent sphere diameter 0.55μm, equivalent sphere diameter
Coefficient of variation of 20%, normal crystal, mixed twin grain, diameter/thickness
ratio 1.0)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount 0.85 Zera
Chin
　　　　　　　　　　　　　　　　　　　　　　　　　
2.00 ExS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4 Ex
S-2
3.0
×10-4 ExS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-5 ExC-1
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16 ExC-2
　　　　　　　　　　　　　　　　　　　　　　　　　
8.0×10-2 ExC-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0
．． 17 ExC-7
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5×10-2 ExY-1
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-2
ExY-2
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-2 Cpd-10
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4
High-boiling organic solvents (see Table A)
0.1
5th layer (highly sensitive red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high
AgI type, equivalent sphere diameter 0.7μm, equivalent sphere diameter
Coefficient of variation of 30%, twinned mixed particles, diameter/thickness ratio 2.0
)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount 0.70 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
1.60 ExS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4 ExS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-
4 ExS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-5 ExC-5
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-2
ExC-6
　　　　　　　　　　　　　　　　　　　　　　　　　
8.0×10-2 ExC-7
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5×10-2 high
Boiling point organic solvent (see Table A)
0.15
High-boiling organic solvents (see Table A)
8.0×1
0-2 0194 6th layer (middle layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.10 P-2
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 Cpd-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Cpd-
4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 Solv-1
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-2 7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high A
gI type, equivalent sphere diameter 0.3μm, equivalent sphere diameter
Coefficient of variation 28%, normal crystal, mixed twin grain, diameter/thickness ratio
2.5)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount 0.30 gelatin
hmm
　　　　　　　　　　　　　　　　　　　　　　　　　
0.50 ExS-4
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-4 ExS
-5
2.0×
10-4 ExS-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3×10-4 ExM-1
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-
2 ExM-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 ExY-1
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-2
Cpd-11
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-3 Solv-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 01
96] 8th layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high A
gI type, equivalent sphere diameter 0.55μm, equivalent sphere diameter
Coefficient of variation of 20%, normal crystal, mixed twin grain, diameter/thickness
ratio 4.0)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount 0.70 Zera
Chin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00 ExS-4
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-4 Ex
S-5
2.0
×10-4 ExS-6
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-5 ExM-1
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3 ExM-2
　　　　　　　　　　　　　　　　　　　　　　　　　
2.5×10-2 ExM-3
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5×10-2
ExY-1
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0×10-2 Cpd-11
　　　　　　　　　　　　　　　　　　　　　　　　　
9.0×10-3
Solv-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 9th layer (highly sensitive green emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high
AgI type, equivalent sphere diameter 0.7μm, equivalent sphere diameter
Coefficient of variation of 30%, normal crystal, twinned mixed particle, diameter/thickness
ratio 2.0)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount 0.50 Zera
Chin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.90 ExS-4
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-4 Ex
S-5
2.0
×10-4 ExS-6
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-5 ExS-7
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10
-4 ExM-1
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-1 ExM-4
　　　　　　　　　　　　　　　　　　　　　　　　　
1.9×10-2
ExM-5
　　　　　　　　　　　　　　　　　　　　　　　　　
1.6×10-2 Cpd-2
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-2
Cpd-9
2
．． 0x10-4 Cpd-10
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-4 Solv.
-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 Solv-2
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-2 10th layer (yellow filter layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.90 Yellow colloidal silver
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-2
Cpd-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 Solv-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15 0
199] 11th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high A
gI type, equivalent sphere diameter 0.5μm, equivalent sphere diameter
Coefficient of variation 15%, octahedral particles)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount 0
．． 40 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00 ExS-
8
2.0×1
0-4 ExY-1
　　　　　　　　　　　　　　　　　　　　　　　　　
9.0×10-2 ExY-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
90 Cpd-2
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-2 High boiling point organic solvent (
(See Table A)
0.30 12th layer (highly sensitive blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high
AgI type, equivalent sphere diameter 1.3μm, equivalent sphere diameter
Coefficient of variation of 25%, normal crystal, mixed twin grain, diameter/thickness
ratio 4.5)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount 0.50 Zera
Chin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.60 ExS-8
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4 Ex
Y-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.12 Cpd-2
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-3 High boiling point
Organic solvent (see Table A)
4.0×10-2 020
1] Thirteenth layer (first protective layer) Fine grain silver iodobromide (average grain size 0.07 μm, Ag
I 1 mol%) 0.20 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.80 UV-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 UV
-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 UV-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20
Solv-3
4
．． 0×10-2 P-2
　　　　　　　　　　　　　　　　　　　　　　　　　
9.0×10-2 0202
] 14th layer (second protective layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.90 B-1 (diameter 1
．． 5μm)
0.10B
-2 (diameter 1.5μm)
0.1
0 B-3
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-2 H-1
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.400203 Furthermore, storage stability, processability, pressure resistance
, anti-mold, anti-bacterial, anti-static, and to improve applicability.
For this purpose, the following Cpd-3, Cpd-5, Cpd-6, C
pd-7, Cpd-8, P-1, W-1, W-2, W-
3 was added. In addition to the above, n-butyl-p-hydroxy
Sibenzoate was added. Furthermore, B-4, F-1,
F-4, F-5, F-6, F-7, F-8, F-9, F
-10, F-11, and iron salt, lead salt, gold salt, platinum salt
, iridium salt, and rhodium salt. next book
The chemical structural formula or chemical name of the compound used in the invention is shown below.
Indicated. [Formula 51] [Formula 52] [Formula 52] [Formula 57] [Formula 54] [Formula 54] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] Samples 101 to 10 prepared as above
7 is cut into 35mm width and 9m length each, 50 looks.
After exposure to white light for 0.01 seconds, an automatic processor
The treatment was carried out using the following conditions. In addition, the stabilizer
Replace them in order and perform each process under the same conditions.
A sample for image storage evaluation was prepared. Processing process and treatment
The liquid composition is shown below. However, as shown in Table B, the stabilizing solution is
They were replaced and treated for each experiment. [0219]
processing process process
Processing time Processing temperature Refill amount
* tank capacity
(℃)
(ml) (liter)
Color development 3 minutes 5 seconds 3
8.0 600 17
Bleach 50 seconds
38.0 140 5
Bleach fixing 50 seconds
38.0 -
5 Fixation 50
seconds 38.0 420
5 Wash with water
30 seconds 38.0 980
3 Stable (1)
20 seconds 38.0 -
3 Stable (
2) 20 seconds 38.0
560 3 dry
Drying 1 minute 60
*The amount of replenishment is per 1 m2 of photosensitive material.
The volume stabilizing solution is a countercurrent method from (2) to (1).
All of the overflow liquid from the washing water was introduced into the fixing bath.
. To refill the bleach-fixing bath, use the top level of the bleach tank of an automatic processor.
Make a cut at the top of the fixing tank and then proceed to the bleaching tank and fixing tank.
All overflow liquid generated by supplying replenisher
was allowed to flow into the bleach-fixing bath. Note that the developer may drift.
Amount brought into the whitening process, how long the bleaching solution lasts in the bleach-fixing process
Amount of bleach-fix solution brought into the fixing process and fixing
The amount of liquid carried into the washing process is approximately 1 m2 of photosensitive material.
65ml, 50ml, 50ml, 50ml respectively.
Ta. Also, the crossover time is 6 seconds in both cases.
, this time is included in the processing time of the previous step. Also, supplement
The liquid was replenished with the same liquid as each tank liquid. less than
The composition of the processing liquid is shown. (Color developer) Unit (g)
starting liquid
Replenisher diethylenetriaminepentaacetic acid
2.0
2.0 1-hydroxyethylidene-
1,1-diphosphonic acid 3.3
3.3 Sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
3.9 5.1 Potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
37.5 39
．． 0 potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4 0.4 Potassium iodide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.3 mg ────
hydroxylamine sulfate
2.4
3.3 2-Methyl-4-[N-ethyl-N-(
β-hydro 4.5 6.0
xyethyl)aminoaniline sulfate with water
In addition
1.0 liter
Tor 1.0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
10.05
10.15 (Bleach solution) Unit (g)
starting liquid
Replenisher 1,3-diaminopropanetetraacetic acid 2nd
Iron ammonium 130 1
95 Mu-water salt Ammonium bromide
80
120 Ammonium nitrate
　　　　　　　　　　　　　　　　　　　　　　　　　
15 25
hydroxyacetic acid
50
75 Acetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
40
60 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter 1.0 liter p
H [Adjust with ammonia water]
4.3
4.00222 (Bleach-fix solution) Start of bleaching above
Mix the solution and the following fixing start solution in a ratio of 15:85 (volume ratio).
Solution (pH 7.0) (Fixer replenisher)
　　　　　　　　　　　　　　　　　　　　　　　　　
Unit (g) Ammonium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
55 Ammonium thiosulfate
aqueous solution (700g/liter)
840ml imidazole
　　　　　　　　　　　　　　　　　　　　　　　　　
50 Ethylenediaminetetravinegar
acid
40 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0
liter pH [adjusted with aqueous ammonia and acetic acid]
7
．． 45 (Fixer start solution) Triple the fixer replenisher with tap water.
Diluted solution (pH 7.4) (Washing water) Tap water was exchanged with H-type strongly acidic cations.
Replacement resin (Amberlite IR- manufactured by Rohm and Haas)
120B) and OH type strongly basic anion exchange resin (the same
Mixed bed column packed with Amberlite IRA-400)
water to increase calcium and magnesium ion concentration.
3 mg/liter or less, followed by isocyanate dichloride.
Sodium nurate 20mg/liter and sodium sulfate
150 mg/liter of mucilage was added. The pH of this solution is 6
．． It was in the range of 5 to 7.5. (Stabilizing liquid) Unit (g)
Start solution/refill solution
Sodium p-toluenesulfinate
0.1 polio
xyethylene-p-monononylphenyl ether
0.2 (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt
0.05 Image stability
agent
Listed in Table B
Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH
　　　　　　　　　　　　　　　　　　　　　　　　　
7.2 0226
[Evaluation of image preservation] Each sample after the above processing was
With a photographic densitometer FSD103 manufactured by Shinfilm Co., Ltd.,
After measuring the low, magenta, and cyan concentrations, the
After aging for 2 months under conditions of 55% relative humidity, each
The concentration was measured. For yellow and cyan, the minimum
For magenta, the density is around 1.5 just before aging.
Changes over time were evaluated at each concentration. (Yellow, cyan; △Dmin) (magenta; M
Color) [Measurement of formalin vapor pressure] The above treatment
Prepare each stabilizing solution using a plate and add 500 ml of each to a bead.
Place it in a car (opening area 200 square centimeters) and
It was placed in a 5 liter sealed glass container. 40℃
After aging for 2 days, evaporate formalin in a glass container.
Formaldehyde L-type direct reading gas manufactured by Gastech
Measured using a detection tube. (HCHO concentration) Furthermore, each stable solution
Prepare a concentrated solution obtained by concentrating 25 times, and adjust the above HCHO concentration.
Formalin vapor pressure was measured using the same method. (Concentrate H
CHO concentration) Type and amount of each image stabilizer used in Table B
, shows the amount of formalin and each evaluation result. [Table 6] [Table 7] [0230] As can be seen from Table B, general formula (A) or (
When using a compound other than X), for example, a comparative compound
Even if a and b are used, "M fading" is large, and c (hort)
"M fading" is a good thing if you use maldehyde).
It can be seen that the HCHO concentration in the sample is significantly high. (No.
1, 3, 5, 6, 13, 16, 19) In addition, when using a compound other than the high boiling point organic solvent of the present invention,
In this case, the compound (A) or (X) of the present invention may be used.
It can be seen that the increase in Dmin is large. (No. 2
, 4) In contrast, by satisfying the configuration of the present invention, "M retirement"
color, △Dmin and HCHO concentration,
It can be seen that good values can be obtained. Especially general formula (X) table
If you use a compound that is
Despite this, it has excellent magenta fading and small ΔDmin.
, the concentration of formalin can also be significantly reduced and more
It can be seen that favorable results can be obtained. Example 2 On a subbed cellulose triacetate film support,
Multilayer color is created by coating each layer with the composition shown below.
Samples 201 to 205, which are photosensitive materials, were prepared. (Photosensitive layer composition) Numbers corresponding to each component are in units of g/m2.
For silver halide, the coating amount is expressed as
Indicates the amount of coating applied. However, for sensitizing dyes, the same layer
The coating amount per mole of silver halide is shown in mole units.
. 1st layer (antihalation layer) Black colloidal silver
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.18 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.40 2nd layer (medium)
interlayer) 2,5-di-t-pentadecylhydroquinone
0.18E
X-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.18 EX-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020E
X-12
2.
0x10-3 U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.060U
-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.080 U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10
HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 HBS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020 ze
latin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.04 [0233] Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion A
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.25 Silver iodobromide emulsion B
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.25 Sensitizing dye
I
6.9×1
0-5 Sensitizing dye II
　　　　　　　　　　　　　　　　　　　　　　　　　
1.8×10-5 sensitizing dye
A
3.1×10-4
EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020
EX-14
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070
U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050 U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070
High boiling point organic solvent (see Table C)
0.
060 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.87 0234 Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion G
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 1.00 Sensitizing dye I
　　　　　　　　　　　　　　　　　　　　　　　　　
5.1×10-5 increase
Sensitive dye II
1
．． 4×10-5 Sensitizing dye A
　　　　　　　　　　　　　　　　　　　　　　　　　
2.3×10-4 EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2
0 EX-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01
5 EX-14
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 EX-15
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050
U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070 U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.0
50 U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070 High boiling point organic
Solvent (see Table C)
0.10 Zera
Chin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.30 [0235] Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion D
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 1.60 Sensitizing dye I
　　　　　　　　　　　　　　　　　　　　　　　　　
5.4×10-5 increase
Sensitive dye II
1
．． 4×10-5 Sensitizing dye A
　　　　　　　　　　　　　　　　　　　　　　　　　
2.4×10-4 EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.0
97 EX-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.010 EX-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.080
High boiling point organic solvent (see Table C)
0.22
〃 （ 〃）
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.63 0236
] 6th layer (middle layer) EX-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.040 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020 Zera
Chin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.800237 Seventh layer (first green-sensitive emulsion layer) Silver iodobromide emulsion A
Silver
0.15 Silver iodobromide emulsion B
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.15 Sensitizing dye X
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-5 sensitization
Dye V
1.
0x10-4 Sensitizing dye VI
　　　　　　　　　　　　　　　　　　　　　　　　　
3.8×10-4 EX-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3
EX-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01 EX-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 EX-8
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.025 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 HBS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.010
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.63 [0238] 8th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion C
Silver
0.45 Sensitizing dye X
　　　　　　　　　　　　　　　　　　　　　　　　　
2.1×10-5 Sensitizing dye V
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-5
Sensitizing dye VI
　　　　　　　　　　　　　　　　　　　　　　　　　
2.6×10-4 EX-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 EX-
7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 EX-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.018 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16
HBS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
8.0×10-3 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.50 0239 9th layer (3rd green-sensitive emulsion layer) Silver iodobromide emulsion E
Silver
1.20 Sensitizing dye X
　　　　　　　　　　　　　　　　　　　　　　　　　
3.5×10-5 Sensitizing dye V
　　　　　　　　　　　　　　　　　　　　　　　　　
8.0×10-5
Sensitizing dye VI
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-4 EX-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.013EX
-11
　　　　　　　　　　　　　　　　　　　　　　　　　
0.065 EX-13
　　　　　　　　　　　　　　　　　　　　　　　　　
0.019 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.25
HBS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.54 0240 10th layer (yellow filter layer) Yellow colloidal silver
Silver
0.050 EX-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.080 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
030 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.95 [0241] Eleventh layer (first 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 Sensitized
Pigment VII
3.
5×10-4 EX-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.042 EX-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
72 High boiling point organic solvent (see Table C)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.28 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.10 12th layer (2nd blue milk)
Silver iodobromide emulsion G
Silver
0.45 Sensitizing dye VII
　　　　　　　　　　　　　　　　　　　　　　　　　
2.1×10-4 EX-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1
5 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-3 High boiling point organic solvent (see Table C)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.78 02
42] Thirteenth layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion H
Silver
0.77 Sensitizing dye VII
　　　　　　　　　　　　　　　　　　　　　　　　　
2.2×10-4 EX-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2
0 High boiling point organic solvent (see Table C)
0.
070 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.69 [0243] 14th layer (first protective layer) Silver iodobromide emulsion I
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.20 U-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.11 U-5
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-2 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00 1st
5 layers (second protective layer) H-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40 B-1 (diameter 1.7μ
m)
5.0×10-2 B-2 (diameter 1.
7μm)
0.10 B-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1
0 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.20 02
44] In addition, all layers are preservable, processable, pressure resistant, and mold-proof.
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-11, F-12, F-13 and
, iron salts, lead salts, gold salts, platinum salts, iridium salts, rhodium
Contains salt. Structural formula or formula of the compound used in the present invention
or chemical name is shown below. [Table 8] [Table 9] [Formula 64] [Formula 64] [Formula 65] [Formula 65] [Formula 66] [Formula 66] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] [Chemical formula 76]
Sample 201 was used for each stabilizing solution in the same manner as in Example 1.
-205 processing was performed, and an image storage property test was conducted. [0261]
Treatment method Process
Processing time Processing temperature Refill amount
* tank capacity
(℃)
(ml) (liter)
Color development 3 minutes 15 seconds 3
8 33 20
Bleach 6 minutes 30 seconds
38 25 4
0 Wash with water 2 minutes 10 seconds
24 1200
20 Fixation 4 minutes 20 seconds
38 25
30 Wash with water (1) 1 minute
05 seconds 24 -
10 Washing with water (2)
1 minute 00 seconds 24 12
00 10 cheap
Fixed 1 minute 05 seconds 38
25 10
Drying 4 minutes 20 seconds 55
*Replenishment amount is 35mm wide and 1m long.
Countercurrent piping method for water hitting (2) to (1) 02
62 Next, the composition of the treatment liquid will be described. (color developer)
Mother liquor (g)
Replenisher (g) Diethylenetriaminepentaacetic acid
1
．． 0 1.1 1-hydroxye
Tylidene-1,1-diphosphonic acid 3.0
3.2 Sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0 4.4 Carbonic acid
Rium
30.0
37.0 Potassium Bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4 0.7 Potassium iodide
Umu
1.5 mg
── Hydroxylamine sulfate
2.4
2.8 4-[N-ethyl-N-β
-Hydroxyethylamine 4.5
5.5 Amino]-2-methylaniline sulfur
acid salt add water
1
．． 0 liter 1.0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
10.05
10.10 (Bleach solution)
Mother liquor (g)
Replenisher (g) Ethylenediaminetetraacetic acid
Ferric sodium trihydrate 100.0
120.0 Ethylenediaminetetraacetic acid dibasic acid
Thorium salt 10.0
10.0 Ammonium Bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
140.0 160.0
ammonium nitrate
30.0
35.0 Ammonia water (27%)
　　　　　　　　　　　　　　　　　　　　　　　　　
6.5ml 4.0ml Add water
Yes
1.0 liter
1.0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
6.0 5
．． 7 (Fixer)
Mother liquor (g)
Replenisher (g) Ethylenediaminetetraacetic acid di
Sodium salt 0.5
0.7 Sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0 8.0
sodium bisulfite
5.0
5.5 Ammonium thiosulfate aqueous solution (70
0g/liter) 170.0ml
Add 200.0ml water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter 1.0 liter
pH
　　　　　　　　　　　　　　　　　　　　　　　　　
6.7 6.6 0265
] (Stabilizer)
Mother liquor (g)
Replenisher (g) Image stabilizer (listed in Table D)
Listed in Table (D)
Amount listed in Table (D)
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5 of
Double amount polyoxyethylene-p-monononylphene
0.3 0.
45 Nyl ether (average degree of polymerization 10
) Ethylenediaminetetraacetic acid disodium salt
0.05 0.
08 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter 1.0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0-8.0
5.0 to 8.0 [0266] Each test after the above treatment
The samples were allowed to age in the same manner as in Example 1, and the changes were evaluated.
. The results are shown in Table D. As is clear from Table D, Example-1
Good results can be obtained by following the configuration of the present invention.
Ru. Especially better results when using compound (X)
was gotten. [Table 10] Example 3 On a subbed cellulose triacetate film support,
Multi-layer coloring is achieved by coating each layer with the composition shown below.
Photosensitive materials 301 to 305 were produced. (Photosensitive layer composition) Numbers corresponding to each component are in g/m2 unit.
For silver halide and colloidal silver,
The amount of coating is shown in terms of silver. However, regarding sensitizing dyes,
Then, the coating amount per mole of silver halide in the same layer is
Expressed in moles. 1st layer (antihalation layer) Black colloidal silver
　　　　　　　　　　　　　　　　　　　　　　　　　
0.35 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.50
UV-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 CC-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05C
M-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05 Solv-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 2nd layer (middle layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.50 UV-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01
Solv-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01 [0270] Third layer (low sensitivity red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (average silver iodide content 7.5
mol%, average particle size 0.46μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
1.10 Monodisperse silver iodobromide emulsion (average iodination
Silver content 2.0 mol%, average particle size 0.32μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.60 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1
．． 50 ExS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
2.5×10-4 ExS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
2.5×10-4
ExS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-5 ExC-1
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00
ExC-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05 CC-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.0
5 ExD-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.002 High boiling point organic solvent (
(See Table E)
0.50 4th layer (highly sensitive red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (average silver iodide content 6.0
mol%, average particle size 0.78μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
2.30 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.50
ExS-1
2
．． 0x10-4 ExS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-4 ExS
-3
1.0×
10-5 ExC-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.015 ExC-3
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.25 CC-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.015 ExD-
2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05 High boiling point organic solvent (see Table E)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.50 0272 Fifth layer (middle layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.50 6th layer (low-sensitivity green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (average silver iodide content 7.5
mol%, average particle size 0.46μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
1.20 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00
ExS-4
5
．． 0x10-4 ExS-5
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4 ExM
-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40 CM-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05E
xD-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.015 ExD-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02S
olv-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.60 7th layer (middle layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.80 Solv-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2
8th layer (highly sensitive green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (average silver iodide content 6.0
mol%, average particle size 0.78μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
1.60 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00
ExS-6
1
．． 5×10-4 ExS-7
　　　　　　　　　　　　　　　　　　　　　　　　　
2.5×10-4 ExS
-8
5.0×
10-5 ExM-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05 ExM-
3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15 CM-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05Ex
D-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01 Solv-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.500275 9th layer (yellow filter layer) Yellow colloidal silver
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.80
Cpd-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Solv-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10
10th layer (low sensitivity blue-sensitive emulsion layer)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3 Monodisperse silver iodobromide emulsion (average silver iodide content
(7.5 mol%, average particle size 0.46μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.35 Monodisperse silver iodobromide emulsion
(Average silver iodide content 2.0 mol%, average grain size 0.32μ
)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.35 Zera
Chin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00 ExS-10
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-4 ExY
-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.50 ExY-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10Ex
D-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01 High boiling point organic solvent (see Table E)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15 Layer 11 (Highly sensitive blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (average silver iodide content 8.0
mol%, average particle size 0.95μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.70 Monodisperse silver iodobromide emulsion (average iodination
Silver content 7.5 mol%, average particle size 0.46μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.30 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1
．． 10 ExS-9
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4 ExS-10
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-4
ExY-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.30 ExY-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05
High-boiling organic solvents (see Table E)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.07 [0278] 12th layer (first protective layer) Fine grain silver iodobromide emulsion (silver iodide content 2.0 mol)
%, average particle size 0.08μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.50 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00 UV
-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 UV-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05
Cpd-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.50 Cpd-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20
Solv-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Solv-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 02
79] 13th layer (second protective layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.60 Alkali soluble
Matting agent (average particle size 2μ)
0.10 Slip agent
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
04 ExF-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.005 ExF-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
01 W-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.0050280] Furthermore,
In addition to the above compounds, each layer contains coating aid W-2 and dispersion aid W.
-3, hardener H-1 and H-2, preservative Cpd-4, antiseptic
Fixed agent Cpd-5, antifoggant Cpd-6 and Cpd-
7 was added. The structural formula of the compound used above is as follows:
It is. [Table 11] [Chemical formula 77] [Chemical formula 77] [Chemical formula 78] [Chemical formula 79] [Chemical formula 80] [Chemical formula 82] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] [Chemical 90] [Chemical 91] [Chemical 92] [Chemical 92] [Chemical 92] Samples 301 to 30 prepared as above
5 to 35mm width and 9m length each, 50 looks.
After exposure to white light for 0.01 seconds, an automatic processor
The treatment was carried out using the following conditions. In addition, the stabilizer
Perform each process under the same conditions except for the images.
A sample for image preservation evaluation was prepared. Treatment process and treatment liquid
The composition is shown below. 0299
processing process process
Processing time Processing temperature Refill amount
* tank capacity
(℃)
(ml) (liter)
Color development 3 minutes 5 seconds 3
8.0 600 17
Bleach 50 seconds
38.0 140 5
Fixation (1) 50 seconds
38.0 ---
5 Fixation (2) 50
seconds 38.0 420
5 Stable (1)
30 seconds 38.0 980
3 Stable (2)
20 seconds 38.0 ────
3 Stable (3)
20 seconds 38.0 5
60 3 dry
Drying 1 minute 60
*The amount of replenishment is per 1 m2 of photosensitive material.
The volume stabilizing liquid is a countercurrent method from (3) to (1),
The fixer is of a countercurrent type from (2) to (1). developing
Amount of liquid brought into the bleaching process, bleaching liquid carried into the fixing process
The amount of indentation and the amount of fixer carried into the washing process are determined by exposure to light.
65ml, 50ml, 50m per 1m2 of material respectively
It was l. Also, the crossover time is 6
This time is included in the processing time of the previous step. Also, each replenisher should be filled with the same liquid as the respective tank liquid.
Ta. The composition of the treatment liquid is shown below. (Color developer) Unit (g)
starting liquid
Replenisher diethylenetriaminepentaacetic acid
2.0
2.0 1-hydroxyethylidene-
1,1-diphosphonic acid 3.3
3.3 Sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
3.9 5.1 Potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
37.5 39
．． 0 potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4 0.4 Potassium iodide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.3 mg ────
hydroxylamine sulfate
2.4
3.3 2-Methyl-4-[N-ethyl-N-(
β-hydro 4.5 6.0
xyethyl)aminoaniline sulfate with water
In addition
1.0 liter
1.0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
10.05 10
．． 15 0301 (Bleach solution) Unit (g)
starting liquid
Replenisher 1,3-diaminopropanetetraacetic acid 2nd
Iron ammonium 130 1
95 Mu-water salt Ammonium bromide
80
120 Ammonium nitrate
　　　　　　　　　　　　　　　　　　　　　　　　　
15 25
hydroxyacetic acid
50
75 Acetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
40
60 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter 1.0 liter pH [
Adjust with ammonia water]
4.3 4
．． (Fixer replenisher)
　　　　　　　　　　　　　　　　　　　　　　　　　
Unit (g) Ammonium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
55 Ammonium thiosulfate
aqueous solution (700g/liter)
840ml imidazole
　　　　　　　　　　　　　　　　　　　　　　　　　
50 Ethylenediaminetetravinegar
acid
40 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter
pH [adjusted with aqueous ammonia and acetic acid]
7.4
5 (Fixing start solution) Dilute the fixing replenisher 3 times with tap water.
Solution (pH 7.4) 0303 (Stable solution) Unit (g)
Start solution/refill solution
Sodium p-toluenesulfinate
0.1 polio
xyethylene-p-monononylphenyl ether
0.2 (Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt
0.05 Image stability
curing agent (listed in Table F)
Listed in Table F Add water
hand
1.0
liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
7.2 0304
Evaluation of image preservation] Each sample after the above treatment was
Yellow with photographic densitometer FSD103 manufactured by Ilum Co., Ltd.
, magenta, and cyan, at 25°C and relative humidity.
After aging for 2 months under the condition of 55%
was measured. Minimum density for yellow and cyan
, for magenta, at the density 1.5 position just before aging.
Changes in concentration over time were evaluated. (Yellow, cyan; △Dmin) (magenta; M
Color) 0305 [Measurement of formalin vapor pressure] The above treatment
Prepare each stabilizing solution using a plate and add 500 ml of each to a bead.
Place it in a car (opening area 200 square centimeters) and
It was placed in a 5 liter sealed glass container. 40℃
After aging for 2 days, evaporate formalin in a glass container.
Formaldehyde L-type direct reading gas manufactured by Gastech
Measured using a detection tube. (HCHO concentration) Furthermore, prepare a concentrated solution by concentrating each stable solution 25 times, and add the
Formalin vapor pressure was measured using the same method as for HCHO concentration.
Ta. (Concentrated solution HCHO concentration) Table F shows the type and amount of each amine compound used,
The amount and each evaluation result are shown. [Table 12] From Table F, the compound represented by the general formula (A)
By using the compound, both "M fading" and HCHO concentration can be reduced.
It can be seen that good results can be obtained. Also, △Dmin
, the high-boiling organic solvent has the general formula (I) or (
By using the compound represented by II), good results can be obtained.
You can get results. Furthermore, the above-mentioned high boiling point organic solvent has the general formula (I
A compound represented by I), and a substituted alkyl group or moiety
In the case of a compound having a branched alkyl group, ΔDmin is
It can be seen that the change is good. (For No. 4 to 8
, No. 13, 14, 15, 16) Furthermore, the compound (X
), especially good results such as formalin concentration can be obtained.
Ta. Example-4 Processing No. of Example 1. Furthermore, pyrazole is added to the stabilizing solution of 7.
was carried out by adding 0.04 mol per liter of treatment solution.
Good results were obtained. [0309] Effect of the invention: By carrying out the present invention, the time course can be improved.
Stabilizes magenta dye images without degrading color intensities
However, the formalin vapor pressure can be lowered.

Claims (2)

[Claims] 1. A method for color developing a silver halide color photographic light-sensitive material that has been imagewise exposed, wherein the light-sensitive material has at least one red-sensitive or blue-sensitive silver halide emulsion layer containing a compound having the following general formula (I). ) and/or general formula (I
I) containing at least one high boiling point organic solvent, and after color development, the photosensitive material is treated with a processing solution containing at least one of the compounds represented by the following general formula (A) and/or general formula (X). 1. A method for processing a silver halide color photographic material, the method comprising: processing a silver halide color photographic material; General formula (I) [Formula 1] (In the formula, Ra, Rb and Rc each independently represent an alkyl group, a cycloalkyl group or an aryl group.) General formula (II) [Formula 2] (In the formula, Rd and Re each independently represents an alkyl group, cycloalkyl group, or aryl group, Rf represents a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an alkoxycarbonyl group, and a is 0 to
Represents an integer of 3. When a is 2 or more, a plurality of Rf's may be the same or different. ) General formula (A) [Chemical formula 3] (In the formula, atom or an atom selected from sulfur atoms.) General formula (X) [Chemical formula 4] (In the formula, X0 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heteroaromatic ring.Rh and Ri may be the same or different and each represents an alkyl group or an alkenyl group.Rh and Ri are bonded to each other and are 4-
An 8-membered ring may be formed. ) 2. The high boiling point organic solvent is represented by the general formula (II)
2. The method for processing a silver halide color photographic material according to claim 1, wherein Rd and Re are each a substituted alkyl group or an alkyl group having a side chain.