JPH02118568A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility by adding a compd. which forms the dye of the hue suitable for color masking at the time of processing to the photosensitive material. CONSTITUTION:The compd. expressed by the formula I is incorporated into the title photosensitive material. In the formula, A denotes a residual coupler group or oxidation reduction group which releases -(L)n-DP imagewise as the function of silver halide development; DP denotes a residual dye precursor group having a nitroso group; L denotes a combination group or timing group; n denotes 0 or 1. The compd. expressed by the formula can be added to a desired emulsion layer or the adjacent layer thereof when A denotes the residual coupler group. The compd. expressed by the formula II, etc., are usable.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material and a processing method thereof. More specifically, the present invention relates to a silver halide photographic material having high sensitivity and improved brown color reproducibility.

(Prior Art) In silver halide color light-sensitive materials, in order to form a color image, yellow magenta and cyan dyes are produced by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. So-called dye-forming couplers (hereinafter simply referred to as couplers) are used. It is desirable that the yellow, magenta, and cyan dyes produced from these couplers exhibit vivid hues that absorb only light in the blue, green, and red regions, respectively. However, it is currently widely used as a magenta dye! - The azomethine dye of pyrazolone has sub-absorption in the blue region, and the phenol and naphthol-based indoaniline dyes used as cyan dyes have unnecessary absorption in the blue region and the /'- or green region. Furthermore, the yellow coupler's absorption of the azomethine dye is also less than ideal. In order to correct the color turbidity caused by this unnecessary absorption, one technique used in color negative films is a method of color correction by masking using colored couplers. However, since colored couplers are colored substances, they are basically accompanied by a decrease in sensitivity. For example, a magenta colored cyan coupler is added to the red-sensitive layer itself in order to correct the fact that the cyan coupler color forming dye has sub-absorption of green light. It has been found that because of absorption of the magenta colored cyan coupler on the long wavelength side, the amount of light on the short wavelength side of the red-sensitive layer is insufficient. For example, as a cyan coupler, US Patent No. Hiroshi, JJ! , Tatata issue or the same da, ≠j/,! When using the phenol-based cyan coupler disclosed in No. Significant.

Furthermore, for the same reason as mentioned above, it has been found that when a yellow-colored magenta coupler is used in the green-sensitive layer, the amount of light on the short wavelength side of the green-sensitive layer is insufficient, resulting in a decrease in sensitivity.

Furthermore, in a multilayer color negative film having blue, green and red sensitive layers, if a colored coupler is used in the upper layer, light will be absorbed there, which naturally reduces the sensitivity of the lower layer. For example, a multilayer film in which a blue-sensitive emulsion layer and a green-sensitive emulsion layer are coated in this order from the exposed side has the following disadvantages. In a typical subtractive color negative film, the blue-sensitive emulsion layer contains a yellow coloring coupler as an image-forming coupler. In order to correct the unnecessary absorption of green light by the color forming dye of the yellow coupler, it is necessary to use a magenta colored coupler together with the yellow coupler in the blue-sensitive emulsion layer. However, at this time, the amount of light in the lower green-sensitive emulsion layer was insufficient9, resulting in a fatal decrease in sensitivity. For the same reason, it has been difficult to use a yellow colored coupler in combination with a magenta coupler in a multilayer color negative film having a green-sensitive emulsion layer as the top layer.

On the other hand, extensive research has been conducted over many years in search of couplers that produce dyes of excellent hue and satisfy other performance requirements of photographic couplers. To give an example of the results, /H-pyrazolo[3,λ-C)-/, 2.
≠-triazole magenta coupler, % opening 51-
/H-pyrazolo[ described in / 7 / y zt issue
/,j-b]-/,,2. Couplers with excellent hues such as ≠-triazole magenta couplers have been developed, but colored couplers have also been developed in color negative films incorporating /H-pyrazolo [3, Kohdan]-/, J, ≠-triazole magenta couplers. The reality is that they are used in combination, and the problems mentioned above still remain.

In addition, ligand-releasing couplers (
Leuco dye-releasing coupler (JP-A-717μ7), fluorescent agent-releasing coupler (US Pat. No. 77, No. 1/l/),
Couplers that release a compound having a formyl group (US Pat. No. 777, No. 0) and the like are known.

(Object of the Invention) An object of the present invention is to solve the above-mentioned problems in silver halide photographic materials. That is, the object of the present invention is to provide a photographic material containing a compound that has only colorless or substantially harmless color when exposed to light and produces a dye of a hue suitable for color masking when processed.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, which is represented by the following general formula (1). This was achieved by a silver halide photographic material containing the compound.

General formula (I) A-(L)n-DP where A is imagewise -(L) as a function of silver halide development.
) represents a group releasing n-DP, where DP represents a dye precursor residue having a nitroso group. I, fl represents a covalent linking group or timing group, and n represents O or l.

(Structure of the Invention) The compound represented by the general formula (I) is a compound that releases -(L)n-DP by reacting with an oxidized form of a developing agent generated during development of silver halide in a developer solution, DP is preferably a compound that diffuses from A or L into the treatment solution after cleavage. DP is a compound in which a nitroso group and a developing agent react to form an azo dye during development. Dlj Regardless of whether the silver halide in the vicinity is exposed to light or not, it reacts with the developing agent to form a dye, but in the exposed area, it is released from the omitted compound represented by the general formula (I) as described above. Therefore, the dye generated from DP flows out of the film system. Therefore, the dye generated from the DP in the unexposed areas remains in the film. The present invention uses the dye produced here for masking for color correction and image formation.

In addition to being used as a masking compound in a color negative film as explained above, the compound represented by the general formula (1) of the present invention can be used in combination with a negative emulsion or a positive emulsion to form a positive color image or a negative color image, respectively. It can also be used in image forming methods such as

In general formula (1), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (for example, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide),
Magenta coupler residues (e.g. pyrazolone type, pyrazolotriazole type or pyrazoloimidazole type coupler residues), cyan coupler residues (e.g. phenol type, naphthol type or European Published Patent No. 2)
211jJ) and colorless coupler residues (for example, indanone-type or acetophenone-type coupler residues). Also, U.S. Patent No. '73/1070, 1t
/1373.2, 11171194, 36
It may be a heterocyclic coupler residue described in No. 19j or μ/7/co No. 23.

When A represents a redox group, the redox group is a group that can be cross-oxidized by an oxidized developing agent, such as hydroquinones, catechols, pyrogallols%'1
Mention may be made of ≠-naphthohydroquinones, l,-naphthohydroquinones, sulfonamidophenols, hydrazides or sulfonamidonaphthols. These groups are specifically, for example, JP-A-4/-230/J! No. 62-2117476, t/-27113-2
No. 336, U.S. Patent No. 0.22, U.S. Patent No. 337, U.S. Pat.
iJ,org,chem,,at,5ty(iytp>
This is what is described in .

In general formula (1), A preferably represents a coupler residue.

When A represents a coupler residue in general formula (1), A
Preferred examples are the following general formulas (Cp-/), (Cp-2)
, (Cp-J), (Cp-G), (Cp-7), (Cp
-1), (Cp-7), (Cp-ff), (Cp-ta)
Or, when it is a coupler residue represented by (Cp-10).

These couplers are preferred because of their high coupling speed.

General formula (Cp-/) General formula (Cp-2) General formula (Cp-j) General formula (Cp-4') -Cp-r) General formula (Cp-J) General formula (Cp-to ) General formula (Cp-7) General formula (Cp-, r) General formula (Cp-y) In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group.

In the above formula, FiR51, R52, R'sa, R54,
R55% FL56s R157% R58% ”59
%B60% When R61, R62 or Raa contains a diffusion-resistant group, it means that the total number of carbon atoms is ! The number of carbon atoms is selected to be between μ0 and μ0, preferably between IO and 30, otherwise the total number of carbons is preferably lj or less. In the case of bis-type, telomer-type or polymer-type couplers, any of the above substituents represents a divalent group and connects repeating units, etc. In this case, the range of carbon numbers may be outside the specified range.

R51 to R63, d and e will be explained in detail below. In the following, R4Z represents an aliphatic group, an aromatic group, or a heterocyclic group, R42 represents an aromatic group or a heterocyclic group, and R43, R44, and R45 represent a hydrogen atom, an aliphatic group,
Represents an aromatic group or a heterocyclic group.

几51 represents the same meaning as R41. R52 and R5
3 each represents the same meaning as R42. R54 is R418
02N- group, 11,418- group, R43〇- group, N atom, and also represents FiR41N- group. d represents 0 to 3. When d is a plurality of R59s, the plurality of R59s represent the same substituent or different substituents. Further, each R59 may become a divalent group and connect to form a cylindrical structure. Examples of the divalent group for forming a cyclic structure include a group having the same meaning as HR41. aSa and R57
each has the same meaning as the R43 group, R, IS- group, R43
Represents a 〇- group, R4IC0N- group, or R41802N- group. R58 represents a group having the same meaning as R41. R
A representative example of 59 is a group having the same meaning as R41. Here, g represents an integer from NdO to G, and g represents an integer from O to G, respectively. Represents a group having the same meaning as R601JR4t. R61nR, a group with the same meaning as 41, R62
is a group having the same meaning as R41, R4IC0NH- group, R41
0CONH- group, Gen atom or R41N- group. R63 represents R41R43 R430CO- group, R43O-8oz- group, norogen atom, nitro group, cyano group or R43CO~ group.

e represents an integer from O to ≠. Multiple R62 or h
When a63 is present, each represents the same or different thing.

In the above, the aliphatic group has 1 to 3 carbon atoms, preferably F
i/-22 saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group. Typical examples are methyl, ethyl, propyl,
Isopropyl, butyl, (1)-butyl, (i)-butyl, (1)-amino, hexyl, cyclohexyl, 2-
Ethylhexyl, octyl, /, /,! ,! -tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

Aromatic means a phenyl group having t-20 carbon atoms, preferably substituted or unsubstituted, or a substituted or unsubstituted naphthyl group.

A heterocyclic group is a substituted or unsubstituted heterocyclic group having 7 to 20 carbon atoms, preferably a nitrogen atom, an oxygen atom, or an iodine atom having 7 to 7 carbon atoms, preferably #: tj-membered to t-membered ring. It is.

Typical examples of heterocyclic groups include cobiridyl, cochenyl, -monfuryl, /-imidazolyl, l-indolyl, phthalimide, i, s, a-thiadiazol-2-yl, 2-quinolyl, λ, 4! -dioxo-7,3-imidazolidin-3-yl, u, 4(-dioxo-/, J-
imidazolidin-3-yl, succinimide, /, 2.
II-) A lyazole-koyl group or l-pyrazolyl.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include a halogen atom, 几470-1R46S-1R47C0N-R47N8
02-1R46802-1R47oco-1 or a nitro group. Here, 几46 represents an aliphatic group, an aromatic group, or a heterocyclic group, R47, R48 and R4
9Fi each represents an aliphatic group, an aromatic group, a hetero group, or a hydrogen atom. Aliphatic, aromatic or heterocyclic have the same meanings as defined above.

Next, preferred ranges of R51 to R63, d and e will be explained.

R51 is preferably an aliphatic group or an aromatic group.

R52, R53 and R55 are preferably aromatic groups.

R54ViR41CONH- group or R41-N- group is preferred. R56 and R57 are aliphatic groups, a41O
- group or a41S- group is preferred. R'ss is preferably an aliphatic group or an aromatic group -0 In general formula (Cp-4), R59 is a chloro atom, an aliphatic group or R4IC0
NH- group is preferred. d is preferably 1 or -. R2O
is preferably an aromatic group. In general formula (Cp-7))
'Lss is preferably an R41CONH- group.

In general formula (Cp-7), qd is preferably l.

R61 is preferably an aliphatic group or an aromatic group. General formula (
In Cp-za), e is preferably O or l. R62
Preferably, R41OCONH- group, R41CONH- group or R41802NH- group is substituted at the position of the 7 toll ring! Preferably. General formula (Cp-ta)
In, R63 is 几4ICONH- group, R41S
Preferably, O2NH- group, R4□N502- group, R41802- group, R41NCO- group, nitro group or cyano group.

In general formula (Cp-10), R63 is R43NC0-
group, R43CC〇- group or R43Co- group is preferred.

Next, a typical example of R51"R63 will be explained.
51 is (1)-butyl, l-methoxyphenyl,
Examples include phenyl, J-(,2(21 μm di-t-amylphenoxy)butanamido)phenyl, or methyl. iJ-chloro-j-dodecyloxycarbonylphenyl as R52 and R53, cochroro! -Hexadecylsulfonamidophenyl, cochrolow! −
Tet-2-decaneamidophenyl, cochloroz-(1-
(J.

μmdi-t-amylphenoxy)butanamido)phenyl, -monochloro-! -(co(2,≠-di-1-amylphenoxy)butanamido)phenyl, comethoxyphenyl, comethoxy! -tetradecyloxycarbonylphenyl, cochloro-j-(/-ethoxycarbonylethoxycarbonyl)phenyl, J-pylJdyl,
Cochloro-7-octyloxycarbonylphenyl,
2゜II-dichlorophenyl, λ-chlorot-('/
-dotesyloxycarbonylethoxycarbonyl)phenyl, s-chlorophenyl'! and u2-ethoxyphenyl.

R54 is 3-(co(,2,4A-di-1-amylphenoxy)butanamide)benzamide, 3-(
≠-(J, p-di-t-amylphenoxyacetamide) benzamide, λ-chloro! -dodecenyl succinimide anilino, cochloro-2-(λ-
(J-1-butyluda-hydroxyphenoxy)tetradecanamide)anilino, 2,2-dimethylpropanamide, -1(J-,z-ntadecylphenoxy)butanamide, pyrrolidino and #-tN,N-dibutylamino. . R55 includes J, 41. ．． 4- I
J Chlorophenyl, cochlorophenyl, λ.

! -dichlorophenyl, 'l''/chloro7enyl,
S, t-cyclol-methoxyphenyl, ≠-(2-
(Co,4!-di-t-amylphenoxy)butanamido)phenyl or J,A-dichloro-≠-methanesulfonylphenyl are preferred examples. Examples of R56 include methyl, ethyl, isopropyl, methoxy, ethoxy, methylthio, ethylthio, 3-phenylureido, or j-(2°gouge-t-amylphenoxy)propyl. R57 is 3-(ko, 4A-Gt-
amylphenoxy)propyl, J-(4C-(2-(<
2-(<<-hydroxyphenylsulfonyl)phenoxy)tetradecanamido)phenyl]propyl, methoxy, methylthio, ethylthio, methyl, l-methyl-co(λ-octyloxy-j-[co-octyloxy-
3-(/,/,J,J-tetramethylbutyl)phenylsulfonamide]phenylsulfonamide]needle, 3-(μm(tardodecyloxyphenylsulfonamide)phenyl)furovir, l,/-dimethyl- 2-(
Examples include 2-octyloxy-, t-(/,/,!,!-tetramethylbutyl)phenylsulfonamido]ethyl, or dodecylthio. R'ss Toshiha 2-
Chlorophenyl, antaproophenyl, heftafluoroprobyl, t-(x,ti-di-t-amylphenoxy)propyl, 3-(,2,44-di-t-amylphenoxy)propyl, co, darzi t-amylmethyl,
Or frills. R59 is a chlorine atom, methyl, ethyl, propyl, butyl, isopropyl,
Co(λ,4cm di-1-amylphenoxy)butanamide, -1(λ,4t-di-t-amylphenoxy)hexanamide, 2-(co,4cm di-1-octylphenoxy)octanamide,! Examples include -(J-chlorophenoxy)tetradecanamide, co(ter-(4!-hydroxyphenylsulfonyl)phenoxy)tetradecanamide, and td2-(co(2°googe-t-amylphenoxyacetamide)phenoxy)butanamide. R60 ≠-cyanophenyl, cocyanophenyl, ai-thylsulfonylphenyl, ii-furobylsulfonylphenyl, ≠-chloro-3-cyanophenyl, l-ethoxycarbonylphenyl, th3.4
A-dichlorophenyl is mentioned. R61 is dodecyl, hexadecyl, cyclohexyl, 3-(co, l
-di-t-amylphenoxy)propyl, 44-(J,
4! -di-t-amylphenoxy)butyl, 3-dodecyloxypropyl, -butyl, λ-methoxy, monododecyloxycarbonylphenyl, and 1ltl-naphthyl. Examples of R62 include isobutyloxycarbonylamino, ethoxycarbonylamino, phenylsulfonylamino, methanesulfonamide, benzamide, trifluoroacetamide, 3-7 dilureido, butoxycarbonylamino, or acetamide. As R63,! .

Gooji-t-amylphenoxyacetamide, co-(J
, #-di-t-amylphenoxy)butanamide, hexadecylsulfonamide, N-methyl-N-octadecylsulfamoyl, N,N-dioctylsulfamoyl, pt-octylbenzoyl group, dodecyloxycarbonyl, chloro Atom, nitro, cyano, N-(gu(
2, Gooji-t-amylphenoxy)butyl)carbamoyl, N-j-(2,μm di-t-amylphenoxy)
Mention may be made of flobilsulfamoyl, methanesulfonyl or hexadecylsulfonyl.

The group represented by L in general formula (1) is a group that leaves as L-DP when A reacts with the oxidized developing agent. That is, L is used to adjust the reactivity of the compound represented by the general formula (1) with the oxidized developing agent. Examples of the group represented by L include those known as coupling-off groups and those known as timing groups. Examples of the former include aromatic oxy groups, aromatic thio groups, aliphatic thio groups, nitrogen-containing heterocyclic groups bonded to A at the nitrogen atom (for example, !-pyrazolyl, l, co, ≠-triazole-/(or 4lyl, /-imidazolyl, /-benzotriazolyl, l-benzimidazolyl, imidazolidine-2,
≠-dione-3-yl, oxazolidine-2, goudion-3-yl%/1u, 4Z-) lyasiridine-3,1
-dione-U-yl, phthalimide or succinimide) or an aliphatic oxy group. These groups can be bonded to DP in substitutable positions. Moreover, you may have a substituent other than DP. The definitions of the aromatic group and aliphatic group, and the substituents that the aromatic group, aliphatic group, and heterocyclic group may have have the same meanings as described above for R41. When L represents a timing group, the bond between L and DP can be cleaved after leaving A as L-DP. Examples of such timing groups include groups that cause a cleavage reaction using an intramolecular nucleophilic reaction described in U.S. Patent No. 42; No. 323 or No. 4
! , 4Ccol, a group that causes a cleavage reaction using an electron transfer reaction described in r≠j, or a group that causes a cleavage reaction using the electron transfer reaction described in No. 2. Examples include groups that cause a cleavage reaction using an ester hydrolysis reaction described in No. A, 2A, 777.

When L represents a timing group, DP is bonded to L at a heteroatom contained therein (for example, an oxygen atom, a sulfur atom or a nitrogen atom).

The group represented by DP in the general formula (1) is a group containing a nitroso group, and the nitrone group and the developing agent react to form an azo dye without any redox reaction.

Specifically, DP is represented by general formula (II).

General formula (If) et , ·′. (No) a ゛ sa (X) b ゛ Q (Here, Het represents an oxygen, sulfur, or nitrogen atom and bonds with A-(L)n- of the general formula (1).

Q represents a group of nonmetallic atoms necessary to form an unsaturated ring together with the carbon atom (C), and X represents a substituent. a
represents an integer of 1 or more, and b represents an integer of 0 or more. When b represents an integer of 2 or more, all X's may be the same or different. ) Preferably in general formula (U) #'
ia is 1 or 0, particularly preferably Fi/.

b is preferably an integer from ijO to da, particularly preferably an integer from O to 2. Preferred nonmetallic atoms for forming the unsaturated ring skeleton in Q include carbon,
Examples include nitrogen, sulfur, oxygen, and phosphorus atoms, and carbon, nitrogen, sulfur, and oxygen atoms are particularly preferred. Further, in Q, the number of nonmetallic atoms forming the unsaturated ring skeleton (excluding hydrogen atoms on the ring) is preferably 3 to 10, and particularly preferably G/J. There are no particular restrictions on X as long as it does not adversely affect photographic properties.

The effects of the compounds of the present invention are particularly remarkable in the following cases.

The compound of general formula (1) of the present invention can be applied to a multilayer multicolor photographic material having at least one different spectral sensitivity on a support.
It can be applied mainly for the purpose of improving color reproducibility and increasing sensitivity. Multilayer natural color photographic materials usually have at least one each 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 required.

Furthermore, the compound of the present invention represented by the general formula (1) can be used in any layer such as a high-speed layer, a low-speed layer, or a medium-speed layer, and can also be used in a photosensitive silver halide emulsion layer or a layer adjacent thereto. Can be used.

Addition IIF of the compound of the present invention represented by general formula (1)
Although it varies depending on the structure and use of the compound i, /X/(7
-6 to 0 mol, particularly preferably H/~10-3 mol to 0. It is j mole.

When the compound of the present invention is used in the same color-sensitive layer as a coupler for forming a yellow color image, the group represented by DP is
Preferably, it is a magenta dye precursor or a cyan dye precursor.

When the compound of the present invention is used in the same color-sensitive layer as a coupler for forming a magenta color image, the group represented by DP is
Preferably, it is a cyan dye precursor or a yellow dye precursor.

When the compound of the present invention is used in the same color-sensitive layer as a coupler for forming a cyan color image, it is preferable that the group represented by DP is a yellow dye precursor or a magenta dye precursor.

When the couplers of the present invention are used in combination with image-forming couplers in the same photographic layer, they are particularly preferably used in combination with coequivalent couplers.

The compound of the present invention represented by general formula (1) may be used alone in a certain layer, or may be used in combination with a known coupler. When used in combination with other color image-forming couplers, the molar ratio of the compound of the present invention to the other color image-forming coupler (compound of the present invention/other color image-forming coupler) is 0. //Tata, Riri O/10. Preferably // tata ~ zo7zo
It is.

Specific examples of the compound of the present invention represented by general formula (I) are shown below. However, it is not limited to these.

(Compound example) (I) -+2) (I) -(8) 5fllN(1) -+61 α 1Nfit-Rishi112t-02LJ2J1(1)-
α [ α (1)-〇〇H BeU (1) -(1B (1)-α罎1) -(lη (JH Summer)-(11G H (1) -H (1)-α9 (1) - (to) (f) - EnH (1) - (c) Cε (1) - (c) OH (scheme λ) In scheme/SJ, base represents a base, specifically triethylamine, sodium carbonate, Sodium hydride, /, /, 3,3-tetramethylguanidine, etc.

(Production Example 1) Synthesis of Exemplary Compounds (1)-(11) The compound represented by the general formula (I) of the present invention can be synthesized by the method shown below.

In the case of a phenol or naphthol coupler (Cp-OH) substituted with a hydroxyl group at the da position, it can be synthesized by the method shown in Scheme 1.

j (Scheme 1) In addition, a coupler having a substituent such as no-rogen at the active position (Cp-Hal) can be synthesized by the method shown in Scheme λ.

Compound (A) (i/, og) and compound B (3°0 g) were reacted in DMF (/00 ml) in the presence of /, /, J, J-tetramethylguanidine (+, Ag) at room temperature for 20 hours. Ta. Thereafter, 1 ml of ethyl acetate was added, and the mixture was washed with water, /N hydrochloric acid, and an aqueous sodium carbonate solution, and then concentrated. The obtained residue was purified using a silica gel column (ethyl acetate-hexane t:io) to obtain 1.2 g of Exemplary Compound CI)-(1).

The compound obtained as a result of mass spectrometry was confirmed to be the target compound.

The light-sensitive material of the present invention only needs to be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, a red-sensory layer, and a silver halide emulsion layer on a support. There are no particular restrictions on the number or order of the emulsion layers and non-light-sensitive layers; a typical example is to create a plurality of silver halides with substantially the same color sensitivity but different sensitivity on the support. A silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of an emulsion layer, the light-sensitive layer being a unit light-sensitive layer sensitive to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in the following order from the support side: a red photosensitive layer, a green sensitive layer, and a blue sensitive layer. Depending on the situation, the above-mentioned order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-chromic layer.

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

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

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1.121,470 or British Patent No. 923.045. 2JW configuration can be preferably used. Usually, it is preferable to arrange the halogen emulsion layers so that the photosensitivity decreases in order toward the support, and a non-photosensitive layer is provided between each halogen emulsion layer. Also, JP-A-57
-112751, 62-200350, 62-
As described in Nos. 206541 and 62-206543, 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 photosensitive layer (BL) / high sensitivity blue photosensitive layer (811) / high sensitivity green photosensitive layer CGH) / low sensitivity green photosensitive layer 71 (G
L)/high sensitivity red sensitive layer (RH)/low sensitivity red sensitive layer (RL), or 811/BL/GL/GH/R
H/RL order or Bll/BL/GH/GL/RL
/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 lower sensitivity, and the lower layer 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 disposed and the photosensitivity gradually decreases toward the support. Even when composed of 3N having different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, a medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-speed emulsion layer may be arranged in this order from the side remote from the support.

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 chlorobromide containing about 30 mol% or less of silver iodide. be. 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) Nα17643
(December 1978), pp. 22-23, “1. Emulsion preparation and
1B716 (1979
(November 2013), 64B pages, Graphic "Physics and Chemistry of Photography", published by Paul Montell (P, Glafkide
s, Chemic et Ph1sique Pho
tograph-ique+ Paul Montel
+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin.

Photographic E++ulsion Ch
e+aistry (Focal Press+196
6) ), “Production and Coating of Photographic Emulsions” by Zelikman et al.
Published by Focal Press (V, L, Zelik+5a
net al, + Making and Coati
ng Photographic Emul-sion
t Focal Press+ 1964).

U.S. Patent Nos. 3,574.628 and 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 in Cutoff, Photographic Science and Engineering.
ence and Engineering) % No. 14 @ pages 248-257 (1970); U.S. Patent No. 4
．． No. 434,226, No. 4.414.310, No. 4,
433.048, British Patent No. 4,439.520, and British Patent No. 2.112.157.

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

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

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure N[L
17643 and NcL1B716, and the relevant parts are summarized in the table below.

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

For mulberry tabby plate seed plate ■Treasury L Muzuejie'' l Chemical sensitizer page 23 Page 648 right column 2 Anger intensity increasing agent Same as above 3 Spectral aggravating agent,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25, right page 650, left to right column 8 Dye image stabilizer, page 25 9 Hardener, page 26, page 651, left column 1O binder, page 26 Same as above 11 Plasticizer, lubricant, page 27, page 650, right column 12 Coating aid,
Pages 26-27 Page 650 Right column Surfactant 13 Static Page 27 Same 1 Inhibitor In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
．． It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure + -
(RD) Nl117643, vi-c-c.

As a yellow coupler, for example, U.S. Pat. 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. 5B-10739, British Patent No. 1.425.020, British Patent No. 1.476.760, US 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 Mazenk coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Patent No. 4.31
No. 0.619, No. 4.351,897, European Patent No. 73.636, US Patent No. 3.061.432, US Patent No. 3.725,064, Research Disclosure No. 24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure NIIL
24230 (June 19B4), JP-A-60-43
No. 659, No. 61-72238, No. 60-35730
No. 55-118034, No. 60-185951, U.S. Patent No. 4.500.630, U.S. Patent No. 4.540.
No. 654, No. 4.556.630, Koto 0 (PC?)
Particularly preferred are those described in No. 88104795.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4,052.212.
No. 4.146.396, No. 4.228.23
No. 3, No. 4.296.200, No. 2.369.9
No. 29, No. 2,801.171, No. 2,772.
No. 162, No. 2.895.826, No. 3.772
．． No. 002, No. 3.758.308, No. 4.33
4.011, 4.327.173, West German Patent Publication No. 3゜329.729, European Patent No. 121.365
A, No. 249°453A, U.S. Patent No. 3.446
．． No. 622, No. 4.333.999, No. 4,75
No. 3,871, No. 4.451.559, No. 4.4
No. 27.767, No. 4,690,889, No. 4
, 254.

No. 212, No. 4.296.199, JP-A-61-4
Those described in No. 2658 and the like are preferred.

Colored couplers for correcting unnecessary absorption of color-forming dyes are described in Research Disclosure Nα17643, Section ■-G, U.S. Patent No. 4,163,670, and Japanese Patent Publication No. 5
No. 7-39413, U.S. Patent No. 4.004,929,
No. 4.138,258, British Patent No. 1.146.3
No. 68 is preferred, and US Patent No. 4.
It is also preferred to use a coupler that compensates for unnecessary absorption of the coloring dye by means of a fluorescent dye released during coupling, as described in No. 774,181.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, European Patent No. 96.570 and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 20, No. 4,576°910, British Patent No. 2.10
2.173 etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
．． The patent described in paragraphs 1 and 1, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4,248.96
The one described in No. 2 is preferred.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, 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 photosensitive 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 described in JP-A-60-185950, JP-A-62-24252, etc., DIR coupler-releasing couplers,
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜3
Couplers that release dyes that produce aftercolor after separation, described in No. 02A, R, D, Somu 11449, 24241, JP-A-61
-201247 etc. bleach accelerator releasing couplers,
Gantt-emitting couplers described in U.S. Pat.
Examples include couplers that emit fluorescent dyes, as described in No. 1.

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

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

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid esters (dibutyl tucrate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amyl phenyl)). phthalate, bis(2,4-di-t-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.)
, benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
hydroxybenzoate, etc.), amide g (N, N-
diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2
．． 4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2,ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-
2-butoxy-5-tert-octylaniline, etc.)
, hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 501°C.
Any organic solvent having a temperature above about 160°C or below can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

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

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, page 28 of NCL 17643 and Nl11 of the same
8716, 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 the entire aqueous colloid layer on the side having the emulsion layer is preferably 28 μm or less, and the film swelling rate T1/ is preferably 30 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate TI/□ can be measured according to a method known in the art.6 For example, Photographic Science and Engineering (Photogr, Sci, Bng,), Vol. 19, 2 by A. Green et al.
%, can be measured by using a swellometer (swelling membrane) of the type described on pages 124 to 129, and TI/Snow is the maximum swelling membrane reached when treated with a color developer at 30°C for 3 minutes and 15 seconds. 90% of the thickness is defined as the saturated film thickness, and is defined as the time required to reach the film thickness of L/z.

Membrane swelling rate? +/□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above, using the formula: (maximum swollen film thickness -
It can be calculated according to (film thickness)/film thickness.

The color photographic material according to the present invention has the above-mentioned RD, k
17643, pages 28-29, and NlX1871
6, 615, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl, N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. 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, bromide salts, iodide salts,
Development inhibitors or anticapri agents such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo(2,2,2)octane), etc. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, and fogging agents such as sodium boron hydride. , auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediamine. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1
,1-diphosphonic acid, nitrilo-N,N,N-)limethylenephosphonic acid, ethylenediamine-N,N,N,N-
Tetramethylenephosphonic acid, ethylene glycol (0-
Typical examples include hydroxyphenylacetic acid) and their salts.

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

The pl+ of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that The amount of replenishment of these developers depends on the color photographic material to be processed, but -In
31 or less per square meter of photosensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be set to 00d or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

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

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■), Kobal) (I
Compounds of polyvalent metals such as I), chromium (IV), @ (II), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron ([1) or cobalt (I[[)];
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.; Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (nl) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention, and aminopolycarboxylic acid iron (II) complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. are particularly useful in both bleach and bleach-fix solutions. One of the bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (III) complex salts
) 11 is typically 5.5-8, but for faster processing, lower p! (You can also process it with

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;
．． No. 290.812, No. 2,059.988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group as described in JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, Research Disclosure kt7129 (July 1978), etc.; JP-A-50-140129 Thiazolidine derivatives described in Japanese Patent Publication Nos. 45-8506, 52-20832, 53-32735, and U.S. Pat. No. 3,706,561; West German Patent No. 1.127 .71
No. 5, iodide salts described in JP-A-58-16.235;
Polyoxyethylene compounds described in West German Patent No. 966.410 and West German Patent No. 2.748.430;
Polyamine compounds described in No. 836; other JP-A-49-
No. 42.434, No. 49-59.644, No. 53-9
No. 4,927, No. 54-35.727, No. 55-26
．． No. 506, the compound described in No. 58-163.940;
Bromide ion etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in US Pat.
The compounds described in U.S. Pat. No. 630 are preferred, and the compounds described in U.S. Pat. These bleach accelerators are particularly effective when bleach-fixing.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urn-al of the 5ociety of
Motion Picture and Te1e-v
ision [! ngineers Volume 64, P, 2
48-253 (May 1955 issue),
You can ask for it.

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. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microbial It is also possible to use the fungicides described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" published by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

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

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

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

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3.342.59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

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

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 5B-115438.

The various processing liquids used in the present invention are used at a temperature of 10°C to 50°C, and the standard temperature is usually 33°C to 38°C, but it is possible to use a higher temperature to accelerate the processing and shorten the processing time. Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

In addition, West German Patent No. 2,226.7 was developed to save silver on photosensitive materials.
70 or US Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Also, the halogenation of the present invention! ! The photosensitive material is U.S. Patent No. 4
, 500.626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and European Patent No. 210,660^2.

(Left below) Example: On a cellulose triacetate film support coated with an undercoat,
Sample 01, which is a multilayer color light-sensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rrT units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in g/rrT units. The coating amount is expressed in mol units per 1 mol of halogenated tai.

(Sample 101) 1st layer (Haley silane prevention layer) Black colloidal silver Silver 0.18 Gelatin 0.40 27th il
(Middle layer) 2.5-di-L-pentadecylhydroquinone 0.18E
-10,07 E X-10 B5-1 Gelatin 4th layer (second red-sensitive emulsion N) Emulsion G Sensitizing dye! 0.002 0.06 0.08 0.10 0, 10 0.02 1.04 9 0.25 Silver 0.25 6.9XIO-5 1,8X10-' 3, lX10-' 0.335 0.020 0.060 0.87 Silver 1.0 5, lX10-' Sensitizing dye■ Sensitizing dye■ X-2 X-3 X-10 B5-1 Gelatin No. 511 (third red-sensitive emulsion layer) Emulsion sensitization Dye I Sensitizing dye ■ Sensitizing dye ■ X-3 X-4 X-2 B5-1 B5-2 Gelatin No. 67i (intermediate layer) 050 0.015 0.060 1.30 tB 1.60 5.4X10-' 1.4X10 bow 2.4X10-' 0.010 o, os.

O,097 0,22 0,10 1,63 0,040 B5-1 gelatin 7th layer (first green emulsion layer) Emulsion A Emulsion B Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-6 X-1 X-7 X-8 B5-1 B5-3 gelatin 8th layer (second green emulsion layer) Emulsion C Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ 0.020 0.80 Silver 0.15 Silver 0.15 3.0X10 bow 1.0X10-' 3.8X10”-’ 0.260 G, 021 0.030 0.025 o, to.

O,010 0,63 Silver 0.45 2, lX10-' ? ,0X10-' 2.6X10-' X-6 X-8 X-7 B5-1 B5-3 gelatin 9th jli (3rd green emulsion layer) Emulsion E Sensitizing dye■ Sensitizing dye■ Exacerbating pigment■ X-13 X-11 X-1 B5-1 B5-2 gelatin No. tOW <Yellow filter layer) yellow colloidal silver X-5 0,094 o,ots O,026 0,160 0,008 0,50 Silver 1.2 3.5X10-' s,oxio”’ 3.0X10-' 0.015 0.100 0.025 0.25 0.10 1.54 ! ! 0.05 0.08 B5-1 gelatin No. 11N (first blue-sensitive emulsion N) Emulsion A Emulsion B Emulsion F Sensitizing dye■ X-9 X-8 B5-1 gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye■ X-9 X-10 B5-1 gelatin 13th layer (3rd blue-sensitive emulsion N) Emulsion H 0,03 0,95 Silver 0.08 Silver 0.07 Silver 0.07 3.5X10-' 0.721 0.042 0.28 1.10 Grudge 0.45 2, IX 10-' 0.154 0,00? 0.05 0.78 Silver 0.77 Sensitizing dye■ EX-9 B5-1 gelatin 14th N (1st protection N) Emulsion ■ υ−5 B5-1 gelatin 15th layer (second protective layer) polymethyl acrylate particles (Diameter approximately 1.5μm) gelatin In addition to the above ingredients, each layer contains H-1 and a surfactant were added.

EX-1 Shil EX-2 H EX-3 Silver 2.2X10-' 0.20 0.07 0.69 0.5 0.11 O017 0,05 1,00 0,54 0,20 1,20 Gelatin Curing agent EX-4 EX-5 EX-6 CJ+s(n) EX-7 EX-8 EX-9 EX-13 Shi1 Shi1 EX-10 Shi! EX-12 CJsO3Oρ Sensitizing dye V Sensitizing dye ■ Aggravating dye ■ Preparation of sample ioλ~104 The 1st/layer, 1st co-layer and 73rd layer of sample 10/
Samples 102-iot were prepared in the same manner as Sample 10/, except that the couplers shown in 1 were added. The obtained sample was
It was cut to a width of 3 mm.

Samples 10/-10t were exposed to uniform green light, then imagewise exposed to blue light, and developed as described below. At this time, the yellow density is Turnip +3-1-/, O
The interlayer effect was determined by subtracting the magenta density in the area not exposed to blue light from the magenta density at an exposure amount of . The results are shown in Table/I/C.

Processing process Process Processing time Color development 3 minutes/j seconds Bleached white 6 minutes 30 seconds Water wash 2 minutes 10 seconds Fixed arrival time: 1 minute λO seconds Washing with water (1) / minute 01 seconds Washing with water (2) 1 minute 00 seconds Stable 1 minute O! seconds Dry Dry Hirobunko O seconds Processing temperature 1r0C Ir0C Ha0C IOC ,2≠0C 2g 0C jf’c j0c Next, the composition of the treatment liquid will be described.

(color developer) diethylenetriaminepentaacetic acid l-hydroxyethylidene- 1,/-diphosphonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate Goo (N-ethyl-N-β- hydroxyethylamino) -Comethylaniline sulfate salt add water H (bleach solution) Ferric ethylenediaminetetraacetate (Unit: g) 1.0 3.0 μ, O Jo, 0 ／　、　≠ /, jmg +2, μ Gu, j /,0L 10.0! (Unit: g) sodium trihydrate Ethylenediaminetetraacetic acid dibasic acid thorium salt ammonium bromide ammonium nitrate Ammonia water (27ch) add water H (Fixer) Ethylenediaminetetraacetic acid dibasic acid thorium salt sodium sulfite sodium bisulfite Ammonium thiosulfate aqueous solution (70 chi) add water H (stabilizer) ioo,.

10, O 7 da Q, 0 Jo, O A, jm /、OL 6.0 (Unit: g) 　6　j 7.0 ! , 0 /70.0ml /、OL 4.7 (Unit: g) Formalin (37chi) polyoxyethylene-p-mo Nononylphenyl ether (Average degree of polymerization io) Ethylenediaminetetraacetic acid dibasic acid thorium salt add water H ! Ko, 0m1 0, J O, Oj /、OL , or.

As is clear from the table, Samples 102 to 10t of the present invention have substantially uniform magenta density and are excellent in printing and color reproducibility.

In addition, a color photosensitive material obtained in the same manner was used in a 33 m/
The sample was exposed to light using an optical knife after being cut into m widths, and was then processed in an automatic processor using a processing step (U) having the following processing steps and composition. As a result, we were able to obtain a photosensitive material with excellent color reproducibility, similar to the previous one.

(color developer) diethylene triamine pentaacetic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate μm (N-ethyl- N-β-hydroxy ethylamino) 111 methyl ani phosphorus sulfate l-hydroxyethyl mother liquid (b) ! , θ μ, 0 30, θ /, J /, 2mg λ, O l, 7 Ridden/,/ diphosphonic acid add water H bleach solution) replenisher) 7, O t, 0 3! , 0 0.2 ≠, O 6,j /,! -diaminozo ro/ξ-tetraacetic acid II Iron complex salt /,3-diaminop lono(tetraacetic acid) ammonium bromide acetic acid ammonium nitrate add water with acetic acid and ammonia H (Fixer) /-Hydroxyethyl 3.0 1.011 10, Oj mother liquid level) /20 (0,JJ mol/l) J, 0 /DO ! 0 /,011 q, 0 Mother liquid (g) Hiro, O /,011 10,　λ　O Replenisher (g) /10 (o, r.

mole/l) j, Q/! O t θ 4! O /, Ol 3.3 Replenisher (g) Reden-/, /- Diphosphonic acid 7.0 10.0 Ethylenediaminetetraacetic acid disodium salt 7.0 10.0 Ammonium sulfite it, o Coj, 0 Ammonium thiosulfate solution < 700g/l), 2'10m1 10m13
．． 6-Sythia l.

! -Octanediol! , 8 7.0 Add water
t, ol t, 01 p with acetic acid and ammonia
HA, j /:, j (Washing water) Common tap water for mother liquor and replenisher is mixed with H-type strongly acidic cation exchange resin (Rohm and Haas's Anno De Iite IR-/JOB) and OH-type anion exchange resin ( Same Anne Zo-Light IR-u00)
Filled with water and passed through a nine mixed bed column to reduce the concentration of calcium and magnesium ions to below Jmg/L, followed by adding sodium isocyanurate dichloride JOmg/L and sodium sulfate 0/j g/L. did.

The pH of this solution is 4. It was in the range of j-7,j.

(Stabilizing liquid) Mother liquid level) Replenishing liquid (g) Formalin (37%), Oml J, 0ml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0. ψ! Ethylenediaminetetraacetic acid disodium salt o, oz o, oz Add water /, OL /, 0LpH, t
, or, or, or,.

Example 2 On a subbed cellulose triacetate film support,
Sample 201, 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/m of silver for silver halide and colloidal silver, and the amount expressed in g/rrr for coupler additives and gelatin. The number of moles of the dye is expressed per mole of silver halide in the same layer.

1st layer (anti-halation N) Black colloidal silver...0.2 Gelatin...1.3Ex
M-8-0,06 UV-1...0. l UV-2・・・・・・ 0.2 Solv-1= 0.01 Solv-2”-・-0,01 2nd layer (intermediate layer) Fine grain silver bromide (average grain size 0.07 μm) ・・・・・・・ 0.10
Gelatin ・・・・・・ 1.5U
V-1・-・・・0. 06 υV-2...0.03 ExC-2・----0,02 EχF-1...0,004 Solv-1= 0. 1 Solv-2”... 0.09 3rd FJ (first red-sensitive emulsion N) Silver iodobromide emulsion (Ag1 2 mol%, internal high Agl type, equivalent sphere diameter 0.3 μm, variation in equivalent sphere diameter Coefficient 29%, normal crystal, twin crystal mixed grain, diameter/thickness ratio 2.5) Coated silver amount...
... 0.4 gelatin ...
・・ 0.6ExS-1=-1,0XIO-' ExS-2= 3.0XIO-' ExS-3= lXl0-' ExC-3-・-・-0,06 ExC-4・・・・-0 ,06 ExC-7---0,04 ExC-2...0.03 Solv-1=0.03 Solv-3="0.012 Fourth layer (second red-sensitive emulsion layer) ) Silver iodobromide emulsion (Ag1 5 mol %, internal tube Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twin mixed grains, diameter/thickness ratio 4) Amount of coated silver・・・・・・
・・・ 0.7 gelatin ・・・・・・
・0.5ExS-1= lXl0-' ExS-2= 3X10-' ExS-3= lXl0-' ExC-3= 0. 24 ExC-4=0. 24 ExC-7=0. 04 ExC-2...0. 04 Solv-1-" 0.15 Solv-3= 0.02 5th layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 110 mol%, inner cylinder Agl type, sphere equivalent diameter 0.8 μm, sphere Equivalent diameter variation coefficient 16%, normal crystal, twin crystal mixed grain, diameter/thickness ratio 1.3) Coated silver amount ・・・・・・ 1.0 Gelatin ・・・・・・ 1.0Ex
S-1= lXl0-'ExS-2...3X10-'ExS-3=
lXl0-'ExC-5=0. 05 ExC-6...0. I So 1 v-1:...0. Ol5olv
-2-0,05 6th layer (middle N) Gelatin 1.0Cp
d-1...0.03 So 1v-1=, 0.05 7th layer (first green emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal cylinder Agl type,
Equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 28%, normal crystal, twin crystal mixed grains, diameter/thickness ratio 2.5) Coated silver amount ...... 0.30 ExS-4 = 5X10- 'EχS-6...0.3X10-'ExS-5
”” 2X10°4 Gelatin ・・・・・・ 1.0E
xM-9・----0,2 ExY-14...0.03 ExM-8...0.03 SO1v-1...0.5 8th Layer (second green emulsion N) Silver iodobromide emulsion (Ag1 4 mol%, internal cylinder Agl type, equivalent sphere diameter 0.6 μm, coefficient of variation of equivalent sphere diameter 38%, normal crystal, mixed twin grains, diameter /thickness ratio 4) Coated silver amount...0.4 Gelatin - Old... 0.5ExS
-4... 5X10-'ExS-5= 2X
10-'ExS-6...0.3X10-'ExM-9
= 0.25 ExM-8=... 0.03 ExM-10... 0.015ExY-14・
...0.01 Solv-1 = 0.2 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal cylinder Agl type,
Equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 80%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 1.2) Coated silver amount ・・・・・・ 0.85 Gelatin ・・・・・・・1.0E
xS-7... 3.5X10-'ExS-8・
=... 1.4X10-'ExM-11・-・-・
0.01 ExM-12..."-0,03 ExM-13... 0.20 ExM-8= 0.02 ExY-15... 0.02 Solv-1"" 0.20 5olv-2-0.05 1st ON (yellow filter layer) Gelatin 1.2 Yellow colloidal silver 0.08
cp d-2...0. l5olv-1-
...0.3 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high Agl type,
Equivalent sphere diameter: 0.5 μm, coefficient of variation of 1 sphere equivalent diameter: 15%, octahedral particles) Coating amount of silver: 0.4 Gelatin: 1.0E
xS-9・= 2X10-' ExY-16= 0. 9 ExY-14...0.07 Solv-1=0. 2 12th layer (second blue emulsion N) Silver iodobromide emulsion (Ag1 10 mol%, internal high Agl type,
Equivalent sphere diameter 1.3 μm, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twin crystal mixed grains, diameter/thickness ratio 4.5) Coated silver amount ...... Gelatin ......ExS- 9
...... ExY-16... 5olv-1... Thirteenth layer (first protective layer) Gelatin ......UV-t
・・・・・・UV-2・・・・・・
・ 5olv-1... 5olv-2... 14th layer (second protective layer) Fine grain silver bromide (average particle size 0.07 μm)... Gelatin
...Polymethyl methacrylate particles (diameter 1.5 μm) ...H-1...
... Cpd-3... 0.5 0, 6 txto-' 0.25 0.07 0.5 0.45 0.2 0.4 0.5 cp d-4... ... 0.5 In addition to the above ingredients, a surfactant was added to each layer as a coating aid. Sample 20 was prepared as above.
It was set to 1.

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

5olv-1 ni tricresyl phosphate 5olv-2: dibutyl phthalate 5olv-3: Bis(2-ethylhexyl) phthalate ExM-8: UV-2: ExF-1+ ExC-2: II ExY-15: ExC-5: CH.

Crystal 8 Product ExY-14: ExC-6: 0I+ ExM-9: ExM-13: ExM-11: ExM-12: Cpd-1: H Cpd-2: ExS-1: ExS-2: ExS-3+ ExS -4: ExS-8: ExS-9: H-1: Ext-6+ Ext-7+ Cpd-3: Cpd-4: (Preparation of sample, 202~cot) 3rd layer, 3rd layer of sample 20/ Samples 20λ to 204 were prepared in the same manner as Sample 20/, except that the coupler of the present invention was added to the third layer. The obtained sample was cut to a width of 3 mm.

Samples KO/-JO& were uniformly exposed to green light, then imagewise exposed to red light, and developed as described below. At this time, a value obtained by subtracting the magenta density in the red light unexposed area from the magenta density at the exposure amount at which the cyan density becomes fog +7.0 was determined as the interlayer effect. The results are shown in Table 2.

Table 3 Treatment step (II) Process Processing time Color development 3 minutes! seconds Bleach White 7 minutes 00 seconds Bleach fixing 3 minutes/j seconds Water washing (1) 4tO seconds Washing with water (2) 7 minutes 00 seconds Stability Gu O seconds Drying 7 minutes lj seconds Processing temperature jr’c Jr’C Ir0C 33°C 3!0C r0C zz’c Next, the composition of the treatment liquid will be described.

(color developer) diethylenetriaminepentaacetic acid l-hydroxyethylidene- /,/-diphosphonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate Goo (N-ethyl-N-β- hydroxyethylamino) -1-Methylaniline sulfate salt add water pH (bleach solution) Ethylenediaminetetraacetic acid 2nd c unit g) /, 0 3.0 Hiro, O Jo, O 7. Da /, jmg Ko, ≠ ≠　　　　j /, 01 10, Oj (Unit: g) Iron ammonium dihydrate Ethylenediaminetetraacetic acid dibasic acid thorium salt ammonium bromide ammonium nitrate bleach accelerator Ammonia water (27%) add water pH (bleach-fix solution) Ethylenediaminetetraacetic acid 2nd Iron ammonium dihydrate Ethylenediaminetetraacetic acid dibasic acid thorium salt sodium sulfite Ammonium thiosulfate aqueous solution / Ko O.

10.0 100.0 10.0 ．． 00! mole 13.0m1 ,ol 6.3 (Unit: g) jO.

! l CO, 0 (70%) JIIO, 0 ml ammonia water (27%) t, 0 ml water added i, ol pH 7,2 (washing solution) Tap water was mixed with H-type strongly acidic cation exchange resin (Amber manufactured by Rohm and Haas) Water was passed through a mixed bed column filled with OH-type anion exchange resin (Amberlite IR-goo) to reduce the concentration of calcium and magnesium ions to below Jmg/l, and then Sodium incyanurate dichloride 20mg/l and sodium sulfate/! Omg/73 was added.

The pH of this solution is 4. It is in the range of j-7,j.

(Stabilizing liquid) (Unit: g) Formalin (37%) 2.0 ml polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) o, 3 Add ethylene diamitrium brine and add H-tetraacetic acid! 0, Oj i, ol -j As is clear from the table, Samples 202 to 202 of the present invention have substantially uniform magenta density and are excellent in color reproducibility.

Claims (1)

[Claims] (1) A silver halide photographic material having at least one silver halide emulsion layer on a support, characterized in that it contains a compound represented by the following general formula (I): . General formula (I) A-(L)_n-DP In the formula, A is imagewise -(L) as a function of silver halide development.
)_n-DP represents a group releasing DP, where DP represents a dye precursor residue having a nitroso group. L represents a divalent linking group or a timing group, and n represents 0 or 1.