JPH02262140A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material superior in color reproducibility and fastness of color images by incorporating a specified compound in at least one layer. CONSTITUTION:The silver halide color photographic sensitive material contains in at least one layer the compounds represented by formula I in which each of R1 and R2 is 2 - 24 C alkyl, alkoxy, or the like, independent of each other; each of R3 and R4 is a group substitutable on the benzene ring; L is a group capable of releasing A-DI after being released as (L)1-A-DI; A is a group to be allowed to release DI by reaction with the oxidation product of a developing agent; DI is a development inhibitor or its precursor; i is 0, 1, or 2; each of m and n is an integer of 0 - 4, independent of each other; and when each of i, m, and n is > 1, each of plural L, R3, or R4 optionally same or different, thus permitting both of color reproducibility and color image fastness to be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic material having excellent color reproducibility and color image fastness.

(Prior Art) In a silver halide color photographic light-sensitive material, the material is exposed to light and then subjected to color development, whereby an oxidized aromatic primary amine developer and a coupler react to form an image. is formed. In this system, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively.

Now, many techniques have been developed or proposed for improving color reproducibility. One example of this is the improvement of DIR couplers. That is, the DIR coupler is used for the purpose of improving sharpness by an edge effect and also improving color reproducibility by a multilayer effect. Many DIR couplers are known, but among them, highly reactive yellow coloring DIR
As a coupler, for example, the coupler described in US Pat. No. 4,149,886 is known. Further, as a type of DIR coupler in which the compound cleaved from the coupler is further oxidized to cleave the development inhibitor, for example, US Pat. No. 4,618
, No. 571, JP-A No. 61-233741 or No. 61
The coupler described in Japanese Patent No. 238057 is known.

(Problems to be Solved by the Invention) Although the above-mentioned known DIR couplers exhibit a certain degree of performance, further improvements have been desired. That is, a highly reactive yellow coloring DIR coupler has a problem in that the fastness of the obtained color image is low, particularly under storage conditions of heat and high humidity. In recent color negative photosensitive materials, when aiming at faithful color reproduction, there is a tendency to use DIR couplers in larger amounts than before, and there has been a strong desire for improvement in color image fastness.

That is, an object of the present invention is to provide a silver halide color photographic material having excellent color reproducibility and color image fastness.

(Means for Solving the Problem) The above object has been achieved by a silver halide color photographic light-sensitive material containing at least one layer of a compound represented by the following general formula [I].

General formula [I] In the formula, R1 and R2 each independently have 2 to 2 carbon atoms.
24, alkyl group, alkoxy group, alkylthio group,
Alkoxycarbonyl group, alkoxysulfonyl group or acylamino group, alkylsulfonyl group having 1 to 24 carbon atoms, aryl group, arylthio group, aryloxy group or arylsulfonyl group having 6 to 24 carbon atoms, or 7 to 24 carbon atoms represents an aryloxycarbonyl group, R5 and R1 represent groups that can be substituted on the benzene ring, L represents a group that cleaves A-DI after cleavage as (L), -A-DI, and A represents a group that cleaves A-DI after cleavage. Represents a group that reacts with the oxidized main agent to cleave DI, DI represents a development inhibitor or its precursor, and i represents O or 2
m and n each independently represent an integer of 0 to 4. However, when Lm or n represents a plurality, the plurality of glues, Rs or R4 represent the same or different things.

The coupler represented by the general formula (1>) used in the present invention will be described in detail below.

In the formula, the alkyl group or aryl group contained in the group represented by R and R2 is a halogen atom (fluorine atom,
chlorine atom, bromine atom, iodine atom), alkoxy group, aryloxy group, alkylthio group, arylthio group, aryl group, alkoxycarbonyl group, carbamoyl group, carbonamide group, sulfonamide group, sulfamoyl group, hydroxy group, acyl group, It may be substituted with an acyloxy group, an imide group, an alkylsulfonyl group, an arylsulfonyl group, or the like. Further, the alkyl group moiety may be branched or cyclic, and the aryl moiety may be substituted with an alkyl group. Specific examples of R1 and R2 include alkyl groups (e.g. ethyl, n-butyl, n-hexyl, n
-octyl, n-decyl, 2-decyl, phenethyl),
Aryl groups (e.g. phenyl, 1-naphthyl, 4-butoxyphenyl), alkoxy groups (e.g. ethoxy, n-
Butoxy, n-hexyloxy, n-octyloxy,
2-ethylhexyloxy, n-decyloxy, n-dodecyloxy, 2-decylthioethoxy, 2-hexyldecyloxy, 3-dodecyloxyprobyl), aryloxy groups (e.g. phenoxy, 4-t-butylphenoxy, 4-octyloxyphenoxy), alkylthio groups (e.g. n-octylthio, 2-ethylhexylthio, n-decylthio, n-dodecylthio, n-hexadecylthio), arylthio groups (e.g. phenylthio, 4-
dodecylphenylthio), alkylsulfonyl groups (e.g. n-octylsulfonyl, 2-ethylhexylsulfonyl, phenethylsulfonyl, n-decylsulfonyl,
methanesulfonyl, n-dodecylsulfonyl, 3-dodecyloxyprobylsulfonyl), arylsulfonyl groups (e.g. p-tolylsulfonyl, 4-methoxyphenylsulfonyl, 4-dodecylphenylsulfonyl), alkoxycarbonyl groups (e.g. n-butoxycarbonyl, n-hexyloxycarbonyl, n-octyloxycarbonyl, 2-ethylhexyloxycarbonyl, 1
-(octyloxycarbonyl)ethoxycarbonyl,
n-decyloxycarbonyl, n-dodecyloxycarbonyl, n-hexadecyloxycarbonyl), an alkoxysulfonyl group (e.g. n-octyloxysulfonyl, n-decyloxycarbonyl), an alkoxycarbonyl group (e.g. phenoxycarbonyl), and acylamino groups (for example, butanamide, 2-dimethylpropanamide, tetradecaneamide), and the like.

R1 or R1 is preferably an alkoxy group, an alkylsulfonyl group or an alkoxycarbonyl group, and more preferably an alkylsulfonyl group or an alkoxycarbonyl group.

In general formula CI), R8 and R4 represent groups that can be substituted on the benzene ring, specifically halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl groups (e.g. methyl, trifluoromethyl, trichloro methyl,
ethyl, isopropyl, t-butyl, cyclopentyl,
cyclohexyl, t-pentyl, 1,1,3.3-tetramethylbutyl, n-decyl), aryl groups (e.g. phenyl, p-tolyl, 2-chlorophenyl), alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy , benzyloxy, butoxy, n-octyloxy),
Aryloxy groups (e.g. phenoxy, 4-methoxyphenoxy), alkylthio groups (e.g. methylthio, ethylthio, hexylthio, benzylthio), arylthio groups (e.g. phenylthio, 4-chlorophenylthio),
Alkylsulfonyl groups (e.g. methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl), arylsulfonyl groups (e.g. phenylsulfonyl, I)-
), acyl groups (e.g. formyl, acetyl, benzoyl), acyloxy groups (e.g. acetoxy, benzoyloxy), carbonamide groups (e.g. acetamide, trifluoroacetamide, benzamide, octanamide), sulfonamide groups (e.g. methanesulfone) amide, trifluoromethanesulfonamide, toluenesulfonamide), hydroxyl group, carboxyl group, sulfo group, cyano group, alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl)
, aryloxycarbonyl (e.g. phenoxycarbonyl, 4-methoxyphenoxycarbonyl), amino group (e.g. amino group, N-methylamino, N,N-dimethylamino, pyrrolidino, piperidino, morpholino), heterocyclic group (e.g. 2 -furyl, 2-thienyl, 4-pyridyl), imido groups (e.g. succinimide, phthalimide), carbamoyl groups (e.g. N-methylcarbamoyl), sulfamoyl groups (e.g. N.

N-dimethylsulfamoyl), etc. m and n are θ
It is an integer of ˜4, but 0-2 is more preferable.

The total number of carbon atoms in (Rx)- or (R4)ll is 0 to 2
It is 4.

R3 or R4 of the compound represented by general formula [I]
A compound in which one of the substituents is an electron-withdrawing substituent is preferable because it has a high coupling activity with the oxidized product of an aromatic primary amine developer.The electron-withdrawing substituent in the present invention refers to Hammet's a .

A substituent having a value of 0 or more, preferably 0.2 or more, and specific examples include halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), trichloromethyl group, trifluoromethyl group, cyano group, acyl group, Nitro group, carboxyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, aryloxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, heterocyclic group (e.g. tetrazolyl, pyrrolyl, benzotriazolyl) benzoxacylyl), imido group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group,
Examples include trifluoromethoxy group, thiocyanate group, alkylsulfinyl group, and arylsulfinyl group. In addition, Hammet's σ2 value is C, Hansch et
al., J., Med.

Chem, 16, 120.7 (1973) and the same day.

304 (1977) etc. Among these electron-withdrawing groups, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkoxycarbonyl group, or an alkylsulfonyl group are preferred in the present invention.

The groups represented by the formula (I) may or may not be used. When the groups represented by the above are used, the following are preferred.

(1) Groups that utilize the hemisecure cleavage reaction, such as U.S. Pat. No. 4,146,396, JP-A-60-24
This group is described in No. 9148 and No. 60-249149 and is represented by -Noshiro below. Here, the mark * represents the position bonded to the coupling carbon atom of the coupler residue portion of the compound represented by general formula (1), and the mark ** represents the position where A is bonded to the coupling position carbon atom.
- Represents the position where it binds to DI.

General formula (T-1) In the formula, W is an oxygen atom, a sulfur atom or -NR&? RAS and R66 represent a hydrogen atom or a substituent, and R6? represents a substituent, and t represents 1, hS or 2. When t is 2, two -W-CA6's represent the same thing or different things. When R65 and R66 represent a substituent, representative examples of R67 are R69 group, RbqCO- group, R6,5(h-R?), respectively.
OR? 0 is mentioned. Here, R69 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R7° represents an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. R6s, R1 and R&? Each represents a divalent group, and cases in which they are linked to form a cyclic structure are also included. Specific examples of the group represented by -Noshiro (T-1) include the following groups.

(2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction, such as a timing group described in US Pat. No. 4,248,962. The following can be expressed in Noshiro.

General formula (T-2) *-Nu-L 1nk-E-** In the formula, * and ** represent the same meanings as explained in general formula (T-1), and Nu is a nucleophilic group. , an oxygen atom or a sulfur atom is an example of a nucleophilic species, and E represents an electrophilic group, which is a group that can undergo nucleophilic attack from Nu to cleave the bond with the mark **.Link is a link between Nu and E. represents a linking group that is sterically related so that it can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by -Noshiro (T-2) are as follows.

CH.

Water (3) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system.

For example, US Pat. No. 4,409,323 or US Pat. No. 4,4
It is described in No. 21,845 and is a group represented by -Noshiro below.

General formula (1-3) % formula % In the formula, * mark, ** mark, WlRbs, R66 and t are (
It has the same meaning as explained for T-1). Specifically, the following groups may be mentioned.

(4) A group that utilizes a cleavage reaction due to ester hydrolysis.

For example, the linking groups described in West German Published Patent Application No. 2,626,315 include the following groups.

In the formula, * and ** have the same meaning as explained for general formula (T-1).

General formula (T-4) -Noshiro (T-5)CH2-
Fujia *-Q-C-** *-3-C-**(
5) A group that utilizes the cleavage reaction of iminoketal.

For example, it is a linking group described in US Pat. No. 4,546,073, and is a group represented by the following limited formula.

General formula (T-6) In the formula, * marks, ** marks and W have the same meanings as explained in general formula (T-1), and R61 represents the same meaning as R1. Specific examples of the group represented by -Noshiro (T-6) include the following groups, and the group represented by DI in the general formula
This is a group represented by D-2). The * mark in the formula is the general formula (1)
represents the position of bonding with (L)i.

-Noshiro (D-1) ``Z'', ``Z+'' is preferably a non-containing compound necessary to form, together with -C=N-, a 5- to 7-membered heterocycle which may be a substituted or fused ring. Represents a group of metal atoms.

Examples of such heterocycles include pyrazole, triazole, tetrazole, imidazole, pyrrole, oxazole, thiazole, oxadiazole, thiadiazole, benzimidazole, pyridine, pyrimidine, or indazole. Particularly preferred among these are tetrazole, 1,3.4-thiadiazole, 1.3°4-oxadiazole, and 1,2.4-
It is a triazole.

General formula (D-2) *-N ""' Z i' Zz preferably represents a 5- to 7-membered heterocycle which may be substituted together with a nitrogen atom. Examples of such heterocycles include imidazole, 1,2,4-triazole, 1,
2.3-triazole, benzodriazole, pyrazole, virole, imidacillin-2-thione, oxazoline-2-thione, 1,2.4-) liazoline-3-thione, or 1,3.4-thiadiazolin-2-thione can be mentioned. Among these, 12.4 is particularly preferable.
-triazole, 1.2.3-triazole and benzotriazole.

The development inhibitors represented by -Noshiro CD-1) and (D-2) include cases where they are substituted with the substituents listed as R3 or R4 above. Specific examples of these development inhibitors are given in U.S. Pat. Nos. 3.227.554 and 39335.
No. 00, No. 4,149.886, No. 4,095,98
No. 4, No. 4 477.563, No. 4,421,845
No. 4.579,816, No. 4,782,012, JP-A No. 57-93344, No. 57-128335, No. 59-131934, No. 60-233650,
No. 61-11743, No. 61-230135, No. 6
No. 2-251746, No. 63-38938, No. 63-
No. 70252, No. 63-116153, No. 63-16
No. 9644, No. 63-261262, or No. 63-
It is described in No. 254453, etc.

The group represented by A in the general formula [I] is formed by the coupling reaction of the coupler represented by Noshiro [I] with the oxidized developing agent, the released (L), and the cleavage reaction of -A-DI.
A group that becomes a redox group or a coupler when -DI is released. The group represented by A is, for example, disclosed in JP-A-63-6
No. 550, the group represented by B, U.S. Pat.
No. 38,193, the group represented by coup(B), No. 4,618,571, the group represented by RED, Japanese Patent Application No. 63-50732, A-(L
), or in Japanese Patent Application No. 63-68299, a group represented by a 5-membered heterocyclic residue that binds to A-(LIDn. A is a heterocyclic residue contained therein). It is bonded to (L) represented by the general formula [I] at an atom, preferably an oxygen atom, a sulfur atom or a nitrogen atom.

- The group represented by A in Noshiro ['I] is preferably,
Redox group, hydroquinones, catechols,
Examples include sulfonamide phenols, aminophenols, pyrogallols, 3-pyrazolidones, and hydrazides.

These groups may be substituted with the substituents listed for R3 or R4 above.

Next, specific examples of the compound represented by the general formula [I] will be given, but the present invention is not limited thereto.

(Compound example) CH2C02C4H9 H3 Synthesis example (synthesis of exemplified compound (1)) It was synthesized using the following synthetic route.

20 g of compound 1, 13.5 g of compound 2 and 3.3 g of potassium carbonate were mixed with N,N-dimethylformamide 2
00ml and reacted at room temperature for 3 hours. Add 300ynl of ethyl acetate to the reaction mixture! Then, 300 ml of water was added, and the mixture was transferred to a separatory funnel and washed with water.

After washing with water until neutral, the oil layer was taken, and the solvent was distilled off under reduced pressure. The residue was developed by column chromatography (silica gel packing material), fractions containing the target product were collected, and the solvent was distilled off under reduced pressure. 13.8 g of amorphous Exemplified Compound (1) was obtained.

The compound of general formula [I] of the present invention can be applied to a multilayer multicolor photographic material having at least three different spectral sensitivities on a support.
It can be applied mainly to improve sharpness, sensitivity, and color reproducibility. Multilayer natural color photographic materials usually have at least one of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. The compounds of the present invention are used in the emulsion layer or its adjacent layer. Furthermore, the compound of the present invention can be used in any layer such as a high-sensitivity layer, a low-sensitivity layer, or a medium-sensitivity layer.

The amount of the compound of general formula [I] to be added varies depending on the structure of the compound, but preferably silver 1 is present in the same layer or an adjacent layer.
Per mole it is from 1X10-' to 0.5 mol, particularly preferably from 1X10-' to 1X10-mol.

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 light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same 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 includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
03. ．． Coupler, DIR compound, etc. as described in No. 7, No. 61-20038, etc. may be included, and a color mixing inhibitor as commonly used may be included.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
West German Patent No. 1.121,470 or British Patent No. 9
As described in No. 23,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer 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. 62-200350, No. 62-2
As described in No. 06541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL), or BH/BL/GL/GH/RH/RL, or BH/BL/GH//GL/RL/ They can be installed in the order of RH, etc.

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

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer that is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is arranged and the photosensitivity decreases sequentially toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support. In addition, they may be arranged in the following order: high-speed emulsion layer/low-speed emulsion layer/medium-speed emulsion layer or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer. Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

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

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

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

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

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), No. 1764.
3 (December 1978), pp. 22-23, °'1. Emulsion preparation
nd types)” and the same No. 18716
(November 1979), 648 pages, graphic "Physics and Chemistry of Photography", published by Paul Montell (P.

Glafkides, Chemie et Ph1s
ique PhotographiquePaul M
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffi)
n.

Photographic Emulsion Che
Mistry (Focal Press.

1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelik
Manet al, Making and Coat
ing Photographic Emulsion,
Focal Press, 1964).

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

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
nce and Engineering), 1st
4, pp. 248-257 (1970); U.S. Patent No. 4
, No. 434.226, No. 4,414,310, No. 433.048, No. 4,439,520, and British Patent No. 2,112,157. I can do it.

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

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

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are described in the aforementioned Research Disclosure No. 17643 and Research Disclosure No. 18716, and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and the relevant descriptions are shown in the table below: 1. Chemical sensitizers 2. Sensitivity enhancers 3. Spectral sensitizers , supersensitizers 4 brighteners 5 antifoggants and stabilizers 6 light absorbers, filter dyes UV absorbers 7 antistain agents dyes image stabilizers hardeners binders plasticizers, lubricants coating aids, surface actives Agent 13 Static inhibitor RD 17643 23 pages 23-24 pages 24 pages 24-25 pages 25-26 pages 25 pages right column 25 pages 26 pages 26 pages 27 pages 26-27 pages 27 pages RD 18716 648 pages right column Same as above page 648 Right column - Page 649 Right column Page 649 Right column - Page 649 Right column - Page 650 Left column Page 650 Left - Right column Page 651 Left column Same as above Page 650 Right column Same as above Same as above In addition, it prevents deterioration of photographic performance due to formaldehyde gas. Therefore, it is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde as described in U.S. Pat. No. 4,411.987 and U.S. Pat. No. 4,435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure.
(RD) No. 17643, ■-C to G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401.752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425°020, British Patent No. 1,476.760, U.S. Patent No. 3,973,968, British Patent No. 4,314,
No. 023, No. 4,511,649, European Patent No. 24
9.473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, same No. 4. ．． 351897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60
-33552, Research Disclosure No.
24230 (June 1984), JP-A-60-4.3
No. 659, No. 61-72238, No. 60-35730
No. 55-118034, No. 60-185951, U.S. Patent No. 4,500.630, U.S. Patent No. 4,540,
No. 654, No. 4,556,630, International Publication W08
Particularly preferred are those described in No. 8104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. 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. 2.80f, No. 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. 4.451,559, No. 4.4
27. ．． No. 767, No. 4,690,889, No. 4
．． Preferred are those described in No. 254.212, No. 4,296,199, JP-A-61-42658, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No. 17643.
Paragraph ■-G of U.S. Patent No. 4,163.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929, Japanese Patent No. 4,138°258, British Patent No. 1,146.
The one described in No. 368 is preferred. Also, U.S. Patent No. 4
It is also preferable to use a coupler which corrects unnecessary absorption of the coloring dye by means of a fluorescent dye released during coupling, as described in No. 774.181.

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

Typical examples of polymerized dye-forming couplers are disclosed in U.S. Pat. Nos. 3,451,820 and 4.080, . 211
No. 4,367.282, No. 4,409,32
No. 0, No. 4,576.910, British patent cylinder 2,10
It is described in No. 2,173, etc.

In addition to the coupler represented by the general formula (, I) of the present invention,
Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patent listed in Section VII-F, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, US Pat. No. 4,248,962 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound releasing couplers or DIR coupler releasing couplers, DIR coupler releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc. couplers, DIR coupler-releasing redox compounds or DIR redox compound-releasing redox compounds, couplers that release dyes that turn yellow after separation as described in EP 173,302A, R,D
, No.l 1449, No. 24241, JP-A-61-2
Bleach accelerator releasing couplers described in US Pat. No. 01247 etc., ligand releasing couplers described in US Pat. , 774.181, etc., which emit a fluorescent dye.

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 U.S. Pat. No. 2,322.027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutylphucrate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate). , decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
-Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetra decylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2.4
-di-t-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate,
Diocdyl azelate, glycerol tributyrate,
isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5-t-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), etc. . Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and Patent Application No. 1983-
Benzisothiazolone, n-butyl p-hydroxybenzoate, phenol, 2-(
It is preferable to add various preservatives or antifungal agents such as 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 same No. 187
16, 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 28 μm or less, more preferably 23 μm or less, and even more preferably 20 μm or less. Further, the membrane swelling rate T1/2 is preferably 30 seconds or less, and 20 seconds or less.
More preferably seconds or less. Film thickness is 25℃ relative temperature 55%
It means the film thickness measured under humidity control (2 days), and the film swelling rate T
172 can be measured according to techniques known in the art. For example, Knee Green (A,
Photographic Science and Engineering (Photogr. Green) et al.

Sci Eng, ), Volume 19, No. 2, 124~
It can be measured by using a swellometer (swelling membrane) of the type described on page 129, and T1/2 can be measured by
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when the film is treated at 0° C. for 3 minutes and 15 seconds, and is defined as the time required to reach the film thickness of T1/2.

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 is defined as the time taken to reach the saturated film thickness of T172, with 90% of the maximum swollen film thickness under the conditions described above being defined 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
o, 17643, pages 28-29, and same No. 187
16, No. 651, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-N-β-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 hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, ethylene glycol, diethylene glycol, etc. organic solvents such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as l-phenyl-3-pyrazolidone, tackifiers. , various chelating agents such as aminopolycarboxylic acid, aminopolyphosponic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxy Ethyliminodiacetic acid, l-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-)limethylenephosphonic acid,
Typical examples include ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, ethylene glycol (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-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 32 m2 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 m1.
! You can also do the following: 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. In other words, the capacity of the processing liquid (C
b) The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.

As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, methods using a movable lid as described in Japanese Patent Application No. 62-241342, Examples include the slit development method described in Japanese Patent No. 63-216050.

It is preferable to reduce the aperture ratio not only in both color development and black-and-white development steps, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a bleach-fixing treatment.

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 CIll), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (Ill),
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(m) complex salts, including ethylenediaminetetraacetic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) complex salt, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. . Furthermore, iron(III) aminopolycarboxylate
Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (III
) of a bleach or bleach-fix solution using a complex salt p) (usually 4
．． 0 to 8, but for faster processing, it is possible to process at an even lower pl.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290, 812, 2. o59.988, JP 53-32736, JP 53-57831, JP 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 Research Disclosure No. 17129 (July 1978), etc.;
Thiazolidine derivatives described in JP-A-50-140129; JP-A-45-8506, JP-A-52-20832
No. 53-32735, U.S. Patent No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 127
Iodide salts described in No. 715 and JP-A-58-16235; polyoxyethylene compounds described in West German Patent Publication Nos. 966.410 and 2748.430;
Polyamine compounds described in No. 836; other JP-A-49-
No. 42434, No. 49-59644, No. 53-949
Compounds described in No. 27, No. 54-35727, No. 55-26506, and No. 58-163940: bromide ions, etc. can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and in particular, compounds described in U.S. Pat. Compounds are preferred.

Further 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 are compounds having an acid dissociation constant (p k a ) of 2 to 5, and specifically preferred are acetic acid, propionic acid, and the like.

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. It is also preferable to use a thiosulfate in combination with a thiocyanate, a thioether compound, thiourea, or the like. As a preservative for fixer and bleach-fixer,
Preferred are sulfites, bisulfites, carbonyl bisulfite adducts, and sulfinic acid compounds described in EP 294,769A.

Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the 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℃~
The temperature is 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 stirring be as strong as possible.

A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62183460.
No. 62-183461, a method of impinging a jet of a processing liquid on the emulsion surface of a photosensitive material, and JP-A-62-18
A method of increasing the stirring effect using the rotating means of No. 3461,
Furthermore, there are methods to improve the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade installed in the solution, creating turbulence on the emulsion surface, and methods to increase the circulation flow rate of the entire processing solution. can give.

Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate.

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 processor used for processing the photosensitive material of the present invention is disclosed in Japanese Patent Application Laid-open Nos. 60-191257, 191258, and 1988.
It is preferable to have a means for conveying a photosensitive material as described in No. 1259. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-over of the processing liquid from the front bath to the rear 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.

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is J
our own of the 5ociety of
MotionPicture and Te1evis
ion Engineers Vol. 64, p. 248-2
53 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Others, such as benzotriazole, are described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal Agents J, Hygiene Technology Kinen" Sterilization, Disinfection, and Antifungal Technology of Microorganisms, and "Encyclopedia of Antibacterial and Antifungal Agents" by Japan Society for Antibacterial and Antifungal Research. Fungicides can also be used.

p) of the washing water in the processing of the photosensitive material of the present invention (is 4
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, the temperature range is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. 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 Nos. 57-8543 and 58-14
All known methods described in No. 834 and No. 60-2203.45 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-medilol compounds, hexamethylenetetramine, and aldehyde bisulfite adducts, and nonionic surfactants are preferred, especially alkyl Phenyl ether-based and silicon-based compounds are preferred. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process. When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

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 the 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, Schiff base-type compounds described in Research Disclosure No. 14850 and Research Disclosure No. 15159, Research Disclosure No. 13
Aldol compounds described in '924, U.S. Patent No. 3.71
Metal salt complex described in No. 9,492, JP-A-53-1356
Examples include the urethane compounds described in No. 28.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. A typical compound is disclosed in Japanese Patent Application Laid-open No. 1983. -64339, No. 57-144547, No. 58-115438, etc.

Various processing solutions in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, 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. be able to. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226,770 or U.S. Patent No. 3
．． A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674.499 may also be carried out.

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
No. 9-218443, No. 61-238056, European Patent No. 210,660. It can also be applied to heat-developable photosensitive materials such as those described in No. A2.

(Effects of the Invention) The silver halide color photographic light-sensitive material of the present invention is excellent in both color reproducibility and color image fastness (light fastness and fastness under storage conditions of heat and high humidity).

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/rrr of silver for silver halide and colloidal silver, and the amount expressed in g/rrr for couplers, additives and gelatin is increased. For sensitive dyes, silver halide 1 in the same layer
Expressed in moles per mole.

1st layer (antihalation layer) Black colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・OoE
xM-9・・・ゝ・・・・・・・・・・・・・・・
・・・・・・・・・・0UV-1・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・09
UV-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・01UV-3・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・0゜5olv-1・・・・・・・・・・・・・・・
・・・・・・・・・・・・01SoLv-2・・・・・・
・・・・・・・・・・・・・・・・・・・・・0゜5o
lv-3・・・・・・・・・・・・・・・・・・
・・・・・・0゜Second layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0UV-t・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・0゜E x C= 4 ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0ExF−
1・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・0゜5olv−1・・・・・・・・・・・・
・・・・・・・・・・・・・・・01SoIV-2・
・・・・・・・・・・・・・・・・・・・・・・・・
・O1 third layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter /thickness ratio 3.0) Coated silver amount...1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.
3μ, coefficient of variation of equivalent sphere diameter 15%, spherical particles, diameter/thickness ratio 1.0) Coated silver amount...0.6 Ceratin
・・・・・・・・・・・・n1・・・n1・・・・
・0.8ExS-1...n1...old...
Old・dan・4X10-4ExS=2 river・n1...n
1...n1...5X10-'ExC-1/old...
・・・・・・・・・n1・・・old・0.05ExC-2
......n1...old...n1...0.50E
xC-3...n1...old...
・・・0.03ExC-4・・・・・・・・・・・・Dan・
...n1...0.12ExC-5...
・・・・・・・・・・・・・・・Old・・Dan・0.01
4th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 1:
1 internal high AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-shaped particles, diameter/thickness ratio 5.0) Coated silver amount...0.7 Gelatin
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.8ExS-1・・・・・・・・・
・・・・・・・・・・・・・・・・・・3X10
-'ExS-2・・・・・・・・・・・・・・・・・・
・・・・・・2.3X10-'ExC-6・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.
11ExC-7・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.05ExC-4・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・0.05S o 1 'v -1・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.05Sol
v-3・・・・・・・・・・・・・・・・・・・・・
・・・・・・0.05 5th layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.5Cpd-1・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・0. 1Solv-1・・・・・・・・・・・・・・・
......05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio 1:
1 surface height AgI type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 4.0) Coated silver amount...0.35 Silver iodobromide emulsion ( AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0
．． 3LL, coefficient of variation of equivalent sphere diameter 25%, spherical particles, diameter/thickness ratio 1.0) Coated silver amount...0°gelatin ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・1゜ExS-3・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・5×ExS-
4・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・3×ExS-5・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・1×ExM-8
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・0゜ExM-9・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0゜ExM-10
・・・・・・・・・・・・・・・・・・・・・・・・
・・0゜ExY-11・・・・・・・・・・・・・・・
・・・・・・・・・・・・0゜5olv−1・・・・・・
・・・・・・・・・・・・・・・・・・・・・01S
olv-4・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜7th layer (high sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio 1:
3 internal high AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 5.0) Coated silver amount...0°gelatin ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・04ExS-3・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・5×ExS−
4・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・3X10-'ExS-5・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・lXl
0-'ExM-8・・・・・・・・・・・・・・・・・・
......River...0. 1ExM-9...
・・・・・・・・・・・・・・・・・・・・・・・・
0.02ExY-11・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.03ExC-2・・・・
・・・・・・・・・・・・・・・Old・・・・・・・・・0
．． 03ExM-14・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.01Solv-1・・・・
...Old...Old and old...0.2Solv-4
・・・・・・・・・・・・・・・・・・・・・・・・
・0.01 8th layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.5cpci-x ・
・・・・・・・・・・・・・・・・・・n1・・・・・・
0.05Solv-1...Old...Old...0.029th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 2 mol%,
Internal high AgI type with core-shell ratio 2:1, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 15%, plate-shaped particles, diameter/thickness ratio 6.0) Coated silver amount...0.35 iodine Silveride emulsion (AgI 2 mol%, internal high AgI type with a core-shell ratio of 1:1, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter/thickness ratio 6.0) Coated silver Amount: 0゜gelatin ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・0゜ExS-3・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・8×ExY-13
・・・・・・・・・・・・・・・・・・・・・・・・
・・OExM-12・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0゜ExM-14・・・・・・
・・・・・・・・・・・・・・・・・・・・・0゜5o
lv-1・・・・・・・・・・・・・・・・・・
・・・・・・O1 10th layer (yellow filter layer) Yellow colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0Cp
d-2・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜5olv−1・・・・・・・・・
・・・・・・・・・・・・・・・Mountain 01cpa-i
・・・・・・・・・・・・・・・・・・・・・・・・
...0゜11th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (A'gI 4.5 mol%, uniform-AgI type,
Equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount...0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount...O.

Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・1゜ExS-6・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
2xExC-16・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0゜ExC-2・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0゜E
xC-3・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜ExY-13・・・・・・・・・
・・・・・・・・・・・・・・・・・・00ExY-
15・・・・・・・・・・・・・・・・・・・・・
・・・・l5olv-1・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0, 12th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter 1.0μ, sphere Coefficient of variation of equivalent diameter 25%, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver amount...0.5 Gelatin... ...
・・・・・・・・・・・・0゜ExS-6・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
1×ExY-15・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜ExY-13・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・00Sol
v-1・・・・・・・・・・・・・・・・・・・・・
・・・・・・0゜13th layer (first protective layer) Gelatin ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0゜UV-4・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0゜UV-5・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0゜5olv−1・・・・・・
・・・・・・・・・・・・・・・・・・・・・0゜5
olv-2・・・・・・・・・・・・・・・・・・
......O0 14th layer (second protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.07 μ) ......・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0゜gelatin ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・0゜Polymethyl methacrylate particle diameter 1.5μ ・・・・・・・・・・・・・・・・・・
・・・・・・0゜H-1・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・00c
pa-5・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜Cpd-6・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・ 0.5 In addition to the above-mentioned sensitivity, each layer contains emulsion stabilizer Cpa-3 (0.5
,04g/rr? ), surfactant cpti4 (0,
02g/rr+') was added as a coating aid.

Bu UV-Hiro TJ V -j Solv-/Solv-2 Tricresyl phosphate dibutyl phthalate S□! v-3 Cpd-J H Cpd-ReCpd-, t Cpd-4 Solv-Hiroshi Cpd-/ Cpd-2 ExC-λ ExC-3 6H13! ExC-g ExC-j ExM-g ExM-taExC-A H2 C(CHa)3 X S-, J ExS-Hiro α ExC-/A ExS-/ ExS-j ExS-6 -t CH2=CH-8o 2-CH2-CONH-CH2C
H2=CH-8o2-CH2-CONH-CH2=CH
-t ・C2H50S03゜ (Creation of samples 102 to 109) ExY-13 in the 11th layer and 12th layer in sample 101
Sample 101 was prepared in the same manner as sample 101, except that the couplers shown in Table 1 were added in equimolar amounts instead.

(Coupler for comparison) ExY-17 (Cub Sea described in U.S. Pat. No. 4,149,886) ExY-19 (Japanese Patent Application Laid-open No. 61-2380
After exposing samples 101 to 109 of ExY-18 (a coupler described in US Pat. No. 4,618,571) to sample 109, the following treatments were performed.

In order to examine the color image preservation of the obtained processed sample,
One sample was stored in the dark at 70% RH for 14 days at ℃, and the other was irradiated with a xenon light source (180,001 ux) for 24 hours. Dark fading and photobleaching were evaluated for each sample.

The results are shown in Table 1.

The magnitude of the multilayer effect was evaluated as follows.

First, each sample was exposed to uniform green light, the exposure amount was adjusted so that the G density was 1.5, and the exposed sample was then imagewise (wedge) exposed to blue light. Afterwards, the development process shown below is carried out, resulting in a yellow color image as shown in Figure 1). (1) and a density curve (2) of a magenta color image were obtained. When the blue-sensitive emulsion layer is developed from the unexposed area (point A) to the exposed area (point B), the density curve of the green-sensitive emulsion layer given uniform exposure changes from the blue-sensitive emulsion layer to the green-sensitive emulsion layer. The degree of suppression experienced by the green-sensitive emulsion layer (ΔD,
) is meant to indicate.

That is, in the first cycle, curve 1 represents the characteristic curve of the yellow color image of the blue-sensitive emulsion layer, and curve 2 represents the magenta color image density of the green-sensitive emulsion layer upon uniform exposure to green light.

Point A represents the minimum density portion of the yellow color image, and point B represents the exposure amount portion that provides a yellow density of 2.0.

The density difference (ΔDQ) between the magenta density (D, = 1.5) at the unexposed area point A and the magenta density (Db) at the same point B
=D-Db), and this ΔD was evaluated as a measure of the multilayer effect.

The above method was used for samples 101 to 109. The results are shown in Table 1.

Processing method Process Processing time Color development 3 minutes 15 seconds Bleach White 1 minute 00 seconds Bleach fixing 3 minutes 15 seconds Washing with water (1140 seconds Washing with water (2) 1 minute 00 seconds Stability 40 seconds Drying 1 minute 15 seconds Next, the composition of the treatment liquid will be described.

(Color developer) Diethylenetriaminepentaacetic acid l-Hydroxyethylidene-1゜1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxyamine sulfate 4-(N-ethyl-N-β-H treatment temperature 38°C 38 °C 38 °C 35 °C 35 °C 38 °C 55 °C (unit g) 1,0 Droxyethylamino)-2- Add methylaniline sulfate solution to pH (bleach solution) Ethylenediaminetetraacetic acid ferric ammonium trihydrate Ethylenediaminetetraacetic acid Disodium acetate Salt Ammonium bromide Ammonium nitrate Aqueous ammonia (27%) Add water to pH (bleach-fix solution) Ethylenediaminetetraacetic acid ferric a4,5 1.0℃ 10.05 (Unit g) 120.0 10, 0 100.0 10,0 15.0m4 1,0Flood6,3 (Unit g) Ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12. O ammonium thiosulfate aqueous solution (70%) 240.0 m flooded ammonia water (27%) 6.0 Add water '1. OpH7,2 (Washing liquid) A mixed bed filled with tap water filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through the column to reduce the concentration of calcium and magnesium ions to 3 mg/β or less, and then 20 mg/I2 of sodium isocyanurate dichloride and 150 mg/β of sodium sulfate were added.

The pH of this solution is in the range of 6.5-7.5.

(Stabilizing liquid) Formalin (37%) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add ethylenediaminetetraacetic acid disodium salt solution to pH 5° (unit: g) 2,0 Ttl [I 0, 30 , 05 1, 04 0-8° It can be seen that in samples 101 to 103, both dark fading and photofading worsened by adding the DIR coupler of the comparative example. However, if a DIR coupler having the structure of the present invention is used, as can be seen from the results of samples 104 to 108,
It is desirable that both dark fading and photofading are improved, and the multilayer effect is large. Sample 109 had relatively good color image fastness, but poor multilayer effect. This indicates that the reactivity of the DIR coupler with the oxidized developing agent is low and the reaction does not occur sufficiently during development.

Example 2 Samples 101 to 109 prepared by the method described in Example 1 were cut to a width of 35 mm, and a standard subject was photographed.
Fuji Photo Film ((7) Color Negative Processor FP
A running test of 500 m was conducted using the -350 according to the method described below.

After the running, samples 101 to 109 were wedge-exposed with white light, and the following treatments were performed, and dark fading and photofading were evaluated in the same manner as in Example 1.

As a result, as in Example 1, in Example 2 as well, results were obtained that the sample to which the coupler having the structure of the present invention was added had excellent dark fading and photobleaching, and had a large multilayer effect.

Processing method Color development 3 minutes 15 seconds 38℃ 45mtiog bleaching 1 minute 00 seconds 38℃ 20ml 4J2 bleach fixing 3 minutes 15 seconds 38℃ 30TII [! 10
β water washing (2) 1 minute OO seconds 35℃ 30m1 4℃ low
Constant 40 seconds 38℃ 20m1 4 times dry
1 minute 15 seconds 55°C The amount of replenishment is per 35 mm width and 1 meter length.In the above process, the amount of bleach-fix solution brought into the washing process is 2 Tnl per 1 meter length of photosensitive material with a width of 35 mm/m!
Met.

Next, the composition of the treatment liquid will be described.

(color developer) Mother liquor (g) Replenisher (g) diethylenetriamine pentaacetic acid 1-hydroxyethyl Chin-1,1-dipho Sulfonic acid 3゜ Sodium sulfite 4゜ Potassium carbonate 30° Potassium bromide 1゜ Potassium iodide l.

Add hydroxylamine sulfate 2゜4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate water H 1,0 4,55,5 1, Oj2 1.0j2 10.05 10 .10 1, 1 0 3, 2 0 4, 4 0 37, '0 4 0, 7 mg 4 2, 8 (Bleach solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid ferric ammonium trihydrate Ethylenediaminetetraacetic acid diacetate Sodium salt Ammonium bromide Ammonium nitrate Bleach accelerator Aqueous ammonia (27%) Add water to pH (Bleach-fix solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid Ferric ammonium trihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite (units) g) 120.0 1O00 100, 0 1O00 0,005mol 15.0TIl[1 1,0β 6.3 (Unit g) 50, 0 5, 0 12, 0 Ammonium thiosulfate aqueous solution (70%) 240.0m 117 TIl 7 Water (27%) 6.0ml! Add water to pH 1.04 pH 7.2 (Washing solution) Mother liquor and replenisher Common tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-120B manufactured by Rohm and Haas). Water was passed through a mixed bed column packed with Light I R-400) to reduce the concentration of calcium and magnesium ions to 3 mg/A or less, followed by sodium dichloride isocyanurate 20 mg/I.
2 and 150 mg/β of sodium sulfate were added.

The pH of this solution was in the range of 6.5-7.5.

(Stable solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 2.0 TIl [! Polyoxyethylene-rumonononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water
1.0°C pH 5.0'-8.0 Example 3 The same test as in Example 2 was conducted except that only the treatment steps in Example 2 were changed to the treatment steps shown below. The multilayer effect was evaluated.

As a result, as in Example 1, in Example 3, dark fading and
The results showed that the photobleaching was excellent and the interlayer effect was large.

Processing method Color development 2 minutes 30 seconds 40℃ 10ml 8℃ bleach fixing 3 minutes 00 seconds 40℃ 20ml 8I2 water washing (2) 20 seconds 35℃ 10m[l Stable 20 seconds 35℃ ion drying 50
seconds 65°C Replenishment amount per 35 mm width and 1 m length Next, the composition of the processing solution is described.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid l-hydroxyethyritine-1,1-dipho2,0 2.2 Sulfonic acid 3.0 3.2 Sodium sulfite 4.0 5.5 potassium carbonate
30.045.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxyamine sulfate 2.4 3.04-[N-
Add ethyl-N-(β-hydroxyethyl)amino]-2-methylaniline sulfate to pH 1,0I2 7,5 1,02 4.5 10.20 10.05 (bleach-fix solution) mother liquor, replenisher Common ferric ammonium ethylenediaminetetraacetate ethylenediaminetetraacetic acid disodium salt sodium sulfite ammonium thiosulfate aqueous solution (unit g) 50,0 5, 0 12,0 (70%) Acetic acid (98%) Bleach accelerator 260, 0 TIl [1 5 ,0ml 0.01mol Si (add water 1.0I2pH6
, 0℃ (Water solution) Mother liquor and replenisher Common tap water was mixed with H-type acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through the packed mixed bed column to reduce the concentration of calcium and magnesium ions to 3 mg/I2 or less, and then 20 mg/I2 of sodium incyanurate dichloride and 1.5 g/ρ of sodium sulfate were added.

The pH of this solution is in the range of 6.5-7.5.

(Stable solution) Common to mother solution and replenisher solution (Unit: g)
? ') (37%) 2.0 m [1 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water
1.04p8
5.0-8.0

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between the characteristic curve of a yellow image and the density curve of a magenta color image with the multilayer effect.

Claims (1)

[Scope of Claims] A silver halide color photographic material, characterized in that it contains a compound represented by the following general formula [I] in at least one layer. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. or an acylamino group, an alkylsulfonyl group having 1 to 24 carbon atoms, an aryl group, arylthio group, aryloxy group, or arylsulfonyl group having 6 to 24 carbon atoms, or an aryloxycarbonyl group having 7 to 24 carbon atoms; , R_3 and R_4 represent groups that can be substituted on the benzene ring, L represents a group that cleaves A-DI after cleavage as (L)_i-A-DI, and A reacts with the oxidized developing agent, DI represents a group that cleaves, DI represents a development inhibitor or its precursor, i represents an integer of 0 to 2, and m and n each independently represent an integer of 0 to 4.However, i
, m or n represents a plurality, a plurality of L, R_3
Or R_4 represents the same or different. )