JPS6165248A - Silver halide color photograhc sensitive material - Google Patents

Abstract

PURPOSE:To improve the fastness of a color image to light and color formability (color forming efficiency) by using a specific pyrazoloazole magenta coupler. CONSTITUTION:The pyrazoloazole type magenta coupler which is expressed by formula I and is combined with at least one group expressed by formula II is used. In formula I, R1 denotes a hydrogen atom or substituent, X denotes a hydrogen atom or the group which can be eliminated by the coupling reaction with an arom. primary amine developing agent oxidant, Za, Zb and Zc denote methine, substd. methine, =N- or -NH-. In formula II, R2 denotes a hydrogen atom, halogen atom, etc., Y denotes formula III, R3, R4 denote a hydrogen atom, alkyl group, halogen atom or aryl group, R5 denotes a hydrogen atom, alkyl group, aryl group, acyl group or sulfonyl group, (m) denotes 1-4 integer. The amt. of the coupler to be used is made 1X10<-3>-5X10<-1> for each 1mol of the silver halide.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic light-sensitive material with improved color development and color image fastness to light. It is related to. More specifically, it is a pyrazoloazole-based magenta coupler, and relates to a silver halide color yoshin light-sensitive material containing a magenta coupler linking at least seven hydroxyphenyl groups. Silver color photographic materials often use so-called dye-forming couplers, which form dyes by reacting with the oxidation products of light-sensitive silver halide emulsions and aromatic-grade amine developing agents, and are usually yellow couplers and cyan couplers. It is well known that it is used in combination with couplers and magenta couplers.

This one is often used as a magenta coupler! −
Pyrazolone couplers have an azomethine dye of 4tj
Major problems in terms of color reproduction include the presence of C side absorption in the vicinity of Onmm and the poor cut-off of the absorption spectrum on the long wavelength side.

Therefore, in order to solve this problem, a magenta color image forming coupler has been developed for a long time.
: Pyrazolobenzimidazole bone core described, US patent! , 72! , No. 047C=Pyrazolotriazole bone cores have been proposed.

Also recently (new special request show!? - Ko J4tJit
/H-imidazoC/, I-b) pyrazole skeleton described in Japanese Patent Application No. 1997-41JTJ/2;

1-1-'J azole skeleton, patent application Sho jr-7'1210
/H-pyrazolo (/ , j -1) described in No. 7
Tetrazole skeleton, special request Shoit-/! The /H-pyrazoloC/, r-b]-pyrazole skeleton described in the following paper has been proposed.

However, although the above-mentioned problem regarding hue has been solved with this series of couplers, the couplers cannot be developed when developed under conditions where a sufficient amount of oxidized aromatic-grade amine developing agent is generated in the silver halide emulsion M. It has been found that there is a problem in that the maximum color density (hereinafter abbreviated as Dmax) decreases because the amount of light converted from azomethine to an azomethine dye (hereinafter abbreviated as coloring motor) is low.

Known methods for increasing the coloring effect include a method of introducing a leaving group at coupling active position 1, a method of adding a coloring enhancer, and a method of changing the pallast group to one that matches the coupler skeleton.

On the other hand, the color image light fastness ε formed from these skeletons is very poor in the pyrazolotriazole described in U.S. Pat. No. 3.72J, 047; It had excellent robustness.

(Objective of the Invention) The first object of the present invention is to provide a silver halide color photographic light-sensitive material with improved coloring property using a pyrazoloazole magenta coupler with improved coloring property (coloring motor). be.

A second object of the present invention is to provide a silver halide color photographic material with improved color image fastness to light.

(Means for Solving the Problems) In order to achieve the above object, in the present invention, various substituents were investigated for a pyrazoloazole magenta coupler having high color image fastness, and as a result, at least seven hydroxy By substituting phenyl groups, we have achieved a group of couplers that have excellent color development and light fastness of color images.

Conventionally, as a coupler having a hydroxyphenyl group in the molecule of a magenta coupler, U.S. Patent No. 3. ! /ri, 4t2
No. 9 C2 was listed! - Couplers with photostable groups introduced into the pyrazolone skeleton, and U.S. Pat. No. 41, J14TJ, 6
A coupler having a hydroxyphenylsulfonyl group introduced therein described in No. 36 is known. In the case of the former (:) house,! -Pyrazolone skeleton! = limited, and the pyrazoloazole coupler of the present invention has not been studied yet. In the latter case:: is /H-pyrazoloCsr/
C] ( / 1 In particular, the light fastness of color images was not improved.

Therefore, as a result of various studies, the present inventors have found that the object of the present invention is to provide a pyrazoloazole type magenta coupler represented by the following general formula (I), and at least seven of the following general formula (II).
) It was discovered that this can be achieved by a silver halide color photographic light-sensitive material characterized by containing a fintacoupler linking groups represented by the following.

General formula (I) %Formula% General formula (I) (Rz)m What is the compound represented by the general formula [■]? It is an f-membered condensed nitrogen complex coupler, and its color-forming nucleus exhibits isoelectronic aromaticity with naphthalene, and has a chemical structure that is generally referred to as azapentalene. Preferred compounds among the couplers represented by the general formula [1] are /H-imidazo[: t , J -b]pyrazoles, /H-pyrazolo[/, r-b]pyrazoles, /H-pyrazolo[/
, t-b][/, co+l+-lyazoles, /H-pyrazolo[/,j-d]tetrazoles and river(-pyrazoO
[/,! -a) Benzimidazoles, each having the general formula (I-/], (I-,2), (I-j)
, [1-g] and [1-j:l, among which particularly preferred compounds are [1-/) and CI-/)
(I-,!] (I--?)
[:I-da] (I-, t) Substituents R6, R of general formula [T-/] to [1-j]
7 and R8 are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group,
represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an anlu group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X is a hydrogen atom, a halogen atom, Represents a carboxy group, or a group that is bonded to a carbon at a coupling position via an oxygen atom, nitrogen atom, or sulfur atom, and is decoupled.

The case where R6, R7, R8 or X becomes a divalent group and forms a bis body is also included.

More specifically, X is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxyl group, or a group linked with an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group). group, 2,4t-dichlorobenzoyloxy group, ethoxyoxaroyloxy group, pyrrhinyloxy group, nnnamoyloxy group, fenoquine group, coucyanophenoxy group, goomethanesulfonamidophenoxy group, coumethanesulfonylphenoxy group, α -Naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, cocyanoethquine group, benzyloxy group, copheneteroxy group, -phenoxyethoxy group, !-phenyltetrazolyloxy group , copenzotheazolyloxy group, etc.), groups linked via a nitrogen atom (
For example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide M%
J+j+4t+j+4 -<ntafluoropenzamide group, octane sulfonamide group, p-cyanophenylfreido group, N,N-diethylsulfamoylamino group, /-pyridyl group, j,j-dimetheluco, 4t-
Dioxo-3-oxazolidinyl group, /-benzyl-ethoxy-3-hydantoynyl group, -N-/, /-dioxo-J(,2H)-oxo-/, 2-benzisodeazolyl group, λ-oxo/ 2.2-dihydro/-pyridinyl group, imidazolyl group, pyrazolyl group, 3. ! -diethyl-/,co,4t-)lyazole-/-yl,! - or t-promobenzotriazol-7-yl,! −
Methyl/, 2. j, < to -triazol-/-yl group, benzimidazolyl group, 3-benzyl-/-hydantoinyl group, /-benzyl-yo-hexadecyloxy-3-hydantoinyl group, ! -methyl-/-tetrazolyl group, coumethoxyphenylazo group, goupivaloylaminophenylazo group, -monohydroxy-goopropanoylphenylazo group, etc.) Groups linked by a sulfur atom (for example, phenylthio group, cocalpoquinphenylazo group) Thio group, comethoxyj-t-octylphenylthio group, g:t-cutanesulfonylphenyltheo group, g:tcutanesulfonamidophenyltheo group, copetoxyphenyltheo group 1
．． 2-(2-hexane sulfonyl ether) -j -t
er t-octylphenylthio group, benzylthio group, cocyanoetherteo group, /-ethoxycarbonyltridecylthio group,! - Phenyl 2. J, 41.3-
Tetrazolylthio group, 2-benzothiazolylthio group, codedecylthio-yo-thiophenylthio group, λ-phenyl-3-dodecyl-7,2,'! -Triazolyl-
thio group, etc.).

The group defined in general formula i) is linked to R6, R7, R8 or X (=Thus, a group of couplers of the present invention is completed.

Regarding the synthesis of the group of couplers of the present invention, the framework is as follows: British Patent No. 04T7, 6/2, Patent Application Sho! r-, 2j@
Same as j4! r-4t1! /No.2, same! r-/4t2
tO1, No. 11-/41210/, etc., and U.S. Patent 3. ! /the law of nature.

Da, No. 29, Da, 4t4tj, No. 136, etc.
Regarding the connection of leaving groups, please refer to the patent application Sho i! -9! ! /), etc. (= Specific examples of pyrazoloazole couplers used in the present invention that can be synthesized by the method described are shown below, but the invention is not limited thereto.

+31
CH3C3H17(t) -y(t) 4t'i9(electro) N=N a3 H3 Below (:, a specific synthesis example of the magenta coupler of the present invention is shown.

Synthesis example/(Synthesis of exemplary coupler (/7)) B
c D B (I) Synthesis of intermediate t-butylhydroquinone! Of and 9 ml of pyridine were added to 400 ml of acetonitrile, and the mixture was stirred while cooling in a water bath. Add 32ml of acetic anhydride dropwise to this,
Stir for a minute. The reaction mixture was poured into ice water and extracted with ethyl acetate. After washing the organic layer once with water, add anhydrous sulfuric acid)
Dry over 9km and concentrate. The residue was recrystallized from hexane to obtain a compound with jθ, 7r (, rz%).

Compound A4t/, jf, 2-bromododecanoic acid eterc! , -1 and anhydrous potassium carbonate 979 to N,N-dimethylformamide
oC (heated twice and stirred for 2 hours. After cooling, insoluble matter eP
After separating, the mixture was poured with water twice and extracted with ethyl acetate. The organic layer was washed twice with water, dried over anhydrous sodium sulfate, and concentrated to obtain 20% crude compound B. This was dissolved in 300 ml of methanol. This 1: Sodium hydroxide aqueous solution (33f of sodium hydroxide in water/j
(dissolved in Oml) at room temperature with stirring, then
The mixture was heated under reflux for 7 hours. After cooling, the reaction mixture was poured with water, acidified with concentrated hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed twice with water, dried over anhydrous magnesium sulfate, and concentrated. The residue was extracted with hexane. Recrystallization yielded 301! (3j%) of Compound C.

Compound C2θV and 72 ml of pyridine were added to acetonitrile ioomi and stirred at room temperature. To this, 7.7 mJ of acetic anhydride was added dropwise, and the mixture was further stirred for 30 minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed once with water and dried over anhydrous sodium sulfate. After concentration, the eluate was fractionated on a silica gel column and concentrated to l♂t (77%
) was obtained as a slightly yellow oil.

Nuclear magnetic resonance spectrum (CDα3) J(pI)m) 4. ? ♂(jH, d, J=3.
0Hz), 4. r3(jH, dd, J゛:3.0゜?,
(7H2), 6.6! (jH, d, J=9.0Hz)
,a,I,9(jH,t,J=6.θHz)1.2. ．．
2j(,?H,S)1,2. ．． 2-7. /(27H, m
), 0. r9(jH,brt) (Co) Synthesis of the exemplary coupler (/2) Compound DI♂1 and phosphorus pentachloride 9, , /f '73
After adding m1 of benzene to the mixture and heating under reflux for 7 hours, the solvent was distilled off under reduced pressure to obtain Compound E.

Special request! No(3-(y-aminophenyl)propyl)=6-methylpyrazolo(/,j-b)(/l) synthesized by the method described in Turf 0/4tt.

ri] Triazole/Q, cotton and sodium acetate 3°? t
was added to 7 oml of acetic acid, and the mixture was stirred at room temperature.

To this, step I: an acetic acid solution of the synthesized compound E (compound E
The reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was washed twice with water.

The organic layer was dried over +7 um of anhydrous sulfuric acid, concentrated, and then subjected to silica gel column chromatography (eluent;
It was fractionated using a chloroform-vinegar solution (1 liter = 10:/). The eluate was condensed to dryness to obtain compound F20f (70 units).

Add compound F a o y to 200 ml of digcolomethane.
1m.

After dissolving the mixture, 3.3v of corosuccinimide was added, and the mixture was stirred at room temperature for 70 minutes. After washing the reaction mixture three times with water, it was dried on an anhydrous sulfuric acid sulfur ram and concentrated. The residue was dissolved in methanol ijoml and stirred at room temperature. This (= sodium hydroxide aqueous solution (sodium hydroxide J,
4F was added dropwise with water θm1 (=dissolved) and heated to 70°C at room temperature.
Stir for a minute.

Water this! The mixture was poured into a volume of 0.00ml, neutralized with concentrated hydrochloric acid, and the precipitate was separated and washed with water. This solid was purified by silica gel column chromatography (eluent: chloroform-ethyl acetate = 9:/), and the eluate was concentrated to dryness./3. t
An exemplary coupler (/7) of y (7b%) was obtained.

Elemental analysis C% H% N% calculated value A7.9j '7. λ //, 0/measured value 67.76 7.9r 10. rg nuclear magnetic resonance spectrum (CDα3) δ (ppm)/,! ,,2/ (/H,br),/
,.

/(,2H,br),7,. 2-4.7 (jH, m),
1,,j7 (JH,br),44,4.3 (/H
,br),J,/-/,/(JjH,m),a,x
Ta (3H.

S), 0, /4 (jH, brt) Synthesis example = (Synthesis of exemplary coupler (/)) OH01 (111゛~1t'h,\ri7 1tmine (I) Synthesis of intermediate S Hydroquinone 301 was added to a mixed solvent of 300 ml of acetic acid and 00 mil of acetic acid, and the mixture was stirred at room temperature.

To this, benzenesulfinic acid 10MJ'7m/hydrate 7
7F was added and stirred for 30 minutes. The reaction mixture was poured into water, the organic layer was separated, and the organic layer was washed once with water.

The organics were dried over anhydrous sodium sulfate and concentrated. The residue was recrystallized from acetonitrile to form the compound Ps/, ty(
7♂壬) was obtained.

7θ'C + di-heated acetic anhydride // 30 ml of boric acid
．． C2 was gradually added under stirring. After cooling at room temperature, 2! , Of Compound P was added thereto, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was poured with water/θeC, and the precipitate was separated, washed with water, and dried to obtain a crude product of Compound Q, 26°4tf (77%).

Crude product λ of compound Q in N,N-dimethylformamide tomb, 4. <tf and 32 f of anhydrous potassium carbonate were added, heated to zo"c, and stirred. This (embodied benzyl/!2) was added dropwise and stirred at that temperature for 3 hours. After cooling, insoluble matter was removed from door to door. The F solution was poured into 2 Oml of water and extracted with dithyl acetate.The organic layer was poured into saturated brine/Oml.
After washing twice with
= Dissolved, an aqueous sodium hydroxide solution (sodium hydroxide 7, dissolved in water θmlj) was added, and the mixture was stirred at room temperature for 70 minutes. Add this reaction mixture to 600 ml of water.
+ = poured, hydrated with concentrated hydrochloric acid, and then extracted with ethyl acetate. The organic layer was washed twice with water and then dried over anhydrous magnesium sulfate. After concentration, silica gel column chromatography (eluent; chloroform:ethyl acetate = 70:/
), and the eluate was concentrated to dryness to yield //, /f(j?1
%) of compound R was obtained.

Compound R/2 in N,N-dimethylformamide somA
．． 3r and 27f% of anhydrous potassium carbonate were added, heated to ♂θ0C, and stirred. This C: Add 7 t of copromododecanoic acid IR and add more! ~/10'C
The mixture was stirred for 3 hours. After cooling, the insoluble materials were separated, and the P solution was poured into water/jOrJ' and extracted with ethyl acetate. Yes!
After washing twice with M-layer saturated brine, it was dried over anhydrous magnesium sulfate and concentrated. The obtained oil was dissolved in methanol/coml, and an aqueous sodium hydroxide solution (sodium hydroxide 6/l dissolved in water) was added, and the mixture was heated under reflux for 7 hours. The reaction mixture was poured with 1:1 of water, made acidic with concentrated hydrochloric acid, and then extracted with ethyl acetate.The organic layer was washed once with water and then dried over anhydrous magnecum sulfate.After concentration, silica gel column chromatography (eluent; The eluate was fractionated with chloroform:ethyl acetate:/J:/), and the eluate was concentrated to dryness.
Compound S of or(y3%) was obtained.

(2) Synthesis of the exemplified coupler (/ri) Compound 8ty, rt and Rinph pentachloride, 4f! Oml += was added and heated under reflux for 7 hours. Under reduced pressure I: The solvent was distilled off to obtain Compound T.

λ-(J-(a-aminophenyl)furovir)-6-methylpyrazolo[/, j-b) (/, co.

] Triazole 7.7f and sodium acetate 2°! 2 was added to J and gml of acetic acid, and the mixture was stirred at room temperature.

This (:, acetic acid solution of compound T synthesized earlier (compound T
(dissolved in m4 acetic acid/water) was added dropwise, and the mixture was stirred for a further f hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed twice with water and then dried over anhydrous magnesium sulfate. The residue was concentrated and fractionated by silica gel column chromatography (eluent: 10% of chloroform-ethyl acetate). Concentrate the eluate to dryness/6. a
Compound U of s+(7,2ti) was obtained.

/! Dissolve compound U of jf in tetrahydrofuran jml, add 10% palladium/activated carbon of co,
The mixture was stirred for an hour at θ''C under a hydrogen atmosphere of 0 atm. After the catalyst was removed, dichloromethane/!Oml was added and stirred at room temperature.

To this, N-chlorosuccinimide 2. Add t2 and get 7
Stir for 0 minutes. The reaction mixture was washed three times with water and then dried over anhydrous magnecum sulfate.

After concentration, the residue was fractionated by silica gel column chromatography (eluent: chloroform-ethyl acetate = 1:/). The eluate was concentrated to dryness to a concentration of 72.3? An exemplary coupler (♂j%) of (♂j%) was obtained.

The pyrazoloazole couplers used in the present invention may be used alone or in combination of two or more.

The amount of this coupler used is per 7 moles of silver halognide/X
/(7~!×/θ mol, preferably /X/(7-2
~! XI ("molar range.

The halogenated color photographic material of the present invention includes, for example,
Color negative film, color positive film, color 4-
The couplers of the present invention and the couplers used in combination can be introduced into the silver halide emulsion layer (for example, by known methods, such as the method described in U.S. Pat.
, No. 32.2.027! = The method described above is used. Examples include phthalic acid alkyl esters (dibdelphthalate, dioctyl phthalate, etc.),
diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl lauryl amide) ), fatty acid esters (e.g. dibutquin ethersuccinate, diethyl azelate), trimesic acid esters (e.g. tripudyl trimesate), etc., or organic solvents with a boiling point of about yo0C to /t o'C, such as ethyl acetate, acetic acid. After dissolving in lower alkyl acetate such as butyl, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxy ether acetate, methyl cellosolve acetate, etc.
Dispersed in hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Tokuko Shoj/-391jj, Tokukai Sho! /-! The dispersion method using polymers described in Wagaku No. 3 can also be used.

When the coupler has a carboxylic acid or sulfonic acid group, a hydrophilic colloid is prepared as an alkaline aqueous solution:
A person is interrogated inside.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin. I can do it.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Guais (Academic Press, published in 1996).

In the photographic emulsion layer 1 of the photographic light-sensitive material used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used as silver halide, and is preferred. Silver halide is/! It is silver iodobromide containing silver iodide less than molti. Particularly preferred is silver iodobromide containing silver iodide in the range of 2 molar percent to /-molar percent.

The average grain size of silver halide grains in a photographic emulsion (the grain diameter is taken as the grain diameter for spherical or approximately spherical grains, and the ridge length is taken as the grain size for cubic grains, and expressed as an average calculated by the projected area) is Although not particularly limited, the particle size is preferably 3 μm or less, and the particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have a regular crystalline structure such as a cube or a hexagonal, or may have a spherical or hexagonal shape.
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of mixing forces of particles of various crystalline forms.

Also, the diameter of the particle is the same as its thickness! Ultra-tabular silver halide grains more than double the total projected area! An emulsion that occupies 0 or more cells may be used.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is P, Qlafkides.
Written by Chimie et Physique Phott＞
griffique (published by Paul Monte1, / 1967), G, F, Duffin Police Department Photog
rapic emulsion chernist
ry (The Focal Press, 1966), v, L, 7. elikman et a
li Making and Coating Pho
tographic Bmulsion(The
Focal Press, /944) can be prepared using the method described in Nat.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more silver halide emulsions formed separately may be used in combination.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization (; is, for example, H. prieserii
“Die QrundlagenderPhotog
raphischen Prozesse mit8i
lber-halogeniden” (Akademi
scheverlagsgesel 1schaf
t, /9 t J') /l 7! The method described on page 734 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound that can react with activated gelatin or silver (e.g., thiosulfate, t-ureas, mercapto compounds, rhodanine); Reduction sensitization method using tin salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds; noble metal compounds (e.g., total complex salts, etc.)
A sensitization method using complex salts of metals of group 1 of the periodic table, such as Ir + Pd, etc. can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, 2)+2benzimidazoles, gucolopenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially /-phenyl-j-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines ; thioketo compounds, such as oxadolinthione; azaindenes, such as triaza-indenes, tetraaza-indenes, especially cupidroxy-substituted (/, 3.3a, 7)
A number of compounds known as antifoggants or stabilizers are added, such as tetraaza-indenes), hantaaza-indenes; benzenetheonurquoic acid, benzenesulfonate, benzenesulfonamide, etc. be able to.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
A variety of surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, derivatives of polyalkylene oxide such as ethers, esters, and amines, thioether compounds, and thiomorpholines for the purpose of increasing sensitivity, increasing contrast, and promoting development. , quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

In the photographic light-sensitive material containing two phases of the present invention C, for the purpose of improving dimensional stability in the photographic emulsion layer and other hydrophilic colloid layers,
Dispersions of water-insoluble or sparingly soluble synthetic polymers can be included. For example, alkyl (meth)acrylates, alkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylconitrile, olefins, styrene, etc. alone or in combination; Or these and acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate,
A polymer containing a combination of sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holophoradianine dyes, hemicyanine dyes, steryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used in cyanine dyes as the basic heterocyclic nucleus can be applied to these dyes (:). Namely, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus. , selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus , benzindolenine nucleus.

Indole nucleus, benzoxadol nucleus, toftoxazole nucleus, benzothiazole nucleus, naphthotheazo tv4
17. , benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei are pyrazoline-! as a nucleus having a ketomethylene structure in the umerocyanine dye or the extracted IJ cyanine dye which may be substituted on a carbon atom. j -A-membered heterocyclic nuclei such as -on nucleus, thiohydantoin nucleus, λ-dioxazolidine-λ, kudione nucleus, thiazolidine-2, kudione nucleus, rhodanine nucleus, and thiobarbital acid group can be applied.

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

A sensitizing dye is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 9933, 39θ, 3.43!, 7
2/2/), aromatic organic acid formaldehyde condensates (e.g., U.S. Patent J, 74tJ, t/θ (
), cadmium salts, azoindene compounds, etc.

The invention is also applicable to multilayer, multicolor photographic materials having at least one different spectral sensitivity on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer f: a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. can.

The same or other photographic emulsion layer of the photographic light-sensitive material prepared using the present invention or the non-light-sensitive 1 (ft) may include other dye-forming couplers as well as the power-l puller represented by the above general formula [■]. That is, a compound that develops color by oxidative coupling with an aromatic 7th class amine developer (eg, phenylene diamine derivative, aminophenol derivative, etc.) may be used in the color development process.

Typical examples of color couplers include tophthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of cyan, minter and yellow couplers that can be used in the present invention are RD /71,4t3
(/97Lr/month)■-ri term, same/♂7/7(/9
January 1979; described in the cited patent.

These couplers preferably have ballast groups or are polymerized and diffusion resistant.

It is preferable that the coupling position is substituted with a leaving group rather than a hydrogen atom. Couplers in which the chromophore has an appropriate diffusivity, colored couplers, colorless couplers, or couplers which release a development inhibitor or IA image accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in combination with the present invention is an oil-pack type acylacetamide coupler. A specific example is US Patent No. 2.
Daθ7. -/σ No., same No. 2. /7j, No. 037 and No. 3. Kotj, fO Otsu No., etc. (2 are listed. In the present invention, 2-equivalent yellow couplers can be preferably used,
US Patent No. 3,4tθ♂, /? No. 4, No. 3 of the same. 4t
7. Octopus No. 3,933.307 and same g.
ri0/,7! Oxygen atom separation type yellow couplers described in Japanese Patent Publication No. 1073, U.S. Pat.
1// issue, RD//θj3 (/ri 7 ri da month), British patent No. 1.4t2! , 0.2θ, West German Application Publication No. Ko, Ko/9.9/7, No. 2. Koro/, 36/ issue, same issue, 3 Kota,! ! No. 7 and No. 2゜4t33.272
A representative example of this is the nitrogen atom dissociative yellow coupler described in No. α-pivaloylacetanilide couplers are characterized by the robustness of the ordering element.
On the other hand, α-benzoylacetanilide couplers are characterized by good color development.

Mabinta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably yoichi pyrazolone couplers, and pyrazoloazole couplers such as pyrazolotriazoles outside the present invention. ! -The pyrazo-11 coupler is 3-
Those in which the position is substituted with an arylamino group or an acylamino group are preferable from the viewpoint of the hue of the chromophoric dye and the color relationship. J//, Orλ No. 2,3 G3+ 703, No. 2,600,7//, Orλ No. 01.673, No. 3.06 r+
4 jJ No. 3. /! Ko,! No. 96 and No. 3 of the same.
Dej4.0! Of the 92 equivalents listed such as r. −
Pyrazolone couplers are preferred, and the leaving group is a nitrogen atom leaving group as described in US Patent No. TL, 310,4/9 or US Pat.

? ! / , 797 is preferred. Also European Patent No. 73.6! The j-pyrazolone coupler having a ballast group described in No. r has high color-forming reactivity.

As a pyrazoloazole coupler, US Patent No. 3.
369. ,! ``Pyrazolobenzimidazoles described in US Pat. Pyrazolotetrazoles described in -θ (/ri? June 9), RD Co. 41230
Pyrazolopyrazoles described in (June/9♂g) and patent application Sho 5r-4tt! Examples include imidazopyrazoles described in 7.2 No. 1;

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers; US Pat. U.U., 293, preferably the naphthol couplers described in U.S. Pat.
．． 0!2.21 issue, same issue, /4t6,,? ? No. A, No. G, Coco r, No. 233 and No. 4t, 291s.
As a representative example, a highly active-equivalent naphthol coupler of the oxygen atom elimination type described in , No. 200, No. 200 is cited. Specific examples of phenolic couplers include U.S. Pat.
No. 92, No. 2,4t23.730, No. 2,77
Ko, No. 762, No. J, /θ/, /7/ and No. J
, r9j, No. 12A, etc.

Cyan couplers that are robust to heat, humidity, and temperature are preferably used in the present invention, exemplified by U.S. Pat. No. 3.77,! , phenolic cyan coupler described in θ0co, US Patent No. x, 77.2. /No.42, No.3.7! r, number 30, same number da, /26, jri6
No., ゛Same No. DA, 334t, 0// No., Same No. DA,! 27.
/'73, West German Patent Publication No. J,! 29.7.29 issue and special request! 2, which was written in ♂-Guko 47/issue etc.
Terdiacylamino-substituted phenolic couplers and U.S. Pat.
These include phenolic couplers having a phenylureido group at the 11th position and an acylamino group at the ter position, which are described in Patent No. 77G7 and the like.

In order to satisfy the characteristics required of a photosensitive material, two types of couplers can be used together in the same layer, or the same compound can be added to two or more different layers.

In order to correct unnecessary absorption in the short wavelength region of the magenta and cyan coupler chromophores, it is preferable to use a colored coupler in combination with the color photosensitive material for photographing. U.S. Patent No. G/Otsu 3. Otsu No. 70 and Tokuko Sho 37-39
Gua No. 3, etc.
, 2! No. ♂ and British Patent No. 1. /44. Typical examples include the magenta-colored cyan coupler described in No. j/i♂.

These color couplers that can be used in combination may also form a polymer having a polymer body or more. Typical examples of polymerized couplers are:
U.S. Patent No. 3. What! /, No. 120 and the same a, o, t
o, No. xii.

Specific examples of polymerized magenta couplers are given in British Patent No. 2.
/θ2. No. 73 and U.S. Pat. No. 4t, 347.27
It is stated in No. 2.

In addition, the graininess can be improved by using a chromophore diffusing coupler, and such a coupler is described in US Patent No. '1.
3t&, 237 and British Patent No. Co.

Specific examples of magenta couplers are shown in /26 and j70, as well as in European Patent No. 773 and West German Patent Publication (OL8
)! ,32ri,! No. 33 describes specific examples of yellow, magenta, and cyan.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer.
For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes, (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (/, !, tar, etc.) Triacryloyl-hexahydro-5-) riazine.

/, 3-vinylsulfonyl-copropanol, etc.),
Active halogen compounds (2, goo-dichloro-6-hydroxy-S-) riazine, etc.), mucochloric acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

In the photosensitive material produced using the present invention, if the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc. The photosensitive material produced may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.The photosensitive material produced using the present invention may contain a hydrophilic colloid layer. For example, benzo-11 azole compounds substituted with aryl groups (such as those described in US Pat. No. 3.333.7 tag), guteazolidone compounds (such as those described in US Pat. No. 3.j/41. 7 tag issue,
Same 3, 3j.

No. 617 (described in 2), benzophenone compounds (e.g., those described in JP-A-271), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,7 or, rQj
Same number? , No. 707.373 (as described in:), butadiene compounds (e.g., US Pat.

0'lj, J, 17), or benzoxidole compounds (e.g., U.S. Pat. No. 3,700,
'ljj) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler), an ultraviolet absorbing poly-2-, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material (=) produced using 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. , oxonol dyes, hemioxonol dyes, steryl dyes, merocyanine dyes, anionine dyes and azo dyes.Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

When carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination. Examples of the inhibitor include hydroquinone phase conductors, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

For photographic processing of the layer consisting of the photographic emulsion made using the present invention, any of the known methods and known processing solutions as described in Research Disclosure 77, No. 6-3Q, may be used. The treatment temperature that can be applied is usually chosen between //''C and 10°C, but /♂
The temperature may be lower than 0C or higher than TOOC.

The color developer consists of an alkaline aqueous solution containing a general color developing agent.The color developing agent is a known general aromatic amine developer, such as phenylene diamines (for example, guamino-N, N-dieteranisine, !-methyl- Kuamino-N, N-diethylaniline, Guamino-N
-ethyl-N-β-hydroxyethylaniline, 3-
Mesol-guamino-he-ethyl-N-β-hydroxyethylaniline, 3-methyl-guamino-he-ethyl-he-β-methanesulfamide etheraniline, guamino-3-methyl-N-ethyl-N-β- methoxyethylanisine, etc.) can be used.

Other than this 1. p, Photo-grap by AJdason
hicprocessing Chemistry (
Focal Press, 7966) P2 Coro~
Kokota, U.S. Patent No./93.01j, 2. ．． g9
2,364, JP-A-4TT-A4T No. 33, etc. may be used.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. Optionally, water softeners, preservatives such as human mixylamine,
Organic solvents such as benzyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium borosonolide, auxiliary developers such as phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents, It may also contain antioxidants and the like.

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

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately C1. As a bleaching agent, for example, iron(I)
, compounds of polyvalent metals such as cobalt (I), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds.

For example, ferricyanide, dichromate, iron (IF)
organic complex salts of (I), such as aminopolycarboxylic acids such as ethylenediamine acetic acid, nitrilotriacetic acid, 3-diaminocoprobanoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; Sulfates, permanganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide\ferric (I) ethylenediaminetetraacetate and ammonium ethylenediaminetetraacetate are particularly useful. Ethylenediamine iron(I) acetate complexes are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixer (: may contain a water-soluble aluminum salt as a hardener.

(Example) Below, the present invention will be described in Examples (-Thus, further (= = explained),
The present invention is not limited to these.

Example / As a coupler, exemplified compound (iy)q, /l; = tri(2-ethylhexyl) phosphate //ml, ethyl acetate xtml was added and dissolved by heating,
A fine emulsified dispersion of the above coupler was obtained by a mechanical method by adding sodium dodecylbenzenesulfonate into 100 ml of an aqueous solution containing θf. 10
ot (including kg&,, rf) plus 2 as a hardener.
% u, 10 ml of 4t-dihydroxy-t-chloro-s-triazine sodium salt was added and the silver coating amount was s0.
A sample was prepared by coating the sample on a paper support laminated with polyethylene on both sides so as to have a density of 0 mf/m2, and providing a gelatin layer on top of this coated layer. This is designated as sample A.

Next, the coupler (/7) is converted into the exemplified compound (/9)/θ, 3
ft')(,2-ethylhexyl)phosphate 2/
Sample B was prepared according to the FJM method (= Sample B was prepared in accordance with the FJM method).

Historically, the compounds listed below have been used as comparative couplers.
1. tag, 1
Comparative samples a, b, I created c.

These samples were subjected to 10θoC, M, 8. The sample was exposed to Quetzur light and processed with the following processing solution to obtain four magenta colored images.

Developer solution benzyl alcohol / rml diethylene triamine - acetic acid J' fKBr
θ, tag Na2SO3s f Na2C0330f Hydroxyamine sulfate, 2F Guamino-3-methyl-Hβ-(methanesulfonamide) Etheraniline 3/zH2sO4- H2Cg, jP Make up to 1000ml with water pH 1o, / Bleach-fix solution Thiosulfate 7mm ? -r7mu (70W1%) 7
60mlNa2SO3ry Na(Fe(EDTA)) 4t
o yFliDTA
pH 4,, r Processing process temperature Time Developing solution 33'C 3 minutes 30 seconds Bleach-fix solution 33'C 7 minutes 30 seconds Washing with water 2?
The magenta color images of each sample obtained after ~3roc for 3 minutes were clear and highly saturated.When the photographic characteristics of these four colored images were measured, the following results were obtained. Using another sample processed according to the exposure and development method described above,
Attach a UV filter to the front of the sample to block UV light with a wavelength shorter than θnm, and place it in a Gisenon fading tester (/
A light fastness test of the magenta dye image was carried out by exposing the magenta dye image to light (θ, 0,000 lux) for 7 days. The results are shown in Table 2.

Table 2 Color image fastness values are magenta density after fading test at initial densities i and o. () are density values measured with a blue filter in non-colored areas (
Stin).

In addition, regarding the fastness of the color image, we tested one for t weeks under high temperature and high humidity at t O'C, Tθ RH, and the other for 7 days at high temperature at IOθ''C, but almost no fading was observed. death,
No occurrence of stain was observed.

From the results shown in Tables 1 and 2, it was confirmed that the couplers of the present invention were excellent in photographic properties such as sensitivity, gradation, and maximum density. This is thought to be due to the high coupling activity and high conversion efficiency into dyes. Second, it has become clear that the coupler of the present invention is an excellent coupler in that the produced dye has excellent stability against light and is a fast dye, and there is little staining caused by residual coupler.

Example: The first sample was placed on a paper support laminated with polyethylene on both sides.
The layers (lowest layer) to 7 layers (top layer) were coated as shown in Table 3 to prepare a color photographic material.

The composition of the coating solution containing the emulsified dispersion and emulsion of the magenta coupler used in the third layer was prepared and coated in accordance with Example (I).

A B-G-R three color separation filter was attached to these samples,
Exposure was given in the same manner as in Example/, and the color development time was 2.
Exactly the same treatment was performed except that the time was changed to 3 minutes, 3 minutes and 30 seconds, and 6 minutes.

The changes in photographic characteristic values when the color development time was changed were as shown in Table 2.

On the other hand, apart from the above-mentioned colored images, samples with similar color images were processed, and some were processed in a xenon fading tester (100,000 Lutz) for 7 days, and the other 7 were heated at 60°C and θ%. R
H for 6A under high temperature and high humidity, and for another part /θo0c
Table 3 shows the results of a 7-day color image fading test.

From the results in Table y and Table 5, it can be seen that the coupler of the present invention has high coupling activity and high coloring efficiency.
Both gradation and maximum density have little dependence on color development time, exhibiting photographic characteristics with small fluctuations even with short development times, and the obtained magenta color image is sensitive to light, high temperature and high humidity.
It is clear that it is an excellent coupler that is stable even under high-temperature conditions and has no magentastin that occurs from residual coupler (Ninatatsu patent applicant Fuji Photo Film Co., Ltd. Procedural Amendments 1992/2013) Month; Lc1st

Claims (1)

[Scope of Claims] A pyrazoloazole type magenta coupler represented by the following general formula (I), at least one of the following general formula (II)
A silver halide color photographic light-sensitive material characterized by containing a magenta coupler linking groups represented by: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents a hydrogen atom or a substituent, and X is separated by a coupling reaction with a hydrogen atom or an oxidized aromatic primary amine developer. represents a group that can be Za, Zb
and Zc is methine, substituted methine, =N- or -NH
-, one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. Zb-Zc
is a carbon-carbon double bond, R_1, X or Za, Zb, Zc, including when it is part of an aromatic group.
Dimers may be formed with substituted methines. However, when Zc is methine or substituted methine, Za and Zb are not =N- or -NH- at the same time. ] General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_2 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, an acyl group,
alkoxy group, aryloxy group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group,
It represents a ureido group, an alkoxycarbonyl group, an alkoxycarbonylamino group, a sulfonyl group, an alkylthio group, an arylthio group, a cyano group, a nitro group, a carboxy group, and Y represents -O-, -S-, ▲Numerical formula, chemical formula, table, etc. There are ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ represents R_3 and R_4 represent a hydrogen atom, an alkyl group, a halogen atom, or an aryl group, and R_5 represents a hydrogen atom, an alkyl group, an aryl group,
Represents an acyl group or a sulfonyl group. m represents an integer from 1 to 4. ]