JPS623252A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproductivity by incorporating at least one kind of a specified colored coupler. CONSTITUTION:At least one of the colored couplers represented by the formula shown on the right is contained generally in combination with a cyan dye image forming coupler in an amount of 1-50mol%, preferably, 5-30mol% of the cyan coupler. This colored coupler is added to one of layers high, middle, and low in sensitivity, and their adjacent layers, in an amount of 1X10<-5>-5X10<-1>mol per mol of silver halide, thus permitting the obtained photosensitive material to have absorption lambdamax in the long wavelength region, to be superior in color correction effect and fastness of a cyan dye image, and to obtain stable cyan image density.

Description

[Detailed description of the invention] (Field of industrial application)
・：′□The present invention provides high cyan image density,
This invention relates to a silver halide photographic material with excellent brown color reproducibility. More specifically, the present invention relates to a silver halide photographic material containing a novel magenta colored coupler.

(Prior art) When a silver halide photographic material is exposed to light and then subjected to color development, a color developing agent such as oxidized aromatic primary amines and a dye-forming coupler react to form a color image. be done. Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively. In this case, phenols or naphthols are often used as cyan dye-forming couplers.

A cyan image formed by a cyan coupler should ideally absorb only red light, but generally also has sub-absorption in green and blue light. As a method for correcting this side absorption, a masking method using colored couplers has been put into practical use in the art.

Now, among the known magenta colored cyan couplers, useful ones are, for example, U.S. Patent No. J,
T/! , No. 402, 3,03 Hiroshi.

No. 222, s, IAt/, 7u/, 3. usri,
J1 issue, same J! 13, PO No. 2, 3゜7r4
', No. 313, 3. r//, rPJ No. 3, r
This is a coupler described in Koda, 7ri No. 3, etc. However, there are many absorption maximum wavelengths of these couplers! λOn
m or less, and those with longer wavelengths have a coupling reaction rate of 1'''''Jf''''' with the oxidized developing agent! ”“5””
If 691・a*zm*t*t □, then the maximum absorption wavelength of the maze/red color image formed by the magenta coupler (!
It is efficient to match the maximum absorption wavelength of the magenta colored cyan coupler to 40 nm). Therefore, the above-mentioned known couplers are unsatisfactory, and further improvements are desired.

For this purpose, a magenta colored coupler was considered that would release water-soluble dyes. For example, US Patent No.

oo! A.? No. 25F, II, /J! , No. 2jlr. Although this type of colored coupler allows the maximum absorption wavelength to be selected relatively freely, the dye portion must necessarily be water-soluble, which has resulted in various drawbacks. That is, they have drawbacks such as contaminating the developer, being unable to emulsify and disperse them together with oil-soluble internal couplers, and being too active and causing overmask.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to provide a color photographic material with excellent color reproducibility by using a colored coupler which has solved the conventional drawbacks. Second aspect of the present invention
The object of the present invention is to provide a color photographic material which is easy to produce and is therefore inexpensive by using a colored Kashi 2 suitable for emulsion dispersion.

(Problem t - Means for Solving) The above object has been achieved by a silver halide color photographic light-sensitive material characterized by containing at least one type of colored coupler represented by the following general formula (I).

General Formula (I) In the formula, Cp represents a cyan coupler residue; Here, R□ and R4 represent an aliphatic group, an aromatic group, a hydrogen atom, or a heterocyclic group, and R2 represents an aliphatic group, an aromatic group, or a heterocyclic group; Aromatic group, heterocyclic group, ^ 100Rt7'c represents -3 (J2R, R6 is
A hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, R7 represents the same meaning as 几2, and R8 and 几9 represent the same meaning as 几2.

However, when n is plural, R may be the same or different, or may combine with each other to form a ring.

Furthermore, Xl or R and X2 may be combined to form a ring. Also, R1 and 几 几 and 燠 or kL
8 and 几0 are 3% of each other 4 15'
% may be bonded to each other to form a ring.

In the above general formula, the aliphatic group specifically refers to a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted or unsubstituted. The number of carbon atoms is 7 to 301, preferably /, JQ. The aromatic group refers to a substituted or unsubstituted aryl group, and may be a condensed ring. The number of carbon atoms is t~30. Preferably it is t~koO. The heterocyclic group refers to a substituted or unsubstituted monocyclic or condensed ring heterocyclic group. The number of carbon atoms is λ~3
0. Preferably, 2 to 20 heterocyclic groups are mentioned.

In general formula (1), R is a group (
Typical examples include halogen atoms, hydroxyl groups, amino groups, carboxyl groups, sulfonic acid groups, cyano groups, aromatic groups, heterocyclic groups, aliphatic groups, carbonamide groups, sulfonamide groups, and carbamoyl groups. group, sulfamoyl group, ureido group, acyl group, acyloxy group,
Aliphatic oxy group, aliphatic oxycarbonylamino group, aromatic oxy group, aromatic oxycarbonylamino group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group , a nitro group, an imido group, etc., and the number of carbon atoms contained in the group is 0-JO. Examples include n=dioxy group.

Examples of the cyclic substituent formed by R and X2 include a piperidino group (moCH2±, N)l-) and a methylenedioxy group. Examples of the ring formed by bonding R and R+3, R4 and R, or R and Ro include, for example, a pyrrolidino group and a morpholino group.

In the general formula (1), Cp represents a cyankazolar residue, such as a naphthol type or a phenolic cazolyl residue.

Next, preferred examples of substituents in the present invention will be explained.

When R1, R2, R3, R4, R5, R6, R7, R and R represent an aliphatic group, the number of carbon atoms is 1 to 30. Preferably 1-10 aliphatic groups (for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, octyl group,
cyclohexyl group, coethylhexyl group, dodecyl group, octadecyl group, etc.). Preferred substituents for aliphatic groups include alkoxy groups (e.g. methoxy group, dodecyloxy group), aryloxy groups (e.g. phenoxy group, a-t-7" tylphenoki7 group, 2.pi-di-t-
amylphenoxy group), aromatic group (e.g. phenyl group,
naphthyl group), halogen atom (e.g. chloro atom, fluorine atom), acylamino group (e.g. acetamide group, benzamide group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group), hydroxyl □... hair □, ゛ group, carboxyl group, alkylthio group (e.g.
1. ; tylthio group, butylthio group, octylthio group), p:11' arylthio group (e.g. phenylthio group, dermal
-1'', -9 toxyphenylthio group), sulfonyl group (e.g.
□゛゛methanesulfonyl group, inzenesulfonyl group) , :')・) ar・middle cyclocarbo=~ group (e.g. methoxycarbo
j.

nyl group, dodecyloxycarbonyl group), ary-□゛′
, ″, phenoxycarbonyl group (e.g. phenoxycarbonyl group)
″, □ Nyl group, pt-amylphenoxycarbutyl(TM),
'-: □ or acyloxy group (e.g. benzoyloxy
・j4, Ayaga, Oya,, ga, car. □.
゛・:.

゛.

, I Ro, 几2, R3, R,, R5, R6, R7, 2R+8
and 几represent an aromatic group, preferably
“Kuke phenyl group or 7 tyl group, these
Preferred substituents for the aromatic group ' are aliphatic groups ``'''' (e.g. methyl group, t-butyl group, hantadecyl group), aromatic groups (e.g. phenyl group, 3-chlorophenyl group), alkoxy groups ( (e.g., methoxy group, butoxy group, tetradecyloxy group), aromatic oxy group (e.g., phenoxy group, ≠-methylphenoxy group), halogen atom (e.g., chlorine atom, fluorine atom)
, cyan group, hydroxyl group, acyl group (e.g. acetyl group, benzoyl group), carbonyl group, acylamino group (e.g. acedoyl group, benzamide group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group), alkoxycarbonyl groups (e.g. methoxycarbonyl group, hexadecyloxycarbonyl group, dodecyloxycarbonyl group), nitro group, carbamoyl group (e.g. N,N-diethylcarbamoyl group), sulfonyl group (e.g. methanesulfonyl group, benzenesulfonyl group), butanesulfonyl group), sulfamoyl group (
for example N,N-diethylsulfamoyl group), alkylthio group (e.g. methylthio group) or arylthio group (e.g.
For example, phenylthio group).

When R1, R2, R3, R4, R5, R6, R7, R8 and Ro represent a heterocyclic group, a nitrogen atom, a sulfur atom or an oxygen atom is selected as the heteroatom! A membered or t-membered heterocyclic group is preferred. For example, copyridyl group, φ-pyridyl group, cochiazolyl group,
Examples include a λ-furyl group and a cochiazolyl group. Preferred substituents for these heterocycles include the nine listed as preferred substituents for the aliphatic group.

In general formula (1), for R and n, n=.

To be sure, l is preferable, and R is an alkoxy group (e.g. methoxy group, ethoxy group), alkylthio group (e.g. methylthio group, ethylthio group), hydroxyl group, halogen atom (e.g. chlorine atom, fluorine atom), aliphatic group (e.g. methyl group, butyl group, allyl group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group), acylamino group (e.g. co(co,≠-di-t-1, amylphenoxy)hexanamide group, acetamide group) , benzamide H1x-(Co, Hiro-di-t-amylphenoxy)butanamide group, trifluoroacetamide group), aliphatic oxycarbonylamino group (e.g. ethoxycarbonylamino group, imbutoxycarmenylamino group), aromatic oxycarbonylamino group group (e.g. phenoxycarzenylamino group), or ureido group (e.g. phenoxycarzenylamino group),
Examples include 3-phenylureido group and 3-ethylureido group.

In general formula (I), preferred Cp is the following general formula (II
) or (I).

General formula (If) General formula (II) In the formula, the free bond indicates the position bonded to the azo group of the general formula (I), and □. and R□2 represents an aliphatic group, aromatic group or heterocyclic group, □□ and □3 each represent a substituent, m and l represent an integer from Q to -, and p is O or represents l.

R10 and 几□2 have the same meanings as in the detailed explanation for i几, and 几 and fL13 have the same meanings as in the detailed explanation for 几.

Particularly preferred couplers in the present invention are listed below.

In the general formula (I), X□ is -OR□ or, preferably, when n is 7, R is preferably an aliphatic oxy group or an aliphatic group. Here, a more preferred example is when 几□ and 几 are an aliphatic group or an aromatic group, and R4 and 几 are an aliphatic group or a hydrogen atom.

Furthermore, the following couplers are particularly excellent couplers because they have excellent color image fastness and can provide cyan images of sufficiently high density when processed through a bleaching process with weak oxidizing power.

In general formula (II), R10 is an aromatic group, m
= 0, or 几□. is an aliphatic group and m
A preferred example is when ``11'' represents a substituent at the 3-position of naphthol, which is an acylamino group, a sulfonamide group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, or a ureido group.

In the general formula (III), a preferred example is when p=l, □2 is an aromatic group, l=/, and 3 represents a substituent at the 3-position of phenol, which is an acylamino group. .

The colored couplers of this invention are generally used in conjunction with cyan imaging couplers. The amount of the coupler of the present invention added to the cyan coupler used in combination is 1 to 7, preferably! It is used in amounts of 1 to 30 mmol.

The layer to which the colored coupler of the present invention is added is a high-speed layer, a medium-speed layer, a low-speed layer, or a layer adjacent thereto. The colored coupler of the present invention is from /×l0-5 mol per mol of silver halide in the added layer or the adjacent layer! X10
1 mol, preferably 1 x 10 mol or 1 x 10 mol
Use Moruwo.

Specific examples of the coupler of the present invention are shown below, but the coupler is not limited thereto.

(1)
='QC)i3
・CH3 CH3 C2H,0COHN N C2H5 CH3 H 00002H.

QC)13 CH3 0CH3 0C2H5 CH3 CR3 OCH3,・ CH3 CR3 (°′)　　　　　　. H CR3 NH30□NH2 (Synthesis example) Specific synthetic methods for representative compounds of the present invention are shown below.

Other casolers can also be synthesized using synthetic methods similar to those described below.

. Synthesis Example I Synthesis of Exemplary Compound (1) It was synthesized using the following synthetic route.

CH3 CH3 CH3 Exemplary compound (1) Step ■: Synthesis of intermediate compound λ /J, Of, reduced iron j! , 3f, ammonium chloride j, j f, acetic acid J ml to isozolopanol/!
The mixture was added to a mixed solvent of Oml and water and heated under reflux for 1 hour. The mixture was passed through the mouth while still hot, and ethyl acetate 00/ was added to the mouth fluid, followed by washing with water. The organic layer was separated and the solvent was distilled off under reduced pressure.
．． Compound 2 of Of was obtained.

Step ■: Synthesis of Exemplified Compound (1) ! f was dissolved in methanol 2094, and ≠1 ml of 36% hydrochloric acid was added under a water bath.

Next, sodium nitrite/7f was added dropwise while maintaining the temperature at o'C. After reacting for 10 minutes, this solution was added dropwise to a sodium hydroxide solution of 2-(λ-tetradecyloxyphenylcarpamoyl)-7-naphthol of 7,72 dissolved in 20xl of methanol at a temperature of lo''c. After reacting for an hour, 2 ml of 36-dihydrochloric acid was added for neutralization, and crystals were precipitated.The mixture was drained and washed with water to obtain the desired exemplary compound (1).

Synthesis Example 2 Synthesis of Exemplary Compound (5) Synthesized using the following synthetic route.

CH3 CH3 Exemplary compound (5) Step ■: Synthesis of intermediate compound 1 of 3! , 7f, isostearyl alcohol t, rf1
100Wli of dimethylaminopyridine was dissolved in dimethylformamide rOtxlVc, and dicyclohexylcarbodiimide u and ry were added dropwise at room temperature. After 2 hours, the reaction mixture was passed through the mouth, 200 ml of ethyl acetate was added to the oral solution, and the solution was washed with water. The organic layer was separated and the solvent was distilled off under reduced pressure to obtain the first compound.

Stage ■: Intermediate compound! synthesis of 2. obtained in step ■. ! 2. Reduced iron/l, tf.

Ammonium chloride 1. Of, acetic acid/,! ml was added to a mixed solvent of inzolopanol Ir0wt1 and water/2117, and the mixture was heated under reflux for 1 hour. The mixture was passed through the mouth while hot, and 00 ml of ethyl acetate J was added to the mouth fluid, followed by washing with water. Separate the oil layer and distill off the solvent under reduced pressure to obtain compound 7.22! I got it.

Step ■: Obtained in synthesis step ■ of exemplified compound (5)! 7.2t of the solution was dissolved in 440.1ml of methanol, and 4'l/liter of trithihydrochloric acid was added in an ice bath. Then, sodium nitrite/4Cf was added dropwise while maintaining the temperature at o'C. After 70 minutes, this solution was dissolved in 20 ml of methanol and added dropwise to a sodium hydroxide solution of 9μ,/f of cornaphthylcarpamoyl-1-naphthol at a temperature of to''c.

After reacting for 1 hour, 2 ml of 3t thihydrochloric acid was added to neutralize, and crystals were precipitated. After filtration, the desired exemplary compound (
5) t-J.

/f The absorption of the obtained compounds (1), (2), (5), and (30) was measured in ethyl acetate. The maximum absorption wavelength is shown below.
□□ Comparative coupler (A) Comparative coupler (B) Comparative coupler (C) As is clear from the above, the compounds of the present invention exhibit long-wave absorption.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited thereby.

Example 1 A photosensitive material consisting of each layer having the composition shown below on a cellulose acetate film support, Sample/II-/1
0 was created.

(Sample 101) 1st layer: Red-sensitive emulsion layer coating amount of silver ・・・・・・・・・・・・・・・・・・ /
, 799/ln2 sensitizing dye I......4 xio moles per mole of silver Sensitizing dye ■......... per mole of silver/, ni' x 10 Molar coupler C-t...O0O≠molar coupler C-2...0.002 mol per mol of silver High boiling point organic solvent Dioctyl phthalate 0, jt/coupler/f 2nd layer: Protection Layered polymethyl methacrylate particles (approx. 1 in diameter).

! In addition to the above composition, H-/ and a surfactant are added as a hardening agent to each gelatin layer containing .mu.).

The sample prepared as described above was designated as sample ioi.

(Sample 10) Sample 10/ was prepared in the same manner as Sample 10/, except that the coupler EX-/ was added to the first layer in an amount of 0,000 oz mol per mol of silver.

(Samples 103 to 10) They were prepared in the same manner as Sample 1Oλ, except that the couplers added to EX-/ and C-/ in Sample 10 were changed as shown in Table 7.

Compound sensitizing dye I used to prepare the sample: Anhydro! ,! '-dichloro-3,3
/-di(γ-sulfopropyl)-terethyl-thiacarbocyanine hydroxide pyridinium salt sensitized color on: anhydro-terethyl-3,3'-di(r-sulfopropyl)-μ,! , see'-! '-dibenzothiacarbocyanine hydroxide triethylamine salt C-/C-λ-J C-Reference H (t)U, 1t9 (JU(JNH EX-/(U.S. Patent No. 3.r, 7ri!) Written in EX-
2 (coupler described in U.S. Pat. No. 3,7114.31rJ) EX-j (coupler described in U.S. Pat. No. 1 fi, /31,211) H-/ Continuous for obtained sample II/-/10 After exposure to red light using a wedge at 5 ooo lux for 17 ioo seconds, the following processing was performed.

jr'c 1 color development ・・・・・・・・・ 3 minutes!
Second 2 Bleaching ・・・・・・・・・ 6 minutes 30
Wash with water for 3 seconds ・・・・・・・・・ 3 minutes!
Second 4 Fixation ・・・・・・・・・・・・ 1 minute 20
Second 5 Wash with water ・・・・・・・・・ 3 minutes 12
Second 6 Stable ・・・・・・・・・・・・ 1 minute oz
The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrotriacetate Sodium sulfite -0oy Sodium carbonate
30・at potassium bromide
1. ≠2-hydroxyclamine sulfate
2.4A Tada-(N-ethyl-N-β-hydroxyethylamino)-comethyl-aniline sulfate ≠8 2 Add water /1 Bleach solution Ammonium bromide /40. Of ammonia water (2♂chi) 2! , 0.1 ethylenediamine-tetraacetic acid sodium iron salt /J (7f glacial acetic acid
l≠ Add water resistance
/1 Fixer Sodium Tetrapolyphosphate 2. Ofsodium sulfite φ,oy ammonium thiosulfate (70ti) /7! , Od Sodium bisulfite ≠, 4f Add water
/1 stabilized formalin r, oMz Add water /l.

The density of the developed film was measured through red and green filters. The results for sample 10/ are shown in FIG.

Here, ΔD (G) is defined as shown in equation (1), and the values of this ΔD (c) are calculated for several exposure doses for each of Samples 10/-110. All in one place.

Here, D (G) represents the optical density through a green filter at a certain exposure amount.

In the case without colored coupler (sample 10/),
The magenta density also increases imagewise with respect to the cyan density, but this is considerably alleviated when the colored couplers EX-/l or EX-co are added (sample ioco or 103).

When adding tx colored coupler EX-J (sample t
In oe), the low exposure area is overly masked, whereas the high exposure area is insufficiently masked.

All of these are non-uniform masking,
This cannot be said to be at a satisfactory level from the viewpoint of uniform color correction, which is currently required.

On the other hand, when the coupler of the present invention was used as a colored coupler (sample Ioz 5-tio>, a substantially uniform mask was obtained, and it is clear that the colored coupler of the present invention is superior. .

Example 2 The samples ioλ~tot obtained in Example 1 were subjected to the same exposure and processing as in Example 1, and then a color image fastness test was conducted on these processed samples. Table 3 shows the decrease in the density of the cyan image (a) when each sample was stored in the dark for 3 days in an atmosphere with no humidity control.

Table 3 As is clear from Table 3, the colored coupler of the present invention (
1) or (5) (sample IQ! or 1o
t) shows extremely excellent color image preservation.

Example 3 As a sample, a multilayer color photosensitive material 3 consisting of each layer having the composition shown below was prepared on a cellulose triacetate film support.
0/ was produced.

1st layer: antihalation layer black colloidal silver 0,11
197m2 Ultraviolet absorber Q-/ ・・・・・・ 0,
1697m” UV absorber Q-co ・・・・・・ 0,
Gelatin layer λ layer containing 779/m2: Intermediate layer compound H-/ 0
, 1197m" silver iodobromide emulsion (silver iodide 7 molt, average grain size 0.07μ) Silver coating amount (same below) o, gelatin layer containing izy7m2 3rd layer: 1st red-sensitive emulsion layer silver iodobromide Emulsion ・・・・・・・・・・・・・・・ 0.
729/m2 (6 moles of silver iodide, average grain size O9!
μ) Sensitizing dye I-a...7.0x1 per mole of silver
0 mol Sensitizing dye ■-a...+2.0xlO per 1 mol of silver
Molar sensitizing dye [1-a...Co, ♂ x 10 per mole of silver
Molar sensitizing dye ■-a...2.0 yen, 10 per mole of silver
Mol coupler Q-3・・・・・・・・・・・・O0 Hiroof
/m2 Kazolar Q-≠ ・・・・・・・・・・・・ 0
, 0/97m" coupler Q-1...
・・・・ Gelatin layer containing ``O0O Hirof/m'' Third layer: Second red-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・ l,
f/1n2 (silver iodide 10 moles, average grain size/
jμ) Sensitizing dye 1-a...2x per mole of silver
10 mol sensitizing dye [-a...1.6X10 per mol of silver
Molar sensitizing dye [[-a... co, 1xio per mole of silver
-<molar sensitizing dye 1t/-a...silver 1-! for nil/, t
XI0 Molar coupler Q-A ・・・・・・・・・・・・ o, 2
Jf/m” coupler Q-≠ ・・・・・・・・・・・・
0.0/f/m2 coupler Q-z ・・・・・・・・・
... Gelatin layer containing o, oay7m2! Layer: Third red-sensitive emulsion layer Silver iodobromide emulsion 2.
Ou9/m2 (silver iodide 10 moles, average grain size/,
rμ) Sensitizing dye 1-a...z, rX per mol of silver
io molar sensitizing dye fJ-a...for 1 mole of silver/, jX/
0 mol sensitizing dye [1-a... per mole of silver, 2X10
Molar sensitizing dye ■-a.../ per mole of silver, tXI
O mole coupler Q-J ・・・・・・・・・・・・ 0.1
0f/m2 coupler Q-7・・・・・・・・・・・・
Gelatin layer containing 0,0♂y 7 m2 6th layer: Intermediate layer Gelatin layer containing compound H-10,0λt 7 m2 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・ 0,
1197m2 (silver iodide t morch, average grain size O0μ
μ) Sensitizing dye v-a...3 per mole of silver, rXi
o molar sensitizing dye M-a...j for 1 mol of silver, Ox/
0 Molar coupler Q-r ・・・・・・・・・・・・ 0,2
ri2/m2 coupler Q-ta ・・・・・・・・・・・・
O1O Hirof/m ”Coupler Q-to...
... O0O≠y 7 m2 coupler Q-Hiroshi ...
... Gelatin layer containing old -0,0/'f/m'' Second layer: Second green-sensitive emulsion layer Silver iodobromide emulsion ...... /,
O17m2 (silver iodide 10 moles, average grain size 1.2
μ) Sensitizing dye V-a...Co, 7 yen per mole of silver
10 mol sensitizing dye ■-a...2 per 1 mol of silver, I x 70
Molar coupler Q-1/ ・・・・・・・・・ O0O≠y
7m 2 coupler Q-μ ・・・・・・・・・ 0.
00λ2/m2 coupler Q-/2 - ・-・-0,0
/f/m2 coupler Q-to -...-o, oorf
Gelatin layer containing 7 m2 Second layer: Third green-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・／,
117 m” (10 moles of silver iodide, average grain size 7.1
rμ) Sensitizing dye 'J-a...J per mole of silver,
OX/ 0 Sensitizing dye ■-a...2 for 7 moles of silver, ≠×lO mole coupler Q-// 0.0Jf
/m2 coupler Q-10=----0,00117m2
Gelatin layer containing IO layer: yellow filter layer yellow colloidal silver ・・・・・・・・・・・・ 0.0≠
f/m2 coupler -Q-ta ・・・・・・・・・・・・
0, / Of / m2 compound) (-/ ・
・・・・・・・・・・・・・・・ 0.20f! Gelatin layer 1/layer containing /m2; First blue-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・ 0.
J cof/m2 (iodide scissors 3 molti, average particle size 0.j
μ) Coupler Q-/3 ・・・・・・・・・ 0,4
197m2 coupler Q-Hiro ・・・・・・・・・・・・
Gelatin layer containing 0,0397 m2 12th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・ O,
Cotata/m” (silver iodide 10 moles, average grain size o, rμ) Coupler Q-/3 ・・・・・・・・・O
Gelatin layer containing 1λ2f/m2 Thirteenth layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion 0.
7m2 (silver iodide/≠mole, average grain size/
, rμ) Sensitizing dye■・・・・・・・・・J for 1 mole of silver,,! ×10 Molar coupler Q-/j −−−−・−・・−0,/'? ?
Gelatin layer containing /m2 1st ≠ layer: 1st protective layer ultraviolet absorber Q-/ 0.2097m
”Ultraviolet absorber Q-2...OoriOf/
Gelatin layer 1st containing m 2! Layer: λth layer polymethyl methacrylate particles (diameter 1.tμ)...
... 0, Oj f / yys 2 In addition to the above composition, a gelatin hardening agent Q-/Hiroshi and a surfactant were added to each gelatin layer. The sample prepared as described above was designated as sample 30/.

The compounds used to prepare the samples are shown below.

Q-/ 1-C4H.

Q-j t-C, HI3 Q-Hiroshit H3 Q-! (Coupler described in U.S. Patent No. 1I, /31..2jr) t C3H1゜Q-ii α Q-tcoα Q-/φ (CH=CH802CH2CONHCH2+2H Sensitizing dye I-a Sensitizing dye 11-a Sensitizing Dye 111-a (CH2) 3803Na Sensitizing dye ■-a Sensitizing dye V-a Sensitizing dye 'S/ia-a Sensitizing dye ■-a The couplers in the red-sensitive emulsion layer of Sample 30/ are as shown in Table 3. Samples t-JO2 to JO6 were prepared in exactly the same manner as Sample J (7/) except that the sample was changed to t-JO2 to JO6.

In the table below, a change in coupler means a molar replacement.

Structure of couplers used other than the above couplers (t) C5H
1□ Q-/6 (coupler described in U.S. Pat. No. μ, 00≠, Takota) Q-/r (coupler described in U.S. Pat. No. 3,03≠, No. 272) Obtained samples 30/-306 Perform wedge exposure and perform the color development process shown below.

■Pre-bath λ7±/10 seconds ■Backing removal, 7~1. , seconds and spray washing■ Color development ≠/, /+0. i J minute ■
Stop 27-31 3117 Excerpt ■Water Wash 2
7-31130 seconds ■ Bleach Jr + I j minutes ■ Washing with water 27-31 / minutes ■ Fixing j I + / minutes ■ Washing with water
27-31. 2 minutes [phase] Stable 27-31
The formulation of the treatment liquid used in each 10 second treatment step is as follows.

Prescription of each treatment liquid 27 ~ JJ' 0 (Water 100111
1. Sand (10 hydrated salt) 20. Of Sodium Sulfate (Anhydrous) 100F Sodium Hydroxide / Add Of Water
/, 001p)l (core °C)
Ta・452 /-j lr oCtDwaterr
! Oxl Kodak Anti Calcium A 2
, 0 ml sodium sulfite (anhydrous) 2.
Of Eastman Anti-Fog Shop PO, 2 Co. 1 Sodium Bromide (Anhydrous) /, 20f Sodium Carbonate (Anhydrous) 25.69 Sodium Bicarbonate 2.71F Amidoethyl)-m-) Luijin Hiroshi, 01 Add Water / . 00 (1pH (core °C)
10. ．． 2゜λl~31r11C water 90ON17, oN sulfuric acid
j Add Oml water
1,001pH (,27'C)
o, yj 2-14 J e'CO water 900ral potassium ferricyanide ≠ o, op sodium bromide (anhydrous) 2! , Add water
/, 001pH (27'C)
t・020～31 @Co water
700gl Kodak Anti Calcium≠
J, Ogl! Ammonium thiothiosulfate solution
/r! tl sodium sulfite (anhydrous) 10,
09 Sodium bisulfite (anhydrous > r, ≠ 2 with water /, 001 pH (27
°C) 4. Octopus/-V core °C water t, ool Kodak Stabilizer Additive 0. /4L Att Formalin (37, J-Chi solution) /,jOytlAlso, instead of step (1) in the development process (A), bleaching was accelerated at 276C for 30 seconds using the following bleaching acceleration bath (step ■'), use the following persulfuric acid bleach bath instead of step ■! Development processing CB) was carried out in the same manner as development processing (A), except that the film was whitened at 7°C for 3 minutes (referred to as step 2').

water 20
01112 Sodium bisulfite (anhydrous) 10. Of
Glacial acetic acid 2z, o*1 Sodium acetate io, oyEDTA-pN
ao, 7fPBA-/
! ,! ? add water
7.01pH (27°C) J,
r+0.2 (PBA-/represents 2-dimethylaminoethylisothiourea λ hydrochloride,,) xta ~3t'CC ice water r 00
ml gelatin O,! ? Sodium persulfate! 3.0? Sodium chloride /j, Of sodium phosphate (anhydrous), Ov phosphoric acid (rt)
2. add water
/, 04pH (27'C) 2
．． 3+0.2 The results obtained are shown in Table 1.

Screen DB: Density in development process B at the exposure amount that gives the density of /, j by development process A.

From the results shown in Table ≠, it was found that the sample according to the present invention showed little decrease in the density of the cyan image even when subjected to bleaching treatment with weak oxidizing power.

(Effects of the Invention) As described above, the objects of the present invention can be achieved by using the colored coupler represented by the general formula (1) of the present invention in a silver halide color photographic light-sensitive material. That is, the colored coupler of the present invention has appropriate coupling activity and can perform uniform masking.

The colored coupler of the present invention has a long wavelength absorption λmax without using a water-soluble dye, and has an excellent color correction effect. Among the colored couplers of the present invention, when a coupler core within a particularly preferable range is used, the solidity of the cyan image is excellent. Stable cyan image density can be obtained even when processed with a tired bleaching solution. These excellent performances are obtained by having -C-X and X2 substituents in general formula (I). Furthermore, the colored coupler of the present invention has a wide selection range of Cp, X□, X2, and the like, and the coupling rate can be appropriately adjusted according to the selection. This also means that the colored couplers of the present invention can be used in combination with various cyan coloring main couplers.

[Brief explanation of drawings]

FIG. 1 relates to a test method for investigating the masking effect, and shows characteristic curves measured by passing a developed film through red and green filters.几 and G are the characteristic curves with red and green filters, respectively, and Dmin (white) and D (G) are the characteristic curves G.
The lowest density and other exposure values are shown. Patent applicant Fuji Photo Film Co., Ltd.
.

Claims (1)

[Scope of Claims] A silver halide color photographic material containing at least one colored coupler represented by the following general formula. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, Cp represents a cyan coupler residue, and X_1 is -
Represents R_1, -OR_1, -SR_2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and X_2 is -OR_4, -
SR_4 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R represents a substituent that can be substituted on the benzene ring, and n
represents an integer from 0 to 3. where R_1 and R_
4 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, R_2 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R_3 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. group, -COR_6 or -SO_2R_6, R_5
is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -COR
＿7, -SO_2R_7, Represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, R_6 and R_7 have the same meaning as R_2, and R_8 and R_
9 represents the same meaning as R_1. However, when n is plural, R may be the same or different, or may be bonded to each other to form a ring. Further, R and X_1 or R and X_2 may be combined to form a ring. Also, R_1 and R_3, R_4 and R_5
, or R_8 and R_9 may be bonded to each other to form a ring.