JPH03130764A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the graininess, sharpness, color reproducibility and preservable property with lapse of time of the sensitive material by incorporating silver halide particles having a specific silver iodide content above than a prescribed amt. and a specific compd. into the photosensitive material. CONSTITUTION:The emulsion layer of this photosensitive material contains the emulsion in which the silver halide particles having >=9mol% silver iodide content occupy >=40wt.% of the total silver halide particle in the layer. The compd. expressed by formula I is incorporated into this emulsion layer. In the formula I, R1 to R4 denote H, lower alkyl; R5 denotes H, acylamino, etc.; n denotes 1 to 4; TIME denotes a timing group; DI denotes a development restrainer. The compd. in which Z is the group of formula III is usable when the formula I is expressed by formula II.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and in particular contains a silver halide emulsion with a high silver iodide content and a Taiminog type DIR coupler, and has a granular shape. The present invention relates to a silver halide photosensitive material that has extremely excellent properties such as sharpness, sharpness, color reproducibility, and photosensitive material storage stability.

(Prior Art) In recent years, silver halide photosensitive materials, especially photographic photosensitive materials, have been developed using I Souθ, which has high image quality with an ISO sensitivity of 100.
There is a demand for photosensitive materials, such as θ photosensitive materials, which are highly sensitive, have excellent graininess, sharpness, single-color reproducibility, and have excellent storage stability.

Among these, JP-A-11-A Kotada No. 2 was used for the purpose of improving sharpness, color reproducibility, and storage stability of photosensitive materials.

No. 3-373, etc., new IR compounds were proposed. It is true that these compounds have improved sharpness and single-color reproducibility, but the long-term storage stability of photosensitive materials is unsatisfactory, and the Photographic Society of Japan
P! As pointed out in Vol. 2/pages 60-111 (ivyP), it has become clear that these compounds are inferior in graininess to conventional DIRIR compounds.

Regarding silver halide emulsions containing high silver iodide, #i, JP-A-60-/473337, JP-A No. 5r-tt1037,
Same AO-/Col φ-tei 3, Same 1-24'j/j/,
Although it is described in JP-A-62-41932 and JP-A-1-1IA'FJI, the sharpness and color reproducibility of these proposed photosensitive materials were unsatisfactory.

(Problems to be Solved by the Invention) An object of the present invention is to provide a photosensitive material that satisfies graininess, sharpness, one-color reproducibility, and storage stability over time.

(Means for Solving the Problems) The objects of the present invention have been achieved by the following color photosensitive materials.

In a silver halide color photographic light-sensitive material having at least seven silver halide emulsion layers provided on a support, the silver halide grains in the emulsion layer have a silver iodide content of ←O or more by weight or more. 1. A silver halide color photographic light-sensitive material comprising grains and containing a compound represented by the following general formula (I) in the emulsion layer.

General formula (1) In the formula, R1, R2, R3 and R4 each represent a hydrogen atom or a lower alkyl group, and R5 represents a hydrogen atom, an acylamino group, a sulfonamide group, a phosphonamide group, an alkoxycarbonylamino group, or an aryloxy group. Represents a luponylamino group, an alkoxysulfo/amide group, an aryloxysulfonamide group, a carbamoylamino group, or a sul7amoylamino group, an integer from n #-i/ to da, T
In IME, the compound represented by the general formula (1) reacts with a color developing agent and is released together with DI, and then D
I represents a timing group capable of releasing, and DI represents a development inhibitor.

The present invention will be explained in detail below.

Silver halide emulsions useful in the present invention are:

Contains more than 2 molar percentage of silver iodide! ...Silver rodanide particles.

The emulsion is such that the weight ratio of all the silver halide grains in the core layer is greater than Daθ, preferably greater than 60%, and particularly preferably greater than #'irθ%.

The distribution of silver iodide within the grains may be uniform or non-uniform, but in the case of silver halide such as double structure grains as described below, the distribution of silver iodide within the grains is This means that the average value of is greater than or equal to Tamoru Hajime.

The silver iodide content of individual silver halide grains can be measured using, for example, an X-ray microanalyzer, and by this method, the weight ratio of silver halide grains containing 2 or more moles of silver iodide can be measured. can be determined.

The upper limit of the iodine content of the effective female high iodo silver halide emulsion used in the present invention is determined by the solid solubility limit value, and is approximately 0 mole. Therefore, in the present invention, the silver iodide content is more than 2 moles or more than about 4 moles.
A silver halide emulsion having a molar content of tO or less, preferably a silver halide emulsion having a silver iodide content of 10 molar or more and 30 molar or less, more preferably a silver iodide content of 12 molar or less. More than 2 moles φ! A silver halide emulsion having a molar range of less than 1 molar range is used in combination with a compound represented by the general formula (1) of the present invention. When the silver iodide content is below the lower limit of the above range, the effect of improving graininess, which is the object of the present invention, is generally not significant. On the other hand, if it exceeds the upper limit, problems such as delayed development, soft contrast, and poor desilvering tend to occur.

Further, the high iodo silver halide emulsion of the present invention may have any grain size. Good 1st place 0゜2-4.0p
m, more preferably 0. When a high iotono-rhodanide silver emulsion with a particle size of J to 2.0 μm is used in combination with the general formula (1) of the present invention, a color photographic light-sensitive material with excellent sharpness, graininess, color reproducibility, and storage stability of the photosensitive material can be obtained. It will be done.

The high iodine emulsion used in the present invention can be prepared using various methods! !
ll can be made. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble salt with the soluble rhodan salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which No. Rogge/silver oxide is produced is kept constant, that is, a controlled double jet method can be used. As another type of simultaneous mixing method, a triple jet method can also be used in which soluble/% Rogge 7 salts of different compositions are each added independently (for example, soluble silver salt, soluble bromine salt, and soluble iodine salt). When preparing relatively large emulsions, it is preferable to use silver halide solvents such as ammonia, rhodan salts, thioureas, and amines (see the above-mentioned book by James, page 2). It is well known in the art to obtain favorable photographic properties by adjusting pH and pAg during particle formation, and depending on the method of particle preparation, pH, pAg,! Preferably, it varies between 10 and 10.

The high iodine emulsion of the present invention may have a regular crystal shape such as hexahedron, octahedron, dodecahedron, or dodecahedron.
Furthermore, the h0 emulsion grains may have a crystalline shape such as a spherical or tabular shape, and may have a uniform halogen composition, even if the interior and surface of the h0 emulsion grains have different halogen compositions. Inside the particle (Cor
Part e) is silver iodochlorobromide or silver iodobromide containing a high concentration of silver iodide, and the outer side of the grain (5he11 parts) is silver iodobromide or silver iodobromide with a low content of silver iodide. Kaisho 40-/4
t333/issue, same/-2ψ! /! Double-structure grains or multi-structure grains such as 1 are suitable as the emulsion of the present invention.

You can choose the silver ratio between Core part and 5hel part in a wide range! /l~//j is good.

The object of the present invention can be achieved in the case of a silver halide emulsion in which the average value of the silver iodide content in one grain is 2 mol φ or more in such double-structure grains or multi-structure grains. be done. More specifically, it is preferable that the silver iodide t in the core portion is at least /j molar, more preferably 2! More than a mole fly, preferably 3! The value is selected between the molar ratio and the silver iodobromide solid solubility limit value (see page 2 of the book by James). It is preferable that the silver iodide content in the She 11 portion be 3 mol or less, or more preferably 3 mol φ or less.

During the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. may be allowed to coexist. good.

After the emulsion is precipitated or physically ripened, soluble salts are usually removed. For this purpose, the long-known Nudel water washing method, which involves gelatinization, may be used. Inorganic salts consisting of 5, such as sodium sulfate.

Precipitation methods (flocculation) using anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or seratin derivatives (e.g. aliphatic acylated seratin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) ) may be used.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, e.g.
Die Grundlagen der Photog
raphischenprozesse mit Si
lberhalogeniden” (Akademis
The method described in Verlagsgesellschaft/Retl'')t7j-7317 can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodania); reducing substances (e.g., stannous salts, Reduction sensitization method using amines, hydrazines/derivatives, formamidine sulfinic acid, silane compounds): Noble metal compounds (e.g., total complex salts as well as Pt, I
A metal sensitization method using a complex salt of a metal of group (I) of the periodic table, such as r%Pd, can be used alone or in combination.

The photographic emulsion used in the present invention is used for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance.

Various compounds can be included. That is, azoles 1 such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promohenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (4! to 7-phenyl-!-mercaptotetrazole), etc.; Mercaptovirimidines; Mercaptotriazines; Thioketo compounds, such as oxadolinthiono; Azaindenes, such as triazaindene; kind,
Tetraazaindenes (% u-hydroxy substituted (/
, J, 3a, 7) tetraazaindene), tetraazaindene 7): known as antifoggants or stabilizers such as henzene thiosulfonic acid, benzene sulfinic acid, nitrogen sulfonic acid amide, etc. . Many compounds can be added.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyania dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyania dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nucleus, etc.: A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., 1, 2/drenine nucleus, benzindolenine nucleus.

Indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

The merocyanine dye case or composite merocyanine dye has a pyrazoline-! -on nucleus, thiohydantoin nucleus, 2-thioxazolidine-j
, 4t-dione nucleus, thiazolidine-2,φ-dione nucleus,
It is possible to apply heterocyclic ring nuclei such as rhodanine nuclei and thiobarbital acid radicals.

Useful sensitizing dyes include, for example, German patents at, o
ro4! r, U.S. Patent 2,23/, tj1, same, q
No. 3,7ψ, same, j03.77A, same, j
/ri, 00/issue, same J, p/j, jko 2, same 3. Ti
t, 9j issue, same 3,672゜t def issue, same 3.6 free, 217, same name, Oko! , No. 3171, same ψ, 0gt
,! No. 72, British Patent/, No. 2172,110, Japanese Patent Publication No. 4444-117030, same! Examples include those described in No. 2-2vtea.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

A typical example is US Pat. Ko2ri issue, 3,327.060, 3,!
No. 22.012, same J, jJ7. Aψ1, same J, 4/
7.2 PJ No. 3. t2r, Y6gu, same j, A4A
,! No. 1O, No. 1J, A7J.

ryr No. J, A75', 4 (Jf No. 3,703
．． No. 377, 3.7t, No. 30, 3゜fill
, A09 No. 3,137,162, same φ, Okot
, No. 707, British Patent 7.3 Guda, 2r/No., Same/, 6
No. 07,103, Tokuko Shoda 3-ψ236, No. 13-/
No. 2,371, Tokukai Sho! J-/10. T/♂ issue, same fj
-10, No. 22/.

Along with sensitizing dyes, dyes that do not themselves have spectral sensitizing effects or substances that do not substantially absorb visible light, 1
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Patent J, P33.30, P3.63!, 7
2), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,7≠J, JLO), cadmium salts, azaindene compounds, and the like. US Patent 3. T/! , No. 613, 3. t
it, tv issue 1, same 3. Bu/7. Ko? ! No. J, 4
Particularly useful is the combination Fi described in No. 37.7J/No.

Next, general formula (I) will be explained.

R is a water atom box or a lower alkyl group with carbon number/~ψ (
For example, methyl group, ethyl group, n-propyl group, n
-butyl group, etc.), but TIME- of the general formula N)
DIt- Hydrogen is preferred from the viewpoint of release rate! Yes. R2 and R3 each represent a hydrogen atom or a lower alkyl group having carbon number/~ψ (e.g., methyl group, ethyl group, propyl group, 1so-propyl group, butyl group, 1so
-butyl group, 5ec-butyl group, etc.). This alkyl group may have a substituent such as a hydroxyl group, an alkylthio group (eg, methylthio group), or an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.).

In each case, R2 and R3 are hydrogen atoms.

R4 is a hydrogen atom or a lower alkyl group having l-g carbon atoms (
For example, methyl t, ethyl group, propyl group, 1so-propyl group, butyl group, 1so-butyl L, sec-
butyl group, etc.). This alkyl group may be substituted with a hydroxyl group or an alkoxy group (eg, methoxy group, ethoxy group, etc.). R4 is particularly preferably a hydrogen atom or a methyl group, since the cyan dye produced as a result of the coupling reaction between the developing herbal drug and the compound represented by the general formula (1) has good flowability from the light-sensitive material. preferable. R5 is a hydrogen atom, an acylamino group,
Sulfonamide group, phosphonamide group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Represents an alkoxysulfonamide group, an aryloxysulfonamide group, a carbamoylamide 7 group, or a sulfamoylamide 7 group, but is substituted with a hydrogen atom, an alkyl group having a carbon number of ~5, an acylamino group, a sulfonamide group,
An alkoxyacylamino group is preferred. TIME is released together with DI because the compound represented by the general formula (1) reacts with the oxidized form of the color developing agent, and then DI
i represents a releasable timing group. An example of a timing group represented by T I M E is U.S. Patent No. Q, 24.
tJ', No. 742, JP-A-57-! PUGi by intramolecular nucleophilic substitution reaction disclosed in tl'37
Things that emit, JP-A-5T-II name 5Pφ6, JP-A-Show J7-/! Examples include those that release PUG through an electron transfer reaction along a conjugated chain, as disclosed in φ2341 Specification V and the like. Others, JP-A-57-/1RO
Js issue, direction j1-917211-91fu 21/173!
No. l', No. to-xxsraa, No. 6.

-222030, 4θ-233tψri, tO-
Also mentioned are the timing groups disclosed in No. 2371111 and No. 60-237'Al17.

TIME useful in the present invention includes the following general formula (It),
It includes, but is not limited to, those shown in (m) and (IV).

General formula (■) 7 In the formula, X represents a group 8 of atoms necessary to complete a benzene ring or naphthalene ring which may have a substituent. Y represents 10-1-S-1-N-gold.

In the compound represented by the general formula (I) (hereinafter referred to as l-naphthol coupler group), R6, R7, and R8 represent a hydrogen atom, an alkyl group, or an aryl group. Also, one C-group is substituted at the 7 ortho or para position to Y, and is bonded to it.

General formula (fil) In the hetero atom contained in DI, Y, R6, and R7 each have the same meaning as in general formula (It). R9 is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic residue, and RIO is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amino group, acid amide group,
Sulfonamide group, carboxy, alkoxycarbonyl group, carbamoyl group, 77/f. In addition, this timing group is represented by Y as in the general formula (2), and the general formula CI
) is bonded to the cup R7 of the /-naphthol coupler group.

Next, an example of a timing group that releases DIt-by an intramolecular nucleophilic substitution reaction is shown by general formula (IV).

General formula (IV) Nu -E- In the formula, Nu is an electron-rich R acid, @yellow or nitrogen atom tV
is a nucleophilic group represented by the general formula CI) /-
It is attached to the campling position of the naphthol coupler group. Efl is an electronless group having an electron-poor carbonyl, thiocarbonyl, phosphinyl or thiophosphinyl group and is bonded to the heteroatom of DI. X has a steric relationship with Nu and E=i, and from the /-naphthol coupler group represented by the general formula (1), Nu
is released, undergoes an intramolecular nucleophilic substitution reaction with the formation of a 3- to 7-membered ring, and thereby I)I
z - is a linking group capable of being released.

DIH development suppression? ii' II agents, and representative examples thereof include U.S. Pat.
tψ, 6! No. 7, same No. 3, 6/Yo! No. 06, No. 3.
No. t/7,22/, No. 3.733,207 and British Patent No./, Gu! Mercaptotetrazole group, selenotetrazole group, mercaptobenzothiazole group, selenobenzothiazole group, mercaptobenzoxazole group, selenobenzoxanol group, mercaptobenzothiazole group, which are described in No. 0,417F specification etc.
Selenobenzimidazole group, benzotriazole group,
These include benzodiazole groups and iodine atoms.

Specific representative examples of the compounds of the present invention are shown below, but the compounds of the present invention are not limited thereto.

Exemplary compound O2 [About R] CH2CH2C00CH3 -CH2CH2COOC2H5 -CH2CH2COOC3H7(iso)-CH2CH
2COOC4H9 -CH2CH2COOCH2CH20H-CH2CH2
C00CH2CH20CH3-CH2C00CH3 -CH2COOH -CH2CH2COOH -CHCOOCH3 CH3 -CHCOOCR3 C3H7(iso) -CHCOOCH3 CH2H2CH3 CH3 -CHCOOC2H5 H20H -CHCOOCR3 CH2CH28CH3 -CHCOOCH3 CH2COOCH3 -CHCOOCH3 CH2CH2COOCH3 -CH2CH2CH2COOCH3 -CH2CH2CH2CH2COOCH3H 2 [About Z] (19n02 (20) 02 ( 21) (22) NO3 (23n (24) (25) NHCOC port H23 (26) C5H1t(t) (27) (28) (29) COOC4H9 (30) (31) (32) ○ (33) (36 ) H (37) H These compounds represented by the general formula (1) are described in U.S. Patent Broomstick, !≠r, 5'Z, T No., JP-A-Sho S Otsu-7/ψ Tag No. 6, 3! -/6.2 ψ and A 3-J
It can be synthesized by the method described in No. 73-0.

The compound represented by the general formula (I) of the present invention is preferably added to a photosensitive silver rhodanide emulsion layer or a layer adjacent thereto in a light-sensitive material, and the amount added is 44/X1O-6.
−jXlo ”mol/m2, preferably 3X
10-JXlo mol/m2, more preferably tri/xIO-1x10'mol/m.

The compound represented by the general formula CI) of the present invention can be added in the same manner as for ordinary couplers, as described below.

The compound vlJ represented by the uninvented general formula (I) has two types of DI, which are development inhibitors, in order to improve color reproducibility by improving interlayer effect and improve sharpness by adjacent development effect and on pulp. It is particularly preferable to use the above.

The compound represented by the general formula (I) is shown below /i
It is particularly preferable to use it in a light-sensitive emulsion layer other than the red-sensitive emulsion layer, that is, the blue-sensitive emulsion f-1 and the green-sensitive emulsion layer.

In the present invention, it is particularly preferable to contain a compound represented by the following general formula [11] and/or [■] or a salt thereof for the purpose of improving the storage stability of the photosensitive material.

General formula [■] 2 [In the formula, Xl and Xzld acid cumulative atoms or -NH group,
R and R2 are hydrogen atoms, acyl groups, or substituents t-
R3 and R4 are hydrogen atoms, hydroxyl groups, amino groups that may have a substituent, hydrocarbon residues that may have a substituent, or 10R groups (R is (Hydrocarbon residue which may have a substituent) R3 and R4 may be connected to form a two-membered saturated carbocyclic nucleus. However, R1 and R2 are not aqueous methyl groups, and both Xl and X2 are oxygen atoms, and R3
And when R4 is a group other than an amino group which may have a substituent, or R3 and R4 are connected! When ~ forms a saturated carbocyclic nucleus, at least one of R and R2 is a hydrogen atom. ] General formula (1) [wherein, X3 and X4 are oxygen atoms or =NH group, R
5 and R6 are a hydrogen atom, an acyl group or a hydrocarbon residue which may have an # substituent, and R7 is an imino group which may have an additional substituent or a hydrocarbon residue which may have a substituent. Mk represents. However, R5 and R6 are rarely hydroxyl methyl groups, and when X3 and X4 are both trivalent atoms and R7 is a hydrocarbon residue which may have a substituent, V? - At least one of R5 and R6 is a hydrogen atom.

] Specific examples of these compounds are listed below.

(S-/) (s-r) (S-2) (S-6 ) (S-J) (S-7) (S-ψ) ( s-r) (S-ta ) (S-10 ) (s-ii ) (S-/, 2 ) (S-/3 ) ( S-/F) (S-/ the law of nature ( S-／　Otsu ) (S-/ ) (S-/f ) (S-/ the law of nature ) 4H9 (S Ko O) (S , 2 l) (S-,2,2 ) (S-, 23 ) (S-2≠) H3 (S-2ri) H3 (S-,?J) H3 (S-27) (S xr＞ (S-22) H (S-30) (S-J/) C) (3 (S-3,2 ) 0CH3 (S-33) (S-3g) (S-3t) (S-36) (S-37) (S-31) (S-37 ) (S-tt.

) (S-←/) (S-4tJ) (S-ψ3) These compounds are available from, for example, Bulletin of the Chemical Research Institute of Japan.
of the Chemical 5oci
etyofJapan)3! Volume 7/! 17-/j
/, 7 pages, /73←~/73g pages (/PJ4>, Chemische Berichte
te) jlcB volume/r0.2-1133 pages, j4Z! /
-24'7P page 1/92/) f (can be synthesized according to the method described in .

There are 7 types of these compounds! A combination of two or more of these compounds may be added to any subsequent layer in the light-sensitive material, but they may be added to auxiliary layers other than the light-sensitive emulsion layer, such as intermediate layers, filter layers, protective layers, antino-lane/layer layers, etc. is good.

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 order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the halogenated 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.

What constitutes each unit photosensitive layer? ji number of silver halide emulsion layers is disclosed in West German Patent No. 1. ．． As described in British Patent No. 121,470 or British Patent No. 923,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used. Usually, the sensitivity increases sequentially toward the support. It is preferable that the halogen emulsion layers be arranged in such a manner that the height of the halogen emulsion layer is lower than that of the halogen emulsion layer, and a non-photosensitive layer may be provided between each halogen emulsion layer.
As described in No. 206541 and No. 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 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)
They can be installed in the order of BH/BL/GL/GW/RH/RL, or the order of 811/BL/GH/GL/RL/R1+.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/Gll/
They can also be arranged in the order of R11/GL/RC. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/R)I may be arranged in this order from the farthest side from the support. You can also do it.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer with a low density is arranged, and three layers having different photosensitivity are sequentially lowered 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, 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, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the following order: low-speed emulsion layer/medium-speed emulsion N/high-speed emulsion layer.

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

To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4,705,744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.

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

The preferred silver halide other than the present invention contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides: Particularly preferred is about 2 mol%.
silver iodobromide or silver iodochlorobromide containing up 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.

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) No.

17643 (December 1978), pp. 22-23, “
``1. Emulsion preparation
ion and types)”, and the same No.
18716 (November 1979), 648 pages,
"Physics and Chemistry of Photography" by F. Grafkides, for Beaumontel (P, GIafkides, Chemie et
Ph1sique Photographique,
Paul Montel, 1967), Duffin,
"Photographic Emulsion Chemistry", for Focal Press (G, F, D
uffinPhotographic Emulsio
n Chen+1try (Foca! Pres
s1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., for Focal Press (ν, L, Zelik
Manet al. Making and Coati
ng Photographic Emulsion
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 by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
．． No. 434,226, No. 4,414.310, No. 4,
433,048, 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 it may be formed by epitaxial bonding! Silver halides having different properties may be bonded, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

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 Nα1
7643 and Nα18716, 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.

Silkworm ■●且 1? D17643 RD18716
1 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Antifoggant Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, Page 650 left column Ultraviolet absorber 7 Anti-stain agent Page 25, right column Page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column lO 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 as above Inhibitor Various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure (
RD) Nα17643, described in the patent described in ■-C-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. L 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 Mazenk coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Patent No. 4,31
0.619, European Patent No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3.061,432, European Patent No. 3.725.067, Research Disclosure Nα24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure No. 242
30 (June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 5
No. 5-118034, No. 60-185951, U.S. Patent No. 4.500.630, U.S. Pat. No. 4,540,654, U.S. Pat.
Particularly preferred are those described in No. 795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052.212.
No. 4.146,396, No. 4, 228,
No. 233, No. 4,296.200, No. 2.369
．． No. 929, No. 2,801.171, No. 2,77
2. I62, No. 2.895.826, No. 3.
772□002, same No. 3.758,308, same No. 4
, No. 334.011, No. 4,327.173, West German Patent Publication No. 3.329.729, European Patent No. 121.
No. 365A, No. 249°453A, U.S. Patent No. 3,
No. 446,622, No. 4,333,999, No. 4
, 775,616, 4,451,559, 4,427,767, 4,690.889, 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 coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.258, British Patent No. 1,146.36
The one described in No. 8 is preferred. Also, U.S. Patent Nos. 4 and 7
No. 74,181, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling, and a coupler that reacts with a developing agent to form a dye, as described in U.S. Pat. No. 4.777.1.20. It is also preferred to use couplers which have a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
, No. 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. Nos. 3,451,820; 4,080,211; 4,367.282;
No. 4,576°910, British Patent No. 2.102.
It is described in No. 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, in addition to those of the present invention, the patents described in the above-mentioned RD 17643, Items ① to F, JP-A-57-151944, JP-A-57-154234,
No. 60-184248, No. 63-37346, No. 6
Preferred are those described in US Pat. No. 3-37350, US Pat. No. 4,248.962, and US Pat. No. 4.782.012.

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 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-6224252, etc., DIR coupler-releasing couplers, D
IR coupler-releasing redox compound or DIR redox-releasing redox compound, European Patent No. 173.30
R, D, No. 1144, a coupler that releases a dye that recolors after separation, as described in No. 2A and No. 313,308A.
9, No. 24241, bleaching accelerator releasing couplers described in JP-A No. 61-201247, etc., U.S. Pat. No. 4,553.
Ligand releasing coupler described in No. 477 etc., JP-A-63
Couplers that emit leuco dyes as described in US Pat. No. 4,774,181 and couplers that emit fluorescent dyes are mentioned.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Patent 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 phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-monoamylphenyl) phthalate, bis(2,4-di-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2
-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid ester! ! (2-ethylhexylhexyl p-
hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4
-diter t-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl)
sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl cimylate, etc.), aniline derivatives (N,N-diptyl 2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodenlebenzene, diisopropylnaphthalene, 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, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of the process, effects, and latex for impregnation of the Latin lath dispersion method 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 JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)henzimidazole.

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 Nα17643 and Nα18716
It is written from the right column of page 647 to the immediate left side of page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and even more preferably 20 μm or less. Further, the membrane swelling rate T1/2 is preferably 30 seconds or less, more preferably 20 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.

For example, a swellometer (swelling) of the type described by Green, A. et al. membrane), it can be measured and TI/!
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30°C for 13 minutes and 15 seconds, and is defined as the time required to reach 1/2 of the saturated film thickness.

The membrane swelling rate TI/□ 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 rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD, N
Pages 28 to 2 of α17643, and NCL1871 of the same
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-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates and hydrochlorides Alternatively, examples include p-toluenesulfonate. Among these, in particular, 3-methyl-4-amine-N-ethyl-N
β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

Color developers include pHJl buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzothiazoles, developing compounds such as benzothiazoles or mercapto compounds. It typically contains an inhibitor or antifoggant. In addition, if necessary, hydroxylamine, diethylhydroxyl 5
sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, various preservatives such as phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, and polyethylene. Development accelerators such as glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1, phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids. ,
Various caloric acid agents such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenecyamine tetranodic acid, nitrilotriacetic acid, diethylenetriamine pentacholic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, ■- Hydroxyethylidene-I11~diphosphonic acid, nitrilo-N,N,N-) IJ Methylenephosphonic acid, ethylenecyarine-N,N N,N tetramethylenephosphonic acid, ethylene diamine di(0-hydroxyphenylacetic acid) and salts thereof can be cited as a representative example.

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.

Generally, the pl of these color developing solutions and black and white developing solutions is 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but -i is 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
−Can also be less than or equal to: When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, Capacity of treatment liquid (C-) 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 liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slint development method described in Japanese Patent No.-216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it in all steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.It is also possible to reduce the amount of replenishment by using a means that indicates the accumulation of bromide ions in the developer. can.

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. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (I[[), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (III), such as aminopolymer salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Carboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron [II] complex salts, including ethylenediaminetetraacetate iron ([1) 18 salt and 1,3-diaminopropane tetraacetate iron (m) complex salt, are used from the viewpoint of rapid processing and environmental pollution prevention. I like it. In addition, iron aminopolycarboxylate ([[I)
Complex salts are particularly useful in both bleaching and bleach fixing solutions. These aminopolycarboxylic acid iron (III
) The pi+ of bleach or bleach-fix solutions using complex salts is usually 4.
．． 0-8, but lower p for faster processing
It can also be treated with H.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290.812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Na17129 (July 1978), etc.: JP-A-50-140129 Thiazolidine derivatives described in No.
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3.706.561
Thiourea derivatives described in West German Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748,430
Polyoxyethylene compounds described in No. 1973-
Boriagon compounds described in No. 8836; other JP-A-1988
-42.434, 49-59.644, 53-
No. 94,927, No. 54-35,727, No. 55-2
Compounds described in No. 6.506 and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,858.
No., West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983-9
Preferred are the compounds described in US Pat. No. 5,630.9 Also preferred are the compounds described in US Pat. No. 4,552,834.

These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pea) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphones Ml to the fixing solution or bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C-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. Specific methods for strengthening agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461, and the method of JP-A-62-183461. A method of increasing the stirring effect using a rotating means, and a method of further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. , a method of increasing the circulation flow rate of the entire processing liquid. Such agitation enhancement means include bleaching solutions,
It is effective in both bleach-fixing solutions and fixing solutions. Improved stirring speeds up the supply of bleach and fixing agent into the emulsion film,
It is thought that this increases the desilvering rate as a result. Also,
The above-mentioned pil and push-open means are more effective when a bleach accelerator is used, and the accelerating effect can be significantly increased and the fixing inhibiting effect caused by the bleach accelerator can be eliminated.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

It is preferable that the silver halide color photographic material of the present invention undergoes a water washing and/or stabilization process after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, 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 factors. It can be set over a wide range depending on the conditions. 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
Motion Picture and Te1evi
sion Engineers Volume 64, P, 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but 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, as a solution to this problem,
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
Isothiazolone compounds and thiabendazole compounds, chlorinated disinfectants such as chlorinated sodium isonurate, and other chlorinated disinfectants such as hensitriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technology" Full volume “Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Industrial Technology Society, Japan Antibacterial and Mildew Society Line “Encyclopedia of Antibacterial and Antifungal Agents” (
It is also possible to use the fungicides described in (1986).

The pif 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, a range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40'C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

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

Further, following the water washing treatment, a further stabilization treatment may be performed, such as a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final coating bath for color photosensitive materials for photography. can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

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

In a process using an automatic processor or the like, when each of the above-mentioned processing liquids becomes fimtM due to evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate it, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. 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-5343
Examples include urethane compounds described in No. 5628.

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

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

The various treatment liquids in the present invention are used at 10'C to 50C. Normally, the standard temperature is 33"0 to 38°C, but it is possible to increase the temperature to accelerate processing and shorten processing time, or conversely to lower the temperature to improve image quality and improve the stability of the processing solution. can be achieved.

In addition, West German Patent No. 2,226,7 for the use of photosensitive materials for both eyes
70 or U.S. Pat. No. 3,674.499 using cobalt or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500.626, JP-A No. 60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210,66042, and the like.

(Example) less than, The present invention is illustrated by examples. Explain in more detail To clarify, The present invention is not limited to these do not have.

Example/ Silver halide emulsions A and B were produced in the following manner.

0, It1 mole of potassium bromide and 0.01. Contains mole C potassium iodide! 2 Polygelatin aqueous solution 100θcc
oocm (while stirring, add 00 cc of an aqueous solution containing 1/CO, 33 moles of silver nitrate in a container for 20 minutes,
After 20 minutes of physical ripening, an aqueous solution containing 0.67 mol of silver nitrate/000 cc and an aqueous potassium bromide solution of 0.67 mol/E are added at the same time! O was added for 1 minute, and the pAg was adjusted to f4 during that time. After desalting, 10-5 mol of sodium thiosulfate and 10-s mol of chloroauric acid were added and chemically sensitized at 60''C for 60 minutes. An iodobromide emulsion containing silver oxide was obtained.This will be referred to as Emulsion A.A 2% aqueous gelatin solution containing 0.37 mol of potassium bromide and 0.10 mol of potassium iodide was prepared. In the same process, more than 10 moles of silver iodide of i.o.mu.m was obtained as silver iodobromide emulsion B.

Next, each layer having the composition shown below was coated on an undercoated cellulose triacetate film support to prepare sample 10/, which is a multilayer color light-sensitive material.

(Sensitivity Enhancement Composition) The number corresponding to each portion indicates the coating amount in units of g/m2, and for silver halide, the coating amount in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 10)) 1st layer; antihalation layer black colloidal silver...silver 0. /Za gelatin... O, UO second layer; middle layer,! -d-t-pentadecylhydroquinone...0. /ZEX-/
... 0.07EX-3...
・ 0.02 EX-/ko... o, ooxU-7
・ ・ ・ 0.04 U-co ・ ・ ・ o
, orU-J ・ ・
・O,10HB S −/
・ ・ ・ 0.10HBS-2・ ・ ・
0.02 Gelatin/...i, oge 3rd layer (
1st red-sensitive emulsion N) Monodispersed silver iodobromide emulsion (silver iodide molar ratio, average grain size 0)
．． ! μ, coefficient of variation regarding particle size 0°/j
...Silver θ, 3! Sensitizing dye I...6
．． ri xio-s sensitizing dye■.../, r×1
0 5 Sensitizing dye■ ...1. /X10-4 sensitizing dye ■...u, 0x10-5EX-λ
... θ, 3! θEX-io
...-o, or.

Gelatin ... /, 00 qth layer (first red-sensitive emulsion N) Tabular silver iodobromide emulsion (silver iodide 3 mol φ, average grain size 0
．． 7μ, average aspect ratio! ,! .

Average thickness O, μ) Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-,z EX-3 EX-7゜ gelatin 1st layer (3rd red-sensitive emulsion layer) Emulsion A Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-7゜ EX-J EX-μ HB S -/ B5-2 ...Silver 0.70 ・! , /X10-5 ・/, 41X10-5 ・　2.3　×　10-4 ・j, OX/O-5 ・　・　・　O, 4t　Oθ ・　・　・　o　　　,ot.

・　・　・　0.0/! ・　・　・　　　　／　,θ　θ ...Silver i, s.

・J-, ItXlo-5 ・／　、gu　X10-5 ・＋2　protection×l　θ−4 ・3. /X10-5 ・　・　・　0． 007 ・　・　・　0＃4tO ・　・　・　o　　,　　i　　　+2　.

・ ・ ・ 0.2 +2 ・ ・ ・ 0. / θ Seratin... 1. Koo No. 6
Layer (middle layer) EX-s...0.0≠Of-■
BS-/---o, o2゜gelatin...0. fO No. 7 (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide ψ molar ratio, average grain size 0)
．． 1μ, average aspect ratio t,o.

Average thickness o, is)...Silver o, 4L.

#1 Sensitizing Dye■ ...J, O×10-5 #7 Sensitizing Dye■ .../, 0X10-4 Sensitizing Dye■
...3. zaX1O-4EX-4...o,,
xt.

EX-i...0.0λ1EX-
7...0.030 EX-, r---o, oxsl-
IBS-/...0.100H
f3S-// ... 0,010 gelatin ... 0.10 g/sai (second green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide q mole, average grain size 0
．． 7μ, coefficient of variation regarding particle size 03llr)
...Silver 0. A0 sensitizing dye■ ...2
．． /×10-5 sensitizing dye Vl ---7,o
xto-s sensitizing dye ■...ko, t×1O-
4EX-7...0. /za0 EX-za...θ, 010EX-y
--・o, oorEX-7...
0.0/2 HB S −/ ... θ, /60H
BS-// ... o, oog gelatin ... OloriO second layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (iodide @ bmol, average grain size 1.0μ
)... Silver/, 2 sensitizing dye■
...3. jT×10-5 sensitizing dye■...
1.0×/θ-5 sensitizing dye■...3,0X
10 4EX-1...o, otr EX-r ---o,
o 2゜EX-/ / ・
・ ・ 0.030EX-7・ ・ ・ 0.02! HBS-/---0, J
jHB S -x ・
・ ・ 0.10 gelati/ ・ ・
/ , 20th 107th (yellow filter layer) Yellow colloid button...Silver 0.0! EX-s
---o, orHB S-/
... 0.03 gelatin
... 0.12 1st/layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide gmol content, average grain size 0)
．． 1μ, average aspect ratio 7.3, average thickness 0. /g)
...Silver O, Coψsensitizing dye■ ...j
, jXlo-4E X-ta...
0.1! EX-za...o, or
yHBS =/ ・−・ 0.21'
Serachi/..., 1.00 1st
2rfiIC second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (6 moles of silver iodide, average grain size 0)
．． , rμ, coefficient of variation θ with respect to particle size.

lj) ...Silver 0.41! Sensitizing dye■
...λ, /X10 4EX-ta
・ ・ ・ 0.20EX-10...0
,0/! HBS-t...0.03 Gelatin・Umbrella・O1 thing! 73rd layer (third positive emulsion layer) Silver iodobromide emulsion (silver iodide ψ molar predominance, average grain size i, 3μ
)...Silver 0.77 sensitized color cumulative■
...2. ．． 2X10 4EX-2... O, KoO f (B S -i...0.07 Gelatin...0.70 1st q layer (7th protective layer) Silver iodobromide emulsion (3 moles of silver iodide %, average particle size 0107
μ) ... Silver 0. jU−ψ
・ ・ ・ 0, / /U-
r・・・・
O1/711138-/...
Oori O gelatin... /, θO
1st)'tj<λth protective layer) Polymethyl acrylate particles (diameter approx. /, jt μm) ... o, r name Exemplary compound 5-29 ... Q, /! Exemplary compound S
-/7... 0.0! gelatin
... 0,72 In addition to the above-mentioned portions, gelatin hardener) 1/1/1-1-J and a surfactant were added to each layer.

(Sample 10.2.1o3) EX-y of the third layer, q-th layer, and first layer of sample 10/
Samples 102 and 103 were prepared by replacing o with 2.1 times the molar amount of Turnip 2 (1), Button (20) of the present invention, respectively.

(Samples 1041-1ot) Emulsion A in the first layer of Samples ioi-103 was replaced with Emulsion B to prepare Samples 1041-/θ2.

(Sample/17) Sample 107 was obtained by removing (S-22) and (S-/7) added to the 1j layer of sample IOA.

These samples were exposed to red imagewise light and subjected to the following color development, and the relative sensitivity is shown in Table 1 as the logarithm of the reciprocal of the amount of internal light that gives a cyan density of (fog + 0.2).

'It was also measured using an aperture with a diameter of 1 μm (Cub I
J+0.2)! Table 1 shows the RMS value of each button.

Furthermore, M'l'F of 777 images at 20 cycles/mm
I found the value. Measurement of MTF value is performed using TheTheory.
of the Photographic Proc
ess.

The method was followed as described in 3rd ed. (for Macmillan, by Mies).

These samples were stored for 7 days under conditions of uo 0c phase relative change & 0% (forced deterioration conditions) and then color developed, and the fluctuations in cyan fog density are also shown in Table 1. Also, cyan density/
The value obtained by subtracting the magenta fog density from the magenta density at exposure giving , j is shown as the degree of color turbidity.

Color development processing was carried out underground at 3♂ 0C using an automatic developing machine.

Color development 3 minutes/! Second bleach 7 minute bleach fixing
3 minutes! Washing for seconds ■ Washing for θ seconds ■ Stable for 7 minutes ≠ θ seconds Drying (jOoC)/min l! Sec. In the above treatment steps, water washing (1) and (2) were performed using a countercurrent water washing method from (1) to (2). Next, the composition of each treatment liquid will be described.

The replenishment amount of each processing solution is 1200 m1 for color development per m2 of color photosensitive material. Everything else is done on google including washing with water.
And so. Also, the amount of pre-bath carried into the water washing process is 1 for color photosensitive materials.
The amount was 10ml/m2.

(Color developer) Mother solution Replenisher Diethylenetriaminepentaacetic acid /, Og Hydroxyltilib /-/, /- Diphosphonic acid Sodium sulfite Potassium carbonate Potassium iodide Hydroxylamine sulfate ψ-(N-ethyl-N-β -Hydroxyethylamino) 2-methylaniline sulfate ψ, tg Add water /, 01 pH 10, θ (Bleach solution>Mother solution/replenisher common ethylenediaminetetraacetic acid ferric ammonium salt, q g 0g 1t, Og 3θ, Og 73g /, Jmg, / g, 2g, ψ g, Og.7g, Ag 6.0g /, 011 / O, θ! /20.Og Ethylenediami7tetraacetic acid disodium salt Ammonium nitrate Ammonium bromide bleach accelerator 10, Og10, Og100, Og!; Ammonia sulfate aqueous solution (70%) Add ammonia water and add water to pH 6.3 /, 01! 0.0 g 1, Og / Co, Og 2 g Oml pH 7.3 (Washing water > Calcium ion 3xmg / Tap water containing 7.3 mg/l of magnesium ion was passed through a column filled with a type II strongly acidic cation exchange resin and an OH type strongly basic anion exchange resin, and calcium ion 7/, 2 mg/l
1. Add sodium isocyanurate dichloride to water treated with magnesium ion O,g mg/l at 20% per liter.
mg was added and used.

(Stabilizing solution) Mother solution/replenisher common formalin (37% w/v) 2, 0ml
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g Ethylenediaminetetraacetic acid disodium salt 0.03g Add water /lpH! ,,r Drying> The drying temperature was set to 0c.

From Table 1, the samples of the present invention have less fog under forced aging conditions, excellent graininess expressed by RMS value, sharpness expressed by M and TF values, and excellent color reproducibility expressed by color turbidity. That is clear.

Example 2 Comparative emulsion C> and high iodosilver halide emulsion R and E of the present invention were prepared in accordance with the following method. 0.11
While stirring 10θOcc of a J% gelatin aqueous solution containing 1 mol of potassium bromide and 0.0 t mol of potassium iodide with a jz'c, 100 cC of an aqueous solution containing 0.33 mol of silver nitrate was added over 30 minutes. After physical aging for 20 minutes, 0. 1oooc of an aqueous solution containing lr7 mol of silver nitrate
cHo, t7 mol/l potassium bromide aqueous solution was simultaneously i
o.

The solution was added for a minute, and the pAg was maintained at r,O during that time. After desalination/X10−5 moles of sodium thiosulfur and 2×
Chemical sensitization was carried out at 600 C for up to minutes by adding 10-5 chloroauric acid. In this way, a silver iodobromide emulsion C containing 6 moles of silver iodide with an average size of O8 μm was obtained. 0.37 mol of potassium bromide and o,i.

An aqueous gelatin solution containing 1 mole of potassium iodide was prepared, and a silver iodobromide emulsion containing 10 moles of silver iodide having a diameter of 0.9 μm was obtained in substantially the same manner as in Emulsion C.

A 2% gelatin aqueous solution containing 0.3 smol of potassium bromide and 0.172 mol of potassium iodide was prepared, and in almost the same process as Emulsion C, 72 mol% of silver iodide of 0.9 μm was prepared. Silver iodobromide emulsion E was obtained.

(Sample Ko O/) Sample 10/7th wI, G layer F-Y, and EX-
.

(Sample KoOko, 103) Sample 20/7th layer, rN$- and 2nd layer EX-/
Samples 20λ and 203 were obtained by replacing 3 with the couplers (1) and (22) of the present invention at 0.7 times the mole.

(Samples 20 to 20F) Samples 2011 to 206 and samples,
207～. 2θ angle.

These samples were evaluated according to the method evaluated in Example 1. However, red exposure was replaced with green exposure, and shea/density was replaced with magenta density.

Table 1 shows that the samples of the present invention are excellent in graininess, sharpness, one-color reproducibility, and photosensitive material storage stability.

Examples/Compounds used in U-/ -2 -3 April 9th I no Li ! EX / EX-ko EX-J H EX EX the law of nature EX 0 IN(J2 EX-i / EX /2 α JX 3 1-(B S-/ tricresyl phosphate 11 B S-1 Ji n-butyl phthalate )IBS-// I / Ko sensitizing dye ■ C2H5 C2I■5 Patent issuer Fuji Photo Film Co., Ltd. Procedural amendment

Claims (2)

[Claims] (1) In a silver halide color photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support, 40% by weight or more of the silver halide grains in the emulsion layer have a silver iodide content of 9 mol. % or more of grains, and the emulsion layer contains a compound represented by the following general formula (I). General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, R_2, R_3 and R_4 each represent a hydrogen atom or a lower alkyl group, and R_5 represents a hydrogen atom, an acylamino group, a sulfonamide group, or a phosphonamide group. basis,
represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxysulfonamide group, an aryloxysulfonamide group, a carbamoylamino group, or a sulfamoylamino group, n is an integer from 1 to 4, and TIME is the general formula (I) DI represents a timing group capable of releasing DI after a compound represented by reacts with a color developing agent and then releases DI, and DI represents a development inhibitor. (2) The silver halide color photographic material according to claim (1), further comprising a compound represented by the general formula [II] and/or [III] or a salt thereof. General formula [II] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X_1 and Represents an atom, hydroxyl group, amino group, hydrocarbon residue, or -OR group (R is a hydrocarbon residue that may have a substituent), and R_3 and R_4 are connected to form a 5- to 6-membered saturated carbon ring nucleus. may be formed. However, R_1 and R_2 are not methyl hydroxide groups, and when X_1 and X_2 are both oxygen atoms and R_3 and R_4 are both groups other than amino groups, or R_3 and R_4 are connected and When forming a 6-membered saturated carbocyclic nucleus, at least one of R_1 and R_2 is a hydrogen atom. ] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X_3 and X_4 are oxygen atoms or =NH group, R_5 and R_6 are hydrogen atoms, acyl groups or hydrocarbon residues, and R_7 is imino group or represents a hydrocarbon residue. However, R_5 and R_6 are never methyl hydroxide groups, and when X_3 and X_4 are both oxygen atoms and R_7 is a hydrocarbon residue, R
At least one of _5 and R_6 is a hydrogen atom. ]