JPH01183643A - Silver halide color sensitive material - Google Patents

Abstract

PURPOSE:To prevent the flattening of gradation of the title material due to a rapid processing by incorporating specified silver halide, pyrazoloazole type coupler and mercapto heterocyclic ring compd. in the sensitive material. CONSTITUTION:The emulsion layer of the silver halide color sensitive material is composed of a silver chlorobromide particle comprising >=90mol.% of silver chloride, and >=50wt.% of an emulsion having the localized phase of silver bromide is incorporated in the surface of the particle. And, one or more kinds of the couplers shown by formula I are incorporated in the emulsion layer. And, one or more kinds of the compds. shown by formula II or III are incorporated in the emulsion layer or an another colloidal layer as the stabilizer of the sensitivity and the gradation of the photosensitive material. In the formula, Za and Zb are each (substd)methine or -N= group, R1 is H or a substituting group, Y1 is halogen atom or a releasable group, R11 and R12 are each alkyl or aryl group, etc., X1 is H or an alkali metal, etc., V1 is O or S atom, etc., L is a linking group, (n) and (n') are each 0 or 1.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photosensitive material that has rapid development suitability and excellent color reproducibility, and in particular has excellent stability in continuous development processing. The present invention relates to a surface latent image type silver halide color photosensitive material that has excellent sensitivity and gradation stability during the production of the photosensitive material.

(Prior Art) Silver halide color light-sensitive materials, especially color negative light-sensitive materials for photography and color print light-sensitive materials, contain substantially no silver iodide or contain high silver chloride in order to speed up and simplify the development process. It is known that a silver chlorobromide or arsenic chloride emulsion having a silver chloride content of 10 mol % or more is used. However, this high silver chloride emulsion is known to have difficulties in increasing sensitivity and suppressing fogging. Fukufuku's ideas have been proposed for this improvement. For example, a method using multilayer structured particles, especially core/shell type particles, a method in which a thin layer of silver bromide and a thin layer of silver bromide are provided on the surface of the particle, a method in which dissimilar metal ions, such as cadmium, zinc, lead, platinum, etc. Methods of doping palladium, iridium, rhodium, nickel, ruthenium, methods of using specific sensitizing dyes, etc., for example, WO♂7-11334, BP-2
3039AZ, 23/, S'7/AZ, Tokukai Sho! l'
-9373z issue, same! ! -101133, same ax-i
t3ri! No. 3, same 6 cor/riμ2! λ No. 62-λJ
t0413g issue, 50-2221 Hiromu! No., same tO-2
Number 22♂Hiroshi, number 6λ--Hiroshi 50≠, four otsu Koko j
It is described in the specifications of No. 31 Ko No. 2 to No. 62-213/G♂. It is also generally known that water-soluble iridium salts are used to improve reciprocity law failure and increase contrast sensitivity. For example, special public show≠3-≠23j, DE-2,22
Otsu, Za77, U.S. Patent No. 3.703, Jza≠No. and Special Public Shoguza-j! It is described in the specification of No. 373. It is also known that water-bathable rhodium salts are used as desensitizers and contrast enhancers, particularly in direct positive silver halide emulsions. Especially t￥j Kaisho t2-233/II! The specification describes that the silver halide grains have a silver chloride content of tro to tatamol% as a whole, and are grains in which a high silver bromide-containing phase can be clearly distinguished as a peak by X-ray diffraction. , it has been described that doping metal ions into the high chloride phase results in excellent pressure resistance.

For example, the use of a mercapto heterocyclic compound to suppress pressure blur in a halide emulsion with a high silver chloride content is disclosed in the above-mentioned Japanese Patent Application Publication No. 2J3/≠! As taught in the specification of No. Moreover, this Example 3 describes that a pyrazolotriazole type magenta coupler is incorporated into an emulsion consisting of silver halide grains in which the surfaces of high silver chloride grains are uniformly covered with a silver bromide layer.

(Problem to be solved by the invention) However, research by the Ministry of the Invention and others has revealed that when this type of coupler is added to a high silver chloride emulsion suitable for rapid processing, it causes a serious gap in photographic performance. Became. That is, it has been found that when a coating solution is left for a long period of time during the production of a light-sensitive material, the gradation becomes noticeably softer, and furthermore, when a bleach-fixing solution is mixed into a color developing solution, a noticeable softening of the gradation also occurs.

At present, when silver halide color light-sensitive materials are required to have high image quality and extremely high finishing quality, this problem cannot be solved only by applying the above-mentioned techniques. Although it is possible to achieve high sensitivity and suppress the occurrence of fog, it is not possible to obtain a color photosensitive material that has excellent color reproducibility in continuous development processing and also has satisfactory performance in terms of sensitivity and gradation stability.

Therefore, it is an object of the present invention to provide a halogen compound that prevents the above-mentioned softening of gradation that occurs when a pyrazolotriazole type coupler with excellent color reproducibility is added to a high silver chloride emulsion that has suffered from rapid processing. Our objective is to provide silver chemical color photosensitive materials.

(Means for Solving the Problems) The inventors have studied the structure of silver chlorobromide grains with a high silver chloride content and defects in couplers useful for color reproducibility, and achieved the objects of the present invention. Gadesa.

Specifically, the object of the present invention is to provide a light-sensitive material comprising at least seven light-sensitive emulsion layers containing surface latent image type silver halide grains on a support. In the layer, all 7-halogen (90 mol% or more (average value) of arsenic constituting each silver halide grain is silver chloride, and moreover, it is silver chlorobromide containing substantially no silver iodide. an emulsion f consisting of silver halide grains having a localized silver bromide phase in a non-uniform, discontinuous or isolated state on the surface of the grain;
% or more, further contains at least one layer of a pyrazoloazole type Kaglar represented by the following general formula (1), and further contains at least one layer of a pyrazoloazole type Kaglar represented by the following general formula (1), and further contains at least one layer of a pyrazoloazole type Kaglar represented by the following general formula (1), and further contains at least one layer of a pyrazoloazole type Kaglar represented by the following general formula (1), Furthermore, the following general formula (II-2
), or (II-b), using a silver halide color light-sensitive material containing at least one compound represented by (II-b).

General formula (I) (wherein Za and zb represent methine, substituted methine or -N=, and R1 represents a hydrogen atom or a substituted group.

Yl represents a halogen atom or a group capable of leaving during a coupling reaction with an oxidized product of an aromatic primary amine developing agent (referred to as a leaving group). General formulas (II-a) (II-b) (wherein, R1□ is an alkyl group, an alkenyl group, a heterocycle) group or an aryl group.Xl represents a hydrogen atom, an alkali metal atom, an ammonium group, or a precursor thereof.vl represents an oxygen atom, a sulfur atom, =NH5=N-
(L)-, R□2, R has the same meaning as "11", L represents a divalent linking group, =N-R□3, -tail-
C0-1〒14 etc. Here) t13% R14, '15%
each represents a hydrogen atom, an alkyl group, or an aralkyl group, and n and n' represent O or /) One of the features of the present invention is that in at least one silver halide emulsion layer on a support, The total content of the high silver chloride emulsion as described above is 10% by weight or more, preferably 70% by weight or more, and most preferably 90% by weight or more. The weight percent of this emulsion means the proportion of emulsion lI41 when a plurality of emulsions are mixed and used in one photosensitive layer, and of course the emulsion according to the present invention may be used alone (100 wt-m%). .

(Silver Halide Emulsion) The silver halide grains in the present invention are silver chlorobromide in which 90 mol % or more (average value) of the total silver halide constituting the grains is silver chloride. Even better! Silver chlorobromide grains are silver chloride containing mol% to 27.2 mol% of silver chloride, and are substantially free of silver halide (i.e., have a silver iodide content of 0 mol% or less, more preferably (contains no silver iodide)
It is a particle.

Similarly, the above halogen composition values are average values.

The "average value" refers to all the silver halide grains contained in a type of silver halide emulsion used in the present invention.
This is the average value of the halogen composition of each particle.

The silver bromide localized phase in the silver halide grains does not have a connected layered structure, but exists in a non-uniform, discontinuous or isolated state, and the silver bromide content in the localized phase is There is a substantial difference from that of other particle parts. Silver halide grains with such a structure have excellent rapid developability, have a relatively high silver bromide gold M ratio on the grain surface, which causes less fogging, and have a heterostructure, which makes it easy to obtain high sensitivity. .

In addition, in many of the silver oxide grains with such a heterostructure, the development initiation point is the local phase! Since it is easy to concentrate at or near it, it is possible to adsorb antifoggants, stabilizers, etc. without interfering with the development starting point, and to fully exhibit their functions.

This makes it possible to suppress fog and obtain high sensitivity, and furthermore, it is also possible to adjust the development progress completely smoothly without changing the development start speed.

What is the silver bromide content of the localized phase in the silver halide grains? It is preferably mol% or more (more preferably 20 mol% or more). In particular, it is preferably 20 mol% or more and less than 70 mol%. If the silver bromide content of the localized phase is too high, pressure desensitization may occur, or the sensibility or gradation may easily fluctuate during continuous printing. When the localized phase grows more and the protrusions of the epitaxial particles appear, it becomes difficult to achieve high sensitivity.

The degree of difference in the silver bromide content of the localized phase and the silver bromide content between the substrate (the part other than the localized phase in the silver halide grains) and the localized phase is determined by the fine grain bromide content relative to the host silver halide used. It is determined by the molar ratio of silver and hard-to-bath materials used, the rate of supply of water-soluble bromide to the host silver halide emulsion, and the pAg and pHK of the reaction solution. That is, the localized phase is created by adding a silver nitrate solution and halide ions to a host silver halide emulsion at a predetermined rate while controlling the pAg and pH of the reaction solution. It can also be produced by adding a sparingly soluble bromide such as fine grain silver bromide to a luxurious host iron halide emulsion and subjecting it to physical ripening, or it can also be produced by replacing host silver chloride with bromide ions. Heterogeneous, discontinuous or isolated localized phases which are particularly advantageous in the present invention are, for example, Japanese Patent Application No. 6/-3///3/1983, Sho J, 2-
1't2ta, No. 2, Showa t2-za No. 3113, Showa 62
-rzits issue, Showa tλ-7000! No. and Showa ax-
It is preferable to use a so-called CR-compound described in ISλ330, etc., and add water-soluble bromide and silver nitrate, or add fine silver bromide particles and physically ripen it.

In the present invention, the silver bromide content of the localized phase can be determined by the X-ray diffraction method (for example, as described in the Chemical Society of Japan, edited by Jikkenkajikakuza 6, published by Structural Analysis Maruzen, etc.) or by the rriXP8 method (for example, by the surface Analysis, methods such as "Applications of IMA, Auger electron, and photoelectron spectroscopy" published by Kodansha, etc.In particular, the silver bromide content of localized phases that are uneven or isolated on the surface of silver halide grains, especially at edges and corners. is the EDX method (Energ
yDispersive X-ray analysis
s) (For example, described in Hiroyoshi Soejima's "Electron Beam Micro-Amerisys" published by Nikkan Kogyo Shimbun Co., Ltd. in 1970) -C
Using an EDX swichtrometer equipped with a transmission electron microscope, approximately 0. It is possible to measure with an accuracy of about tamol% in an anomalous structure with a diameter of / to O12 μm.

The silver halide grains used in the present invention include cubic or otahedral grains having (100) faces, or lgahedral grains, (/
//) Has a face! Normal crystal grains such as hedrons are preferred, but tabular grains may also be used. pAg and pHs of the reaction solution that forms silver halide grains CI (-compound * (described in the above specification) or other organic compound that adsorbs to the case or selectively to the (100) or (///) plane These silver halide grains can be dispersed by selectively using .Particularly preferred are hexahedral or /μ-hedral grains having a localized phase at the corner part of the surface, which has a (100) structure. Alternatively, a localized phase may be present at a corner portion or an edge portion of the surface of a tabular grain.

Average grain size of the silver halide emulsion used in the present invention (
The average diameter of the equivalent sphere in terms of volume is 2μ or less and 0. /μ or more is preferable. Particularly preferred is /, 4Lμ or less. /
! μ or more.

Is the particle size distribution narrow? Monodispersed emulsions are preferred because of their good texture. In particular, monodisperse emulsions with regular shapes are preferred for the present invention. ±20 of the average particle size in particle number or weight
Emulsions in which 25% or more of the total grains are contained within the range of 90% or more are particularly preferred.

The silver chlorobromide emulsion used in the present invention is P, GIaf-k i
Chimie et Physique by d e s
PhotographiqueJ (Paul M.
Published by ante1, /L? t7 years), G, F, Duffi
“Photographic Emulsio” by n.
n Chemis-tryj (Focal Pre
Published by sssha, / 7J), V, L, Zelikma
“Makingand Coati” by n et al.
ng PhotographicEmulsionJ
(Published by Focal Press, / Ribu≠)
It can be prepared using the method described in et al. That is, the acidic method, neutral method, ammonia method, etc. may be used, but the acidic method is particularly preferred.

Further, the method for reacting the soluble silver salt and the soluble halogen salt may be any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof. A simultaneous mixing method is preferred to obtain the monodisperse particles of the present invention. It is also possible to use a method in which gold particles are formed under conditions of excess gold and silver ions (so-called back mixing method).

As one type of simultaneous mixing method, a method in which the silver ion concentration in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondral double jet method can also be used. According to this method, a monodisperse silver halide emulsion having a regular crystal shape and a narrow grain size distribution suitable for the present invention can be obtained. It is preferable that the above-mentioned particles used in the present invention are prepared based on a simultaneous mixing method.

Known silver halide solvents (e.g. ammonia, potassium thiocyanate, or U.S. Pat. No. 3.-7/, 137)
No., Tokukai Akira! /-/ko3tO, JP-A-63-424t
O1, Tokukai Akira! ! -/ '1113 / issue, Tokukaisho! lt-1007/7 or Unexamined Japanese Patent Publication Showa Jμm/ja
When physical ripening is performed in the presence of thioethers and thione compounds described in No. Yes.

KB, Nour water + 5L flocculation sedimentation method, ultrafiltration method, or the like can be used to remove soluble silver salts from the emulsion after physical ripening.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. That is, active gelatin, a sulfur sensitization method using a compound containing sulfur that can react with silver ions (for example, thiosulfate, thiourea compound, mercazoto compound, rhodanine compound, etc.), or a sulfur sensitization method using a reducing substance (
For example, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc.), reduction sensitization using kumquats, and metal compounds (such as total complex salts, Pt, I
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as r, Pd, Rh, Fe, etc.) can be used alone or in combination. In the monodispersed silver chlorobromide emulsion of the present invention, sulfur sensitization or selenium sensitization is preferably used, and during this sensitization, it is also preferable to leave the emulsion in the presence of a hydroxyazaindene compound.

In the present invention, the use of dispersed sensitizing dyes is important. As the spectral sensitizing dye used in the present invention, cyanine dyes, merocyanine dyes, composite merocyanine dyes, etc. are used.

In addition, complex cyanine dyes, holopolar-7 anine dyes, hemicyania dyes, steryl dyes, and hemioxonol eX are used. As cyanine dyes, simple cyanine dyes, carbocyanine dyes, and dicarphocyanine dyes are preferably used.

The spectral sensitizing dye is preferably added after the host particles are formed. It is also preferable to add it before or during chemical sensitization. Next, preferred cyan dyes are shown.

General Formula (III) In the formula, Zlol and Z1o2 each represent an atomic group necessary to form a heterocyclic nucleus.

Examples of the heterocyclic nucleus include a j-J membered ring nucleus containing a nitrogen atom and other heteroatoms, such as a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom (a fused ring may be further bonded to these rings). , or further substituents may be bonded)
is preferred.

Specific examples of the heterocyclic nucleus include a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, an oxazole nucleus, a be/dioxazole nucleus, a naphthoxazole nucleus, and an imidazole nucleus. , a benzimidazole nucleus, a naphthimidazole nucleus, a gooquinoline nucleus, a viroline nucleus, a pyridine nucleus, a tetrazole nucleus, an indolenine nucleus, and a benzindophenethyl group.

m represents O1/, 2 or 3. m□. When □ represents 1, R103 is a hydrogen atom, a lower alkyl group,
Represents an aralkyl group or an aryl group.

Specific examples of the aryl group include substituted or unsubstituted phenyl groups.

Rin,. 4 represents a hydrogen atom. When m10□ represents - or 3, "103 represents a hydrogen atom and R□. 4 represents a hydrogen atom, a lower alkyl group, an aralkyl group, etc."
Connect with 102! A membered to six-membered ring can be formed. Further, when ``101'' represents 2 or 3 and 几 represents a hydrogen atom, FL103 may be linked with another ``103'' to form a hydrocarbon ring or a heterocycle. These rings! ~2-membered ring is preferred. JIO□, k represents O or /, and X1o1 is an acid anion'! i1″ representation, nl
O-ku represents 0 or /.

Among the sensitizing dyes used in the present invention, the sensitizing dyes used in the red-sensitive emulsion layer, that is, the emulsion layer spectrally sensitized in the wavelength range from zro to 7 nm, are used in the blue-sensitive emulsion layer and the green-sensitive emulsion layer. The stability of sensitivity is significantly degraded compared to that of . This is particularly noticeable in the high silver chloride-containing chlorobromide@ or silver chloride host emulsions according to the present invention.

However, among the sensitizing dyes that spectrally sensitize the wavelength range from j♂0 to 7jOnm, the reduction potential is -7, core (V, vs
A sensitizing dye having a value less than or equal to 5CE) is excellent in high sensitivity and excellent in sensitivity and stability of a latent image. Among them, the reduction potential -/, 27 (V, vs 5
A sensitizing dye having a value of CE)'E or more base and having a chemical structure in which one or two of the methine chains conjugated between N atoms are condensed is preferred. For example, preferred are pentamethene cyanine dyes having a benzothiazole nucleus, pentamethine cyanine dyes having a penzozernazole nucleus, and trimetensyanine dyes having a gooquinoline nucleus. The value of the reduction potential can be optimized by completely substituting an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, etc. on this heterocyclic nucleus.

The reduction potential can be measured using phase-discriminative second-harmonic AC polarography. A mercury dropping electrode is used as the working electrode, a saturated calomel YL electrode is used as the reference electrode, and platinum is used as the counter electrode.

In addition, measurement of the reduction potential by phase-discriminative second-harmonic current-modulating portammetry using platinum as the J41 electrode was published in the Journal of Imaging Science J.
nal of Imaging 5science
), Vol. 30, pp. 27-3j (/year).

Specific examples of preferable red-sensitive sensitizing dyes used in the present invention are listed below. However, it is not limited to this.

Next, typical examples of other sensitized color layers used in the present invention will be listed.

S-yoS-+ S-ta (CH2)3SO3- (CH2)3S03NaS-
/ / S-/2 S-/3 S-/ Da S-/! S-/Otsu S-/7 S-/♂ S-/RiO3- 8-lO In the localized phase of the silver halide grains of the present invention or its substrate,
It is preferable to contain a metal ion selected from group metal ions or a complex ion thereof.

For example, iridium ions are used in the localized phase as the king, and metal ions or complex ions selected from osmium, iridium, platinum, ruthenium, rhodium, palladium, iron, cobalt, nickel, etc. are mainly used as the substrate. It is preferable to change the type and concentration of metal ions between the phase and the substrate and use one or more metal ions alone or in combination. Furthermore, metal ions such as cadmium, zinc, lead, mercury, and thallium can also be used.

In this way, a silver halide emulsion having excellent reciprocity law failure and excellent sensitivity and gradation stability can be produced. The preferred amount of these metal ions or complex ions to be added is in the range of 10 to 10@-5 mol based on silver halide.

In particular, when iridium ions are contained in the localized silver bromide phase, reciprocity law failure is improved, high sensitivity and contrast are obtained, and latent image stability is improved.

Chemical sensitization in the present invention can be carried out by the conventional method as described above so as to mainly form a latent image on the surface of the silver halide grains. Particularly in the present invention, in which the silver halide grains have a localized phase on their surface, it is important to control the balance between the substrate grain and the localized phase in chemical sensitization. This control includes special application number 7/-3///3/, same town 2-g2λyo 2, same town 42-rtltJ, same town t2-rt/A! The methods described in the specification, particularly the appropriate use of CR-compounds, are used.

(Sensitivity and gradation stabilizer) The reduction in sensitivity and gradation due to the addition of the pyrazolotriazole coupler used in the present invention is due to This can be effectively prevented by combining with heterocyclic compounds.

These compounds will be explained in detail below.

General formula 1a) In the formula, R□1 represents an alkyl group, an alkenyl group, a heterocyclic group, or an aryl group. Xl represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor. Examples of the alkali metal atom include a sodium atom and a potassium atom, and examples of the ammonium group include a tetramethylammonium group and a trimethylbenzylammonium group. In addition, the precursor is X under alkaline conditions, =
Hman'C is a group that can be an alkali metal, such as an acetyl group, a cyanethyl group, a methanesulfonylethyl group, etc.

In 1 above, the alkyl group and alkenyl group include unsubstituted and substituted groups, and also include alicyclic groups. Substituents for substituted alkyl groups include halogen atoms, nitro groups,
Cyan group, hydroxyl group, alkoxy group, aryl group, acylamino group, alkoxycarbonylamino group, ureido group, amino group, heterocyclic group, anlu group, sulfamoyl group, sulfonamide group, thioureido group, carbamoyl group, alkylthio group , an arylthio group, a heterocyclic thio group, and also a carbo/acid group, a sulfonic acid group, or a salt thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amine group are each unsubstituted,
Including those substituted with N-alkyl and those substituted with N-aryl. Examples of the aryl group include a phenyl group, a substituted phenyl group, and a naphthyl group, and examples of the substituent include an alkyl group and the substituents for the alkyl group listed above.

A specific example of the heterocyclic group for R11 is (1) a pyridyl group.

Further, details of the alkyl group and aryl group represented by R1□ and R1□ in the general formula CI [-b) are shown in the formula [1l-
The matter explained regarding a) is that'! 1 applicable.

The amount of the compound of the general formula (II-a) or (ll-1) :] is 1 molar silver halide/X10 ~
10 moles are preferable, and further /×IO'~/X10
Moles are preferred.

Specific examples of compounds of the general formula [n-a, l or N1-b, l include JP-A-62-co/! No. j of the specification of the publication No. 27λ
/-A-,? written in J♂Sada? 44~A-! 30
．． A-J, A, trin A-Att.

A-72de~A-7+g, A-7ri! ~A-1/2 can be mentioned.

Among them, particularly preferred ones are listed below.

H (2N H H 5H H H 2H5 ■ N-(CH3) 4 As mentioned earlier, in high-silver chloride emulsions with excellent rapid processability, all iridium is present in the localized phase of the silver halide grains. When it is contained, reciprocity law failure is improved and high sensitivity and high contrast can be obtained, but it has the disadvantage that the leg gradation tends to be soft.On the other hand, rhodium ion -?fc is a complex ion. Although this drawback can be improved by doping with , it has been revealed through research by the present inventors that this effect is significantly impaired by exposure to light such as safelight light.

In order to further improve the effect of stabilizing the sensitive layer and gradation in the present invention, the maximum absorption wavelength in the gelatin film must be adjusted! 7
Dyes located in the wavelength range of θ to lAO nm are useful. Although there may be strong absorption on the shorter or longer wavelength side than the maximum absorption wavelength, the main sensitivity wavelength range of the evening-sensitive photosensitive layer, the green-sensitive photosensitive layer, and the red-sensitive photosensitive layer, for example, aOO to 4AIjn.
If there is too strong absorption in the wavelength range of rn, j30 to j&Onml or l, JO'fz to 700 nm, the effective sensitivity of each photosensitive layer will be reduced. The maximum absorption wavelength is preferably a molar absorption coefficient of 102, β, mo//.

cln-1 or higher is preferable. Commonly known dyes such as azomethine dyes, steryl dyes, butadiene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, hemicyanine dyes, diarylmethane dyes, triarylmethane dyes, azomethine dyes, azo Dyes, metal chelate dyes, anthraquinone dyes, chalcone dyes, chalcone dyes, indophenol dyes R
You can choose from a TV group. For example, U.S. Patent No. 3. rro, tjr issue, same j, 93/, /! ! issue,
No. 3,232,310, No. 3. 3λ, 3r/issue, same 3. Ri4tco, Ri27, Jay Fabian, H Hartmann (J, Fabia mouth.

'Light Absorption of Organic Colorants' by H. Hartmann)
Absorption of OrganicC
olorants) (published by Springer Verlag) (or diffusion-resistant fc analogues). The dye used in the present invention is
Functional dye shown in Japanese Patent Application Sho t2-iotr No. 2, Specification of Japanese Patent Application No. 6/-11r62z, Japanese Patent Application Sho&/-/3t
≠ IO of Specification No. 7 page 117 Yamata Patent Application Sho t
It can be selected from those described in λ-μ3701/- and the like that match the spectral absorption characteristics and leave no residual color after development.

(Antifoggant) The high silver chloride silver halide emulsion having a localized phase according to the present invention has excellent rapid developability equivalent to that of a silver chloride emulsion, and has a silver bromide content of 20 mol% or more. Although it provides the same sensitivity as an emulsion, the generation of fog can be practically effectively stopped by using the following antifoggants in combination.

Preferred antifoggants include mercaptotetrazoles, mercaptotriazoles, benzotriazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotriazoles, and nucleic acid decomposition products such as adenine.

These antifoggants are largely adsorbed on particle surfaces other than the development start point, and can suppress fog that occurs during the development process without reducing the development start speed.

(Color coupler) As the pyrazoloazole coupler represented by the general formula (1) used in the present invention, US Pat.
Pyrazolo (j, /-C] (/, 2
, 4t) triazoles, among which US Pat. imidazo [i, λ
-b] pyrazoles are preferred, U.S. Patent No. ≠, r4t
o.

Pyrazolo (t, r-b) (/
.

C, 4') triazoles are particularly preferred.

Others, Tokukai Showa 4/-4j Ko≠! A pyrazolotriazole coupler in which a branched alkyl group is directly connected to the 2,3 or 6 position of the pyrazolotriazole ring as described in No. Virazoa azole cazole containing a sulfonamide group, pyrazoloazole coupler having an alkoxyphenylsulfonamidoparast group as described in JP-A No. 67-/Hiroshi 7λyo+, and European Patent (Publication) No. 224.14' It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group in the t-position as described in No.

Specific examples of the pyrazoloazole couplers used in the present invention are listed below.

Along with pyrazoloazole couplers! - Pyrazolone couplers can be used. As the j-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the coloring dye.
, 3//, Oru No. 2.31t3.703, Oru No. J, Joo, 7rr, No. 2,908',
j73, same No. J, 062, tjj No. 3, 1
j2. ♂Ribu issue and the same number 3. It is described in JJ, issue 0//, etc. As the leaving group for the two-equivalent j-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat.
The arylthio group described in No. 7 is preferred. European Patent No. 7.3. It has a pallast group as described in No. tJt! - Pyrazolone couplers provide high color density.

In the present invention, as the yellow coupler, piparoylacetanilide yellow couplers, benzoylacetanilide thread yellow couplers, and the like are preferably used.

For details on pivaloylacetanilide yellow couplers, see U.S. Pat.
Column/! Column 3 from line to column ≠, 4.2j, 1st G column of G/J specification! It is described in the θ line to the 447th line of the first column.

For details on benzoylacetanilide yellow couplers, see U.S. Patent 3. Hiroor, iri ≠ issue, same 3. ri3
J, No. 10, same 4tlθ≠Otsu, 7J No., same II, /
33. the law of nature! No., same≠, da0/.

There is a description in 7yo2, etc.

Specific examples of pivaloylacetanilide yellow couplers include the aforementioned US patents≠ and ≦here.

, Column 37 of the 2J'7 specification~! Compound examples (Y-/) to (Y-32) described in the μ column can be cited, among them (Y-/), (Y-Hiro), (Y-J), (Y-7),
(Y-/j), (Y-ko/), (Y-22), (Y-2
3), (Y-kot), (Y-3yo), (Y-JJ), (
Y-37), (Y-3♂), (Y-32), etc. are preferred.

Also, the aforementioned U.S. patent≠, t, 23. Compound examples (Y-/) to (Y-jj) in column 1 to column 1 of the TLT specification can be cited, and among them, (Y-2), (Y-7), (
Y-r), (Y-/, 2), (Y-λO), (Y-2/
), (Y-z 3), (Y-kota), etc. are preferred.

Other preferred examples include US Patent 3゜pot,
Typical specific example of writing the number in the i-rihiro specification in the column (3≠)
, same 3. 3.3, Compound examples described in column r of specification No. 501 (/l) and (/ri), same≠, θμ4, 373
Compound examples (ri) described in columns 7 to ♂ of the specification, 4II
, /33. the law of nature! Compound example (1) described in Nos. j to 6a of No. ♂ Specification No. ≠.

4tO/, No. 7F Co. specification! Compounds listed in the column can be mentioned. Particularly preferred is a λ-equivalent coupler in which the nitrogen atom is the leaving atom.

In the present invention, phenolic cyan couplers and naphthol cyan couplers are preferably used as the cyan couplers.

As a phenolic cyan coupler, US Patent λ, 3
6ri, riλri issue, same≠,! /r, 1. ♂ No. 7, same da!
//, has an acylamino group at the 2-position of the phenol nucleus, as described in No. 1 Gua and No. 1 J, 772, 00-, etc.
There are also compounds (including polymer couplers) that have an alkyl group at the 5-position, and a typical example thereof is Canadian Patent 6λ! , Example-2 couplers described in US Pat. No. 3,772.002, compound (1) described in US Pat. No. 3,772.002,
t+4t.

! Compounds (I-≠) and (I-4) described in No. 90, JP-A-Sho t/-37θ≠! Compounds (1), (2), and
(3), (λg), and the compound (C-2) described in No. 62-701'46.

As a phenolic cyan coupler, the US patent λ
, 772,762, same λ, tri j, r2, same ≠,
3317, 0// issue, same number, 100゜453 and Tokukai Sho! Tar/J4L Yujyo issue,! - There are diacylaminophenol couplers, typical examples of which are disclosed in U.S. Pat.

Compound (V) described in Rij, No. 124;

! j7. Compound (17) described in Tatata issue, Dohiro, jA
t, No. 777K Thei [) Compound (2) Ya (12),
Same≠.

/2g, compound (4) described in No. 32, same g, Otsu/3
,! Examples include the compound (I-/ri) described in Hiroshi.

As a phenolic cyan coupler, it also has a US patent! 27. / No. 73, Dohiro, ! All, jf7, 44, 4130, 1423, JP-A-Shoj/-3
As stated in riO≠t1 and patent application Shoj/-100ko2-,
There are compounds in which a nitrogen-containing compound ring is condensed with a phenol nucleus, and a typical example thereof is disclosed in U.S. Pat.
Couplers (1) and (3) described in the issue, Dohiro, j44L,
Compounds (3) and (16) described in jrJ issue, same≠,≠3
Examples include compounds (1) and (3) described in No. 0.4t23.

Other examples of phenolic cyan couplers include U.S. Pat.

No. 152, same≠, 1su, No. 272, 4 μ, Hiro-7, 7≠
No. 7, same! , J-7F, No. 113, European Patent (EP
)047. There are known couplers described in JR5FB/ issue, etc., and typical examples include U.S. patents≠,
333, the coupler described in Tatata issue (78 same≠, ≠ta/, !!Coupler (1) described in issue 7, same da, ≠ Hirogu,
? Coupler described in No. 72 1') % Dohiro, Gu 27,
Coupler (3) described in No. 767, same≠, 10, J/
Coupler (6), (24), 4 μ, j71 described in No.
．． Coupler described in No. 111 (1) Y (11), ll
& State Permit No. (EP) Ot7. Examples include the coupler (45) described in TL No. 87 and the coupler (3) described in JP-A-61-≠λ6-r.

As a naphthol-based cyan coupler, N-alkyl-N-7 is present at the 2nd position of the naphthol nucleus! Those with a J-rucarpamoyl group (eg, US Pat.

3/3,616), those with an alkylcarbamoyl group at the 2-position (for example, U.S. Pat. things (for example, Tokko Sho! 0-/μj No. 23),
Those having a carbonamide or sulfonamide group at the 5-position (for example, JP-A-Sho t.

-237≠4tr, same t/-/Hiroyo! No. 7, same j/
-/JiltμO), those with an aryloxy leaving group (e.g., U.S. Patent No. 3.
, / Tata No.), and those having a glycolic acid leaving group (for example, Japanese Patent Publication No. 277 of Sho AO-J).

Below are cyan couplers that can be preferably used in the present invention! - Typical examples of pyrazolone magenta couplers and yellow couplers are listed below.

C-(1) H α H (t)C5H11 ffi+ F H Shil (lO) α M-(1) ctC/ Y-(1) H Shiotsu The standard usage amount of color coupler is photosensitive halogenated 90.00/mole to 1 mole of silver, preferably yellow couplers with dO,0/fz to 0
．． 1 mole, 0.003 to 0.00 for magenta coupler.
3 mol, and l-, fO,002 to 0.3 mol for cyan coupler.

In the light-sensitive material in which the color coupler of the present invention is used, the preferred halogenated coating lid is /, 197 m - 0° 797 m2 (more preferably /, 217 m2 or less) when a reflective support is used, and is transparent. When using a support, 72/m ~ o, 2? /m2 (more preferably 3
y/m2 or less).

An oil dispersion method can be applied to these couplers, in which they are dispersed in the coexistence of at least -a of a high boiling point organic solvent and incorporated into the emulsion layer. Preferably, a boiling point organic 6 medium represented by the following general formula (A) or E) is used.

General formula (A) I w　2-o-p=.

General formula (B) w -coo-w2 General formula (C) General formula (D) W \ / General formula (E) W-O-~■2 (In the formula, W□, W2, and W3 are each L<ij
Mt-substituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group 'kN, W4 is Wl,
represents OWl or 5-wl, n is an integer in the range /, and when n is 2 or more, W4 may be the same or different from each other; may be formed.

Also, there is a method of dispersing a mixed solution of a coupler and a water-insoluble but organic solvent-soluble polymer such as bunal acrylate polymer or N-butyl acrylate methacrylate polymer into a hydrophilic colloid, and US Pat. No. 1, 322,027 No. Ya-J No. 44. /Tata, No. 363, or by using any of these methods in combination with oil dispersion.

(Anti-fading agent, anti-color mixing agent, anti-stinting agent) The photosensitive material produced using the present invention can be used as a color anti-fogging agent or an anti-stinting agent, such as hydroquinone derivatives, aminephenol derivatives, amines, gallic i1! derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers,
It may contain a chromophoric dye-eluting coupler or a sulfonamide phenol derivative.

In the light-sensitive material of the present invention, various anti-fading agents can be used. Namely, organic anti-fading agents for cyan, magenta and/or yellow images include hydroquinones,
t-hydroxychromans, j-4:)-loxitamarans, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, amine phenols, Typical examples include hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, gold nugget complexes such as (bissalitelaldoximato)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of specific anti-fade agents are described in the following patent specifications:

Hydroquinones are U.S. Patent No. 2,3tO, λ90,
Same 2nd. g/za, No. 473, No. 2,7oo, ≠j3, No. 2,70/, No. 77, No. 2,721. tj
No. Y, No. 2.7J, No. 2,300, No. 2.73! ,
No. 743, No. 3,912, Hari No., No. 30.
≠2! No. 1,3t3,927, U.S. Patent No. 2,710.10/, No. x, ri6. Oxr, etc., t-hydroxytaloman,! -Hydroxycoumarans and spirochromans are disclosed in U.S. Patent No. 3゜H.32.3.
No. 00, No. 3.173.010, No. 3, t71
A, J27 No. 3,491,907, No. 3,7
6 Hiro, No. 337, Tokukai Shoj2-/! λ Coco J etc.
Spiroindanes are covered by US Patent No. ≠, 3tO,! No. ♂, ρ-alkoxyphenols have US VF meter No. λ, 7.
3j, 766, British Patent No. 2. Olt, 7J issue, Tokukai Shojter IO! No. 32, Special Public Shoj7-/ri 7441.
Hindered phenols are disclosed in U.S. Patent No. 3.7.
00, ≠jt issue, Tokukaisho! 2-7λ22! No., US shipping license No. 22♂, λ3j No., Tokukosho! Gallic acid derivatives, methylenedioxybenzenes, and amine phenols are disclosed in U.S. Pat. ≠! 7
, 07th issue, same issue, 332, ♂♂6, Tokko Akira! 4-
2//Hindered amines are patented in the United States, such as in Gu Hong No. 3. j3t.

No. 731, same No. ≠, 2 o r, z 3, British Patent No. 1,
32, f♂ri issue, 1st and 3rd! Hiroshi, No. 373, No. 7. Hiro 10. R Kou No. 2, Tokko Akira! l-/4420 issue, JP-A-Shoj♂-//1fOJt issue, same! Tarj Jr≠ issue,
Similarly, ether and ester derivatives of phenolic hydroxyl groups are described in U.S. Pat.
! No., same No. ≠, /7 g, No. 220, same No. 2! '1,
2/Otsu No., Same No. ≠, Coco 2≠, Fu O No., Tokukai Sho! Goo/
4t! J30, same! ! -Jj co/issue, same! ♂-10!
/Gua, same as Ta 10, 37, Tokko Akira! 7-37♂
J6, US Patent No. ≠, 27F, 220, Special Publication Shoj
3-32z3 etc., metal complexes are disclosed in U.S. Pat.
o, ri No. 3g, same No. 7. Kohiro/.

No. 163, British Patent No. 2,027,73/(A), etc. These compounds are commonly used for the corresponding color couplers! Naishioo*
The objective can be achieved by co-emulsifying the m% with the coupler and separating it into the photosensitive layer. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an external ray absorber into the layers K on both sides adjacent to the cyan coloring layer.

Among the above-mentioned antifading agents, spiroindanes and hindered amines are particularly preferred.

In the present invention, it is preferred to use the following compounds together with the above-mentioned couplers, especially with the virazoloazole couplers.

PIJ chemically bonds with the aromatic amine developing agent remaining after the color development process to form a chemically inert and substantially colorless compound (A) and/or the compound (A) remaining after the color development process. For example, the use of a compound (B) that chemically bonds with the oxidized product of an aromatic amine color developing crude drug to produce a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, during storage after processing. This is preferable in order to prevent the occurrence of staining and other side effects due to the formation of colored pigments due to the reaction of the coupler with the remaining developing agent or its oxidized product during the development.

A preferred compound (A) has a second-order reaction rate constant 1k2 (in trioctyl phosphate of fO'c) with p-aningine: /, 01/m01°5eeA-/x10
It is a compound that reacts in the range of 5/mol-sec.

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. - If k2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to completely prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention. .

A more preferable compound (A) can be represented by the following general formula (AI) or (AII).

General formula (AI) -(A) n-X General formula (All) R2-C-Y ■ In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 7'-1 or 0. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents the addition of an aromatic amine developing agent to the compound of general formula (An). Represents a promoting group.

Here, R1 and X, Y and R2, or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are direct conversion reaction and addition reaction.

For specific examples of compounds represented by the general formulas (AI) and (An), please refer to Japanese Patent Application No. 1973-/! Za34t No. 2, Same A, 2-
/rltlt3, 12-272.2jr, fBJ
t2-. 2/4tAI No. 1, same &, 2-228'03≠
No. 72♂G No. 3, etc.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzo)IJ azole external radiation absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferably /
Mol/ml.

! It is set in the range of ×10 mol/m.

In the usual color o and e- sensitive material layer configuration, an ultraviolet absorber is contained in one layer on both sides adjacent to the red-sensitive emulsion layer containing the shear cuff color, preferably in the layers on both sides. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When UV absorbers are added to the protective layer, another protective layer may be applied as the outermost layer. This elasticity-retaining layer may contain a mixture of matting agents of arbitrary particle sizes and latexes of different particle sizes.

In the uninvented photosensitive material tFrC, an ultraviolet absorber 1] can be added to the hydrophilic colloid layer.

(Supporting Far body) As a reflective support that can be used in the present invention, it is preferable to use a reflective support that improves reflectivity and makes the dye image formed in the halogenated emulsion layer clear. The body is made of a plate laminated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate dispersed on a support, or a solid vinyl resin containing a light-reflecting substance dispersed therein. The material used as a support is included in the trench. For example, baryta paper, polyethylene-covered paper, polypropylene yarn synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyethylene terephthalate,
Examples include polyester films such as cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films, and polystyrene films, and these supports can be appropriately selected depending on the purpose of use. Also, JP-A No. 27031Itt, patent application Sho t/-/otrro.

A support having a specular reflection surface or a type 2 diffuse reflection surface is used, as described in Japanese Patent No. 1, No. 2007, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, and No. 1, No. 1, and No. 1, No. 1, and No. 1, No. 1, and No. 1, No. 1, and No. 1, No. 1, and J. A transparent support is also used in the present invention.

(Layer Structure) As described above, the present invention can be preferably applied to a multilayer, multicolor photographic material having at least λ different spectral sensitivities on a support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected as necessary.

Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between two or more emulsion layers having the same color sensitivity. .

In the color light-sensitive material according to the present invention, in addition to the silver halide emulsion layer, auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a pack layer are preferably provided on the support.

It is advantageous to use gelatin as the binder case or preservation colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, 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 hydroxyethyl cellulose, carboxydimethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
Synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyhinyl alcohol partial acetal, polyN-hinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, and Phot.

Enzyme-treated gelatin as described in Japan, Ifx/A, page 30 (/74) K may also be used;
Hydrolyzed gelatin and enzymatically decomposed products can also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. A typical example of these additives is Research Tissue Florger/76≠
3 (/7Ir 72) Oyohido /17/l (197
9, 77).

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

Another feature of the present invention is the rapid stabilization of color development processes, preferably less than 3 minutes and 0 seconds.
It can be done in a shorter time than 30 seconds or even minutes.

A small coating amount of silver halide is extremely advantageous not only for color development but also for speeding up the desilvering process.

(Color Development Process) The aromatic primary amine color developer used in the color developer in the present invention includes known ones that are widely used in various color photographic processes. These developers include amine phenol and p-phenylene diamine derivatives. Preferred examples include hp-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-/N, N-diethyl-p-phenylenediamine D-2λ-amino! -From diethylaminotolu-7,
2-amino-β-(N-ethyl-N-laurylamino)
Toluene D-≠ ≠-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-3 Comethyl-Hiroshi-[N-ethyl-N-(β-hydroxyethyl)amine]aniline D-4≠-amino 3-Methyl-N-ethyl-N-(β
-(methanesulfonamide)ethylcyaniline D-7N-(2-amino-diethylaminophenyl ether)methanesulfonamide D-♂ N,N-dimethyl-p-phenylenediamine D-tag Amino-3-methyl-N -Ethyl-N-methoxyethylaniline D-10 Hiro-amino-3-methyl-N-ethyl-N-β
-ethoxyetheraniline D-// ≠-amino-3-methyl-N-ethyl-N
-β-phthoxyethylaniline These p-phinidine diamine derivatives may also be salts such as 4A acid salts, hydrochlorides, sulfites, and ρ-toluenesulfonates. The amount of aromatic-grade amine developing agent used is preferably from about 0.572 to about λor per liter of developer solution.
, more preferable 1! 2 to about 10 S'.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

However, in order to improve the color development properties of the color developer, it is preferable that the amount of sulfite ion added be small.

In addition, as a compound for directly collecting the color herbal medicine, each hydroxylamine, patent application Sho t/-/166
Hydroxamic acids described in No. 39, J/-/707! Hydrazines and hydrazides listed in the No. 6/-/♂
Phenols described in No. 174t Co. and No. 203 No. J3, α-hydroxyketones and α-aminoketones described in No. 1 of No. 174t No. 2/-203, J/-it♂7/1, and/or No. 7/-
It is preferable to add various saccharides described in No./♂041t. Also, when used in combination with the above compounds, IP! j Ganshoj/-/1
No. 47123, J/-/, <No. J474Z, t/-
7 Otsu! Z2/issue, same t/-7tμ! /! No., N6/-/
707♂ri issue and the same t/-/Jza/! Monoamines described in No. 1, etc., AI-/736 No. 6, No. 1/-/Otsu 4'! / No. 6, diamines described in No. 7/-/rt350, etc., No. J/-/7! z2/ issue, and same t/-/J
Polyamines described in No. 7♂R, polyamines described in No. a/-it♂O/R, nitroxy radical compounds described in No. 15i'771.0, t/-/l'tj1 ．．
Alcohols described in / and t/-/ri717/ri, oximes described in 2/-/ri♂♂♂7, and tertiary alcohols described in t/-/ri♂♂♂7, and t/-/ri♂♂♂7 Preference is given to using amine fabrics.

Other stool collection agents include JP-A-Shoj 7-4' 4Z/μg
JP-A-Sho! Salicylic acids listed in JP-A-F
G'-3! Alkano-1 described mins described in No. 3.2, JP-A-Sho! Otsuta ≠ 34t mark polyethyleneimine,
The aromatic polyhydroxy compounds described in U.S. Pat. In particular, aromatic polyhydroxy compounds, triethanolamine, and patent application 1981-cot! It is preferable to add compounds listed in /II.

The color developer g used in the present invention preferably has a pH of ~/2, more preferably pH ~//, O, and the color developer contains other known developer component compounds. I can put 1.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,≠-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, λ-amino-comethyl-/! -Prono-resistant diol salts, valine salts, florin salts, trishydroxyaminomethane salts, lysine salts, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are bath-soluble, pH-reducing,
These buffers have the advantage of having excellent buffering ability in the high pH range of 0 or higher, having no adverse effects on photographic performance (such as turnip υ) when added to color developers, and being inexpensive. It is particularly preferable.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, sodium tetraborate (!-sodium sulfosalicylate), ! -Potassium sulfo λ-hydroxybenzoate (!-potassium sulfosalicylate) and the like can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is O11 mol/e.
or more, particularly o, imol/11-0
．． Particular preference is given to μmol/l. In addition, it is used as an anti-settling agent for calcium and magnesium in color developers, or to improve the stability of color developers.
Various chelating agents can be used.

The chelating agent is preferably an organic acid compound, such as the aminopolycarboxylic acids described in Japanese Patent Publication No. Sho-Guri R-30≠Gi-no. and Da-Hiro-30λ31; t-47J4L7
No. Tokko Akira! A-393! Y and West German Patent No. 2. Ko2
Organic phosphonic acids described in No. 7,63P, JP-A-Sho! Cor 1
0J, issue 72, same! 3-G No. 2730, same! Goo/2
//No. 27, same j! -/j12 Hiro 1 and the same! ! -7j
Phosphonocarboxylic acids described in No. 106, etc., and other%
Kaisho! ? -/ri! ? ≠J issue, same tJ'-203μ Hiro O issue and Tokko Akira! Examples include the metal compounds described in No. 3-≠0700. Specific examples are shown below, but the invention is not limited to these.

・Nitrilotriacetic acid, ・Diethylenetriaminepentaacetic acid, ・
Ethylenediaminetetraacetic acid, ・N,N,N-trimethylenephosphonic acid, ・ethylenediamine-N,N,N',N
'-tetramethylenephosphonic acid, trans-cyclohexanediaminetetraacetic acid, /.

Codiaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, cophosphonobutane/, 2. Hiroshi-tricarboxylic acid, ./-hydroxyethylidene-/,/-diphosphonic acid, .N,N'-bis(-monohydroxybenzyl)ethylenediamine-N,N'-diacetic acid These chelating agents may be added to 2a as necessary. The above may be used in combination.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example /4
It is about 00/2 to ioy per hit.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means 2 ml or less per developer/e, preferably 1
In other words, it does not contain at all.

The foregoing compounds used in the present invention provide significant benefits in processing steps using color developers that are substantially free of benzyl alcohol.

Other development accelerators include Tokko No. 37-/7ore, No. 37-4917, No. 31-7.1', No. 2, No. ≠ Hiro-/23♂O, No. ≠j-ta θ/ 3,1/3,2147, etc., JP-A-Sho! Ko≠ri l22 and giant IJ-0-
/3! ! p-phinidine diamine compound represented by No. II, JP-A No. ShojO-/377, JP-A No. Akihiro Akihiro-3
007≠ issue, JP-A-Sho t+-1rtrdt issue and the same! ≠ grade ammonium salts represented by Coat t3≠No. 22, etc.
U.S. Patent No. λ, 4t Tag, No. 203, 3. /Ko? .

/r-No. 47.230.7Pt, fr5Jj, J
! 3, RI/RI No. 37, US Patent No. λ, Hiroshi 12. The flit issue, the same one! Ri Otsu, Ri 2 Otsu and 3, ! l'2, amine compounds described in 3≠6, etc., Machikosho 37-/101♂, Doko 2--Tako O
No. 7, U.S. Patent No. 3I72g, /r3, Special Publication Sho≠/-
//μ37, Guko No. 23113 and U.S. Patent Department 3
,! Polyalkylene oxides represented by No. 3.2.30/, etc./-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, and j-nitroinindazole. -Methylbenzotriazole,! Representative examples include nitrogen-containing heterocyclic compounds such as -nitropenzotriazole, terchlorobenzotriazole, corchiazolylbenzimidazole, -monothiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, and atenine. can.

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, Hiroshi, Ri'-
Diaminorco1,2'-disulfostilbene compounds are preferred. The amount added is o-, tr/β, preferably 0. /S
'-Hiroshi? /7? It is.

Further, if necessary, one surfactant such as alkyl sulfo/acid, aryl phosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid, etc. may be added in its entirety.

The processing temperature of the color developer of the present invention is 20-100C, preferably 3O-4t00C. Processing time is 20 seconds!
The preferred time is 3C seconds to -minutes.

It is preferable that the amount of replenishment is small, but preferably 00ml per m2 of photosensitive material! It is 300m1. Historically, it is preferably 100wt1 to -00rttl.

Next, the desilvering step in the present invention will be explained.

Generally, any process such as a pumping process-fixing process, a fixing process-bleach-fixing process, a bleaching process-bleach-fixing process, a bleach-fixing process, etc. may be used for the iron removal process. In the present invention, the effect of the present invention becomes more significant when the process time of the desilvering step is shortened. That is, less than 2 minutes, more preferably /! Desilvering process that takes from seconds to seconds The bleaching solution, bleach constant MH, and bleach fixing solution used in the desilvering process will be explained.

As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
III) organic complex salts (e.g. ethylenediaminetetraacetic acid,
complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarbo/acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, etc. preferable.

Among these, organic complex salts of iron ([I) are preferable for bamboo from the viewpoint of rapid processing and prevention of environmental pollution. All aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or their salts useful for forming organic complex salts of iron (Ill) are listed as follows: ethylenediaminetetraacetic acid, diethyleneditriamine/pentaacetic acid tw, i, 3-diaminopro/
Examples include hair diaminetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, meteliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, iron(II[)
Complex salts are preferred because they have a high degree of acceptance.

These ferrous ion complex salts may be used in the form of complex salts, or may be used in the form of ferrous and ferric ion salts, such as ferrous sulfate, ferric chloride, ferric chloride, and ferrous ion complex salts.
Forming a ferric ion complex salt in a solution using ferric acid, ferric ammonium sulfate, ferric phosphate, etc., and a chelating agent such as aminopolycarboxylic acid, aminepolyphosphonic acid, phosphonocarboxylic acid, etc. You may let them. Further, the solating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron complexes, aminopolycal phosphate iron complexes are preferred, and the amount added is o, oi to 0 mol/l, preferably o, or-o, ro mol/e.

The whitening solution, bleach-fixing solution and/or their pre-baths may contain specific chemical compounds as bleach accelerators. For example, US patent 'j'; 3r 'ri 31g! Specification No. g, German Patent No. 1,290. r/λ specification, Japanese Patent Application Laid-open No. 3-3-2011! Compounds having a mercapto group or a disulfide bond described in Publication No. t30, Research Disclosure No. 17/2 (July issue/7r), and Tokko Sho ur-rr.

No., Japanese Patent Publication No. 32-20132, J! j-3.27
3rd issue, U.S. Patent No. J, 70t,! Thiourea-based compounds described in rt No. 1, etc., or compounds such as iodine and bromide ions are preferred in that the bleaching blade can be extended by 1ψ.

In addition, the bleach or bleach-fix solution used in the present invention may contain beautifying substances (e.g., potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride) or iodine. monster(
For example, a rehalogenating agent such as ammonium iodide) may be included. Boric acid, borax, sodium metaborate I as necessary
Jum, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid,
An ammonium salt or a corrosion inhibitor such as ammonium nitrate or guanidine can be added to an inorganic acid or an organic acid having a pH buffering capacity such as sodium citrate or tartaric acid, or an alkali metal casing thereof.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thioneanate such as sodium thiocyanate or ammonium thiocyanate; or ethylene. Bisthioglycolic acid, J,j-dithia-7
,! These are water-soluble silver halide dissolving agents such as thioether compounds such as r-octanediol and thioureas, and these t-1 types or a mixture of one or more types can be used. Also, Tokukai Akihito! -/j! 3! A special bleach-fixing solution consisting of a combination of the fixing agent described in No. μ and a large amount of a halide such as potassium iodide may also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per liter is preferably 0.3 to λ mol, more preferably O0j to 0 mol. The pH range of the bleach-fix solution or fixer is preferably 3 to IO, more preferably 5 to IO.
Particularly preferred.

Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and fixing solution in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, bisulfite, etc.) as preservatives. potassium, etc.), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately O0O in terms of sulfite ions.
λ〜O0! θmol/! The content is preferably 0.0≠~09 μO mol/e.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, all the carbonyl compounds etc. may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.

In the processing of the present invention, after desilvering processing such as fixing or bleach-fixing, aqueous and/or stabilizing processing is generally performed.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the material used, such as Cazoler), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set to . Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers.
alof the 5ociety of M
tion Picture and Te1evi
sion Engineers) Vol.
You can ask for it. Usually, the number of stages in the multi-stage countercurrent system is preferably 1 to 2, particularly preferably - to μ.

According to the multi-stage countercurrent method, the amount of water used for washing can be greatly reduced, for example, by 90.0% per meter of photosensitive material. ! (1 to 1/l or less is possible, and the effect of the present invention is remarkable. However, due to the increased residence time of water in the tank, there are problems such as bacteria propagating and the generated suspended matter adhering to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems, the method for reducing calcium and magnesium described in Japanese Patent Application No. Sho &/-/J/13- is very effectively used. In addition, chlorine compounds such as isothiazolone compounds and thiabendazoles described in JP-A-17-17-rJ-Hiroshi λ, chlorinated sodium 7-anurate described in JP-A No. 4/-/20/Hiro! Type fungicide, special patent application Sho AO-10j
Benzotriazole, copper ions, etc. described in No. 4 #7, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi, Hygiene Technology Kanawa [Sterilization, sterilization, and antifungal technology of microorganisms], Japan Antibacterial and Antifungal Science Kanawa It is also possible to use bactericidal agents described in "Encyclopedia of Bacterial and Antifungal Agents".

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound that can be substituted for formalin, or a film suitable for stabilizing the dye.
Examples include buffering agents and ammonium compounds for adjusting to H. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, a surfactant, a fluorescent brightener, and a hardening agent can also be added. In the processing of the photosensitive material of the present invention, when stabilization is achieved directly without going through a water washing process,
♂! ≠No.3! ♂-/gu13gu, to-λ-〇3≠!
In addition, it is also preferable to use a chelating agent such as /-hydroxyethylidene-/, /-diphosphonic acid, ethylenediaminetemethylenephosphonic acid, or a magnesium or bismuth compound. It is.

In the present invention, a so-called rinsing solution is also used as a washing solution or a stabilizing solution used after the desilvering treatment.

The pH of the water washing step or stabilization step of the present invention is between gu and 10, preferably! ~r. Temperature depends on the use of photosensitive materials,
Various settings can be made depending on the characteristics, etc., but in general /! ~guj'C
Preferably 20-≠06C. Although the time can be set arbitrarily, the effect of the present invention is more significant when it is short, and is preferably 30 seconds to ≠ minutes, and more preferably 30 seconds to λ minutes. The smaller the amount of replenishment, the lower the running cost, the less emissions, and
This is preferable from the viewpoint of ease of handling, and the effects of the present invention are also great.

A specific replenishment amount is 0.05 to 10 times, preferably 3 to 0.0 times, the amount brought in from the front bath per unit area of the photosensitive material. or less than /e per 7m of photosensitive material,
Preferably! 00. l or less. Further, replenishment may be carried out continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to reduce the amount of waste liquid by flowing the wash water reduced by a multi-stage countercurrent system into the over-to-roller and the bleach-fixing bath that is the preceding bath, and replenishing the bleach-fixing bath with concentrated liquid.

The method of the invention can be applied to any processing step. For example, color uninomy, color reversal can be applied to the processing of -par, color direct positive photosensitive materials, color positive film, color negative film, color reversal film, etc., but in particular, color processing can be applied to 1per, color reversal paper, etc. Application is preferred.

Example 1 Sodium chloride 6,≠ in a 3% aqueous solution of lime-treated gelatin
1 was added, and 3.2 rttl of N,N'-dimethylimidazolidine-corchion (7% aqueous solution) was added. While vigorously stirring an aqueous solution containing 0.2 mol of nitric acid*, an aqueous solution containing 0.0≠mol of potassium bromide and 0.14 mol of sodium chloride! It was added and mixed at 0C. Next, an aqueous solution containing O0r mole of nitric acid @, and an aqueous solution containing 0.11 mole of potassium bromide and 0.6 mole of sodium chloride were vigorously stirred! Added at -00,
Mixed. Seven minutes after the addition of the silver nitrate aqueous solution and the alkali halide aqueous solution was completed, r-[s-phenyl-r-(
r-(t-phenyl-3=(2-sulfonatoethyl)benzoxazoline-λ-yritenemethyl)-/-futhynyl)-3-benzooxazolio]ethanesulfonic acid pyridinium salt 21j, 7TI1gi71o engineering*. j
u' (after holding for 4" lj, desalting and washing with water were carried out. Furthermore, lime-treated gelatinata o and oy were added, triethylthiourea was added, and chemical amplification was carried out optimally to obtain a surface latent image type emulsion. The obtained silver chlorobromide (silver bromide 20
(mol%) emulsion was finished as Emulsion A-/.

Next, 3.32 kg of sodium chloride was added to a 3% aqueous solution of lime-treated gelatin, and 3°-d of N,N'-dimethylimidazolidine-thione (7% aqueous solution) was added. An aqueous solution containing O 9 moles of silver nitrate in this solution, o 9 moles of potassium bromide and 0 moles of sodium chloride. /ri6
and an aqueous solution containing mol at 52°C with vigorous stirring.

Subsequently, an aqueous solution containing o, r mol of silver nitrate and an aqueous solution containing 0.0/1 mol of potassium bromide and 0.7 g mol of sodium chloride were added at 52°C with vigorous stirring.
Mixed. Seven minutes after the addition of the silver nitrate aqueous solution and the alkali halide bath solution was completed, -1[j-phenyl-r-[
216.7 m9 of x-(t-phenyl-3-(X-sulfonatoethyl)penzoxazoline-coylidenemethyl]-7-butenyl 1-3-penzooxazolio]ethanesulfonic acid pyridinium salt was added.52 After being kept at °C for 73 minutes, it was desalted and washed with water.Additionally K, lime-treated gelatin, OY2, and triethylthiourea were added, followed by optimal chemical sensitization to obtain a surface latent image type emulsion. The resulting silver chlorobromide (silver bromide 2 mol %) emulsion was emulsion B-/.

Next, 3.32% of sodium chloride was added to a 3% aqueous solution of lime-treated gelatin, and N,N'-dimethylimidazolidine-
2-thione (7% aqueous solution) was added for 3.2 d. There was no total silver nitrate in this solution. While vigorously stirring an aqueous solution containing λ mol and an aqueous solution containing 0.2 mol of sodium chloride! λ
Addition and mixing was carried out at 0C. Subsequently, silver nitrate was added to 0. Aqueous solution containing phtamol and 0.7 sodium chloride! While vigorously stirring the aqueous solution containing moles! It was added and mixed at λ0C. Addition of silver nitrate aqueous solution and sodium chloride aqueous solution; i! ＞Ei
L7'C/ min&ni l-[! −Phenylucaw(λ−
[! -Phenyl-j-(u-sulfonatoethyl)benzoxazoline-1-yritenemethyl]-/-butenyl 1
-3-penzooxazolio]etha/sulfonic acid pyridinium salt + 2♂A and 7 ragf were added. After being kept at 52°C for 11 minutes, a water bath solution containing O,OS moles of silver nitrate, 0°02 moles of potassium bromide, and 0.02 moles of sodium chloride was added.
While vigorously stirring the aqueous solution containing 03 moles, ≠O0C
and mixed. Thereafter, it was desalted and washed with water.

Further, 70.091f of lime-treated gelatin and triethylthiourea were added to carry out optimal chemical sensitization so as to obtain a surface latent image type emulsion. The obtained silver chlorobromide (silver bromide 2
(mol%) emulsion was designated as Emulsion C-7.

Next, 3.32% sodium chloride was added to a 3% aqueous solution of lime-treated gelatin, and N,N'-dimethylimidazolidine-
3.2 kg of 2-thione (7% aqueous solution) was added. An aqueous solution containing 0.12 mol of silver nitrate and an aqueous solution containing 0.92 mol of sodium chloride were added and mixed at 0° C. with vigorous stirring. Next, an aqueous solution containing nitric acid @0.773 mol in total and an aqueous solution containing 0.776 mol of sodium chloride were vigorously stirred! Addition and mixing at 2 °C. Seven minutes after the addition of the silver nitrate aqueous solution and the sodium chloride aqueous solution was completed, l-[! -Phenyl-(j-(j-
Phenyl-3-(λ-sulfonatoethyl)benzoxazolin-2-ylidenemethyl]-/-butenyl)-3-
It was added to 6.7 m9 of penzoxazolio]ethanesulfonic acid pyridinium salt λr. ! After maintaining at -00 for 73 minutes, a water bath solution containing 0.02 moles of silver nitrate and a water bath solution containing 0.02 moles of potassium bromide and o, oor moles of sodium chloride were added at an aooc rate while stirring vigorously. Mixed. Thereafter, it was desalted and washed with water. Furthermore,
Lime-processed gelatin? 0.02 was added, triethylthiourea was added, and chemical sensitization was carried out optimally so as to obtain a surface a-image type emulsion. The obtained silver chlorobromide (silver bromide 2 mol%
) The emulsion was finished as Emulsion D-/.

For emulsions C-/ and D-/, potassium hexacyanoferrate (II) trihydrate λ-0m9 k was added to the sodium chloride aqueous bath solution added the second time, and potassium hexacyanoferrate (II) trihydrate λ-0m9 k was added to the aqueous alkali halide solution added strictly the third time. hexachloroiridium (I)
V) Emulsions C-2 and D-2 were prepared with the only change in gold being the addition of R potassium/, 0.

For the three types of silver halide emulsions A-i to D-s thus prepared, grain shapes, grain sizes, and grain size distributions were determined from electron micrographs. A-/
The silver halide grains contained in the emulsions from to D-2 are:
All were cubic. The particle size was expressed as the average value of the diameter of a circle equivalent to the projected area of the particles, and the particle size distribution was calculated using the value obtained by dividing the standard deviation of the particle size by the average particle size.

Next, the 7-halogen composition of the emulsion grains was determined by measuring X&1 diffraction from the halide recording crystal. Using monochromatic CuKa radiation as a radiation source, the diffraction angle of the diffraction line from the (200) plane was measured in detail. /%O While a diffraction line from a crystal with a uniform composition gives a single peak, a diffraction line from a crystal having localized phases with different compositions gives a plurality of peaks corresponding to those compositions. By calculating the lattice constant from the diffraction angle of the measured peak, it is possible to determine the halogen composition of the silver a-oxide constituting the crystal. The result was 1 on the first robe.

Next, magenta coupler (a) λ, Otsu 2 and color image stabilizer (b) r, RI 2, (c) //, ♂? Dissolve 30.0rrl of vinegar ffi ether, 3♂ of solvent (d), and jtul in a galley bath, and add this solution to a 10% aqueous gelatin solution containing 70% sodium dodecylbenzenesulfonate λ0ttlt.
The mixture was emulsified and dispersed in 0xl to prepare an emulsified dispersion (a) vI4.

Next, magenta coupler (e) J/, jr, color image stabilizer (c)/7.7y, stain inhibitor (f) 2.7y,
(g)-2,11, ethyl acetate tI! al and solvent (h
) / / , Jrsl, (i) Add and dissolve Ju, Ad, and add this @ solution to 10% gelatin aqueous solution J2 containing 10% sodium dodecylbenzenesulfonate + 20tlf
The mixture was emulsified and dispersed at 0 td to prepare an emulsified dispersion (o).

The silver halide emulsion thus obtained and the emulsified dispersion of magenta coupler were combined to prepare a coating solution having the composition shown in Table 2, and the coating solution was coated on a paper support laminated on both sides with polyethylene. Two types of photosensitive materials '#+ were prepared by coating with the layer structure shown in Table 2.

The gelatin hardening agent for each layer is /-oxy-3°! −
Dichloro5-) riazine sodium salt was used.

(a) Magenta coupler α (b) Color image stabilizer H (C) Color image stabilizer HCCH3 (d) Solvent (e) Magenta coupler C3H17(t) (f) Stain inhibitor α α (g) Stain inhibitor (h) Solvent (i) Solvent (08H17 Suhinoki p=.

The performance was tested using the thus obtained coated sample of 2-g.

First, when creating the same coated sample, we investigated the difference in photographic performance between the sample coated on the support 30 minutes after preparing the coating solution and the sample coated after a certain period of time. .

Each coated sample was exposed to light for 0.1 seconds (2000 MS) through an optical wedge and a green filter, and color development was performed using the development process and developer shown below.

The reflection density of the obtained treated sample was measured and a so-called characteristic curve was determined. Sensitivity is defined as the reciprocal of the exposure amount that gives a degree of O,S higher than the fogging density, and after preparing sample E7,
It is expressed as a relative value, with the sensitivity of the sample coated in minutes being 700. Also, from the exposure amount that calculated the sensitivity, O0! Find the difference between the density corresponding to the increased exposure amount and the point Qfs degree where the sensitivity was calculated,
It was a contrast.

In addition, for samples coated for 30 minutes after preparation, a photofading test was performed for 12≠ hours using a xeno/tester with an illuminance of 100,000 lux after treatment, and the concentration of the sample before light irradiation was determined to be The degree of discoloration due to light irradiation was expressed as a density difference.

Furthermore, the photographic properties of the samples coated for 30 minutes after preparation were also investigated when they were developed with a solution in which Keyaki Shiro fixer was mixed in a color developing solution at an amount of 0.J ttl/l.

These results are shown in Table μ.

Processing process Temperature Time Color development
3r0c 4tt seconds bleach constant N 30~3!
Rinse 0C for seconds■ 30~3z0c Rinse for 2o seconds■
30~3s0c 2o seconds/s ■ 3o-3r
0c 2o second rinsing■ 30-Jyo'C3o second drying 70~♂0'C Otosho (3-tank countercurrent blade type for rinsing ■→■) The composition of each treatment solution is as follows. be.

water ♂
00.1 Ethylenediamine - N, N, N.

N-tetramethylenephosphonic acid /, triethylenediamine (/, ≠ diazabicyclo(2,2,co)octane), t,oy sodium chloride /, Hiro? Potassium carbonate -! iN-ethyl-N-
(β-methanesulfonamide ether)-3-methyl-≠-aminoaniline sulfate Yo, O, N, N
-diethylhydroxylamine ≠, λ? Fluorescent brightener (U
VITEX CK Chipagaiki Co., Ltd.) 2. Add OV water to 1000FL1pH (xt
'C) lo, /.

bleach fixer water
≠00 Goteosulfate ammonium (70%)
100tttl sodium sulfite
/I? Ethylenediaminetetraacetic acid Iron acetate I [) Ammonium! ! ? Ethylenediaminetetraacetic acid disodium 31 ammonium bromide 4 lots glacial acetic acid
II Add water
1ooo punishment pH (koj 0C)
! ,! Rinse solution ion exchange water (calcium and magnesium each at jpp)
m or less) Comparing the tested emulsions, the sample using emulsion A-/ (
E7, E7, Low/, Loaf) have low contrast due to slow development speed. Emulsion B-72 with increased silver chloride content improves the development speed, but the sensitivity is low and is not suitable for practical use. It can be seen that the emulsions C-/, C-co, D-/ and D-λ having a silver bromide localized phase exhibit high development speed and high sensitivity. However, when the magenta coupler of the present invention, which is excellent in photofading, is combined, the contrast deteriorates significantly when the coating solution ages or when processed with a developer mixed with a bleach-fixing solution, making it impossible to put it to practical use.

By using the compound of the present invention in combination, for the first time, an emulsion with a high development rate and a coupler with excellent photofading can be combined to obtain an excellent light-sensitive material with little performance fluctuation during manufacturing and with little processing fluctuation. be able to.

In addition, Fe(II), Ir(IV) as impurity ions
An even higher contrast H- can be obtained with emulsions doped with (C-2, D-1).

Example 2 The emulsion λ prepared in Example 1 was modified to have a grain size of 7.0 by changing the temperature during silver halide grain formation and the time required for adding an aqueous silver nitrate solution and an aqueous alkali halide solution.
A 3μ emulsion was prepared. However, iron hexacyano(II)
The amount of potassium hexachloroiridate (It/) added was 0. /
Change to λ■, and then low [! -Phenyl-r-(r-
(, t-phenyl-J-(+2-sulfonatoethyl)penzoxazoline-coylidenemethyl]-/-buty=
/l/l -3-penzooxazolio]ethanesulfonic acid pyridinium salt λ, l'J, 7
λ- [! -chloro3-(3-sulfonatopropyl)benzothiazoline-λ-ylidenemethyl]-3-naphtho-
[/, 5-d) Thiacyl primary propanesulfonic acid triethylammonium salt/72°r~ was used. The resulting emulsion was E-/finished. The grain size distribution of this emulsion is 0.0
It was 7. Also, from X-ray diffraction measurements, this emulsion grain has a main peak of 100% silver chloride, as well as silver chloride j3 to 90%.
showed a sub-peak corresponding to %.

Next, the emulsion D-co prepared in Example 2 is 2-[j-phenyl-co(λ-[j-phenyl-3-(2-sulfonatoethyl)benzoxazoline-coylidenemethyl)-/-butenyl 1-3-Penzooxazolio]ethanesulfonic acid pyridinium salt t6.7 Instead of pyridinium salt iodide.

μm(λ,--dimethyl-/,3-propano)-t-(
+-Methyl-3-bentylbenzothiazoline-coylidene)-/, 3-pentagenyl-3-ether-6-
Emulsion F-/ was prepared, the only difference being that methylbenzothiazolium t0.0 t was added in total.

Using the silver halide emulsions thus obtained, multilayer coating was performed with the compositions, layer structures, and emulsion combinations shown in Tables 5, 7, and 7 to produce H4 class color light-sensitive materials. . The coating solution for each layer was prepared in the same manner as in Example 1. The gelatin hardening agent for each layer is /-oxy-3,! -Dichloro8-triazine sodium salt was used.

(j) Yellow coupler (k) Color image stabilizer C1) Color mixing inhibitor H (m) Ultraviolet absorber C4H9 (t) and C4H9 (ri and no/', mixture of j:3 (molar ratio) (II) Color mixing Inhibitor H (0) @ medium (i so C9H,, O+-3P=0(p) Cyan coupler (r) Stabilizer number average molecular weight to, ooo of the above polymer (q)
Color image stabilizer C4H9(ri) and C4H9(riando/', !:3 mixture (molar ratio) (V) Magenta coupler C3H17(t) It represents the total number of moles added per mole of molasses.

Exemplary compound (9) was dissolved in methanol and added when preparing green-sensitive emulsions D-/ and D-1, respectively.

The following compounds were used as anti-irradiation dyes for each layer.

For the green-sensitive emulsion layer For the red-sensitive emulsion layer All 11' coats #+ of bar/~knee μm thus obtained were tested for photographic performance.

In the same manner as in Example 1, changes in photographic properties of the green-sensitive emulsion layer coating solution over time, photofading properties of magenta color images, and changes in photographic properties when a bleach-fix solution was mixed into a color developing solution were investigated.

These results are shown in Table r.

As is clear from the results of No.
The fact that almost no decrease in sensitivity or contrast is observed when a bleach-fix solution is mixed in is also noticeable in multilayer color photographic materials.

Example 3 A similar test was conducted using the coating sample used in Example λ, but changing the development process and processing solution to those shown below.

The results showed the remarkable effects of the present invention as in Example-2.

Color development 3 to 0C Hiroj seconds bleach fixing 30 to 40C ≠! Second device setting■
30-37°C - 0 seconds Stable ■ 30-37°C λO seconds Stable ■ 30-J 7 °Cro seconds Apparatus setting ■ 30-37°0 30 seconds Dry 70-♂j 0c tO seconds (Stable) (2) The composition of each treatment liquid is as follows.

water r0
0xl Ethylenediaminetetraacetic acid 2.02 Triethanolamine Za, O? Sodium chloride /, ≠potassium dicarbonate
, 2, O? N-ethyl-N-(β
-methanesulfonamidoethyl)-3 -methyl-≠-aminoaniline sulfate! , O? N,N-diethylhydroxylamine, 21j, &-dihydroxybenzene 1/,j, gutrysulfonic acid 0.3f fluorescent brightener (≠, 10100O with addition of 4t'-diamine water) (/
0, / 0 Bleach-fix solution water
4t00td Ammonium Thiosulfate (70%)
100ffl sodium sulfite
/l'? Ethylenediaminetetraacetic acid iron (III) ammonium jj? Add water to ethylenediaminetetraacetic acid disodium 3 to make 1ooo, zp) (!, j Stabilizing liquid formalin (37%) o, iy Formalin-sulfite adduct 0.72!-Chloro-
1-methyl-hiro-inthiazolin-3-one o,oiv-1methyl-μmisothiazolino-3-one o,oit copper sulfate
o, add oozy water
1ooo, zpHμ, O (Effects of the Invention) The present invention is suitable for rapid color development processing, has good color reproducibility, and has excellent fastness of dye images, and also reduces the aging of the coating solution and the contamination of bleaching and fixing solutions. Silver halide color light-sensitive materials with little reduction in sensitivity or contrast can be obtained.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment (Pupeji, 1986! July 7th, Commissioner of the Patent Office, x,”'-x1,
Indication of the case: Showa t3 year patent application No. 710Y 2
, Name of the invention )) Silver halogenide color photosensitive material 3 Contact information for the person making the correction Address: 2-26-30 Nishi-Azabu, Minato-ku, Tokyo 106 Fuji Photo Film Co., Ltd. Tokyo Head Office Tel: (406) 2537 t Date of amendment order Showa end in January? Z day (shipping mortar) & subject of amendment Statement 6, engraving of the details of the amendment (no change in content)? I will submit it.

Claims (1)

[Claims] (1) In a photosensitive material in which at least one photosensitive emulsion layer containing surface latent image type silver halide grains is provided on a support, each silver halide grain in the photosensitive emulsion layer is 90 mol% or more (average value) of the total silver halide constituting the grain is silver chloride, and silver chlorobromide substantially does not contain silver iodide, and the surface of the grain is unevenly distributed. A pyrazoloazole coupler containing 50% by weight or more of an emulsion consisting of silver halide grains having a localized silver bromide phase in a continuous or isolated state, and further comprising a pyrazoloazole coupler represented by the following general formula (I). and at least one compound represented by the following general formula (II-a) or (II-b) in at least one layer of the photosensitive emulsion layer or other hydrophilic colloid layer. A silver halide color photosensitive material characterized by containing. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Za and Zb represent methine, substituted methine, or -N=, R_1 represents a hydrogen atom or a substituent. Y_1 represents a halogen atom, Or, it represents a group that can leave (referred to as a leaving group) during a coupling reaction with an oxidized product of an aromatic primary amine developing agent.It forms a dimer or more multimer with R_1, Za, Zb or Y_1. General formula (II-a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II-b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1_1 is an alkyl group, an alkenyl group, or an aryl group. Represents a group. .L represents a divalent linking group, =N-R_1_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -S-, ▲Mathematical formulas, chemical formulas, tables, etc. etc. ▼ etc. Here, R_1_3, R_1_4, R_1_5 each represent a hydrogen atom, an alkyl group, or an aralkyl group, and n and n' represent 0 or 1)