JPH04270344A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the method for processing the silver halide color photographic sensitive material having formaldehyde vapor production remarkably reduced but its film strength not reduced. CONSTITUTION:The silver halide color photographic sensitive material is subjected to the development processing method characterized by containing at least one of a formaldehyde releasing compounds in at least one of baths after color development and at least one of gelatin hardeners except the formaldehyde in at least one of baths after the color development.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to silver halide color photography.
It concerns the processing method of photosensitive materials, especially the working environment.
This invention relates to a new processing method that aims to improve. [Prior Art] Processing of silver halide color photographic materials
usually undergoes color development, bleaching, fixing, washing, stabilization, and drying.
What is completed after each process and what is black and white development (first development)
Beginning, washing, color development, adjustment, bleaching, fixing, washing, stabilization
Silver halide color reaction is completed through each step of fixing and drying.
There is a process for transfer photosensitive materials. Typical processing of the former
The method is C41 treatment specified by Eastman Kodak Company.
CN-16 processing specified by Fuji Photo Film Co., Ltd. is known.
It is being In addition, typical processing for color reversal photosensitive materials
The method is E-6 specified by Eastman Kodak.
Known for CR-56 processing specified by Riya Fuji Photo Film Co., Ltd.
It is being [0003] The stabilizing bath in the final step of the above treatment contains holograms.
Marine is used, and its purpose is to produce photosensitive materials after processing.
Magenta dye fading due to residual magenta coupler in
It is well known that it prevents color. Therefore, Hol
When preparing a stabilizing bath containing marine, or when the stabilizing solution is
When drying photosensitive materials, some formaldehyde must be evaporated.
Qi is generated. [0004] Inhalation of formaldehyde is harmful to the human body.
It is known that formal
0.5 ppm is recommended as the allowable concentration of dehyde in the working environment.
ing. Therefore, from the perspective of improving the working environment,
Efforts to reduce formalin concentration and switch to formalin substitutes
Power is being exerted. [0005]Specifically speaking about color reversal processing,
, U.S. Pat. No. 4,921,779 describes hexane in the conditioning bath.
Formaldehyde preca such as methylenetetramine
Bleaching accelerators such as bleach and monothioglycerol
At the same time, formalin is removed from the stabilizing bath, and the matrix is
Preventing fading of Zenta dyes and formaldehyde in the working environment
A method for reducing the amount of emissions is disclosed. Also, US special
No. 4,960,682 describes the bleaching bath that follows the conditioning bath.
Add the same formaldehyde precursor as above to
, and the same effect as above except for formalin from the stabilizing bath.
A method for obtaining the results is disclosed. [Problem to be Solved by the Invention] According to the above US patent,
, it is true that formaldehyde vapor generation can be significantly reduced.
However, the inventors found that compared to conventional treatments, the treated halogen
The film strength of silver oxide color photographic light-sensitive materials decreases significantly.
I found out. This is because the pores in the stabilizing bath in conventional processing
Rumarin has a gelatin hardening effect and can be used in conditioning baths or
The formaldehyde precursor in the bleach bath
It is thought that the latin hardening effect is insufficient. [0007] Due to the above-mentioned significant decrease in film strength, development processing
Not only is it easy to scratch the photosensitive material that has already been used, but also
There is a risk of scratches on the membrane during the drying process of automatic roller conveyor machines.
be. [0008] Therefore, the object of the present invention is to
Achieving an improvement in the working environment by significantly reducing the amount of air generated.
At the same time, silver halide color printing that does not reduce film strength is possible.
An object of the present invention is to provide a method for processing a photosensitive material. [Means for Solving the Problems] The above object of the present invention is to
A method for developing silver halide color photographic materials.
formaldehyde in at least one bath after color development.
Contains at least one compound that releases hydride and develops color
At least one bath after development contains something other than formaldehyde.
characterized by containing at least one gelatin hardening agent
Depending on the processing method of silver halide color photographic light-sensitive materials,
was achieved. Next, the present invention will be explained in detail. Main departure
Ming silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials)
Typical processing steps after color development
The process is as follows: 1) Color development - Adjustment - Bleaching - Fixing - Washing - Stability 2)
Color development - washing with water - bleaching - fixing - washing with water - stability 3) Color development
Image - Adjustment - Bleaching - Washing - Fixing - Washing - Stability 4) Color development
Image - Washing - Bleaching - Washing - Fixing - Washing - Stable 5) Color development
Image - Bleaching - Fixing - Washing - Stable 6) Color development - Bleaching - Bleaching
White fixing - water washing - stability 7) Color development - bleaching - bleach fixing -
Fixing - Washing - Stable 8) Color development - Bleaching - Washing - Fixing -
Washing with water - Stability 9) Color development - Adjustment - Bleach fixing - Washing with water - Stable
Stability 10) Color development - Water washing - Bleach fixing - Water washing - Stability 11
) Color development - bleach fixing - water washing - stability 12) Color development
- Fixing - Bleach-fixing - Washing - Stable 13) Color development - Adjustment
- Bleaching - Bleach-fixing - Washing - Stability 14) Color development - Adjustment
- Bleach-fixing - Fixing - Washing - Stability. Above 1
) ~ 14) In the treatment process, immediately before the stabilization process,
The water washing step may be removed, or the water washing step may be performed after the stabilization step.
Alternatively, a rinsing step may be performed. Also, the above 1) to 14
) In either case, a drying step is performed after the final step above.
be. [0011] Note that the stabilization step refers to conventional formalin-containing
This is a process that prevents fading of magenta images by
However, in the present invention, formaldehyde release is included in this step.
Containing a compound has a stabilizing effect, but without it
Since it has no stabilizing effect, it is inappropriate to call it a stabilization process.
It should be called a finishing bath, but for convenience it will be referred to as a stable bath below.
It is called. Other baths also contain formaldehyde-releasing compounds.
Contains washing bath, adjustment bath, bleach bath, fixing bath, bleach fixing bath.
Bathing, etc. are stabilized bath, adjustment stabilized bath, bleach stabilized bath, respectively.
, fixing stabilizing bath, bleach-fixing stabilizing bath, etc., but for convenience
The above will be explained using the former name. [0012] In the present invention, other than formaldehyde
Gelatin hardener is used in the conditioning bath in the typical processing steps mentioned above.
, water washing, bleach bath, fixing bath, bleach-fixing bath, stabilizing bath and
contained in at least one of the baths;
later baths than those containing compounds that release aldehyde.
Preferably contained in the final bath of the development process such as a stabilizing bath.
is most preferable. i.e. bleach bath, fixing bath, bleach-fixing bath
, and gelatin in the desilvering process and the previous process of the conditioning bath.
When containing a tin hardening agent, the photosensitive material in the desilvering process
The swelling becomes smaller and the desilvering rate becomes slower. On the other hand, the developing
If gelatin hardening agents are included in the final bath of the process, desorption
It does not slow down the silver speed and contains gelatin hardener.
Not only gelatin hardening in a bath, but also in the post-process of the final bath.
The gelatin can be expected to harden even during drying. In conventional processing, formalin in a stabilizing bath
The gelatin hardening effect of
It is thought that it is expressed even if it is present. [0014] In the present invention, formaldehyde is released.
Among the typical treatment steps listed above, compounds that are
Washing baths, bleaching baths, fixing baths, bleach-fixing baths, stabilizing baths and phosphorus
contained in at least one of the baths, and the curing agent and
Conditioning bath, bleaching bath, which may be the same bath or different baths
, in at least one of a fixing bath and a bleach-fixing bath.
Preferably, it is contained, and most preferably contained in the conditioning bath.
preferable. That is, compounds that release formaldehyde
When the substance is included in the final bath of the above representative processing steps,
During the drying process, the final bath is added to stabilize the magenta color image.
It is not as strong as when containing the amount of formalin required to
However, the amount of formaldehyde released tends to increase.
, which is not desirable. Formaldehyde releasing compound in the present invention
Forms an equilibrium state with formaldehyde in the treatment bath
All you need is something to do. [0017] Contained in at least one bath after color development of the present invention.
Typical examples of formaldehyde-releasing compounds include:
, N-methylol compounds, hexamethylenetetramine and
Hexahydrotriazine and its derivatives
, sodium bisulfite formaldehyde, metabisulfite
Examples include sodium formaldehyde. Holmua
The aldehyde releasing compounds are as follows. [Hexamethylenetetramine and its
Derivatives] Specifically, “Beilstein’s Handbook”
Beils
teins Handbuch der Organi
Shen Chemie), Volume II, Supplementary Edition, Volume 26, P. 2
00-P. Compounds described in 212 can be used.
In particular, hexamethylenetetramine and the following general formula
Compounds (I) are preferred. General formula (I) 0019
] [Chemical formula 1] In general formula (I), R1 is a hydrogen atom
, represents an alkyl group, an alkenyl group or an alkynyl group
, R1 alkyl group, alkenyl group or alkynyl group
is a halogen atom, carboxyl group, sulfonyl group,
Droxyl group, phenyl group, alkoxy group or amino group
It may be replaced with etc. As a preferable example of R1
Methyl group, ethyl group, allyl group, 3-chloroallyl
It is the basis. X- represents an anion, and a specific example is chlorine ion.
ion, sulfate ion, bromine source ion, iodide ion, nitrate ion
ion, paratoluenesulfonate ion, oxalate ion, etc.
What can I say? Also, R1 is an anion and the molecule
When forming an inner salt, X- is not required. These utensils
The most preferred are hexamethylenetetramine and
R1 is a 3-chloroallyl group and X- is a chlorine ion
It is a compound. Specific examples of the above compounds are shown below, but this
The invention is not limited to these. [Formula 2] [Formula 3] [Formula 4] [Formula 4] [Hexahydrotriazine and its derivatives
] Specifically, “Heterocyclic Compounds S
- Triazines and Derivatives” (HET
EROCYCLIC COMPOUNDS S-TRI
AZINES AND DERIVATIVES)
Morin Rapoport (SMOLINRAPOPORT)
Written by Interscience Publishers (INTE)
Published by RSCIENCE PUBLISHERS)
However, the following general formula
Compounds represented by (II) are preferred. General formula (II) [0026] In the above general formula, R2 and R3 are
Each represents a hydrogen atom or a substituent, and the substituent is
Alkyl group, aryl group, alkenyl group, alkynyl group
, aralkyl group, amino group, alkoxy group, hydroxy
group, acyl group, sulfonyl group, alkylthio group, aryl group,
ruthio group, heterocyclic residue, carbamoyl group or sulfur
Famoyl group can be mentioned. These substituents are
Other substituents (e.g. hydroxyl, acyl, sulfur)
Honyl group, halogen atom (e.g. chlorine, bromine), sia
Examples include , amino group, carboxyl group, etc.
Wear. Preferably a hydroxyl group or a halogen atom
. ) may be further replaced. R2, R3
The total number of carbon atoms in the substituents represented by is preferably 10 or less.
Yes. R2 is a hydrogen atom, an alkyl group, or
Ryl group, alkenyl group, aralkyl group, hydroxyl group
groups, acyl groups, sulfonyl groups, and heterocyclic residues are preferred.
Particularly preferred are hydrogen atoms and alkyl groups. Also,
R3 is a hydrogen atom, an alkyl group, an aryl group, or an alkyl group.
Preferred are alkenyl groups, aralkyl groups, and heterocyclic residues;
Particularly preferred are hydrogen atoms and alkyl groups. Specific examples of the above compounds are shown below.
The present invention is not limited to these. [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] [N-methylol compound] Amine compound (
A methylol group (-CH
Compounds in which 2 OH) is substituted can be used.
Wear. Preferred N-methylol compounds include:
N-methyl of the nitrogen-containing compound of the following compound group (III)
Preferred is a substituted product. Compound group (III) - Urea, thiourea, guanidine, melamine, hydantoin, glycine, pyrrole, pyrrolidine, methylamine, dimethylamine, ethylene urethane, urazole, pyrazole, triazole [0034] N-methylol substituted product of pyrazole compound
will be explained in detail. In the present invention, the following general formula (
The compound represented by IV) has a magenta color image stabilizing effect.
is also excellent and desirable. General formula (IV) [Image Omitted]
It is an important group of nonmetallic atoms. However, the element that bonds with the nitrogen atom
The child is an atom selected from carbon, oxygen, or sulfur atoms.
It is a child. ) Further details of the compound represented by general formula (IV)
Explain in detail. The 4- to 8-membered ring formed by Z is left unplaced.
may be replaced or substituted. Also, by Z
The formed 4- to 8-membered ring has at least two or more substituents.
If so, substitutions in positions ortho to each other among them
The groups may be combined to form a 5- to 7-membered ring. this house,
Compounds with condensed benzene rings have reduced solubility;
Compounds in which the benzene ring is not condensed are preferred. General formula (I
Among the compounds represented by V), preferred are carbon atoms
The total number of children is 15 or less, more preferably 10 or less
. Among the compounds represented by the general formula (IV), the following general formula
Those represented by (IVa) are more preferred. general formula
(IVa) ##STR11## In the formula, R41, R42 and R43 are the same.
may also be different, each representing a hydrogen atom, an alkyl group, or an alkyl group.
alkenyl group, aryl group, heterocyclic group, halogen atom,
Nitro group, cyano group, sulfo group, carboxyl group, phosphor group
group, acyl group, sulfonyl group, sulfinyl group, acyl group,
carboxy group, alkoxycarbonyl group, carbamoyl group
, represents a sulfamoyl group, an amino group or -YRa. -Y represents -O- or -S-, and Ra is
Alkyl group, alkenyl group, aryl group or heterocyclic group
represent. These groups may be further substituted. Also
R41 and R42 or R42 and R43 combine with each other to form 5
~ You may form a 7-membered ring. More specifically, R41, R42 and R43 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)
yl), amino groups (e.g. amino, diethylamino)
, alkoxy groups (e.g. methoxy, ethoxy), alkoxy groups (e.g. methoxy, ethoxy),
Kylthio group (e.g. methylthio, octylthio),
aryloxy group (e.g. phenoxy), arylthio
groups (e.g. phenylthio), heterocyclic oxy groups (e.g.
(1-phenyltetrazol-5-oxy), hetero
Represents a ring thio group (eg, benzothiazolylthio). R41, R42 and R43 are thermal fading properties of cyan images or
From the perspective of preventing yellow stain, hydrogen atoms or carbon
Unsubstituted alkyl groups of number 1 to 3 are preferred, and more preferred.
or at most one of R41, R42 and R43.
A methyl group and a hydrogen atom compound are particularly preferred.
In other words, it is a compound consisting entirely of hydrogen atoms. Below, N-mail
Specific examples of tyrol compounds are shown, but the present invention is not limited to these.
It is not determined. [Formula 12] [Formula 13] [Formula 13] [Formula 14] [Formula 15] [Formula 16] [Formula 16] [Formula 17] [Formula 18] ##STR19## Compound represented by the general formula (IV) of the present invention
The compound can be combined with the corresponding amine compound and formaldehyde or
easily by reacting with laformaldehyde.
can be synthesized into These synthesis methods include, for example,
National Patent No. 2883392, European Patent No. 60222,
Chem. ber. , 85, 820 ('52), J. O
rg. Chem. , 15, 1285 ('50), Khi
m. Geterotsikl. Soedin. ,(2)
, 251 ('80) [Chemcal Abstra
cts, 93:46530w].
It can be synthesized according to the same method. The pyrazole derivative is T
he Chemistry of Heterocyc
This is the 22nd volume of lic compounds. R.
H. Wiley “Pyrazoles, Pyra
Zolines, Pyrazolidines,
Indazoles and Condensed R
ing” , INTERSCIENCE PUBLI
The method described in SHERS ('67) or similar
It can be synthesized by the following method. [0050] The following is a compound represented by the general formula (IV).
A synthesis example is shown. Synthesis Example 1 Synthesis of Compound (IV-8) 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 finishing, perform filtration and concentrate the filtrate under reduced pressure at below 40℃.
Ta. The obtained concentrate was crystallized from ethyl acetate (300 ml).
did. Compound (IV-8) was obtained as colorless crystals. (
Yield 72g, melting point: 79-84℃) The chemical structure is
It was confirmed by analysis and various spectra. Among the compounds that release formaldehyde
Preferred are I-1, I-2, II-2, II-8
, sodium bisulfite formaldehyde, IV-1, I
It is V-8. Formaldehyde-releasing compounds of the invention
The product contains two or more species in at least one bath after color development.
They may be used in combination. Also, two or more baths each have different
containing one or more formaldehyde-releasing compounds.
May have. The formaldehyde releasing compounds of the present invention are
1 x 10-4 to 10 mol in at least one bath after color development
It is appropriate to contain 1 x 10-3 / liter.
~1 mol/liter is preferred, 3 x 10-3 ~ 1 mol
/liter is more preferable, and 1×10−2 to 1×10−2
Particularly preferred is 1 mol/liter. Examples of gelatin hardening agents that can be used in the present invention include
For example, T. H. Edited by James “The Theory of the
Photographic Process” (The Theor
y of thePhotographic Proc
ess), 4th edition, Chapter III P. 77-87
has been disclosed. However, gelatin that can be used in the present invention
The gelatin hardening agent is a gelatin hardening agent other than formaldehyde.
be. For example, as an inorganic gelatin hardening agent, chromium salt,
Represented by potash alum and ammonium alum
Aluminum salts are known. Then organic gelatin hardens
Here are some examples of agents. 1. Aldehyde gelatin hardener Croton
Aldehydes, acrolein, glyoxal, glutar
aldehyde, succinaldehyde, adipaldehyde,
Diglycoaldehyde 2. N-methylol compounds and other
Protected aldehyde gelatin hardeners Formaldehyde and various aliphatic linear or cyclic aliphatic
easily obtained by condensation with mido, urea, and nitrogen-containing heterocycles.
Many N-methylol compounds such as 2,3-dihydroxydioxane and its derivatives, dial
Acetate esters of dehydes and their hemiacetals, various heavy
Sulfite adduct, 2,5-dimethoxytetrahydrofura
0057]3. Ketone gelatin hardener 2,3-butane
dione, CH3 COCOCH3, 1,2-cyclope
tannedione, 2,5-hexanedione, 0058
4. Carboxylic acids, carbamic acid derivatives, polyacid anhydrides,
Acid chloride, 5. Sulfonic acid ester and sulfonylhala
Idobis(methanesulfonate), bis(sulfonylfluori)
D), 0060]6. Active halogen compound 7. s-triazines cyanuric chloride, 2,4-dichloro-6-hydroxy
C-s-triazine 8. Epoxide 00639. Aziridines Bisaziridine with an appropriate activation group introduced on the nitrogen atom
10. Active olefins divinyl ketone
, resorcinol bis(vinylalphonate), 4,6
-bis(vinylsulfonyl)-m-xylene, bis(vinylsulfonyl)-m-xylene,
(nylsulfonylalkyl) ether or amine, 1
,3,5-tris(vinylsulfonyl)hexahydro-
s-triazine, 1,3,5-triacryloylhexa
Hydro-s-triazine, diacrylamide, 1,3-
Bis(acryloyl)urea 11. protected
active olefin bis(2-acetoxyethyl)keto
3,8-dioxodecane-1,10-bis(pyridine)
perchlorate) 0066]12. Isocyanate Diisocyanate hydrogen sulfite adduct [0067]13. Carbodiimide and isoxoliu
Salt 0068 14. Gelatin hardening with multiple functions
Agents and mixtures acrolein (mentioned above), mucochloric acid, mucobromic acid [
15. Polyvinyl gelatin hardener
alcohol or partially acetylated cellulose
Maleic acid half ester, glycidyl acrylate
Copolymer, Acrylic Acid Copolymer, Chloroto
Polya, an amino acid polymer with pendant riazine
Hydrogen sulfite adduct of chlorein [0070]
The gelatin hardening agents that can be used are limited to the above compounds.
It's not. [0071] Preferred gelatin hardening agents in the present invention
is represented by potash alum and ammonium alum.
aluminum salts, glyoxal, glutaralde
Hyde, succinaldehyde, mucochloric acid, mucobrome
It is acid. In the present invention, at least
The amount of gelatin hardener added to one bath is
1 liter of each bath, depending on the type and bath added.
The amount is preferably 1 x 10-5 to 10 mol per mol.
, more preferably 1 x 10-4 mol to 1 mol.
, especially from 3 x 10-3 mol to 3 x 10-1 mol.
is preferred. [0073] The photosensitive material used in the present invention is
silver halide in the blue-sensitive layer, green-sensitive layer, and red-sensitive layer.
It is sufficient that at least one emulsion layer is provided, and halo
The number and order of silver emulsion layers and non-photosensitive layers are
There are no restrictions. A typical example would be to place a substantially
Multiple halogens with the same color sensitivity but different sensitivity
has at least one photosensitive layer consisting of a silver emulsion layer
It is a silver halide photographic light-sensitive material, and the light-sensitive layer is blue-light sensitive.
, a unit sensitive to either green light or red light
A photosensitive layer, a multilayer silver halide color photographic light-sensitive material
In general, the arrangement of unit photosensitive layers is on the support side.
A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order.
It will be done. However, depending on the purpose, the above installation order may be reversed.
, and it seems that different photosensitive layers are sandwiched within the same color sensitive layer.
The order of installation can be taken as follows. [0074] Between and above the silver halide photosensitive layers,
Non-photosensitive layers such as various intermediate layers are provided on the top and bottom layers.
Good too. [0075] For the intermediate layer, Japanese Patent Application Laid-Open No. 61-43748
, No. 59-113438, No. 59-113440,
In the specifications of No. 61-20037 and No. 61-20038
Contains couplers, DIR compounds, etc. as described
It may contain a color mixing inhibitor as is commonly used.
You can stay there. Multiple halogens forming each unit photosensitive layer
The silver oxide emulsion layer is manufactured by West German Patent No. 1,121,470 or
is highly sensitive as described in British Patent No. 923,045.
A two-layer structure consisting of a high-speed emulsion layer and a low-speed emulsion layer is preferably used.
I can do that. Usually, the sensitivity decreases gradually toward the support.
It is preferable that each halogen emulsion be arranged so that
A non-photosensitive layer may be provided between the layers. Also,
JP-A-57-112751, JP-A 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-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH
)/High sensitivity green photosensitive layer (GH)/Low sensitivity green photosensitive layer (G
L)/High-sensitivity red-sensitive layer (RH)/Low-sensitivity red-sensitive layer (RH)
RL) or BH/BL/GL/GH/RH/R
In order of L or BH/BL/GH/GL/RL/RH
They can be installed in any order. [0077] Also described in Japanese Patent Publication No. 55-34932
Blue-sensitive from the side farthest from the support as shown
They can also be arranged in the order of layer/GH/RH/GL/RL.
Ru. Also, JP-A-56-25738, JP-A No. 62-6393
As described in Specification No. 6, the farthest point from the support
Blue photosensitive layer/GL/RL/GH/RH are arranged in this order from the opposite side.
You can also queue. [0078] Also described in Japanese Patent Publication No. 49-15495
The upper layer is made of silver halide, which is the most sensitive.
The emulsion layer and the middle layer are silver halide emulsions with lower sensitivity.
The agent layer and the lower layer are made of silver halide, which has lower photosensitivity than the middle layer.
The emulsion layers are arranged and the sensitivity gradually decreases toward the support.
An example of this is an array consisting of three layers with different photosensitivity.
Ru. When it is composed of three layers with different photosensitivity like this
However, it is stated in the specification of JP-A No. 59-202464.
In the same color-sensitive layer, the side far from the support
In order from medium speed emulsion layer / high speed emulsion layer / low speed emulsion layer
may be placed. Others: high-sensitivity emulsion layer/low-sensitivity emulsion layer/medium
High-speed emulsion layer, or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer
They may be arranged in the order of the sensitive emulsion layer, etc. Also, 4
Even in the case of more than one layer, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat.
, No. 663,271, No. 4,705,744, No. 4,705,744, No. 4,705,744, No.
No. 4,707,436, JP-A-62-160448,
BL, GL, as described in the specification of No. 63-89850,
The multilayer effect has a different spectral sensitivity distribution from the main photosensitive layer such as RL.
A donor layer (CL) is arranged adjacent to or close to the main photosensitive layer.
It is preferable to set the As mentioned above, the purpose of each photosensitive material is
Various layer configurations and arrangements can be selected depending on the requirements. contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention.
The preferred silver halide contains about 0.2 to about 30 mole percent
Silver iodobromide, silver iodochloride, or silver iodide, including silver iodide.
Silver chlorobromide. Particularly preferred is from about 2 mol% to about
Silver iodobromide or iodine containing up to 25 mol% silver iodide
Silver chlorobromide. Silver halide grains in photographic emulsions are
Has regular crystals like cubes, octahedrons, and tetradecahedrons
Crystals with irregular crystal shapes such as spherical or plate-like
, those with crystal defects such as twin planes, or
It may also be a composite form. [0082] 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. [0083] Can be used in the photographic material used in the present invention
Silver halide photographic emulsions that can be
Closure (RD) No. 17643 (1978)
December), pp. 22-23, “I. Emulsification
ion preparation and type
s)” and No. 18716 (November 1979)
Month) 648 pages, same No. 308119 (1989
(February), pp. 993-995, etc.
It can be prepared using [0084] US Patent No. 3,574,628, US Patent No. 3,
655,394 and British Patent No. 1,413,748
The monodispersed emulsions described in No. 1, etc. are also preferred. Also, as
Tabular grains with a spectral ratio of about 3 or more are also applicable to the present invention.
Can be used. Tabular grains are produced by Gatoff, Photography.
Science and Engineering (Gut)
off, Photographic Science
e and Engineering), Volume 14
pp. 248-257 (1970); U.S. Patent No. 4,4
No. 34,226, No. 4,414,310, No. 4,43
No. 3,048, No. 4,439,520 and British patents
easily by the method described in No. 2,112,157 etc.
It can be prepared. 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. Photosensitive material used in the photosensitive material used in the present invention
The sexual silver halide emulsion is disclosed in JP-A No. 63-264,740.
It may also be a core/shell type internal latent image type emulsion as described in
. The method for preparing this core/shell type internal latent image emulsion is
It is described in 1983-133542. This emulsion
The thickness of the shell varies depending on the development process, etc., but the thickness of the shell is 3~
40 nm is preferred, and 5 to 20 nm is particularly preferred. Silver halide emulsions are usually subjected to physical ripening, chemical
Use those that have been subjected to chemical ripening and spectral sensitization. This way
Additives used in the eel process are research disclosures.
Jar No. 17643 and the same No. 18716
, same No. 308119, and the applicable
The locations are summarized in the table below. Photosensitive material used in the photosensitive material used in the present invention
Regarding silver halide emulsions, grain size, grain size
At least one of distribution, halogen composition, particle shape, and sensitivity
Two or more types of light-sensitive silver halide emulsions differing in terms of
They can be mixed and used in the same layer. [0089] The photosensitive material used in the present invention has US patents.
No. 4,082,553
Silver halide grains, U.S. Pat. No. 4,626,498, esp.
Covering the inside of the particle described in 1985-214,852
photosensitive halogenated silver halide grains, colloidal silver
Silver emulsion layer and or substantially non-photosensitive hydrophilic colloid
It can be preferably used for the hard layer. Halogenation inside or on the surface of the particle
Silver emulsion refers to the unexposed and exposed areas of a photographic light-sensitive material.
Halogenation enables uniform (non-imagewise) development
Refers to silver emulsion. The inside of the particle or the surface covered with
A method for preparing silver halide grains is described in U.S. Pat. No. 4,626,4
No. 98 and JP-A No. 59-214,852.
Ru. [0091] Core/shell type halves in which the inside of the particle is covered
The silver halide that forms the inner core of the silver halide grains and the outer
The silver halide that forms the shell has the same halogen composition.
The halogen composition may be different from the halogen composition. [0092] Halo with fogging inside or on the surface of the particle
Silver genides include silver chloride, silver chlorobromide, silver iodobromide, and silver chloride.
Any silver bromide can be used. These turnips
There are no special limitations on the grain size of silver halide grains.
No, but the average particle size is 0.01-0.75 μm
, particularly preferably 0.05 to 0.6 μm. [0093] Furthermore, there are no particular limitations on the particle shape.
, may be regular or irregular particles, and perhaps
A powder emulsion may be used, but monodispersion (the weight of silver halide grains or
or at least 95% of the number of particles is ±40% of the average particle size
It is preferable that the particles have a particle size within [0094] The photosensitive material used in the present invention contains substantially
Non-photosensitive, non-prefogged particulate halogen
Preferably, silver oxide particles are used. This virtually non-
Photosensitive fine-grained silver halide grains are used to obtain dye images
During imagewise exposure, the development process is performed without being exposed to light.
are silver halide grains that are not substantially developed in
. [0095] The fine grain silver halide has a silver bromide content of
0 to 100 mol%, optionally containing silver chloride and/or
Alternatively, it may contain silver iodide. Preferably silver iodide is 0
．． It contains 5 to 10 mol%. Fine grain silver halide has an average grain size (projection surface
The average value of the equivalent circle diameter of the product is preferably 0.01 to 0.5 μm.
More preferably, the thickness is 0.02 to 0.2 μm. [0097] Fine grain silver halide is an ordinary photosensitive halide
It can be prepared in the same way as silver genenide. In this case, halogen
The surface of the silver oxide grains does not need to be optically sensitized;
Also, spectral sensitization is not required. However, if this is added to the coating solution,
Before adding triazole and azai,
benzothiazolium, or mercapto
Addition of known stabilizers such as compounds or zinc compounds
It is preferable to keep it. This fine silver halide grain containing
Colloidal silver can be preferably contained in the layer.
. Known photographic additives that can be used in the present invention
As stated in the three research disclosures above,
The relevant information is shown below. Additive type RD17
643RD18716R
D308119 1 Chemical sensitizer
Page 23 Page 648 Right column
Page 996 left column 2 Sensitivity enhancer
　　　　　　　　　　　　　　　　　　　　　　　　　
Same as above Same as above 3
Spectral sensitizers, pages 23-24
Page 648 right column ~ Page 996 right column ~
supersensitizer
Page 649 right column
Page 998 left column 4 Brightening agent
24 pages
Page 998, right column 5?
Anti-fog agent pages 24-25
Page 649 right column ~ Page 998 right column ~
and stabilizers
　　　　　　　　　　　　　　　　　　　　　　　　　
1000 Page right column 6 Light absorber, film
Pages 25-26 Page 649 Right column ~
1003 Page left ~ Filter dyeing
fee, 65
Page 0 left column right column
Ultraviolet absorber 7 Stain inhibitor Page 25 right column
Page 650 left column to right column Page 1002 right column
8 Dye image stabilizer page 25
10
02 Page right column 9 Hardening agent
Page 26 Page 651 Left column
1004 page right column~
　　　　　　　　　　　　　　　　　　　　　　　　　
10
05 Page left column 10 Binder
Page 26 Same as above 11 Plasticity
agent, lubricant page 27 65
0 page right column 1006 page left to right column 12
Coating aids, pages 26-27
Page 650 right column Page 1005 left
Column ~ Surfactant
　　　　　　　　　　　　　　　　　　　　　　　　　
1006 Page Left Column 13 Static Prevention
Agent page 27 Same as above
1006 Page right column 14 Matting agent
　　　　　　　　　　　　　　　　　　　　　　　　　
1008 pages
left~
　　　　　　　　　　　　　　　　　　　　　　　　　
1009 Page left column 009
9] Also, deterioration of photographic performance due to formaldehyde gas
In order to prevent
Formaldehyde described in No. 4,435,503
A compound that can be immobilized by reacting with the photosensitive material is added to the photosensitive material.
It is preferable. [0100] The photosensitive material used in the present invention is
-107029, JP 60-252340, JP 60-252340, JP
Described in Hei 1-44940, JP 1-45687, etc.
A fogging agent is formed by a redox reaction with an oxidized form of a developer.
Contains compounds that release development accelerators, silver halide solvents, etc.
can be made to have [0101] The photosensitive material used in the present invention has US Patent No.
No. 4,740,454, JP-A-62-018539,
U.S. Patent No. 4,788,132, JP 1-28355
It is possible to contain the mercapto compound described in No. 1 etc.
Wear. [0102] The photosensitive material used in the present invention is disclosed in Japanese Patent Application Laid-Open No.
-106052 etc.
fogging agents, development accelerators, and halogens regardless of the amount of silver in the image.
Contains compounds that release silveride solvents or their precursors
can be done. [0103] The photosensitive material used in the present invention has international publication
Number WO88/04794, special table Hei 1-502912
Dyes dispersed by the method described in the European Patent No.
EP-0317308A2, US Pat. No. 4,420,5
No. 55, JP-A No. 1-259358, etc.
It is preferable to have it. [0104] There are various types of photosensitive materials used in the present invention.
Color couplers can be used, specific examples of which are given above.
Research Disclosure (RD) No. 17
643, VII-C to G
ing. As a yellow coupler, for example, U.S. Patent No. 3,93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Special Publication No. 58-10739, British Special Publication No.
No. 1,425,020, No. 1,476,760
, U.S. Patent No. 3,973,968, U.S. Patent No. 4,314,
No. 023, No. 4,511,649, European Patent No. 24
No. 9,473A, etc. are preferred. 5-pyrazolone as magenta coupler
and pyrazoloazole compounds are preferred;
Permit No. 4,310,619, No. 4,351,897
, European Patent No. 73,636, US Patent No. 3,061,
No. 432, No. 3,725,067, Research D.
Closer No. 24220 (June 1984)
, Japanese Patent Publication No. 60-33552, Research Disclosure
Jar No. 24230 (June 1984), Tokukai Sho
No. 60-43659, No. 61-72238, No. 60-
No. 35730, No. 55-118034, No. 60-18
5951, U.S. Patent No. 4,500,630, U.S. Pat.
, No. 540,654, No. 4,556,630, International
Particularly preferred are those described in published WO88/04795 etc.
Yes. As cyan couplers, phenolic and
U.S. Patent No. 4,0
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2
, No. 369,929, No. 2,801,171, No. 369,929, No. 2,801,171, No.
No. 2,772,162, No. 2,895,826, No. 2,895,826, No. 2,895,826, No.
No. 3,772,002, No. 3,758,308,
Same No. 4,334,011, Same No. 4,327,173
, West German Patent Publication No. 3,329,729, European Patent No. 1
No. 21,365A, No. 249,453A, U.S. Patent
No. 3,446,622, No. 4,333,999,
Same No. 4,775,616, Same No. 4,451,559
, No. 4,427,767, No. 4,690,889
No. 4,254,212, No. 4,296,19
No. 9, JP-A No. 61-42658, etc. are preferred.
Yes. 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. 2,102,137, European Patent No. 341,188A
It is described in etc. Coloring pigment has appropriate diffusivity
As a coupler, U.S. Pat. No. 4,366,237,
British Patent No. 2,125,570, European Patent No. 96,5
No. 70, described in West German Patent (Publication) No. 3,234,533.
The one listed is preferred. [0108] Color for correcting unnecessary absorption of coloring dye
The code coupler is Research Disclosure No.
．． Section VII-G of 17643, U.S. Patent No. 4,16
No. 3,670, Japanese Patent Publication No. 57-39413, U.S. Patent No.
No. 4,004,929, No. 4,138,258, English
Preferably, the one described in National Patent No. 1,146,368
. Also, the cup described in U.S. Pat. No. 4,774,181
Fluorescent dye released during pulling eliminates the need for coloring dye
Couplers that correct for absorption and U.S. Pat. No. 4,777,1
Colors that can react with developing agents to form dyes as described in No. 20
Using a coupler with an elementary precursor group as a leaving group
It is also preferable that Photographically useful residues associated with coupling
Compounds that release can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the RD1 described above.
7643, the patent described in Sections VII to F, JP-A-5
No. 7-151944, No. 57-154234, No. 60
-184248, 63-37346, 63-3
7350, U.S. Pat. No. 4,248,962, U.S. Patent No. 4,7
82,012 is preferred. Nucleating agent or development accelerator in image form during development
As a coupler that releases an agent, British Patent No. 2,097
, No. 140, No. 2,131,188, JP-A-59-
Those described in No. 157638 and No. 59-170840
is preferred. [0111] Other materials used in the photosensitive material used in the present invention
Couplers that can be used include U.S. Patent No. 4,1
Competitive couplers such as those described in U.S. Pat. No. 30,427, U.S. Pat.
, No. 283,472, No. 4,338,393, No. 4,338,393, No.
4,310,618, etc., JP-A No. 4,310,618, etc.
No. 60-185950, JP-A No. 62-24252, etc.
DIR redox compound releasing couplers described in DIR
Coupler-emitting coupler, DIR coupler-emitting redox
compound or DIR redox releasing redox compound
, European Patent No. 173,302A, European Patent No. 313,308
A coupler that releases a dye that restores color after separation as described in item A;
R. D. No. 11449, 24241, JP-A-6
Bleach accelerator releasing coupler described in No. 1-201247 etc.
, U.S. Patent No. 4,555,477, etc.
Release coupler, Roy described in JP-A No. 63-75747
Co-dye releasing coupler, U.S. Pat. No. 4,774,1
Examples include couplers that emit fluorescent dyes as described in No. 81.
It will be done. [0112] Color used in the photosensitive material used in the present invention
The puller can be introduced into the photosensitive material using various known dispersion methods.
can. Examples of high boiling point solvents used in oil-in-water dispersion method are
Described in U.S. Patent No. 2,322,027, etc.
. The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalate ester
esters (dibutyl phthalate, dicyclohexyl phthalate)
di-2-ethylhexyl phthalate, decylphthalate
rate, bis(2,4-di-t-amylphenyl)phthalate
rate, bis(2,4-di-t-amylphenyl)iso
Phthalate, bis(1,1-diethylpropyl)phthalate
esters of phosphoric or phosphonic acids (such as
Riphenyl phosphate, tricresyl phosphate,
2-Ethylhexyl diphenyl phosphate, trisic
lohexyl phosphate, tri-2-ethylhexyl phosphate
Sphate, tridodecyl phosphate, tributoxy
Ethyl phosphate, trichloropropyl phosphate
, di-2-ethylhexylphenylphosphonate, etc.)
, benzoic acid esters (2-ethylhexylbenzoate)
dodecyl benzoate, 2-ethylhexyl-p-
hydroxybenzoate, etc.), amides (N,N-di
Ethyldodecaneamide, N,N-diethyllaurylamide
(de, N-tetradecylpyrrolidone, etc.), alcohols
or phenols (isostearyl alcohol, 2,
4-di-tert-amylphenol, etc.), aliphatic carbon
Rubonic acid esters (bis(2-ethylhexyl) seba
cate, dioctyl azelate, glycerol tributyl
lactate, isostearyl lactate, trioctyl lactate
), aniline derivatives (N,N-dibutyl-2
-butoxy-5-tert-octylaniline, etc.),
Hydrocarbons (paraffin, dodecylbenzene, diisopropylene)
(e.g., lopylnaphthalene). Also, auxiliary melting
The agent has a boiling point of about 30°C or higher, preferably 50°C or higher.
Organic solvents with a temperature of about 160°C or less can be used, and typical examples include
Ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxy
Ethyl acetate, dimethylformamide, etc.
It will be done. [0113] In the photosensitive material used in the present invention,
To dissolve and disperse the magenta coupler used in the green sensitive layer.
High boiling point organic solvents are compounds with a dielectric constant of 6.50 or less.
Preferably, the dielectric constant is 6.0 or less, more preferably 1.9.
These are high boiling point organic solvents. In addition, high boiling point organic solvents are
It may be a mixture of more than one species. Here, the dielectric constant is 6.5
Formal to unreacted magenta coupler
This is preferable because the reactivity of the dehyde-releasing compound gradually decreases.
Not good. [0114] A high boiling point organic solvent is one whose boiling point at normal pressure is 17
Represents an organic solvent with a temperature of 5°C or higher. [0115] In the present invention, the dielectric constant refers to the dielectric constant at 25°C.
This value indicates the dielectric constant at the transformer bridge.
By measuring with method (Ando Electric TRS-10T),
can be easily determined. [0116] Preferably used high boiling point organic solvent
is the following general formula (A), (B), (C), (D) or (
Examples include those shown in E). General formula (A) 01
17] [Chemical formula 21] General formula (B) [0118] [Chemical formula 22] General formula (C) [0119] [Chemical formula 23] General formula (D) [0120] [Chemical formula 24] General formula (E) [0121] [0122] (wherein, W1, W2 and W3 are
Substituted or unsubstituted alkyl group, cycloalkyl
group, alkenyl group, aryl group or heterocyclic group.
, W4 represents W1, OW1 or -S-W1
and n is an integer from 1 to 5, and when n is 2 or more, W
4 may be the same or different from each other, and the general formula (E
), W1 and W2 may form a fused ring
. ) Preferred high boiling point organic solvents in the present invention are
General formula (A), (B), (C), (D) or (E)
In the high boiling point organic solvent represented by, substituent W1,
The sum of carbon atoms in W2, W3 or W4 is the general formula
(A), (B), (C), (D) or (E) of about 8 or more
Compounds that correspond to the above and have a dielectric constant of 6.0 or less
is applicable. The general formula (A), (B), (C) or
In (E), W1, W2 and W3 have substituents
If so, this substituent may be a group having one or more bonding groups selected from the following. In general formula (A), (B), (C), (D) or (E)
, expressed as W1 , W2 , W3 or W4
The alkyl group may be either straight chain or branched. for example
, methyl, ethyl, propyl, butyl, pentyl, hex
Syl, heptyl, octyl, nonyl, decyl, undecyl
dodecyl, tridecyl, tetradecyl, pentadecyl
hexadecyl, heptadecyl, octadecyl, nona
These include decyl and eicosyl. These alkyl groups
Taking the case of general formula (A) as an example, the acceptable substituents are as follows:
For example, halogen atoms, cycloalkyl groups,
Aryl group, ester group, such substituted alkyl group
For example, substitution of halogen (F, Cl, Br)
body (-C2 HF4, -C5 H3 F8, -C9
H3 F16, -C2 H4 Cl, -C3 H6
Cl, -C3H5Cl2, -C3H5ClB
r, -C3 H5 Br2, etc.), [Chemical Formula 27] [Chemical Formula 28] [Chemical Formula 28] Also in the general formulas (B) to (E),
The same substituents as in the alkyl group of general formula (A)
It may be substituted with a kill group. Furthermore, general formula (E)
In , W1 and W2 are oxilas forming a condensed ring.
It may be a ring, an oxolane ring, or an oxane ring. W1
, W2 , W3 or W4
Kyl groups are, for example, [Image Omitted] and substituted cyclohexyl groups are, for example,
For example, [0131] [Image Omitted] and the like. W1 , W2 , W3 or
The aryl group represented by W4 is, for example, [0133] and the like, and the substituted aryl group is, for example, 01
These include substituted benzoic acid esters such as [35] [Image Omitted] and the like. Al
Kenyl group is -C4 H7, -C5 H9, -C6
H11, -C7 H13, -C8 H15, -C10H
19, -C12H23, -C18H35, etc., and the substitution
Alkenyl groups are, for example, halogen atoms (F, Cl, Br
), -OC8 H17, [Image Omitted] and the like. General formulas (A), (B), (C), (D)
The high boiling point organic solvent according to the present invention represented by and (E) is
may be used alone or in combination within the scope of achieving the purpose of the present invention.
or in combination with other conventionally known high boiling point organic solvents.
You can also do it. These conventionally known high boiling point organic solvents include
, e.g. tricresyl phosphate, tri-2-ethyl
Hexyl phosphate, 7-methyloctyl phosphate
Phosphate esters such as tricyclohexyl phosphate
solvent, 2,5-di-tert-amylphenol,
Phenols such as 2,5-di-sec-amylphenol
Examples include solvents. The general formulas (A), (B), (C), (
D) and (E) with a high dielectric constant of 6.0 or less
Specific examples of boiling point organic solvents are shown below, but are not limited to these.
It's not. [Formula 34] [Formula 34] [Formula 35] [Formula 35] [Formula 36] [Formula 37] [Formula 37] [0148] The photosensitive material used in the present invention has a high boiling point.
The organic solvent is adjacent to the layer containing green-sensitive silver halide.
It is preferable to use it by adding it to a non-photosensitive layer. Also that
The amount used in the layer containing green-sensitive silver halide and the adjacent
Weight ratio relative to the total amount of coupler contained in the non-photosensitive layer
is preferably 0.01 to 20, and more preferably 0.0
It is especially preferable that it is 3-10. Couplers and
/ or other organic materials dissolved in the gelatin solution.
As a dispersion aid when dispersing using mechanical or ultrasonic waves.
Anionic surfactants, nonionic surfactants, carbon
Thiionic surfactants can be used. Also coupler
Assist when dissolving organic materials such as - in high boiling point organic solvents.
Ethyl acetate, butyl acetate, ethyl propionate as solvents.
Low boiling point solvents such as chill can also be used. [0150] 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.
Ru. [0151] The photosensitive material used in the present invention contains
Netyl alcohol and JP-A No. 63-257747, No. 6
No. 2-272248, and Japanese Patent Application Laid-open No. 1-80941.
1,2-benzisothiazolin-3-one, n-
Butyl, p-hydroxybenzoate, phenol, 4
-chloro-3,5-dimethylphenol, 2-phenokyl
Cyethanol, 2-(4-thiazolyl)benzimidazo
It is possible to add various preservatives or antifungal agents such as
preferable. The present invention is applicable to various color photosensitive materials.
be able to. Color negatives for general use or movies
color reversal film for slides or televisions
color paper, color positive film and color
A typical example is inverted paper. [0153] Can be used in the photosensitive material used in the present invention
Suitable supports include, for example, the aforementioned RD. No. 176
43, page 28, and the same No. Page 647 of 18716
It is described from the right column to the left column of page 648. The light-sensitive material used in the present invention has an emulsion layer.
The total thickness of all the hydrophilic colloid layers on the side with which it is present is 28 μm.
It is preferably not more than 23 μm, more preferably not more than 23 μm.
stomach. Also, the membrane swelling rate T1/2 is preferably 30 seconds or less.
, more preferably 20 seconds or less. Film thickness is 25℃ relative humidity
Means the film thickness measured under 55% humidity control (2 days).
The speed T1/2 is determined by methods known in the art.
Therefore, it can be measured. For example, A. Green
(A. Green) et al.
Engineering & Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129
Use a swell meter (swell meter) of the type described in
T1/2 can be measured using a color developer at 30°C.
90% of the maximum swollen film thickness reached when treated for 3 minutes and 15 seconds
is the saturated film thickness, and until reaching 1/2 of the saturated film thickness,
Define as time. [0155] The membrane swelling rate T1/2 is
Adding a hardening agent to the gelatin before application or
It can be adjusted by changing the aging conditions. Further, the swelling rate is preferably 150 to 400%. swelling rate and
is given by the formula: (
It can be calculated according to the maximum swelling film thickness - film thickness)/film thickness. [0156] The amount of silver coated in the photosensitive material used in the present invention is
, preferably 6.0 g/m2 or less, and 5.0 g/m2 or less
is more preferable, and 4.5 g/m2 or less is most preferable. The light-sensitive material used in the present invention has an emulsion layer.
The total film thickness is 2 μm to 20 μm on the side opposite to the side with
A hydrophilic colloid layer (referred to as a back layer) is preferably provided.
can be done. This back layer contains the aforementioned light absorber,
Filter dyes, UV absorbers, static inhibitors, hardeners
Film agents, binders, plasticizers, lubricants, coating aids, surface activation
It is possible to preferably contain a sex agent and the like. this bag
The swelling ratio of the layer is preferably 150 to 500%. [0158] Next, processing solution for color photographic light-sensitive material of the present invention
and processing steps will be explained. color photographic material
In the processing process, only color reversal processing, color development process
Previously, color negative processing was done by involving a black and white development process.
, color paper processing, etc. [0159] Processing steps for color photographic material of the present invention
The steps from black and white development to color development are as follows:
be. 1) Black and white development - water washing - reversal - color development 2) Black and white
Development - Water washing - Light reversal - Color development 3) Black and white development - Water washing
-Color development process 1) to 3) washing process are all based on U.S. Patent No. 4
, 804, 616, the treatment
It is possible to simplify the process and reduce waste liquid. Next, the color photographic light-sensitive material of the present invention is developed.
The processing liquid for the chemical process will be explained. used in the present invention
Known developing agents can be used for the black and white developer.
. As a developing agent, dihydroxybenzenes (for example,
hydroquinone), 3-pyrazolidones (e.g. 1
-phenyl-3-pyrazolidone), aminophenols
(e.g. N-methyl-p-aminophenol), 1-
Phenyl-3-pyrazolines, ascorbic acid and US
1,2,3,4- described in Patent No. 4,067,872
The tetrahydroquinoline ring and the indolene ring are bonded together.
Heterocyclic compounds, etc., used alone or in combination
be able to. The black and white developer used in the present invention includes
Preservatives (e.g. sulfites, bisulfites), buffers
(e.g. carbonates, boric acid, borates, alkanolamines)
), alkaline agents (e.g. hydroxides, carbonates), dissolving tablets
agents (e.g. polyethylene glycols and these
ster), pH adjusters (e.g. organic acids such as acetic acid),
Sensitizers (e.g. quaternary ammonium salts), development accelerators,
Contains surfactants, antifoaming agents, hardening agents, viscosity imparting agents, etc.
can be set. [0161] The black and white developer used in the present invention contains halogenated
It is necessary to include a compound that acts as a silver solvent, but
Sulfites, which are usually added as preservatives mentioned above, play this role.
fulfill the eyes. This sulfite and other possible halogenated
Specifically, silver solvents include KSCN, NaSCN, and K.
2 SO3 , Na2 SO3 , K2 S2 O5
, Na2S2O5 , K2 S2 O3 , Na2 S
2 O3 etc. can be mentioned. [0162] In addition, in order to impart a development accelerating effect,
Accelerators are used, especially as described in JP-A No. 57-63580.
The use of compounds and organic thioether compounds described in
I can do that. The amount of these silver halide solvents used should be
If the amount is too low, the development progress will be slow, and if it is too high, the development progress will be slow.
Because it causes fog in the silver halide emulsion, it is preferable by itself.
However, the amount can be easily determined by a person skilled in the art.
It is possible. For example, SCN- is calculated per liter of developer.
0.005 to 0.02 mol, especially 0.01 to 0.01
It is preferable that it is 5 mol, and SO32- is 0.0
It is preferably 5 to 1 mol, particularly 0.1 to 0.5 mol.
Yes. The black and white developer of the present invention has the purpose of water softening.
Various chelate compounds are used in These chelates
As a compound, aminopolymer, which was explained in the color developing solution, is used.
Ricarboxylic acids, organic phosphonic acids, phosphonocarboxylic acids
Preference is given to using acids. Moreover, the black and white development of the present invention
In addition to the sulfite mentioned above, the solution contains a color developer as a preservative.
Various compounds explained in section can be added.
. [0165] In the black and white development process of the present invention, development fog is prevented.
Various antifoggants may be added for the purpose of preventing fogging. mosquito
Potassium bromide, sodium bromide, iodide as anti-brittle agents
Alkali metal halides such as potassium and organic turnips
Preferably, anti-reactive agents are used. Examples of organic antifoggants include
benzotriazole, 6-nitrobenzimidazole
, 5-nitroisoindazole, 5-methylbenzotri
Azole, 5-nitrobenzotriazole, 5-chloro
-benzotriazole, 2-thiazolyl-benzimida
sol, 2-thiazolylmethyl-benzimidazole,
Nitrogen-containing heterocyclic compounds such as hydroxyazaindolizine
and 1-phenyl-5-mercaptotetrazole 2-
Mercaptobenzimidazole, 2-mercaptobenzo
mercapto-substituted heterocyclic compounds such as thiazole, and
Mercapto-substituted aromatic compounds such as thiosalicylic acid
can be used. These antifoggants are
They are eluted from color reversal photosensitive materials during processing, and these are developed.
Including those that accumulate in liquids. [0166] pH value of the developer thus adjusted
is selected to a sufficient extent to give the desired density and contrast.
but ranges from about 8.5 to about 11.5. It takes
Standard processing is usually used for sensitization using black and white developers.
The time can be extended by up to three times as long. At this time
Raising the processing temperature will shorten the extended time for sensitization.
can be done. The reversal bath used after black and white development is
It may contain known fogging agents. i.e. stannous
Ionic-organophosphate complex salts (U.S. Pat. No. 3,617,28
2 specification), stannous ion organic phosphonocarboxylic acid
Complex salt (Japanese Patent Publication No. 56-32616), stannous iodine
Aminopolycarboxylic acid complex salt (U.S. Pat. No. 1,209)
, 050 specification), hydrogenated stannous ion complex salts such as
Boron compounds (U.S. Pat. No. 2,984,567)
), heterocyclic amine borane compounds (UK Patent No. 1,011
, 000), and the like. The pH of this fogging bath (reversal bath) ranges from acidic to alkaline.
pH ranges from 2 to 12, preferably
preferably in the range of 2.5 to 10, particularly preferably in the range of 3 to 9.
Ru. Instead of using a reversal bath, perform light reversal processing by re-exposure.
Alternatively, the above fogging agent may be added to the color developer.
Accordingly, the reversing step can be omitted. [0167] The color developing solution of the present invention is preferably aromatic.
Alkaline water whose main ingredient is a primary amine color developing agent.
It is a solution. Aromatic primary amines used in color developers
Aminophenol compounds are also used as color developing agents.
Although useful, p-phenylenediamine derivatives are preferred;
Representative examples are shown below, but are not limited to these.
. D-1 N,N-diethyl-p-phenylenediamine
D-2 2-amino-5-diethylaminotoluene D
-3 2-amino-5-(N-ethyl-N-lauryl
amino) toluene D-4 4-[N-ethyl-N-(β-hydroxyethyl
thyl)amino]aniline D-5 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 N-(2-amino-5-diethylaminophenyl
ethyl) methanesulfonamide D-8 N,N-dimethyl-p-phenylenediamine
D-9 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N
-β-ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N
-β-Butoxyethylaniline Particularly preferred among the above p-phenylenediamine derivatives
are exemplary compounds D-2, D-4, D-5 and D-6
. [0168] In addition, these p-phenylenediamine derivatives
Conductors include sulfate, hydrochloride, sulfite, and p-toluene sulfonate.
It may also be a salt such as a phosphate salt. The aromatic primary amine group
The amount of image agent used is preferably about 0 per liter of developer.
．． 1 g to about 20 g, more preferably about 0.5 g to about 15
It is the concentration of g. [0169] In the present invention, the color developing solution substantially contains a base.
It is preferable not to contain alcohol. substantially
A color developer that does not contain benzyl alcohol is a color developer that does not contain benzyl alcohol.
The concentration of alcohol is 3 per liter of color developer.
×10−2 mol or less, preferably benzyl alcohol
Indicates a color developing solution that does not contain [0170] The color developing solution of the present invention contains sulfite.
It is preferable to do so. Sulfite is sodium sulfite
, potassium sulfite, sodium bisulfite, potassium bisulfite
um, sodium metabisulfite, potassium metabisulfite
etc. can be mentioned. The preferred amount of sulfite added is
, in terms of sodium sulfite, 1 liter of the color developer
1 x 10-5 mol to 5 x 10-2 mol per mol, and
The amount is preferably 1 x 10-4 mol to 5 x 10-2 mol.
more preferably 1 x 10-4 mol to 2 x 10-2 mol
It is le. [0171] The color developing solution of the present invention also contains the aromatic
A compound that directly preserves primary amine color developing agents.
JP-A-63-5341 and JP-A No. 63-106655
Various hydroxylamines (especially sulfo group
A compound having a carboxy group or a carboxy group is preferable. ) Japanese Patent Publication No. 6
Hydroxamic acids described in No. 3-43138, No. 63-1
Hydrazines and hydrazides described in No. 46041, No. 6
3-44657 and 63-58443
Nols, α-hydroxy described in No. 63-44656
Ketones and α-aminoketones, No. 63-36244
Examples include the various saccharides listed above. Also, above
In combination with compounds, JP-A-63-4235, JP-A-63-
No. 24254, No. 63-21647, No. 63-146
No. 040, No. 63-27841 and No. 63-256
Monoamines described in No. 54, etc., No. 63-30845
, No. 63-14640, No. 63-43139, etc.
Diamines listed in No. 63-21647, No. 63-26
Polyamines described in No. 655 and No. 63-44655
and nitroxy radicals described in No. 63-53551.
, No. 63-43140 and No. 63-53549
Alcohols, oximes described in No. 63-56654
and tertiary amines described in No. 63-239447.
can be used. [0172] As other preservatives, JP-A-57-441
Various metals described in No. 48 and No. 57-53749,
Salicylic acids described in JP-A-59-180588, JP-A-59-180588
Alkanolamines described in No. 54-3532, JP-A No. 54-3532
Polyethyleneimines described in No. 56-94349, rice
Aromatic polyhydro described in National Patent No. 3,746,544
It may contain an xy compound or the like as necessary. especially aromatic
The addition of group polyhydroxy compounds is preferred. [0173] The color developing solution used in the present invention is preferably
preferably pH 9 to 14, more preferably 9 to 13;
The color developer may also contain a combination of known color developer components.
can contain substances. To maintain the above pH
It is preferable to use various buffering agents. [0174] 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. However, the present invention
It is not limited to these compounds. [0175] The amount of the buffer added to the color developing solution is 0.
．． It is preferably 1 mol/liter or more, especially 0
．． Particularly preferably 1 to 0.4 mol/liter
. [0176] In addition, the color developing solution contains calcium and
As a magnesium precipitation inhibitor or for color development
Use various chelating agents to improve liquid stability
Can be done. [0177] As the chelating agent, an organic acid compound is preferable.
For example, aminopolycarboxylic acids, organic phosphonic acids
, phosphonocarboxylic acids. less than
Specific examples are shown, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriamine penta
Acetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylate
Renphosphonic acid, ethylenediamine-N,N,N',N
'-tetramethylenephosphonic acid, transcyclohexa
diaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid,
Hydroxyethyliminodiacetic acid, glycol ether diacetic acid
Amine tetraacetic acid, ethylenediamine orthohydroxyphene
Nylacetic acid, 2-phosphonobutane-1,2,4-trical
Bonic acid, 1-hydroxyethylidene-1,1-diphospho
phosphoric acid, N,N'-bis(2-hydroxybenzyl)ethyl
Diamine-N,N'-diacetic acid These chelating agents may be used in combination of two or more as necessary.
good. [0179] The amount of these chelating agents added depends on the color development.
It is sufficient as long as the amount is sufficient to sequester the metal ions in the liquid.
. For example, about 0.1g to 10g per liter of color developer
degree. [0180] The color developing solution may contain any developing agent if necessary.
Although an accelerator can be added, JP-A-52-498
p-Fe expressed in No. 29 and No. 50-15554.
Nylene diamine compound, JP-A-50-137726
, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-15682
6 and No. 52-43429, etc.
Ammonium salts, U.S. Pat. No. 2,494,903, ibid.
No. 3,128,182, No. 4,230,796, No. 3
, No. 253,919, Special Publication No. 41-11431, United States
Patent No. 2,482,546, Patent No. 2,596,926
and amine compounds described in No. 3,582,346, etc.
, Special Publication No. 37-16088, No. 42-25201,
U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-114
No. 31, No. 42-23883 and U.S. Patent No. 3,53
Polyalkylene oxide represented by No. 2,501 etc.
, other 1-phenyl-3-pyrazolidones, imidazo
etc. can be added as necessary. [0181] In the present invention, any optional
Antifoggants can be added. As an antifoggant, salt
Aluminum salts such as sodium chloride, potassium bromide, and potassium iodide
Potash metal halides and organic antifoggants can be used.
Ru. Examples of organic antifoggants include benzotriazo
6-nitrobenzimidazole, 5-nitroiso
Indazole, 5-methylbenzotriazole, 5-di
Trobenzotriazole, 5-chloro-benzotriazole
2-thiazolyl-benzimidazole, 2-thia
Zolylmethyl-benzimidazole, indazole, hydrogen
Nitrogen-containing compounds such as droxyazindolizine and adenine
Rocyclic compounds can be cited as a representative example. [0182] The color developing solution used in the present invention contains fluorescent light.
It may also contain a brightener. The fluorescent whitening agent includes 4,
4'-diamino-2,2'-disulfostilbene compounds
Preferably. The amount added is preferably 0 to 5 g/liter.
It is 0.1 to 4 g/liter. Also, if necessary,
Killsulfonic acid, arylphosphonic acid, aliphatic carbonate
Even if various surfactants such as acids and aromatic carboxylic acids are added,
good. The processing temperature with the color developing solution of the present invention is 20 to 50°C.
Preferably it is 30 to 40°C. Processing time is 20 seconds to 8
minutes, preferably 30 seconds to 6 minutes. Those who need less replenishment
is preferable, but 100 to 3000 m per m2 of photosensitive material.
1, preferably 100 to 2500 ml, more preferably
It is preferably 100 to 2000 ml. Also, the color developing bath
Divide into two or more baths as necessary, with the first bath or the last bath
Replenish the color developer replenisher from the bath to shorten the development time and
The amount of replenishment may also be reduced. Moreover, the color development of the present invention
The liquid contains citradinic acid, J acid, and H acid for the purpose of tone adjustment.
Colorless by reacting with the oxidized form of color developing agent, such as
contains a so-called competing compound that produces a compound of
be able to. The light-sensitive material of the present invention is subjected to bleaching treatment after color development.
Or bleach-fixed. These treatments are carried out after color development, etc.
It may be carried out immediately without going through the processing steps of
, prevents unnecessary post-development and air fog, and reduces emissions during the desilvering process.
In order to reduce the amount of color developer brought in, we also
Photos and sensitive material parts such as sensitizing dyes and dyes contained in the material
Washing out color developing agents impregnated into photosensitive materials and rendering them harmless
In order to perform color development, stop, adjust, and wash with water.
After which processing steps, it is bleached or bleach-fixed.
This is particularly preferred in the case of reversal photosensitive materials.
It is a mode. [0184] The above conditioning bath contains ethylene diamine tetra
Acetic acid, diethylenetriaminepentaacetic acid, 1,3-propane
Diaminetetraacetic acid, like cyclohexanediaminetetraacetic acid
aminopolycarboxylic acids; sodium sulfite, sulfite
Can contain sulfites such as ammonium
Ru. In addition, for the purpose of preventing scum, U.S. Patent No. 4,839,2
of fatty acids substituted with ethylene oxide described in No. 62
Sorbitan esters, US Pat. No. 4,059,446
and Research Disclosure Vol. 191, 191
Polyoxyethylene compound described in 04 (1980)
It is preferable to include a substance or the like. These compounds are
Use in the range of 0.1g to 20g per liter of adjustment liquid
However, it is preferably in the range of 1g to 5g.
Ru. [0185] The pH of the adjustment solution is usually in the range of 3 to 11.
preferably 4 to 9, more preferably 4.5
~7. The treatment time in the conditioning bath is 30 seconds to 5 minutes.
It is preferable that Also, the amount of replenishment of the adjustment bath should be determined based on the amount of light-sensitive material.
30ml to 3000ml per m2 is preferable, but especially
It is preferable that it is 50 ml to 1500 ml. adjustment
The treatment temperature of the bath is preferably 20°C to 50°C, especially 30°C.
It is preferable that it is ℃~40℃. Used in bleach and/or bleach-fix solutions
As bleaching agents, ferric complex salts of aminopolycarboxylic acids,
Oxides (e.g. sodium persulfate) can be used, but
, aminopolycarboxylic acid ferric complex salts are preferred. This way
Ethylenediamine is an aminopolycarboxylic acid.
Tetraacetic acid, 1,3-diaminopropanetetraacetic acid, glycol
Etherdiaminetetraacetic acid, cyclohexanediaminetetraacetic acid
acid, 1,4-diaminobutanetetraacetic acid, 1,2-propylene
diaminetetraacetic acid, thioglycol ether diaminetetraacetic acid
Acetic acid, 1,3-butylenediaminetetraacetic acid, methylimino
Examples include diacetic acid. [0187] The above-mentioned amount of bleach added is based on the bleaching solution or
is preferably 0.05 mol to 1 mol per liter of bleach-fix solution.
Preferably, it is 0.1 mol to 0.5 mol. Also, the above
Compounds of two or more types of ferric nopolycarboxylic acid complex salts
It can also be used as a bleaching agent. this place
The mixing ratio of the two is preferably 1:10 to 10:1. Also
The total concentration of both iron complex salts is 0 per liter of treatment liquid.
．． 05 mol to 1 mol, preferably 0.1 to 0.5 mol
be. Other bleaching solutions and/or bleach-fixing agents of the present invention
The solution contains the aforementioned aminopolycarboxylic acid iron (III) complex.
In addition, aminopolycarboxylic acid salts can be added. The preferable addition amount is 0.0001 mol to 0.1 mol/liter.
more preferably 0.003 to 0.05 mol/liter
It is le. Aminopolycarboxylic acid and its ferric complex salt
are usually used in the form of alkali metal or ammonium salts.
It is preferred that ammonium salts are used for solubility and bleaching.
It is preferable because it has excellent strength. In addition, the above ferric ion complex salt
Bleach and/or bleach-fix solutions containing cobalt other than iron
, metal ion complex salts such as copper may be contained. of the present invention
Various bleach accelerators are added to the bleach solution and/or bleach-fix solution.
Can be added. [0190] Regarding such bleach accelerators, for example,
, U.S. Patent No. 3,893,858, German Patent
No. 1,290,812, British Patent No. 1,138
, No. 842, Japanese Unexamined Patent Publication No. 53-95630, Ri
Search Disclosure No. 17129 (1978
Mercapto group or disulfide group described in July issue)
Compounds having the following are preferred. The amount of bleach accelerator added depends on the bleaching
Preferably 0.01g to 20g per liter of liquid with
The average weight is 0.1g to 10g. Bleaching solutions and/or bleaching constants constituting the present invention
In addition to bleach and the above-mentioned compounds, bromide, e.g.
Potassium bromide, sodium bromide, ammonium bromide or
is a chloride, such as potassium chloride, sodium chloride, chloride
May contain rehalogenating agents such as ammonium
. The concentration of the rehalogenating agent is 0.00% per liter of bleach solution.
The amount is 1 to 5 mol, preferably 0.5 to 3 mol. other,
Nitrates such as sodium nitrate and ammonium nitrate, boric acid,
Borax, sodium metaborate, acetic acid, sodium acetate, charcoal
sodium acid, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate
citric acid, sodium citrate, tartaric acid, etc.
one or more inorganic acids, organic acids, and other acids having pH buffering capacity;
Known additives that can be used in normal bleaching solutions, such as these salts.
Additives can be added. [0192] The bleach-fix solution and/or fixer solution of the present invention includes
, thiosulfate can be used as a fixing agent. Thio
The amount of sulfate added is 0.1 to 3 mol/liter,
0.3 to 2 mol/liter is preferred. Thiosulfate compounds
Ammonium thiosulfate, sodium thiosulfate,
Potassium thiosulfate, calcium thiosulfate, thiosulfate mag
Examples include nesium, but it has good solubility and
Ammonium thiosulfate also increases the fixing speed.
is preferred. Definition of the bleach-fix solution and/or fix solution of the present invention
In addition to the above thiosulfate compounds as adhesives or fixing accelerators
thiocyanate compounds (especially ammonium salts) and thiocyanate compounds (especially ammonium salts)
Urea, thioether, urea, etc. can be used. child
As the concentration of these auxiliary fixing agents or fixing accelerators,
is 1.1 to 3.0 mol/liter in total with the thiosulfate compound.
liter, preferably 1.4 to 2.8 mol/liter
It is le. The bleach-fixing solution and/or fixing solution of the present invention includes
, sulfites as preservatives, e.g. sodium sulfite,
Potassium sulfite, ammonium sulfite and hydroxy
It can contain luamine, hydrazine, etc. Furthermore, various optical brighteners, antifoaming agents, surfactants,
Contains organic solvents such as polyvinylpyrrolidone and methanol
However, especially as a preservative, a patent application filed in 1980
The sulfinic acid compound described in -283831
It is preferable to use Furthermore, various types of liquids are used for the purpose of stabilizing the liquid.
Addition of aminopolycarboxylic acids and organic phosphonic acids
preferable. In particular, 1-hydroxyethylidene-1,1-
Diphosphonic acid is effective. The amount of these additions is
0.01-0.3 mol/liter, preferably 0.05
~0.2 mol/liter, especially in fixer fluids.
It is effective. p of the bleaching solution and/or bleach-fixing solution of the present invention
H is generally 9 to 1, preferably 7.5 to 1.
5, most preferably 7.0 to 2.0. in bleach solution
In particular, 5.0 to 2.0 is preferable. Preferred pH range
has less bleaching fog and excellent desilvering performance.
. The pH of the fixer of the present invention is generally 9.0 to 5.0.
However, 7.5 to 5.5 is particularly preferable. [0196] Supplements for the bleaching solution and/or bleach-fixing solution of the present invention
The filling amount is 50ml to 3000ml per m2 of photosensitive material, preferably
Preferably, it is 100 ml to 1000 ml. fixer supplement
The filling amount is 300ml to 30ml per 1m2 of photosensitive material.
00ml is preferred, but more preferably from 300ml
It is 1000ml. However, the above replenishment amount is
, if you perform oxidation regeneration of the processing solution, silver recovery treatment, etc.
can be reduced to a small amount. In addition, the above desilvering process
The replenishment method is as follows:
Normally, the fluid is replenished and the overflow fluid is disposed of as waste.
However, there is a forward flow system that directs the overflow liquid from the previous bath to the subsequent bath.
Replenishment method, directing overflow liquid from subsequent bath to pre-bath,
A countercurrent replenishment system can also be applied. For example, washing water or
Transfer the overflow liquid from the stabilizing bath to the fixing bath or bleach-fixing bath.
You can also lead. [0197] The shorter the total time of the desilvering step of the present invention, the shorter the total time.
The effects of the present invention can be significantly obtained. The preferred time is 1 minute or more
It is 10 minutes, more preferably 1 minute to 6 minutes. Also, processing temperature
The temperature is between 25°C and 50°C, preferably between 35°C and 45°C.
. In the preferred temperature range, the desilvering rate increases and
First, the occurrence of stains after treatment is effectively prevented. [0198] In the desilvering process of the present invention, stirring is not possible.
The effect of the present invention will be more effective if the
This is preferable in terms of performance. As a specific method to strengthen stirring
JP-A No. 62-183460, No. 62-183461
No. 4,758,858.
A method of impinging a jet of processing liquid on the emulsion surface of an optical material, and a special
Stirring effect using rotating means of No. 183461/1986
How to raise the temperature, and also how to use a wiper blade installed in the liquid.
Move the photosensitive material while touching the emulsion surface, and
A method and treatment for improving the stirring effect by creating turbulent flow.
One method is to increase the circulation flow rate of the entire physical solution. child
Stirring improvement means such as
It is effective in both cases. Improved agitation in the emulsion film
speeds up the supply of bleach and fixing agents, resulting in faster desilvering speeds.
It is thought to increase the Further, the agitation improving means
It is more effective when using white accelerators and improves the accelerating results.
It can significantly increase or eliminate the fixation inhibiting effect caused by bleach accelerators.
You can make it disappear. [0199] The automatic developing machine used in the present invention is
No. 60-191257, No. 60-191258, No. 6
No. 0-191259, Research Disclo
Sure Item No. 29118 (1988
(July 2016), as described in U.S. Patent No. 4,758,858.
It is preferable to have a photosensitive material conveying means. Before
As described in Japanese Patent Application Laid-Open No. 60-191257, this
The conveying means causes significant carry-over of processing liquid from the front bath to the rear bath.
It is highly effective in preventing deterioration in the performance of the processing liquid. The means described in the above RD are also preferable. This kind of effect
This reduces the processing time in each process and reduces the amount of processing solution replenishment.
It is particularly effective in reducing These methods of strengthening stirring are effective in desilvering.
It is effective not only for processing, but also for washing and developing processes.
It is desirable to shorten the processing time and reduce the amount of replenishment. The processing method of the present invention includes the above-mentioned color development, bleaching, and bleach fixing.
It consists of processing steps such as adhesion and fixing. Here, the drift
After the white fixing or fixing process, treatments such as water washing and stabilization are necessary.
Although it is common practice to perform physical processes,
Stabilization treatment without substantial water washing after bathing with
A simple treatment method can also be used. [0200] The washing water used in the washing process may contain
Depending on the stabilizing solution, chelate compounds and/or pH buffers may be added.
It is preferable to include an agent. As a chelate compound
are aminocarboxylic acids, aminophosphonic acids, polyphosphonic acids.
Examples include compounds such as phosphoric acid and phosphonocarboxylic acid.
In particular, the following compounds or their alkali metal salts, ammonia
Preferred are nium salts.・Ethylenediaminetetraacetic acid・Diethylenete
lyaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,2-propylenediaminetetraacetic acid, 2-propanoldiaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, cyclohexane Diaminetetraacetic acid/Ethylenediaminetetramethylenephosphonic acid/hydro
xyethyliminodiacetic acid, iminodiacetic acid, methyliminodiacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylene
Diamine diacetic acid, ethylenediamine dipropionic acid, dihydroxyethylglycine, nitrilotripropionic acid, 1-hydroxyethylidene-1,1 diphosphonic acid 0
202 These compounds are added at a concentration of 1 per liter of stabilizer.
It is preferable to add x10-5 mol to 1 x 10-1 mol.
Especially when adding 1 x 10-4 mol to 5 x 10-2 mol,
It is preferable that [0203] As a pH buffer added to the stabilizing solution, pK
It is preferable that a is 5.0 or more, especially 6.0 to 1
It is preferably 0.40, more preferably 6.0 to 9.0
It is preferable that As such a pH buffer,
, alkali metal salts or ammonium salts of the following compounds:
can be mentioned.・Phosphates, sulfites, tetrapolyphosphates, tripolyphosphates, phthalates, boric hydrochlorides, and hydrochlorides of compounds such as imidazole and guanidine,
Compounds such as sulfates can also be preferably used. [0204] Regarding these pH buffers, their pKa
Although the values are listed in many publications, e.g.
3rd edition, “Chemical Handbook Basics II” Edited by the Chemical Society of Japan II-
337 pages to II-357 pages (1984).
Many compounds have been described. The amount of pH buffer added is
1 x 10-4 mol to 1 x 10 per liter of stabilizer
-1 mol is preferred, especially 1 x 10-3 mol to 5 x 1 mol.
0-2 mol is preferred. Most of the above pH buffers
The compounds are commercially available and can be easily obtained.
Ru. In addition, in the stabilizer of the present invention, from the viewpoint of solubility,
, most of the cation components can be ammonium salts.
preferable. [0205] The stabilizing liquid contains metal compounds such as Bi and Al.
, optical brighteners, fungicides, fungicides, surfactants, etc.
I can be there. As a fungicide, 5-chloro-2
-Methyl-isothiazolin-3-one, 1,2-ben
Thiazolone compounds such as tisothiazolin-2-one
It is valid. [0206] In addition, the stabilizer contains
To prevent the sulfidation of thiosulfate ions, sulfites, especially
Sulfinic acid compound described in 1982-143048,
Bisulfite adduct described in Japanese Patent Application No. 2-298935, rice
Alkanolamide described in National Patent No. 4,786,583
It is preferable to add compounds such as [0207] The appropriate pH of the stabilizing solution is 3 to 8.5.
is preferably 5 to 8.4, particularly preferably 6.1 to 8.3.
stomach. The replenishment amount of the stabilizer of the present invention is per 1 m2 of photosensitive material.
, preferably 30ml to 3000ml, especially 50ml
It is preferable that it is 1500 ml. Processing temperature of stabilizer
The temperature is preferably 20°C to 50°C, especially 30°C to 40°C.
It is preferable that [0208] In addition, the water washing process and stabilization process are carried out in a multi-stage counter-current direction.
The formula is preferred, and the number of stages is preferably 2 to 4 stages. 2 types
The stabilizing solution may be used in multiple stages. As for the replenishment amount
1 to 50 times the amount brought in from the prebath per unit area, preferably
is 2 to 30 times, more preferably 2 to 15 times. washing with water
The shorter the processing time of the stabilization process, the more effective the present invention will be.
, from the point of view of rapid processing, the total processing time of water washing and stabilization process is 1
0 to 50 seconds is preferable, especially 10 to 30 seconds is effective.
is remarkable. [0209] Also, the smaller the amount of replenishment during the washing and stabilization processes, the better
The effect of the invention is large: 50ml to 40ml per m2 of photosensitive material.
0 ml is preferable, particularly 50 to 200 ml is particularly preferable.
stomach. Used in these water washing or stabilization steps
As water, in addition to tap water, ion exchange resin etc.
Deionization treatment to reduce Ca and Mg concentration to 5 mg/liter or less
Water that has been sterilized using halogen, ultraviolet germicidal lamps, etc.
It is preferable to use Also, water washing process or stabilization process
The overflow liquid flows into the pre-bath, which has fixing ability.
Reduce the amount of waste liquid by using the method of
You can also do that. [Example] The present invention will be explained in more detail with reference to Examples below.
However, the present invention is not limited thereto. Example 1 205μ thick triacetic acid with primer coating on both sides of the film
Each of the following compositions was deposited on a cellulose film support.
A multilayer color photosensitive material consisting of layers was prepared, and sample 101 and
did. The coating amount of each composition is the value per 1 m 2 of the sample. Na
For silver halide and colloidal silver, convert to equivalent amount of silver.
The calculated weight is shown. 1st layer: antihalation layer black colloidal silver
　　　　　　　　　　　　　　　　　　　　　　　　　
0.25g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.9 g
UV absorber U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.04g UV absorber U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g UV absorption
Agent U-3
0.1 g
UV absorber U-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g UV absorber U-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g additive
F-10
0.
2 g High boiling point organic solvent Oil-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g 2nd layer: middle layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40g Compound Cpd
-D
10mg
Dye D-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4 mg high boiling point organic solvent
Oil-3
40mg
Dye D-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g 0212 Third layer: Intermediate layer Fine grain silver iodobromide milk covered on the surface and inside
agent (average particle size 0.06 μm, coefficient of variation 18
% AgI content 1 mol%)
Silver amount 0.05g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4 g
4th layer: Low sensitivity red sensitive emulsion layer Emulsion A
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.2 g Emulsion B
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3
g Additive F-14
　　　　　　　　　　　　　　　　　　　　　　　　　
1mg gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.8 g Compound Cpd-K
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g Coupler C-
1
0.15g
Coupler C-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g Coupler C-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g
Puller C-10
0
．． 10g Compound Cpd-D
　　　　　　　　　　　　　　　　　　　　　　　　　
10mg additive
F-2
0.1
mg High boiling point organic solvent Oil-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10g Additive F-12
　　　　　　　　　　　　　　　　　　　　　　　　　
0.5 mg 021
3] 5th layer: Medium-sensitivity red-sensitive emulsion layer Emulsion B
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.2 g Emulsion C
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.3
g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.8 g Additive F
-13
0.05m
g Coupler C-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2 g Coupler C-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g
Coupler C-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2 g Additive F-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 mg
High boiling point organic solvent Oil-2
0.1
g6th layer: Highly sensitive red-sensitive emulsion layer Emulsion D
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.4 g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.1
g Coupler C-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.7 g Coupler C-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3g
Additive P-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g Additive F-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g
7th layer: middle layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.6 g Color mixture prevention agent Cp
d-L
0.05g
Additive F-1
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5 mg Additive F-7
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0 mg
Additive M-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3 g Color mixing prevention agent Cpd-K
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g UV absorption
Agent U-1
0.1 g
UV absorber U-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g Dye D-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g
Dye D-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g 8th layer: Intermediate layer Silver iodobromide emulsion (plain) covered on the surface and inside
Average particle size 0.06 μm, coefficient of variation 16%, A
gI content 0.3 mol%)
0.02g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0
g Additive P-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2 g Color mixture prevention agent Cp
d-J
0.1 g
Color mixing prevention agent Cpd-M
0
．． 05g Color mixing prevention agent Cpd-A
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g 0215 9th layer: Low-sensitivity green-sensitive emulsion layer Emulsion E
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.3 g Emulsion F
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.1
g Emulsion G
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.1 g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.5
g Coupler C-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20g Coupler C-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10g
Coupler C-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10g Coupler C-11
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10g Compound C
pd-B
0.03
g Compound Cpd-E
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g Compound Cpd-F
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g compound
Object Cpd-G
0.
02g Compound Cpd-H
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g Compound Cpd-D
　　　　　　　　　　　　　　　　　　　　　　　　　
10mg
Additive F-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 mg Additive F-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2 mg
Additive F-11
　　　　　　　　　　　　　　　　　　　　　　　　　
0.5 mg high boiling point organic solvent Oi
l-2
0.2 g 10th layer: medium-sensitivity green-sensitive emulsion layer Emulsion G
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.3 g Emulsion H
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.1
g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.6 g Coupler C-
4
0.1
g Coupler C-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g Coupler C-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g
Coupler C-11
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g Compound Cpd-B
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03g Compound Cp
d-E
0.02g
Compound Cpd-F
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g Compound Cpd-G
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g compound
Cpd-H
0.0
5g Additive F-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.08mg high boiling point organic solvent
Oil-2
0.01g 11th layer: Highly sensitive green-sensitive emulsion layer Emulsion I
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.5 g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0
g Coupler C-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4 g Coupler C-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2 g
Coupler C-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2 g Coupler C-12
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g
Compound Cpd-B
0
．． 08g Compound Cpd-E
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g Compound Cpd-F
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g
Compound Cpd-G
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g Compound Cpd-H
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g Additive F
-2
0.3
mg High boiling point organic solvent Oil-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.04g Additive F-13
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05mg 0218 12th layer: middle layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.6 g Additive F-
1
2.0
mg additive F-8
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0 mg Dye D-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1
g Dye D-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.07g Dye D-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.0
3g Dye D-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g 0219 Layer 13: Yellow filter layer Yellow colloidal silver
Silver
Amount 0.1 g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.1 g
Dye D-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g Color mixing prevention agent Cpd-A
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01g additive
F-4
0.
3 mg High boiling point organic solvent Oil-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01g Dye D-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03g 14th
Layer: Middle layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.6 g Dye D-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02
g0220 Layer 15: Low-speed blue-sensitive emulsion layer Emulsion J
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.4 g Emulsion K
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.1
g Emulsion L
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.1 g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.8
g Coupler C-13
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g Coupler C-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.6 g
Additive F-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2 mg Additive F-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4 mg
Additive F-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05mg 0221 Layer 16: Mid-sensitivity blue-sensitive emulsion layer Emulsion L
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.1 g Emulsion M
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.4
g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.9 g Coupler C-
13
0.1 g
Coupler C-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3 g Coupler C-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3g
Additive F-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.04mg Additive F-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.04mg 17th layer
:High sensitivity blue sensitive emulsion layer Emulsion N
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.4 g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.2
g Coupler C-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.7 g Additive F-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4 m
g Additive F-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02mg Additive F-9
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
1mg 0222 18th layer: 1st protective layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.7 g UV absorber U
-1
0.04g
UV absorber U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01g UV absorber U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03g UV absorber U-
4
0.03g
UV absorber U-5
0
．． 05g UV absorber U-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g High boiling point organic solvent Oi
l-1
0.02g formali
Scavenger Cpd-C
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2 g Cpd-I
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4
g Dye D-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g Additive F-1
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 m
g Additive F-6
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 mg Additive F-
7
0.5
mg 0223 Layer 19: Second protective layer Colloidal silver
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.1 mg Fine grain silver iodobromide emulsion
(Average particle size 0.06 μm, AgI content 1 mol%)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver amount 0.1 g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4
g0224 Layer 20: Third protective layer Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4 g polymethylmeth
Acrylate (average particle size 1.5μm)
0.1g Methyl methacrylate and a
4:6 copolymer of acrylic acid (average particle size 1.5μ
m)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g silicone oil
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03g
Surfactant W-1
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0 mg Surfactant W-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03g 21st layer (back
layer) gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
10g UV absorber
U-1
0.05g
UV absorber U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g High boiling point organic solvent Oil-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01g 0225 22nd layer (back protection) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
5g polymethyl
Methacrylate (average particle size 1.5μm)
0.03g methyl methacrylate and
4:6 copolymer of acrylic acid (average particle size 1.5μ
m)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g Surfactant W-
1
1
mg surfactant W-2
　　　　　　　　　　　　　　　　　　　　　　　　　
10mg 0226 Each halogen
Additive F-2 was added to the silveride emulsion layer. Also, each layer
In addition to the above composition, gelatin hardening agent H-1 and coating
Surfactants W-3 and W-4 are used as surfactants for emulsification.
W-5 was added. Furthermore, phenol is used as a preservative and anti-mold agent.
1,2-benzisothiazolin-3-one, 2-fluor
phenoxyethanol, phenyl isothiocyanate, and
Phenethyl alcohol was added. [Table 1] [Table 2] [Table 2] [Table 3] [Table 4] [Chemical formula 41] [Chemical formula 41] [Chemical formula 43] [Chemical formula 43] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image [Chemical 58] [Chemical 59] Next, the layer structure and the compounds used in each layer are explained.
The coating amount, emulsion type, and coating amount are the same as sample 101.
Do exactly the same thing and use it for the green sensitive layer (9th, 10th, 11th layer).
Samples 102 and 103 were prepared using the oil shown in Table 5.
Manufactured. [Table 5] [0252] Next, the following processing solutions were prepared for the adjustment bath, bleaching bath, and fixing bath.
Formaldehyde releasing compound and gelatin hardening bath, stabilizing bath
Processing solutions 1 to 17 to which a curing agent was added were prepared. Table 6
It was shown to. For samples 101 to 103, color temperature 480
Provide sensitometric exposure using a 0°k filter.
The obtained sample was treated with treatment solutions 1 to 17 in the following treatment process.
It was. [Processing process] [Time
〕 〔Temperature〕
Black and white development 6 minutes
38℃
First water wash 2〃
38〃 Anti
Turn 2〃
38〃 Color development
Statue 6〃
38 Adjustment
2〃
38〃 Bleaching
6〃
38〃 Fixation
4〃
38 Second washing (1)
2〃
38 Second washing (2)
2〃 38〃
stable
2〃 38〃[
[Black and white developer] Nitrilo-N,N,N-trimethylenephosphonic acid.
5 sodium salt
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0g Jie
Tylentriamine pentaacetic acid pentasodium salt
3.0g sulfite
Rium
3
0.0g Hydroquinone/potassium monosulfonate
20.
0g potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
33.0g 1-phenyl-4-meth
Thyl-4-hydroxymethyl-3-pyrazodone
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
2.5g Chi
Potassium ocyanate
　　　　　　　　　　　　　　　　　　　　　　　　　
1.2g potassium iodide
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 2.0mg water
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
9.60pH is salt
Adjusted with acid or potassium hydroxide. [Reversing liquid] Nitrilo-N,N,N-trimethylenephosphonic acid.
5 sodium salt
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0g chloride
Stannous dihydrate salt
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0g p-aminophenol
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1g sodium hydroxide
　　　　　　　　　　　　　　　　　　　　　　　　　
8.0g ice
acetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 15.0ml water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0
liter pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
6.00pH is hydrochloric acid or hydroxide
Adjusted with sodium. [Color developer] Nitrilo-N,N,N-trimethylenephosphonic acid.
5 sodium salt
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0g Jie
Tylentriamine pentaacetic acid pentasodium salt
2.0g Sodium sulfite
thorium
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0g Tripotassium phosphate dodecahydrate
　　　　　　　　　　　　　　　　　　　　　　　　　
36.0g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0g Potassium iodide
Rium
　　　　　　　　　　　　　　　　　　　　　　　　　
90.0mg Sodium hydroxide
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0g citradinic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5g N-ethyl-(β-methanesulfonamide
ethyl)-3-methyl-4-aminoaniline sulfur
acid salt
10.5g 3,6-dithiaoc
Tan-1,8-diol
Add 3.5g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0
liter pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
11.90 pH is hydrochloric acid or potassium hydroxide.
Adjusted with Rium. [Adjustment solution] Ethylenetriaminetetraacetic acid, disodium salt, diwater
Salt 8.0g Sodium sulfite
thorium
12
．． 0g 1-thioglycerin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4ml TWEEN 20*
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0ml
add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter pH (2
5℃)
6
．． 2 pH was adjusted with hydrochloric acid or sodium hydroxide. TWEEN 20* :ICI American
an Inc. Surfactant 0258 [Bleach solution] Ethylenediaminetetraacetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0g Ethylenediaminetetraacetic acid ferric anhydride
Monium dihydrate salt 150.0g
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
124.0g ammonium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
120.0g
ammonium nitrate
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 25.0g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter
pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
4.20 pH is adjusted with acetic acid or aqueous ammonia.
I arranged it. [Fixer] Ethylenediaminetetraacetic acid, disodium, dihydrate
1.7g Ben
Sodium dualdehyde-o-sulfonate
20.0g sodium bisulfite
Rium
15.0g
Ammonium thiosulfate (700g/liter)
340.0ml water
In addition
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
4.00p
H was adjusted with acetic acid or aqueous ammonia. [Stabilizer A] Ethylenediaminetetraacetic acid, disodium salt, dihydrate salt
0.05g 5-chloro
rho-2-methyl-4-isothiazolin-3-one
0.02g polyoxyethylene-p-mo
Nononylphenyl ether (average degree of polymerization 1
0)
Add 0.30g water
Yes
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
5.8
~8.0 [0261] [Stable liquid B] Ethylenetriaminetetraacetic acid, disodium salt, diwater
Salt 0.05g 5-chloro
-2-methyl-4-isothiazolin-3-one
0.02g formalin (37%)
　　　　　　　　　　　　　　　　　　　　　　　　　
1.3 g polyoxye
tyrene-p-monononylphenyl ether
(Average degree of polymerization 10)
0.3
Add 0g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
5.8 to 8.0 [0262] [Table 6] [0263] Regarding the sample after processing, magenta color depth
Measure the temperature and store it for 4 weeks at 30℃ and 70%RH.
Find the density change in the part with a density of 1.5 and display the results.
7. The smaller the value of this density change, the better the color image preservation.
It can be said to be excellent. Similarly, the emulsion side of the sample after processing
Continuously load the surface with a stainless steel needle with a diameter of 0.1 mm.
I scratched it while applying it. The membrane surface is destroyed by scratching.
The resulting load is shown in Table 7. of this load
It can be said that the smaller the value, the weaker the film strength. [Table 7] [0265] Separately, in a 5 liter airtight container,
Formaldehyde in constant solutions B and A, treatment solutions 3 to 16 in Table 6
For comparison, the solutions in Table 6
Formalin (3
7%) in 1 liter of each bath.
Add 100ml each and leave at 50℃ for 4 hours.
After placing the
o. Formua in the gas phase of a 5 liter sealed container with 91 L
The concentration of aldehyde gas was measured. As a result, stable bath B and
, when formalin is added to the conditioning bath, bleaching bath, and fixing bath.
The concentration of formaldehyde gas in the gas phase is high, and each
In order, 6.2ppm, 6.4ppm, 6.0ppm, 6
．． It was 3 ppm. Stabilizing solution A and processing solution 3~ in Table 6
5, 7 to 15, formaldehyde-releasing compounds are added to the conditioning bath.
, bleach bath, fixing bath, formalde in the gas phase.
The concentration of hydrogen gas was 0.5 ppm or less. Also, processing
Add the formaldehyde-releasing compound of solutions 6 and 16 to a stabilizing bath.
If so, what is the concentration of formaldehyde gas in the gas phase?
Perhaps for this reason, the concentration was 0.9 ppm, which was slightly higher than in the case of other baths. [0266] From the results in Table 7, the present invention provides a stable bath with formal
Similar to the case of treatment with treatment solution 1 containing phosphorus, mazen
The rate of change in concentration is small, and the load that destroys the membrane surface is large.
Hey. In other words, it has excellent magenta color image preservation and strong film strength.
stomach. Moreover, the value of formaldehyde gas concentration is
compared to the case of using
It can be said that there are few negative effects. On the other hand, formaldehyde release
Even if it contains compounds, it does not contain gelatin hardening agents.
If not, the magenta color image preservation is excellent, but the film
The strength is weak. Also, even if you add a gelatin hardener to the stabilizing bath,
formaldehyde release in at least one bath after color development;
If the compound does not contain the compound, the color image storage stability deteriorates. Example 2 For sample 101 of Example 1, the treatment liquid shown in Table 8 below was used.
The same experiment as in Example 1 was conducted for
It was shown to. Treatment liquids 18 to 33 in Table 8 are treatment liquids of Example 1.
Table 7 formaldehyde-releasing compounds and gelatin hardening agents
Completely the same treatment as treatment solution 7 except for using the compound shown in 8.
It is a liquid. [0268] Sample 101 was exposed and treated in the same manner as in Example 1.
Processed with physical solutions 1 to 3, 7, and 17 to 33 to improve color image preservation and film
The strength was determined in the same manner as in Example 1, and the results are shown in Table 9.
did. For the adjustment baths of processing solutions 18 to 33, Example 1 and
Measure the formaldehyde gas concentration in the gas phase in the same way.
In all cases, it was 0.5 ppm or less. [Table 8] [Table 9] [Table 9] From the results in Table 9, the present invention provides
As with the case containing phosphorus, it has excellent color image preservation and film strength.
It is clear that Moreover, as mentioned above, in the gas phase
Formaldehyde gas concentration stabilizes in the bath
compared to the case where the
It can be said that there is little negative impact on the human body. Example 3 The development process of Example 2 was carried out using the following processing steps. Example
Similar to 2, a formaldehyde-releasing compound is added to the conditioning bath.
and gelatin hardener was added into the stabilizing bath. in this case
The same results as in Example 2 were also obtained. [Processing process] [Time
〕 〔Temperature〕
Black and white development 6 minutes
38℃
First water wash 2〃
38〃 Anti
Turn 2〃
38〃 Color development
Statue 6〃
38 Adjustment
2〃
38. Bleach fixing
6〃
38 Second washing (1)
2 3
8〃 Second washing (2)
2〃 38〃
stable
2〃 38〃[0
274] Among the above processing steps, liquid composition for steps other than bleach-fixing
The preparation was exactly the same as in Example 2. The bleach-fix solution is as follows:
I made it. [Bleach-fix solution]
　　　　　　　　　　　　　　　　　　　　　　　　　
Mother liquid ethylenedi
Amine tetraacetic acid, disodium salt, dihydrate salt
2.0g ethylenediaminetetravinegar
Ferric acid ammonium dihydrate salt
70.0g ammonium thiosulfate (700g/li)
) 200.0
g Ammonium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
20.0g 1-thioglycerin
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 0.4ml water
hand
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
6.60pH is
Adjustment was made with acetic acid or aqueous ammonia. Example 4 The following commercially available photosensitive materials were subjected to the same processing steps as in Example 1.
Fujichrome Velvia (emulsion number 502013), Fuji
Chrome 100D (emulsion number 125021), Fujikuro
400D (emulsion number 223003), Fujichrome
P1600D (emulsion number 412002), Ektaclaw
Emulsion No. 945026C06A), Ektachrome
emulsion number 400 (emulsion number 605D23A),
The same exposure as in Example 1 was applied and processing was performed. Here
Dichrome P1600D black and white development processing time extended by 2 minutes
I went. As a result, the treatment method described in the present invention can also be used.
Good image preservation on any photosensitive material when used
The results showed high performance and strong film strength. Effects of the Invention The present invention improves color image storage stability and film strength.
Formalde has a negative effect on the human body without causing any
Silver halide color photograph showing low gas concentration in the gas phase of hydride
Provides processing solutions for photosensitive materials, and its effects
is extremely significant, and the practical benefits are extremely large.
.

Claims (1)

[Claims] 1. A method for developing a silver halide color photographic light-sensitive material, wherein at least one bath after color development contains at least one compound that releases formaldehyde; A method for processing a silver halide color photographic light-sensitive material, which comprises containing at least one gelatin hardening agent other than formaldehyde.