JPS5999437A - Color photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a high color developing rate and improved solubility in a high b.p. solvent and giving high maximum density of developed color by adding a specified two-equiv. magenta coupler having a specified group eliminable by coupling at the active position for coupling. CONSTITUTION:A two-equiv. magenta coupler of H-pyrazolo[3,2-C]-S-triazole type such as a compound represented by formula II or III is added. The coupler has a group represented by formula I (where each of A1 and A2 is H, alkyl, aryl, heterocyclic, acyl, sulfonyl, carbamoyl, sulfamoyl, alkoxycarbonyl or aryloxycarbonyl, A1 and A2 are not H at the same time, they may bond to each other to form a 5- or 6-membered ring together with N, and the ring may be condensed with a benzene ring or a heterocyclic ring) as a group eliminable by coupling at the position where the coupler couples with the oxidized product of a developing agent. The titled material contg. said two-equiv. magenta coupler, having a high color developing rate and improved solubility in a high b.p. solvent, and giving high maximum density of developed color is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material containing a novel iH-pyrazolo[3·λ-C]-8-triazole derivative. Furthermore, iH-pyranoC1(3・λ-C)
-8-) A two-equivalent magenta cazole with a novel coupling-off group in the coupling active position in a γ-zole type coupler? The present invention relates to a silver halide photographic light-sensitive material containing the present invention.

By color development on a silver halide color restoration material, the oxidized f'L7 is reacted with an aromatic/M amine color developer main mulberry and a coupler to produce indophenol, indoaniline, indamine, azomethine, cyanoxazine, phenazine. It is well known that pigments and similar pigments can be produced to form color images. Ha, to form a magenta color image out of these! -Virazonalpha, cyanoacetophenone, indasilone, pyrazolobenzimidazole,
Pyrazolotriazole couplers are used.

Until now, most of the magenta color image forming couplers have been widely used and researched! - It was pyrazo-a. ! -The dye formed from the pyrazolone coupler Katame has excellent fastness against heat and light, but ≠3
It has been known that unnecessary absorption with a yellow component exists near 0 nm and causes color turbidity. British Patent No. 1,0117 describes a magenta image forming coupler that reduces this yellow component. Pyrazolobenzimidanol bone core described in No. A12, US Patent No. 3
, 770. The indacilone bone core described in ≠Ko 7 and the pyrazolotriazole bone core described in US Pat. No. 3,72,067 have been proposed.

Among them, US Patent No. 3,725,067, British Patent No. 2
! lH-pyrasolo [3.
The azomethine dye formed from the λ-C)-8-) lyazole type coupler has little unnecessary absorption in the vicinity of 30 nm in a solvent such as ethyl acetate, and has excellent sharp cutting properties on the long wavelength side. However, the couplers described in the specifications of the above-mentioned patents do not contain high-boiling organic solvents (e.g. tricresyl phosphate) used in the oil protection system, which is a well-known technique among those skilled in the art, when incorporated into the actual four-way film. , dibutyl phthalate, etc.), and in addition, the color development speed was slow even when passed through a normal color development processing bath, and the color development rate was high and the maximum color development rate was not high. As a result of various considerations, the inventor of the invention found out whether there are any of these drawbacks? I have arrived at a group of couplers to improve. death? Therefore, the object of the present invention is to provide a novel silver halide color photosensitive material containing a 2-equivalent magenta cazolyl compound for photography, which is excellent in both color development speed and maximum color development density, and has improved solubility in high-boiling organic solvents. The purpose is to provide. The purpose of the above is a lH-big mouth [3・CoC]-8-) lyazole coupler, in which the following general formula
This could be achieved by including a C-substituted two-equivalent magenta coupler.

(The lH-pyrazolo[3·λ-C]-8-) lyazole bone core is known from the above-mentioned US Pat. No. 37λj, ot7) General formula I However, Al and A2 may be the same or different, Each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an oxycarbonyl group, and both Al and A2 are hydrogen atoms. There isn't. 1 1 and A2 may be combined with each other to form the form j negative or 6 negative with the nitrogen atom. This 5
The negative or iia-membered ring may further be fused with a benzene ring or a heterocycle.

Among the couplers of the present invention, preferred are those represented by the general formula (2).

General formula ■ In the formula, AI and A2 may be the same or different, and each represents a hydrogen atom, an alkyl group (1, preferably 1 to 22 carbon atoms), and
an alkyl group such as a methyl group, an ethyl group, a butyl group, an octyl group, a coethylhexyl group, and a halogen atom, a hydroxyl group, a cyano group, an aryl group, a carboxy group,
Alkoxy group, aryloxy group, acylamino group, sulfonamide.

group, imido group, alkoxycarbonyl group, carbonyl group, alkylthio group, alifrethio group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, aryloxycarbonylamino group ,
(ureido group, acyl group, alkyl group substituted with an alkylamino group or arylamino group, etc.), aryol group (
Preferably, an aryl group having t to 32 carbon atoms, such as a phenyl group, a naphthyl group, and an aryl group which may be substituted with a substituent at the above-mentioned alkyl group, etc.), a Hegel monocyclic group, etc. (For example, copyridyl group, λ-quinolyl group, λ-benzothiazolyl group, λ-furyl group, copyrimidinyl group,
etc.), acyl groups (e.g. acetyl group, butanoyl group, hetesanoyl group, trifluoroacetyl group, heftafluorobutanoyl group, benzoyl group, naphthonyl group, pentafluorobenzoyl group, pentachlorophenyl group, -furancarbonyl group 1 .2-quinolinecarbonyl group, etc.), sulfonyl group (e.g., t, methanesulfonyl group, hexanesulfonyl group, benzenesulfonyl group, naphthalenesulfonyl group, and the above alkyl groups)
Alkanesulfonyl group, arylsulfonyl group, etc., which may be substituted with a substituent, carbamoyl M (for example, 1dN-
Methylcarbamoyl Ji, N-)'tethylcarbamoyl group, N,N-diethylcarbamoyl group, N-phenylcarbamoyl group, and N-alkylcarbamoyl group substituted with the substituent described above for the alkyl group. , N,N-dialkylcarbamoyl M, N-7IJ −
k f) L/(moyl group, N, N-diarylcarbamoyl group, etc.), sulfamoyl group (e.g. Eva, N-methylsulfamoyl group, N-n-octylsulfamoyl M, N-phenylsulfamoyl group, N, N-diethylsulfamoyl group, and N-alkylsulfamoyl group optionally substituted with the substituents mentioned above for the alkyl group.

N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.], alkoxycarbonyl group (e.g., t is methoxycarbonyl group), tyloxycarbonyl group, dodecyl oxycarbonyl group, λ-ethylhexyloxycarbonyl group, alkoxycarbonyl group which may be substituted with the bare c substituent mentioned above for the alkyl group, etc.) [where AI and A2 are both hydrogen atoms] do not have.

Well, for the j-negative or t-membered ring formed by tAi and A2 bonding together with a nitrogen atom, for example, a nitrogen atom? 7C is an aromatic heterocyclic group constituting a lOπ electron system (for example, l-pyrrolyl group, l-imidazolyl group, l-pyrazolyl group, l-(/, 2.4'-1 riazolyl group) - '('.

λ, 3-triazolyl group), /-(/, 2,3°gutetrazolyl group), /-(/ ,,,2,3.r-
tetrazolyl group], l-indolyl group, λ-isoindolyl group, l-benzimidazolyl group, / -benzo)
IJ azolyl group and the above aromatic heterocyclic group, halogen atom, cyan group, nitro group, alkyl group, aryl group, carboxy group, alkoxy group, aryloxy group, acylamino group, sulfonamide group, imide group, alkoxy carbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, alkyl-sulfonyl group,
Aromatic group optionally substituted with a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonylamino group, a ureido group, an acyl group, an alkylamino group, an arylamino group heterocyclic groups, etc.), saturated or unsaturated heterocyclic groups containing a nitrogen atom and not formed on an aromatic ring (e.g., l-pyrrolidinyl group, l-hyheridinyl group, N-morpholinyl group,
N-(l, 2,3.≠-tetrahydroquinolyl group, l-
pyrrolinyl group, l-imidazolinyl group, l-pyrazolidinyl group, coisoindonyl group, l-indolinyl group,
and the above saturated or 7C is an unsaturated heterocyclic group, which may be substituted with the substituent mentioned above for the aromatic heterocyclic group, etc.), a cyclic imide group (for example, N- Succinimide group, N-phthalimide group, /-N-hydantoinyl group, J-N-2,4t-dioxo-oxazolidinyl group, +-N-urazolyl group, etc., and the above-mentioned imide group, the aromatic hetero ring It is also possible to substitute an xt substituent as described in the group section.
3-(2H)-okine-l, 2-benzisothiazolyl group (saccharin), the aromatic heterocyclic group may have the substituent described in Section C-1-N-/, /-dioxo-3-(2H)-ox:/-/, 2-benzisothiazolyl group, =, or -N= (z representation, R3 and 几4 are hydrogen atoms or the above-mentioned aromatic ring group The substituents mentioned above may also be present.Also, R3 and R4 may form a condensed ring.For example, preferable groups include 2(/H)-pyridone group, phthaladione group, etc.) and 7j. At λ, R3, R
4 may have a hydrogen atom or the zt substitution described above for the aromatic heterocyclic group. Also, a fused ring with R3 and R4?
may be formed.

For example, preferred groups include λ-oxo-l-pyrrolidinyl group, λ-oxo-l-piperidinyl group, etc.).

R1 and 几2 may be the same or different, and each represents a hydrogen atom, an alkyl group (e.g. methyl group, furoyl group, t
-butyl group, hexatecyl group, co('t≠, 7-tIJ
chlorophenyl)ethyl group, j=-(j-bentadecylquenoxy)propyl group, 3-(co,≠-di-tert
-amylphenoxy)propyl group, λ-[α-(J-L
tert-butyl-guhydroxyphenoxy [tetradecanamidoethyl] group, etc.), aryl group (e.g.
Phenyl group, α-or β-su7tyl group, ≠-methylphenyl group, λ, Hiro, 6-dolychlorophenyl group, ≠-[
α-(co,l-di-tert-amylphenoxy)butyramide]phenyl group, ≠-[α-(J-tert-butyl-tei-hydroxyphenoxy)tetradecanamide]-2,2-dichlorophenyl group, etc.), hetero Ring group (
For example, pyridyl group, chenyl group, quinolyl group, etc.),
Acylamino group (e.g., acetylamino group, benzamide group, 3-(2,≠-di-tert-amylphenoxy]butyramide group, J-(j-pentadecylphenoxybutyramide group, etc.), alkylamino group (e.g., methylamino group, diethylamino group, n-dodecylamino group, etc.), anilino group (e.g., phenylamino group, λ-chloro-1-tetradecanamide phenylamino group, F-(α(3-1-butyl-≠-hydroxy) phenoxy)tetradecanamide]anilino group, isonealkoxycarbonyl group (e.g., methoxycarbonyl group, tetradecyloxycarbonyl group, etc.), alkylthio group (
For example, hexylthio group, dodecylthio group, etc.)? In this expression, R1 and R2 are never hydrogen atoms at the same time.

Specific examples of typical magenta couplers according to the present invention are shown below, but are limited by these (p / l λ l 3 1 ≠ t / j 7 / t l λ l 22 3 and a fused heterocyclic ring). The performance is particularly good for the purpose of the present invention when the amount of addition Fi of the coupler of the present invention is
It is preferably d/XlO, JXIO' moles per mole of silver.

Next, a general method of assembling these couplers will be described.

/H-pyrazolo(j, 2-C]-8-) lyazole core and ballast group sequence is described in British patent lλz, 2a
It can be synthesized by the method described in US Pat. No. 3,703-4.

(1) Introducing an amino group into the coupling active position,
Method for modifying the amino group: Introduction of an amine group into the coupling active position is described in US Patent 3≠
The active position of the cuff ring is nitrosated using a suitable nitrifying agent such as sodium nitrite, isoamylnitrite, etc., and then reduced by an appropriate method. (
For example, palladium carbon etc? It can be easily obtained by a hydrogenation method using hydrogen gas as a catalyst or a chemical reduction method using stannous chloride or the like.

The leaving group as a two-equivalent coupler within the scope of the present invention that can be obtained by modifying this amino group is A1 in the above formula (1).
7ciJA2 is an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and A 1-hal
7t is A 2-h a 1 (R1 and R2 have the same meanings as described above, and hal represents a halogen atom such as a chlorine atom or a bromine atom), and the amino substance Kai o0cxp et al. 1oo0c Inert solvents (e.g. acetic acid, methylene chloride, chloroform, benzene,
pyridine, dimethylformamide, dimethylsulfoxide, acetonitrile, etc.).

In addition, during the reaction, it is preferable to use a suitable dehydrohalogenating agent (for example, triethylamine, diazabicyclo[λ·co·kokuoftane, sodium acetate, etc.).

The couplers synthesized using this method are CI)-j, g,!
, 6.7, male, ri.

Substitution method: A method for introducing hal (hal is, for example, a base atom, a bromine atom) into the coupling active position, 7-position, of the hal iH-pyrazolo[J, 2-C)-8-) lyazole bone core is described in U.S. Patent No. No. 372!067, i.e. a suitable halogenating agent such as sulfuryl chloride, chlorine gas, bromine, N-
This can be carried out using chlorosuccinimide, N-bromosuccinimide, or the like.

The leaving group as a two-equivalent coupler within the scope of the present invention that can be obtained by completely substituting the halogen atoms is the above formula (2), where A1 or A2 is an alkyl group, an aryl group, a heterocyclic group, or A1 A2 is an alcoholic solvent (e.g. ethanol, isopropyl alcohol, etc.) within a degree range of each other.
, an aprotic polar solvent (e.g., dimethylformamide, sulfolane, hexamethylphosphotriamide, etc.) dissolved in a hydrocarbon bath medium (e.g., methylene chloride, chloroform, etc.) and a suitable base (e.g., The reaction can be carried out in the presence of triethylamine, sodium hydroxide, potassium hydroxide, diazabicyclo[λ·co·λ]octane, anhydrous potassium carbonate, etc.). (%Kiaki!t
-Hori3ta)) The coupler can be synthesized using this method,
691%-110, //, /, 2.13, ll/-1l
! , 16.17, l♂, lri, -〇, 2/% 22.2
It is 3.

In addition, when introducing a tπ or 7 (lOπ electron system aromatic nitrogen heterocycle), the method described in Japanese Patent Publication No. 7-46677, that is, the halogen substituted product and the 6π or 7c is a 10π-electron aromatic nitrogen group I:I
Add at least twice the mole of the cyclized adduct t to the halogen-substituted product and heat to 000 to 100°C in the absence of a solvent or in an aprotic polar solvent (e.g. dimethylformamide, sulfolane, hexamethyl, phosphotriamide, etc.). 300
It can be heated to C~160' and allowed to react.

The coupler synthesized by this method is ('p-/j, 16.
17, II, /i JOT: A-pz.

Couplers that can be used in the present invention in addition to the couplers of the present invention include the following dye-forming couplers:
That is, in the color development process, aromatic/grade amine developer (
For example, magenta couplers include j-pyrazolone couplers, pyrazolopenzimidazole couplers, cyanoacetylcoumaron couplers, and open-chain acylacetonitrile couplers. etc., as a yellow coupler,
Examples include acylacetamide couplers (eg, benzoylacetanilides, pivaloylacetanilides), and cyan couplers such as naphthol couplers and phenol couplers. Do these couplers have hydrophobic groups called ballast groups in their molecules? Non-diffusible ones with a casing or polymerized fr7 (fr7) are preferable.Couplers may be either ≠ equivalent or di-equivalent to the ions.Also, colored couplers with color correction effects, or A coupler that releases a development inhibitor upon development (a so-called DIR coupler may also be used).

In addition to DIR couplers, there are also colorless DIR couplers in which the product of coupling reaction is colorless and which releases all of the development inhibitor.
Coupling monster? May include.

In order to satisfy the characteristics required of a photosensitive material, two or more types of the above couplers etc. can be used together in the same layer, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

coupler? In order to introduce it into the silver halide emulsion layer, known methods such as those described in US Pat. No. λ, J, 2.2.027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate, Benzoic acid esters (e.g. octyl benzoate, alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dibutyl phthalate, trimezine, trimesic acid esters (e.g. tributyl trimesate), etc.), or 300C to 13
After dissolving in an o0C organic solvent such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl zolopionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it becomes a hydrophilic colloid. distributed. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, special public Sho J-/-jri 1r3, special public Sho J/-! The polymer dispersion method described in Tata 4L3 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

Is the photographic coloring agent used for intermediate scale images? The maximum absorption band of the cyan dye formed from the cyan coloring agent ρ, which has a good location, is about toovλ et al. 72
The maximum absorption band of the magenta dye formed from the magenta color former ηλ is approximately 0 nm! 007Dh et rronm
The maximum absorption band of the yellow dye formed between the yellow color former and the yellow color former is about yo.

and 4 Atonm.

When carrying out F3A'a of the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of 12 or more.

Known anti-fading agents include, for example, U.S. Pat.
Otsu 0,2゛ri No. 0, same 2,1/-11゜4r3, same 2
．． t7ta, No. 317, same λ, 701, luri No. 7, same,
704t, No. 713, 2゜7λg, Otsu! No., same λ,
No. 732,300, 2.73! , 7t! No. 2.7
1o, to1 issue, same 2. Tit, No. 021, British Patent 't 31r j.

Hydroquinone derivatives described in U.S. Patent No. 3,4tjf7,07, U.S. Pat. .

Gallic acid derivatives described in No. 2r, etc., U.S. Patent No. 2,
73! , 7t Jr., same j, AYE, 909, special public Showa 4tter 20.977, same! λ-1,623 and 7cp-alkoxyphenols, U.S. Pat.
No. 132.300, ibid. j, 673.

No. 020, 3. ! 7g, No. 427, 3, 76≠, 3
No. 37, JP-A-52-3! ;433, same! 2-/4t
No. 74tJ4, 32-1! p-oxyphenol derivatives described in Ko λ2 evening issue, U.S. Patent No. 3,700,1
76! There are bisphenols listed in this issue.

Invention? The photosensitive material prepared using the above-mentioned photosensitive material may contain all of hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. as color anti-capri agents, and specific examples thereof include U.S. Pat.
No., λ, 33t.

No. 327, same, No. 2,4103.721, same λ, ≠lt
, Otsu No. 13, Same 2,67! , 3/≠ issue, same λ.

70/, /ri No. 7, same λ, 70≠, 7/3 No. 7, same 2.
7.21. tj! -T, same, 73λ, JOO, same, 73! f, 7 otsu! issue, JP-A-Sho J'O-ta λ2tr issue, same IO-ta 1 issue, same! Q-232λr, same j
O-/No. 10337, same! It is described in λ-/44λ3j issue, Tokko Shoyo o-, zJrii issue, etc.

The photosensitive material prepared using the photosensitive material of the present invention may entirely contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation whitening. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are listed in the British Patent ZR
+, No. 409, same/, /77.4t, No. 22, JP-A No. 4
AI-1ziJo, Gutatata, Otsu 2θ, 4/
-7-//1Al120, same t, z-ioir.

/ /j, U.S. Patent U, 271/-, 7J', No. 2, same.

j33, 4t72, same 2. evening! t, 17th issue, same 3
, /III, No. 117, 3. i77, o7 number, same 3.2'17. /No.27, same 3,! 110
, 1/l7 No. j, 173', No. 7011, same j,
l, J-3, No. 201, No. 3,71, ≠ No. 7-, Dohiro, 07/.

31.2, 4A, 070j, 3J-, No. 2.

The four true emulsion layers of the photographic light-sensitive material of the present invention contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, and f-one-thyl compounds for the purpose of increasing sensitivity, contrast J: increasing, and 7C promoting development. , thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US patent λ, 4LOO
, No. 132, same λ, 4tλ3. rpy number, same, 7/l
, No. 06.2, No. 3.10,003, No. 3.77.2゜02/, No. 3,101,003, British Patent I.

The materials described in '7Z1 and the like can be used.

Invention? The photosensitive material produced using the photosensitive material may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, with an aryl group! benzotrianol compounds (e.g. those described in U.S. Pat. Al1], benzophenone compounds (e.g., those described in JP-A-271-271), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,
No. 701.101, No. 3.707.37/, butadiene compounds (for example, those described in U.S. Pat.

041! , 2.25', or 1-benzooxide compounds (e.g., U.S. Pat.
oo, what is described in arJ' issue)? Can be used. Further, U.S. Pat. No. 3,4 L Tata, No. 762, 4! Kaishoj4'−≠r! 3! You can also use those listed in this issue. UV-absorbing couplers (e.g. α-naphthol-based cyan dye-forming couplers) or UV-absorbing polymers? May be used. These ultraviolet absorbers may be mordanted in specific layers.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. Examples of dyes that can be used include cyanine dyes, merocyanif dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl 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 for cyanine pigments can be applied to these pigments as basic heterogeneous nuclei. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxanol nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, apti, indolenine nuclei, benzindolenine nuclei,
Indole nucleus, benzoxadol nucleus, naphthoxazole bale, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. The nucleus of c) may be substituted on a carbon atom.

Merocyanine dye or complex merocyanine = 7 The dye has a pyrazoline-! as a core with a ketomethylene structure! −
on nucleus, thiohyguntoin nucleus, corchioxazolidine-λ, ≠-dione nucleus, thiazolidine-2,4A-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus, etc.! ~6
Member heteroartic ring nucleus? Can be applied.

Useful sensitizing dyes include, for example, German patent Takota, o
ro, U.S. Patent No. 2,23/, 661, same, ≠23
, 74At No., same λ, to3,771゜ No., same Ko, J-
/ri, No. 001, same 2. ri 12,3 λri No. 3, 6 tat, tatata, ri 3, 1, 72゜ri No. 7, ri 3.6
riμ, No. 217, same≠, 02j, 3≠ri No., same≠, Og No. 4.67.2, British Patent/, 2≠No. 2,311, Special Publication Show! 44-/1AO30, same j2-2≠? Items listed in item ≠≠ can be mentioned.

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

Typical examples are U.S. Pat. ．． No. 222, No. 3,327m0to, No. J
, No. 122,06λ, same J, 127. t≠7, same! ,
A/7. ．． No. 223, J, l, 21. No. 64, 3. ttt, 4#0 issue, same J, t7.2゜rye issue, same! , 679. If-21, No. 3,703.377,
3,7tF, 30/ issue, 3j1i4t, AOY issue,
3,137, rJ, No. 2, Dohiro, 02 Otsu, No. 707, British Patent T, 3aa, Koza No. 7, Ibid/, 607. ? 0
No. 3, Special Public Showa 4L3-4t 31. Same issue! 3-/2
, No. 374', Tokukai Sho! 2-/10. tlr issue, 12
-109.921.

Does it itself have a spectral sensitizing effect along with the sensitizing dye? Unreliable pigment or visible light? A substance that is not substantially absorbed,
Strong color sensitization? The indicated substances may be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat.
2/), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,74A3. and No. 10), cadmium salts, azaindene compounds, etc.?
May include. US Patent 3. t/j, l, No. 13, same 3
．． Bu/r, No. 4441, j, j/7.2ri No. 5, same,
i, 43! , No. 72/ is particularly useful.

For the four-dimensional processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. Also, the processing temperature is usually 1r0c7)
The temperature is selected to be between 0 and 0C (7), but temperatures below 1roC or above 0C2 may be used. Development processing to form a silver image (black and white photographic processing) depending on the purpose
, or any color 4 true processing consisting of a developing processing cam to form a dye image can be applied.

Color developer is generally a color developing agent? It consists of an alkaline aqueous solution. The main color development system is a known primary aromatic amine developer, such as phenylenediamines (for example, ≠
-amino-N, N-diethylaniline, 3-methyl-day-amino-N, N-diethylaniline, ≠-amino-N
-ethyl-β-hydroxyethylaniline, 3-methyl-≠-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-7-amino-N-ethyl-N-β-methanesulfamide ethylaniline, Hiro-amino -3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, photo-grap by F. A. Mason
hfc Processing Chemistry
PJ of y (published by Focal Press, 1946)
-6-22, U.S. Patent No. 3,01j, same.

! It is also possible to use the sounds described in T., JA4L, and Japanese Patent Application Laid-Open No. Sho FJ'-tllY33.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors such as bromides, iodides, and organic antifoggants, and anticapri agents.  Can be included. Also, if necessary, water softeners, preservatives such as hydroxylamine,
Mechanical solvents such as benzyl alcohol, diethylene glycol, diethylene glycol, and quaternary ammonium salts.

Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as l-phenyl-3-pyrazolidone, tackifying agents, US Pat.

θg,? The polycarboxylic acid chelating agent described in , No. 723, the antioxidant described in West German Publication (OL8), z, , g, +co, ri, No. 50, etc. may also be included.

The photographic emulsion layer after color development is usually bleached! A is managed.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (■), chromium (■), and copper (n), peracids, quinones, and nitroso compounds are used. For example, ferricyanide, dichromate,
Iron(III)- or cobalt(I[J) complex salts, such as ethylenediaminetetraacetic acid, nitrilotriic acid e, 1.
Aminopolycarboxylic acids such as 3-diamino-λ-propatoltetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitrosophenols, and the like can be used.

Of these, potassium ferricyanide, iron(I) ethylenediaminetetraacetate (nonodium ethylenediaminetetraacetate) and ammonium iron(I) ethylenediaminetetraacetate are particularly useful.
-Also useful in bath bleach-fix solutions.

For bleaching or bleaching foot dressings, see US Patent J, 0≠2.52
No. 0, copper 3. λ≠/, No. 766, Tokko Sho≠, t-rto
No. A, Tokko Akira≠! - Bleaching accelerator described in No. 13, etc., published by JP-A-Sho! In addition to the thiol compound described in No. 3-6!732, various additives can also be added.

Example 1 Film A; 10 oC of trioctyl phosphate and 20 ccz of ethyl acetate were added and dissolved in 1O7 of coupler 22 of the present invention,
This bath solution was added to 100 cc of lO gelatin containing sodium ketodecylbenzenesulfonate, and stirred and emulsified using a homogenizer emulsifying machine 2. The obtained emulsion was coated on a cellulose triacetate support and dried to obtain a sample film. This sample film has good transparency and a smooth surface.

Film B: Comparative coupler Ai shown below A sample film was prepared in the same manner as above, and had poor transparency and a rough surface. Coupler A precipitates and η1 shows that the compound of the present invention has better i@dissolution and emulsion stability? show.

Coupler A (for comparison) Example 2 Coupler 3 of the present invention was prepared in the same manner as film A of Example 1.
1♂,y,it,i7. The solubility and emulsion stability of i♂ were investigated.90 These samples had good transparency and a clean surface of 70≧.Also, the emulsions were left in the refrigerator for several days, and then a film was made using this method. However, these also had good transparency and smooth surfaces.

Example 3 Film C; Comparative coupler B shown below, trioctyl phosphate at 2f)ll:N):) licresyl phosphate! mark,
Dissolve the solution in ethyl acetate, add it to 100 y of a 10% gelatin bath solution containing sodium butylnaphthalene sulfonate, and stir and emulsify using a homogenizer emulsifier to obtain an emulsion of 2 and 7 ml. Emulsion? Green-sensitive silver chlorobromide emulsion (Br4t mol%, α!
! Mob%) 300ft (Silver 13, if mixed with gold, coating aid; sodium dodecylbenzenesulfonate, hard MttIjl with -2-hydroxy-≠, 6-dichloro-5-B azine and cellulose triacetate Further, a gelatin coating solution was applied as a protective layer on this pigeon and dried (gelatin/f/m2).

Film D; coupler of the invention, 2/'z 631, green-sensitive emulsion λo
Same film as above film C except that oy2 was used.

C%D film samples were exposed with a photosensitive needle at i, ooo lux for 1 second and processed with the following processing solution.

Developer benzyl alcohol /jdNa
2 S 03 j f
'KBr o, 4ty
Hydroxylamine sulfate [29 ≠-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl]-p-phenylenediamine 7rNa3CO3
(/water salt) 301 Add water to make up to 1 liter (pH/ 0, / ) Bleach-fix ammonium thiosulfate (70wt%)/jOtdN
a 2 S O37z y Na [Fe (EDTA)]
170yEDTA
Add 4'r water to make it il (pH 4,
2) Processing process temperature: Time Developer: 330C 3 minutes Original white fixing N solution 33°C/minute 30 seconds Water washing λr ~ 330CJ minutes drying processing Temporary dye development Concentration Summer t Macbeth Densitometer Status AA filter.

331 Coupler of the present invention? It was found that the 2D film used had a high degree of color development despite the small amount of silver coated. Example 4 In Film D of Example 3, a green-sensitive silver iodobromide emulsion (■... tmolti, Br...ri≠mol%)
Sample E was prepared in the same manner as in Example 3, except that 200g (containing 2 silver) and the coupler listed in Table 1 were used.
, Ni cultivation, and similar treatment were performed to measure the maximum concentration. The molar ratio of silver and coupler (AP/CI) was adjusted so that both were equal to each other.
λ λ, 20F 3
2. ．． 1IJ-Q 7
2.410H
, 2. , 2! I i,z
,z,t,.

J/4 2. Otsuyo K
/j 23! rL/
7 2. tyoM/ta
λ3゜N λl λ, Otsu! As shown in Table 2, the coupler of the present invention exhibits high color development.
It's clearly a joke.

Also Example 11.2↓9 Good solubility? It is clear that he has it.

Patent applicant: Fujisai Shin Film Co., Ltd. Showa II λ
Director General of the Japan Patent Office, Mr. 1, Incident Display Showa! 7th year patent application 1st rj3r
No. 2, Name of the invention Silver halide color photographic light-sensitive material 3. Relationship with the person making the amendment Patent applicant Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Date of amendment order
Showa! 5゜February λ, 2013 Subject of the amendment: Mei Ayo 6, I will submit an engraving of the detailed statement of the amendments (no changes to the contents).

Procedural amendment to the Commissioner of the Japan Patent Office 1, Indication of the case Showa Tough Year Patent Application No. 1 Ryoha 31 2, Title of the invention / Silver halide color photographic light-sensitive material 3, Person making the amendment Relationship to the case Patent applicant 4. Subject of amendment Please submit the statement in the "Claims" column and "Detailed Description of the Invention" column 5 of the specification, and the "Claims" column of the description of the amendment in the attached document. Correct.

The description in the "Detailed Description of the Invention" section of the specification is amended as follows.

1) Page 2, line 3 "[3・λ-C)-8-J" [[3,,z-C:]-8-J and correct it.

2) Line 2 on page 2 “[3・C]-8-J [[3,,2-C)-8-J and correct it.

3) 2nd page/3rd line ", Noah" ", Hue" and correct it.

4) Page 3, line 3 "heat light" "Heat, light" and correct it.

5) Page 3/line 7 [[3・λ-C)-8-J TJ [3,,2-C]-8-J and correct it.

6) ≠ page // line “- connoisseur’s” "a series" and correct it.

7) Page 77th line “[3・--CEJ [J, -2-C]j Correct it.

8) Evening page λth line [[3・Cor C) J r(3,-2-C]J and correct it.

9) Evening page, line 13 “formed together” “Formed together” and correct it.

10) From the second page l/line to/second line "Arifretio group" "Arylthio group" and correct it.

11) Page 6/L line "Alkyloxy-carbonyl" "Alkyloxycarbonyl" and correct it.

12) 7th page line "Hexanoyl" "Hexanoyl" and correct it.

13) Page 7, line io "Heptafluoro" "Heptafluoro" and correct it.

14) Page 7 // line "Naftonil" "Naftoil" and correct it.

15) Insert the entire aryloxycarbonyl group (for example, phenoxycarurinyl L, etc.) J after ", etc.)" on page r/line 2.

16) Page 2, line 73 "Carboxy group" 1 carboxyl group and correct it.

17) Page 7/7th line "Alkyl-sulfonyl" "Alkanesulfonyl" and correct it.

18) Page 1 O is line 1 "Isoindonyl" "Isoindolinyl" "Ethylco group," "Conityl group," and correct it.

20) Page 13! row r+−cα” “≠−[α−” and correct it.

21) Compound 10 on page 1♂ was corrected as follows22)
Compound/2 on page 17 is corrected as follows.

10H21 23) 2nd evening page/≠ line "Continuation of" "The concatenation of is" and correct it.

24) Page 27, line 2θ "Oftan" "Octane" and correct it.

25) Page 30/≠ line "Samethyl, Phospho" "Samethylphospho" and correct it.

26) Page 30/Sunset "～/Evening O0" "~lri0'C" and correct it.

27) Insert Attachment 2 between the bottom line of page 30 and the evening line from the bottom.

28) The 4th page is on the evening page/J row. “To 100Cr4” "to ioog" and correct it.

29)! 4tJ page r line = Correct.

30) I/Page//Line "(A, 9/cp)J r(A,!il/Cp)J and correct it.

Attachment/Claims/H-pyrazolo[3,2-C']-8-) lyazole coupler, the following general formula is substituted as a coupling-off group at the position where it couples with the oxidation product of the developing agent. A silver halide photographic light-sensitive material characterized by containing a two-equivalent Mazenk coupler having the following properties, provided that A1 and A2 may be the same or different, and each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, It represents an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and A1 and A2 are not both hydrogen atoms. *A t and A2 may be bonded to each other to form a 5-membered or 2-membered ring with the nitrogen atom. This 5-membered or t-membered ring may be further fused with a benzene ring/heterocycle. Hebutafluorobutyramide-2-
Synthesis of propyl-/H-pyrazolo[3,coC]-8'-triazole (Exemplary coupler 3) 3-(
3-(,2,4t-tert-amylphenoxy)
Furovir)-J-propyl-1H-pyrazolo[3,2~
c) Add all of the -s-triazole to Oml of glacial acetic acid,
Stir at room temperature.

To this was added a solution of 2゜3≠g of inamyl nitrite in glacial acetic acid (,2
The mixture was added dropwise over 5 minutes and stirred for an additional 1 hour.The reaction mixture was slowly poured into a volume of water and stirred for 7 hours. Quantify the precipitate and add water
The precipitate was washed with ooml. It was dried in a vacuum desiccator containing calcium chloride, and 1.9 mg (1) of 3-
(3-(2,≠-di-tert-amylphenoxy)propyl)-7-nitro7-&-propyl-7H-pyrazolo[3°λ-C]-8-)riazole was obtained.

This was dissolved in 10ml of ethanol and heated and stirred under a nitrogen stream to bring it to reflux. A concentrated hydrochloric acid solution (≠omi) of stannous chloride and OI was added dropwise to this over 5 minutes. After the dropwise addition was completed, it was cooled with water, poured into a room with water, and extracted with ethyl acetate.The entire organic layer was dried over anhydrous magnesium sulfate, concentrated to dryness, and 7-amino-3-(3-2 , Hiro-G-tert-amylphenoxy)propyl)-+-propyl-/H-pyrazolo[3,2
-C1-8-1v azole was obtained. Add this to pyridine io
oml and stirred while cooling with water under a nitrogen stream. To this, 620 jif of anhydrous hebutafluorobutyric acid was added dropwise, and the mixture was further stirred for 30 minutes. This reaction mixture was mixed with water/l.
and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography. Eluate 0
The product was fractionated with loform:methanol (10 o:/), and the eluate was concentrated to dryness to obtain the desired product (coupler 3) as a white powder of lo, gllCr3%).

Elemental analysis theoretical value H (lj!%) C (t7.A9%) N (//,
0.2%) Experimental value H (1<44-%) CDg, t2%) NC10
,9t%) Synthesis Example 2 3-(/-(,2-ethoxyethoxy)tridecyl)-
Synthesis of 6-methyl-7-(/-pyrazolyl)-/H-pyrazolo(: 3. ,:z -C]-8-triazole (Example coupler 27) 7゜♂rig of 3- (/ -(, 2-ethoxyethoxy)tridecyl)-7ri-methyl/H-pyrazolo(3,
, z-C)-8-) lyazole was added to dichloromethane and stirred at room temperature. To this, N-bromosuccinimide I-3 and tg were added and stirred for 20 minutes. Wash this dichloromethane solution with water / 00vcl×
3), dried over anhydrous magnesium sulfate. This dichloromethane solution was concentrated to completely remove soot. to this,
Add pyrazole/3°tuft and add 120 ml under nitrogen atmosphere.
Pressed on oil bath at °C. After cooling, the reaction mixture was dissolved in 200% ethyl acetate and washed with water (OmJxJ). The organic layer was dried over anhydrous magnesium sulfate and then concentrated. This was subjected to 'silica gel column chromatography (silica gel 200g, eluent benzene: ethyl acetate-10
:/), and the eluate was concentrated to dryness to yield 13 g (2
0%) of white powder coupler 21 was obtained.

Elemental analysis theoretical value H(7,23chi)C(otta,≠7chi)N(/♂,32%
) Experimental value

Claims (1)

[Claims] An iH-pyrazolo[3·λ-C] to s-h lyazole coupler, in which the following general formula is substituted as a coupling-off group at the position where it couples with the oxidation product of the developing agent. A silver halide photographic light-sensitive material characterized by containing a two-equivalent magenta cazolar, provided that A1 and A2 may be the same or different, each of which is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or an acyl group. , a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and AI and A2 are not both hydrogen atoms. Ma7ζA1 and A2 are bonded to each other and together with the nitrogen atom! Negative or six-membered monkeys may be fully formed. this! The membered or 6-membered ring may further be in association with a benzene-heterocycle.