JPH03296050A - Silver halide photographic sensitive material having superior rapid processability, improved color retention and shelf stability - Google Patents

Abstract

PURPOSE:To improve rapid processability, color retention and shelf stability by incorporating >=10mol% silver chloride into a silver halide emulsion and dispersing a hydrophobic coupler having low mol. wt. in a solid state. CONSTITUTION:At least 10mol% silver chloride is incorporated into the silver halide emulsion of at least one of constituent layers and a hydrophobic coupler having low mol. wt. is used as a coupler in the same layer and dispersed in a solid state. The dispersed coupler does not practically contain a coupler solvent such as a high b.p. solvent in the dispersed coupler particles. The silver halide emulsion layer contg. the dispersed coupler is made to exist on the base with one or more silver halide emulsion layers in-between. A color photographic sensitive material for photographing having superior rapid processability, improved color retention and shelf stability can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic material, and more specifically, a silver halide color photographic material which has excellent rapid processability and improved color retention and storage stability. Regarding materials.

(Prior Art) Silver iodobromide emulsions have conventionally been widely used in color photographic materials. Silver iodobromide emulsions have excellent characteristics such as high sensitivity and good graininess, and have been considered indispensable for photographic light-sensitive materials. However, with the rapid spread of rapid development processing in recent years, light-sensitive materials using silver iodobromide emulsions are becoming an impediment to rapid processing.

-Although it was known that silver halide emulsions containing silver platelets had excellent rapid processing properties, they generally had low sensitivity and could not be used in glass-photographic materials for photography. .

However, in recent years, research on sensitization of silver halide containing silver chloride has progressed, as disclosed in JP-A-63-264749 and JP-A-63-2129.
32. As seen in Japanese Patent Application Laid-Open Nos. 2-43534 and 2-43535, research has been conducted on the application of this method to color photographic materials for photographing. Although light-sensitive materials using silver halide emulsions containing silver chloride have excellent rapid processing properties, they have drawbacks such as high residual color after printing due to the use of sensitizing dyes and poor storage stability over time under high humidity. It had

(Object of the Invention) The object of the present invention is to improve the above-mentioned drawbacks of light-sensitive materials containing silver chloride, and to provide a color photographic light-sensitive material for photographing that has excellent rapid processing properties and improved color retention and storage stability over time. It's about doing.

(Structure of the Invention) An object of the present invention is to provide a silver halide color photographic material comprising constituent layers containing a silver halide emulsion and a coupler coated on a support, wherein at least one of the constituent layers A halogen characterized in that the silver halide emulsion of the layer contains at least 10 mol% or more of silver chloride, and the coupler contained in the same constituent layer has a low molecular weight, is hydrophobic, and is dispersed in a solid state. The inventors of the present invention have discovered that this can be achieved using silver oxide color photographic materials.

The silver halide emulsion contained in the photographic constituent layer according to the present invention contains at least 10 mol % or more of silver chloride, preferably 50 mol % or more, particularly preferably 9 mol % or more.
It is 5 mol% or more. As the silver halide other than silver chloride, silver bromide is preferred, but silver iodide may be contained in an amount of 15 mol % or less. When silver iodide is contained, it is preferable that silver chloroiodide, silver iodobromide, or silver chloroiodobromide be localized inside the silver halide grains. silver iodide is 2
It is preferable that the amount is between 10 mol% and 10 mol%.

The coupler contained in the photographic constituent layer according to the present invention is dispersed in a solid state.

In the present invention, a coupler dispersed in a solid state means that the dispersed coupler particles do not substantially contain a coupler solvent such as a high boiling point solvent, and "substantially free of coupler solvent" means that the coupler particles are substantially free of a coupler solvent such as a high boiling point solvent. The content (weight) of the coupler solvent is 20 or less, preferably 5% or less, based on the weight of
Particularly preferably, it is 1% or less.

In the present invention, the average particle size of the coupler dispersed in a solid state is preferably 0.1 layer m to 0.6 μm, particularly preferably 0.15 μm or more and 0.3 μm or less.

The silver halide emulsion layer containing a coupler dispersed in a solid state according to the present invention is preferably applied to an emulsion layer separated from the support by sandwiching one or more silver halide emulsion layers, and particularly preferably. It is preferable that the two layers are separated by two or more layers.

Further, the silver halide emulsion layer containing a coupler dispersed in a solid state according to the present invention may be other than the highest sensitivity layer when substantially the same color-sensitive layers are composed of two or more layers having different sensitivities. Preferably, it is particularly preferably the lowest sensitivity layer.

In the present invention, the coupler having a low molecular weight refers to a coupler having a molecular weight of 2,000 or less, preferably 1,000 or less.

In the present invention, a hydrophobic coupler is defined as distilled water at 25°C.
The solubility in 00g is 0.1g or less, preferably 0.0g.
0.01g or less, particularly preferably 0.0O19 or less.

Particularly preferred couplers are those having no sulfonic acid group, carboxylic acid group, or phosphoric acid group.

The silver halide color photographic light-sensitive material according to the present invention is preferably formed by coating red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers on a support. Green sensitivity and blue sensitivity are 600-750, respectively.
It has maximum spectral sensitivity in the wavelength ranges of 500 to 600 nm, and 400 to 500 nm, and is controlled by commonly used photographic sensitizing dyes.

As the sensitizing dye, monomethine or trimethine cyanine dyes are preferably used.

In the silver halide color photographic light-sensitive material according to the present invention, the arrangement of the color-sensitive layer on the support is arbitrary, but the following arrangement is particularly preferred.

■ Antihalation layer, (intermediate layer),
Red photosensitive layer, (intermediate layer), green photosensitive layer, (intermediate layer), yellow filter layer, blue photosensitive layer, (intermediate layer), protective layer.

■ Antihalation layer, (intermediate),
A first red photosensitive layer, (intermediate layer), a first green photosensitive layer, (intermediate layer), a second red photosensitive layer, (intermediate layer), a second green photosensitive layer,
(intermediate layer), yellow filter layer, blue sensitive layer, (intermediate layer), protective layer.

■ Colloidal silver antihalation layer, (
(intermediate layer), first red-sensitive layer, (intermediate layer), first M! Photosensitive layer, (intermediate layer), first blue photosensitive layer, (intermediate layer), second
Red photosensitive layer, (intermediate layer), 21st & photosensitive layer, (intermediate layer), (yellow filter layer), 2nd blue photosensitive layer, (
intermediate layer), protective layer.

In the above example, 0 may be omitted.

Further, each emulsion layer may be divided into two or more layers having different sensitivities. When the same color-sensitive layer is composed of two or more layers having different sensitivities, it is preferable that the sensitivities are sequentially increased from the layer closest to the support to the outermost layer.

Bonds that are cleaved under alkaline conditions in couplers preferably used in the present invention include ester bonds and sulfonyloxy bonds.

Couplers having the above-mentioned cleavable bond at the terminal portion of the molecule are particularly useful.

-1 -3 U2 -5 -6 shiυ○shi+hHko3(n) CHzCOOC4Hs(n) CHxCOOC3HvCn) A -1゜ A-11 7 -18 0 I'+3 -14 5 -16 In addition to the above, the present invention includes: You can also

CHzCHzCOOCHs Using the following couplers -9 B-6 k 0 -8 and U In the present invention, the method for obtaining a solid fine particle dispersion of couplers is as follows: (1) As a precipitation method, the coupler is dissolved in a water-miscible organic solvent. (2) A mechanical pulverization method in which the coupler is pulverized using high energy such as ultrasonic waves, and then dispersed in a neutral or acidic water or hydrophilic colloid solution. There are methods such as dispersing the coupler in a colloidal solution, wetting the coupler in water or a poor solvent, and dispersing the coupler into fine particles using a mill.

In the present invention, devices for dispersing solid fine particles include ball mills, roll mills, sand mills, etc.
A sand mill is preferred. A wide range of commercially available sand mills can be used, and a representative example is the Dyno Mill manufactured by Shinmaru Enterprises.

Materials for the media used in the present invention include glass,
Examples include alumina, zirconia, agate, stainless steel, and nylon, with glass, zirconia, and alumina being preferred. When glass is used, it is particularly preferable to use glass containing 60% by weight or more of silicon dioxide.

The media is preferably spherical, and the particle size is not particularly limited, but is usually 0.1 m + o - 20 mm5, preferably 0.2 mm.
5-10 mm l, particularly preferably 0.5 mm l ~5
．． It is 0 mm-.

Specifically, examples of the glass media include Bright Glass Peas manufactured by Prite Saiban Kogyo Co., Ltd.

When solid fine particle dispersion of the coupler is carried out, a preferable solid fine particle dispersion can be obtained by carrying out the dispersion at a high temperature. The temperature during dispersion is usually 30°C or higher, preferably 40°C or higher, particularly preferably 50°C or higher and 80°C or lower. Temperatures higher than 80° C. are undesirable because aggregates may occur or the coupler may deteriorate.

In the present invention, the hydrophilic colloids used when preparing the solid fine particle dispersion of the coupler include those having high protective colloid properties, such as gelatin, gelatin derivatives, albumin, casein, gum arabic, poly-N-vinylpyrrolidone, and hydroxyl colloids. Methyl cellulose, polyacrylamide, polyacrylic acid, etc. can be used, but
In the precipitation method, gelatin is preferred, and in the mechanical grinding method, polyN-vinylpyrrolidone is preferred.

In the present invention, it is preferred that an acid, particularly an organic acid, such as acetic acid, citric acid, oxalic acid, tartaric acid, etc., be added to the coupler solid fine particle dispersion or hydrophilic colloid solution.

The water-miscible solvent is not particularly limited as long as it can dissolve the photographic reagent without decomposing it and is miscible with water. Typical examples include alcohols (e.g. methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, diacetone alcohol, ethylene glycol motuptyl ether, etc.), glycols (e.g. ethylene glycol, dethylene glycol, propylene glycol) ), cyclic ethers (e.g. dioxane,
(eg, tetrahydrofuran, etc.), nitriles (eg, acetonitrile, etc.), amides (eg, dimethylformamide, etc.), and N-methyl-2-pyrrolidone. From the viewpoint of dispersion stability, n-propyl alcohol is preferable.

In the light-sensitive material of the present invention, at least one coupler may have a low molecular weight and be hydrophobic, and other couplers such as high molecular weight couplers may also be used in combination.

In addition to the above-mentioned various dispersion methods, the high molecular weight coupler may be added by producing the coupler as a latex polymer and adding it.

The anionic surfactant preferably used as a dispersant for the coupler according to the present invention has the following general formulas [I] to [
VI], and these are particularly preferably used.

General formula II] [Wherein, R represents a hydrogen atom or a methyl group;

and R1 each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, which may be the same or different, and W is -COO
M1SOsM10PO(OM)z is represented, and M represents a hydrogen atom or a cation. ml represents an integer of 0 to 5Q(7), or n represents an integer of 0 to 4. [11] [In the formula, R represents a hydrogen atom or a methyl group, R1 represents an alkyl group or an alkenyl group having 6 to 20 carbon atoms, and W is 1000M, -3o3M, -0PO (OM)
.

, and M represents a hydrogen atom or a cation.

m2 represents an integer from 0 to 50, R2 represents an integer from 0 to 4,
Further, a represents an integer of 0 or l. ] General formula [II[] [wherein R6 and R9 each have 6 to 20 carbon atoms]
represents an alkyl group, and M represents a hydrogen atom or a cation. general formula [VI] [wherein R6 and R6 each have 6 to 18 carbon atoms]
represents an alkyl group, and M represents a hydrogen atom or a cation. 1 General formula [IV] In the formula, R1 represents an alkyl group having 6 to 2 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, and X represents C00M or -5O,M, Moreover, M represents a hydrogen atom or a cation. n represents an integer of 1 to 4.

] General formula [V] R - (J (-Ltl : 1) lJ3 to 1 or a cation.] Each of the alkyl groups represented by R1 to R1□ includes those having a substituent, and in this case, the number of carbon atoms does not include the substituent.The cations include sodium ion, Examples include potassium ion and ammonium ion.

Among those represented by general formula [I] to general formula [1], particularly preferred are those represented by general formula [I], general formula III], and general formula [V].

Examples of specific compounds will be listed next, but the invention is not limited to these.

-1 a-2 -3 -4 Cr 2H! s-0+CH2CHzO 升云CHzh
SOJ-5 C16H330 (CHzCHzOh 云CH2+rSOs
Na-5 CrzHx, 05OsNa -7 CrJza o-+cH,cH,o)-r SO,N
aCrrHzs-C-0+CH,CH,O)75o3N
a1 2 -13 -14 5 -16 I'I! CrJssOP(ONa)2 As a nonionic surfactant preferably used as a dispersant for the coupler according to the present invention, H
A nonionic interface that combines a substance with an LB value of 1 to 7 and a substance that is substantially insoluble in water, that is, a hydrophobic substance, and a substance with an HLB value of 8 to 20 and a substance that is substantially water-soluble or hydrophilic. Preferably, the active agent has an HLB value of 1 to 7 and 8 to 20, respectively, according to griffin, and its formula structure is not particularly limited as long as it falls within these ranges. Also,
The surfactant is particularly preferably one that is in a liquid state at 25°C, but even if it is solid at 25°C, any surfactant that becomes liquid in a dispersed state can be used within the scope of the present invention.

If the HLB value exceeds 20, it is not only impossible to obtain good dispersibility but also economically unfavorable.

Concerning the nonionic surfactant used in the present invention, specific compounds are listed, but those listed here are examples of the most preferred ones, and the present invention is not limited thereto.

First, specific examples of nonionic surfactants having an HLB of 1 to 7 will be given.

N-1 Sorbitan monolaurate -2 -3 -4 -5 -6- 7- -9 -1O - II - 12 N-13 Sorbitan monooleate Sorbitantol oil fatty acid ester Sorbitan castor oil fatty acid ester polyoxyethylene oleate Polyoxygen 7 Ethylene Olive Oil Fatty Acid Esters with 5 or Less Ethylene Oxide Chains (hereinafter abbreviated as n) =1-6) Polyoxyethylene nonylphenyl ether (n-2-6) Polyoxyethylene oleyl ether (n-2-6) N-14 polyoxyethylene sorbitol fatty acid ester (n-2-6) N-45 glyceryl Monoalkyl ether (alkyl group has 8 to 18 carbon atoms) N-16 polypropylene oxide N-17 oxyethylene/oxypropylene block polymer (ethylene oxide weight% 5%) Next, a nonionic surfactant with an HLB of 8 to 20 Specific examples of agents are given below.

n I CraHsyO+CHxCHxOho H
n 2 C+5HsyO(CH2CJO%g Hn
3 CrsHsgOecHzcHzhs Hn
4 CrzHzsOecHzcHzohs Hn
-5 -6- 7- n 9 CrrHzsCOO%CH2CJO)
zo Hn − 10 C+5HsyOO−(−
CH2CHzO)xo Hn-11 Polyoxyethylene sorbitan monolaurate (n = 20) n 12 C+J*sCON[(CHzCHzO)
2 o H]! n-13 Oxyethylene/oxypropylene block polymer (ethylene oxide weight % 40%) The surfactant used as a dispersant for the coupler according to the present invention is used in an amount of 0.1 to 15 weight % based on the coupler.

Particularly preferred activators include those having three or more ethyleneoxy groups and a hydrocarbon moiety having 6 to 24 carbon atoms, with anionic activators being particularly preferred.

The most preferred surfactants include di-alkali metal salts of half esters of sulfosuccinic acid and alkoxy alcohols or aryloxy alcohols, particularly dialkali metal salts of half esters of sulfosuccinic acid and alkoxy (preferably alkoxy having 10 to 12 carbon atoms) alcohols. The disodium salt of the ester is preferred.

Particularly preferred surfactants are illustrated below.

〔item〕

Normal composition manufacturing method epitaxial (page of RD308119) 993 I-A section 993 I-A section and 994E section 93 I-A section Q: 10-12, m: 3-5 Aerosol A 102 (manufactured by Cyanamide) m: 5 ~1
0 Aerosol A 103 (manufactured by Cyanamide) CrJ2i
0 (CJCH20%3 SO3Na Polystep B
23 (Stepan Chemical Co., Ltd.) In the present invention, the silver halide emulsion is prepared according to Research Disclosure 30811.
9 (hereinafter abbreviated as RD308119) can be used.

The table below shows the locations.

Halogen conversion Negative/positive sensitive material (contains internal fog particles) to which monodisperse solvent containing halogen-substituted metal is added Desalting using mixed emulsion I -C section 1 -C section I -D section I -F section I -F section I - Section 8 I - Section 8 I-J Section n-A Invention J: In the silver halide emulsion used, it has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17643. No. 18716 and No.
308119 (each hereinafter referred to as RD17643.RD
18716 and RD308119).

The table below shows the locations.

[Item] (Page of RD308119) Chemical sensitizer 996 III-A integral photosensitizer 996
1V-A-A, B, C, D, H, I, J supersensitizer
996 1V-A-E, Section J Antifoggant 998
■ Stabilizer 998■ (RD17643) [RDI8716) 23 64
8 23-24 648-9 23-24 648-9 24-25 649 24-25 649 Known photographic additives that can be used in the present invention are also described in the above Research Disclosure.

The relevant entries are shown in the table below.

[Item] (Page of RD308119) Color clouding prevention agent 1002 ■-I section Dye image stabilizer 1001 ■-J section Brightener 9
98v UV absorber 1003 ■-C1 light absorber
1003 ■ Light scattering agent 1003 ■ Filter dye 1003 ■ Binder 1003 RX static inhibitor 1006 1111 Hardener 10
04 X Plasticizer 1006 m Lubricant 1006 n Activator/coating aid 1005 II Matting agent
1007 1VI developer (contained in photosensitive material) 1
011 Section 11B A variety of couplers can be used in the present invention, specific examples of which are described in Research Disclosure, supra.

(RD17643) (RD18716) 25 6
50 5 4 xm-c section 25-26 25-26 The relevant descriptions are shown in the table below.

[Item] (page of RD308119)
Yellow coupler 1001 ■-term magenta coupler 1001 ■-term cyan coupler
1001 ■-D section colored coupler 1002
■-G term DIR coupler 1001 ■-F term BAR coupler 1002 ■-F term [:RD1
7643] (RD18716) ■ Section CG ■ Section CG ■ Section 10 ■ Section F Alkali-soluble coupler 1001 ■ Section E This section 4 The additives used in the invention are described in RD308119XIV It can be added by a dispersion method or the like.

In the present invention, the aforementioned RD1764328 page, RD1
The supports described in pages 8716647-8 and RD308119 XU can be used.

The photosensitive material of the present invention can be provided with auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned RD308119-.

The photosensitive material of the present invention can have various layer structures such as the i-layer, inverse layer, and unit structure described in the above-mentioned RD308119--.

The present invention covers color negative films for general use or movies, color reversal films for slides or televisions,
Color paper It can be applied to various color photosensitive materials such as color positive film and color reversal paper.

The photosensitive material of the present invention is RD1764328-29, RD
It can be developed by the usual method described in page 18716615 and RD308119 (■).

(Example 1) Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the following Examples, the amount added in the halogenated a photographic light-sensitive material is expressed in grams per 1 m2 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver. Sensitizing dyes are expressed in moles per mole of silver.

A multilayer color photographic element sample 101 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample-101 (comparison) 1st layer: Antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-S) 0.20 Colored coupler (c c -1) 0.02 High boiling point solvent (O1 (2 -1) 0.20 High boiling point solvent (Oi (2-2) 0.20 Gelatin 1.6 2nd layer: 1st intermediate layer (IL-1) Gelatin 1.3 3rd layer: Low sensitivity red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (Em-1)
0.4 silver iodobromide emulsion (E m -2)
0.3 sensitizing dye (S-1) 3.2X 1
0-' (mol/silver 1 mol) sensitizing dye (S-2) 3.
2x to-' (mol/mol silver) sensitizing dye (S-3
0.2X 10-' (mol/silver 1 mol) Cyan coupler (C-1) 0.50 Cyan coupler (C
-2) 0.13 colored cyan coupler (CC-1) 0.07 DIR compound CD-1) 0.0
06 DIR compound (D -2) 0.01 High boiling point solvent (O112-1) 0.55 Gelatin 1.0 4th layer: High sensitivity red-sensitive emulsion layer (R-H) Silver iodobromide emulsion (E m - 3
) (L99 sensitizer (S-1) 1.7X
10-' (mol/silver 1 mol) sensitizing dye (S-2')
1.6810-'C mole/silver mole) sensitizing dye (S
-3) 0. lX 10-'C mol/silver 1 mol) Cyan coupler (C-2) 0.23 Colored cyan coupler (CC-1'') 0.03D
IR compound (D-2) 0.02 High boiling point solvent (Oi (2-1) 0.25 Gelatin 1.0 5th layer: Intermediate layer (IL-2) Gelatin 0.8 6th layer: Low sensitivity green sensitivity Emulsion layer (GL) Silver iodobromide emulsion (Em-1)
0.6 silver iodobromide emulsion (Em-2)
0.2 sensitizing dye (S-4) 6.7x 10
-' (mol/silver 1 mol) Sensitizing dye (S -5) 0.8
x 10-' (mol/silver 1 mol) magenta coupler (M
-1) 0.17 magenta coupler (M -
2) 0.43 colored magenta coupler (
CM-1) 0.1DIR compound (D-3')
0.02 high boiling point solvent (OiQ -2)
0.7 gelatin
1.0 7th layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (E m -3) 0.9 Sensitizing dye (
S-6) 1. IX 10-' (mol/silver 1 mol) sensitizing dye (s-7) 2. ox 10" (mol/silver 1 mol) sensitizing dye (s-8) (13x 10-' (mol/silver 1 mol) magenta coupler (M-1')
0.03 magenta coupler (M-2) 0.13 colored magenta coupler (CM-1) 0.04DI
R compound (D-3) 0.004 High boiling point solvent (OiQ-2) 0.35 Gelatin 1.0 8th layer: Yellow filter layer (YC) Yellow colloidal silver
0.1 Additive (H3-1) 0.
12 additive (HS-2) 0.07
Additive (SC-1) 0.12 High boiling point solvent (Oi (1-2) 0.15 Gelatin 1.0 9th layer: Low sensitivity blue-sensitive emulsion layer (B - L) Silver iodobromide emulsion (Em- 1)
0.25 silver iodobromide emulsion (E m -2)
0.25 Sensitizing dye (S-9) 5.8X
10-' (mol/mol of silver) yellow coupler (Y-
1) 0.60 yellow coupler (Y-2
) 0.32DIR compound (D-1)
0.003DIR Compound CD-2)
0.006 High boiling point solvent (OIQ-2) 0°18 Gelatin 1.3 10th layer:
High-speed blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (E m
-4) 0.5 sensitizing dye (s -10)
3. Ox 10-' (mol/silver 1 mol) sensitizing dye (S
-11) 1.2X 10-' (mol/silver 1 mol) Yellow coupler (Y-1) 0.18 Yellow coupler (Y-2) 0.10 High boiling point solvent (
0022) 0.05 gelatin
1.0 11th layer: 1st protective layer (PR
O-1) Silver iodobromide emulsion (E m -5) 0.3 Ultraviolet absorber (UV -1) 0.07 Ultraviolet absorber (UV -2) 0.1 Additive (H5-1) 0 .2 Additive (H5
-2) 0.1 high boiling point solvent (OiΩ-
1) 0.07 high boiling point solvent (Oi<2-
3) 0.07 gelatin
0.8 12th layer: 2nd protective layer (PRO-
2) Alkali-soluble matting agent 0.13 (average particle size 2 μm) Polymethyl methacrylate 0.02 (average particle size 3 μm) Gelatin 0.5 In addition to the above composition, each layer also contains coating aid SU2 and dispersion aid. agent 5U-
1. Hardeners H-1 and H-2 and dyes Al-1 and Al-2 were added as appropriate.

The emulsions used in the above samples are as follows. Both are monodisperse emulsions.

Em-1 + Average AgI content 7.5 mol% Em-2: Average AgI content 2.5 mol% Em-3: Average AgI content 8.0 mol% Em-4: Average AgI content 8.5 mol %Em-5: Average Agl content 2.0 mol% 0.55μ
0.36μ 0.84μ 1.02μ 0.08μm Octahedron Octahedron Octahedron -1 M c-i - 1 - -8 -9 -2 - 0 -11 I-2 S C ■ Mixture (2: 3) C, H.

0i I2-4 Next, in sample 101, the coupler in each emulsion layer was changed to the solid state dispersed coupler according to the present invention, and sample 10
2 to 110 were created. Unless otherwise specified, the colored coupler and DIR compound in each emulsion layer were dissolved in a high boiling point solvent of the same weight as the compound, dispersed in oil in a gelatin solution, and then added. A method for solid dispersing couplers will be explained. 4 times the amount of n-propertool and 1.5 times the amount of 33% 3% anilosol 1 for the weight of equimolar coupler as the coupler used in each emulsion layer of sample 101.
02 (number of carbon atoms with sulfosuccinic acid and ethoxy group l)
Disodium salt of half ester with alcohol of O~12 (manufactured by Cyanamid Co., Ltd.) was added and dissolved at 65°C, and this was dissolved at 65°C.
The mixture was fed into a dispersion machine containing 30 times the amount of water as the coupler for 30 seconds and vigorously stirred. At this time, the reaction chamber was kept at room temperature. The solvent was continuously removed from the dispersion using a semipermeable membrane to obtain a dispersion.

S-1 S-2 U-1 The odors of sample 101 are the couplers in each emulsion layer.The colored coupler and the DIR compound were simultaneously dissolved in a high boiling point solvent and added after being dispersed in oil in the gelatin solution.

Silver iodobromide emulsion EII used in samples 101-110
Samples 201 to 210.301 to 310.401 to 410 were prepared by using silver halide emulsions with different halogen compositions as shown in Table 2 instead of l-1-Em-4.

(Example 2) Samples 101-110 and 201-21 created in Example 1
In order to examine the sensitometric properties, rapid processability, and storage stability of O9301-310 and 401-410, the following development treatments were performed after white wedge exposure. Regarding storage stability, at 25°C, 60%RH and 40°080%RH,
After each sample was kept for 3 days, the above evaluation was performed and the sensitivity difference (desensitization) was compared.

The results are shown in Table-3.

As a result, it was found that the samples according to the present invention had excellent suitability for rapid processing, and the degree of desensitization under high humidity was significantly improved.

Processing process Temperature Time Development color development 3
5.0±0.3°C 15 seconds bleach constant tr 35.0±
0.5℃ 45 seconds stabilization 30-34℃
Dry for 90 seconds 60-80℃ 60
Second color developer pure water 800IT1g
Triethanolamine 10gN,
N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite
0.3g 1-hydroxyethylidene 1,1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid 1.0g catechol-3,
Disodium 5-diphosphonate 1.0gN-ethyl-N
-β-methanesulfonamidoethyl-3-methyl-4-
Aminoaniline sulfate (color developing agent) 4.5g optical brightener (4,4'-diaminostilbendisulfonic acid derivative) l, 0g potassium carbonate
Add 27g water to make the total volume 1Q, pH=
Adjust to 10.10.

Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% aqueous solution) 100mQ ammonium sulfite
(40% aqueous solution) Add 27.5 mff of water to bring the total volume to IQ, and adjust the pH to -5.7 with potassium carbonate or glacial acetic acid.

5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid vinegar 1.0 g hydroxide Ammonium (20% aqueous solution) 3.0g Optical brightener (4,4
'-diaminostilbendisulfonic acid derivative)
Add 1.5 g of water to make the total amount IM, and add sulfuric acid or hydroxide.Table 3 The results are shown in Table 4.

Underline Sample of the present invention (Example 3) Sample 101-110.201-21 created in Example 1
In order to investigate the amount of residual dye after processing the O2301-310 and 401-410 samples, each unexposed sample was prepared in Example 2.
The processing was similar to the development process described above except that the color developing agent was removed from the color developing solution, and the density was measured using green light (the density of the colored coupler was subtracted). As can be seen from Sample Table 4, the samples of the present invention had a low residual dye density after development, and were found to have a significant improvement effect on color retention.

Claims (1)

[Claims] A silver halide color photographic light-sensitive material comprising a constituent layer containing a silver halide emulsion and a coupler coated on a support, wherein at least one of the constituent layers contains at least 10 mol % of the silver halide emulsion. A silver halide color photographic light-sensitive material containing the above silver chloride and characterized in that the coupler contained in the same constituent layer has a low molecular weight, is hydrophobic, and is dispersed in a solid state.