JPH03130761A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the color reproducibility and preservable property of the photosensitive material by incorporating the fine crystal dispersion of specific dyes into hydrophilic colloidal layers and specifying the content of the silver iodide in emulsions to a specific value or below. CONSTITUTION:The fine crystal dispersion of the dyes of >=1 kinds among the dyes expressed by formulas I to VI are incorporated into >=1 layers of the hydrophilic colloidal layers of this photosensitive material and the average content of the silver iodide in the entire emulsion is specified to <=8mol%. In the formulas, A, A' denote an acidic nucleus; B denotes a basic nucleus; X, Y denote an electron-withdrawing group; R denotes H or alkyl; R1, R2 denote alkyl, aryl, etc.; R3, R6 denote H, hydroxy, etc.; R4, R5 denote H or the atom group necessary for forming desired rings respectively with R1, R2; L1 to L3 denote methine; (m), (p) denote 0, 1; (n), (q) denotes 0 to 2; B' denotes carboxyl, sulfamoyl, etc. A dissociatable group having a prescribed pKa value is combined with the dyes expressed by the formulas.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic material having excellent color reproducibility and improved storage stability. This relates to color photographic materials□.

(Prior art) In silver halide photographic light-sensitive materials, constituent layers of the light-sensitive material are used to absorb specific wavelengths for the purpose of using light absorption filters, preventing halayones, or adjusting the sensitivity of light-sensitive emulsions. Colloidal silver containing 111 has been provided therein. However, this colloidal silver often causes an increase in the fog of photosensitive silver halide emulsions adjacent to the colloidal silver or deteriorates the storage stability.

- For the purpose of contrasting with the colloidal silver described above, methods of coloring the hydrophilic colloid layer with dyes have been studied. Dyes used for such purposes must: (1) have appropriate spectral absorption according to the purpose of use;

(2) It is desired to be bleached during the photographic processing process, or to be eluted into the casing, processing solution, or washing water, and leave harmful coloring on the photographic material after processing.

(3) Do not diffuse from the dyed layer to other layers.

(4) Excellent stability over time in solutions or photographic materials and no discoloration or fading.

In addition to this condition, it must be photochemically inert.

That is, it is particularly important to have an adverse effect on the performance of the copper halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity, latent image regression, or fog.

Many efforts have been made to find dyes that meet these requirements.

US% Liver Day, Day 20. No. jjj uses an open-chain methylene type benzylidene dye as described below in the yellow filter layer, but this dye has the disadvantage that it diffuses into other layers and desensitizes the blue-sensitive emulsion I-.

JP-A No. 62-2222vt solves this problem of dye diffusion to other layers and provides a yellow dye layer with excellent filtering effect. Although it achieves the purpose of achieving double diffusion to other layers, it has the drawback that it may leave a residual color after treatment.

In addition, as a method to satisfy the conditions (3) and (4) above required for dyes, a hydrophilic polymer having a charge opposite to that of the dissociated anionic dye is made to coexist in the layer as a mordant,
A method of causing the dye to exist in a specific layer through interaction with dye molecules is described in U.S. FF2゜rat, R6U, No. 44, /217, Erlr No. 3, 4.2.
j, disclosed in A5'φ No. Kasa.

A method of dyeing a specific layer using a residual water-insoluble dye solid is disclosed in Japanese Patent Application Laid-open No. 1-T263Y and No. 5R-ISRZ.
Ro issue, same! j-/11! jI No. 13-27131, No. 43-/979413 European Special FRm/s, Lot
No. 274', '7JJjl J7G, jAA No.
Same JfF, No. 4tlr, World n% FF (WO) J'
I/04'79'I, etc.

In addition, the method of dyeing the entire decorative layer using metal salt fine particles adsorbed with dye is ranked 2.7/R in the United States.

orr No. 2, 179&, rlAI No. 2, direction 2.
It is disclosed in Data 6, Rmei No. 3, and Japanese Patent Application Laid-Open No. 60-41237. However, in these methods, if the selection of photosensitive silver halide grains to be combined with the method is incorrect, the interimage effect, which is an important factor in color reproduction, may be impaired, and color reproduction may be destabilized. It is clear that there are disadvantages such as 1.

Therefore, it is an object of the present invention to overcome such problems and
It is an object of the present invention to provide a halogen metabolic color photographic photosensitive F4 family which has excellent color reproducibility and improved storage stability.

(Means for Solving the Problems) The above purpose is such that at least one hydrophilic colloid layer is
, (1) Ill) IIV), (V) and (Vl) A total light-sensitive silver halide emulsion containing a microcrystalline dispersion of a compound with a small amount of indulgence/maki selected from the group consisting of The average silver iodide content of silver halide grains in the emulsion is t
Silver halide color photographic materials, which are characterized by a molar content of less than 1,000, lost consecutively.

Below is a detailed explanation of the invention.

In the present invention, the following - Monka (1), (II).

A microcrystalline dispersion of at least seven compounds selected from the group consisting of (ill), (IV), (V) and (Vl). A' = General formula (TV) A = (LLt) Z-, =B General formula (VT) (In the formula, A and A' may be the same or different, each represents an acidic nucleus, and B represents a base R represents a sexual nucleus, X and Y may be the same or different, and each represents an electron-withdrawing group;
represents a hydrogen atom or an alkyl group, R8 and R2 each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and R and Rt may be linked to form a 5- or 6-membered ring.

Rx and R each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group, or a halogen atom; Lt, Lx, and R, which represent a group of nonmetallic atoms necessary to form a ring, each represent a methine group.

m represents O or 1, n and q each represent 0, 1 or 2, P represents O or 1, when p is 0, R3 represents a hydroxy group or a carboxyl group, and R4 and R, B r representing a hydrogen atom represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group.

However, the compound represented by -Momonana (I) or Vl) has a pKa in the range of 4 to 11 in a mixed solution in which the volume ratio of water and ethanol is 1:1 in one molecule. It has at least one functional group. ) First, the compound represented by -i formula (1) or VT) will be explained in detail.

The acidic nucleus represented by A or A' is preferably 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbylic acid, thiobarbylic acid, indandione, pyrazolo. Represents pyridine or hydroxypyridone.

The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole or pyrrole.

Examples of heterocycles of B' include virol, indole,
Thiophene, furan, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine,
phenoxazine, indoline, thiazole, pyridine,
These include pyridazine, thiadiazine, pyran, thiovilane, oxadiazole, benzoquinolidine, thiadiazole, pyrrolothiazole, pyrrolopyridazine, and tetrazole.

A group having a dissociable proton with a pKa (acid dissociation constant) in the range of 4 to 11 in a mixed solution of water and ethanol at a volume ratio of 1:1 makes the dye molecule substantially water-insoluble at pH 6 or below. There is no particular restriction on the type and substitution position on the dye molecule as long as it makes the dye molecule substantially water-soluble at pH 8 or above, but preferably a carboxyl group, a sulfamoyl group, a sulfonamide group, A more preferred hydroxy group is a carboxyl group. The dissociative group may be substituted not only directly on the dye molecule, but also via a divalent linking group (eg, alkylene group, phenylene group).

Examples via a divalent linking group include 4-carboxyphenyl, 2-methyl-3-carboxyphenyl, 2,4-
Dicarboxyphenyl, 3,5-dicarboxyphenyl, 3-carboxyphenyl, 2,5-dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl,
2.4゜6-Doryhydroxyphenyl, 3-benzenesulfonamidophenyl, 4-(p-cyamibenzenesulfonamido)phenyl, 3-hydroxyphenyl, 2-
Hydroxyphenyl, 4-hydroxyphenyl, 2-hydroxy-4-carboxyphenyl, 3-methoxy-4
-carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4-carboxybenzyl, 2-carboxybenzyl, 3-sulfamoylphenyl, 4-
Sulfamoylphenyl, 2.5-disulfamoylphenyl, carboxymethyl, 2-carboxyethyl, 3
-carboxypropyl, 4-carboxybutyl, 8-carboxyoctyl and the like.

The alkyl group represented by R, R, or R has 1 to 1 carbon atoms.
10 alkyl groups are preferred, and examples include groups such as methyl, ethyl, n-propyl, isoamyl, n-octyl and the like.

The alkyl group represented by R+ and Rz is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-probyl, n
-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) are preferred; ), alkoxycarbonyl group (e.g. methoxycarbonyl, i-propoxycarbonyl),
(e.g., phenoxy group), phenyl group, amido group (e.g., acetylamino, methanesulfonamide), carbamoyl group (e.g., methylcarbamoyl,
ethylcarbamoyl), sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

The oryl group represented by R8 or R2 is preferably a phenyl group or a naphthyl group, and the substituents include the groups listed as substituents for the alkyl groups represented by R1 and R1 above, and the alkyl group ( e.g. methyl, ethyl)
is included. ].

The acyl group represented by R6 or R2 is preferably an acyl group having 2 to 10 carbon atoms, such as acetyl, propionyl, n-octanoyl, n-decanoyl, imbutanoyl, benzoyl, etc.
Examples of the alkylsulfonyl group or arylsulfonyl group represented by □ include methanesulfonyl, ethanesulfonyl, n-methanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, 0
- Groups such as hydroxybenzenesulfonyl and the like can be mentioned.

The alkoxy group represented by R3 or Rh has 1 to 1 carbon atoms.
Preferably, 0 alkoxy groups include groups such as methoxy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, and isopropoxy. Examples of the halogen atom represented by R5 or R4 include chlorine, bromine, and fluorine.

Examples of the ring formed by linking R1 and R4 or R2 and R1 include a julolidine ring.

Examples of the 5- or 6-membered ring formed by connecting R3 and R2 include a piperidine ring, a morpholine ring, and a pyrrolidine ring.

The methine group represented by L, , L o or H may have a substituent (for example, methyl, ethyl, cyano, phenyl, chlorine atom, hydroxypropyl).

The electron-withdrawing groups represented by X or Y may be the same or different, and include a cyano group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group that may be substituted, such as acetyl, propionyl, hebucnoyl, dodecanoyl, hexadecanoyl, 1-oxo-7-chloroheptyl), arylcarbonyl group (arylcarbonyl group that may be substituted, e.g. benzoyl, 4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl)
, alkoxycarbonyl group (an alkoxycarbonyl group that may be substituted, such as methquincarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyl Oxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-
Methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2-(2-chloroethoxy)ethoxycarbonyl, 2-(2-(2-chloroethoxy)ethoxy]ethoxycarbonyl), Good aryloxycarbonyl groups, such as phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4
-Fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2
．． 4-di(t-amyl)phenoxycarbonyl), carbamoyl group (carbamoyl group which may be substituted,
For example, carbamoyl groups ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-di(t-amyl)phenylcarbamoyl, 2-chloro-3-(dodecyloxycarbamoyl)phenylcarbamoyl, 3-(hexyloxycarbonyl)phenylcarbamoyl ) represents a sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), a sulfamoyl group (a sulfamoyl group that may be substituted, such as sulfamoyl, methylsulfamoyl).

Next, specific examples of dyes used in the present invention will be given.

-4 I-5 -6- 7- -9 ■-11 -13 ■-14 ■ 15 ■-17 ■-18 -19 ■-21 ■-25 ■-26 -2 ■ +1-4 1 Shihko ■-5 11-6 ■ ○ 11-3 -4 -5 ■ 1l-7 I[1-9 ■-10 1[+-11 ■-12 ShiH3 14 ■ 6 ■-17 ■-18 ■-19 ■ 0 ■ 1 ■ 2 ■-24 ■-25 ■ 29 CH3 CH3 ■-30 ■-31 CH.

CH2 0CL COCH.

zHs C-H1 z　Hs CHx CzHs CzHs ■-12 ■-15 CzHs CzHs H3 ■ 4 -5 -6- 7 below, A specific example of the general formula <Vl) is B' part of I will show you.

NHSO2CH3 ■－． z CH2Cl　2Co2H ■−φ Vl-,t ■-7 ■-r O2H CO2)( ■-/.

O2H ■ / / ■-/2 The dye used in the present invention has international NWOrr7θ4t7
No. F4, European Watch EPO Ko7da 723A/No.,
No. 276.544, -] 2 Tata, ψ3! No., Tokukai Shoj
, No. 2-22776, 5r-is! 3! θ, direction 11
-/! ! 3j/ issue, direction 6/-20 tata 3ψ issue, direction t-
Af4Jj, US Special Iyf No. 2!27!13, Same 3
Da1rttr No. 7, Mukai J7FAjJP, Mukai 3'? 3
37Fr issue, same←13θ44J issue, same da θψorai
It can be easily synthesized according to the method described in No. 1, etc.

In the present invention, the dye is formed into a solid fine powder dispersion for inclusion in a layer, such as a hydrophilic colloid layer, coated on a photographic element. The fine powder dispersion can be prepared by precipitating the dye in the form of a dispersion and/or in the presence of a dispersant by means of known comminution methods, such as ball milling (ball mill, vibratory ball mill, planetary ball mill, etc.) and sanding. □It can be formed by ring, colloid milling, jet milling, roller milling (1).In that case, a solvent (for example, water, alcohol/L-, etc.) may be coexisting.Alternatively, the dye can be formed in a suitable solvent. After dissolving the dye, a non-solvent for the dye may be added to precipitate the dye into fine particles, in which case a dispersing agent may be used.Alternatively, the pH of the dye may be controlled. The dye particles in the dispersion may have an average particle size of /θ μml.
The particle size is preferably 2 μm or less, particularly preferably 0.1 μm or less, and in some cases, it is preferably a fine powder with a particle size of nO,/Am or less.

The amount of dye used in the present invention is /η~/θθOm9
/m. Good luck! ■〜t
The dye dispersion of the present invention can be added to any layer, whether it is an emulsion layer or an intermediate layer.

Partially or completely replaced with colloidal silver, which is commonly used in the yellow filter layer and/or the anti-truncation layer.
When used, the effects of the present invention are remarkable.

The silver halogenide contained in the photographic emulsion r* of the photographic optical material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing vfi iodide. The silver iodide grains used in this article have an average silver iodide content of less than g mole in the entire photosensitive layer, preferably 1L<rzl, θ~
6. □ key to make the θmol whisper! & will be tested.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof. Mixtures of particles in various crystalline forms may also be used.

The grain size of silver halide may be fine grains of about Q,/□ 200 ft or less, or large grains with a projected area diameter of about 70 microns, and have a narrow distribution. ! It may be a monodisperse emulsion with a wide distribution, or a polydisperse emulsion with a wide distribution.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method.
Volume 176, scrap/74$3 (December/7r), J 2
~J page 3, °1. Emulsion production (Emulsion Pr)
and Types)” and the same, volume iv, A/r714 (/7P year//month),
The method described on page 6φ can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie et.
PhysiquePhotography
Paul Montel, /P67), Duffin's ``Photographic Emulsion Chemistry'', published by Focal Press (G, F
, I) uf f in , PhotographicE
Mulsion Chemistry (Focal
Press + l 66), "Manufacture of photographic emulsions and fabrics" by Zelikman et al., published by Focal Press (V-1,.

Zelikman et al., Making
andCoating Photographic E
mulsion+Focal Press, 7Yt
II) gMI can be produced using the method described in 11. In other words, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the dissolved soluble halogen salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. may also be used. It is also possible to use a method in which particles are formed under an excess of gold and silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Nilcondrold double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Dissolved in known silver halide solvents such as ammonia, Rodankali or US C. 3.27/.

No. 137, Tokukai Sho! /-/No. 2360, Tokukai Sho! 3-r
2←θr issue, Tokukai Sho! 3-/ψψ3/ヂ issue, Tokukai Akira! ←
-10θ7/7 or Tokukai Sho! Physical ripening can also be carried out in the presence of thioethers and thione compounds vI) described in ≠-/311 Cor No. R. Also by this method, a silver rhodanide emulsion with regular crystalline shape and nearly uniform grain size distribution can be obtained.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling I)Ag and I)H during grain formation. For more information,? 11 Photographic Science and Engineering
hic 5science and Engineer
ing) Volume 6, /79-/4 Evening page (/!7J, 2);
Journal of Photographic Science (J
our own of Photographic 5c
ience), 72 volumes, 2 gko~kota/negative (726 g)
, U.S. Clock No. 3.6! , 3Pψ and UK% Liver No. 1
, u/3.7←r.

Also, as a monodispersed emulsion, silver halide grains with an average grain diameter larger than about 0.17 microns, and a small amount of silver halide grains, can be used. Typical emulsions are those in which V3 VL is greater than ±ψθ% of the semiuniform grain diameter. Average particle diameter is 0.1! ~
2 microns, at least 9! At least the weight % size a (number of particles)! Emulsions having excellent silver halide grains in a range of average grain diameters can be used in the present invention. The method for producing such an emulsion is described in US Patent Ff No. 3.
! 7←.

lJr, FG3. T! ! , No. 3?44 and British Special, ff No. 1. It is described in ψ/3,74t1.

Also, Tokukai Sho-t, tr-trtoo issue, same! /-1902
No. 7, l'iJ]t /-J' 30ri No. 7, direction! l-
1-/37/33 issue, 1 Tsukasa! ψ-Guri l1, heading! ψ
- Tata ψ / No. 7, 11-3761! No., Mukai 5r-ay
Monodisperse emulsions such as those described in No. yJt can also be preferably used in the present invention.

Additionally, tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
, 434,226, 4,414.310, 4,
433,048, British Patent No. 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.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide photographic film having a small number of light-sensitive layers (one light-sensitive layer) consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities on a support. 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 side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer.However, depending on the purpose, even if the above-mentioned order of installation is reversed, it may still be the same. The arrangement may be such that different photosensitive layers are sandwiched between color-sensitive layers.

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 is disclosed in Japanese Patent Application Laid-open Nos. 61-43748 and 5941.
No. 3438, No. 59-113440, No. 61-200
No. 37 and No. 61-20038, couplers, DIR compounds, etc. may be included, and a color mixing inhibitor as commonly used may be included.

A plurality of silver halide emulsion layers forming the bottom of each unit photosensitive layer are a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1.121.470 or British Patent No. 923,045. A two-layer structure can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
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 (8L) / high-sensitivity blue-sensitive layer (B) / high-sensitivity green-sensitivity! (G)l) /Low-sensitivity green photosensitive layer (G[
, )/high-sensitivity red-sensitive layer (R11)/low-sensitivity red-sensitive layer (RL), or BH/BL/GL/GH/RH
/RL order, or BH/BL/GW/GL/RL/R
1 (can be installed in the order of

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
I(/GL/RL 1@).Also, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive They can also be arranged in the order of layer/GL/RL/Gll/R1.

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 the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, medium-sensitivity The emulsion layer/high sensitivity emulsion layer/low sensitivity emulsion layer may be arranged in this order.

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 1i/high-speed emulsion layer, etc.

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

In order to improve color reproducibility, the U.S. patent cylinder 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 structures and arrangements can be selected depending on the purpose of each photosensitive material.

Known photographic additives that can be used in the present invention include Research Disclosure Na 17643 and Research Disclosure Na 187.
16, and the relevant descriptions are shown in the table below.

Chemical sensitizer 2 Sensitivity increasing agent 3 Spectral sensitizer, Super sensitizer RD17643 Rules ■ Tanri Mutual Page 23 Page 648 Right column Same as above Page 23-24 Page 648 Right column - Page 649 Right Column 4 Brightener Page 24 5 Antifogging agent 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 Stin Inhibitor Page 25, right column Page 650, left to 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 I2 Coating aid, pages 26-27 Page 650, right column Surfactant 13 Static, page 27 Same Process stopper Also, for improving photographic performance with formaldehyde gas In order to prevent deterioration, US Patent No. 4,411.987 and US Pat.
It is preferable to add to the light-sensitive 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) Nl1117643, described in the patent listed in ■-C-C.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 5840739, British Patent No. 1,425,020, British Patent No. 1476.760, U.S. Patent No. 3,973,968, Japanese Patent No. 4.314,02
3, European Patent No. 4,511,649, European Patent No. 249.
No. 473A, etc. are preferred.

As the magenta coupler, 5-viladuron and viladuroazole compounds are preferred, as disclosed in U.S. Patent No. 4.31.
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 Nα24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure Nα24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Patent No. 4゜500.630, No. 4.540.654
No. 4,556,630, International Publication WO3810
Particularly preferred are those described in No. 4795 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. 121.365
No. A, No. 249°453A, U.S. Patent No. 3,446
, No. 622, No. 4,333,999, No. 4,77
No. 5,616, No. 4.45L559, No. 4,42
No. 7,767, No. 4,690,889, No. 4,2
No. 54゜212, No. 4,296,199, JP-A No. 6
1-42658 and the like are preferred.

Colored couplers to correct unnecessary absorption of coloring dyes are listed in Research Disclosure 17643.
- Section G, U.S. Patent No. 4,163,670, Special 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 during coupling; and a coupler that reacts with a developing agent to form a dye, as described in U.S. Pat. No. 4,777.1.20. It is also preferred to use couplers which have 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, EP 96,570 and DE 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 20, No. 4.576910, British Patent No. 2.102
．． It is written in Copy No. 173.

Couplers that release photographically useful residues upon cambling can also be preferably used in the present invention. DIR couplers that release development inhibitors are R[l 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.

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redonx compound releasing couplers described in JP-A-60-185950, JP-A-6224252, etc., DIR coupler-releasing couplers, D
IR coupler-releasing redox compound or DIR redonx-releasing redox compound, European Patent No. 173.30
R, D, Nα11449, a coupler that releases a dye that recolors after separation, as described in No. 2A and No. 313.308A;
No. 24241, bleach accelerator releasing coupler described in JP-A-61-201247, etc., U.S. Patent No. 4,553.47
Ligand releasing coupler described in No. 7 etc., JP-A-63-7
Couplers that release leuco dyes described in US Pat. No. 5,747, couplers that release fluorescent dyes described in US Pat. No. 4,774,181, and the like.

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'
Specific examples of high boiling point organic solvents with C or higher include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-monoamyl phenyl) )
phthalate, bis(2,4-di-amyl phenyl) isophthalate, bis(l,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (
Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridobnorphosphate, tributoxyethylhonuphat, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonates, etc.), benzoic acid esters! (2-ethylhexylhenshade, dodecylbenzoate, 2-ethylhexyl-p
-hydroxyhenzoate, etc.), amide [(N,!1
-diethyltodecanamide, N,IJ diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols [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.), and the like.

Further, as the auxiliary solvent, a solvent having a boiling point of about 30°C or more, preferably 50°C or more and about 160°C or less can be used, and typical examples include ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are disclosed in U.S. Pat. etc. are listed.

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

The present invention can be applied to various color 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, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, and the same N(L
18716, from the right column on page 647 to the left column on page 648.

In the light-sensitive 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, and even more preferably 20 μm or less. Further, the membrane swelling rate TI/□ is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness means the llI thickness measured at 25°C and 55% humidity control (2 days), and the film swelling rate TI/□ can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photogr, Sci, Eng,) by Green et al.
It can be measured by using a swellometer (swelling membrane) of the type described in Vol. 19, pp. 24-129 of 2LL, and T1
/2 is defined as the time required to reach 1/2 of the saturated film thickness, with 90% of the maximum swelling V thickness reached when treated with a color developing solution at 30° C. for 13 minutes and 15 seconds as the saturated film thickness.

The membrane swelling rate T1/2 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.

The color photographic material according to the present invention includes the above-mentioned RD,
N (pages 28-29 of L 17643, and NCL1 of the same
8716-6] 5 The development process can be carried out by the usual methods described in the left column to the right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably alkaline water containing an aromatic primary amine color developing agent as a main component. It is 8 liquids. Aminophenol compounds are also useful as color developing agents, but p-
Phenylene-based compounds are preferably used, typical examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl, 4-amino-N-ethyl-N-
〇-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-Nβ-hydroxyethylaniline sulfate is particularly preferred.

Two or more of these compounds can 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, benzothiazoles or mercapto compounds. In addition, as necessary, various preservatives such as hydroxyl amine, diethylhydroxylamine, sulfite, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, and catechol sulfonic acids are used. , organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary development such as 1-phenyl-3-pyrazolidone. Active ingredients, viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, alkylphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediaminetetraacetic acid. Acetic acid, hydroquinethyliminodiacetic acid, l-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid,
Representative examples include ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediaminedi(0-hydroxyphenylacetic acid), and salts thereof.

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-virapritones such as l-phenyl-3-virapritone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pl+ of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is 31 or less per 1 square meter of -S light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 50
It can also be set to 0- 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 of lowering the aperture ratio in this way, it is possible to install a shield such as a float on the surface of the photographic processing solution in the processing tank, as described in Japanese Patent Application Laid-Open No. 1-8
Method using a movable lid described in No. 2033, JP-A No. 6
The slit development processing method described in No. 3-216050 can be mentioned. To reduce the aperture ratio,
It is preferable to apply it not only to both the color development and black and white development steps, but also to all subsequent steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.
The amount of replenishment can also be reduced by using means to suppress the accumulation of bromide ions in the developer solution.

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 salt, 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, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired 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 iron (In) organic complex salts,
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts including ethylenediaminetetraacetic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) if salt are used from the viewpoint of rapid processing and prevention of environmental pollution. preferred. In addition, a [iron nobolicarponate (I)
[l) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (I
[[) The pH of the bleach solution or bleach-fix solution using if salt is usually 4.0 to 8, but it can also be processed at a lower pl+ in order to increase the air speed of the processing.

A bleach accelerator may be used in the bleach solution, bleach constant @ solution, and their pre-baths, 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. 53-104232
Compounds having a mercapto group or a disulfide group as described in JP-A No. 53-124424, No. 53-141623, No. 53-2842G, Research Disclosure No. Nα17129 (July 1978), etc.; JP-A-50-140129 Thiazolidine derivatives described in No.
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 No. West German Patent No. 1.127,7
No. 15, iodide salts described in JP-A-58-16.235;
Polyoxyethylene compounds described in No. 1973-
Polyamine compound described in No. 8836: Other Tokuma 1977
-42,434, 49-59,644, 53-
No. 94,927, No. 54-35.727, No. 55-2
Compounds described in No. 6°506 and No. 58-163.940; 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 Tube 1, No. 290□812, JP-A-53-
The compounds described in No. 95,630 are preferred. 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, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic 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 fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A 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 of 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 step, 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 the photosensitive material conveying means described in Japanese Patent Application No. 191259. As described in JP-A No. 60-191257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

It is preferable that the silver halide color photographic material of the present invention undergoes a water washing and/or stabilization process 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 Te! e-v
ision Engineers Volume 64, P, 24
8-253 (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 the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. Problems such as this 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
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Full volume of technology “Microbial sterilization, sterilization, and anti-mildew technology J (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 pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range 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. be able to. Examples of the dye stabilizer 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 resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the dehydration process.

In processing using an automatic developing machine etc., each of the above processing 7
If night is concentrated due to evaporation, it is preferable to add water to correct the concentration.

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 a color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
No. 1 and No. 15.159, aldol compounds described in No. 13,924, and 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 JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38"C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved.

In addition, West German Patent No. 2,226,7 for the use of photosensitive materials for both eyes
70 or US 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 can also be applied to the heat-developable photosensitive materials described in No. 9-218443, 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 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

The amount of colloidal silver or the compound of the present invention added and the silver iodide content of the silver halide grains contained in the photosensitive silver halide emulsion are summarized in (Table 1).

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rrr units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles based on moles of silver halide in the same layer.

(Sample 101) First layer (Haleyshigon prevention layer) Black colloid il! ! 0.18 Gelatin 1.40 Second layer (
Intermediate layer) 2.5-di-t-becdecylhydroquinone X-1 X-3 X-12 -1 J-2 -3 B5-1 B5-2 Gelatin third layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ Snake X-2 X-10 -1 0,18 0,07 0,02 0,002 0,06 0,08 0,10 0,10 0,02 1,04 Silver 0.25 Silver 0.25 6.9X10-'1.8X10-'3゜lXl0-' 0.335 0.020 0.07 -2 -3 B5-1 Gelatin 4th layer (second red Emulsion G Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ X-2 X-3 X-10 -1 -2 -3 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion sensitizing dye I Sensitizing dye ■ 0.05 0.07 0.060 0.87 Silver 1.0 5, lX1O-s 1.4X10-'2.3X10-' 0.400 0.050 0.015 0.07 0. 05 0.07 1.30 Silver 1.60 5.4X10-'1.4X10-' Sensitizing dye m EX-3 EX-4 EX-2 HB S-1 F (BS-2 Gelatin 6th layer (intermediate layer) ) EX-5 BS-1 Gelatin 7th layer (first green emulsion N) Emulsion A Emulsion B Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-1 EX-7 2,4X10 o, ot .

o, oa.

O,097 0.22 0゜10 1.63 0.040 0.020 0.80 i艮0.15 Silver 0.15 3.0X10-' i,oxio~4 3.8XIO''4 0.260 0. 021 0.030 EX-8 ) (BS-1 B5-3 Gelatin 8th layer (second green emulsion N) Emulsion C Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-, 6 EX-8 EX- 7 B5-1 F (BS-3 Gelatin 9th layer (3rd green emulsion N) Emulsion E Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ 0.025 0.100 0.010 0.63 Silver 0. 45 2, lX10-'7.0X10-'2.6X10-' 0.094 0.018 0.026 0.160 0.008 0.50 i艮 1.2 3.5X10-'8.0X10-' 3. 0X10-' EX-13 EX-11 EX-1 HB S -1 HB S -2 Gelatin 1st O layer (yellow filter layer) Yellow colloidal silver EX-5 B5-1 Gelatin 1] Ji (first blue-sensitive emulsion layer) ) Emulsion A Emulsion B Emulsion F Sensitizing dye ■ EX-9 EX-8 B5-1 Gelatin 0.015 0.100 0.025 0.25 0.10 1.54 0.05 0.08 0.03 0. 95 Silver 0.08 Silver 0.07 Silver 0.07 3.5X10-' 0.721 0.042 0.28 1.10 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye ■ EX-9 EX-10 f (BS-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Milk 1fqH Sensitizing dye■ EX-9 B5-1 Gelatin i4th layer (first protective layer) Emulsion I -4 -5 B5- 1 Gelatin 15th layer (second protective layer) Silver 0,45 2,lX10-' 0.154 (1,007 0,05 0,78 810,77 2,2X10-' 0.20 0.07 0.69 Silver 0.20 0.11 0.17 0.05 1.00 Polymethyl acrylate particles (diameter approx. 1.5 μm) 0.543
-1 0.20 Gelatin 1.20 In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer.

X X X H H I X-4 41 X CJ+5(n) Sensitizing dye■ Sensitizing dye m Sensitizing dye V Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ -1 rH9 -1 CH2=CH-502CH2C0NHCLCH2=CH
-5Ox CHZ C0NHCHZ Preparation of Sample 102> Sample/θ2 was prepared in exactly the same manner as Sample 10/, except that the silver iodide content of the entire photosensitive emulsion of Sample/θl was made to be more than 1,000 mols.

Preparation of sample 103> Sample lθ3 was prepared in exactly the same manner as sample 10/, except that the total silver iodide content of sample 10/ was increased by 6 moles.
was created.

Preparation of sample/θV> Sample ioa was prepared in exactly the same manner as sample 10/, except that the silver iodide content of 11 in the entire photosensitive emulsion of sample lθl was made r molar.

<Preparation of sample 101> Sample 10jr was prepared in exactly the same manner as sample /Q/ except that the silver iodide content of the entire photosensitive emulsion of sample 10/ was changed to about 10 mol.
was created.

<Preparation of sample 106> Silver iodide-containing lid of the entire photosensitive emulsion of sample /θl /! Exactly the same as sample lθ/ except that the molar ratio is increased to V, then sample lθt
was created.

<Sample 107. /10. //3. //4. //Y.

Preparation of 1 Co. 2> Colloidal silver of the first layer and the 10th layer of sample 10/ (Table-/
) Sample/
Sample lθ7゜/10 with θ/totally-'' strain, //
3, //6, //9, /22f were produced.

Test, j+101. ///, //←, //7. /20°/23 Preparation> Colloidal silver of the 1st layer and 10th layer of sample ioz (Table 7
Sample i except that it can be replaced with the exemplified compound of the present invention described in )
Try P+/Or in exactly the same way as oi.

/// , //≠, //7. /, 20.723 was created.

<Sample 10F, //2. //ta, i/r, /+2/.

/241 Preparation> Colloidal silver of #1 and #10 of sample ior (Table-/
) Sample i except for replacing it with the small invention exemplified compound described in K.
Sample/θ2°t/2. //j,/
/r, /2/, /24tf were created.

<Preparation of samples /21, /26, /J7> Sample 107
Sample/2! is a total photosensitive emulsion with a silver iodide content of 2 moles more! , t mol% sample /26, /! The sample was converted to mol% and was designated as 27 samples.

The silver iodide content of the photosensitive silver halide emulsion was adjusted by changing the iodide ion weight added to the silver halide grain forming 58VC.

Fine powder dye dispersion 8-/~S-tco v411! ! The legal dye was dispersed in a vibrating ball mill according to the following method.

Water (2/, 7Rt) and! Multi-aqueous solution of p-octylphenoxyethoxyethoxy7ethane/sulfonic acid N-da3red,! Poly-aqueous solution of p-octylphenoki 7 poly(degree of polymerization 'θ) oxyethylene ether O0! Add the dye of the present invention to a 700 tal bottom mill.

Beads of OOg and zirconium oxide (diameter/mm)
! θ0rnlf was added and the contents were dispersed for t-2 hours. The vibrating ball mill used was a BO type manufactured by Chuo Kakoki.

Take out the contents, /2. j% gelatin aqueous solution rg and the beads were filtered to obtain a dye seratin dispersion.

When using a mixture of two or more dyes, each dye was mixed in equal weight ratio.

The sample lθl~/26 thus produced was evaluated as follows.

(1) Preservability evaluation sample /Q/-/J4 o 'C and! θ0C! ! S.R.H.
After being left in the atmosphere for 3 days, it was exposed to white light through a continuous wedge and developed as described below. Then, the density of cyan, magenta, and yellow is measured and the lowest density If (Dm
in) f was calculated. The minimum concentration change due to changes in storage conditions was determined as follows.

Cyan coloring flAK change LDmin (R) - Dmin (to°Cjj%R)l preservation) - Dmin (O'C preservation) Magenta coloring ay change △
Dmin(G), yellow color density change △Dmin(
B) was also determined in the same manner. The results are shown in Table 1.

(2) Interimage effect evaluation sample 10/~/
The roller was exposed to red light through the continuous wedge and subjected to the following development process. Next, the three colors of light were adjusted so that the sample was exposed and developed with white light (red light + green light + blue color tone) and was passed through a continuous wedge so that the sample 10/-/J
4 was exposed to light and developed in the same manner. In addition, the exposure amount of red light during red FT exposure and the red light during white exposure was the same.

The density of the developed sample was measured, and the density was measured when exposed to red light and when white f! ! ,party&! The cyan intensity at the time of light was Dmin+/, and the difference in exposure amount Δlog E(R) was determined as an interimage effect on the red-sensitive silver rhodanide emulsion.

In the same manner, the interimage effect on the green-sensitive Roge/silver oxide emulsion layer and the positive-sensitivity silver oxide emulsion layer was determined. These results are shown in Table 2 and 4.

Processing process 4) Supplementary light i1: per Jjmm width of photosensitive material/m length.

(Color developing solution) Mother solution G) Replenisher solution) Hydroxyethyliminodic acid! , O 6,0 Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine/sulfate Goo[N-ethyl-N-β-hydroxyethylamino]-2-Methylaniline Sulfate Add aqueous solution to pH (bleach solution)/ ,! -diaminopropanetetraacetic acid ferric complex salt/, J-diaminopropane/tetraacetic acid ammonium bromide φ, 0 3θ, O /, J 18,2η 2.0! ,! 37.0 θ,! 3.6 7.0×/θ-2 mol/, JX/θ-2 mol/, θl/θ, θθ Mother liquid G) /30 J, (7 r!/, θl/θ, l! Replenisher liquid Po) /? θg, θlkoθ acetic acid! O Ammonium nitrate 30 Add water /, 01 Intoxication and ammonia pl-14<, JpHIiIJ
Adjustment (fixer) 7θ cO 1, θj pH3,! Mother liquor G) /-Hydroxyethyl 2.0 Den-/, /-Diphosphonic rice ethylenediamine 4I! l [o, r Modified disodium salt sodium sulfite 10-θ Bitonite 8L enemy sodium r,.

Ammonium thiosulfate /70.01R1 water bath! ftA
7001/l) Rhodan ammonium ioo,.

Thiourea 3.0 3.6-Sithia/, J, (17r-octanediol replenisher G) 7.0 θ, 7 /2.0 /θ+0 200, θml /10-0! ,θ! , O Add water and ammonium acetate to pH (Stable solution) Mother solution, replenisher Common formalin (37%) Terchloro-2-methyl-←-inthiazoline-3-oncomethyl-ψ-inthiazolin 3-one surfactant /, Ol 6,! /, 2111 t, o 3.0 da θ, da t, ol 6.7 Ethylene glycol /, 0 Water was added to pH /, ol 1.0-7 + θ (Table 2). 107, 10f, /
10. ///, //! , //u, //l.

//7. //も, /20, /22, /23
, /2! , /24, it can be seen that the change in minimum density due to changes in storage conditions is small, and photographic performance with a large interimage effect is achieved.

Example B Preparation of Sample 201 A multilayer color light-sensitive material consisting of each layer having the following composition was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm, and designated as Sample 201. The numbers indicate the amount added per unit, and the effects of the added compounds are not limited to the described uses.

The amount of colloidal silver or the compound of the present invention added and the silver iodide content of the silver halide grains contained in the photosensitive silver halide emulsion are summarized in (Table 3).

1st layer: Antihalation layer Black colloidal silver 0.25g Gelatin 1.9g Ultraviolet absorber U-
10,04g Ultraviolet absorber U-20,1g Ultraviolet absorber U-30,1g Ultraviolet absorber U-60,1g High boiling point organic solvent ○1l-10,1g 2nd layer: Intermediate layer gelatin 0°0g Compound Cpd- D 10 mg High boiling point organic solvent ○ 11-340 mg 3rd layer: Fine grain silver iodobromide emulsion covered with intermediate layer (average grain size 0.06 gm, Ag I content 1 mol%) Silver 1
0.05 g gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.4 gm, Ag I content 4. (1:1 mixture of 5 mol% monodisperse cubes and monodisperse cubes with average particle size 0.3 μm and Ag+ content 4.5 mol%) Gelatin coupler C-1 Coupler C High boiling point organic solvent 0i1-2 5th layer : Medium-sensitivity red-sensitive emulsion layer silver amount 0.4g 0,8g 0.20g 0.05g 0.10g Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0) .5 μm, monodispersed cubes with Agl content of 4 mol%) Silver content: 0.4 g gelatin
0.8g Coupler C-10.2g Coupler C-20.05g Coupler C-30.2g High boiling point organic solvent 0i1-20.1g 6th layer: High sensitivity red-sensitive emulsion layer sensitizing dyes S-1 and S-2 Silver iodobromide emulsion spectrally sensitized with (monodispersed twin grains with average grain size 0.7 μm and Agl content 2 mol%) Gelatin coupler C-3 Coupler C-1 7th layer: Intermediate layer gelatin dye D-1 8th layer: Intermediate layer silver amount 0.4g 1,1g 0,7g 0,3g 0゜0゜g 2g Fogded silver iodobromide emulsion (average grain size 0.06μm, Ag
! Content 0.3 mol%) 0.02g gelatin
1.0g Color mixing prevention agent Cpd-A
0.2g 9th layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size 0.4 μm, Ag l content 4.5 mol%) A 1:l mixture of monodisperse cubes and monodisperse cubes with an average particle size of 0.2 μm and an AgI content of 4.5 mol%)
Silver amount 0.5g gelatin
0.5g Coupler C-40, 20g Coupler C-70, 10g Coupler C-80, Log Compound Cpd-BO O, 03g Compound Cpd-E O, 02g Compound Cpd
-F 0.02g Compound Cpd-G
O,02g Compound Cpd-H0,02
g High-boiling point IIa solvent 041-10.1g High-boiling point organic solvent ○1l-20.1g 10th layer: Medium-sensitivity green-sensitive emulsion layer Silver iodobromide spectrally sensitized with sensitizing dyes S-3 and S-4 Emulsion (monodisperse cubic with average particle size 0.5 μm and Agl content 3 mol%) SiI 2.4 g gelatin
0.6g Coupler C-40, 1g Coupler C-70, 1g Coupler C-80, 1g Compound Cpd-B O, 03g Compound Cpd-E 0. 02g Compound Cp
d-F 0102g Compound Cpd-G
O,05g Compound Cpd-HO,0
5g High-boiling point j11 solvent 04l-20, O1g 11th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size when converted to spheres: 0.5g) 6 μm, Agl content: 1.3 mol%, monodisperse plate with an average value of diameter/r!L of 7)
w&IO, 5g gelatin coupler C-4 coupler C-7 coupler-C-8 compound Cpd-B compound CPd-E compound Cpd-F compound Cpd-G compound Cpd-H high boiling point organic solvent 0i1-1 high boiling point organic solvent Of ! -2 12th layer: Intermediate layer gelatin dye D-2 13th layer: Yellow filter layer Yellow colloid t! ! Silver amount Gelatin Color mixing inhibitor Cpd-A High boiling point organic solvent 0i1-1 14th layer: Intermediate layer g g g g 8g 2g 2g 2g 2g 2g 2g 5g g g 1g 1g Gelatin 0.6g 15th layer:
Low-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Average particle size 0.4μm, contains Agl! 1:l mixture of 3 mol % monodisperse cubes and monodisperse cubes with average particle size 0.2 μm and Agl content 3 mol %) Silver amount 0.6 g Gelatin 0.8 g Coupler C
-50.6g High boiling point organic solvent ○1f -20.02g 16th layer: Medium-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Monodispersed cubes with average particle size 0.5 μm and Agl content 2 mol%) Silver amount 0.4 g gelatin
0.9g Coupler C-50, 3g Coupler C-60, 3g High boiling point organic solvent ○ 1l - 20.02g 17th layer: Highly sensitive blue-sensitive emulsion layer Sensitized with sensitizing dyes S-5 and S-6 Iodobromide emulsion (tabular grains with an average grain size of 0.7 μm in terms of spheres, Agl content of 11.5 mol%, and an average diameter/thickness value of 7)
Silver amount 0.4g gelatin
1.2g coupler C-60, 7g 18th layer: 1st protective layer gelatin 0.7g ultraviolet absorber U-1 0.04g ultraviolet absorber U-3
0,03g Ultraviolet absorber U-40,03g Ultraviolet absorber U-50,05g Ultraviolet absorber U-60,05g High boiling point organic solvent ○1f-10,02g Formalin scavenger Cpd-C0,8g Dye D-30 ,05g No. 19N=Fine grain silver iodobromide emulsion covered with second protective layer (average grain size 0°06μ
m, Agl content 1 mol%) Silver amount 0.1 g gelatin
0.4g 20th layer: Third protective layer gelatin 0.4g polymethyl methacrylate (average particle size 1.5 μm) 0.1 g 4=6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5 μm) 0.1g silicone oil 0.03g surfactant W-13,
0■ In addition to the above composition, gelatin hardener 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.

-2 H R H -4 (CHz -CHhT----1 → CH! -CH knowledge.

-5 -6 C-7 Kabra-C H 11-1 Dibutyl phthalate 11-2 Tricresyl phosphate pd-A H pd-B pd-C pd-D H pd-E CsH+ + (t) pd-G H3 CH t13 L+I+1 1 -2 -4 -6 ■ -2 -4 C-, HS -5 tHs SOJN(CJs)z -2 )υ3K bu ni-3 H-1 CHz=CH5OzCHzCONHCHzCHx=CH
S(hC)IzCONHGHz-1 L <Preparation of sample 2θ> Sample 20/1st pigeon, 1st pigeon! layer, second layer, first O layer, first
Sample 2θ2 was prepared in exactly the same manner as Sample θ/, except that the silver iodide content t of each photosensitive silver halide grain in the / layer, the first T layer, and the 17th layer was made to be more than 2 moles.

Preparation of Sample No. 03> The silver iodide content of the total photosensitive emulsion of Sample P20/ was reduced to 6 mol%V.
Sample 203 was prepared in exactly the same manner as sample θl except for rubbing.

Preparation of Sample 204t Sample 20g was prepared in exactly the same manner as Sample 2θ/, except that the silver iodide content of the total photosensitive emulsion of Sample 2θl was changed to g moles of gold.

Preparation of Sample 20/ Sample 2 was prepared in exactly the same manner as Test j#+2θ/ except that the silver iodide content of the total photosensitive emulsion of Sample 20/ was made to be more than lθ molar.
01 was produced.

Preparation of sample 2θ6> Silver iodide content of all photosensitive emulsions of sample 20/! Sample 2θ6 was prepared in exactly the same manner as sample 2θ/, except that the molar ratio was increased.

<Samples 207, 210. Ko/3, 2/bu, 2/9゜2.
Preparation of 22〉 Colloidal silver of the 1st pigeon and 13th f@ of sample θl (Table-
Sample 21177゜/θ
2/3,. 2/4.2/W, 222 was produced.

Sample 201, co//, 2/u, λ/7, 220°1
Preparation of Sample 23> Sample 2θ3 was prepared in exactly the same manner as Sample θ3 except that the colloidal silver-gold of the 13th JZ (Table 3) was substituted with the exemplified compound of the present invention.

2/ / , 2/It , 2/7.220.223f were produced.

Test f420Y, 2/2.2/! , 2/r, 22/.

Preparation of 22-tei> Sample Q! Sample lθ! except that the colloidal silver in the 1811th and 13th layers of was replaced with the unexploded #iA exemplary compound listed in (Table 3). Sample 2θ was prepared in exactly the same manner as 2/2.2
1! , 2/l', 22/, and 2211f were prepared.

Sample 22! , Coit, Co27> Sample 22! The entire photosensitive emulsion of Sample 2θ7 was made up of 2 moles of silver iodide-containing dozen! , sample 2 with r moles, /! Sample 227 was obtained by increasing the molar ratio.

The silver iodide content of the photosensitive silver halide emulsion was controlled by changing the amount of iodide ions added during the formation of silver halide grains.

Preparation of Fine Powder Dye Dispersion 8-/-5-72 The dye was dispersed in a vibrating hole mill by the following method.

Water (2/, 7R1> and! An aqueous solution of p-octylphenyl/ethoxyethane sulfone [7-ta3,! Aqueous solution of p-octylphenyl/poly(car body aiO) oxyethylene ether θ, !g and f700ml The dye of the present invention/in a bot mill.

00g and zirconium oxide beads (diameter/mm)! O
θ Red whole meat was added and the contents were dispersed for 2 hours. The vibrating ball mill used was a BO type manufactured by Chuo Kakosei.

Take out the contents, /2. ! % Seratin aqueous solution rg and the beads were filtered to obtain a dye gelatin dispersion.

When using a mixture of two or more dyes, VC was mixed so that each dye was in an equal weight ratio yc.

The sample 0/~42t thus produced was evaluated as follows.

(1) Preservability evaluation sample J, 0/-22tfO'C and ro oczz%r
After being left in an LH atmosphere for 3 days, it was exposed to white light through a continuous wedge and developed as described below. Then, measure the density of cyan, magenta, and yellow, and measure the maximum density (D
max) was calculated. All changes in maximum concentration due to changes in storage conditions were determined as follows.

Cyan color development m degree change Dm a x (R) = Dm a x (θ0C preservation)
-Dmax (tO'C, 1% RH storage) Magenta color density change △Dmax (Gl, Yellow color density change △
Dmax (Bl was also determined in the same manner.

The results are shown in Table ≠.

(2) Evaluation of interimage effect Sample 20/~2tVC red color was exposed through a continuous wedge and developed as described below. Did. Next, white light (red party tenen color candle +
Samples 20/-226 were exposed to light and developed using three colors of 9 vI41i and passed through a continuous wedge so that the sample turned gray, and the sample was developed in the same manner. Note that the exposure amounts of red light during red light exposure and red light during white light exposure were the same.

The density of the developed sample was measured, and the difference in exposure amount △l was found when the cyan density was /, 0 when exposed to red light and when exposed to white light.
og E(R) was determined as an interimage effect on the red-sensitive silver halide emulsion layer. In the same manner, the interimage effect on the green-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer was determined.

These results are summarized in (Table ←).

[Development process]

Black and white development in 6 minutes! r'C/21 2.2 l/m
2 First water washing 21 31 11t 7.
1 reversal 21 31' 1At /, /color development 6'! r' /21 2.2 adjustment ν
H←1 Ha/ Bleach 61 31' /21
0.2.21 constant N4 (min 31 'CIl
/, / l/m2 2nd water wash 4tl 31'
J'l 7. The composition of each treatment solution was as follows.

black and white development Nitrilo-N, N, N- trimethylene phosphone acid·! sodium salt sodium sulfite hydroquinone monos Potassium sulfonate Ko, 01 2. Og 0g ! 0fl Ko Og koθl potassium carbonate /-phenyl-ψ-methy Ru←−Hydroxyme Chil-3-pyrazolide hmm potassium bromide Potassium thio7anate potassium iodide add water 39 2.0g ! , ! ;f1 7.2g λ, □ta9 3g 2.09 /, ig 7.2g pH ri, zOta, 1r0 The pH is T! i! A-conditioned with acid or potassium hydroxide.

reversal liquid Nitrilo-N, N, N- trimethylene phosphone Gi Tanatorium Basin Negative tin monohydrate salt p-aminophenol Sodium hydroxide 3.0g /, 09 o,ig to mother liquor Direction glacial acetic acid /tm/V pHt, 0θ The pH was adjusted to 11 with hydrochloric acid or sodium hydroxide.

Color developer Nitrilo-N, N, N- trimethylene phosphone Ei・! sodium salt Sodium drink ] Trisodium chloride 12 water salt potassium bromide potassium iodide Sodium hydroxide Ntrazine awakening N-ethyl-(β-meta) sulfonamidoethyl )-3-methyl-g -aminoaniline sulfate d, 0g 2.0g 7.09 7.0g tg tp /, θθ Deθ■ i,og 1. Ri I 11g 3.0g /, rig 11g t-dithia-7 , r- /, 0g /,Ofl octanediol pH //, 10 /2. θO pJ(ha, Adjusted with hydrochloric acid or potassium hydroxide.

Adjustment liquid Ethylenediaminetetraacetic acid ! , θg to mother liquor ! Sodium salt 2 Direction water salt sodium sulfite /2,9 1-thioglycerin θ, ψmt Sorbitan ester* θ, /l/ pH 69,2θ p11, Adjustment was made with hydrochloric acid or sodium hydroxide.

red and white liquid Mother liquor replenisher Ethylene diamine ψ citric acid Ko, Og ψ, θg ・Disodium salt ・2 water salt Ethylenediamine←acetic acid ・Fe(III)・Ammo nium dihydrate salt potassium bromide ammonium nitrate /+20g oofj 10! ! 2φOθ ,zoog 2θI pH6,70j,jO pH was adjusted with hydrochloric acid or sodium hydroxide.

Fixer ammonium thiosulfate r, oy Sodium acid s, oi Sodium bisulfite r, og Mother liquor pH 6,60 pH is stabilized with hydrochloric acid or aqueous ammonia.

Mother liquor replenisher formalin (37%) j, ONl Mother liquor contains polyoxyethylene-p O0! Red same monononylphenyl ether (average electrical degree/θ) Sorbitan ester (w + x + y + z - θ) As shown in (Table-j), samples 207, 20If, 2
10, 2//, 2/3, 2/4t, 2/l.

J/7.2/ri, 2λθ, 22.2.223.22,
It can be seen that in the case of 2-color, there is little change in maximum density due to changes in storage conditions, and photographic performance with a large interimage effect is achieved.

slender man on a boat Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] At least one hydrophilic colloid layer has the following general formula (I
), (II), (III), (IV), (V) and (VI); Emulsion A silver halide color photographic material characterized in that the average silver iodide content of silver halide grains in the emulsion is 8 mol% or less. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (III) A=L_1-(L_2=L_3)_n-A' General formula (I
V) A=(L_1-L_2)_2_-_q=B General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A and A' may be the same or different and each represents an acidic nucleus; B represents a basic nucleus; X and Y may be the same or different and each represents an electron-withdrawing group.
represents a hydrogen atom or an alkyl group, R_1 and R_2 each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and R_1 and R_2 may be linked to form a 5- or 6-membered ring. R_3 and R_6 each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group, or a halogen atom, and R_4 and R_5 each represent a hydrogen atom or R_1
represents a group of nonmetallic atoms necessary for R_4 or R_2 and R_5 to connect to form a 5- or 6-membered ring. L_1,
L_2 and L_3 each represent a methine group. m represents 0 or 1, n and q each represent 0, 1 or 2, p represents 0 or 1, when p is 0, R_3 represents a hydroxy group or a carboxyl group, and R_4 and R_
5 represents a hydrogen atom. B' represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group. However, the compounds represented by general formulas (I) to (VI) have dissociative properties that have a pKa in the range of 4 to 11 in a mixed solution with a volume ratio of water and ethanol in one molecule of 1:1. It has at least one group. )