JPH03130758A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the putrefaction of a hydrophilic colloidal compsn. at the time of production, at the time of storage or after coating by incorporating a prescribed compd. and >=2 among the prescribed compd. groups different therefrom. CONSTITUTION:The compd. expressed by formula I and >=2 of the compds. expressed by formulas II to IV are incorporated as antiseptic agents into this photosensitive material. In the formulas, R1 denotes (substd.) alkylene; X denotes H, halogen, etc.; R8 denotes H, alkyl, etc.; R9, R10 denotes H, alkyl, etc.; R13 denotes H, alkyl, etc.; R14 denotes H or alkyl; Y denotes halogen, nitro, etc.; M' denotes H, alkaline metal, etc.; (m), (n), (p) respectively denote prescribed numbers. These compds. may be added to any of the photograph constituting layers contg. the hydrophilic colloid.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material), and particularly to a hydrophilic colloid preservative used as a binder for the light-sensitive material.

(Prior Art) In general, photosensitive materials are prepared by coating at least one photosensitive emulsion layer on a support, and optionally forming photographic constituent layers such as a subbing layer, an intermediate layer, an antihalation layer, and a protective layer. It will be painted.

Hydrophilic colloids used as binders for these photographic constituent layers include gelatin, colloidal albumin, agar, gum arabic, alginic acid, cellulose derivatives such as hydrolyzed cellulose acetite, carboxymethyl cellulose, hydroxyethyl cellulose, and methyl cellulose. , synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, polyN,N-dimethylacrylamide, polyN-vinylpyrrolidone, U.S. Pat. No. 3,341,332,
Water-soluble polymers such as those described in U.S. Pat. No. 3,615.424, U.S. Patent No. 3,860,428,
Gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin as described in U.S. Pat. No. 14.928 and U.S. Pat. No. 2,525,753; Examples include gelatin graft copolymerized with polymerizable ethylene group-containing monomers such as acrylic acid (ester), methacrylic acid (ester), and acrylonitrile, as described in No. 767. These binders can be used as a compatible mixture of two or more, if desired.

It is known that hydrophilic colloids used as binders for photosensitive materials are easily affected by microorganisms such as bacteria, yeast, and mold. In particular, when a photographic hydrophilic colloid' is coated on a support, the influence of microorganisms becomes significant because the coating is carried out at a temperature suitable for microbial growth. For example, when a hydrophilic colloid rots or decomposes due to microorganisms, the viscosity of the coating solution decreases, the strength of the applied film decreases,
Bacteria coagulate and form small clumps, resulting in comet-shaped defects and an uneven coating.
Metabolites of microorganisms may cause adverse photographic effects.

Furthermore, if a photosensitive material is left under high temperature and high humidity conditions, mold and the like will grow, which may significantly impair the quality of the photosensitive material.

In order to prevent such defects caused by bacteria, yeast, mold, etc. in hydrophilic colloids used in photosensitive materials, it is known to add a bactericidal agent or a fungicidal agent to the photosensitive materials.

In general, preservatives or fungicides for this purpose include, for example, compounds having a carbonyl group such as formaldehyde, paraformaldehyde, chloroacetaldehyde, geltaraldehyde, chloracetamide, methylolchloroacetamide, or benzoic acid, Carboxylic acids or their esters such as monobromoacetate, sorbic acid, or amines such as hexamethylenetetramine, alkylguanidine, nitromethylbenzylethylenediamine, disulfides such as tetramethylthiuram disulfide, 2-mercaptobenzthiazole, 2-( 4-thiazolyl)-
Nitrogen-containing heterocyclic compounds such as benzimidazole, 2-methoxycarbonylaminobenzimidazole, or organic mercury compounds such as phenymercuric acetate, phenylpropionate, mercuric phenyloleate, or neomycin, kanamycin, polymycin, streptomycin, flamycin, etc. Several antibiotics are known, and some of these are also known for use in photography.

However, these substances may be harmful to living organisms, effective only against specific bacteria, harmful to photography, or have no bactericidal effect due to interactions with other photographic additives. Often enough. For example, aldehydes such as formalin are effective against bacteria, but are less effective against mold, are harmful to living organisms, and tend to fog photosensitive materials. Antibiotics such as neomycin and kanamycin are effective against bacteria, but not against mold and yeast.

If a large amount of disinfectant is used, it will adversely affect the physical properties of the coating solution, such as causing agglomeration of the binder, and will also deteriorate the photographic properties of the finished light-sensitive material.

Therefore, it is desirable that the amount of the bacterial agent added be as small as possible.

As mentioned above, there has been a strong desire to develop a bactericide for photographic hydrophilic colloids that has remarkable bactericidal and antifungal effects against bacteria, yeast, mold, etc. even in small amounts.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a hydrophilic colloid composition that is used for coating a photographic constituent layer of a photosensitive material containing a hydrophilic colloid during production, storage, or after coating. The purpose of this invention is to provide a new preservative method that preserves the environment.

The second object is to provide a preservative for hydrophilic colloids that has no effect on photographic performance (sensitivity, fog, graininess, sharpness, etc.).

(Means for Solving the Problems) As a result of various studies, the present inventors have found that the object of the present invention is to incorporate a compound represented by the following general formula [I] into a hydrophilic colloid for photosensitive materials, and further It has been found that the present invention can be achieved by a silver halide photographic material containing at least two of the compounds represented by formulas [I] to [IV].

General formula [I] In the formula, R1 represents an unsubstituted or substituted alkylene group,
X represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a cyano group, a lower alkyl group, a lower alkoxy group, an aryl group, an alkenyl group, a slew-So, M, and R2 represents a hydrogen atom, -0M, a lower alkyl group , aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyl group R3, R, are each a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group,
-COR,, -5o2R1, which may be the same or different, and R5 and R6 each represent a hydrogen atom, a lower alkyl group, an aryl group, or an aralkyl group, and may be the same or different. R7 represents a lower alkyl group, aryl group, or aralkyl group, and M represents a hydrogen atom, an alkali metal atom, and an atomic group necessary to form a monovalent cation. Further, m represents an integer from 1 to 6, and n represents an integer from 0 or 1 to (6-m). When m and n are 2 or more, the above groups may be the same or a plurality of them may be combined.

General formula [II] In the formula, R1 is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, each R is a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group , R represents an alkylsulfoxy group or an alkylsulfonyl group;

and RIO may be bonded to each other to form an aromatic ring.

Ro and R12 each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.

General Formula [III] NO7 In the formula, R1 represents a hydrogen atom, an alkyl group, or a hydroquinemethyl group, and represents a group.

General formula [IV] 4 is a hydrogen atom, In the alkyl formula, Y is a halogen atom, nitro group, hydroxy group, cyano group, lower alkyl group, lower alkoxy group, aryl group, alkenyl group, sulfonyl group, SO, M'' represents,
RIS is a hydrogen atom, -0M' lower alkyl group, aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyl R+a, Rl + is a hydrogen atom, lower alkyl group, aryl group, aralkyl group, -COR, respectively.

, -3o2R2°, which may be the same or different from each other, R1 and R4 each represent a hydrogen atom, a lower alkyl group, an aryl group, or an aralkyl group, and may be the same or different from each other. Preferably, R1 is a lower alkyl group,
represents an aryl group or an aralkyl group; M' and M'' represent a hydrogen atom, an alkali metal atom, and an atomic group necessary to form a monovalent cation; p represents an integer from 1 to 5; In the case of 5, Y may be the same group or a combination of two or more of the above groups.

Furthermore, the compound of the present invention will be explained in detail.

In the general formula [I], R represents an unsubstituted or substituted lower alkylene group (e.g., ethylene group, propylene group, methylethylene group, etc., and substituents include a halogen atom, nitro group, hydroxy group, cyano group, lower an alkyl group, a lower alkoxy group, an aryl group, an alkenyl group, a sulfonyl group, an aralkyl group, etc., and an alkylene group having 1 to 6 carbon atoms is particularly preferred.

X is a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, fluorine atom), a nitro group, a hydroxy group, a cyan group, a lower alkyl group (e.g. methyl, ethyl, 1so-propyl, tert-butyl), a lower alkoxy group ( For example, methoxy, n-butoxy, 2-methoxyethoxy),
Aryl groups (e.g. phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), alkenyl groups (e.g. allyl, l-butenyl), sulfonyl groups (e.g. methylsulfonyl, benzenesulfonyl), aralkyl groups (e.g. benzyl, p-1so -propylbenzyl, 0-methylbenzyl) R2 is a hydrogen atom, -0M, a lower alkyl group (e.g. methyl, n-butyl,), an aryl group (e.g. phenyl, 4-chlorophenyl, 3-nitrophenyl), an aralkyl group (e.g. benzyl, piso
-propylbenzyl, 0-methylbenzyl) lower alkoxy groups (e.g. f-methoxy, n-butoxy, 2-methoxyethoxy), aryloxy groups (e.g. phenoxy,
naphthoxy, 4-nitrophenoxy), aralkyloxy group (e.g. benzyloxy, p-chlorobenzyloxy), R, and R, respectively represent a hydrogen atom, a lower alkyl group (
methyl, ethyl, 2-ethylhexyl), aryl groups (e.g. phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), aralkyl groups (e.g. benzyl, 0-chlorobenzyl), -COR, -
8o2R, which may be the same or different, R,,R.

are hydrogen atoms, lower alkyl groups (e.g. methyl, 1s
o-propyl, 2-cyanoethyl), aryl groups (e.g. phenyl, 4-ethoxycarbonylphenyl, 3-nitrophenyl), aralkyl groups (e.g. benzyl, p-
chlorobenzyl), which may be the same or different, and R7 represents a lower alkyl group (e.g. ethyl, 2
-methoxyethyl, 2-hydroxyethyl), aryl groups (e.g. phenyl, naphthyl, 4-sulfophenyl,
4-carboxyphenyl), M represents a hydrogen atom, an alkali metal atom (e.g. sodium, potassium) and 1
It represents an atomic group necessary to form a valent cation (eg, ammonium cation, phosphonium cation), m represents O or l, and n represents 0 or an integer from 1 to 5.

The lower alkyl group and lower alkoxy group described in the above general formula (1) preferably have carbon atoms in the range of 1 to 8. Next, typical examples of the compound represented by the general formula [■] (hereinafter referred to as compound I) will be shown, but the compound represented by the general formula [I] of the present invention is not limited to these.

(Exemplary compounds) -7 ■ ■ 9 -11 ■ 3 ■-10 ■ 2 ■-14 -15 ■-17 -19 ■ 6 ■-18 ■ 0 Most of these exemplified compounds are commercially available as reagents, It is easily available and can also be easily synthesized using existing synthetic methods. For example, J, A
m, Chem, Soc, vol. 41, p. 669 (191
Some of the compounds where n=1 can be easily synthesized by the method described in 9).

In general formula [II], R7 is a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group (e.g. methyl, ethyl, tert-butyl, n-octadecyl, 2-
hydroxyethyl, 2-carboxyethyl, 2-cyanoethyl, sulfobutyl, N,N-dimethylaminoethyl), substituted or unsubstituted cyclic alkyl groups (e.g. cyclohexyl, 3-methylcyclohexyl, 2-oxocyclopentyl), substituted or unsubstituted cyclic alkyl groups alkenyl group (
(e.g. allyl, methylallyl), substituted or unsubstituted aralkyl groups (e.g. benzyl, p-methoxybenzyl,
○-Chlorobenzyl, p-is.

-propylbenzyl), substituted or unsubstituted aryl groups (e.g. phenyl, naphthyl, 0-methylphenyl, m
-nitrophenyl, 3. 4-') chlorophenyl),
Heterocyclic group (2-imidazolyl, 2furyl, 2-thiazolyl, 2-pyridyl), R4 is each hydrogen atom, substituted or unsubstituted alkyl group (e.g. methyl, ethyl, chloromethyl, 2-hydroxyethyl, tert-butyl) , n-
octyl), substituted or unsubstituted cyclic alkyl groups (e.g. cyclohexyl, 2-oxocyclopentyl), substituted or unsubstituted aryl groups (e.g. phenyl, 2-methylphenyl, 3,4-dichlorophenyl, naphthyl, 4
-nitrophenyl, 4-aminophenyl, 3-acetamidophenyl), cyano groups, heterocyclic groups (e.g. 2-imidazolyl, 2-thiazolyl, 2-pyridyl), substituted or unsubstituted alkylthio groups (e.g. methylthio, 2-cyanoethyl thio, 2-ethoxycarbonylthio) substituted or unsubstituted arylthio groups (e.g. phenylthio, 2-ethoxycarbonylthio)
-carboxyphenylthio, p-methoxyphenylthio), substituted or unsubstituted alkylsulfoxy groups (e.g. methylsulfoxy, 2-hydroxyethylsulfoxy)
, represents a substituted or unsubstituted alkylsulfonyl group (eg, methylsulfonyl, 2-bromoethylsulfonyl), and R8 and R1 may be bonded to each other to form an aromatic ring (eg, benzene ring, naphthalene ring).

R6 and R each represent a hydrogen atom or a substituted or unsubstituted alkyl group (eg, methyl, ethyl, is.

propyl, 2-cyanoethyl, 2-n-butoxycarbonylethyl, 2-cyanoethyl), substituted or unsubstituted aryl groups (e.g. phenyl, naphthyl, 2-methoxyphenyl, m-nitrophenyl, 3,5-dichlorophenyl, 3- acetamidophenyl), substituted or unsubstituted aralkyl groups (e.g. benzyl, phenethyl, p-1
so-propylbenzyl, 0-chlorobenzyl, m-methoxybenzyl).

Next, a compound represented by general formula [II] (hereinafter compound ■
Typical specific examples of compounds (referred to as ``(referred to as ``)'') are shown below, but the compound ① of the present invention is not limited thereto.

(Exemplary compounds) ■ ■ T-3 ■ ■ -2 -4 ■ ■ -9 ■-10 ■ 1 ○ ■ 2 ■ 13 ■ 4 ■ 5 ■-16 l-17 ■ 8 l-19 ■-22 ■-24 -20 ■-23 ■ 5 ■ 7 ■-29 ■ 1 ■ 6 ■ 8 ■ 0 ■-32 ■-37 ■ 2 ■ 8 ■-43 Some of the above compounds are commercially available and can be easily obtained. Possible and French patent l.

It can be synthesized according to the synthesis method described in No. 5.55.416.

Next, the compound of general formula (I) will be described.

R1 represents a hydrogen atom, a lower alkyl group (e.g. methyl, ethyl, 1so-propyl), or a hydroxymethyl group; R9 represents a hydrogen atom, a lower alkyl group (e.g. methyl,
n-butyl, 1so-amyl). The lower alkyl group preferably has 1 to 5 carbon atoms, particularly 1 carbon atom.

Typical specific examples of the compound represented by the general formula (III) (hereinafter referred to as compound (1)) are shown below, but the compound (2) of the present invention is not limited thereto.

(Exemplary compound) I[[-1 r HO-CH2-C-CH20H O2 ■ r ■ r HOCH.

C Ha O2 ! I[-4 r -C- CH-OH NO□ CH.

■ ■ r ”　Cs C-CH2 CH 02 I[I-7 No.

Some of these compounds are commercially available from San-Ai Sekiyu ■. Further, the synthesis can be performed with reference to the following literature.

(1) Henry Recueil des tr
avaux chiniques des Rays-B
as Upper 6 251(2) Mass, Chemi
sches Zentralblatt 1899
179 (31E, Schmidt, Berichte de
rDeutchen Chemischen Ge5e
llschaft, 5297 (4) E, Schmidt, 1bid 55
317(5) Henry Chemiches
Zentralblatt, 1897■ 33
8 In this case, the synthesis of I[I-1 is based on literature (1), (2) or 3), the synthesis of lll-2 is based on literature (2), the synthesis of II[-3 is based on literature (5), I[r It is better to follow the combination of -4 or document (2).

Next, the compound of general formula [IV] will be described.

In the general formula [IV], Y is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, a nitro group,
hydroxy group, cyano group, lower alkyl group (e.g. methyl, ethyl, 1so-propyl, tert-butyl),
Lower alkoxy groups (e.g. methoxy, n-butoxy, 2
-methoxyethoxy)aryl groups (e.g. phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), alkenyl groups (e.g. allyl, ■-butenyl)
, sulfonyl groups (e.g. methylsulfonyl, benzenesulfonyl), aralkyl groups (e.g. benzyl, p-1s
o-propylbenzyl, 0-methylbenzyl) RI3 is a hydrogen atom, -0M1, a lower alkyl group (e.g. methyl, n-butyl), an aryl group (e.g. phenyl,
4-chlorophenyl, 3-nitrophenyl), aralkyl groups (e.g. benzyl, p-1so-propylbenzyl, 0-methylbenzyl), lower alkoxy groups (e.g. methoxy, n-butoxy, 2-methoxyethoxy), aryloxy groups (e.g. phenoxy, naphthoxy, 4-nitrophenoxy), aralkyloxy group (e.g. benzyloxy, p-chlorobenzyloxy), R16, R1?
each represents a hydrogen atom, a lower alkyl group (e.g. methyl, ethyl, 2-ethylhexyl), an aryl group (e.g. phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), an aralkyl group (e.g. benzyl, 0-
chlorobenzyl), -COR,, 5O2R20, which may be the same or different, and R4, Ro
are hydrogen atoms, lower alkyl groups (e.g. methyl, 1s
o-propyl, 2-cyanoethyl), aryl groups (e.g. phenyl, 4-ethoxycarbonylphenyl, 3-nitrophenyl), aralkyl groups (e.g. benzyl, p-
chlorobenzyl), which may be the same or different, and R2° represents a lower alkyl group (e.g. ethyl,
2-methoxyethyl, 2-hydroxyethyl), aryl group (e.g. phenyl, naphthyl, 4-sulfophenyl, 4-carboxyphenyl), M' and M' are hydrogen atoms, alkali metal atoms (e.g. sodium, potassium). and represents an atomic group necessary to form a monovalent cation (e.g. ammonium cation, phosphonium cation), p represents an integer from 1 to 5, and when p is 2 to 5, even if Y is the same group as above, It does not matter if a plurality of groups are combined.

Next, typical examples of the compound represented by the general formula C■) (hereinafter referred to as compound ■) will be shown, but the general formula [■] of the present invention
The compounds are not limited to these.

(Exemplary Compounds) IV-9 ■-11 ■ 3 ■-10 ■ 2 IV-14 ■-15 IV-18 ■ 9 In the present invention, hydrophilic colloids for photosensitive materials are used to coat various photographic constituent layers of photosensitive materials. The binders contained in the coating solution used in the facility, i.e. agar including gelatin mentioned at the beginning of the description of the prior art, natural hydrophilic polymers such as colloidal albumin, derivative gelatin, derivative cellulose, Preparation process, storage or dispersion of solutions or dispersions of various water-soluble, sparingly soluble or insoluble compounds used in preparing sols of synthetic hydrophilic polymers such as polyvinyl alcohol, gel-like hydrocolloid liquids, and coating liquids. refers to compositions in the preparation process or finishing coating solutions, such as silver halide emulsions, dispersions of couplers, matting agents, etc., surfactant solutions, dye solutions, and additives. The conditions that must be met for a hydrophilic colloid to be used as a sterilizing and antifouling agent for photosensitive materials are: (I) It must not interact with photographic additives.

[2] A small amount has a large bactericidal and antifungal effect.

[3] No effect on photographic performance such as desensitization, fogging, graininess, sharpness, etc.

[4] Processing performance such as developability, desilvering property, recoloring property, etc. shall not be affected.

[5] There should be no impact on the environmental ecosystem.

[6] There should be no adverse effects on the human body.

etc. is desired.

Compounds I, II, (1), and (2) substantially satisfy these requirements.

Bacteria, bacteria, which commonly grow in hydrophilic colloids,
Usually, not only one type of mold but a mixture of several types of mold reproduce.

For this reason, the use of only one type of bactericide or fungicide does not have a complete antiseptic effect, and often fails to achieve its purpose.

Therefore, the general formula CI) and further (III~[■]
It is preferable to use a combination of at least two or more selected from among the compounds represented by the above, and it is more preferable to use a combination of three or more types.

Compounds 11 (11), (2), and (2) of the present invention can be used in any layer constituting a photosensitive material containing a hydrophilic colloid, such as a silver halide emulsion layer, a subbing layer, an intermediate layer, a filter layer, an antihalation layer, and a protective layer. It may be applied to

Further, in the manufacturing process, when each layer is prepared by mixing two or more liquids, it can be added to each layer.

The amount of compounds [■], (I[), [■], and [IV] added is not particularly limited, but the amount of compound [[] is 1000 to 100,000 ppm, and the amount of compound [■] is 1000 to 100,000 ppm, and the amount of compound [■] is 1000 to 100,000 ppm relative to the hydrophilic colloid.
] is 50 to 110,000 pp, compound (1) is 1 to 1,
000 ppm (IVI is suitably in the range of 10 to 10,000 ppm).

The compounds [■], [■], and (III) of the present invention are soluble in water or organic solvents such as methanol, isopropanol, acetone, and ethylene glycol that do not adversely affect photographic performance, and are hydrophilic as a solution. It may be added to a colloid, coated on a protective layer, or immersed in a disinfectant solution. Alternatively, after dissolving in a high boiling point solvent, a low boiling point solvent, or a mixed solvent of both, emulsifying and dispersing in the presence of a surfactant, and then adding it to a liquid containing a hydrophilic colloid or coating it on a protective layer. It may depend on the method.

The present invention can be applied to various color and black and white photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. can.

Plate-making films such as lithography film or scanner film, direct/indirect medical or industrial X-ray film, negative black and white film for photography, black and white photographic paper, C0M or regular microfilm, silver salt diffusion transfer type photosensitive materials, and The present invention can also be applied to print-out type photosensitive materials.

When the light-sensitive material of the present invention is a color light-sensitive material, at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer is provided on the support. All you have to do is
There is no limit to the number or order of the silver halide emulsion layers and non-light-sensitive layers.

A typical example is a silver halide photograph having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. It is a photosensitive material, and the photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light. In multilayer silver halide color photographic light-sensitive materials, generally The layers are arranged in the following order from the support: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used0
Normally, it is preferable to arrange the halogen emulsion in a pattern in which the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close 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 1'i (BH) /
High sensitivity green photosensitive layer (GH) /Low sensitivity green photosensitive layer (GL
)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (IIL), or Bl(/BL/GL/GH/l
1ll/RL order or BH/BL/GH/GL/R
They can be installed in the order of L/RH.

Furthermore, as described in Japanese Patent Publication No. 55-34932, blue-sensitive N/GH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in the order starting from the one furthest from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer with a low density is disposed and is composed of 3Ns having different photosensitivity, the photosensitivity of which is sequentially lowered toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4,705,744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer t#I rules and arrangements can be selected depending on the purpose of each photosensitive material.

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, preferred silver halide contained in the photographic emulsion layer is silver iodobromide, silver iodo, containing about 30 mol% or less of silver iodide. Silver chloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

When the photographic light-sensitive material of the present invention is a color photographic paper, the silver halide contained in the photographic emulsion layer is composed of silver chlorobromide or silver chloride that does not substantially contain silver iodide. It can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol%.
Hereinafter, it is preferably 0.2 mol% or less. These salt odor (IJIHL agents can have any halogen composition of silver bromide/silver chloride. This ratio can vary widely depending on the purpose, but the silver chloride ratio is 2 mol% or more. So-called high silver chloride emulsions with a high silver chloride content are preferably used for light-sensitive materials suitable for rapid processing.The silver chloride content of these high silver chloride emulsions is 90 mol %. or more is preferable, and 95
For the purpose of reducing the amount of replenishment of the processing solution, which is more preferably mol % or more, an emulsion of almost pure silver chloride having a silver chloride content of 98 to 99.9 mol % is also preferably used.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) k17643 (
(December 1978), pp. 22-23 1 “■, Emulsion Production (
Emulsion preparation and
types)”, and the same N[I18716(19
November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Paul Montell (P, Glafki
des, Chemie et Ph1sique P
photograph-ique, Paul Mont
el, 1967), Duffin, Photographic Emulsion Chemistry J, published by Focal Press (G, F, Duffin.

Photographic Eo+ulsion Ch
emLstry (Focal Press1966)
), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (ν, l, Zelikmanet
al,, Making and Coating P
photographic Emul-sion, Fo
Cal Press, 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering ([;gj□ff, PhotographicSc
ience and Engineering),
Volume 14, pages 248-257 (1970): U.S. Patent No. 4,434,226, U.S. Patent No. 4,414.310, U.S. Patent No. 4
, 433,048, 4,439,520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643 and Ni118716,
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

RD17643 RD187161
Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, 2
Pages 3-24 Page 648 Right column - Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Antifoggant Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorber 7 Anti-stain agent Page 25 right 11Ili Page 650 left ~
Right column 8 Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 right column 12 Coating aid, pages 26-27 Page 650 right column Surfactant 13 Static Page 27 Same as above Inhibitor Also, deterioration of photographic performance due to formaldehyde gas In order to prevent
．． It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Hiroshi 17643, ■-C-C.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, same No. 4,022,620, same No. 4,3
No. 26,024, No. 4,401,752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425.020, British Patent No. 1,476.760, U.S. Patent No. 3,973,968, British Patent No. 4,314,
No. 023, No. 4,511.649, European Patent No. 24
No. 9,473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4,351,897, European Patent No. 73,636, US Patent No. 3.061,432, US Patent No. 3.725.067, Research Disclosure No. 24220 (1984) June), Japanese Patent Application Publication No. 1983
-33552, Research Disclosure No.
24230 (June 1984), JP-A-60-43
No. 659, No. 61-72238, No. 60-35730
No. 55-118034, No. 60-185951, U.S. Patent No. 4.500.630, U.S. Patent No. 4.540,
No. 654, No. 4,556,630, International Publication WO3
Particularly preferred are those described in No. 8104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052.212.
No. 4,146.396, No. 4.228,23
No. 3, No. 4,296,200, No. 2,369,9
No. 29, No. 2,801.171, No. 2,772.
No. 162, No. 2,895,826, No. 3,772
, No. 002, No. 3.758.308, No. 4,33
No. 4.011, No. 4,327,173, West German Patent Publication No. 3゜329.729, European Patent No. 121, 36
5A, 249°453A, U.S. Patent No. 3.44
No. 6,622, No. 4,333.999, No. 4.7
No. 75,616, No. 4,451,559, No. 4,
No. 427,767, No. 4,690,889, No. 4
, 254° 212, 4.296.199, and JP-A-61-42658 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are recommended in Research Disclosure 17643.
- Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4.004,929, U.S. Patent No. 4.138,258, British Patent No. 1,146,36
No. 8 is preferred, and also US Pat. No. 4,7
No. 74.181, a coupler that corrects unnecessary absorption of a color-forming dye by a fluorescent dye released upon coupling, and a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777.120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, European Patent No. 96,570 and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820; 4,080,211; 4,367.282;
No. 4,576°910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon camping are also preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned I? D 1764
3. Patents listed in sections ■ to F, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, No. 63-37350,
U.S. Patent No. 4,248.962, U.S. Patent No. 4,782,012
Preferably, those listed in No.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2.097,140;
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , multi-weight couplers described in JP-A-60-185950, JP-A-6224252, etc., DIR redox compound-releasing couplers, DIR coupler-releasing couplers, D
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜30
R, D, Na 11449, a coupler that releases a dye that recolors after separation, as described in No. 2A and No. 313,308A.
, No. 24241, JP-A-61-201247, etc., bleach accelerator-releasing couplers, U.S. Pat. No. 4,553,4
Ligand releasing coupler described in No. 77 etc., JP-A-63-
75747, a leuco dye-releasing coupler;
Examples include couplers that emit fluorescent dyes as described in U.S. Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

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 phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amyl phenyl) phthalate, bis(2,4-di-t-amyl phenyl) phthalate, (2,4-di-1-amyl phenyl) isophthalate, bis(111-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, etc.)
-ethylhexyl phenyl phosphonate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid ester! ! (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyllaurylamide,
(such as N-tetradecylpyrrolidone), alcohols or phenol f4 (isostearyl alcohol, 2,
4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N , N-dibutyl-
2-butoxy-5-tert-octylaniline, etc.)
, hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.).

Further, as the auxiliary solvent, an aqueous solvent having a boiling point of about 30"C or more, preferably about 501 to about 160"C can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Examples include 2-ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat. etc. are listed.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Or hydrophilic colloid water dissolved in a water-insoluble but organic solvent-soluble polymer? It can be emulsified and dispersed into 8 liquids.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. 188100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, Oyobi JP 1-8
1,2-henzisothiazoline-3 described in No. 0941
-one, n-butyl ρ-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)henzimidazole.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Ko 17643, page 28, and K 18716, page 647 right column to page 648 left column.

In the photosensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 20 μm or less, and the film swelling rate TI /□ is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness means the film thickness measured at 25°C and 55% relative humidity (2 days), and the film swelling rate TI/□ can be measured according to a method known in the art.
For example, A. Green et al., Photographic Science and Engineering (Photogr, Sci, Eng.), 19@.
2, pp. 124-129 (
T1/2 is defined as 90% of the maximum swollen film thickness reached when treated with a color developer for 13 minutes and 15 seconds at 30°C, and 1 of the saturated film thickness.
It is defined as the time required to reach /2.

The membrane swelling rate 'r+zt can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

Color photographic material according to the present invention C=, the above-mentioned RD,
pp. 28-29 of Nα17643, and Doko 18716
615, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl- 4-amino-N-ethyl-N-β
-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and sulfates thereof, Examples include hydrochloride and p-toluenesulfonate. Among these, 3-methyl-4-amino-N-ethyl-
Nβ-hydroxyethylaniline sulfate is preferred, and two or more of these compounds may be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, pendithiazoles or mercapto compounds. In addition, as necessary, various preservatives such as hydroxyl quinone, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, ethylene glycols, alkaline solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as ■-phenyl-3-virapritone; Viscosifier, aminopolycarboxylic acid, aminopolyphosphonic acid,
Various calcinants such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1 , 1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid) and their salts. This can be cited as a representative example.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Also, replenishment of these developers
depends on the color photographic material being processed, but -111
31 per square meter of photosensitive material, and by reducing the bromide ion concentration in the replenisher, 5
It can also be set to 00- or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (I[[), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (I[I), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc. Aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron (I[[) complex salts, including ethylenediaminetetraacetate iron (I[[) complex salt] and 1,3-diaminopropanetetraacetic acid iron (nl) complex salt, are suitable for rapid processing and environmental pollution prevention. Preferable from the viewpoint of iron aminopolycarboxylate (I[
l) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (I[
[) The pH of the bleach or bleach-fix solution using if salt is usually 4.0 to 8, but it can also be processed at an even lower pl+ for faster processing.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290.812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-10.123
No. 2, No. 53-124424, No. 53-141623
No. 53-28426, Research Disclosure No. 17129 (July 1978), etc. Compounds having a mercapto group or disulfide group; Thiazolidine derivatives described in JP-A-50-140129;
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3,706.561
Thiourea derivatives described in West German Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748.430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-42,434, 49-59,644, 53-
No. 94,927, No. 54-35,727, No. 55-2
Compounds described in No. 6,506 and Nos. 58 to 163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,858.
No., West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983-9
Preferred are the compounds described in US Pat. No. 5,630, and also preferred are the compounds described in US Pat. No. 4,552,834.
These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, it is preferable that the bleaching solution or bleach-fixing solution contains an organic acid for the purpose of preventing bleach staining. Particularly preferable aerobic acids have an acid dissociation constant (pKa) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixing solution and the bleach constant solution, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time for the desilvering process is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering process, it is preferable that the stirring be as strong as possible.A specific method for strengthening the stirring is the treatment on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461. A method of colliding liquid jets, a method of increasing the stirring effect using a rotating means as described in JP-A No. 62-183461, and a method of moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid. , a method of improving the stirring effect by creating turbulence on the surface of the emulsion, and a method of increasing the circulation flow rate of the entire processing liquid. Such agitation enhancement means include bleaching solutions,
It is effective in both bleach-fixing solutions and fixing solutions. Improved agitation speeds up the supply of bleach and fixing agent into the emulsion film,
It is thought that this increases the desilvering rate as a result. Also,
The agitation improvement means described above are more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urn-al of the 5ociety of
Motion Picture and Te1evi
sion Engineers Volume 64, P, 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. 6 Problems arise in the processing of color photosensitive materials of the present invention, as a solution to these problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8,542
Chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other chlorinated disinfectants listed in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technical Society “Sterilization, sterilization, and anti-mold technology of microorganisms,” (1982)
“Encyclopedia of Antibacterial and Antifungal Agents” edited by the Society of Industrial Engineers and the Japan Society of Antibacterial and Antifungal Agents (
It is also possible to use the fungicides described in (1986).

The pif of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a temperature range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. Examples of the dye stabilizer that can be used include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

In a process using an automatic processor or the like, when each of the above-mentioned processing liquids undergoes acondensation due to evaporation, it is preferable to add water to perform 'am correction.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate it, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various types of 1-phenyl-3-
Pyrazolidones may also be incorporated.

Typical compounds are disclosed in JP-A-56-6=1339 and JP-A-56-6=1339.
-144547, and No. 58-115438.

The various treatment solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, a salinity of 33°C to 38°C is standard, but a higher temperature is used to accelerate the treatment and shorten the treatment time. Or, conversely, by lowering the temperature, image quality and stability of the processing solution can be improved.

In addition, West German Patent No. 2,226,7 was developed to save silver on photosensitive materials.
70 or U.S. Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It is also applicable to the heat-developable photosensitive materials described in No. 9-2184.13, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 Various preservatives were added to silver halide emulsions containing 6% by weight of gelatin to compare their biological growth inhibiting effects. The silver halide emulsion used here was prepared as follows.

Ammoniacal silver nitrate and aqueous alkali halide solution are allowed to fall naturally into a reaction vessel maintained at 60°C to which an aqueous gelatin solution and excess halide have been added in advance, and then desalted using benzenesulfonyl chloride, gelatin is added, and p
Ag? , 8.1) 86. An emulsion of 0 was obtained. Furthermore, sodium thiosulfate, chloroauric acid, and rhodan ammonium were added, and chemical ripening was performed at 52°C for 70 minutes to obtain 4-hydroxy-6-methyl-1,3,3a.

7-chitrazaindene and 6-nitrobenzimidazole were added, and gelatin was further added to obtain a silver halide emulsion.

A group of test emulsions were infected at the same concentration with bacteria decomposed from a stale gelatin solution.

To promote biological production, infected test emulsions were kept at 37° C. and samples were taken after 24 hours and 3 weeks.

Samples of 1- were used to infect commercial nutrient sources for bacteria and mold, respectively, placed under the same environment for the development of microbial colonies.

Table 1 shows the survey results obtained. Here, (-) indicates no microbiological growth, and (+) indicates significant microbiological growth.

As can be seen from the results in Table 1, by using the compound represented by the general formula [I] and at least two or more of the compounds represented by the general formulas [II] to [IV] in combination, a small amount of each can be used. It is clear that it has a great effect.

This is suitable for preservative properties of hydrophilic colloids for photographic light-sensitive materials, which need to be used in small amounts due to adverse photographic effects.

An example is shown next.

Table 1 (Continued) Example 2 Multilayer color photosensitive material 1 consisting of each layer having the composition shown below on a cellulose triacetate film support as a sample
01 was produced.

1st layer: Antihalation layer Black colloidal silver...0.18g/rrr Ultraviolet absorber C-1...0.04g/rr? Ultraviolet absorber C-2...0.18g/rrfHBS-2...
Gelatin layer 2nd layer containing 0.09 g/rrr: Intermediate layer compound H-1---0,30 g/rrr coupler C
-7...0.07g/BoHBS-1---0,1
Gelatin layer 3rd layer containing 1g/rrrHBS-2----0,O1g/rd; 1st red-sensitive emulsion layer Silver iodobromide emulsion...Amount of coated silver (same below) 0.5
8g/rrr (Silver iodide 5 mol%, average grain size 0.5μ) Sensitizing dye■ Sensitizing dye■ Sensitizing dye m Sensitizing dye■ ... ・For 1 mole of silver? , 0XIO-' mole・2 for 1 mole of silver, QXIO"mole・2.8X10-' mole for 1 mole of silver・2.0XIO-' mole for 1 mole of silver...0.26 g/r& ...Q, O1g/r+? ...0.01g/rrl' Coupler C-3 Coupler C-4 Coupler (4th gelatin layer containing -5; 2nd red-sensitive emulsion layer Silver iodobromide Emulsion: 1.3 g/rr? (silver iodide 6 mol%, average grain size 0.8 μ) Sensitizing dye I
...5.2XIO-'mol sensitizing dye for 1 mole of silver...1.5XIO for 1 mole of silver
-'Molar sensitizing dye ■...2.1XlO per 1 mole of silver
-'Molar sensitizing dye ■...1.5X10 per mole of silver
-5 mole coupler C-12...0.06g/rd coupler C-3...0.04g/m coupler C-13...
...o, O1g/bokapura C-5...0.0
3g/BoHBS-1...0.12g
/rr/HBS-2...5th gelatin layer containing 0.11 g/rrr; 3rd red-sensitive emulsion layer Silver iodobromide emulsion...0.9 g/rrr (silver iodide 10 mol%) , average particle size 1°0μ) Sensitizing dye I
...5.5XIO-'' moles of sensitizing dye per 1 mole of silver...1.6X10 per mole of silver
""Molar sensitizing dye ■...2.2xlO per 1 mole of silver
"Molar sensitizing dye■...1.6X10 per mole of silver
-'Mole coupler C-12...0.04g/rr? Coupler C-3...0.03g/HBS-1...
o, 06g/rr? HBS-2...
・6th layer of gelatin layer containing 0.05 g/n'r: Intermediate layer compound H-1... 7th gelatin layer containing 0.02 g/n'r: 1st green-sensitive emulsion layer Silver iodobromide emulsion ...1.54g/r+? (
Silver iodide 5 mol%, average grain size 0.5 μ) Sensitizing dye■
...3.8X10-' mol sensitizing dye for 1 mole of silver...3.0XIO for 1 mole of silver
-'Molar coupler C-6...0.29g/rrrCoupler C-7---0.05g/rr? Coupler C-8
...o, oag/m coupler C-4...0.
Gelatin layer 8th layer containing HBS-1...0.31g/rf; Second green-sensitive emulsion layer Silver iodobromide emulsion...0.61g/n? (Silver iodide 6 mol%, average grain size 0.8μ) Sensitizing dye■
...2.7X10-' mol sensitizing dye for 1 mole of silver ■...2, lXl0 for 1 mole of silver
"Mole coupler C-6...0.03g/n (coupler
C-9...O,001g/Bokapura 〇-8...
...0.001g/rr? HBS-1---0,03
4g/rr? 9th layer of gelatin layer containing; 3rd green-sensitive emulsion layer silver iodobromide emulsion...0. 7 g/ld
(Silver iodide 10 mol%, average grain size 1.0μ) Sensitizing dye V...3.0 x 10-' mol per 1 mol of silver Sensitizing dye■ 2...2 per 1 mol of silver .4X10
-'Mole coupler C-6...0.03g/coupler resistance C
-8...0.001g/rr? HBS-1...
Seratin layer 10th layer containing 0.04 g/rrr; Yellow filter layer Yellow colloidal silver...0.036 g/m Compound H-■...0.10 g/m' coupler C-7---- 0.08g/rrl'HBS-1...
...0.09g/rr? Gelatin layer 11th layer containing; First blue-sensitive emulsion layer Silver iodobromide emulsion...0.34g/rr? (
Silver iodide 6 mol%, average grain size 0. 5μ) Coupler C-10...0.41g/Pocoupler C-14
...0.03g/BoHBS-1...
12th gelatin layer containing 0.16 g/rrr; 2nd blue-sensitive emulsion layer Silver iodobromide emulsion 0.49 g/m (silver iodide 10 mol%, average grain size 0.9 μ) Coupler C
-10...0.15g/PoHBS-1
13th layer of gelatin layer containing ...0.06 g/rd; 3rd blue-sensitive emulsion layer Silver iodobromide emulsion ...0.75 g/rrr (
Silver iodide 14 mol%, average grain size 1.5μ) Sensitizing dye ■... 2.3 x 10-' mol coupler per 1 mol of silver 〇-10... 0.05 g/bo HBS-1
14th gelatin layer containing ...0.02g/-; first protective layer ultraviolet absorber C-1...0.05g/rd ultraviolet absorber C-2...0.24g/ rrrHBS-2
15th layer of gelatin layer containing 0.12 g/rrr; 2nd protective layer polymethyl methacrylate particles (diameter 1.5μ)...
In addition to the above composition, gelatin hardening agent C-11 and a surfactant were added to each gelatin layer containing 0.05 g/rrr. The sample prepared as described above was designated as sample 101.

The compounds used to prepare the samples are shown below.

C,H.

(i) C, H, 0CNH CH.

CH.

-6 C-7 Shil -10 -11 (CH2=CH3O, CH2C0NHCH, r-12 -13 -14 CH.

CH.

Sensitizing dye■ Sensitizing dye■ (CH2)I SOl Na (shiH2h S(J+ Na C=Hs Sensitizing dye■ Sensitizing dye■ (shiFlth 51J3 i-1・INtL, 211
Next, the compounds shown in Table 1 were added to each layer of sample 101 to prepare samples 102 to 132.

The amount added is expressed as a weight ratio to gelatin in each layer.
The unit was ppm.

The viscosity of the dispersion liquid for the sixth layer used in preparing these samples was measured after aging at 40° C. for 3 days and 6 days. The initial viscosity of this dispersion was adjusted to 60 cp using polystyrene sulfonic acid.

Next, these samples were subjected to image exposure using a known method, and then processed using the processing method described later to determine the relative sensitivity of each layer.

These results are also shown in Table 2.

Table 2 shows that the preservative of the present invention does not lower sensitivity;
It can be seen that the viscosity decreases over time and is very good.

Samples were wedge exposed to white light and processed in the following manner.

Processing process Hoshi-Ren Yutaka-Starting color development 41'C3 public order Stop 38°C 30 seconds Water wash 30 seconds before
Bleach for 30 seconds
〃 Wash with water for 3 minutes 〃
Set for 1 minute, water for 2 minutes
Wash 〃 2 minute stable bath
The treatment solution used for 10 seconds had the following composition.

Color developer Aminotri(methylenephosphonic acid) -5-sodium salt 1.5g Sodium sulfite 2.0g Sodium bromide
1.2g sodium carbonate
26.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sesquisulfate monohydrate Add 4.0g water to make a total amount of 1.01 (pH 10.2)
(adjusted to 0) Stop solution sulfuric acid (7N) Add 50ml of water to total volume 1. Of pre-bath sodium metabisulfite 10,0g glacial acetic acid
25.0 m (!Sodium acetate lo, OgTetrasodium ethylenediaminetetraacetate 1.0g1- (2
-N,N-dimethylaminoethyl) isothiourea dihydrochloride 3.0g Add water Total amount 1.0J Bleach solution Gelatin 0.5g Sodium persulfate 35.0g Sodium chloride
15. 0g monosodium phosphate
9.0g phosphoric acid (85%)
2.5 m 1 water added
Total i 1.0A Fixer Aminotri(methylenephosphonic acid)-5-sodium salt l.

Sodium thiosulfate (58%) 185° Sodium sulfite 10° Sodium bisulfite
8° Add water, total volume 1° Stabilizing liquid formaldehyde (37%) Add water, total volume 1.

0m11 Table 2 Selling a) Selling Table 20 Selling Table 2 Selling G) Reciprocal number, bone, green, red from the top Sensitivity Example 3 The following was applied on a subbed cellulose triacetate film support with a thickness of 127 μm. A multilayer color photosensitive material consisting of each layer of the composition was prepared and designated as Sample 201.

The numbers represent the amount added in weight ratio to gelatin in each layer. Note that the effects of the added compound are not limited to the described uses.

1st layer: Antihalation layer Black colloidal silver 0.25g Gelatin 1.9g Ultraviolet absorber U-1
0.04g Ultraviolet absorber U-20.1g Ultraviolet absorber U-3' 0.1g Ultraviolet absorber U-60.1g High boiling point organic solvent Oi1-10.1g 2nd layer: Intermediate layer Ceratin 0.40g Compound C
pd-D 10mg High boiling point organic solvent 0il-340■ 3rd layer: Fine grain silver iodobromide emulsion covered with intermediate layer (average grain size 0.06μ, AgI content 1 mol%) Silver amount 0
．． 05g gelatin 0.4g 4th layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.4μ, AgI content 4°5 mol%) Monodisperse cubic and average particle size 0.3 μ, AgI content 4.5 mol%
1:1 P mixture of monodisperse cubes) silver content 0
．． 4g Gelatin 0.8g Coupler C-10.20g Coupler C-90.05g High-boiling organic solvent 0i1-10.1g 5th layer: Medium-sensitivity red-sensitive emulsion layer Spectral sensitization with sensitizing dyes S-1 and S-2 Silver iodobromide emulsion (average grain size 0.5μ, monodisperse cube with AgI content 4 mol%) Silver amount 0.4g Gelatin 0.8g Coupler C
-] 0.2g coupler C-20,
05g Coupler C-30, 2g High cotton point organic solvent 0i1-10. Ig 6th layer: High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (monodisperse twinned grains with average grain size 0.7μ and Agl content 2 mol%) ) Silver amount 0゜Gelatin 1゜Coupler C-3
0° Coupler C-10° 7th layer: Intermediate layer gelatin 0° Dye D-10° 8th layer: Interlayer overlaid silver iodobromide emulsion (average grain size 0° Agl content 0.
3 mol%) gelatin l.

4g 4g 4g 4g 2g 06μ, Color mixture prevention agent Cpd-A 0. 2 g 9th layer: Low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (monodisperse with average grain size 0.4 μm and Agl content 4°5 mol%) A 1:I mixture of cubes and monodisperse cubes with an average particle size of 0.2μ and an Agl content of 4.5 mol%) Silver content 0.
5g Gelatin 0.5g Coupler C-40, log Coupler C-70, Log Coupler C-80, 10g Compound Cpd-B 0.03g Compound Cpd-E 0. 1 g compound C
pd-F 011gCompound Cpd-G
o, lg compound Cpd-H
O, 1g 10th layer: Medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (monodispersed cubic with average grain size 0.5 μm and Agl content 3 mol%) ) Silver amount 0.4g Gelatin 0.6g Coupler C
-40,1g Coupler C-70,1g Coupler c-s O,Lg Compound C
pcl-B O,03g Compound Cpd
-E O,l gCompound Cpd-F
O, l g compound Cpd-G
O,05g Compound Cpd-H0,05g High-boiling organic solvent 0il-10,01g 11th layer: Highly sensitive green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (spherical Converted average particle size 0.6 μ, Agl content 1.3 mol%
, monodispersed flat plate with an average diameter/thickness of 7) Silver amount 0.5g Ceratin 1.0
g Coupler C-40,4g Coupler C-70,2g Coupler C-80,2g Compound Cpd-B O,08g Compound Cpd-E O,1g Compound Cpd-
Fo, 1g Compound cpa-co, lg
Compound Cpd-HO, 1g 12th layer: Intermediate layer gelatin 0.6g Dye D-2
0.05g 13th layer: Yellow filter layer gelatin 1.1g Color mixing inhibitor Cpd-A O, O 1g 14th layer: Intermediate layer gelatin 0.6g 15th layer;
Low-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
A 1=1 mixture of monodisperse cubes with an average particle size of 0.4 μ and an Agl content of 3 mol % and monodisperse cubes with an average particle size of 0.2 μ and an Agl content of 3 mol %) Silver amount 0.6 g Ceratin 0.8 g coupler C
-50.6g 16th layer: Medium-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Monodispersed cubes with average particle size 0.5μ and Agl content 2 mol%) Silver content 0.4g gelatin
0.9g Coupler C-50, 3g Coupler C-60, 3g 17th layer: Highly sensitive blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Average particle diameter when converted to spheres: 0.7 μ, AgI content: 1.5 mol%,
Tabular grains with an average diameter/thickness of 7) Silver content: 0.4g Ceratin: 1.2g
Coupler C-60.7g 18th layer: 1st protective layer Ceratin 0.7g UV absorber U-10.04g UV absorber U-30.03g UV absorber U-4 UV absorber U-5 UV absorber U -6 Formalin scavenger PD-C Dye D-3 19th layer: Fine grain silver iodobromide emulsion covered with second protective layer 06μ, Agl content 1 mol%) Silver amount 0.03g 0.05g 0.05g 0 , 8 g 0.05 g (average particle size O1 0.1 Ceratin 20th layer: third protective layer Ceratin 0.4 g polymethyl methacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate and acrylic acid 4 = 6 Copolymer (average particle size 1.5μ) 0.1g silicone oil
0.03g Surfactant W-13.0mg 0.4 In addition to the above composition, gelatin hardening agent H1, coating and emulsifying surfactants, etc. were added to each layer.

In addition, in the emulsion used here, monodisperse means that the coefficient of variation is 20% or less.

-3 Shihachi -4 C 00C+ Hy (iso) Coupler C-8 -9 1l-1 dibutyl phthalate 11-2 Li acid to Li cresyl pd-E tHs 6 S-■ So, HN (C2Hs)z S　Os　HN(CyHsJs )IJs -7 SLJslNa I4 ■ CH2 CH3O2CH, C0NHCH2 CH2 CH3O, CH, CONHCH.

CH.

Next, the compounds shown in Table 3 were added to each layer of sample 201 to obtain samples 202 to 232.

The amount added is expressed as a weight ratio to gelatin in each layer.
The unit was ppm.

The viscosity of the dispersion liquid for the 12th layer used in preparing these samples was measured after aging at 40° C. for 3 days and 6 days.

Next, these samples were subjected to image exposure using a known method, and then processed using the processing method described later to determine the relative sensitivity of each layer.

These results are also shown in Table 3.

Table 3 shows that the preservative of the present invention does not lower sensitivity;
It can be seen that the viscosity decreases over time and is very good.

Processing process Temperature Time 1st development 6 minutes* 38°C 1st water washing
45 seconds 38 no! Reversal 4511
38/1 color development 6 minutes 3811 bleaching 211 3811 bleach-fixing 4 minutes 38°C 2nd water wash (1)
1/l 38//2nd pilot (2) ll〆 38 horn stable 171
25 *In the evaluation of sensitization development suitability, processing for 8 minutes was also performed.

The composition of each treated acid was as follows.

Xing Erlipengtang Nitrilo-N,N,N-)-rimethylenephosphonic acid pentasodium salt Sodium sulfite Potassium hydroquinone monosulfonate Potassium carbonate 1-phenyl-4-methyl-4-hydroxymethyl-3 Pyrazolidone bromide Potassium 2, Og 0g 0g 3g 2゜g 2゜g Add potassium thiocyanate 1.2, potassium iodide 2.0mg
1000ml pH 9.60 pH was adjusted with hydrochloric acid or potassium hydroxide.

Ethylenediaminetetramethylenephosphonic acid 2.0g Disodium phosphate 5.0g Add water
1000mfpH 7.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Aitaka nitrilo-N, N, N-) rimethylenephosphonic acid pentasodium salt stannous chloride dihydrate 3.0g 1゜g p-aminephenol 0.1g sodium hydroxide 8g ice acetic acid
Add 15mn
I OO0ml pH 6,00 pH was adjusted with hydrochloric acid or potassium hydroxide.

Color developer Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt, sodium sulfite, trisodium phosphate, dodecahydrate, potassium bromide, potassium iodide, sodium hydroxide, N-ethyl citrazate-N-(β- Methanesulfonamidoethyl) 2,0g 7,0g 6g 1.0g 0mg 3,0g 1,5g -3-Methyl-4-aminoaniline sulfate 11g3.6-cythiaoctane-I.

8-diol 1.0g water was added to 1000ml pH 11.80 The pH was adjusted with hydrochloric acid or potassium hydroxide.

Mutual crossing Ethylenediaminetetraacetic acid・ Sodium salt/dihydrate salt Ethylenediaminetetraacetic acid/ (III) ・Ammonium・ ammonium bromide ammonium nitrate bleach accelerator e dihydrate salt 0° 10° 0g 20g 00g 0g 005 mole pH6,30 The pH was adjusted with hydrochloric acid or aqueous ammonia.

bleach-fix solution Ethylenediaminetetraacetic acid・ (III) ・Ammonium・ Ethylenediaminetetraacetic acid・ Sodium dihydrate sodium thiosulfate sodium sulfite add water e dihydrate salt 0g 5.0g 0g 12.0g 1,000m1 pH6,60 The pH was adjusted with hydrochloric acid or aqueous ammonia.

Nijo-taka tap water was transferred to a mixed-bed column filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). Water was passed through the flask to reduce the concentration of calcium and magnenium ions to 3/1 or less, and then 20/l of sodium isocyanurate dichloride and 1.5 g/l of sodium sulfate were added.

The pH of this solution is 6° 5~7° It is in the range of 5.

Genkoyan formalin (37%) 5゜ml Polyoxyethylene monononylphenyl ether (average degree of polymerization 10) 0゜5rr+47 pH not adjusted Table 3 Table 3 A selling) Table 3 @ki) Table 3 G selling) Example 4 Paper support laminated on both sides with polyethylene (thickness 10
Sample 301 was prepared by preparing a color photographic material in which the following 1-14th layers were coated on the front side of the film (0 micron), and 15th-16th layers were coated on the back side. The polyethylene on the coating side of the first layer contains titanium oxide (4 g/lr?) as a white pigment and a trace amount of ultramarine 0.003 g/lri' as a bluish dye (the chromaticity of the surface of the support is L'' ,a9,
The values were 88.0, -0.20, and -0.75 for the b* system.

).

(Photosensitive layer composition) The components and coating amount (g/m unit) are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

The emulsions used in each layer were prepared according to the manufacturing method for emulsion EMI described below. However, the emulsion for the 14th layer was a Lippmann emulsion that was not surface chemically sensitized.

1st layer (antihalation layer) Black colloidal silver...0. lO Seratin... 0.70 2nd layer (
Intermediate layer) Gelatin... 0.70 3rd
Layer (low sensitivity red sensitive layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-l, 2.3) (average grain size 0.25μ, size distribution [coefficient of variation] 8%, octahedral) ... 0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1, 2, 3) (silver chloride 5 mol%, average particle size 0.40μ
, size distribution 10%, octahedron)...
・0.08 gelatin... 1
．． 00 cyan coupler (ExC-12,3 1.l:0
．． 2) ... 0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalent) ... 0.18 Anti-stinting agent (Cpd-5) ... 0.003
Coupler dispersion medium (Cpd-6)... 0.03 Coupler solvent (Solv-1, 2, 3 equivalents)... 0.
12 4th layer (high sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average grain size 0.60μ, size distribution 15%)
, octahedron) ... 0.14 Seratin
... 1.00 cyan coupler (ExC-1,
2,3 to 1・l:0.2)...
0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents)
... 0.18 Coupler dispersion medium (Cpd-6) ... 0.03 Coupler solvent (Solv-1, 2, 3 equivalent) 0.12 5th layer (intermediate layer) Seratin ... 1.00 Color mixing prevention agent (Cpd-7) ... 0.08 Color mixing prevention agent solvent (Solv-4, 5 equivalent) ... 0.16 Polymer latex (Cpd-8) 0°O 6th layer (low sensitivity green Sensitive layer) Silver bromide (
Average particle size 0.25μ, size distribution 8%, octahedral)
... 0.04 green sensitizing dye (ExS-4
) spectrally sensitized silver chlorobromide (silver chloride 5 mol%, average grain size 0.40 μ, size distribution 10%, octahedral)...
・ 0.06 Gelatin... 0.80 Magenta coupler (ExM-L2.3 equivalent)... 0.11 Antifading agent (equivalent amount of Cpd-9, 26)... 0.1
5 Anti-staining agent (Cpd-1O111,12,13 in 1
0 near:7:1 ratio) ... 0.025 force puller dispersion medium (Cpd-6) ... 0.05 coupler solvent (
Solv-4, 6 equivalent)... 0.15 7th layer (highly sensitive green-sensitive layer) Silver bromide (
Average particle size 0.65 μ, size distribution 16%, octahedral) ... 0.10 Seratin 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) 0, l 1 Antifading agent (Cp d - 9,26 equivalents)...0.
15 Anti-staining agent (cpa-io, 11.12.13 I
O.7.7:1 ratio)... 0.025 force puller dispersion medium (Cpd-6)... 0.05 coupler solvent (
Solv-4,6 equivalent)... 0.15 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow Colloy I' Silver 0.15 12 (particle size 100 people) Gelatin... 0.70 Color mixing inhibitor (Cpd-7)... 0.03d Color inhibitor solvent (Solv-4,5 equivalent)... 0.10 Polymer latex ( Cpd-8) ... 0.07 10th layer (intermediate layer) 11th layer same as 5th layer (low sensitivity blue sensitive layer) Odor spectrally sensitized with blue sensitizing dye (ExS-5, 6) Silveride (average particle size 0.40μ, size distribution 8%, octahedron) ... 0.07 blue sensitizing dye (ExS-5
, 6) spectrally sensitized with silver chloride (silver chloride 8 mol%,
Average particle size 0.60 μ, size distribution 11%, octahedral) ... 0.14 Seratin ... 0.80 Yellow coupler (ExY-1,2 equivalent) ... 0.35 Antifading agent (Cpd -14) ... 0. IO stain inhibitor (Cpd-5,15 in 1=5 ratio)
... 0.007 force puller dispersion medium (Cpd-6) ... 0.05 coupler melt medium (S
olv-2) =・0. t.

12th layer (high sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.85μ, size distribution 18%, octahedron) ... 0 .15 Seratin
... 0.60 yellow coupler (ExY-12
Equivalent amount)...0.30 Anti-fading agent (Cpd-14)...0. IO stain inhibitor (Cpd-5,15 in I:5 ratio)
... 0.007 force puller dispersion medium (Cpd-6) ... 0.05 coupler solvent (S
o 1v-2) -0,l O 13th layer (ultraviolet absorbing layer) Ceratin... 1.00 Ultraviolet absorber (Cp d -2,4,16 equivalent)...0.
50 Color mixing inhibitor (Cpd-7, ■7 equivalent) ... 0.03 Dispersion medium (Cpcl-6) ... 0.02
Ultraviolet absorber solvent (Solv-2,7 equivalent)...0
．． 08 Anti-irradiation dye ccpci-ts, 19.2
0.21.27 in 10:10:13:15+20 ratio)
... 0.05 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1
μ) ... Acrylic modified copolymer of 0.03 polyvinyl alcohol (molecular weight 50,000)
... Equivalent amount of 0.01 polymethyl methacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) ... 0.05 Gelatin ... 1.80 Gelatin hardening agent ( H-1, H-2 equivalent)... 0.18 15th layer (back layer) Gelatin... 2.50 Ultraviolet absorber (Cp d -2, 4, 16 equivalent)... 0
．． 50 Dye (CM-18, 19, 20, 2], 27 in equal amounts)
... 0.06 16th layer (back protective layer) Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
... 0.05 gelatin
... 2.00 gelatin hardening agent (H-1,, H
-2 equivalents)... 0.14 How to make emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 75°C over 15 minutes with vigorous stirring.
Octahedral silver bromide grains with an average grain size of 0.35 μm were obtained. In this case, 0.3 g of 3,4-dimethyl-1,3 per mole of silver
-Thiazoline-2thione was added. This emulsion was mixed with 6 mg of sodium thiosulfate and 7 μg of chloroauric acid (per mole of silver).
A chemical sensitization treatment was carried out by sequentially adding tetrahydrate salt and heating at 75°C for 80 minutes. The grains thus obtained were used as cores and further grown in the same precipitation environment as the first time, to finally obtain an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7 μm. The coefficient of variation in particle size was approximately 10%. To this emulsion was added 1.5 mg of sodium thiosulfate per mole of silver. A chemical sensitization process was performed by adding chloroauric acid (tetrahydrate) of SNG and heating at 60° C. for 60 minutes to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contains ExZK-1 and ExZK- as nucleating agents.
2 to silver halide at 10-1% by weight and NO-2% by weight, and Cpd-22 as a nucleation accelerator by lo-2% by weight.
Using. Further, in each layer, Alkanol
agefa CF-120 (manufactured by Dainippon Ink Co., Ltd.) was used. (Cpd-23, 24, 25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as sample number 301. The compounds used in the examples are shown below.

xS-1 xS-2 xS-3 ・N (C2Ha)1 5su 5Na SOL xS-4 SOL SO,H 5O5H-N(C2H6)3 Cpd-1 Cpd Cpd 4 100-1000 Cpd pci 2 Cpd-13 Cpd-14 Hz Cpd-1s Cpd-16 Cpd-17 Cpd 8 )S38 O3K Cpd-19 (CHri+ SO,K Cpd-20 Cpd-21 (CHZ)a So, to pd 22 pd 3 pd 4 pd-25 H pd-27 CH,C00K CH,C00K xC ■ xC-3 xM xM xM-3 C'1H17(t) CH.

CMl(+7(t) xY-1 xY-2 olv-I olv-2 olv-3 olv-4 Di(2-ethylhexyl) sebacate trinonyl phosphate di(3-methylhexyl) phthalate tricresyl phosphate 5olv Solv Solv f(-I -2 E x Z K-1 xZK-2 Dibutyl phthalate trioctyl phosphate di(2-ethylhexyl) phthalate 2-bis(vinylsulfonylacetamide) ethane 6-
Dichloro-2-hydroxy-1,3,5-triazine N
a salt 7-(3-ethoxythiocarbonylaminobenzamide)9-methyl-IO-prohagilu 1. 2. 3.
4-Tetrahydroacridinium trifluoromethanesulfonate [4-+3- (3-+3- [5-+1- (2-chloro-5-(1-dodecyloxycarbonylethquinecarbonyl)phenylcarbamoyl io-4-hydroxyl
-naphthyl)tetrazol-1-yl]phenyl)ureido]benzenesulfonamide)phenyl]-1 formylhydrazine Next, to sample 301, the compounds shown in Table 4 were added to each layer to prepare samples 302 to 332.

The amount added is expressed as a weight ratio to gelatin in each layer.
The unit was ppm.

The viscosity of the dispersion liquid for the fifth layer used in preparing these samples was measured after aging at 40°C for 3 days and 6 days. The initial viscosity of this dispersion was adjusted to 60 cp using polystyrene sulfonic acid.

Next, these samples were subjected to image exposure using a known method, and then processed using the processing method described later to determine the relative sensitivity of each layer.

These results are also shown in Table 4.

Table 4 shows that the preservative of the present invention does not lower sensitivity;
It can be seen that the viscosity decreases over time and is very good.

After imagewise exposing the silver halide color photographic light-sensitive material prepared in the above manner, the method described below is carried out using an automatic processor until the cumulative amount of liquid replenishment reaches three times the tank capacity. Processed.

Tank color development 80 seconds 38°C8I! , 300mfl/
m” bleach fixing 40〃33〃33o.

Washing with water (1) 40〃33〃3〃 Washing with water (2) 40〃33〃3〃 Washing with water (3) 15〃33〃0.5 320
30/l 8011 The washing water replenishment method is to replenish the washing water (3) and
The overflow liquid of step 3) is led to the washing bath (2), and the overflow liquid of the washing bath (2) is led to the washing bath (1), which is a so-called direct canal replenishment method. At this time, the amount of bleach-fix solution brought in from the bleach-fix bath to the washing bath (1) due to the photosensitive material is 35 m1/n (and the ratio of the amount of washing water replenished to the amount brought in in the order of bleach-fixing is 9.1 times). Ta.

The composition of each treatment liquid was as follows.

Ethylenediaminetetrakis 0.5g 0.5
g Diethylene glycol methylenephosphonate 10- Benzyl alcohol 12.0t1! Potassium bromide 0.52g I.Rium chloride
0.06g sodium sulfite
2.48NN-diethylhydroxyl 4.0g amine triethylenediamine (1,44,0g diazabicyclo[2,2,21 octane) 3-methyl-4-amino-N-5,6g ethyl-N-(
β-methanesulfonamidoethyl) aniline sulfate Potassium carbonate 27.0g Fluorescent brightener (diaminostyl 1.0g type) 0- 14.4d 2.9g 4.8g 4.8g 6.6g 25.0g 1. 2g get 1ooo* 1oooIIIi
! pH (25'C) 10.50
10.80 Shimemo j54 ethylenediaminetetraacetic acid, di-sodium, dihydrate, ethylenediaminetetraacetic acid, Fe (III), ammonium, dihydrate, ammonium thiosulfate (700g/42) sodium p-toluenesulfinate, sodium bisulfite 12.0g Ammonium bromide 50.0g Ammonium nitrate
30.0g gained 1000z
l pH (25°c) 6.204.0g 55d 20.0g 46.0g Add tap water to the mother liquor and replenisher using H type strongly acidic cation exchange resin (Amberlite manufactured by Rohm and Haas) IR-120B) and an OH type anion exchange resin (Amberlite IR-400) to reduce the concentration of calcium and magnesium ions to 311 g/l or less, followed by isocyanate dichloride. Sodium nurate 20μ/l and sodium sulfate 1. 5 g/l was added. The pH of this solution is 6.
It was in the range of 5 to 7°5.

Table 4 @ki) Table 4 G selling) Table 4 G selling) Tsuji Akira, Yo7:l) Literary, bulb, red sensitivity example 5 On a subbed cellulose triacetate film support,
Sample 401, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in glrd units of silver for silver halide and colloidal silver, and in g/n (units) for coupler additives and gelatin. The number of moles is expressed per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.15
Gelatin °------ 1.
5ExM-8...0.08 UV-1...0.03 UV-2...0.06 Solv-2---0,'08 UV -3... 0,07 Cpd-5... 6X10-4 2nd layer (middle layer) Gelatin... 1.5UV
-1----... 0. 03 UV-2---0,06 UV-3---0.07 ExF-1---0.004 Solv-2---0,07 cpa-s ・・・・・・・ 6X
10-' Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type,
Equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 2.5) Coated silver amount...
・・・ 0.5 gelatin ・・・
...0.8ExS-1...1.0X10-
'ExS-2...3.0XIO-'ExS-3
・----1xlO-s ExC-3...0,22 ExC-4...0.02 cpd-s...3XlO
-'4th layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, internal high AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin crystal Mixed particles, diameter/thickness ratio l) Coated silver amount...
・・・ 0.7 Seratin ・・・
... 1.26ExS-1-= lXl0-" ExS-2... 3X10-'ExS-3-
------1xlO" ExC-3... 0.33 ExC-4... 0.01 ExY-16... 0,01 ExC-7... ...0.04 ExC-2...0,08 Solv-1...0.03 Cpd-5...5XlO-'5th layer (3rd red-sensitive emulsion Layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, twinned mixed grains, diameter/thickness ratio 2) Coated silver amount
・・・・・・ 0.7 gelatin ・・・
...0.8ExS-1------lXl
0-'ExS-2...3X10-'Ex
S-3... lXl0-'ExC-5=
0. 05 ExC-6...0.06 Solv-1・---・-0,15 Solv-2--・-0,08 Cpd-5...3×IO 6th layer (Middle layer) Gelatin 1.0C
pd-5...4XlO-"Cpd-1...
...0.10 Cpd-4...1.23 Solv-1--0,05 Cpd-3...0.25 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 12 mol%, internal high AgI type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 28%, normal crystal,
Twinned mixed particles, diameter/thickness ratio 2.5) Coated silver amount...
... 0.30 Seratin ...
...0.4EXS-4...5XlO
-'ExS-6----0,3X10-'ExS-
5...2X10-'ExM-9...
・0.2 ExY-14・----0,03 ExM-8...0.03 Solv-1...0. 2 Cpd-5...2XlO-" 8th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, internal high AgI type, equivalent sphere diameter 0.55 μm, equivalent sphere diameter Coefficient of variation 20%, normal crystal, twin crystal mixed grain, diameter/thickness ratio 4) Coated silver amount...
...0.6 gelatin ...
... 0.8ExS-4------5X10-' ExS-5... 2XIO-'ExS-6-
...0.3XIO-'ExM-9...
0.25 ExM-8... 0.03 ExM-10... 0.015ExY-14-
・・・・・・ 0. 04Solv-1------0,
2 Cpd-5...3X10-' 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high Agl type, equivalent sphere diameter 0.7 μm 1 sphere equivalent diameter) Coefficient of variation 30%, normal crystal, mixed twin grains, diameter/thickness ratio 2.0) Coated silver amount...0.85 Gelatin
...... 1.0ExS-4----2, Ox
l O-'ExS-5------2,0xlO-'
ExS-6...0.2XlO-'ExS-7-
------3,0XIO-'ExM-12・----
0,06 ExM-13...0,02 ExM-8...0.02 Solv-1-...0.20 Solv-2--0, 05 Cpd-5...4XlO-'1st O layer (yellow filter layer) Gelatin...0.9 Yellow colloidal silver...0.05C
pd-1...0.2 Solv-1...-0,15 Cpd-5...4XIO-"11th layer (1st
Blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high Agl type,
Equivalent sphere diameter: 0.5 μm Coefficient of variation of 1 sphere equivalent diameter: 15%, octahedral particles) Coated silver amount: 0.4 Gelatin: 1.0Ex
S-8-=・2XlO-' ExY-16...0.9 ExY-14-----0,09 Solv-1-----0,3 Cpd-5... ... 4X10-'12th layer (2nd
Blue-sensitive emulsion layer) Silver iodobromide emulsion (A, gI 10 mol%, internal high Agl
Type, ball equivalent diameter 1. 3μm, coefficient of variation of equivalent sphere diameter 25%
, normal crystal, twin crystal mixed particles, diameter/thickness ratio 4.5) Coated silver amount...0.5 gelatin
・・・・・・ 0゜6ExS-8・・・・・・
lXl0-'ExY-16...0.12 Solv-L...0.0
4Cpd-5...2XIO-'13th layer (first protective layer) Fine grain silver iodobromide (average grain size 0.07 μm, Ag 11 mol%)...0.2 Gelatin... ...0.8UV-3・
・・・・・・ 0. l UV-4...0. l UV-5...0.2 Solv-3-=-0,04 Cpd-5...3X10-' 14th layer (2nd
Protective layer) Gelatin: 0.9 Polymethyl methacrylate particles: 0.2 (diameter l.

5 μm) Cpd-5 4Xl (1 H-1...0.4 In addition to the above ingredients, a surfactant was added as a coating aid to each layer. Sample 10
It was set to 1.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

UV 4: CH.

CH.

UV-5 olv l d Li acid to Li cresyl olv 2・ dibutyl phthalate olv 3: Bisphthalate (2 ethylhexyl) ExM-8: ExF-1: ExC-2: (i) C4H,0CONH ExM-14 Hh CH.

ExY-15: ExC-5: ExC-6: ExM-9: (l ExM-12: 1 ExY-16: Cpd-1+ Cpd-2: Cs H+5(n) ExS-1: ExS-3: ExS- 4: ExS 5: ExS-6: ExS-7: (ni?h)t SIJ+ 1Na ExS-8: H-1: CH, =CH-5o2-CH, -CONH-CH2CH
2=CH-8o2-CH! -CONH-C)ItNext, the compounds shown in Table 5 were added to each layer of sample 401 to prepare samples 402 to 410.

The amount added is expressed as a weight ratio to gelatin in each layer.
The unit was ppm.

The dispersion liquid for the sixth layer used in preparing these samples was aged at 40° C. for 3 days and 6 days, and then the viscosity was measured.

Next, these samples were subjected to image exposure using a known method, and then processed using the processing method described later to determine the relative sensitivity of each layer.

These results are also shown in Table 5.

Table 5 shows that the preservative of the present invention does not lower sensitivity;
It can be seen that the viscosity decreases over time and is very good.

Table Example 6 A multilayer color photographic paper sample 501 having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-7)
) to 0.7 g, 27.2 cc of ethyl acetate and solvent (So
lv-3) 8.2g was added and dissolved, and this solution contained 10% sodium dodecylbenzenesulfonate (8cc).
% gelatin aqueous solution (185 cc). On the other hand, silver chlorobromide emulsion (cubic, 3-near mixture of average grain sizes of 0.88 μm and 0.70 μm (silver molar ratio)
The coefficient of variation of the grain size distribution is 0.08, and each emulsion contains 0.2 mol% of silver bromide locally on the grain surface), and the blue-sensitive sensitizing dye shown below is added to a large size per mol of silver. For the emulsions, 2.0 x 10-4 moles were added, and for the small size emulsions, 2.5 x 10-' moles were added, followed by sulfur sensitization. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. l-oxy-3,5-dichloro-5-) riazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

To the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, the following compounds were added in an amount of 2.6×10 3 mol per mol of silver halide.

In addition, ■-(5-methylureidophenyl)-5-
Mercaptotetrazole was added in amounts of 8.5XIO'-' mol, 7.7XIO-' mol, and 2.5X10-' mol per mol of silver halide, respectively.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer structure) The composition of each layer is shown below. The numbers represent coating amounts (g/, ()). Silver halide emulsions represent coating amounts in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ties) and a bluish dye (ulmarine)] -th layer (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Color image stabilizer (Cpd-
1) 0.19 solvent (Solv-3)
0.35 color image stabilizer (Cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv
-1) 0.16 solvent (Solv-4
) 0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of one with an average grain size of 0.55 μm and one with an average grain size of 0.39 μm (Ag molar ratio). Grain size distribution The coefficient of variation is 0.10 and 0.0
8. Each emulsion contained 0.8 mol% of A g B r locally on the grain surface)
0.12 gelatin l, 24
Magenta coupler (ExM) 0.20 color image stabilizer (Cpd-2) 0.03 color image stabilizer (
Cpd-3) 0.15 color image stabilizer (Cpd
-4) 0.02 color image stabilizer (Cpd-9)
0.02 solvent (Solv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (C
pd-5) 0.05 solvent (Solv-5)
0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture (Ag molar ratio) of one with an average grain size of 0.58 μm and one with an average grain size of 0.45 μm. Grain size distribution The coefficient of variation is 0.09 and 0°1
1. Each emulsion contained 0.6 mol% of A g Br locally on a part of the grain surface)
0.23 gelatin l・3
4 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (C
pd-8) 0.04 solvent (Solv-6)
0.15 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture prevention agent (C
pd-5) o, 02 solvent (Solv-5)
0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic of polyvinyl alcohol 0.17 Modified copolymer (degree of modification 17%) Liquid paraffin Oo 3 (ExY) 1=l mixture with yellow coupler (molar ratio) (ExM) l:l mixture (molar ratio) of magenta coupler (Ex M) cyan coupler R=C! Hs and C,H.

and (Cpd-1) color image stabilizer (Cpd-2) color image stabilizer (Cpd 3) color image stabilizer (Cpd-4) color image stabilizer (Cpd-5) Color mixing prevention agent (Cpd-6) color image stabilizer 2:4:4 mixture (weight ratio) of (Cpd-7) color image stabilizer Zu CH, -CH TeT C0NHC=　Ha(t) average molecular weight 60° 00 (Cpd 8) color image stabilizer (Cpd-9) color image stabilizer H (UV ■) UV absorber (Solv-1) melt medium (Solv-2) melt medium 2: 1 mixture (volume ratio) (Solv-3) melt medium (Solv-4) melt medium (Solv 5) melt medium C00C,H,.

(CHa)= COOC, H.

Example 6 The following N-groove bottom multilayer color photographic paper (U material 501) was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

No.-N Coating Solution Preparation Yellow coupler (ExY) 19.1 g, color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (C
pd-7) 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) were added to 0.7 g, dissolved, and the solution was dissolved in 8 c of 10% sodium dodecylhenzenesulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing c. On the other hand, chlorobromide emulsion (cubic, average grain size 0.
3=7 mixture of 88ta and 0.70-(
The coefficient of variation of the particle size distribution (silver molar ratio) is 0.08 and 0.
．． 10. Each emulsion contains 0.2 mol % of silver bromide locally on the grain surface) and the blue-sensitive sensitizing dye shown below per 1 mol of silver for the large emulsion. OX 10-'
molar addition, and for small size emulsions, 2.
Sulfur sensitization was prepared after addition of 5×10 −′ moles.

Example 2 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support coated with polyethylene on both sides. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cp
d-7) Add and dissolve 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) to 0.7 g, and dissolve this solution in 8 cc of 10% sodium dodecylbenzenesulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.8
3=7 mixture of 8t1m and 0.70-
i1 molar ratio). The coefficient of variation of the grain size distribution is 0.08 and 0.10, and each emulsion contains 0.2 mol% of silver bromide locally on the grain surface), and the blue-sensitive sensitizing dye shown below is added to the large size per mol of silver. For emulsions, 2. OX 10-
'molar addition, and for small size emulsions, 2 molar additions each.
．． A sulfur sensitized version was prepared after addition of 5 x 10-' moles.

The above emulsified dispersion and this emulsion are mixed and dissolved to form a coating solution having the composition shown below! Manufactured by Jl.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-5-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer SO3θ 5O3H-N(C2H5)3 (2.OX 10-' mole each for large size emulsions and 2.5X10-' each for small size emulsions per mole of silver halide) moles) green-sensitive emulsion layer (per mole of silver halide, 4.0 x 10-' moles for large size emulsions, 5.6 for small size emulsions)
xlO-' mol) and (7.OX 10-' mol for large-sized emulsions and 1.OX 10-' mol for small-sized emulsions per mol of silver halide) Red-sensitive emulsion layer CzHs I' CsH+ + (halogenated!! 0.9 per mole for large size emulsions)
XlO-' moles, and for small size emulsions 1. lX
For the red-sensitive emulsion layer, 2.6 x 10-' moles of the following compounds were added per mole of silver halogenide.

In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added at 8.5×10 5 mol per mol of the chloride, respectively. 7.7 X 10-' moles,
2.5 x 10-' moles were added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per 1.1 mole of halogenation, 1X10-' mole and 2X10-' mole, respectively. Mol added.

The following dyes were added to the emulsion layer to prevent irradiation.

5O=Na 5OJa and (Layer structure) The composition of each layer is shown below.

Paint the numbers! (g/bo) The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene lagonate [The polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye (ulmarine blue)] No.-N (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 gelatin 1. 86 yellow coupler (εxY) 0.82 color image stabilizer (Cpd-1) 0.19 as carrier (Solv-1)
0.35 color image stabilizer (Cpd-7)
0.06 Second N (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.1
6 solvent (Salv-4) 0
．． 08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of one with an average grain size of 0.55m and one with an average grain size of 0.39-(Ag molar ratio)0 Variation in grain size distribution The coefficients are 0.10 and 0.08,
(Each emulsion contained 8 mol% of AgBrO locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler (ExM
) 0.20 color image stabilizer (Cpd-2
) 0.03 color image stabilizer (Cpd
-3) 0.15 color image stabilizer (C
pd-4) 0.02 Color image stabilizer (Cpd-9) 0.02) Vehicle (Solv-2)
0.40 Fourth layer (UV absorption N) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (Cpd-5) 0.05
Solvent (Solv-5) 0.
24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture of one with an average grain size of 0.58 m and one with an average grain size of 0,45-(Ag molar ratio) 0 Variation in grain size distribution The coefficients are 0.09 and 0.11.
(Each emulsion contained AgBrO, 6 mol% locally on a part of the grain surface) 0.23 Gelatin
1.34 cyan coupler (ExC)
0.32 color image stabilizer (Cpd-
6) 0.17 color image stabilizer (Cp
d-7) 0.40 color image stabilizer (Cpd-8) 0.04 solvent (
Solv-6) 0.15 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture prevention agent (Cpd-5) 0.02
Solvent (So!v-5) 0.
08 Seventh layer (protective layer) Gelatin 1.3 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
) 0.17 Liquid Paraffin 0.03 (Ext) Yellow Coupler C! H.

CH.

1: l mixture (molar ratio) (State E) magenta coupler CH3 C,H 1(n) and CH3 CsHot (Jin) No. 1: l mixture (molar ratio) (ExC) cyan coupler t R-CzHs and C,)I.

and C.I. a 2:4:4 mixture by weight of each (Cpd l) color image stabilizer (Cpd-2) color image stabilizer (Cpd-3) color image stabilizer (Cpd-4) color image stabilizer (Cpd-5) Color mixing prevention agent (Cpd-6) color image stabilizer CiHq(t> c, Ht(t) CaHq(t) '2:4:4 Mixture (weight ratio) (Cpd-7) color image stabilizer -(C)12-C)I)ii- C0NHC,Hv(t) Average molecular t 60,000 (Cpcl-8) color image stabilizer (Cpd-9) color image stabilizer HI C.I.

(UV-1) Ultraviolet absorber CsHtrCt) c, nt(t) 4:2:4 mixture (weight ratio) of (Solv 1) Melt medium (Solv-2)? capacity medium 2: 1 mixture (volume ratio) (Solv-4) Solv. medium (Solv-5)? Capacity medium C00CoH+? (C11□).

Next, to sample 501, the compounds shown in Table 6 were added to each layer to prepare samples 502 to 532.

The amount added is expressed as a weight ratio to gelatin in each layer.
The unit was ppm.

The viscosity of the dispersion liquid for the sixth layer used in preparing these samples was measured after aging at 40° C. for 3 days and 6 days.

Next, these samples were subjected to image exposure using a known method, and then processed using the processing method described later to determine the relative sensitivity of each layer.

These results are also shown in Table 6.

Table 6 shows that the preservative of the present invention does not lower sensitivity;
It can be seen that the viscosity decreases over time and is very good.

First, a sensitometer (manufactured by Fuji Photo Film Co., Ltd.,
A FWH type (light source color temperature: 3200°K) was used to provide gradation exposure of a three-color separation filter for sensitometry. The exposure at this time was 0. 250CMS with 1 second exposure time
The exposure amount was set to .

The exposed sample was subjected to continuous processing (running test) using a paper processing machine until twice the color development tank capacity was replenished in the next processing step.

Processing process Mirror & R mountain Replenisher Tank capacity Color development 35°C 45 seconds 161 i
171 Bleach window 30-35°C 45 seconds 215,
d 171 Rinse ■ 30-35°C 20 seconds
-10f rinse ■ 30~35°C 20 seconds -ton
Rinse ■ 30-35°C 20 seconds 350 J
101 Drying 70 to 80 degrees 060 seconds *The replenishment amount was per 1 m of photosensitive material (3 tank counter-current system was used for rinsing ① to ②.) The composition of each processing solution was as follows.

Color developer tank liquid water supply
800 d 80
0 J ethylenediamine-N,N, 1.5g
2.0g N, N-tetramethylenephosphonic acid potassium bromide 0.015g triethanolamine 8.0g 12.0g Sodium chloride 1.4g Potassium carbonate
25g25gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5g 7.0gN
, N-bis(carboxymethyl)hydrazine 5.0g 7.0g optical brightener (WHITEX 4B.

Sumitomo Chemical) 1.0 2.0 Add water 1010007rLl
looo'pH (25°C) 10.0
5 10.45 Bleach-fix solution (tank solution and replenisher are the same) Water 400m
Ammonium 1thiosulfate (70%) 100mjl
+ Sodium sulfite 17g Ethylenediaminetetraacetic acid (I[I) Ammonium 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide
Add 40g water 1
000mffpH (25°C)
6. 0 rinse group (tank fluid and replenishment fluid are the same) Ion exchange water (calcium, magnesium 3pp each
m or less) 35.0g Table 6 A selling) Table 6 @ki) Table 6 @ki) *Relative sensitivity: Reciprocal of the exposure amount that gives a density of Kafuri + 0.2, blue, green, red sensitivity implementation from top to bottom Example 7 A color photographic material was prepared by coating a paper support laminated on both sides with polyethylene and the following layers from the 1st layer to the 12th layer, and designated Sample N (1601).
The coating side contains titanium white as a white pigment and a small amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amounts in g/rrr are shown below.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin layer) Gelatin ... 1.30 2nd layer (antihalation layer) Black colloidal silver ... 0.10 Gelatin ... 0.70 3rd layer (low sensitivity red sensitivity layer) Red enhancement Silver chloroiodobromide EMI (silver chloride 1 mol%, silver iodide 4 mol%) spectrally enhanced with a sensitive dye (ExS-1, 2, 3))
, average particle size 0.38m1 size distribution 1O%, cubic, core density type core shell) ・
・・0.06 red sensitizing dye (ExS-1, 2, 3))
Silver chloroiodobromide EM2 (silver iodide 5 mol%.
Average particle size 0.45 μm 1 Size distribution 20%, flat plate (aspect ratio = 5)) 0, 10 Gelatin... 1.00 cyan coupler (ExC-1) - 0,14 cyan coupler (
ExC-2) ・0.07 anti-fading agent (Cpd-
2, 3, 4, 9 equivalents)... 0.12 Coupler dispersion medium (Cpd-5)... 0.03 Coupler solvent (Solv-1, 2, 3)... 0.06 4th layer (High-sensitivity red-sensitive layer) Silver iodobromide EM3 spectrally enhanced with red sensitizing dyes (ExS-1, 2, 3) (silver iodide 6 mol%, average grain size 0.
758m1 size distribution 25%, flat plate (aspect ratio = 8
．． Core iodine))... 0.15 Gelatin... 1.00 Cyan coupler (ExC-1)... 0.20 Cyan coupler (ExC-2)... 0.10 Anti-fading agent (Cpd- 2, 3, 4, 9 equivalents)... 0.15 Coupler dispersion medium (Cpd-5)... 0.03 Coupler solvent (Solv-1, 2, 3)... 0.10 5th layer (Intermediate layer) Magenta colloid silver...0602 Ceratin...1.00 Color mixing inhibitor (Cpd-6,7)...0.08 Color mixing inhibitor solvent (Solv-4,5)...0. 16 Polymer latex (Cpd-8) ... 0.10 6th layer (low sensitivity green sensitive layer) Silver chloroiodobromide EM4 (silver chloride 1 mol) spectrally sensitized with green sensitizing dye (ExS-4) %・silver iodide 2.5 mol%, average grain size 0.28 μm, grain size distribution 12%, cubic, core-normal type (core-shell))
- Silver iodobromide EM5 spectrally sensitized with 0.04 green sensitizing dye (ExS-4) (silver iodide 2.8 mol%, average grain size 0.45μ, grain size distribution 12%, tabular (aspect Ratio-5)) ... 0.06 Gelatin ... 0.80 Magenta coupler (ExM-1) ... 0.10 Antifading agent (Cpd-9) ... 0. IO stain inhibitor (Cpd-10)...0. Ol stain inhibitor (Cpd-11)... 0.001 stain inhibitor (
Cpd-12)...0. Ol coupler dispersion medium (Cp
d-5) ... 0.05 coupler solvent (So I
v-4,6)... 0.15 7th layer (high sensitivity green sensitive layer) Silver iodobromide EM6 spectrally sensitized with green sensitizing dye (ExS-4) (3.5 mol of silver iodide) %・Average particle size 0.9
μ, particle size distribution 23%, flat plate (aspect ratio = 5,
Uniform law type))... 0. lO Gelatin...0.80 Magenta coupler (ExM-1)...0.10 Antifading agent (Cpd-9)...0. IO stain inhibitor (Cpd-IQ)...0. Ol stain inhibitor (Cpd-11)... 0.001 stain inhibitor (
Cpd-12)...0. Ol coupler dispersion medium (Cp
d-5) ... 0.05 coupler solvent (Solv
-4,6) ... 0.15 8th layer (yellow filter layer) Yellow colloidal silver ... 0.20 Gelatin ... 1.00 Color mixing prevention agent (Cpd-7) ... 0.06 Color mixing Inhibitor solvent (Sol v-4,5)...0.15 Polymer latex (Cpd-8)...0.10 9th layer (low sensitivity blue sensitive layer) Blue sensitizing dye (ExS-5) Silver chloroiodobromide EM7 spectrally sensitized with silver chloride (2 mol% silver chloride, 2.5 mol% silver iodide, average grain size 0.35μ, grain size distribution 8%, cubic, core density type core shell))・・・
Silver iodobromide EM8 spectrally sensitized with 0.07 blue sensitizing dye (ExS-5) (silver iodobromide 2.5 mol%, average grain size 0.45μ, grain size distribution 16%, flat plate (aspect Ratio = 6)) 0, l O Gelatin... 0.50 Yellow coupler (ExY-1)... 0.20 Stain inhibitor (Cpd-11)... o, o o i Anti-fade agent (Cpd -6) ... 0. IO coupler dispersion medium (Cpd-5) ... 0.05 Coupler solvent (Solv-2) = 0.05 10th layer (high sensitivity blue sensitive layer) Spectral sensitization with blue sensitizing dye (ExS-5) Silver iodobromide EM9 (silver iodide 2.5 mol%, average grain size 1.2
μ, particle size distribution 21%, flat plate (aspect ratio = 14
))... 0.25 Gelatin... 1.00 Yellow coupler (ExY-1)... 0.40 Stain inhibitor (Cpd-11)... 0.002 Anti-fading agent (
Cpd-6) ... 0.1 O force puller dispersion medium (Cpd, -5) ... 0. i5 coupler solvent (
Solv-2) -0,10 11th layer (ultraviolet absorption layer) Gelatin... 1.50 Ultraviolet absorber (Cpd-1, 3, 13)... 1.00 Anti-browning agent (Cpd-6 , 14)... 0.06 Dispersion medium (Cpd-5) Ultraviolet absorber solvent (Solv-1, 2)... 0.1
5 Anti-irradiation dye (Cpd-15, 16) ... 0.02 Anti-irradiation dye 12th layer (protective layer) Fine particle silver chlorobromide (silver chloride 97 mol%, average size 0.2
μ) ... 0.07 modified poval
... 0.02 gelatin
... 1.50 gelatin hardening agent (H-1)
... 0.17 Furthermore, each layer contained Alkanol XC (Dupont) and sodium alkylbenzenesulfonate as emulsification and dispersion aids, and succinate ester and Magefac F-120 (manufactured by Dainippon Ink Co., Ltd.) as coating aids. Using. In the silver halide or colloidal silver containing layer, (Cpd-19°20
．． 21) was used. The compounds used in the examples are shown below.

xS-1 xS-2 xS-3 xS-4 xS Cpd-1 Cpd pd 4 CONHClHe(t) (m 100-1000) pd pd-7 pd Shi113 (n3 pd 3 pd-15 pd 6 pd-17 5LJ+ Mr. pd to SIJ+ 18 pd-19 H pd-20 xC xC-2 ExY-1 aH+t(j) ExY-] olv-I olv-2 olv-3 olv-4 olv-5 olv-6 -1 di(2- Ethylhexyl) phthalate trinonyl phosphate di(3-methylhexyl) phthalate tricresyl phosphate dibutyl phthalate trioctyl phosphate 1, 2 bis(vinylsulfonylacetamide) Next, to sample 601, the compounds shown in Table 7 were added to each layer. These samples were designated as samples 602 to 632.

The amount added is expressed as a weight ratio to gelatin in each layer.
The unit was ppm.

The viscosity of the dispersion liquid for the fifth layer used in preparing these samples was measured after aging at 40° C. for 3 days and 6 days. The initial viscosity of this dispersion was adjusted to 40 cp using polystyrene sulfonic acid.

Next, these samples were subjected to image exposure using a known method, and then processed using the processing method described later to determine the relative sensitivity of each layer.

These results are also shown in Table 7.

Table 7 shows that the preservative of the present invention does not lower sensitivity;
It can be seen that the viscosity decreases over time and is very good.

[Processing process]

First development (black and white development) 38℃ 1'15'' water washing 38℃ 1'30'' reverse exposure
100 Lux or more 1' or more 38°C 38°C 38°C 38°C Color developing water Washing bleach-fixing water Washing [Processing liquid composition] 1st developer Nitrilo N, N, N-trimethylenephosphonic acid pentasodium salt diethylene diamine 5 Acetic acid/pentasodium salt Potassium sulfite Potassium thiocyanate Potassium carbonate Hydroquinone Monosulfonate Potassium salt Diethylene glycol l-Phenyl-4-hydroxymethyl-4-methyl-3 One-pyrazolidone 15'45'00'15' g 4゜30゜1゜35゜25.0g 15.0d g Add potassium bromide potassium iodide water (pH 0, 5g 5, 0■ 1 9.70) Color developer Benzyl alcohol diethylene glycol 3.6-sythyl 1. 8-Octanediol Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt Diethylenediamine pentaacetic acid Pentasodium salt Sodium sulfite Potassium carbonate Hydroxylamine sulfate N-ethyl-N-(β-methanesulfonamidoethyl) -3-Methyl-4-amino 15゜12゜0゜0゜7nl 〇- g g Aniline sulfate Potassium bromide Potassium iodide Add water 5.0g 0.5g 1.0■ 1 (pH 10,40) 2-Mercapto-1,3,4 Triazole 1. Og ethylenediaminetetraacetic acid disodium trihydrate 5.0g ethylenediaminetetraacetic acid Fe(III) ammonium hydrate 80.0g sodium sulfite 15.0g sodium thiosulfate (700g/l liquid) 160.0d glacial acetic acid
5. 〇-Add water
11 (pH 6,50) Table 7 (Continued) Table 7 G sold) Table 7 CjFi sold) Example 8 Preparation of coated sample Prepared by the manufacturing method described in JP-A-62-115035, and emulsion coated. The surface is underlined in advance,
A coated sample 701 was prepared by coating the following layer on a triacetylcellulose support whose back surface was coated with diacetyl cellulose 143 .mu./d and silicon oxide 5 .mu./bo.

1st layer (antihalation layer) Gelatin 1.0g/m%so,
"140 ■ / D 1 CHZCHZSOJ CHZCHZSOSK 26 ■ / Bo CHZCHTSOJ CH, CH, SO3 16 mg / RRR 2nd layer (intermediate layer) Gelatin 0 ゜ 4g / Popolipotasium P -Vinyl Vennetzenzul Honate 5 ■ / RRL 3rd layer (emulsion) Layer) Emulsion (B) was used.

Coated silver amount Gelatin amount 4-Hydroxy-6-methyl-1,3,3a, 7 Tetrazaindene C,,H,50 (CHtCH20)2. ) 11.36g
/bo2,og/bo15mg/boa■/rrl Polypotassium p-vinylbenzenesulfonate bis-(vinylsulfonylacetamido)ethane 4th layer (emulsion layer) Emulsion (A) was used.

Coated silver amount 4. ．． 2g/rrr Gelatin amount 5.5g/bodextran (average molecular weight 150,000) 1.8g/rr+'57■/n
(50■/♂ 4-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene C1H,,O(CH,C)1.0)2sH trimethylolpropane polypotassium p-vinylbenzenesulfonate poly Acrylic acid 5th layer (surface protective layer) Gelatin 41■/d 23■/d 390■/rd 88■/- 54■/bo 0.8■/d 8 5O2 C,H.

N-CH.

OOK H 50mg/rrr l.

8 ■/- Polypotassium p-vinylbenzenesulfonate polymethyl methacrylate fine particles (average particle size 3 μm) 6 ■/m' 24 ■/rrl' Preparation of Example Emulsion (A) Add 25 g of potassium bromide and 15 g of potassium bromide to water 11. A container containing potassium iodide, 1.9 g of potassium thiocyanate, and 24 g of gelatin was kept at a temperature of 60°C, and while stirring vigorously, a silver nitrate aqueous solution and a potassium bromide aqueous solution were added by double jet using the usual ammonia method. Legal content 1
0 mol%, average particle size 1. A thick plate-like silver iodobromide emulsion with a diameter of 0 μm and a relatively amorphous shape was prepared. After this, increase the temperature to 3
After lowering the temperature to 5°C and removing soluble salts by the sedimentation method,
The temperature was raised to 40°C, 82g of gelatin was added, and the pH was adjusted to 6,40°pAg8.80 with caustic soda and sodium bromide.
Adjusted to.

After raising the temperature to 61° C., 213 μ of sensitizing dye A was added. After 10 minutes, sodium thiosulfate 5 permanent 1.2
(1), potassium thiocyanate (28), and chloroauric acid (0.4) were added, and after 65 minutes, the mixture was rapidly cooled and solidified.

Preparation of Sensitizing Dye A Emulsion B A container containing 24 g of gelatin, 25 g of potassium bromide, 7.6 g of thiocyanic acid, and 4.9 g of lium iodide in 1/2 of water was heated vigorously while keeping the temperature at 0°C. While stirring, a silver nitrate aqueous solution and a potassium bromide aqueous solution were double-jet added using the usual ammonia method to form a relatively irregular thick plate-like iodobromide with an average content of 6 mol% and an average particle size of 0.6μ. A silver emulsion was prepared. After that, the temperature was lowered to 35°C and soluble salts were removed by a sedimentation method, and then the temperature was raised to 40'C, 110g of gelatin was added, and the pH was adjusted to 6.60 with caustic soda and sodium bromide.
Ag was adjusted to 8.90.

After raising the temperature to 56℃, 0.8μ of chloroauric acid, 9
(1) potassium thiocyanate and 4 (4) sodium thiosulfate were added. After 55 minutes, add 180 μ of dye A and add 10
After a few minutes, it was rapidly cooled and solidified.

Next, the compounds shown in Table 4 were added to the emulsions to prepare samples 702 to 732.

The amount added was expressed as a weight ratio to the gelatin in the emulsion, and the unit was ppm.

The emulsions were aged at 40° C. for 3 and 6 days, and the viscosity was measured over time.

Sensitometry These samples were stored at 30° C. and 65% RH for 14 days after application. Each sample was tested in the following manner.

(i) Measurement of Sensitivity Each sample was exposed to a tungsten light source with a color temperature of 2854 through an optical wedge at 1/I for 0 seconds.

Each of these was developed with the following developer at 20'C for 7 minutes. For each fixed, washed, and dried sample, a constant density (optical density of 0.2) higher than the fog density was measured using the same method.

Developer solution Metol 2g Sodium sulfite 100g Hydroquinone 5g Borax.l
0820 2g Add water lI! Fixer: Fujifix (manufactured by Fuji Photo Film ■) The results are shown in Table 8.

table table 8 G selling) table 80 selling)

Claims (1)

[Claims] A halogen characterized by containing a compound represented by the general formula [I] and further containing at least two or more compounds among the compounds represented by the general formulas [II] to [IV]. Silver chemical photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an unsubstituted or substituted alkylene group, and X is a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, Lower alkoxy groups, aryl groups, alkenyl groups, sulfonyl groups, aralkyl groups, -COR_2, ▲Mathematical formulas, chemical formulas, tables, etc.▼-
Represents SO_3M, R_2 is a hydrogen atom, -OM, lower alkyl group, aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyloxy group, ▲ formula,
There are chemical formulas, tables, etc. Represents ▼. R_3 and R_4 are each a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, -COR_7, -SO_2R_
Represents 7 and may be the same or different from each other,
R_5 and R_6 each represent a hydrogen atom, a lower alkyl group, an aryl group, or an aralkyl group, and may be the same or different from each other, R_7 represents a lower alkyl group, an aryl group, or an aralkyl group, and M is hydrogen Represents atoms, alkali metal atoms, and atomic groups necessary to form monovalent cations. Further, m represents an integer from 0 or 1 to (6-n), and n represents an integer from 1 to 6. If m and n are 2 or more,
Each of the above groups may be the same or a plurality of them may be combined. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_3 is a hydrogen atom, an alkyl group, an alkenyl group,
Aralkyl group, aryl group, heterocyclic group, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼, where R and R are hydrogen atoms, alkyl groups, aryl groups, and cyano groups, respectively. , heterocyclic group, alkylthio group, alkylsulfoxy group,
It represents an alkylsulfonyl group, and R_9 and R_1_0 may be bonded to each other to form an aromatic ring. R_1_1 and R_1_2 are each a hydrogen atom, an alkyl group,
Represents an aryl group or an aralkyl group. General formula [III] ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_3 represents a hydrogen atom, an alkyl group, or a hydroxymethyl group, and R_1_4 represents a hydrogen atom or an alkyl group. General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ In the formula, Y is a halogen atom, nitro group, hydroxy group, cyano group, lower alkyl group, lower alkoxy group, aryl group, alkenyl group, sulfonyl group, aralkyl group group, -C
OR_1_5, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -
SO_3M", R_1_5 is a hydrogen atom, -OM"
, lower alkyl group, aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyloxy group,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ Represents. R_1_6 and R_1_7 are each a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, -COR_2_0, -
SO_2R_2_0, which may be the same or different from each other; R_1_8 and R_1_9 each represent a hydrogen atom, a lower alkyl group, an aryl group, or an aralkyl group, and may be the same or different from each other; R_2_
0 represents a lower alkyl group, aryl group, or aralkyl group; M', M'' represent a hydrogen atom, an alkali metal atom, and an atomic group necessary to form a monovalent cation; p is an integer from 1 to 5; and when p is 2 to 5, Y may be the same group or a combination of two or more of the above groups.