JPS6049336A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity, gradation, and density and to reduce the amt. of silver halide in a photographic emulsion by incorporating a specified cyan coupler in a silver halide color photosensitive material contg. a 2-equivalent cyan coupler. CONSTITUTION:A silver halide color photosensitive material contains a cyan dye forming coupler represented by formula I or II in which R, R' are each alkyl, aryl, heterocyclic, or the like; X is halogen, alkyl, aryl, sulfonyl, nitro, or the like; Z is a metallic atomic group necessary to form a 5- or 6-ring condensed with the benzene ring; m is an integer of 1-4; and n is 0, 1 or 2, and when m and n are >=2, respectively, any of X may be same or different, and X may be Z. Since said colorless 2-equiv. cyan coupler is excellent in color formation performance, and high in sensitivity, gradation, and density, the amt. of silver halide in a photographic emulsion can be reduced, repid processing can be attained, and further, deterioration of color development density can be prevented even in the case of processing with a bleaching soln. weak in oxidizing power.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides cyan dye-forming couplers such as
Silver halide color copy J containing equivalent cyan coupler
This relates to the lc photosensitive material phase.

When a silver halogenide photographic light-sensitive material is subjected to color development in a non-light condition, the oxidized aromatic hexagroup-class amine developer reacts with the dye-forming coupler to form a color image. . Generally, this method uses a subtractive color reproduction method, and in order to reproduce blue, green, and red, color images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively.

Phenol fatty conductors or naphthol derivatives are often used as couplers to form cyan images. In the color photography method, the color forming agent is added to the developer, but it is incorporated in the photosensitive photographic material 1-1 or other color forming layer, and the color developer formed by development is added to the developer. Forms a non-diffusible dye by reacting with an oxidant.

The reaction between the coupler and the color developing agent takes place at the active site of the coupler, and couplers with hydrogen atoms at this active site are ψ
Equivalent couplers, that is, theoretically require stoichiometrically 1 mole of silver halide having a m (fJ nucleus) to form 1 mole of dye. Those with possible groups are V-equivalent couplers, i.e., couplers that require only 2 moles of silver halide with development nuclei to form 1 mole of dye, and thus for V-equivalent couplers. In general, since the amount of silver halide in the photosensitive layer can be reduced and the film thickness can be made thinner, the processing time of the photosensitive material can be shortened, and the sharpness of the color image formed can also be improved. Typical leaving groups are listed in U.S. Patent J, 737.
．． No. 31j has a sulfonamide group, as described in US Patent No. 3,7≠
73j has an imide group as V, U.S. Watch J, 4.2co, and 321 has a sulfonyl group, U.S. Patent J, +74
．． No. 362, the aryloxy group is
/, No. 1172 has an acyloxy group, American male “3
．． 2/! .

In No. 1137, the thiocya/group is US f(,≠,03
], 311! No. 04111,373 has an inthiocyanate group, U.S. Pat. , 227, 3311, a thiocarbonyloxy group in JP-A No. 32-6/1999, a tril-ylkenylcarbonyloxy group in JP-A-57-≠6o6, jl-co/121 has 7 acyl ami groups, JP-A-5/-32121, JP-K-36-tK371c has ami/methyl groups, JP-A-177
-J7da25. The same J7-20003 has a heterocyclic oxy group, as described in U.S. Pat.
Coater 0ri 3.2, same j3-tatata 31. same! '3-1
032λt1 same j da l≠736, same! ≠-4A/Kota, times jj-3207/, same 5r-tsri j7, same jG-
/931r, jA-A139, j6-12AM-3
,same! 6-λ7/177, 37. -f00111t,
/Tokuko Showa 5o-i+2o33u, same j4'-37122
, same jA-6332, same j7-3ri3da, same s7-ψt
A substituted alkoxy group is known for oto.

Furthermore, by appropriately selecting a leaving group, it is possible to apply, for example, a diffusion transfer method in which a diffusible dye portion is attached to the leaving group, and the released dye is used to spread the dye into the image-receiving layer, forming a dye image of the polar dye. This type of coupler is called a diffusive dye-releasing coupler, for example, the US special d
'F No. 3, 227. jjO No. J, 74j, 1r
f4, U.S. Defense Special Forces, U.S. Defense Special Forces, U.S. Defense Force No. This type of coupler has a masking effect for color correction, and is called a colored coupler.
-26θ31.

In addition, a 2-equivalent coupler in which the separation product has the effect of suppressing development is called a development inhibitor-releasing coupler, and because it suppresses development in proportion to 1
It has effects such as making the image finer, smoothing the gradation, and improving color reproducibility. It can also be used in a diffusion transfer method by utilizing the effect on adjacent layers. This type of coupler is described in U.S. Patent No. 3. λ
,! 7,! jtl1 or CVf Kaisho≠tar/
No. 2.233j, West German Patent Publication U, ψ/≠, No. 001 V.

As described above, λ-equivalent couplers tend to be frequently used in the 7c group because they are essentially superior to Ge-equivalent couplers and have a variety of applicability.

On the other hand, a phenolic cyan coupler having a V-ide group at the 2-position and an abu-amino group at the 5-position has a higher thermal resistance to the color image produced after color development than Sen's 7-enol cyan coupler or naphthol coupler. It is said to have excellent fastness to light, and has been designated as JP-A No. 4612ψ and J7-Co. Da! 13, same, t7-20 $j $4'
, same j7-2゜us da j1 same jf-33 ≠, same 5r
-JJλs.

Kabutsu described in JR-33λsi, JR-31-3.3212, etc. is known, and some two-position cyan couplers are also included therein.

However, the conventionally known ureido group at the 2-position, '
Many of the phenolic shears/casolers that contain acylamino groups have insufficient coupling reactivity, give a significant color cast, have poor dispersibility, and cause coating failures. It has the disadvantage that it is unstable and cannot be stored for a long period of time, and the stability of the color image formed after color development against heat or light is still not sufficient considering the long period of storage.

Therefore, the first object of the present invention is to improve such conventional drawbacks and to provide a silver halide color photographic light-sensitive material using a new cyankazoler having extremely excellent color development and dispersibility. There is V.

Another object of the present invention is to provide a coupler that exhibits almost no decrease in color density even when used with egg white fL, which has weak oxidizing power, or treated with a tired bleaching solution.

It has been found that the object of the present invention can be achieved by a cyan dye-forming coupler 2 represented by the following general formula (1) or (n) and a silver halide color photographic material containing the same.

General formula (1) (wherein ■ represents an alkyl group, an aryl group or a heterocyclic group, R' represents an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group, and represents a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkyl group, an acyloxy group, an acyl group, an alkylthio group, a sulfonyl group, or a t represents the essential non-command atomic group to form a t-membered reduced representation.m
represents a number in 11 of /~f, n represents an integer of θ~l, and n
When l and n are 2 or more, X may be the same or different. Or it may be in the Z that you threw up.

Below, 几, X, Z and R' will be described in detail.

In general formulas (1,) and i), it is an alkyl group (e.g., methyl group, butyl group, pentadecyl group, cyclohexyl group, etc.), an aryl nor (e.g. , phenyl group, cafthyl group, etc.), or heterocyclic group (e.g., 2-
pyridyl group, l-pyridyl group, λ-phenyl group, co-oxazinol group, 2-imidazolyl group, etc.), and these represent an alkyl group, aryl group, heterocyclic group, alkoxy group (e.g. methoxy group, dodecyl group, -methoxyethoxy group, etc.), aryloxy group (e.g., phenoxy, λ, lL-di-tert~amylphenoxy group, J-1ert-butyl-hiro-hydroxyphenoxy, naphthyloxy, γ, etc.), carboxyne group , carbonyl group (e.g., acenal group, tetrazoyl group, benzoyl group, etc.), :f Nice f /l/4 (9Q
For example, methoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy&,7')oxysulfonyl group, toluenesulfonyl group, etc.), amidocarbonyl group (for example, acetylamino group, ethylcarb7yl group, methane/L / e, 1 nylamide group, butylsulfamoyl group), imide group (e.g., succinimide group, hydantoinyl moiety, etc.), sulfonyl group (for example, methanesulfonyl group), hydroxy thread, cyano group, nitro group, and It may be substituted with a substituent selected from halogen atoms.

X is a halogen atom (preferably a chlorine atom or a fluorine atom), an alkyl group with a carbon number/-ff (methyl group, ebul group, t-butyl group, trifluoromethyl group, etc.), an aryl group with a carbon number of 6 to 10 (Hydroxyl group including phenyl group, p-tolyl group, o-chlorophenyl group, number of carbon atoms/
-f alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, etc.), acyloxy group with carbon number 1-♂ (acetoxy group, benzoyloxy group, etc.), carbon number 1! ;-i
o aryloxy group (phenoxy group, p-chlorophenoxy4, etc.), i7 acyl group with 2 to 10 prime numbers (acetyl group, chloroacetyl group, benzoyl group, etc.), carbon number/
~g alkylthio group (methylthio group, ethylboo, etc.), sulfonyl group (methanesulfonyl group &,) having carbon number l~lθ rJ /! ! (methanesulfonyl group, zenesulfonyl group, etc.) or nitro group.

Silk resin formed from benzene salt of the general formula [■] and Z& are naphthalene, quinoline, carbostyryl,
Benzofuran, benzothiophene, phthalimide, phthalazine, etc. can be extracted.

' is the number of carbon atoms / the alkyl of It, i = (for example, methyl group, ethyl group, n-propyl group, i-propyl group,
n-butyl 4, +-butyl group, t-butyl group, n-hexyl group, n-octyl) k, n-dodecyl group, n-octadecyl,! ), carbon number 1~/I(D alkenyl'ii (for example, flobenyl 5, butenyl group, octenyl To, etc.), carbon number 1~1r aralkyl group (e.g. benzyl group, phenylethyl groups), carbon numbers/-/aralkenyl groups (e.g., phenylzorobenyl groups, etc.), cycloalkyl groups (e.g., cyclopentyl groups, cyclohexyl groups, methylcyclohexyl groups,
cycloheptyl group, etc.), an aryl group having 1 or 2 Q carbon atoms (e.g., phenyl group, naphthyl group, etc.), or s
j4 or t is a broken heterocyclic group (this hetero tA may contain or be attached to one nitrogen atom -1 or even an oxygen atom, a sulfur atom and/or a nitrogen atom);

For example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, thiazolyl group, piperazyl group, etc.).

Here, f (alkyl group, alkenyl group, aralgyl group, aralkenyl group, cycloalkyl group represented by /,
The aryl group and the heterocyclic group are each 1#, a substituent such as a halogen atom (fluorine, tetramine or bromine, etc.), a cya/group,
Hydroxyl group, alkoxy group (e.g., methoxy group, ethoxy group, propyloxy group, butoxy group, octyloxy group, etc.), acyloxy group (for example, fenoquino group, etc.), acyloxy group (e.g., acetyloxy group, propio/yloxy group, etc.) , butyroyloxy groups (7 groups, benzoyloxy groups), acylamino groups (e.g., formamide groups, acetylamine groups, 7 propionyl groups, benzoylamino groups, etc.), sulfonamide groups (e.g., i
fj: , methylsulfonamide group, octylsulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (e.g., non-11-substituted sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group, flobylsulfamoyl group) , phenylsulfamoyl group/z, etc.), sulfonyl group (e.g., eva, methylsulfonyl group, ethylsulfonyl group, octylsulfonyl group, benzenesulfonyl group), carbonyl group with one sulfo group, nitro group, arylthio group (e.g. , phenylthio group, etc.), alkylthio group (e.g., methylthio group, ethylthio group), carbamoyl group (e.g., evaporation, ethylcarbamoyl group, phenylcarbamoyl group), alkoxycarbonyl group (e.g., methanesulfonyl group with 1 ethoxycarbonyl group), fj'fl), sulfinyl group (e.g., methylsulfinyl group, phenylsulfinyl group),
It may be substituted with a heterocyclic group (eg, pyrazolyl group, triazolyl group, etc.). These substituents may be further substituted with these substituents, or two or more substituents may be substituted at the same time, and in this case, the substituents v may be the same or different.

Among the groups represented by R', particularly preferred are groups represented by the following general formulas [■(] to [Kari]).

General formula (ill) MoR, 1-0sui (Bon 2nd edition → AR3 General formula (rv’) -Ryo-S-ratio.

General formula (V) -1(11-80-1(+4 General KC■] -It, -802-)t4 General formula [■] General formula [■] One volume - N-802 ratio.

Also It 5 General formula (IX) General formula (X) General formula IJ -1 role ([λ11　) 几.

In the general formulas [1■] to [store], 几 and 112 represent an alkylene group with carbon number/-F, 113 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or a cyan coupler residue group, and 1t4 represents an alkyl group. group, aryl group or t heterocycle 4'k, It5 and R6 each represent a hydrogen atom, alkyl group, aryl group or heterocyclic group, [+7 and I
t8 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, a cyano group, a nitro group, a sulfonylnor, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo crystal, a halogen atom, a carbonamide group, a sulfonamide group , carbamoyl group, alkoxycarbonyl group or sulfamoyl group. X is a positive integer, y is also! ~ A heterocycle in which the necessary non-gold hezo ring is added to the 4-element f-/if, which is necessary to form a 7-membered heterocycle, is (even if it is 4-membered). It may also be fused with a benzene term or a heterocycle.

Pyrrole, imidazole, bizizole, triazole,
Examples include nato 2 zole, benzotriazole, -1 succinimide, phthalimide, diglyco J reimide, imidazolidine dione, oxazolidine dione, thiazolidine dione, and the like.

pyrrole, imidazole, pyrazole, triazole,
Examples include detrazole, oxazole, thiazole, benzimidazole, benzoxol, benzithiazole, pyridine, pyrimidine, tri'azine and the like.

The compound represented by the general formula [1] or i) (hereinafter referred to as the coupler of the present invention) has a phenylureido group substituted in addition to the Noah 7 group at the 2-position of phenol, and j
An acylami/group is placed in the position, and the general formula (10 or [
It is characterized by having a group such as -0-R' defined in (2)], and is considered to be the reason why various good properties were obtained.

In other words, the colorless 2-equivalent cyan coupler of the present invention has excellent color forming properties and can provide extremely high sensitivity, gradation, and maximum Ik, so that the amount of silver halide contained in photographic emulsions can be reduced. Therefore, it is suitable not only for normal processing but also for rapid processing. Furthermore, it has excellent solubility in boiling point M solvents, has good dispersion stability in photographic emulsions, and does not cause fogging or color staining on the photosensitive layer.

The dye obtained from the cyan coupler of the present invention is
It has excellent fastness against heat and humidity, exhibits sharp absorption without unnecessary light absorption, and has good spectral absorption properties. Hera's uninvented coupler has the property of being MI''-3'e, which has a weak oxidizing power, or has almost no low color density F even when processed with a tired bleaching solution.

On the other hand, the aforementioned U.S. patent≠, 333.9 Tata No.
7-20uj'A3, 57-2017j171, samej
7-20≠5Fj, same jI-332g2, same j♂-J3
Even when compared with the extremely strong cyan couplers described in 260, J♂-332s/, JLR-33262, etc., the effect exhibited by the coupler of the present invention was completely superior.

Next, specific couplers included in the scope of the present invention will be illustrated, but the couplers of the present invention used in the present invention are not limited to these.

R and I7' have the same meanings as those described in general formulas (-1) and [■], and '' represents the same. X' represents a halogen atom (F, α, Br, etc.).

(2) represents a group that can be eliminated in a tosyloxy ring nucleophilic substitution reaction.

Synthesis Example 1 Synthesis of Exemplified Compound (1) Concentrated + 6f acid, 2≠Oml under ice cooling, j-fluoro-2-
Add 102f/-ff of methylbenzoxazole, then add 70tst of nitrate (d=/,'IO) and (,+
LHptUW t o.

πl of the mixed acid was added dropwise at a temperature below s'C, and after the completion of the droplet F, the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into ice water, and the precipitated crystals were washed several times with water. After drying, recrystallize with ethanol and -C
A/Body III gold obtained.

Next, p-methoxyphenol ltg was dissolved in tetrahydrofuran (THF), and to%
NaH/1. After adding f and stirring for 75 minutes, A1 body
ojg dissolved in Tl (F 300@l) was added dropwise and reacted at 3s 0c for 3 hours. 1'HF'too
After distilling off the mushroom t under reduced pressure, extracting with ethyl acetate, washing with water, distilling off the solvent under reduced pressure, and crystallizing with ethanol to obtain 8 bodies 10.29
I got it.

Next, 8 liters of concentrated hydrochloric acid s ONt % ethanol j
The mixture of 0011 was reacted at 70'C for 1 hour, poured into drained water, the precipitated crystals were collected, and washed with water to remove the crystals.
I got it.

Next, add C-form t9Q to acetonitrile u00pl,
0~go, 'c in N-phenoki 7 carponyl 2-
Rirollo≠cyanoanili/Agfl was added and reacted for 2 hours. The reaction mixture was poured into gold water, and the precipitated crystals were collected to obtain D 27y.

Next, 2 g of 9/9%/ξ radium-carbon catalyst was added to 25 ml of dimethylacetamide, and catalytic reduction was performed in an autoclave. After consuming the theoretical amount of hydrogen, the catalyst was separated into
ert-amylfe/xy)hexanoyl chloride 73
The reaction solution was poured into water, extracted with ethyl acetate, washed with water, concentrated under reduced pressure, and the resulting residue was mixed with n-hexane/ethyl acetate (mixing ratio -, 4
Chromatography was performed using a silica gel column (//), and the fractionated solution was concentrated under reduced pressure to obtain the desired ν-hydrogen compound (1) in bulk.

Elemental analysis value (C431I5□N406α) Calcd
C; IGl, 31%Hi&J/%N;7. ! , 2%Fo
und c;xIr, /lI% H;& ,riJ% N
i7. j & 4 Synthesis Example 2 Synthesis of Exemplified Compound (4) j-Hydroxy-λ-methylbenzoxazole/l B/pX/, Codibromoethane 2/3f.

Dimethylformamide toge 501 to potassium carbonate ltθf
Wl was added thereto, and the mixture was heated on a steam bath for 3 hours to remove inorganic substances from P, extracted with ethyl acetate, washed with water, and the solvent was concentrated under reduced pressure to obtain oily A-form 112y.

'a4iN, $300 TNL under water cooling, human body 1
021 was added thereto, and nitric acid (d=/, ≠2) was added dropwise in an amount of 10yH while keeping the temperature below /s 0cF.

After stirring for 30 minutes, the reaction mixture was poured into ice water, and 7 crystals were collected and 8 crystals were collected at 10/f (m, p, 1
03-10g'c) was obtained.

Next, prepare B body tata f2 ethanol 3 o o tB (,, prepare 30 g of salt and prepare 1 d1 anti LL at g time with jO-600C
; Pour the water out and remove the precipitated crystals from the door JIV L.
, C-isomer gty was obtained.

Next, add 0 body 13f to acetonyl 3;00 ql,
jO-40'C/-phenoki7carbonylamine/-
≠-Cyanonaphthalene ξty was added and reacted for 2 hours. Pour the reaction mixture B into water and collect the precipitated crystals.
Body 1079 was obtained.

Next, vCD weight≠9XA 2 g of radium-carbon catalyst was added to dimethylacetamide λj'01Ilt, and catalytic reduction was performed in an autoclave. After the theoretical amount of hydrogen has been completely consumed, the catalyst is separated and added to the P liquid (reaction bath 1ei).
λ-(2, Hiro-G-tert-amylphenoxy/)hexanoyl chloride 7311 was added, and stirring was continued at to 0c for 2 hours. After the reaction, the mixture was poured into water, extracted with ethyl acetate, washed with water, and solvent 16 was distilled off under reduced pressure to give 1po.
A residue of y was obtained. Dissolve this 9i residue in chloroform,
Chromatography was performed using a silica gel column, and the fractionated solution was concentrated under reduced pressure. The concentrate was dissolved in methanol, thioglycolic acid/lrl/, sodium hydrattanide,
It was added dropwise to a 300 ttti methanol solution of 2≠1 at room temperature while stirring. After further stirring for 3 hours, the reaction mixture was poured into an acidic aqueous solution of hydrochloric acid, extracted with ethyl acetate, and washed with water. Then, the residue /239 obtained by concentration under reduced pressure was subjected to chromatography using a silica gel column with n-hexane/ethyl acetate (mixing ratio: , J//).
The fractionated solution was then concentrated under reduced pressure and solidified using n-hexane to obtain the target exemplary compound (4) in a dry form.

Elemental analysis value (C44H54N407S) Calcd C
HA7. p9% H; A, Ri! ;% pJ near, u%F
'ound C;47. J, 2% H amount (ri5P%N;
7. /44% Photographic emulsions made using the present invention may be enriched with color image-forming couplers other than the present invention. The coupler is preferably a non-diffusive coupler having a hydrophobic group called a pallast group in its molecule. The coupler may have either ≠ equivalence or λ equivalence with respect to silver ions. 3 It may also include a colored coupler that has a color correction effect, or a coupler that releases a development inhibitor during development (so-called DI R coupler). good.

The turnip may be such that the product of the coupling reaction is colorless.

A known open-chain ketomethylene coupler can be used as the yellow color-forming coupler. Among these, benzoylacetanilide and piparoylacetanilide compounds are advantageous.

As the magenta coloring coupler, pyrazolone compounds, indashilon compounds, cya/acetyl compounds, etc. can be used, and pyrazolo/acetyl compounds are particularly advantageous.

Also, pyrazolotriazole compounds, pyrazoloimidazole compounds, pyrazolopyrazole compounds・? It can be used to your advantage.

As the cyan color-forming coupler, phenolic compounds, naphthol compounds, etc. can be used.

In addition, colored carboxylic acid, DI coupler (D* coupler which releases a highly diffusible development inhibiting substance in !l), etc. can also be used in combination.

In addition to the DIR coupler, there is also a development inhibitor 1bi during development.
Compounds that emit light may be included in the light-sensitive material, for example as described in US Patent No. 3. Koji 7. ≠qj issue, (rs33
, 37 F, j, 2 P, West German patent application (O
LS) λ, II/7, 9/Hiro issue, % Kaisho 32-/! 27
Those described in JP-A No. 3-7//1, No.

Two or more types of uninvented couplers can be contained in the same layer. The same compound may be contained in two or more layers.

The uninvented couplers generally have λ per mole of roots in the emulsion layer.
X10-3 moles to J'X/θ-1 moles, or 2 or 1XIO-2 moles to jXlo' moles are added. When used in combination with the above couplers, it is preferred that all the couplers that produce the same color fall within the above range.

In order to introduce the above-mentioned couplers into the silver halide emulsion layer, known methods such as those described in US Pat. No. 322.027 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 (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. zigtogyethyl succinate,
dioctyl azelate) fL, or boiling point approximately 30°C
to 150°C, F-containing solvents such as ethyl acetate, lower argyl acetate such as vinegar, 1.2-butyl alcohol-21, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve. After dissolving in acetate etc., hydrophilic colloid hair ζ is dispersed. A mixture of the above-mentioned high-boiling-point solvent and a low-boiling-point low-boiling-point solvent may be used.

Tokko Akira again! ;I-3 Riza S3, especially 4 Showa 3 / -!
The dispersion method using a polymer described in Lid 13 can also be used.

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

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (for example, those listed in US Pat.
．． 7ri V No. 3, 332.

Benzophenone compounds described in No. 6g1 (e.g. IfDrUd! A-27F # No. Niggiag
(7)), cinnamate ester compounds *J (for example, US time *F 3° 705, ROS No. J, 707.
No. 37j), butadiene compounds (e.g. as described in U.S. Pat.
, No. 700.4tjj) can be used. Furthermore, US Patent 3. Uri 7, No. 74.2, JP-A-Jφ-ψI! 3! Those described in No. r can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These UV absorbers may be mordanted into certain layers.

The photographic emulsion used in the present invention is P, GIafkides.
i Chimie et Physique Photo
ographique (Pau l Mont te 1
Publishing, 1767), (), F.

Photographb ic Emul by Duffin
s ion Chemistry (The Focal
Published by Press, / 6th year, V, L, Zeli
kman et alMaking and Coa
ting Photographic Emulsion
(Published by Focal Press, 1961), etc., can be used to make Le 14.

In the present invention, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can also be used.

Formed separately. Two or more types of 7-silver halide emulsions may be mixed and used.

The coupler of the present invention may be used in combination with an emulsion in which tabular grains, particularly grains with a grain size/thickness ratio of 5 or more, particularly 5 or more, occupy at least a job of the total projected area.

In the process of silver halide grain formation or physical ripening, coexistence of 1 ton of cadmium, lead salts, lead salts, melium salts, iridium salts or complex salts thereof, rhodicum salts or complex salts thereof, iron salts or iron complex salts, etc. You may let them.

As a support agent or protective colloid for the photo hole 11, it is advantageous to use gelatin.
Raw colloids can also be used.

Misfire 1) The photographic emulsion used in the photosensitive material is subjected to a number of additives to prevent damage during the abuse process of the photosensitive material and during storage (and to stabilize the performance of the photosensitive material). ,1
! I! You can do whatever you want by combining the various combinations. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazole g (
(, mercaptothiazoles, mercaptobenzothianols, mercaptobenzimidazoles, mercaptothiadiazole 1-aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazo1's (%&C/-phenyl -j-mercaptotetrazoles); mercazotovirimidines; mercaptotriazines; thioketo compounds, e.g. (/, 3, Ja, 7) tetrazaindenes), pentaazaindenes; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.; Many known compounds can be added.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains compounds that increase sensitivity, increase contrast, and promote development, such as polyalkylene oxide or its derivatives such as esters, esters, and amines, and thioether compounds. Proboscis, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives; (1,3-pyrazolidones, etc.) may also be included.

The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine color 7 generation, mero/anine pigment, composite 7-r2) coloration, composite merocyanine pigment, holopolar cyanine pigment,
Hemicyanine color-J, styryl pigment, j? and hemioxonol dyes. Particularly useful pigments are cyanine colors (merocyanine pigments and pigments belonging to retromerocyanine pigments. These pigments contain either of the nuclei commonly used in cyanine pigments as a basic outer ring nucleus. Also applicable: viroline nucleus, oxazinone nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, cenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; alicyclic hydrocarbon rings are fused to these nuclei. and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a cut oxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, (benzosennazole nucleus, benzimidazole nucleus, quinoline nucleus, etc.) are commercially available. These nuclei may have one substitution on the carbon atom.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a pyrazolin-5-one nucleus in the ketomethylene structure. z-thioxazolidine=2. 5~ such as φ-dione nucleus, goazolidi/-2, ψ-dione nucleus, rhodanine nucleus, booparvylic acid nucleus, etc.
You can use 4 members of the ring nucleus.

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

Together with the sensitizing dye, it itself had a spectral sensitizing effect 'c%.

A substance that substantially absorbs the dye used or the available YT and exhibits supersensitization, 1. May be included during cutting.

Hydrophilic colloids are used in photosensitive materials made using the present invention!
- It may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and rzo dyes. Among them, oxonol dyes;
Hemioxonol dyes and merocyanine dyes are used for dyes.

In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers IIcd, stilbene-based,
It may also contain a brightening agent such as a triazine type, oxazole yarn or coumarin yarn. These may be water-soluble, or water-insoluble brighteners may be used in the form of dispersions at °C.

When carrying out the present invention, the following known antifading agents may be used in combination, and the color image fixing agent used in the VC of the present invention may be used alone or in combination of two or more.

Commonly used anti-fading agents include hydroxyl derivatives, gallic acid derivatives, p-alkoxyphenol derivatives, p-oxyphenol derivatives, and bisphenol derivatives.

The photosensitive material produced using the present invention contains hyde derivatives, fat conductors, amide/phenol derivatives,
It may also contain gallic acid derivatives, ascorbic acid derivatives, etc.

The present invention is also applicable to multilayer, multicolor photography (family A) having at least two different spectral sensitivities on a support.

The multi-t(4) natural color photographic material has at least one each of a red 11 bean emulsion j-1 green sensitized emulsion layer and a '# sensitive emulsion layer on a regular paper support. One of these layers Select the bile sequence as desired.The red-face emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the parasitic emulsion layer contains a yellow-type J-fire coupler.
]'AAlthough it is usual, different combinations may be used depending on the case.

Any known method can be used to process the thorns of the present invention. A known treatment liquid can be used. The processing temperature is normal) IJllza0C to j
l'(', but the temperature may be lower than /ff'c or higher than jOoC.

Color developers generally consist of an alkaline aqueous solution containing a color developing main system. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g. ≠-ami, t-N, N-diethylaniline, 3-methyl-l-
Amino-N, N-diethylaniline, ≠-amino-N-
Ethyl-N~β-hydroxyethylaniline, 3-methyl-+ -amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-V-amino-N-ethyl-
N-β-methanesulfamide ethylaniline, ≠-amino-3-methyl-N-ethyl-N-β-methquinethylaniline, etc.) can be used.

This Ij12L, F, AoMason Sound Photog
rapicProcessing Cbemistr
227 of y (Focal Press, 1964)
．． -λλ pages, US% total 2, /ri 3. ois issue, same 2.
J22.36≠, those described in JP-A-Sho φg-t Rita No. 33, etc. may be used.

Color developers may also contain buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and +3-capri inhibitors. If necessary, water softeners, stabilizers such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts, and amines may be added. Development accelerators, dye-forming couplers, competitive couplers, fogging agents such as sodium borohydride, auxiliary developers such as l-phenyl-3-pyrazolidone, tackifying agents, US Pat.

The polycarboxylic acid chelating agent described in No. f3,723,
It may also contain antioxidants described in West German Open (OL8), No. z, x, z, z, Riso.

After color development, the photographic emulsion layer is usually subjected to a bleaching treatment (>11). The bleaching treatment may be carried out at the same time as the topping treatment or separately. Examples of bleaching agents include Fu(II), Compounds of polyvalent metals such as cobalt (■), chromium (■), and copper (II), peracids, quinones, and nitroso compounds are used.For example, ferricyanide, dichromate, iron (11 ) or organic complex salts of cobalt (tll), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid H
Aminopolycarboxylic acids such as 1/,3-diamino-2-pro/R-nortetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid, malic acid; persulfates, permanganates; nitrosophenols, etc. are used. be able to. Among these, potassium ferricyanide, sodium ethylenediaminetetraacetate iron (1) and iron ethylenediaminetetraacetate (
ill) Ammonium is particularly useful. Ethylenediaminetetraacetic acid iron (1) complex salt has -
It is also useful in bath whitening fixers.

U.S. Patent 3.0≠2.32 applies to bleach tubes or cool white baths.
No. 0, No. 3, J4c/, YAt No., Special Public Show pj-t
In addition to the bleaching accelerators described in RSO No. 4, Japanese Patent Publication Shoqs-J' I No. 3.4, and the thiol compounds described in JP-A No. 13-137732, various additives can also be added. .

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1 All samples were prepared by coating an emulsion layer and a protective layer on a cellulose triacetate film support in the following order.

Exemplary coupler <1> 1oty dibutyl phthalate/θ
θcc and ethyl acetate lθθcc were added and dissolved by heating at tθ0C, and this solution was mixed with gelatin/00'! and so containing sodium human tecylbenzenesulfonate lOf
0c of aqueous gioooH() and stirred at high speed with a homogenizer to obtain a fine coupler dispersion.

A silver iodobromide emulsion in which the coupler component i3jO (/ is silver'fcroe and the molar ratio of silver iodide and silver bromide is ≠ to t)
kg, and the coupler coating amount was 7×10 on the support.
It was applied at a concentration of 'mol/m2.

A gelatin protective layer having a dry film thickness of lμ was applied on this layer to prepare sample/A.

Using the method of 4 η, using the example couplers (2) and (4), make the color developer (e-schiff m2) and the mixing ratio of the coupler and silver the same as that of sample/A to prepare sample/B,
/C was completely produced.

Furthermore, as a comparative coupler, a coupler (101) other than the present invention
, (102) in exactly the same manner as sample/A,
l/D and /E were produced.

(t) e5ii, After exposing these samples with a sensitometric wedge, the following! , 7 was developed at 3g0C in a physical process.

l Color development...3 minutes/j seconds 2
Wash white... for 3 minutes and 30 seconds with water...
...3 minutes/j seconds 4 Fixing...... minutes 30 seconds 5 Washing...... 3 minutes Is seconds 6 Ans yi... ...The composition of the treatment liquid used in the 3 minutes/j second diameter process is as shown in F.

Color developer Sodium nitrilotriacetate 1.0I/Sodium sulfite xi, oy Charcoal sodium 3θ, og Potassium bromide 7. Wow.

Hydroxylamine 4fte salt λ, ψ2l-(N-ethyl-N-β-hydroxyethylamine/)-λ monomethylaniline sulfurffTm ≠, jg Add water ′
l Bleach solution Ammonium bromide 14o, op Aqueous ammonia (2r%) 2jr, Occ Ethylenediamine-tetraIprll sodium iron salt 13θ, Occ Add water tl Regular solution Sodium tetrapolyphosphate 2. ogsu E sulfur sodium ≠, oy thiosulfate f11 ammonium (70v)! 76.0ccA
IF, sulfurized sodium v, gy water r plus 14 doubtful a (rj.

formalin g-occ Water power 11 ′　l Treatment: t4　m The elasticity of the sample was measured using red light.

The results are shown in Table 1.

As is clear from Table 1, the couplers of the present invention exhibit a significant improvement in sensitivity over the comparative couplers. In addition, the peak spread of the absorption spectrum of the coloring dye, and the cutting edge on the P and i+i wave sides can be measured in 14 pairs.

Next, the durability of each film was tested at 19 locations.

, the robustness when the test T+ was left in the dark for 1 day at 0°C, the robustness when left in the dark at 70°C for 6 weeks, and the xenon tester CIO (10,000 lux). Fastness when exposed to light for 6 days Total +71 Density 1. The low concentration of O2 was investigated. Also go0C,
/≠ days! Increased installation of H-color light in poor fogging areas/Jl! (
6111 was determined.

The results are shown in Table 1K.

The heat resistance of the color image formed by the cabraca of the present invention was sufficient, and there was little tendency to produce stains.

Example 2 A multilayer color photosensitive material sample was prepared on a polyethylene terephthalate film support, each layer having the composition shown below.

1st layer: antihalation layer gelatin layer containing black colloidal steel 2nd layer: intermediate layer λ, gelatin layer containing an emulsified dispersion of j-di-t-octylhydroquinone 3rd layer: 1st red-sensitive emulsion no iodobromation Silver emulsion (silver iodide; 5 mol%)...Silver coating amount
1.49/m2 Sensitizing dye l...P, jxio mole per mole of silver Sensitizing dye ■...1, jxlO mole coupler (101)... per mole of silver For o, ort mole coupler EX-3/urine ×, 1 and 0.003 mole coupler EX-7/&1 mole o +ooo4 mole ≠j; first red-sensitive emulsion layer silver iodobromide Emulsion (silver iodide; 10 mol%)...Silver coating*
/ , u 9/yn2 Sensitizing dye L...3 x 1O mol per mol of silver Sensitizing dye It.../X/θ mol per mol of silver Exemplary coupler (1)... I≦Olo for 1 mole of It
,2+i! Molar coupler EX-J - θ, θ0/l, mole per mole of silver, jth layer; middle 1ii, same as the 1st and 2nd layers, 47th layer; 1st green-sensitive emulsion layer silver iodobromide emulsion (silver iodide :≠mol%)...@, coating f
il, 2! / ノ272 Sensitizing dye ■...j x 7θ molar per mole of silver Sensitizing dye ■... Co x lO molar per mole of silver Ic Coupler EX-≠・01OS per mole of steel Molar coupler EX-S・For 1 mole of silver -C9,001fMolar coupler j 0.00/! for 1 mole of silver Mol No. 71 @; al't 'green hole t'jl 1 layer iodine A ratio silver milk] (su (silver iodide; t mol qb)... Silver coating failure 1
．． 3 fl/m2 Sensitizing dye ■...@3'/, 10' moles for 7 moles Sensitizing color flag ■--...For silver 1 mole/, 2 x 1 O mole coupler EX-7・0.0/7 mole coupler EX-4 for 1 mole of silver ・θ+003 mole coupler EX-10 for 1 mole of silver ・mM 0.000 for 1 mole
3 mol G layer; yellow filter layer containing yellow colloidal silver in gelatin aqueous solution and 2. j-ji-t-
Gelatin layer 7th layer containing an emulsified dispersion of octylhydroquinone; 1st W-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol%)...Silver coating method
0.79/m2 Oak? 10th layer; 2nd W emulsion layer Silver iodobromide (silver iodide) ;6 mol%)...Silver coating result',
lrW/7112 Coupler nx-t-0.06 mol to 1 mol of silver 1st/layer; First protective layer Silver iodobromide (1 mol of silver iodide, average grain size 0.07μ) Silver coating amount θ , j g/77! 2 Ultraviolet absorption cutting UV
- Gelatin layer 1.2 layer containing an emulsified dispersion of 1; 2nd protection 11° - Trimethyl methanoacrylate particles (i & diameter approx. l.

Apply a gelatin layer containing jμ).

In addition to the above composition, a gelatin hardening agent H-/ and a surfactant were added to each layer. The sample prepared as above was designated as sample (2A).

Compounds used to make sample A p The development process used here was carried out using jJ''C as described below.

l Color development...3 minutes lj seconds 2 drifting
Wash white with water for 3 minutes and 3 seconds.
...3 minutes/J seconds 4 Fixation...6 minutes 30 seconds 5 Washing...3 minutes/S seconds 6 Stability... ...3 minutes' / 6 seconds for each process
The treatment and composition were as follows.

For color development, use sodium nitrilotriulate / , OQI stop flow cutting sodium ≠, θy Charcoal 1 wave sodium 30. θf Smell 1 hit 1. ≠1 Hydroxylamine sulfate λ, φg ≠-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate ≠, jg Full-mouth water / l Bleach solution Ammonium bromide /1,0. 0g Ammonia water (formerly 1) 26.0cc Ethylenediamine-40% sodium iron salt i3o, oy Ice d'acid l≠, Occ Add water /1 Chising solution Sodium tetrapolyphosphate λ, Og Sodium sulfate II , Of ammonium thiosulfate (70 t) / 7 t, Occ sodium bisulfite ≠ 3y Add water / 1 Stabilizing liquid formalin ), Samples 2B and 2C were made in the same manner as the two samples except that the comparative couplers (101) and (102) were used.

A 2D model was created.

Fourth, the example coupler (1) of the ψ-th layer is compared with the coupler (10
Sample 1F was prepared in the same manner as above except that the method was changed to 1) and the coating stitch was 0°031 mol per mol of silver.

b) The prepared sample was exposed to white light and treated in the same manner as in Example 1.
f! The results shown in Table 3 were obtained by measuring the optical density using red light.

/ From the results in Table 3, the Kashiji of the present invention showed a significant improvement in sensitivity. In addition, when comparing all the grains with sample 2F, which was made to increase the sensitivity by increasing the coating m of comparative Kasisi, the MS values of samples λA and 2B are θ, θθ, and those of 2E are O0O
It can be seen that Kashiji of the present invention has excellent graininess.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 4', +1' Director-General of the Office of Patents 1. Showing 14 Showa SR Patent Application No. 1, t7! ,2
! No. 2, Title of the invention Silver-halogen color photographic light-sensitive material; 3. Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment In column 5 of the “Detailed Description of the Invention” of the specification, contents of the amendment The description in the section 1 “Detailed Description of the Invention” of the specification is as follows. Correct the standard.

(1) After “for example” on page 13, line 13, [alkyl group (e.g., methyl group, ethyl group, isopropyl group, t-methyl group, t-amyl group, t-hexyl group)
．． t-Octyl group, dodecyl group, pentadecyl group, cyclohexyl group, benzyl group) J is inserted.

(2) Add the following six compound examples after the last line of the second page.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material characterized by containing a cyan dye-forming coupler represented by the following general formula [1] or [■]. General formula ([) where 几 represents an alkyl group, aryl group or heterocyclic group, I't' represents an alkyl group, aryl nor, alkenyl group, cycloalkyl group or heterocyclic group,
X represents a halogen atom, an alkyl group, an ``aryl group, a hydroxyl group, an alkoxy group, an acyloxy group, an aryloxy group, an acyl group, a sulfonyl group, an alkylthio group'' or a nitro group, and 2 represents a benzene ring and V! Represents a group of nonmetallic atoms necessary to form a membered or t-membered condensed ring. m is l−≠ and! ie, n if: Represents a pleasant number from 0 to 2, and when m and n are 2 or more, X may be the same or different -C. X may also be at 2.