JPS62136650A - Silver halide color photographic sensitive material and processing method therefor - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having high image quality and excellent sharpness by incorporating planar silver halide of which the silver halide particles have an average aspect ratio in a prescribed range and >=1 layers of polymer couplers into >=1 layers of silver emulsion layers. CONSTITUTION:At least one layer of the multi-layered silver halide emulsion layers coated on a base contains the planar silver halide emulsion in which at least 50% of the total projection area of the silver halide particles has 5:1-10:1 average aspect ratio and at lest one layer contains at least one kind of the polymer couplers. The polymer couplers to be used are preferably the polymer which is derived from the specific monomer coupler and has a specific repeating unit or a copolymer of an arom. primary amine developing agent and >=1 kinds of non-color formable monomers contg. at least one ethylene group having no power to make oxidative coupling with said agent. The photosensitive material having a high desilvering rate is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material and a processing method thereof.
The present invention also relates to a photosensitive material suitable for quick and easy processing and a processing method thereof.

(Prior art) In recent years, there has been a strong demand in the industry for speeding up processing, that is, shortening the time required for processing, and in particular, shortening the desilvering process, which accounts for nearly half of the processing time, is a major issue. It has become.

Generally, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. In the color development step, the exposed silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former (coupler) to provide a dye image. In the next desilvering process,
By the action of an oxidizing agent (commonly referred to as a bleaching agent), the silver produced in the color development process is oxidized and then dissolved by a silver ion complexing agent, commonly referred to as a fixing agent. By going through this desilvering step, only a dye image is created on the color photosensitive material.

The above desilvering process is carried out in a λ bath containing a bleaching agent (a whitening bath and a fixing bath containing a fixing agent), and in a λ bath containing a whitening bath and a fixing bath containing a bleaching agent and a fixing agent. There are cases where it is done.

As bleaching agents, blush salts, dichromates, ferric chlorides, aminocarboxylic acid metal complexes, and persulfates have been used, but in recent years aminopolycarboxylic acid metal complexes have been used due to toxicity and safety issues. It's starting to look like this.

(While the invention is still trying to solve the problem) However, the bleaching edge of aminopolycarboxylic acid metal complex salts is not necessarily sufficient, and in particular, the bleaching edge of aminopolycarboxylic acid metal complex salts is not necessarily sufficient. When processing high-sensitivity color photosensitive materials, especially color reversal photosensitive materials for photography and color negative photosensitive materials for photography that use high-silver emulsions, there are drawbacks such as poor desilvering and the need for a long time for bleaching. has.

Conventionally, in order to solve these problems, US Patent No. 3゜ry3
．． rtt number, JP-A-Shota 3-Tata 630. Tatar 21,
! 06. Same meditator lA23tAri, sameru-evening 2! ;3
1A, Datata 6301, Japanese Patent Application Publication No. 2003-120001, Datata 6301, Japanese Patent Application Publication No. 2003-120001, a method of adding a bleaching accelerator to a bleach bath, a bleach-fixing bath, or a pre-bath thereof is known. Some of these bleach accelerators do show bleaching accelerating effects, but their effects are not necessarily sufficient (
This technology alone does not meet the demand for shortening processing time.

On the other hand, in recent years, silver halide photographic materials, especially photographic materials, have become extremely sensitive, such as ultra-high-sensitivity materials such as xsoitoo film, and //Q-size cameras and disc-sized cameras. There is a growing demand for photosensitive materials that have high image quality and high sharpness and are suitable for small-format cameras.

Among these, the technology to improve sharpness is US Pat. No. 3, which dyes the film with water-soluble dye to prevent irradiation. U.S. Patent No. ψ0も, ψ33, etc., using a compound (commonly called a DIR coupler) that couples with an oxide of a color developing agent to produce a dye and releases a development inhibitor. j, /4ct, No. 062 and No. 3.227. The method described in Yu J'Hiro issue, etc., similarly uses a compound (commonly called a DIR compound) that releases a development inhibitor without forming a dye by coupling with the oxide of a developing agent. Patent No. 3.432.3
The method described in ≠j issue etc. is known.

Furthermore, U.S. Pat. Showa 37-13 Ko 23 and the same J'≠-/4Lj/
A method of improving sharpness using a DIR compound described in No. 3 and others is disclosed.

Although these methods can significantly improve sharpness, each method has the disadvantage of reducing sensitivity.

Attempts have also been made to improve sharpness by thinning the emulsion film and improving the MTF value in the high frequency range due to irradiation. As for the special public Sho ≠ Yoichiμ0/j issue, 4LJ-22!/3, JP 7-2≠75λ, and the same evening 1r-2za 74.
It is disclosed in Lta issue etc. It is certainly possible to reduce the thickness of the emulsion film with these polymer coupler latexes, and this thinning improves sharpness. However, the sharpness of photosensitive materials photographed by tt□ size cameras and disk cameras using these techniques was still insufficient to meet the demands of society.

Furthermore, the sharpness was not sufficient to meet the demand for smaller formats.

Attempts have also been made to reduce irradiation caused by the silver halide emulsion itself. For example, a method for reducing irradiation by limiting the grain size of silver halide grains is described in Japanese Patent Application Laid-Open No. 124-124-3/, etc., which reduces irradiation by arranging tabular silver halide grains in the coating direction. The method to do this is published in Japanese Patent Publication No.
ri No. 26, same jr-//3 ri No. 27 and same jlf-/
/3ri No. 3μ, etc. It is true that these methods reduce the irradiation in the emulsion film and improve the sharpness, but they are not fully satisfactory.

In addition, compared to grains with a low aspect ratio (aspect ratio of about 1), tabular silver halide grains have a larger specific surface area, allowing the use of a larger amount of sensitizing dye in spectral sensitization with sensitizing dyes, resulting in improved image quality. Although it can increase sensitivity without causing deterioration, it has the disadvantage of poor desilvering properties.

Therefore, a method for accelerating bleaching by adding a compound similar to the general formula [I] of the present invention to a sensitive material or a processing solution is disclosed in the US Patent No.
Although this patent was proposed in No. 2007-2003, the patent only describes a tabular emulsion with a high aspect ratio, and does not mention improvements in sharpness and desilvering properties using polymer couplers. do not have.

In addition, a method has been disclosed in Japanese Patent Publication No. 2003-120022, in which a silver halide 4-layer photosensitive material containing tabular silver halide grains with a grain size of 5 times or more the grain thickness is treated with a bleach-fix solution containing a diethylenetriaminepentaacetate iron (IIl) complex salt. 1986-/37, 7tAμ
However, this patent was effective only with a bleach-fix solution containing a limited number of bleaching agents, and the effect was not sufficient.

Therefore, there has been a strong desire for a light-sensitive material and a processing system for the same that can be processed at a high desilvering rate (bleaching or bleach-fixing rate) and in a stable manner, and also have high image quality.

The purpose of the present invention is, firstly, to provide a photosensitive material with high image quality and excellent sharpness, and with a fast step-out speed, and secondly, to provide a rapid desilvering method for a photosensitive material with high image quality and excellent sharpness. Our goal is to provide the following.

(Means for Solving the Problems) The object of the present invention is to provide a multi-layer coating coated on a support. Preferably, a silver halide color photographic light-sensitive material comprising a tabular silver halide emulsion having an aspect ratio of j to 1 to 10 to 1 and containing a polymer coupler of at least 7 M to at least /s; This light-sensitive material is treated in the presence of a bleach accelerator of general formula (I) and/or (II) below, or the halogenated material containing a bleach accelerator of general formula (I) and/or (I11) is processed. This was achieved by processing the silver color photographic light-sensitive material in a process including a whitening bath from pH≠, r to pH 2, or by bleaching and then bleach-fixing.

Alternatively, the object of the present invention could also be effectively achieved by carrying out the above treatment under conditions in which the compound of general formula CI) and/or (II) was contained in the treatment bath.

General formula (I) General formula (II) Here, A is an n-valent aliphatic linking group, aromatic linking group, or heterocyclic group, and (when H=/, A is a simple aliphatic group or aromatic group) , heterocyclic group, hydrogen atom), X is 10-
1-S-1R, and ■ N- R1 and R represent a substituted or unsubstituted lower alkyl group;
R represents a lower alkylene group, and R4 represents a lower alkyl group. R and R here.

R1 and A, R and R, R and A, or R2 and R3 may be connected to form a ring.

Y represents an anion, l is Q or l, m is O or /,
n is lS2 or 3, p is O or l, and q is 0. /,λ
, or 3.

When n is 2 or more, the substituents connected to A may be the same or different.

1, 2, or 3, R11 and R□2 represent a hydrogen atom, preferably a lower alkyl group having 1-2 carbon atoms, or preferably an acyl group having 1 to 3 carbon atoms. However, R11 and R1□
are not hydrogen atoms at the same time, and R11 and R□2 may mutually form a ring.

Next, details of the present invention will be described.

General formula (I) Here, A is an n-valent aliphatic linking group, aromatic linking group, or heterocyclic linking group (when n=/, A is a leather aliphatic group,
Represents an aromatic group, a heterocyclic group, or a hydrogen atom. ), and the aliphatic linking group represented by A include alkylene groups having 3 to 2 carbon atoms (eg, trimethylene, hexamethylene, cyclohexylene, etc.).

Examples of the aromatic linking group include arylene groups having 6 to 1♂ carbon atoms (eg, phenylene, naphthylene nato).

Examples of the heterocyclic linking group include heterocyclic groups (eg, thiophene, furan, triazine, pyridinepiperidine, etc.) consisting of one or more heterocyclic atoms (eg, oxygen atom, sulfur atom, nitrogen atom).

Here, the number of aliphatic linking groups, aromatic linking groups, and hetero linking groups is usually one, but two or more may be linked, and the linking format may be direct or a divalent linking group (for example, -0-1-S-1R5, N-15O2-1-CO-, or a linking group formed from a linking group of these (R5 represents a lower alkyl group).

) may be connected via.

Further, the aliphatic aromatic group, aromatic linking group, and heterocyclic linking group may have a substituent.

Examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, a sulfo group, a sulfonamide group, and a sulfamoyl group.

X represents -0-1Z-1Y, R4N- represents a lower alkyl group (e.g. methyl group, ethyl group, etc.), R1, R2 represent a substituted or unsubstituted lower alkyl group (e.g. methyl group, ethyl group, propyl group, inpyropyl group, pentyl group, etc.), and substituents include hydroxy group, lower alkoxy group (e.g. methoxy group, methoxyethoxy group, hydroxyethoxy group, etc.)
, amino group (e.g., unsubstituted amino group, dimethylamino group, N-hydroxyethyl-N-methylamine group, etc.)
is preferred. Here, when the substituents are more than or equal to 0, they may be the same or different.

R3 represents a lower alkylene group with a carbon number of l-(methylene, ethylene, trimethylene, methylmethylene, etc.), and Y represents an anion ()/ride ion (chloride ion, bromide ion, etc.), nitrate ion, sulfate ion, p- ) represents luenesulfonate, oxalate, etc.).

Also, R and R are connected via a carbon atom or a heteroatom (for example, an oxygen atom, a nitrogen atom, a sulfur atom), and! A membered or 6-membered heterocycle (for example, a pyrrolidine ring, a lysine ring, a morpholine ring, a triazine ring, an imidazolidine ring, etc.) may be formed.

R1 (or n 2 > and A are connected via a carbon atom or a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom), and a !- or 6-membered heterocycle (e.g., a hydroxyquinoline ring, a hydroxyindole ring, (isoindoline ring, etc.) may also be formed.

Furthermore, R1 (or R2) and R3 are connected via a carbon atom or a heteroatom (for example, an oxygen atom, a nitrogen atom, a sulfur atom), and! or t-membered heterocycles (eg, piperidine ring, pyrrolidine ring, morpholine ring, etc.).

! is O or /, m is O or /, fi is l, co or 3,
p is O or 11 and q is 0. /, λ, or 3.

When n-=2 or more, the substituents connected to A may be the same or different.

Specific compounds represented by the general formula [[] of the present invention are shown below, but the invention is not limited thereto.

CH2N(CH2CH20H)2 (I-/r) (I-/ri) (I--Z(7) CI-21) CI-22) 2CH.

(I-2μ) H3 , NCH2CH20H) 2 Cl-21) CI-26) u5H1l Compounds of general formula (I) are described in generally well-known literature, for example, U.S. Pat. , Tokko Akira!
Hiro-/20! No. 16, Tokukai Sho Tough-/ri 2. It can be synthesized according to the method described in, for example, No. 53.

Next, general formula (If) will be described.

General formula [ll] In the formula, R and R□2 may be the same or different (, hydrogen atom, substituted or unsubstituted lower alkyl group (preferably carbon number / -j, especially methyl group, ethyl group, propyl group) group) or an acyl group (preferably a carbon number of 7 to 3,
For example, an acetyl group, a propionyl group, etc.), and r is an integer of 1 to 3.

R and R1□ may be linked to each other to form a ring.

As R1□ and R02, substituted or unsubstituted lower alkyl groups are particularly preferred.

Here, examples of the substituent that R11 and R12 have include a hydroxyl group, a carboxyl group, a sulfo group, and an amine group.

Next, we will show a specific example expressed by the general formula [■].
It is not limited.

(II)-(I) (II)-(-2) (If)-(3) (■)-(≠) (n)-(evening) (II)-(4) H ♂H (II)- (7) (II)-(f) 1)-(ri) CI)-(I0) These compounds represented by the general formula [■]
- It can be easily synthesized by the method described in rtJO.

When the compound represented by the general formula [■] and/or the general formula [■] of the present invention is added to a light-sensitive material, an antihalation layer, an intermediate layer (between different color-sensitive layers, between the same color-sensitive layers, It may be added to any layer (between a photosensitive layer and a non-photosensitive layer, etc.), a photosensitive silver halide emulsion layer, a non-photosensitive silver halide emulsion layer, a yellow filter layer, a protective layer, etc. It may be added to two or more layers.

Two or more of these compounds may be mixed into the photosensitive material, and the total amount added is /×IQ %/X10-2 mol
/m, preferably 2 x 10-5~YuX/m
0-3mo1/m2, more preferably j
X/ 0 ~-2 X/Omo I/? Fl
It is.

In addition, when the compound represented by the general formula [■] and/or the general formula [II] is added to any bath in the processing step, the bath ( It is preferably added to a developing bath, a bleach bath, or a pre-pass of a bleach-fixing bath. The amount of the compound represented by the general formula CI) or [[] to be added to these processing baths varies depending on the type of photographic material to be processed, the processing temperature, the time required for the desired processing, etc. per t43 x x to-' ~ txto-'' mol/-e, preferably !X10-4 ~ ta x 10-2 mo I/, e
, more preferably λ×10 to t×tO−2 mol
/A.

To add these compounds to a photosensitive material, they can be added to the coating solution as they are, or they can be dissolved at an appropriate concentration in a solvent that does not have an adverse effect on the silver halide color photographic material, such as water or alcohol. It can be added as It is also possible to dissolve these compounds in a high-boiling point organic solvent and/or a low-boiling point organic solvent, emulsify and disperse the solution in water, and then add the solution.

Furthermore, when adding these compounds to the processing solution, it is common to dissolve them in water, alkali, organic solvents, etc. beforehand, but they may also be added directly to the processing solution in powder form.

The polymer coupler used in the present invention has the following general formula [C
A polymer having a repeating unit represented by the general formula (Cut':l) or an aromatic-grade amine developer, which is derived from a strength puller and has at least 7 It is preferable that the monomer coupler is a copolymer with one or more non-color-forming monomers containing ethylene groups.Two or more monomer couplers may be polymerized simultaneously.

General formula (C1) ■ CH=C (-Y + - + AF + Number/% Represents 4c lower alkyl groups or chlorine atoms, and X is -CONH
-1-NHCONH-1-NHCOO-1-COO-1
-8O, So NH-1-NH8O□--OCO-1
-0 CON H--N H-1-NHC〇-1-S-
1-CO-1 or -〇-, Y is -CONH-1
or -CO〇-, A represents an unsubstituted or substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group having /-, -/ 0 carbon atoms, and the alkylene group may be linear or branched. Good too. (Examples of alkylene groups include methylene, methylmethylene, dimethylmethine/, dimethylene, trimethylene, tetramethylene,
pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, arylene groups such as phenylene, naphthylene, etc.) Q is a cyan color-forming compound that can be coupled with an oxidized product of an aromatic-grade amine developer to form a dye. Represents coupler residues, magenta color-forming coupler residues and yellow color-forming coupler residues.

m, n and I represent O or l, but m, n and! are never 0 at the same time.

Substituents for the alkylene group or phenylene group represented here include a monoyl group (e.g. phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (
(e.g., methoxy group), monoloxy group (e.g., phenoxy group), acyloxy group (e.g., acetoxy group), acylamino group (e.g., acetylamino group), sulfonamide group (e.g., methanesulfonamide group), sulfamoyl group (e.g., methylsulfonamide group), famoyl group), chlorogen atom (e.g. fluorine, chlorine, bromine, etc.), carboxy group, carbamoyl group (e.g. methylcarbamoyl group), alkoxycarbonyl group (e.g. methylsulfonyl group), sulfonyl group (e.g. methylsulfonyl group), ). When there are two or more of these substituents, they may be the same or different.

Among the color coupler residues represented by Q, cyan color-forming coupler residues include European Patent Publication 1O/, la2/
[CCIfl] or naphthol type (CIV) described in No. 1 is preferred, and RZ in the formula is the one described in European Patent Publication Toi.

It means the same thing as described in No. 42/.

The magenta color-forming coupler residues are preferably of the pyrazolone or indasilone type or of the pyrazoloazole type, for example R5□ and Z2 are each described in European Patent Publication No. 10/2009.

It is the same as that described in (CV) of No. 621.

Y2 represents a hydrogen atom or a group that can be separated (including an atom that can be separated) during a coupling reaction with an oxidized product of a developing agent, and Za, Zb and Zc are methine, substituted methine,
=N- or -NH-. Za-Zb bond and Zb-
One of the Zc bonds is a double bond and the other is a single bond. The case where zb-Zc is a carbon-carbon double bond includes the case where it is a part of an aromatic ring.

Yellow color-forming coupler residues include those of the acylacetanilide type, especially the piparoylacetanilide type [C■
], benzoylacetanilide [C■], [C■] are preferred, and in the formula R53, R54, R55, R56
and Z3 are the same as those described in European Patent Publication No. 10/, 42/.

In the above general formula [CI], the position where Q is bonded to the vinyl group directly or via a divalent linking group is the above (CI[I]
It is not limited to the positions described in ~[C■] (it can be bonded at any position).

Next, examples of non-color-forming ethylene-like monomers that do not couple with aromatic-grade amine developers and oxidation products include acrylic acid, α-chloroacrylic acid, and α-alacrylic acid (such as methacrylic acid). and esters or amides derived from these acrylic acids (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n
-propyl acrylate, n-butyl acrylate, t
-butyl acrylate, 1so-butyl acrylate,
λ-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl pro- pionate and vinyl laurate), acrylonitrile, methacrylonitrile,
Aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. t-vinyl ethyl ether), maleic acid. Examples include acids, maleic anhydride, maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and Koh and Hiro-vinylpyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together.

For example, n-butyl acrylate and methyl acrylate,
These include styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, etc.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

Polymer coupler latex is made by polymerizing a monomer coupler. After taking out the aqueous polymer coupler, it can be dissolved in an organic solvent and dispersed in the form of latex, or the lipophilic coupler obtained by polymerization can be The polymer coupler bath solution may also be dispersed directly in latex form.

Alternatively, a polymer coupler latex prepared by an emulsion polymerization method or a layered polymer coupler latex may be directly added to the gelatin silver halide emulsion.

U.S. Patent 3 for water-soluble polymeric couplers, /!
! ,! It can be made by the method described in To No. 3,22/, Riyo No. 2, No. 3,2 Tata, No. 0/J, RD-/Re033, etc., and for polymer coupler latex, lipophilic polymer coupler A method of dispersing in latex form in an aqueous gelatin solution is described in US Pat. No. 3. μta/, 1
No. 20 describes a method of directly adding a polymer coupler latex prepared by emulsion polymerization to a gelatin silver halide emulsion, as described in U.S. Pat.
．． No. 912, 3. No. 26Iμ3A, 3.767,
≠No. 12, British Patent/, 21t7. It can be made by the method described in No. trt.

These methods are also applicable to the formation of homopolymers and copolymers.

For an explanation of polymerization and dispersion, see European T￥f Patent Publication 10.
It is described in /, 1, 2/ issues.

The proportion of the coloring part in the polymer coupler is usually t~
Although t% by weight is desirable, 20 to 70% by weight is particularly preferred in terms of color reproduction, color development, and stability. The equivalent molecular weight (grams of polymer containing 1 mole of monomeric coupler) in this case is about 2rO to .mu.000, but is not limited thereto.

Examples of monomeric couplers suitable for polymerization to produce polymeric couplers according to the invention and methods of synthesis can be found in various publications, such as Belgian Patent No. jrtA, kLqtA, Belgian Patent No. 402. J-
/A No. 16, No. 7/, British Patent No. A7,3
No. 03, No. 1. jl0. Jl1 No. 1, 21A7
．． U.S. Pat.
! F&Sho jr-i7/j≠Hiroshi, t+-tr 7ri, tA-ioyo Taro, jA-/404A7,
Seen on my Tough-24t/rig.

Representative examples of monomeric polymers suitable for making the polymer couplers of the present invention include, but are not limited to, those listed below.

(C-/ ) (C-2) α (C-j) (C-+L) (C-jl α (c-b) (C-7) α (C-ta) (C-/7) (C -//1 (C-/λ) OH (C-/j) H2 CH2CH2CN CH2CH3 S(J2uM3 (M-/1) (rvl-7λ) (M-/J) (:JCH3 α (M-/r) (~1-20) α (M-ko1) α (Lvl-22) (M-23) α (M-21) α (M-27) (M-21) H3 - α α (M-J1) 00H3 eH3 (M-JP) (M-≠1) clV+,;t'13 (Y-1) (Y-,2) Cooct-t3 ('' -3)NHCt)CH-CH2 α (Y-u) α (Y-
t) C) i() Ct-13 The polymer coupler latex is preferably added in an amount of o, oor mole to O1j mole, preferably o, oi No, or mole, per mole of silver, based on the coupler monomer.

Methods for synthesizing coupler polymers can be roughly divided into 1) emulsion polymerization, 11) seed polymerization, and 111) solution polymerization, each of which includes 1) polymer coupler latex,
11) layered polymer coupler latex, and; i
+ > A lipophilic polymer cassillor is obtained. The methods for preparing these polymers and adding them to emulsions are as follows:) U.S. Pat. , Geta/,? −It is listed in 〇.

The compositions of polymeric Kakura latexes synthesized according to these patents are shown in Tables 1-3.

In the tabular silver halide emulsion used in the present invention, the average aspect ratio refers to the average value of the ratio of diameter to thickness in silver halide grains. When observed, the entire diameter of a circle with an area equal to the projected area of the particle is assumed. Therefore, the average aspect ratio! 2/ or more means that the diameter of this circle is three times or more the thickness of the particle.

The tabular silver halide grains of the present invention have an average aspect ratio!
The number of pairs/ to 10 pairs/, preferably j pairs/ to r pairs/ or less.

Further, the proportion of tabular silver halide grains in the projected area of all silver halide grains is 10% or more, preferably 70% or more, and particularly preferably 0% or more.

By using such an emulsion, a silver halide photographic photosensitive material with excellent sharpness can be obtained. The reason for the poor sharpness is that light scattering by an emulsion layer using such an emulsion is extremely small compared to a conventional emulsion layer. This can be easily confirmed by experimental methods routinely used by those skilled in the art. The reason why the light scattering of the emulsion layer using the tabular silver halide emulsion is small is not clear, but it is thought to be because the main plane of the tabular silver halide emulsion is oriented parallel to the support surface.

The diameter of a silver halide grain is the diameter of a circle having an area equal to the projected area of the grain. In this technology, the diameter of tabular silver halide grains is 0. J~j, oμ, preferably o, z~J, 0μ.

'Also, the thickness is O, aμ or less, preferably 0.3μ or less,
It is preferably 0.2μ or less.

Generally, tabular silver halide grains have λ parallel faces t
The silver halide grain has a flat plate shape, and therefore, the above-mentioned "thickness" is expressed as the distance between one parallel plane constituting the tabular silver halide grain.

These tabular silver halide grains are
As described in et al., it is also possible to use monodispersed silver halide grains in terms of grain size and/or thickness.

Here, the monodispersion of tabular silver halide grains refers to a dispersion system in which the grains of No. 14 are within ±to% of the number average grain size, preferably within ±0% of the number average grain size. Here, the number average grain size is the number average diameter of the projected area diameter of silver halide grains.

The halogen composition of the tabular material is preferably silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride, or silver iodochloride. Silver iodobromide is particularly preferred for use in high-sensitivity photosensitive materials. In the case of silver iodobromide, the silver iodide content is usually not more than aO molt, preferably not more than 0 molt, more preferably not more than 1j molt.

The tabular grains may have a uniform halogen composition or may consist of two or more phases having different halogen compositions.

For example, when silver iodobromide is used, it is also possible to use silver iodobromide tabular grains having a layered structure consisting of a plurality of phases each having a different iodide content. Japanese Patent Application Publication No.11
Preferred examples of the halogen composition of tabular dog halogenated root particles and the intra-particle distribution of non-N halogen are described in J.Tako No. R and Japanese Patent Application Laid-open No. 33.

A preferred method of using the tabular silver halide grains of the present technology is as described in Research Disclosure A 22 j
J Hiro (/rit3 years/month), same%2! JJo(tyrz
It is described in detail in J., 2007), which discloses, for example, a method of use based on the relationship between the thickness of tabular grains and optical properties.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selection of the type and quality of the solvent, the silver salt used during grain growth, the addition rate of the halide, etc.

When producing the tabular silver halide grains of the present invention, by using a silver halide solvent as necessary, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution,
The growth rate of particles can be controlled. The solvent used is preferably in the range of 10 to 0 weight percent of the reaction solution, particularly preferably in the range of lo-2 to l0-1 weight percent.

In the present invention, any silver halide solvent can be used. Examples of frequently used silver halide solvents include ammonia, thioethers, thioureas, thiocyanate salts, thiazolinthiones, and the like. Regarding thioethers, U.S. Pat.
．． core/,! ! No. 7, No. 3, 17, No. 422, No. 3,720.317, etc. may be referred to. For thioureas, see JP-A No. 42≠or, No. 3l-777j7, for thio7anate salts, see U.S. Pat.
No. 4, No. 3,320,069, and Japanese Patent Application Laid-open No. 33-7 Hirohiro No. 31 can be referred to, respectively, regarding thiazolinthiones.

In the process of forming or physically ripening silver halide grains, 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 coexist. .

When producing the tabular silver halide grains used in the present invention, a silver salt solution (for example, A
A method of increasing the addition rate, amount, and concentration of the g N CJ a aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used.

Regarding these methods, see, for example, British Patent No. 1.33!
,ri2! No. 3,410,777, U.S. Pat. No. '+J7J, No. 5'170, U.S. Pat.
No., Tokukai Shoj-l≠232? No., zz-/zri ≠ No., etc. can be referred to.

The tabular halogenated grains of the present invention can be chemically sensitized if necessary. For chemical sensitization, for example, H
, Frlaser (ed.) “...Fundamentals of the photographic process of the eye with rogensation” (“Die Grundlagen d
er PhotographischenProze
ss mit 80berhalogeniden”)
(Akademische Verlagsgesel
lschaft.

The method described in page 731A of 67j Sada 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, rhodanines); reducing substances (e.g., stannous salts, amines); reduction sensitization method using compounds such as hydrazine, formamidine sulfinic acid, silane compounds;
A noble metal sacrificial sensitization method using complex salts of metals listed in number 1 of the periodic table, such as % Pd, etc. can be used alone or in combination.

Specific examples of these include U.S. Patent No. 1 for sulfur sensitization.
, 17μ, RitI No. 29.27♂.

Tag No. 7, same No. 2.4110.419, same No. 2゜7λ
r, ttt issue, @J, Aj4. Riyo No. 5, etc., and the reduction sensitization method are described in U.S. Patent No. 2. Hiroshi/Ri, No. 27 μ, No. 2
, No. 913, 409, p.

! ≠, μyo r, etc., and U.S. Patent No. 2,399,013, U.S. Pat. No. J,! ! Ir.

No. 010, British Patent No. TAR, 047, etc.

Particularly from the viewpoint of saving silver, the tabular silver halide grains of the present invention are preferably gold-sensitized, sulfur-sensitized, or a combination thereof.

The tabular silver halide grains of the present invention can be spectrally sensitized with methine dyes or the like, if necessary. In addition to the above-mentioned improvement in sharpness, the lithographic silver halide grains of the present invention also have a high spectral velocity. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, and Holopolar-7.
Included are anine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are
It is a pigment that combines cyanine pigments, merocyanine pigments, and complex merocyanine pigments.

Useful sensitizing dyes include, for example, the German patent
oro, U.S. Patent No. 2. Hiroshi 23, 7≠r issue, same issue J
,! No. 03.774, same No. 2. ! /ri, 00/issue, same W
Jλ, P/λ, 3rd issue, 3rd issue, ttt, ri! No. 7,
Same No. 3,472. ♂ri No. 7, Dodai Hiroshi, Okoj, J Hiroshi? No. 1, British Patent No. 1゜λμ2. jrt, special public showμ≠-7≠
These sensitizing dyes may be used singly or in combination, and the combination of sensitizing dyes is particularly suitable for the purpose of supersensitization. often used in

A typical example is U.S. Patent No. 2. ttt, tag No. 3, same No. 77,222, same No. 3,327. Oto issue, same issue J,! No. 22.01-, same No. 3. j+27, Hiro No. 1, same No. J, t/7. λri No. 3, same No. J, t21. Pt'
No. 1, No. 3. ttt, lll0 No. 3. t72.
No. 12, No. 3 of the same. t7ri, ≠ 2, same No. 3. ♂／≠
, toy No. ≠, Oko&, No. 707, British Patent No. 1
, 31tL Hiromu.

No. 227, Tokuko Sho ≠ 3-g? No. 36, Sameta 3-/237
! issue, JP-A-12-1099λ evening issue, same! λ-/104
It is described in No. 1r.

As the silver halide other than the tabular silver halide grains used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The preferred silver halide is /! It is silver iodobromide containing silver iodide in a molar ratio or less.

Silver halide grains may have uniform compositions even if their internal and external compositions are different, but in the case of silver iodobromide emulsions, the internal silver iodide content is high, and the surface silver iodide content is high. Low, so-called double-structured particles are preferred. Further, the particles may be such that the latent image is mainly formed on the optical surface, or may be such that the latent image is mainly formed inside the particle.

The grain size of the silver halide may be fine grains of 0.001 microns or less, or large grains with a projected area diameter of up to 70 microns, and may be a monodisperse emulsion with a narrow distribution of gold, or a polydisperse emulsion with a wide distribution.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, ehjmie et Ph
ysiquePhotographyque Pau
l Montel, 15F Otsu 7), by Duffin,
"Photographic Emulsion Chemistry", published by Focal Press (G, F, D
uffin, Photo-graphic Emu
lsion C: hemistry (Focal P
ress, /ri AA), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Z
Eliman et al.

Making and coating photo
graphicEmulsion, Focal
It can be prepared using the method described in Presa, 9&tA). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, it is also possible to use a method in which 1) Agt in the liquid phase in which silver halide is produced is kept constant, that is, the so-called Chondrold double jet method. According to this method, the crystal form is regular. A silver halide emulsion with nearly uniform grain size can be obtained.

It is also possible to form separate silver halide emulsions and then mix and use more than one type of silver halide emulsion.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and p)lk during grain formation. For more information, please see Photographic Science.
and Engineering (Photographic
5science and Engineering
) Volume, /j9-/laj pages (/P4J); Journal of Photographic Science (Journ
al of Photo-graphic 5c
ience), 12 pages, bar router page 1 (/riaIA)
, U.S. Patent No. 3,413.3≠ and British Patent No. 7
．． ≠7! , No. 7ur.

Further, as a monodisperse emulsion, an emulsion in which silver halide grains having an average grain diameter larger than about 067 microns and at least about 5% by weight of the silver halide grains is within the range of average grain diameter ≠ 0 is suitable. . The average particle diameter is approximately 0. It's uj-2 micron, which is a little small! Total average grain diameter of silver halide grains of at least about 90% by weight or several times ±20
% can be used in the present invention. A method for producing such an emulsion is described in U.S. Patent No. 3. ! 7μ.

No. 621, No. 3,611.39≠ and British Patent No. 7,14/J, 7≠.

In addition, JP-A-Sho tit-rtoo, zi-3yoaZ, ri-r3θri-7, 13-/37/33, j#-44112/, same! 4A-99'A19, same! ? -37431, same! Monodispersed emulsions such as those described in ♂-Bitata No. 3 can also be preferably used in the present invention.

For these emulsions, the same silver halide solvents and metal salts as mentioned above can be used, and the same chemical sensitization as mentioned above can be applied. The same sensitizing dyes as mentioned above can also be used.

The average grain size of the silver halide grains in the photographic emulsion is not particularly limited. Further, the particle size distribution may be narrow or wide. However, it is well known in the art that the magnitude of light scattering varies depending on the grain size of non-tabular silver halide grains. Therefore, in order to improve the group sharpness, it is preferable that silver halide grains of a grain size (which varies depending on the wavelength V' of the light in question) that causes large light scattering are not present as much as possible. For example, the above objective can be achieved by using silver halide grains having a narrow grain size distribution and an average grain size that causes less light scattering. If silver halide grains having a narrow grain size distribution alone have problems such as too narrow exposure latitude, silver halide grains having different average grain sizes may be mixed together.

The halogenated photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of photosensitive materials, or to stabilize photographic performance.
Various compounds can be included. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobe/dimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (Pf!f/-phenyl-j-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines: thioketo compounds, e.g. oxadorinthion; azaindenes, e.g. triazaindenes ,
Tetraazaindenes (% Hiro-hydroxy substitution (/.

J, Ja, 7) tetraazaindenes), pentaazaindenes, etc.; Many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. You can add money.

Various color couplers other than polymeric cassillars can be used in the present invention. The term "color coupler" as used herein refers to a compound that generates a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include 7 toll or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds.

Specific examples of these cyan, magenta, and yellow couplers that may be used in the present invention are provided by Research Disclosure/74 Da! (December 1971) ■-D Section Oyohi, cited in r7/7 (/PjP, 1977) and described in the patent.

The color coupler incorporated in the light-sensitive material preferably has a pallast group and is diffusion resistant. A two-equivalent coupler substituted with a coupling-off group is preferable to a two-equivalent coupler whose coupling active position is a hydrogen atom, since the coating amount can be reduced.

Further, a coupler in which the coloring dye has appropriate diffusivity, a non-coloring coupler, a DI lukazole that releases a development inhibitor or a coupler that releases a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is US Patent No. 2. ! A
No. 07,210, No. 2,173.017 and No. 3. It is described in Ko4, t, No. 106, etc.

The use of a two-wheel yellow coupler is preferred for the present invention, as described in U.S. Patent No. 3. ≠Or, / No. 914, same No. 3. p
a7,921, same No. 3. JJ, No. 101 and No. ≠, 02λ.

Oxygen atom dissociative yellow couplers described in No. 620, etc., or U.S. Patent No. 1073, U.S. Patent No.
No. L(, D/10!! (7979-tei 14), British Patent No. 1.≠Koj, No. 020, West German Application Publication No. 020,
Typical examples include the nitrogen atom separation type yellow couplers described in Ri, Ri No. 17, Ri No. 2, 26/, 367, No. 932, Ri, 527, and No. 2゜μJJ, IIJ. Examples include: The α-piparoylacetanilide-based cazolers have excellent color fastness, particularly light fastness, while the α-benzoylacetanilide-based couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably birazoloazole couplers such as yoichi pyrazolone and pyrazolotriazoles. ! -Pyrazolone-based cazolers are preferably couplers in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include US Pat. J//, 0za No. 2, 0za No. 2゜3
No. 113.703, same No. 2. too, No. 71#, No. 901.173, No. J, 042, No. 4j3, No. 3. /j2,194 and 3rd degree 34.0
1/No. Nitokiyoshi’s! - As a leaving group for pyrazolone couplers, U.S. Patent No. ≠, J10. t
Nitrogen leaving group described in /R issue or U.S. Patent No.≠
Particularly preferred are the arylthio groups described in No. 197, No. 31/, No. 197.

It has a parasto group as described in European Patent No. 73,634! - Pyrazolone couplers provide high color density.

As pyrazoloazole couplers, US Pat.
Ot/, ≠32 pyrazolobenzimidazoles, preferably pyrazolo(t,/-c”:J[/,λ,≠] triazoles, as described in U.S. Pat. No. 3,726.047; Research Disclosure Co≠Coλ0(
/もμJune) and JP-A-11i34 (7-33!!
In No. 2, self-grown pyran° rotitrazoles and research disclosure, 2u230 (June 2012) and W Kaisho tO-4tjj! Examples include the pyrazolopyrazoles described in No. 2. U.S. Pat.

The imidazo(/,,2-b)pyrazoles described in US Patent No. 630 are preferred, and US Pat. Hiro 0. Pyrazolo (/, t-b) (/, z.

μ]triazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers such as those disclosed in U.S. Pat. No. 2,470.

No. 223, preferably the naphthol couplers described in U.S. Patent No. ≠, 0! λ, No.-72, No. Hiroshi.

/4! Typical examples include the acid atom dissociation type di-identical naphthol couplers described in J.T., J.R. No. 6, J.K., No. 2.2F, 233, and J.R.T., No. 200. . Further, specific examples of phenolic couplers are given in US Pat. /No. 12, same No. a, ryr,? 2 is written in the number etc. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. A phenolic cyan coupler having a phenolic cyan coupler, U.S. Pat. No. 2,772,742, J, 7! r, 301
No., p, ix&, 394, μ, 33≠, 0/
/ No. 44. J-core.

173, West German Patent Publication No. 3,3λ, 7 Kota, and European Patent Nos. 1J/, 36/, etc. 2,j
-Diacylamino-substituted phenolic couplers and U.S. Patent No. 3. Hiro #A, No. 4-λ, same No. DA! ! ! , P Kuta issue, same number Gu, Gu! /,Ta! No. 2 and No. ≠, 1A2
7, 7≦7, etc. All have phenylureido groups at the λ-position and! These include phenolic couplers having an acylamino group at the - position. Special request! 2-2J or,
Of the naphthol described in JP-24 Hiro 277 and JP-2≦♂/31! Cyan couplers substituted with a sulfonamide group, an amide group, etc. at the - position also have excellent fastness of colored images, and can be preferably used in the present invention.

These cyan couplers, which are robust in colored images, also have excellent color recovery properties, and are suitable for the low pH bleaching process (C
It can be used particularly preferably.

In order to completely correct the unnecessary absorption in the short wavelength region of the dyes generated from the magenta and cyan couplers, it is preferable to use a colored coupler in combination with the color negative sensitive material for photography. U.S. Patent No. 1I, /43°470 and Special Publication Sho! The yellow-colored magenta coupler described in No. 7-32≠13, etc. is U.S. Patent No. r and British Patent No. 1. /4tt,
Typical examples include magenta-colored cyan couplers described in Jtr.

The coloring dye can be used in combination with a coupler having a suitable amount of diffusivity to completely improve graininess. Such blur couplers are described in U.S. Patent No. G, JAA 237 and British Patent No. 2. Specific examples of magenta couplers are given in No. 170 and European Patent No. Pt.

Examples of yellow, magenta or cyan couplers are described in No. 570 and DE-A-3,23μ,333.

The dye-forming couplers and the above-mentioned special couplers may form binary or higher polymers. Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3, 'tj/
, No. 120 and No. U, oro.

It is described in issue 2//. Specific examples of polymerized magenta couplers are described in British Patent No. 2. /02, 773, U.S. Patent No. ≠, JA7. λr2, special application 1977!
0 Dal, and the same 0-//31 and 6 are +1.

The various couplers used in the present invention can be used in combination of two or more types in the same layer of 1 m of photosensitive material in order to satisfy the characteristics required for the photosensitive material, or the same compound can be used in combination with seven different types. It can also be introduced into two or more layers.

Typical usage amounts for color couplers range from o, ooi to 1 mole per 7 moles of photosensitive silver halide, preferably from o, oi to O0 for yellow couplers.
t moles, 0.003 to 0.3 for magenta couplers
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The present invention may also include a coupler that releases a development inhibitor upon development, a so-called DIR coupler.

Examples of DIR couplers include those that release heterocyclic mercazoto type development inhibitors as described in US Patent No. 3°λ Core, 3114; r-tata 4! A product that releases the benzotriazole derivative described in item -, etc. as a development inhibitor; Tokukosho! So-called colorless DIkL cazoler described in No. /-/4/II/ etc.;
J, which releases a nitrogen-containing heterocyclic development inhibitor with decomposition of methylol after elimination; US Patent No. μ2.
2 Hiro! , No. 62 and JP-A-17-74137, in which the development inhibitor is completely released with an intramolecular nucleophilic reaction after separation; JP-A-74-//lt9'≠6, JP-A-17-74137;
/! 'A23tA, same j7-irroJz, same! r
r-91721, same j r-u 097J A, same, rr-209737, same! r-209731, same! ♂-Koori No. 73 and the same! r-2027≠θ, etc., which releases the development inhibitor by electron transfer through a conjugated system after separation; Those that release a diffusible development inhibitor whose development inhibitory ability is deactivated; those that release reactive compounds described in Japanese Patent Applications Sho J9-Jr Koro No. 3 and J Tar 3 R 4 TJ, etc., Examples include those that generate a development inhibitor or completely deactivate the development inhibitor through a medium reaction. The above mentioned Dll-
Among the L couplers, those that are more preferable in combination with the present invention are JP-A-17-17-/! Developer deactivation type represented by U.S. Pat. It is a reaction type represented by No. 3, and among them, the particularly preferred one is JP-A No. 7-119.
No. 17μ, same number ♂-ko 17ri No. 32, Tokuhan Sho t turf j
μ7μ issue, same! Day? λ, 27th coefficient, same! ? -rJj/
≠ issue and the developer deactivation type DIR coupler described in the same J Tata 0≠ 3r issue and the patent application Sho! ? Reaction type 1) I ordinary coupler described in -32tr No. 3 etc.

In the light-sensitive material of the present invention, a compound that releases a nucleating agent, a development accelerator, or a precursor thereof (hereinafter referred to as "development accelerator, etc.") in an image-like manner during development can be used. Typical examples of such compounds are British Patent No. 2,
No. 097,1 IAO and No. 097,1 IAO, /J/, /rt, and are couplers that release a development inhibitor etc. by a coupling reaction with an oxidized product of an aromatic primary amine developer, i.e. I) It is an AR coupler.

1) AR, the development accelerator released from the coupler, etc.
It is preferable that the halogenated parent has an adsorption group,
A specific example of this twisted AR coupler is published by Tokukai Sho! Tar/
! 7tjr issue and the same! It is described in No. 77orμθ. Particularly preferred are DAR casolers that produce heacyl-substituted hydrazines having monocyclic or fused heterocyclic ring total adsorption groups that detach from the coupling active site of the photographic coupler with a sulfur atom or a nitrogen atom. A specific example is the patent application Sho tr-23710/
listed in the number.

JP-A-40-37 in which the development accelerator portion is contained in all the coupler residues! j1. The patent application is for a compound described in the issue, or a compound that releases a development accelerator through an oxidation-reduction reaction with a developing agent! -, 2/Hirot No. 1 can also be used in the light-sensitive material of the present invention.

D A f (a coupler is preferably introduced into the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention, and is also disclosed in Japanese Patent Application Laid-Open No. 2003-110003/Fuko No. 6≠0 or Japanese Patent Application No. 1-2371)
As described in No. 041, it is preferable to use all substantially non-photosensitive silver halide grains in at least one of the photographic constituent layers.

The D coupler of the present invention can be introduced into the photosensitive material by any known dispersion method such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, more preferably oil droplet dispersion method, etc. can be mentioned. In the oil-in-water dispersion method, the presence of a surfactant is dissolved in either a high-boiling point organic solvent with a 1F point of 17r'c or higher and a low-boiling point so-called auxiliary solvent, either alone or in a mixture of the two. It is then finely dispersed in an aqueous medium such as water or an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Pat.

322.027, etc. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, synchhexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), phosphoric acid esters (triphel phosphate, tricresyl phosphate, co-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, 1-u-ethyl Hexyl phthalate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-λ-
ethyl hexyfluphenyl phosphonate, etc.), benzoin f
i-ministers (-monoethylhexylbenzoate, dodecylbenzoate, λ-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolid/etc.), alcohols or phenols (isostear rialconope
λ, tI-di-tert-amylphenol, etc.) aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, instearyl lactate,
trioctyl nodrate, etc.), aniline derivatives (N,
N-dibutyl-λ-putki7-! -tert-octylaniline, etc.), hydrocarbons (paraffin, dobuflubenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, the boiling point is about J00C or higher,
Preferably, an organic solvent having a ro0c or more and about t&o'C or less can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, coethoxyethyl acetate, dimethylformamide, and the like.

Examples of latex dispersion process steps, effects, and latexes for impregnation are described in U.S. Pat.

El, No. 3, West German Patent Application ((JLS) No. 1, jμ/.

No. 27 and No. 2. J Hiro/, No. 230, etc.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol conductors, ascorbic acid derivatives, colorless couplers, and sulfonamides as color capri-preventing agents or color-mixing preventive agents. Gold-containing materials such as phenol derivatives may also be used.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Known anti-fading agents include no-idokuquinones, 6-hydroquine chromans, and! - Hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminephenols, hindered amines, and the phenolic hydroxyl groups of these compounds Representative examples include fully silylated or alkylated ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer. For example, U.S. Patent No.
,! No. 13.7944, French Patent No. λ3t, oi, i, Special Publication Shoj/-4!170 and European Patent No. 57,1
Benzotriazoles substituted with an aryl group as described in U.S. Patent No. 40, U.S. Pat. , Pork Chefs described in Tatata, US Patent No. 3.70! , 10! No. and J of the same,
707°37! The cinnamic acid esters described in U.S. Patent No. 3. λ/J', No. 130 and British Patent No. 1゜3
Benzophenones described in U.S. Pat. No. 2/, 311, U.S. Pat.

A polymer compound having the following ultraviolet absorption residual group described in U.S. Pat.

U.S. Patent No. 3. Datata, 7t Co., and No. 3゜700
．． Ultraviolet absorbing fluorescent brighteners as described in No. 1413 may also be used. An example of a UV absorber is Hiroko 3.
It is described in RI (/RIRA, June 2013).

The photosensitive material of the present invention contains one or more surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). But that's fine.

The light-sensitive material made using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for irradiation or antihalation or other purposes.

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanino dyes are also useful. be. An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroquine ethyl cellulose, carboxine methyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives: Various synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, polyhevinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As for gelatin, in addition to general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japanese Society of Scientific Photography (Bull).

8oc, Sci, Phot, Japan), A/A
Enzyme-treated gelatin as described in , p. 30 (I5'4A) may be used, and a hydrolyzate of gelatin may also be used.

In the photographic material of the present invention, any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer may entirely contain an inorganic or organic hardener. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), hemethylol compounds (dimethylol urea, etc.).Active halogen compounds (2, Hiro-dichloro-4-hydroxy-/, 3
゜j-triazine, etc.) and active vinyl compounds (/,
3-bisvinylsulfonyl-1-furopanol, /, 2
9N-carbamoylpyridinium salts and haloamidinium salts are also preferred because they oxidize easily on hydrophilic colloids such as gelatin and give stable photographic properties. It's fast and excellent.

The present invention provides at least λ different spectral sensitivities 1 on a support.
[Applicable to multilayer, multicolor photographic materials. .

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 arrangement order of these layers can be arbitrarily selected as necessary. A preferred layer arrangement is in the order of red sensitivity, green sensitivity and blue sensitivity from the support side. Further, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity, or a three-layer structure may be used to further improve the graininess. A non-light-sensitive layer may also be present between two or more emulsion layers having the same color-sensitive gold. A configuration may also be adopted in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity.

Further, in a multilayer multicolor photographic material, a filter layer that absorbs light of a specific wavelength or a layer for the purpose of preventing halation may be provided. Although the above-mentioned organic dyes can be used in these original absorption layers, colloidal silver particles can also be used.

A non-light-sensitive fine-grain silver halide emulsion may be used in one or more non-light-sensitive layers of a multilayer, multicolor photographic material for the purpose of improving sensitivity by reflecting light or trapping development inhibitors.

Generally, the red-sensitive emulsion layer contains a cyan-forming cazoler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. For example, infrared-sensitive II! ' may be used in combination for pseudo-color photography or semiconductor laser light. Sincerely, Tokko Akira! ! -341
As disclosed in ♂/, unnatural color appearance can also be removed by incorporating a coupler T- which develops a color other than a cazoler which develops a color complementary to the color sensitivity wavelength of each layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion I and other layers are made of a flexible support such as plastic film, paper, or cloth, or glass, ceramic, etc., which are commonly used in photographic light-sensitive materials.
A rigid support such as metal/C is coated. Useful support materials include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and baryta layer tf? :, is an α-olefin polymer (e.g. polyethylene, polypropylene, ethylene/butylene/copolymer) 4
The support, such as coated or laminated paper, may be colored with dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports is generally polished to improve adhesion with photo emulsions, fc! 6
Then, the base coat is applied. The support human blood is also coated before the priming process.
After that, all treatments such as glow starvation, corona attack, ultraviolet irradiation, and flame treatment may be performed.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-fired flashbulbs are common.

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, microphones using fluorescent surfaces emitted from phosphors excited by electron beams (such as C-'r), liquid crystals (LCI)) and lead titanium zirconate (PLZT) doped with lanthanum are also available. An exposure means that combines a shutter array with a linear or planar light source can also be used.

If necessary, the spectral distribution used for exposure can be adjusted using color filters.

The color developing solution used in the development of the non-inventive light-sensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phenylenediamine compounds are preferably used. Typical examples thereof include 3-methyl-≠-amino-N, N-diethylaniline, 3-methyl -≠-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-j-amino-N-ethyl-N-β-methanesulfonamide etheraniline, 3-methyl-≠-amino/-N-ethyl-N
- β-methoxyethylaniline and their sulfates,
hydrochloride, phosphate or Up-) luenesulfonate,
Examples include tetraphenylboric acid m, p-(t-octyl)benzenesulfonate. Among these, 3-
Particularly preferred are methyl-≠-amino-N-ethyl-N-β-hydroxyethylaniline salt and 3-methyl-hiro-amino-N-ethyl-N-β-methanesulfonamidoethylaniline salt.

These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

Examples of aminephenol derivatives include 0-aminephenol, p-aminophenol, ≠-amino-λ-
These include metherphenol, 1-amino-3-methylphenol, lowoxy-3-aminophenol, ψ-dimethylbenzene, and the like.

In addition, L, F, A, Maso, "Photographic Processing Chemistry", Focal Press (2006) (L, F, A, Maso
n.

@Photographic Processing
"Chemistry", Focal Press) +
Pages 22t-22, U.S. Patent λ, 1, 0/! No. λ.

! ? 2,31.4c, JP-A No. 2,31.4c, JP-A No. 33, etc. may be used. If necessary, two or more color developing agents may be used in combination.

Color developers include pH buffers such as alkali metal carbonates, borates or phosphates; bromides.

Development inhibitors or antifoggants such as iodides, benzimidazoles, benzothiazoles or mercapto compounds; hydroxylamine, triethanolamine, compounds described in OLS No. 2t22-50, sulfites or Preservatives such as bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Amines, thiocyanate, 3.6-thiaoctane-/
, a development accelerator such as a diol; a dye-forming power puller; a competitive coupler: a nucleating agent such as sodium boron hydride; an auxiliary developer such as phenyl-3-pyrazolidone; a tackifying agent; ethylenediaminetetraacetic acid. , nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid,
Diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and aminopolycarboxylic acids, /-hydroxyethylidene-/, /'-diphosphonic acid, typified by compounds described in JP-A-31-1976/Tata r≠j column, research.・Organic phosphonic acid, aminotris (methylene phosphonic acid), ethylenediamine-N, N, N', N'-
Aminophosphonic acids such as tetramethylenephosphonic acid, JP-A-Sho! Law No. 102726, same! 3-≠No. 2730, same as Hiro-727727, same! ! -Hirori 2≠ issue, same thing-
No. 02j, No. 11-/242≠/, No. J--1s
jjYjj issue, 4yoyo-6yo 256, and research
It may contain a chelating agent such as phosphonocarboxylic acid described in Disclosure No. 1170 (1977, J.).

In non-invention, the color developer is about O8/l per color developer/l? - a concentration of about 309, more preferably about 1/1 to about 1/1 color developer/l. Use at a concentration of The pu of the separated color developing solution is usually 7 or more, and most commonly used is about 73 to about 73. In addition, the color developing solution can also be used to reduce the supplementary light TLK by using a replenisher in which the concentration of halides, color developing agents, etc. is adjusted.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. In this black and white developer, (I) dihydroxybenzenes such as hydroquinone, hydroquinone monosulfonate, 3-pyrazolidones such as /-phenyl-3-pyrazolidone, or amine phenols such as N-methyl-p-aminophenol are added. Black and white developers can be used alone or in combination.

In the present invention, the photosensitive material of the present invention is subjected to a bleaching treatment after color development.
It is also preferable that Further, the bleaching treatment may be carried out simultaneously with the fixing treatment in a one-bath bleach-fixing (Brix) process (-1 may be carried out separately).

Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents used in bleaching or bleach-fixing include compounds of polyvalent metals such as iron (III), cobalt (■), chromium (■), and copper (I) (for example, ferricyanide, Peracids, quinones, nitroso compounds; dichromates; organic complex salts of iron (II) or cobalt (II) (e.g. aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphono complex salts such as carboxylic acids and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, malic acid; persulfates;
Hydrogen peroxide; permanganate, etc. can be used. Among these, organic complex salts and persulfates of iron (In) are preferable from the viewpoint of rapid processing and environmental pollution.
) Useful aminopolycarboxylic acids or aminopolyphosphonic acids or their salts to form organic complex salts include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N, N
', N'-triacetic acid.

ll cordiaminopropane tetraacetic acid, triethylenetetraminehexaacetic acid, Zoropylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, Cyclohexanediaminetetraacetic acid.

/13-diamino-coprobanoltetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxyl iminodiacetic acid, dihydroxyethylglycine ethyl ether diaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminepropionic acid, ethylenediaminenipropionic acid, phenylenediaminetetraacetic acid Acetic acid, λ-phosphonobutane/, Ko, Hiro~triacetic acid.

/, 3-diaminopronominol-N,N,N'.

N'-tetramethylenephosphonic acid.

Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, /,3-propylenediamine-N,N,N',N'
-tetramethylenephosphonic acid l-hydroxyethylidene-7, l'-diphosphonic acid, and the like.

Among these chemicals, the iron (I[l) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, /, 2-diaminopro-ξ-tetraacetic acid, and methyliminodiacetic acid are the most common with bleaching blades. Therefore, iron(III) complex salts of ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid are particularly preferred.

Iron [IIl] complex salts may be used on ready-made complex salts of 1 or more, or iron (In) salts (e.g. ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, A ferric ion complex salt may be obtained by reacting a chelating agent (such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) with a chelating agent (such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid) in a solution. When forming a complex salt in a solution, one or both of the ferric salt and the chelating agent may be used in combination. ready-made complex salt,
In the case of complex salt formation, chelating agents may be used more than chemically. In addition, the bleach or bleach-fix solution containing the above-mentioned ferric ion complex contains metal ions other than iron such as calcium, magnesium, aluminum, nickel, bismuth, zinc, tungsten, cobalt, copper, etc., and complex salts or superoxides of these metals. It may contain hydrogen oxide.

SuperllA for bleaching treatment or bleaching mud layer treatment that can be used in the present invention! ! ! ! Salts include alkali metal persulfates such as potassium persulfate, sodium perfjA, or ammonium persulfate.

Bleach or bleach-fix solutions may contain rehalogenated bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide). It is preferable to include a curing agent. Boric acid if necessary,
Borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. acids and their alkali metal or ammonium salts or
Corrosion inhibitors such as ammonium nitrate and guanidine can all be added.

The appropriate amount of bleaching agent per gram or liter of bleaching is 0.7 to 2 moles, and the preferred pH range of the bleaching solution is 1 to 1, in the case of ferric ion complex salts, O6 to r, o, Especially in the case of ferric ion complex salts of aminopolcarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid @Hiroshi, j-
A, j, and more preferably jo-t, o. For persulfates, 0. I at a concentration of /~2 mol/l
) T( is preferably in the range of / to j.

The fixing agents used for constant N1, Vi, M white fixing are known fixing agents, namely, thio(iiIt salts such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene Bisthioglycolic acid, 3t-dithia-/, I-
These are water-soluble silver halide dissolving agents such as thioetherified adducts such as octanediol and thioureas, and these can be used alone or in combination of λ or more. Furthermore, in the bleach-fixing process, JP-A-Sho J1-/J! 3jl
It is also possible to use a special fixing liquid made of a combination of the fixing agent described in No. f and a large amount of a halide such as potassium iodide.

For fixing or bleach-fixing processing, the fixer concentration is 0.2~
≠mol/l is desirable. In addition, in the bleach-fixing process,
Ferric ion complex salt is 0.1-2 per liter of bleach-fix solution
mole, the fixing agent is 0.2. A range of ~≠molar is desirable. In addition, constant λt, pH of the bleach-fix solution are normal≠, O ~ ri, O
is preferable (7), particularly preferably 3.0 to r, o.

In addition to the above-mentioned additives that can be added to the fixer or bleach-fixer during bleaching, preservatives and
Bisulfite addition of tll salts (e.g. sulfites, potassium sulfites, ammonium sulfites), bisulfites, hydroxylamines, hydrazine, aldehydes, etc.'F! It is preferable to contain I (I+lJ: sodium acetaldehyde bisulfite).

Furthermore, various fluorescent brighteners, antifoaming agents, surfactant injection agents,
M bath medium such as polyvinylpyrrolidone and methanol can be contained.

A bleach accelerator can be further added to the bleach solution, bleach-fix solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specifications:
U.S. Patent No. 3. ♂23. r! ? No. 1, West German Patent No. 1. Ko L
? o, ♂/ko number, l1lr+x.

ory, yrr, JP-A-13-32m, J3-
Yo7♂3/No., No.37≠lt, No.j3-Otsuj732, No.j3-72623, No.3-21630, No.j
3-ta! No. 631, No. 3-10≠23λ, No. 13-
/2 Hiro IAλ≠ issue, same! 3-/Hiroshi/A23, 33-
21μ, No. 2A, Research Disclosure A/
Compounds having a mercapto group or a disulfide group as described in JP-A No. 7/22 (July 1971); JP-A-Sho! O
Thiazolidine derivatives as described in -/Hiro 0/2 issue; Tokuko Akihiro Yoichi ♂ E 01, JP Kokai Shoj 2-2013
No. 2, No. 3-32731, US 1) 1 Patent No. 3,70
1. ．． Thiourea derivatives described in No. 361; West German Patent No. 1
．． Iodide described in /27,7Ij, JP-A-Shojr-/4235; West German Patent No. AA, Koi IO, λ, 7≠
♂, polyethylene oxides described in ≠ No. 30; polyamine compounds described in Tokko Sho≠j-f136; other patent applications Akihiro Terahiro 2 ≠ 3 ≠, JP Kotor J 26 ≠ ≠, same! 3-Tahiro No. 27, Doyo Hiro-3yo No. 727, Dojo jj-
The adducts and iodine and bromine ions described in No. 2&j04 and No. 11-/63 Rihiro O can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a strong promoting effect, and are particularly preferred in US Pat. No. J, lr.
! ,? ! No. g, West German Patent No. 1 and 2, No. 0.112, Japanese Patent Application Publication No. 1973-ta! Compounds described in No. A30 are preferred. Furthermore, the additives described in US Pat.

After the fixing or bleach-fixing process, processing steps such as water washing and stabilization are generally performed.

In the washing process and stabilization process, various known compounds may be added for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, amine polycarboxylic acid, and organic phosphonic acid, bactericidal agents and anti-inflammatory agents that prevent the growth of various bacteria, algae, and molds (for example, Journal of Antibacterial and Antibiotics). Antifungal Agents (J, Antibact, Anti
Fung.

Agents) vol, / /, &j%p 207~2
23 (/913) and the compounds described in 6 "Chemistry of Antibacterial and Antifungal" by Hiroshi Hori), metal salts such as magnesium salts, aluminum salts, bismuth salts, alkali metals and Ammonium salts or surfactants for preventing drying load and unevenness can be added as necessary.

Or by West [Photographic Science and Engineering Link Ppj (Photo.

3cL, Eng, ), Vol. 3, Hirohiro 3 - 3J Tapage (/P6t), etc. may be added. It is particularly effective to add a chelating agent or a pasting agent during sterilization.

In the washing step, it is common to reduce the amount of washing water by one or more times for multi-stage countercurrent washing of λ or more types (for example, a λ tank). What's more, instead of the washing process, it's a special request! 7-♂! ≠Multi-stage countercurrent stabilization treatment process as described in No. 3? You can also roll it up. In addition to the above-mentioned additives, various additives are added to the stabilizing bath for the purpose of stabilizing the image. Various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting membrane pH (e.g. p) Typical examples include monocarboxylic acids, dicarboxylic acids, polycarboxylic acids (used in combination) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides, anti-piping agents (thiazole type, inthiazole type, halogenated phenol, sulfanilamide) , benzotriazole, etc.), surfactants, fluorescent brighteners, hardening agents, metal salts, etc. may be used. May be used together.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

Furthermore, in the case of photographic color sensitive materials, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving treatment). At this time, if the amount of magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably λQ seconds to j minutes.

Various processing solutions in the present invention are used at 100C-jO'C. A temperature of 33 °C or Jr'C is standard, but higher temperatures can be used to accelerate processing and shorten the total processing time, and conversely, lower temperatures can improve image quality and stability of processing solutions. can be achieved. In addition, cobalt intensification as described in West German Patent No. 2,221r, 770 or U.S. Pat. One-bath bleaching method described in U.S. Patent No. 3, No. 3,111
Processing may be performed.

Furthermore, each processing time can be made shorter than the standard time within a range that does not cause any problems, if necessary, in order to speed up the process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent or a precursor of Nana et al. for the purpose of simplifying and speeding up processing. Precursors are preferable for inclusion in the light-sensitive material because they increase the stability of the photosensitive material. Specific examples of developer precursors include, for example, U.S. Pat.
, 3 Hiroshi λ, No. 577, indoaniline adducts, No. 3゜3≠2. ! Tata issue, Research Disclosure/≠Gro issue (/G month 1976) and Ship base type compound described in the same/j/j issue (I976/77); Accessories, U.S. Patent No. 3,
71-ri, metal salt complex described in Hiroki No. 2, JP-A-413-7
There is a urethane compound described in No. 3!62♂, and
&-A23j issue, same! t-/l/33, 61. -!
No. 9232.

tA-47r≠λ, j6-za373hiro, j4
-43733-, 1IyIj6-43736, samej
A-4973! No., jA-r/137, j4-j
II-Li No. 30, same jl, -101.2 Hiro 1, same jA
-107236, j7-27 yo 3/ and yo 7
-, J' j j No. 47, etc., various salt-type precursors can also be used in the present invention.

The silver halide color light-sensitive material of the present invention may contain various /-phenyl-3-pyrazolidones in order to promote color development. A typical compound is disclosed in JP-A-6-6
Ko 33rd issue, [J7-/≠μ! Hiroshi 7, sameyo 7-2/
//≠No. 7, the same ♂-! No. 0332, 11-! 013
No. 4, 111rJj tr -10133, same! ? −
! Or! Same number! 1-jOrJj and samej♂-/
It is described in No. 73413♂.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, etc., as necessary.

When the light-sensitive material of the present invention is a color paper, it is very general, and a color photographic material for photographing can also be subjected to bleach-fixing treatment if necessary.

Preferred embodiments of the present invention are listed below, but are not limited to strain only.

l) A photographic processing method characterized in that the color photographic light-sensitive material according to claim 1 or 2 is processed in a processing step including a zero white bath with kpH≠, pT (j, f).

2. A photographic processing method, which comprises bleaching and then bleach-fixing the color photographic light-sensitive material according to claim 1 or 2.

3) In the processing method set forth in claim 3, i) H≠
, 1r to pHj, r, in a processing step including a bleaching bath.

4) In the processing method according to claim 3, after the bleaching treatment, a bleach-fixing treatment is performed, and more preferably the bleaching treatment is carried out in a low pH range from pH 4<, f to pHj, r.
Photo processing method with all features.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

Example/ Sample 10/, which is a multilayer color light-sensitive material, was prepared on a cellulose triacetate film support coated with an undercoat.

(Composition of photosensitive layer) What is the coating amount of silver halide and colloidal silver? / m 2 t, and for couplers, additives and gelatin the amount in 2/m 2 , and for sensitizing dyes in moles per mole of silver halide in the same layer. Ta.

(Sample 1O1) 1st layer (antihalation layer) Black colloidal silver ・・・・・・・・・o, 4
t Gelatin ・・・・・・・・・／、
3 Colored coupler C-/ ・・・・・・・・・0.
06 Ultraviolet absorber UV-/・・・・・・・・・
o, i Same as above UV-2...0.2
Dispersion oil 0il-/ ・・・・・・・・・0.
0/same as above 0il-2...0.0/
2nd layer (middle Jso) Fine grain silver bromide (average grain size 0.07μ) ・・・・・・・・・o, ir
Gelatin ・・・・・・・・・／, O
Colored coupler〇-2・・・・・・・・・0.02 Dispersion oil 0il-/・・・・・・・・・0. /
Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide t molar ratio, diameter/thickness ratio λ,
j, average particle size 0.3μ) ・・・・・・・・・Silver/, j Gelatin ・・・・・・・・・0.6
Sensitizing dye processing ・・・・・・・・・/, 0X10
'Sensitizing dye■ ・・・・・・・・・3.0
X10' sensitizing dye■ ・・・・・・・・・
・・・・・・l×10-5 coupler C-1・・・・・・
... o, ot coupler C-p ...
Old...0.01 coupler C-r...
...O, Oa coupler C-λ ...
...0. OJ dispersion oil 0il-/・
・・・・・・・・・0.03 Same as above 0i1-j
・・・・・・・・・0.0/2nd Hiro layer (2nd red-sensitive emulsion 1fi) Silver iodobromide emulsion (silver iodide 6 mol ratio, diameter/thickness ratio 3.j
, average particle size 0. jmu) ・・・・・・・・・／、! Sensitizing dye processing ・・・・・・・・・1Xio
'Increase, mysterious pigment■ ・・・・・・・・・
J×10' sensitized dye nails...
・・・／×/θ-5 Coupler C-3・・・・・・・・・
0.2 Hiro coupler C-≠ ・・・・・・・・・
・0.2 Hiro coupler C-r ・・・・・・・・・
・・O9O≠Coupler C-, 2・・・・・・・・・O1
Ohiro dispersion oil 0il-/ ・・・・・・・・・
0. /j Same as above 0i1-J ・・・・・・・・・
...0.02nd jam (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, (5%/thickness ratio/
,! , average particle size 0.7 μ) ...... Silver 2.0 Gelatin 19011191. /, O
Sensitized color processing ・・・・・・・・・／×10
'Sensitizing dye■ ・・・・・・・・・3
×10-4 sensitizing dye ■・・・・・・・・・
・/×l0-5 coupler C-b ・・・・
...Blur C-7 from O20...Old...0.
1 minute 8 oil 0il-/...Old...0.0/
Same as above Oi l-2・・・・・・・・・o, or 6th layer (
Intermediate layer) Gelatin 7.0
Compound cpd-A...Auto...0.0
! Dispersion oil 0il-/ ・Yamakawa...o, or υ1st green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide 6 molar ratio, diameter/thickness ratio λ,
! , average particle size 0.3μ) ・・・・・・・・・0.7 Sensitizing dye■ ・・・・・・・・・! X10
'Sensitized color chart■ ・・・・・・・・・0.3
X10' sensitizing dye■ ・・・・・・・・・
...Co x 10' Gelatin...
....../, 0 coupler C-2...------
0,2 coupler C-s ・Old...0
．． 03 Coupler C-/・・・・・・・・・
0.0! Dispersion oil 011-/・・・・・・・・・
・0. ! Rth layer (second green-sensitive emulsion layer) silver iodide emulsion (silver iodide! molar ratio, diameter/thickness ratio 3.
average particle size o, rμ) ・・・・・・・・・／ , ≠ sensitized color s sharp ■ ・・・・・・・・・ry:
, io 'sensitizing dye■ ・・・・・・・・・
・・・Co×io 'sensitizing dye■ ・・・・・・
・・・0.3×10′ Kabra-C-y
・・・・・・・・・0.21 Coupler C-/
・・・・・・・・・0.03 Coupler C-10・
・・・・・・・・・o, oil coupler C-t
・・・・・・・・・0.0t distributed mail Oi I
-/ ・・・・・・・・・0.2 1st unit (3rd
Green sensitive emulsion N) silver iodide emulsion (silver iodide 10 ml, diameter/thickness ratio/
, j, average particle size 0.7μ) ・・・・・・・・・Silver/, Tagelatin ・・・・・・・・・/, 0
Sensitizing dye■ ・・・・・・・・・3. j×10
' Sensitized color (ri■ ・・・・・・・・・／
≠×10' Coupler C-// ・・・・・・
Group・0. O/Coupler C-/, 2...
...0.03 coupler c-/J...
Mark: 0.20 coupler C-/・n
m...0.02 coupler C-1t...
...0.02 dispersion oil 0il-/ ...
・・・・・・O0λO Same as above 0il-2・・・・
...0.02 No.1 OI So (Yellow Filter No So) Gelatin ....../
, 2 yellow colloidal silver ・・・・・・・・・0
．． / to compound Cpd-B・nm・・0. /
Dispersion oil 0il-/ ・・・・・・・・・0.
3 1st/J So (first night-sensitivity emulsion) gj) Monodisperse silver iodide emulsion (silver iodide t molar ratio, diameter/thickness ratio/, j1 average grain size 0.3μ) ・・・・・・...Silver/, 0 Gelatin 09901100.7.0
Sensitizing dye■ ・・・・・・・・・λ×io
'Coupler C-Hiro ・nm・・O, Takabura C-r ・・・・・・・・・0,0
7 minute oil 0il-/ ・・・・・・・・・0
．． 2 1st t21 (2nd blue-sensitive emulsion layer) Silver iodobromide (silver iodide 10 mmolar diameter/thickness ratio/,!,
Average particle size i, rμ) ...... Silver 0. Tagelatin ・・・・・・・・・0.6
Sensitizing dye ■ ・・・・・・・・・／×10
'Coupler C-/≠ ・・・・・・・・・
0.23 Dispersion oil 0il-/・・1 group・0.
07 73rd layer (first protective layer) Gelatin ・・・・・・・・・O0?
Ultraviolet absorber UV-/・・・・・・・・・0.
/ Same as above UV-λ ・・・・・・・・・0.
2 Dispersion oil 0il-/ ・・・・・・・・・0
．． 0t dispersion oil 0il-2...0.0
t 1st Hiro layer (No. 1 protective layer) Fine grain silver bromide (average particle size 0.07μ) ・・・・・・・・・Q, Tagelatin ・・・・・・・・・O, a
S polymethyl methacrylate particles (diameter/, !μ) ・・・・・・・・・0.2 Hardener) (-/ ・・・・・・・・・O4
≠Formaldehyde scavenger S-/・・・・・・
...O, yo formaldehyde scavenger S-2...
...O, j In each layer, there is a pond of the above ingredients, and a surfactant? Added as a coating aid.

Next, the formulas or chemical names of the compounds used in this example are shown below.

UV-1 0 (3 cI (3 1; x/y=7/J (weight ratio) C-λ -J C-HiroU -(: (J
-C-+ Birth H2 C(CHa)a C-? -20E (Jl mol, wt, about λo, oo.

C-/.

C-// C-/2 C-/3 α C-/ ≠ Cpd A Cpd B sensitizing dye Sensitizing dye■ Sensitizing dye■ (CH2)asOaH-N(U2H5)3 Sensitizing dye■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ S-coCH2=CH-802-CH2-CONH-CH2S-
/ The sample prepared as above was designated as 10/.

Trial+'f102-10 evening It was created as follows.

(Sample 1O2) The following points were changed from sample 10/.

G-th layer; emulsion with silver iodide content and tamor coefficient average aspect ratio t
, 7 pairs/, average thickness 0. /≠μ emulsion replaced with sensitizing dye■
, ■ and ■ were all doubled.

Second layer: All emulsion [arsenic content 6 molar average aspect ratio t, j to l, average thickness 0. The sensitizing dyes ■ and νlIl were doubled in the /Iμ emulsion.

1st/Layer: The emulsion was made into an emulsion with a silver iodide iA molar ratio of 6:11 and an average thickness of 0.10 μm, and the sensitizing dye (2) was doubled.

12th layer; emulsion with silver iodide content 10 molti average ascent ratio 7. j pair/, average thickness Ol, 27μ emulsion, sensitized color water X/.

I increased it by 5 times.

(Sample 1O3) All of the following points have been changed since trial @10/.

7th layer: Replace coupler C-2 with coupler M in Table 3 (equimolar as a coloring unit), Oij-/gold O12
Double, the cloth silver meter f! :0°r times.

No. rl; Place the coupler C-ta in the coupler M in Table 3.
pE (equimolar as a coloring unit), 0it-/fO,
, 2 times, and coating silver tThf7° 1 times.

(Sample 10 Hiromu) All of the following points were changed from the test F4102.

No. 71; Coupler C-metal Coupler M in Table 3 (equal moles as a coloring unit), 0it-/01
2 times, and the coating thickness was increased to 09r times.

No. rt*: Coupler C-ta is added to coupler M in Table 3 (equal moles as a color forming unit), and 01t-/ is added to O
o, 2 times, and the amount of coated silver was increased by 012 times.

(10 samples The following points were changed from sample 10IA.

G-th increase: The emulsion was changed to an emulsion having a silver iodide content of j moles, an average aspect ratio of it to l, and an average thickness of 0.07 μm, and the sensitizing dyes (1), (2), and (2) were increased by a factor of 1.

Second counterfeit: The emulsion was replaced with an emulsion having a silver iodide tlO morch average aspect ratio it vs. / and an average thickness of 0.10 μm, and the sensitizing dyes (■) and (v) were added to /.

I doubled it by j.

72nd skin; emulsion? Silver iodide content: 10 moles, average aspect ratio/! The emulsion had an average thickness of 0.2 .mu.m, and the sensitizing dye (2) was increased by a factor of 1.

These samples were exposed to light for sensitometry, subjected to color development processing according to Process A shown in Example 2, and sensitometric measurements were performed using a positive filter and a green filter.

As a result, fog, sensitivity, and
Gamma was almost the same.

Next, it was exposed to light with a red filter and the MTF value was measured. MT
The measurement of F can be found in "The Theory of the Photographic Process", 3rd edition by T. H. James, "The Theory of the P
photographic Process"Jrd e
The method described in d.) (Matsukumiran Co., Ltd.) was followed. What results did you get? Shown in Table 1.

Example Sample 20/-103 was prepared as follows.

(Sample 201) The following points were changed from sample 102.

r-th layer; emulsion silver iodide flk,! An emulsion with an average aspect ratio of 0.07 μm and an average thickness of 0.07 μm was prepared, and the sensitizing dyes (1), (2) and (2) were further increased by / and j times.

Second layer: The emulsion was changed to an emulsion with silver iodide f10 molten silver, an average aspect ratio of 0.10 μm, and an average thickness of 0.10 μm, and the sensitizing dyes 1 and ν were increased to 1 times.

72nd layer: The emulsion was replaced with an emulsion having silver iodide of 10 mol of gold and an average thickness of O0λ μ of 11 to 1, and the sensitizing dye (2) was further increased by i.

(Sample λ02) Sample IQμ was changed in the following points.

io layer: Compound (I-/) according to the present invention.

O x 10-3 mol/7FL2 was added.

(Sample λ03) Sample 10! was changed in the following points.

First O layer: IO×l of the compound (I-/) according to the present invention
Added 0-3 mol/m2.

Processing A-I performed in this embodiment will be described below.

(Processing A) Standard processing.

(Process B) The bleaching time of Process A was shortened from 4 minutes and 30 seconds to 2 minutes.

(Processing C) The compound (I) according to the present invention is added to the bleaching solution of Processing B.
-ta)2/, oxio''-11-ru/.

(Processing D) A processing process that includes a bleach-fixing process following the bleaching process.

(Processing E) 7.0x10 bleaching solution (ether)
mol/added.

(Treatment F) The pH of the bleaching solution in Treatment B was lowered to tj, j.

(Processing G) pH of bleaching solution for processing! , lowered to j.

(Treatment H) As a precaution, 0x10-2 mol/of treated FK (I-ta) was added.

(Treatment I) Addition of (ether)/0X10-2 mol/ to Treatment G.

Further, each processing step will be explained in detail below.

(Processing A) (Processing B) Color phenomenon 1 phenomenon 3 minutes! seconds 3 minutes/j seconds 3r. c drift
White for minutes 30 seconds 2 minutes 00 seconds water washing 2 minutes 10 paper 2 minutes 70 paper fixing μ minute 0 seconds v minute 20 seconds water washing 3
Min/! seconds 3 minutes it seconds stable 1 minutes oz seconds 1 minutes oz seconds The composition of the treatment liquid used in each step was as follows.

Color phenomenon liquid diethylenetriaminepentaacetic acid i,ot・/-hydroxyethylidene-/,/-diphosphonic acid co,otsodium sulfite ≠,orpotassium carbonate
30.0f potassium bromide
/, lIf potassium iodide i
, 3m9 hydroxylamine sulfate 2.4
! tμm(N-ethyl-N-β-hydroxyethylamino)-λ-methylaniline sulfate ≠, add rt water
/, 01 pH 10,0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100. O? Ethylenediaminetetraacetic acid disodium salt 10. Of ammonium bromide / IO,0? ammonium nitrate
10.0? Ammonia water (co♂%)
Add 7.0ml water /
, 0 tp) (A, O Fixer ethylenediaminetetraacetic acid disodium salt 7.02 Sodium sulfite ≠, Ot Ammonium thiosulfate aqueous solution (70 t) t7r, om1 Sodium bisulfite Hiroshi, 6f Add water
/, 0tpH+, g Stabilizing liquid formalin (Hiro O%) λ, Oml polyoxyethylene-P-monononylphenyl ether (average degree of polymerization approximately 10) 0.39 Add water /, 01 (Processing D) Color development 3 Min/! Seconds 3r0c Bleach 30 seconds Bleaching fixation 7 minutes 30 seconds Rinse / minute IIo seconds Stability Hiro θ seconds The processing liquid composition used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid /, Of/-hydroxyethylidene-i, i-diphosphonic acid 2.01 Sodium sulfite ≠, or potassium carbonate
3o,oy potassium bromide
1. ≠1 potassium iodide /,
3? Hydroxylamine sulfate λ, 4cr≠−
(N-Ethyl-N-β-hydroxyethylamino)-cotatylaniline sulfate μ, jf Add water,
, /, 01 pH 10,0 <Bleach solution> Ammonium bromide / 009 Ethylenediamine ≠ Ferric ammonium acetate / Co01 Ethylenediamine ≠ Acetic acid λ sodium salt 10.0? Ammonium nitrate 10. O? ammonia water
/ Add 7.0rnl water
/ tpH1,,j Ku bleaching constant M solution> Ammonium bromide zo, ot ethylenediamine ferric acetic acid ammonium salt so, oy addressed to ethylene diamine ≠ acetic acid λ sodium salt! , 01 Ammonium nitrate! , 02 Sodium sulfite /2.0? Ammonium thiosulfate aqueous solution (70%) 2 tons 0 tnl ammonia water 10.0 rnl water added 1 t pH 7,j <Rinse solution> Ethylenediamine≠acetic acid 0. ≠ Add 1 sodium salt solution / 1 sodium hydroxide pH 7.0 <stabilizer> Formalin (IAO%) Ko, Om! Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3? Add water / t (processing F)
- Color development 3 minutes! Seconds 3♂00 bleach 2
Wash with water for 00 seconds, fix for 2 minutes and 10 seconds, wash with water for λO seconds, wash for 3 minutes! Stable for 7 minutes 02 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid /, 021-hydroxyethylidene- /, /-diphosphonic acid co, ot sodium sulfite Hiroshi, 01 potassium carbonate
30. Ofpotassium bromide
1. Ko2 iobipotassium /, 3
m9 hydroxylamine sulfate 2. ≠2 Hiro-(
N-ethyl-N-/Y-hydroxyethylamino)-2-methylaniline sulfate ≠, evening? add water
i, otpHlo, 0 Bleach Solution Edge V7 Diaminetetraacetic acid ferric ammonium salt 100. Off ethylenediaminetetraacetic acid disodium salt 10.0? ammonium bromide iro, oy ammonium nitrate
io, ot ammonia water (21%)
3. add orrtl water
/, 01pH! , j Fixer ethylenediaminetetraacetic acid disodium salt i, oy sodium sulfite da, 0? Ammonium thioate aqueous solution (70%) /7j, 0vtl sodium sulfite Hiroshi, jf add water
/, 01pH+, + Stabilizing liquid formalin (G O width) 2.0ml polyoxyethylene-P-monononylphenyl ether (average pH approximately 10) 0.3? Add water /, O1 sample ioi, 10,2
．． After applying OCMS wedge exposure using a tungsten light source to 104A, 10j, 20/~203 and adjusting the color temperature to ≠♂000K with a filter, the above-mentioned process A-
I was given.

The silver remaining in the highest concentration area was analyzed using fluorescent X-ray analysis.
The results of the desilvering gold evaluation are shown in Table 2.

(Effects of the present invention) From the results in Tables 1 and 2 above, it can be seen that the photosensitive material based on the present invention has excellent sharpness and is suitable for rapid processing by shrinking @ in the desilvering process. Understood.

Furthermore, the treatment according to the present invention has excellent desilvering properties.
(It has also become clear that it will be rejected.

Patent applicant: Fuji Photo Film Co., Ltd.

Claims (1)

[Scope of Claims] 1) At least 50% of the total projected area of silver halide grains in at least one layer of a multilayer silver halide emulsion layer coated on a support has an average aspect ratio of 5:1 to 10:1. What is claimed is: 1. A silver halide color photographic material comprising tabular silver halide, and at least one layer containing at least one polymer coupler. 2) The silver halide color photographic material according to claim 1, wherein at least one layer of the silver halide photographic material further contains a compound represented by the following general formula (I) and/or general formula (II). material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. basis,
aromatic group, heterocyclic group, hydrogen atom), X is -O
-, -S-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R^1 and R^2 represent a substituted or unsubstituted lower alkyl group, R^3 represents a lower alkylene group, and R^ 4
represents a lower alkyl group. Here R^1 and R^2, R
^1 and A, R^1 and R^3, R^2 and A or R^2 and R
^3 may be connected to form a ring. Y represents an anion, l is 0 or 1, m is 0 or 1,
n is 1, 2 or 3, p is 0 or 1 and q is 0, 1, 2
, or 3. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ r is an integer from 1 to 3. R_1_1 and R_1_2 represent a hydrogen atom, an alkyl group, or an acyl group (However, R_1_1 and R_1_2 represent a hydrogen atom, an alkyl group, or an acyl group.
1_1 and R_1_2 are never hydrogen atoms at the same time. ). R_1_1 and R_1_2 may mutually form a ring. 3) At least 50% of the total projected area of silver halide grains in at least one layer of the multilayer silver halide emulsion layer coated on the support are tabular silver halide particles having an average aspect ratio of 5:1 to 10:1. In a processing method for desilvering a silver halide color photographic light-sensitive material containing at least one polymer coupler in at least one layer, the following general formula [
1 ] and/or a compound represented by the general formula [II]. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. It has the same meaning as that of the general formula [I] [II] described in the section.