JPH04344641A - Multilayer silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent color turbidity by incorporating the scavenger of the oxidation product of a color developing agent in dispersion without any high- boiling solvent in a layer containing a coupler and/or a nonphotosensitive hydrophulic colloidal layer. CONSTITUTION:The layer containing the coupler and/or the non-photosensitive hydrophilic colloidal layer contains the scavenger of the oxidation prodtuct of the color developing agent in dispersion without any high-boiling solvent. The coupler is also added without any high-boiling solvent into the constituent layer. The scavenger is represented by formula I or II in which R1 H, alkyl, aryl, or the like; each of R2 and R3 is H, acyl, or sulfonyl; X is represented by each of groups of formula III; (n) is 0, 1, or 2; when (n) is 1, R4 is-N(R5)-N (R7)-R8, alkenyl, alkenyloxy, or the like, and when (n) is 2, R4 is H, alkyl, aryl, or the like; and each of R5-R8 is H, alkyl, cycloalkyl, or the like.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color light-sensitive material, and more particularly to a multilayer silver halide color light-sensitive material with improved color turbidity and staining after long-term storage.

0002

BACKGROUND OF THE INVENTION In recent years, there has been a demand for higher image quality in multilayer silver halide color light-sensitive materials, and at the same time, there has been a demand for faster development processing. For example, attempts have been made to reduce the film thickness to improve sharpness, or to speed up development by using active silver halide grains. However, when such highly active silver halide grains are used, the minimum density in non-image forming areas increases, causing staining, and excess oxidized developing agent diffuses into other layers. It can also cause color turbidity. In particular, when the film thickness is thin, there is a strong tendency for color turbidity.

In such cases, compounds that react with the oxidized color developing agent but do not contribute to image formation, so-called scavenger compounds of the oxidized color developing agent (hereinafter referred to as DP), are usually used.
'Scavengers' are used. As DP' scavengers, hydroquinone compounds, pyrogallol compounds, catechol compounds, resorcinol compounds, sulfonyl compounds, and couplers that couple but do not substantially develop color are known.

0004

[Problem to be solved by the invention] However, when these compounds are stored for a long time, their scavenging ability for oxidized color developing agents decreases, and as a result, they are not sufficiently effective in preventing color turbidity and stain prevention. It has the disadvantage that it cannot be obtained, and an improvement has been desired.

The present invention has been made to solve the above-mentioned problems, and its purpose is to provide a multilayer silver halide color photosensitive material that is free from color turbidity and staining even during long-term storage. .

[0006]

[Means for Solving the Problems] As a result of extensive studies, the present inventors have discovered the combination of technologies described below.
This led to the present invention. That is, the object of the present invention is to provide a multilayer silver halide color light-sensitive material having at least one coupler-containing layer on a support, in which the coupler-containing layer and/or the non-photosensitive hydrophilic layer is provided. , contains a scavenger compound of the oxidized color developing agent represented by the following general formula [I] or [II], and at least one of the coupler and/or the scavenger compound substantially frees the high boiling point solvent. This was achieved by a multilayer silver halide color photographic light-sensitive material characterized in that silver halide is dispersed and added to the photographic constituent layers without being contained in the silver halide.

[0007]

[Chemical formula 3]

In the formula, R1 represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group; R2 and R3 each represent a hydrogen atom, an acyl group, or a sulfonyl group;

[0009]

[C4]

[0010] n represents an integer from 0 to 2, and when n is 2, 2
The two X's may be the same or different, and when n is 1, R4 is -N(R6)-N(R7)-R8, alkenyl group, alkenyloxy group, alkenylamino group, alkynyl group, alkynyloxy group, alkynyl Amino group, hydrogen atom when n is 2, alkyl group, aryl group, cycloalkyl group, heterocyclic group, alkoxy group, aryloxy group, amino group, alkenyl group, alkenyloxy group, alkenylamino group, alkynyl group, alkynyl Represents an oxy group or an alkynylamino group. R5, R6, R7, and R8 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or a heterocyclic group.

Z represents an atomic group necessary to form a 5- to 7-membered ring together with -N(R2)-N(R3)-X-.

The present invention will be explained in detail below.

DP' represented by general formulas [I] and [II]
In the scavenger, the alkyl group represented by R1 preferably has 1 to 30 carbon atoms. The aryl group represented by R1 is a phenyl group, a naphthyl group, etc., and preferably a phenyl group.

The heterocyclic group represented by R1 may be saturated or unsaturated, or may be a fused ring. Examples include a pyridine ring, a pyrimidine ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, a quinoline ring, a morpholine ring, a thiophene ring, a thiazole ring, a benzothiazole ring, an oxazole ring, and a benzoxazole ring.

Each group represented by R1 includes a substituent, such as an alkyl group, an alkoxy group, an aryl group, an alkenyl group, an alkynyl group, a substituted amino group, an acylamino group, a sulfonylamino group. group, ureido group, alkoxycarbonylamino group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxyl group, halogen atom, cyano group, nitro group, carboxyl group, sulfo group, Examples include heterocyclic groups.

R1 is preferably an aryl group, an aromatic heterocycle or an aryl-substituted methyl group, more preferably an aryl group (such as a phenyl group), and most preferably an alkyl group, an alkoxy group, an acylamino group, It is a phenyl group having a sulfonamide group or an amino group as a substituent.

Preferably, R2 and R3 are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.

Examples of the substituent represented by R4 include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aralkyl group,
Examples include an alkenyl group, an alkenyloxy group, an alkenylamino group, an alkynyl group, an alkynyloxy group, an alkynylamino group, and the like. X is preferably -CO-, -S
O2-, more preferably -CO-.

[0019] n represents an integer from 0 to 2, preferably 1 or 2.

The ring formed by Z is 5- to 7-membered,
Particularly preferred are 5- to 6-membered rings, including saturated and unsaturated rings, those having substituents, and those fused with other rings.

The ring formed by Z is, for example, disclosed in Japanese Patent Application No.
Examples include those having the ring structure described on pages 5 to 7 of the specification of No. 29084. Below, the general formula [I], [I
Among the compounds represented by [I], specific examples of preferred compounds are shown below, but the present invention is not limited thereto.

[0022]

[C5]

[0023]

[C6]

In addition to the above-mentioned compounds, the following compounds may be mentioned as specific examples.

[0025] (1) to (5) on page 16 of the specification of Japanese Patent Application No. 1-290847, (6) to (10) on page 17 of the same
, (11) on page 18, (37), (3) on page 23
8), (6
) to (12), (13) to (17) on page 13 of the same, (18) to (34) on pages 14 to 16 of the same, Japanese Patent Application No. 1-2
Specification No. 90849, pages 17 to 20 (1), (3
), (19).

Furthermore, the compounds (1) to (33) described on pages 4 and 5 of the specification of Japanese Patent Application No. 1982-27731, and the compounds (1) to (33) described on pages 5 to 10 of the specification of JP-A-1-147455, Compounds (1) to (68), compounds (1) to (48) described in European Patent No. 338785, etc. may also be used in the present invention.

Most preferably, the DP' scavenger is incorporated directly into the silver halide emulsion layer. It may also be added to non-photosensitive layers such as intermediate layers, protective layers, yellow filter layers, and antihalation layers.

The amount of DP' scavenger to be added is preferably in the range of 1 x 10-6 mol to 1 x 10-1 mol, and 1 x 10-5 mol to 1 x 10-1 mol per m2 when added to the silver halide emulsion layer. A range of 2×10 −3 mol is particularly preferred, but the amount added is appropriately selected depending on the type of silver halide, the type of compound, etc. When applied to layers that do not contain silver halide, such as intermediate layers, protective layers, yellow filter layers, and antihalation layers, 1 x 10
The range is preferably from -6 to 1 x 10-2 mol, more preferably from 1 x 10-5 to 1 x 10-3 mol.

In the present invention, a coupler refers to a substance capable of coupling with an oxidized product of a color developing agent at its active site. Also included are those having photographically useful groups such as dyes, desilvering accelerators, development accelerators, fogging agents, and fluorescent agents, or precursors thereof.

Regarding these couplers, research
Disclosure 308119 (hereinafter referred to as RD30811)
9) and 17643 (hereinafter abbreviated as RD17643) can be used.

[0031] Next, related descriptions will be shown.

[Item] [RD308
Page 119] [RD17643]
Yellow coupler 1001 VII
-D section VIIC to G section magenta coupler 1001 VII-D section VIIC to G section cyan coupler 1001 VII-D section
VIIC-G section colored coupler 1002 VII-G section
VIIG section DIR coupler
1001 Section VII-F
VIIF term BAR coupler
1002 Section VII-F Other useful residues
emission coupler
1001 Section VII-F alkali soluble coupler
1001 Section VII-E In the present invention, the high boiling point organic solvent is specifically XIV of the above-mentioned RD308119.
-Compounds described in section A can be used.

In the present invention, dispersion substantially free of high-boiling organic solvents means that the coupler and/or DP'
This means that the high boiling point organic solvent is dispersed in an amount of 5% by weight or less based on the total weight of the scavenger (hereinafter, these compounds will be abbreviated as compounds according to the present invention).

Specific dispersion methods include the precipitation method and mechanical pulverization method described below.

[0035] As a precipitation method, when the compound according to the present invention is soluble in a base, a method of dissolving it in basic water and adding it to an acidic liquid and dispersing it, and when the compound according to the present invention is soluble in an organic solvent, a method is used. , a method in which the compound is dissolved in a water-miscible organic solvent and added to water for dispersion, or a method in which the compound according to the present invention is dissolved in a water-immiscible low-boiling organic solvent to form an oil-in-water dispersion; , a method of removing the solvent by evaporation, etc.

More specifically, (1) a method of dissolving the compound according to the present invention in a basic hydrophilic colloid solution containing a dispersion aid and gradually adding an acid to obtain a dispersion; A method of obtaining a dispersion by dissolving the compound according to the present invention in a solution and gradually adding it to a neutral or acidic hydrophilic colloid solution containing a dispersion aid; H. Willard, L. G
a homogeneous precipitation method in which crystals are gradually precipitated from a solution by Ordon et al.; (2) a method in which the compound according to the present invention is dissolved in a water-miscible organic solvent and then added to and dispersed in a hydrophilic colloid solution containing a dispersion aid; ■ A method of dissolving the compound according to the present invention in a water-miscible organic solvent containing a dispersion aid and adding it to a hydrophilic colloid solution for dispersion; ■ A method of dissolving the compound according to the present invention in a water-immiscible organic solvent. There is a method in which, after mixing with a hydrophilic colloid solution to form a water-in-oil dispersion, the water-immiscible organic solvent is removed by volatilization to form an oil-in-water dispersion by a so-called phase inversion method. These methods are disclosed in the following patents:

[0037] US Pat. No. 2,870,012, US Pat. No. 2,991
No. 177, No. 3658546, No. 4388403,
British Patent No. 1099414, British Patent No. 1193349,
European Patent No. 374837, International Patent No. 90/1083
No. 45, Japanese Unexamined Patent Publication No. 120849/1999, and Research Disclosure No. 16,468.

Gelatin is preferably used as the hydrophilic colloid used in the method for dispersing compounds according to the present invention.

Examples of the gelatin include coal-treated gelatin, acid-treated gelatin, Bull, Soc, Sci, Pho
t, Japan. No. 16, p. 30 (1966) may be used, and gelatin hydrolysates and oxygen-decomposed products may also be used.

[0040] Among gelatins, low-calcium gelatin having a low calcium content is preferred in the present invention. Low calcium gelatin can be easily prepared by subjecting ordinary gelatin to ion exchange treatment. The calcium content of the low calcium gelatin used in the present invention is 1,000 ppm or less, preferably 800 ppm or less, particularly preferably 600 ppm or less.

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, glycols, cyclic ethers, nitriles, amides, and N-methyl-2
-pyrrolidine, etc., and n-propyl alcohol is preferred from the viewpoint of dispersion stability.

As the basic aqueous solution used in the present invention, alkaline solutions such as caustic alkali, alkali carbonate, potassium citrate, lithium citrate, potassium acetate, sodium acetate, and aqueous ammonia can be used.

[0043] In addition, in the present invention, as the anionic surfactant used as a dispersion aid, the following K-1 to K
Surfactants such as -12 and the like can be mentioned.

[0044]

[C7]

[0045]

[Chemical formula 8]

Typical nonionic water-soluble polymers used in the present invention are polypropylene oxide, polyvinyl alcohol, and methylcellulose. Suitable polymers are polyethylene oxide and polyvinylpyrrolidone.

On the other hand, the mechanical pulverization method includes a method in which the compound according to the present invention is made into a fine powder using high energy such as ultrasonic waves, and then added to a hydrophilic colloid solution and dispersed. There is a method in which the compound is wetted with water or a poor solvent, and fine particles are dispersed at high temperature in a mill using media with a narrow particle size distribution in the presence of a dispersion aid and/or a hydrophilic colloid. These methods are described in JP-A-1-1
It is specifically disclosed in No. 72828, No. 2-110547, etc.

[0048] In the present invention, the apparatus for dispersing solid fine particles includes a ball mill, a roll mill, a sand mill, etc., but a sand mill is preferable, and a wide variety of commercially available sand mills can be used.

Materials for the media used in the present invention include glass, alumina, zirconia, agate, stainless steel, and nylon, with glass, zirconia, and alumina being preferred.

When glass is used, silicon dioxide is 6
Particularly preferred is 0% by weight or more. The media is preferably spherical, and the particle size is not particularly limited, but it is usually 0.1 mmφ to
The diameter is 20 mmφ, preferably 0.2 mmφ to 10 mmφ, particularly preferably 0.5 mmφ to 5.0 mmφ.

[0051] Specific examples of the glass media include Bright Glass Beads manufactured by Bright Seki Kogyo Co., Ltd.

[0052] The precipitation method and the mechanical grinding method have been described as methods for obtaining the compound according to the present invention in a dispersed state substantially free of high-boiling point solvents, but in the present invention, the above-mentioned European Patent No. 374837 , and International Patent No. 90/0834
The dispersion method shown in No. 5 is particularly preferred.

One of the photographic constituent layers contains the compound according to the present invention dispersed by the dispersion method according to the present invention,
The compound according to the present invention dispersed in oil may be contained in another layer, or the compound according to the present invention dispersed by the dispersion method according to the present invention and the compound according to the present invention dispersed in oil may be contained in the same layer. You can also do that.

In the present invention, the coupler and the general formula [I
The DP' scavenger represented by ] may be contained in the same layer or in another layer.

In the present invention, at least one of the coupler and/or the DP' scavenger represented by general formula [I] is dispersed substantially free of high boiling point solvent, and the silver halide color is dispersed substantially free of high boiling point solvent. DP' represented by general formula [I] is characterized by being added to photosensitive materials.
Preferably, the scavenger is dispersed substantially free of high boiling solvents. More preferably, both the coupler and the DP' scavenger represented by formula [I] are dispersed substantially free of high boiling point solvents and added to the silver halide color light-sensitive material.

In the present invention, the effects of the present invention are more pronounced when the film thickness of the silver halide color light-sensitive material is thinner. Preferably, the film thickness of the silver halide color photosensitive material is 20
It is not more than μm, more preferably 18 μm.

In the present invention, the silver halide emulsion described in RD308119 can be used as shown below.

[Item]
[RD308119] Iodine composition
993 Section I-A Manufacturing method
993 I-A term and 994 E term Crystal habit Normal crystal
993 Section I-A
twin crystals
993 Section I-A Epitaxial
993 Section I-A
Uniform halogen composition
993 Section I-B
Not uniform 993 I-B term
Halogen conversion 9
94 I-C section Halogen substitution
994 Item I-C Metal content
994 I-D term monodisperse
995 I-F
Section Solvent addition
995 I-F term Latent image formation position Surface 995 I-
G term internal
995 I-G term Applicable sensitive material negative 9
95 Section I-J Mixing and using emulsions
995 Section I-H Desalting

995 Section II-A In the present invention, the silver halide emulsion used is one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17643, No. 1871
6 and no. 308119 (each referred to as RD176
43, RD18716 and RD308119). The table below shows the locations.

[Item] [RD30
Page 8119] [RD17643]
[RD18716] Chemical sensitizer
996 Section III-A
23 648 Spectral sensitizer
996 IV-A-A, B, C
, D, H, I, J terms 23-24 648
~9 supersensitizer 996
IV-A-E, Section J 23-24
648-9 antifoggant
998 VI
24-25 649 Stabilizer
998 VI
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] [RD30
Page 8119] [RD17643]
[RD18716] Color clouding prevention agent
1002 Section VII-I
25 650 dye image stabilizer
1001 Section VII-J
25 Brightener
998V
24 UV absorber
1003 VIII-C, Section XIII-C
25-26 light absorber
1003 VIII
25-26 light scattering agent
1003 VIII filter dye
1003 VIII
25-26 binder
1003 IX
26 651 Static inhibitor 1006 XIII
27
650 Hardener 1004
X 2
6 651 Plasticizer
1006 XII
27 65
0 lubricant 1006
XII
27 650 activator/coating aid
1005 XI
26-27 650 Matting agent 1007 XVI developer (contained in sensitive material) 1011 XXB section In the present invention, the aforementioned RD17643 page 28, RD1871
6 647-8 and RD 308119, XVII can be used.

The photosensitive material of the present invention includes the above-mentioned RD3081.
Auxiliary layers such as filter layers and intermediate layers as described in Section 19VII-K can be provided.

The photosensitive material of the present invention has the above-mentioned RD30811.
Various layer configurations such as forward layer, reverse layer, and unit configuration described in Section 9VII-K can be adopted.

The present invention can be applied to various color photosensitive materials, including color negative films for general use or movies, color reversal films for slides or television, and color positive films.

The photosensitive material of the present invention is RD17643 28
~29 pages, RD18716 647 pages and RD3081
It can be developed by the usual method described in No. 19, XIX.

[0065]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the examples below, the amount added in the silver halide photographic light-sensitive material was 1 m2 unless otherwise specified.
Shows the number of grams per serving. Furthermore, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye is expressed in moles per mole of silver halide in the same layer.

Example 1 A multilayer color photographic material sample 101 was prepared by sequentially forming layers having the compositions shown below on a subbed triacetyl cellulose film support from the support side.

First layer (antihalation layer) black colloidal silver

0.24 Ultraviolet absorber UV-1

0.14 Ultraviolet absorber UV
-2
0.072 Ultraviolet absorber UV-3
0.072
UV absorber UV-4
0.07
2 High boiling point solvent Oil-1 [di(2-ethylhexyl) phthalate] 0.31 High boiling point solvent
Oil-2 (dibutyl phthalate)
0.098 Poly-N-vinylpyrrolidone
0.15 gelatin

2.02
Second layer (middle layer) High boiling point solvent Oil-3 (tricresyl phosphate) 0.011 Gelatin
1
．． 17 Third layer (low sensitivity red-sensitive layer) Silver iodobromide emulsion (Em-1) spectrally sensitized with red sensitizing dyes S-1 and S-2

0.60 Coupler C-1

0.37 High boiling point solvent Oil
-2
0.093 Poly-N-
vinyl pyrrolidone
0.074
gelatin

1.35 Fourth layer (high sensitivity red-sensitive layer) Silver iodobromide emulsion (Em-2) spectrally sensitized with red sensitizing dyes S-1 and S-2

0.60 Coupler C-1

0.85 High boiling point solvent Oil-2
0.21
Poly-N-vinylpyrrolidone
0.09
3 Gelatin

1.56 Fifth layer (intermediate layer) Color mixing prevention agent AS-1

0.20 High boiling point solvent Oil-3

0.25 Matting agent MA-1 [Colloidal silica particles (average particles 3.5 μm)] 0.009
1 Gelatin

1.35 Sixth layer (low sensitivity green sensitive layer) Silver iodobromide emulsion (Em-1) spectrally sensitized with green sensitizing dye S-3

0.70 coupler M-1

0.31 coupler M
-2
0.076
High boiling point solvent Oil-3
0.05
9 Poly-N-vinylpyrrolidone

0.074 Gelatin

1.29 Seventh layer (high sensitivity green sensitive layer) Green sensitized color layer Silver iodobromide emulsion spectrally sensitized with S-3 (Em-2)

0.70 coupler M-1

0.80 coupler
M-2
0.19
High boiling point solvent Oil-3
0.1
6 Poly-N-vinylpyrrolidone

0.12 Gelatin

1.91 Eighth layer (middle layer) Gelatin

0.90 Ninth layer (yellow filter layer) Yellow colloidal silver

0.11 Color mixture prevention agent AS-1

0.068 High boiling point solvent O
il-3
0.085 Matting agent MA-1
0.012
gelatin

0.68 Tenth layer (low sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-4 (Em-1)

0.70 Coupler Y-1

0.86 Image stabilizer
G-1 (Gallic acid dodecyl ester)
0.012 High boiling point solvent Oil-3

0.22 Poly-N-vinylpyrrolidone
0.078 compound
F-1 (5-ureidohydantoin)
0.020 compound
F-2 (hydantoin)
0.040 Gelatin

1.09
Eleventh layer (high sensitivity blue sensitive layer) Silver iodobromide emulsion (Em-3) spectrally sensitized with blue sensitizing dye S-4

0.70 Coupler Y-1

1.24 Image stabilizer
G-1
0.017
High boiling point solvent Oil-3
0.3
1 Poly-N-vinylpyrrolidone

0.10 Compound F-1

0.039 compound
F-2
0.077
gelatin

1.73 Twelfth layer (protective layer-1) Non-photosensitive fine grain silver iodobromide
0
．． 075 Ultraviolet absorber UV-1

0.048 Ultraviolet absorber UV-2


0.024 Ultraviolet absorber UV-3

0
．． 024 Ultraviolet absorber UV-4

0.024 High boiling point solvent Oil-1

0.13 High boiling point solvent Oil-2

0.13 Compound F-1

0.075 Compound F-2

0.15 gelatin

1.2 Thirteenth layer (protective layer-2) Slip agent WAX-1
0.0
41 Matting agent MA-2 [Polymethyl methacrylate particles (average particle size 30.μm)]

0.0090 Matting agent MA-3

0.051 surfactant SU-1

0.0036 gelatin

0.55 (Note: The weight average molecular weight of poly-N-vinylpyrrolidone used in each layer is 350,000.) Also, the emulsions (Em-1 to Em-3) used in the above samples were all It was a monodispersed emulsion, and the width of the average particle size distribution was 20% or less.

Silver iodide content (mol %)
Average particle diameter (μm) Em-1
3.0
0.30 Em-2 3.0
0.8
0 Em-3 3.0
0.85 The average silver iodide content of the silver iodobromide used in the 12th layer was 1.0 mol %, and the average grain size was 0.08 μm.

The silver halide agent used in each photosensitive layer was desalted, washed with water, and then subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid, and ammonium thiocyanate, and then used in each photosensitive layer. Each sensitizing dye for sensitizing silver halide, and 4-hydroxy-6-methyl-1,3,
3a,7-tetrazaindene, 1-phenyl-5-mercaptratrazole, etc. were added.

The compounds used in sample 101 are shown below.

[0072]

[Chemical formula 9]

[0073]

[Chemical formula 10]

[0074]

[Chemical formula 11]

[0075]

[Chemical formula 12]

In addition to the above compounds, the above photosensitive material sample 101 also contained a gelatin hardener 2,4-dichloro-6-
Hydroxy-s-triazine sodium salt, di(vinylsulfonylmethyl)ether and H-2, water-soluble dye A
I-1, AI-2, AI-3, compound DI-1, stabilizer 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, antifoggant 1-phenyl-5-mercaptotetrazole etc. were added as necessary.

[0077]

[Chemical formula 13]

In Sample 101, the coupler in each emulsion layer was dissolved in a mixture of a high boiling point solvent and a low boiling point solvent, emulsified and dispersed in an aqueous gelatin solution, and then added to the emulsion (this dispersion method is referred to as an oil dispersion method). ).

By changing the dispersion method of the coupler and DP' scavenger contained in the 6th and 7th layers of sample 101, sample 1
02-110 were produced. The contents are shown in Table 1.

[0080]

[Table 1]

The structures of couplers A-43 and A-46 used in samples 109 and 110 are shown.

[0082]

[Chemical formula 14]

[0083] The amounts of coupler and gelatin for each sample were the same as those for sample 101.

[0084] The contents of dispersion methods A, B, and C listed in Table 1 are shown in Table 2.

[0085]

[Table 2]

Of the dispersion methods listed in Table 2, A is the oil dispersion method described above, and B and C are the dispersion methods according to the present invention.

An example of the dispersion method (dispersion method B) according to the present invention will be described below. 2 to 10 times the amount of n-propyl alcohol and 1.5 times the weight of the coupler and/or DP' scavenger to 33% Aerosol A102 (a half of sulfosuccinic acid and an alcohol having 10 to 12 carbon atoms and an ethoxy group). Disodium salt of ester (manufactured by Cyanamid) was added and dissolved at 65°C.
Supplied into a dispersion containing 0 times the amount of water and stirred vigorously. At this time, the reaction chamber is kept at room temperature. The solvent is continuously removed from the dispersion using a semipermeable membrane to obtain a dispersion.

Light-sensitive material samples 101 to 110 were exposed to white light through a step wedge for sensitometric measurement, and were subjected to the following development treatment.

[0089] The composition of the treatment liquid used in the above treatment step is as follows.

First developer Sodium tetrapolyphosphate
2g
sodium sulfite

20g hydroquinone monosulfonate
30g
Sodium carbonate (monohydrate)
30g
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2g Potassium bromide

2.5g potassium thiocyanate
1.2g
Potassium iodide (0.1% solution)
2m
l Add water to make up to 100ml and adjust the pH to 9.60.

Inversion liquid Nitrilotrimethylenephosphonic acid hexasodium salt
3g stannous chloride (dihydrate)
1g p-aminophenol
0.1g sodium hydroxide
8g
glacial acetic acid

Add 15ml water to make the volume to 1000ml and adjust the pH to 5.75.

Color developer Sodium tetrapolyphosphate
3g
sodium sulfite

7g Sodium triphosphate (dihydrate)
3
6g potassium bromide

1g potassium iodide (0.1% solution)

90ml sodium hydroxide

3g citradinic acid

1.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate
1
1g 2,2-ethylenedithiodiethanol
1
g Add water to make up to 1000ml, pH 11.7
Adjust to 0.

Conditioning liquid Sodium sulfite

12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin
0.4m
l Glacial acetic acid

Add 3ml water to 1000ml
Adjust the pH of the fried chicken to 6.15.

Bleach solution Sodium ethylenediaminetetraacetate (dihydrate)
2g Ethylenediaminetetraacetate iron(III) ammonium (dihydrate) 1
20g ammonium bromide

Add 100g of water to make the volume to 1000ml and adjust the pH to 5.65.

Stable liquid formalin (37% by weight)

5ml Konidax (manufactured by Konica Corporation)
5ml
Add water to make up to 1000ml and adjust the pH to 7.00.

The obtained developed sample was measured at the minimum green density (Dmi) using a densitometer (Status A).
n) was measured.

In addition, as a substitute test for long-term storage, the sample before being exposed to white light was made into a size of 35 mm x 1.5 m, rolled up into a cartridge, sealed with a resin can, and then placed in a heater at 40°C. I left it for two months. Thereafter, development was performed in the same manner as above, and Dmin was measured.

The results obtained are shown in Table 3.

0099

[Table 3]

As is clear from Table 3, in sample 101 in which the magenta coupler was dispersed by the oil dispersion method, Dmin
Sample 102, in which the coupler and color mixing inhibitor AS-1 were dispersed in oil, and Sample 103, in which the coupler and DP' scavenger were dispersed in oil, had a low Dmin, but the Dmin increased when left for a long time. It gets expensive.

On the other hand, it can be seen that samples 104 to 110 according to the present invention have sufficiently low Dmin and exhibit excellent characteristics even if left for a long time.

Example 2 Silver halide color photographic light-sensitive material sample 201 was prepared by sequentially forming layers having the compositions shown below on a triacetylulose film support from the support side.

Sample 201 1st layer: Antihalation agent (HC) Black colloidal silver
0.15 UV absorber (UV-1)
0.20 Colored coupler (CC-1)
0.02 High boiling point solvent (Oil-1: dioctyl phthalate) 0.20 High boiling point solvent (Oil-2: tricresyl phosphate) 0.20
gelatin
1.
6 Second layer: Intermediate layer (1L-1) Gelatin
1.
3 Third layer: Low sensitivity red-sensitive emulsion layer (R-L)
Silver iodobromide emulsion (Em-1)
0.4 Silver iodobromide emulsion (
Em-2)
0.3 Sensitizing dye (S-1)
3.2×
10-4 Sensitizing dye (S-2)
3.2×10-
4 Sensitizing dye (S-3)
0.2×10-4
Cyan coupler (C-1)
0.50 Cyan coupler (C-2)
0.13 Colored cyan coupler (CC-1) 0.07
DIR compound (D-1)
0.006
DIR compound (D-2)
0.01 High boiling point solvent (Oil-1)
0.55 Gelatin

1.0 4th layer: High sensitivity red-sensitive emulsion layer (R-H) Silver iodobromide emulsion (Em-3)
0.9
Sensitizing dye (S-1)
1.7×10-4
Sensitizing dye (S-2)

1.6×10-4 sensitizing dye (S-3)
0.1×10-4
Cyan coupler (C-2)
0.23 Colored cyan coupler (CC-1)
0.03 DIR compound (D-2)
0.02
High boiling point solvent (Oil-1)
0.25 Gelatin
1.0 5th layer: Intermediate layer (1L-2) Gelatin
0.
8 6th layer: low-sensitivity green-sensitive emulsion layer (GL)
Silver iodobromide emulsion (Em-1)
0.6 Silver iodobromide emulsion (
Em-2)
0.2 Sensitizing dye (S-4)
6.7×
10-4 Sensitizing dye (S-5)
0.8×10-
4 Magenta coupler (M-1)
0.17 Magenta coupler (M-2)
0.43 Colored magenta coupler (CM-1) 0.1
0 DIR compound (D-3)
0.02
High boiling point solvent (Oil-2)
0.70 Gelatin

1.0 7th layer: Highly sensitive green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-
3)
0.9 Sensitizing dye (S-6)
1.1×10-
4 Sensitizing dye (S-7)
2.0×10-4
Sensitizing dye (S-8)
0.3×10-4 Magenta coupler (M-1)
0.30 Magenta coupler (M-2)
0.13 Colored magenta coupler (CM
-1) 0.04 DI
R compound (D-3)

0.004 High boiling point solvent (Oil-2)

0.35 Gelatin
1.
0 8th layer: Yellow filter layer (YC)
yellow colloidal silver
0.1 Additive HS-1 (hydantoin)
0.07 Additive HS-2 (5-ureidohydantoin) 0.07
High boiling point solvent (Oil-2)
0.15 gelatin

1.0 9th layer: Low-speed blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em
-1)
0.25 Silver iodobromide emulsion (Em-2)
0.25
Sensitizing dye (S-9)
5.8×10-4
Yellow coupler (Y-1)
0.6 Yellow coupler (Y-2)
0.32 DIR compound (D-1)
0
．． 003 DIR compound (D-2)
0.006
High boiling point solvent (Oil-2)
0.18 Gelatin
1.3 10th
Layer: High-speed blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (Em-4)
0.5 Sensitizing dye (S-10)

3.0×10-4 Sensitizing dye (S-11)
1
．． 2×10-4 Yellow coupler (Y-1)
0.18
Yellow coupler (Y-2)
0.10 High boiling point solvent (Oil-2)
0.05 gelatin

1.1 Eleventh layer: First protective layer (PRO-1) Silver iodobromide (average grain size 0.08μ
m average iodide silver content 2.0 mol%) 0
．． 3 Ultraviolet absorber (UV-1)

0.07 Ultraviolet absorber (UV-2)
0.10 High boiling point solvent (Oil-1)
0.07 High boiling point solvent (Oi
l-3)
0.07 Additive HS-1 (hydantoin) 0.2
Additive HS-2 (5-ureidohydantoin)
0.1 gelatin

0.8 12th layer: 2nd protective layer (PRO
-2) Compound A

0.04 Compound B

0.004 Polymethyl methacrylate (
Average particle size: 3 μm) 0.02 Methyl methacrylate: Ethyl methacrylate:
Methacrylic acid = 3:3:4 (weight ratio) copolymer
0.13 Gelatin

0.5 The emulsions (Em-1 to Em-4) used in this example were:
All of them are core/shell type monodisperse emulsions, and the width of the average particle size distribution is 20% or less.

Emulsion Average silver iodide content (mol%) Average grain size (μm) (Em-1)
2.0
0.3 (Em-2)
8.0
0.4 (Em-3)
7.5
0.7 (Em-4)
8.5
0.8 Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid, and ammonium thiocyanate, and the sensitizing dye, 4-hydroxy-6-methyl-1,3
, 3a,7-tetrazaindene, and 1-phenyl-5-mercaptotetrazole were added.

In addition to the above composition, the above-mentioned photosensitive material sample 201 contains sodium tri-(isopropyl) naphthalene sulfonate, sodium dioctyl sulfosuccinate, a viscosity modifier, and a hardening agent 2,4- dichloro-6
-Hydroxy-s-triazine sodium salt and di(vinylsulfonylmethyl)ether, stabilizer 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, antifoggant 1-phenyl-5-mercaptotetrazole and polyvinylpyrrolidone (weight average molecular weight 10,000 and 1,100,000), dyes AI-I, AI-2 and compound DI-
1 (9.4 mg/m2).

The compounds used in sample 201 are shown below.

[0107]

[Chemical formula 15]

[0108]

[Chemical formula 16]

[0109]

[Chemical formula 17]

[0110]

[Chemical formula 18]

[0111]

[Chemical formula 19]

[0112]

[C20]

[0113]

[C21]

[0114]

[C22]

[0115]

[C23]

Next, as shown in Table 4, the type and dispersion method of the DP' scavenger added to the 8th layer (Y-C) of sample 201 were changed, and the dispersion method of the coupler in the 6th and 7th layers was changed. Samples 202 to 210 were created by changing.

[0117]

[Table 4]

[0118] The amounts of coupler and gelatin for each sample were the same as those for sample 201. Sample 201-2
No. 10 was exposed to green light through a step wedge for sensitometry and a green filter, and processed under the following conditions.

[0119]

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and their replenisher were used.

Color developer water

800ml potassium carbonate

30g sodium bicarbonate
2.5g
potassium sulfite
3.0
g Sodium bromide

0.3g potassium iodide

1.2mg Hydroxylamine sulfate
2.5g sodium chloride

0.6g 4-amino-3-methyl-N-(β-hydroxylethyl)
Aniline sulfate

4.5g diethylenetriaminepentaacetic acid
3
．． 0g potassium hydroxide

Add 1.2 g of water to make 1 liter, and adjust the pH to 10.06 using potassium hydroxide or 20% sulfuric acid.

Color developer replenisher water

800ml potassium carbonate

35g sodium carbonate
3g
potassium sulfite

5g sodium bromide

0.4g Hydroxylamine sulfate

3.1g 4-amino-3-methyl-N
-ethyl-N-(β-hydroxylethyl) aniline sulfate
6.3g
potassium hydroxide

2g diethylenetriaminepentaacetic acid

Add 3.0 g of water to make 1 liter, and add potassium hydroxide or 2.
Adjust pH to 10.18 using 0% sulfuric acid.

Bleach solution water

700ml 1,3-diaminopropanetetraacetic acid iron(III) ammonium
125g ethylenediaminetetraacetic acid

2g sodium nitrate

40g ammonium bromide

150g glacial acetic acid

Add 40 g of water to make 1 liter, and adjust the pH using ammonia water or glacial acetic acid.
Adjust to 4.4.

Bleach replenisher water

700ml 1,3-diaminopropanetetraacetic acid iron(III) ammonium
175g ethylenediaminetetraacetic acid

2g sodium nitrate

50g ammonium bromide

200g glacial acetic acid

After adjusting the pH to 4.0 using 56 g of ammonia water or glacial acetic acid, add water to make 1 liter.

Fixer water

800ml ammonium thiocyanate
120g ammonium thiosulfate
150g sodium sulfite
15g ethylenediaminetetraacetic acid
Adjust the pH to 6.2 using 2g of ammonia water or glacial acetic acid, then add water to 1l.
shall be.

Fixer replenisher water

800ml ammonium thiocyanate
150g ammonium thiosulfate
180g sodium sulfite
20g ethylenediaminetetraacetic acid
After adjusting the pH to 6.5 using 2g ammonia water or glacial acetic acid, add water to make 1l.
shall be.

Stabilizer and Stable Replenisher Water

900ml Polyoxyethylene-paraoctylphenyl ether (n-10) 2.0
g dimethylol urea

0.5g hexamethylenetetramine

0.2g 1,2-benzisothiazoline-3
−on
0.1g siloxane (UCC L-77)

0.1g ammonia water

Add 0.5ml water to make 1l, then add ammonia water or 50%
Adjust the pH to 8.5 using sulfuric acid.

[0128] The obtained developed sample was measured using a densitometer (Status M) until the Green density reached the minimum density (Dmi).
The Blue density (density difference from Dmin) at n)+1.0 was measured.

In addition, as a substitute test for long-term storage, the sample before being exposed to green light was made into a size of 35 mm x 1.5 m, rolled up into a cartridge, sealed with a resin can, and then placed in a heater at 40°C. I left it for two months. Thereafter, development was performed in the same manner as above, and the Blue density (density difference from Dmin) was measured.

The results obtained are shown in Table 5.

[0131]

[Table 5]

As is clear from Table 5, couplers and D
Sample 20 with P' scavenger added by oil dispersion method
3, although the blue density is lower when exposed to green light,
If left for a long time, the Blue concentration will increase.

On the other hand, it can be seen that Samples 204 to 210 according to the present invention show excellent properties with significantly improved color turbidity even over a long period of time.

[0134]

According to the present invention, a silver halide color photographic light-sensitive material can be obtained which exhibits significantly less color turbidity and staining even during long-term storage.

Claims (1)

[Claims] Claim 1: A multilayer silver halide color light-sensitive material having at least one coupler-containing layer on a support, in which the coupler-containing layer and/or the non-photosensitive hydrophilic layer contains the following general Contains a scavenger compound of the oxidized color developing agent represented by formula [I] or [II], and at least one of the coupler and/or the scavenger compound does not substantially contain a high boiling point solvent. 1. A multilayer silver halide color photographic light-sensitive material, characterized in that silver halide is dispersed and added to a photographic constituent layer. [Formula, R1 is a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group, R2 and R3 are each a hydrogen atom, an acyl group, or a sulfonyl group, and X is [Formula 2] n represents an integer from 0 to 2; when n is 2, the two Xs may be the same or different; when n is 1, R4 is -N(R6
)-N(R7)-R8, alkenyl group, alkenyloxy group, alkenylamino group, alkynyl group, alkynyloxy group, alkynylamino group, when n is 2, hydrogen atom, alkyl group, aryl group, cycloalkyl group, Represents a heterocyclic group, alkoxy group, aryloxy group, amino group, alkenyl group, alkenyloxy group, alkenylamino group, alkynyl group, alkynyloxy group, and alkynylamino group. R5, R6, R7, and R8 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or a heterocyclic group. Z is -N(R2)-N(
R3) Represents an atomic group necessary to form a 5- to 7-membered ring together with -X-. ]