JPS59178460A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain good colorabilty by incorporating a coupler which is a magenta coloring coupler and has a hydroxyphenyl sulfonyl group or hydroxyphenyl sulfoxy group in its molecule in a titled material. CONSTITUTION:A coupler which is the magenta coupler expressed by the formula and has at least one hydroxyphenyl sulfonyl group or hydroxyphenyl sulfoxy group in its molecule is incorporated in a photosensitive material. Said hydroxypheny sulfonyl group or hydroxyphenyl sulfoxy group is incorporated in at least one of A1 and A2 of the formula. If such coupler is used, a substantially satisfactory coloring density is obtd. without using an org. solvent such as benzyl alcohol or the like as a coloring accelerator and the various troubles with the use of the org. solvent for accelerating coloration are prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming color photographic images, and more particularly to a method for forming color photographic images.
The present invention relates to a method of forming photographic images using a color image-forming coupler.

To form color photographic images based on the subtractive color method, silver halide grains of exposed photographic emulsions are generally reduced using aromatic-grade amine compounds, particularly N,N-di-substituted panphenylenediamine compounds, as a developing agent. A process is utilized in which the oxidation products of the developing agent that are simultaneously produced react with the coupler to provide cyan, magenta, and yellow dye images.

The coupler at the end of the above color development method has a phenolic hydroxyl group, an aniline amino group, or an active methylene group, and oxidatively couples with an aromatic-grade amine developer to form a dye that absorbs light in the visible wavelength range. I'll pay for the compounding fee you give me.

The magenta color image shares the absorption of green light in the wavelength range of about SOO to AOOnm. As a magenta coupler,
j-silazolono, cyanoacetyl, coumaron, indanone, pyrazolobenzimidazole, pyrazolo [3, -2
-c ] -] s-triazole or imidazo [l, x
t)] pyrazole, pyrazolo ('+' b) '+2 shown in the applicant's patent application Fi(A) + applicant; Fuji Photo Film Co., Ltd. dated March 77, 1939;
≠-triazole skeletons have been proposed.

On the other hand, the development of groups that leave the coupling active position of couplers during dye formation, so-called two-equivalent leaving groups, has progressed, and various leaving groups have been proposed. Representative known documents are listed below.

U.S. Patent No. 3,227. j! ≠No. 3,006.7!
No. ri, s, 3ii, ≠ No. 76, 4A.

No. 237.217, same reference, 120.1170, same reference
, 2ai, ttr issue, same a, 3io, tty issue, same≠,
30/, No. 233, Around, 2AI! , No. 723, 4
(, 3rd/', J'27, Special Publication Showa 5i-i.

No. 100, Japanese Patent Publication No. 33-311OA+, etc., ie, groups connected by halogen atoms, sulfur atoms, groups connected by oxygen atoms, groups connected by nitrogen atoms, etc.

The 2-equivalent magenta coupler with these radicals introduced is:
Not only is it useful from the point of view of saving resources by reducing the amount of silver halide in the photosensitive material and the amount of coupler used, but the photosensitive material using the 2-equivalent magenta power puller has less fluctuation in photographic properties due to changes in the pa of the processing solution. It is also useful in terms of

However, magenta couplers with these leaving groups generally have a lot of fog, are unstable and decompose during storage, have low color density, and have poor image fastness. However, I still can't say it's enough.

Among these leaving groups, nitrogen atom leaving groups have generally reached the point where the coupler itself is stable and the color density is satisfactory, but in recent years high-temperature rapid processing, which has become popular, high development speeds are required. Because of this demand, color development has become particularly important. Therefore, insufficient color development is a serious problem.

In order to compensate for this insufficient color development, in some cases, an organic solvent such as benzyl alcohol is added to the developer as a color development promoter. However, these organic solvents for promoting color development have several drawbacks. For example, (2) during the development process, it is absorbed into the emulsion layer, so the amount in the developer decreases, resulting in a decrease in color development.

■ It is carried into the bleach or bleach-fix solution, inhibiting desilvering and reducing dye density.

■ Remains in photosensitive materials after processing and reduces color image fastness.

■ B, O, and D of the wastewater mixed into the treated wastewater.

It causes an increase in C, O, and D.

It is highly desirable to remove or reduce the amount of organic solvents used to promote color development.

As a result of research, the present inventors have discovered that couplers represented by the general formula σ) having at least one hydroxyphenylsulfonyl group or hydroxyphenylsulfoxy group in the molecule, and at least one of these couplers By silver halide color photographic material containing
It has been found that the above objectives are achieved.

A and A2 may be the same or different, and each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a carnoζmoyl group, and a sulfamoyl group. , represents an alkoxycarbonyl group, an aryloxycarbonyl group, and A1 and A
Both 2 are never hydrogen atoms. Alternatively, A1 and A2 may be bonded to each other to form a j-membered or 6-membered ring together with a nitrogen atom. this! The membered or 6-membered ring may further be fused with a benzene ring/heterocycle.

Among the uninvented couplers, preferred are general formula (n),
(It is made in ml.

General formula (II) 1 General formula tm+ 81 "2 0 represents a ring group, R2 represents an acylamino group, anilino group, or ureido group, and R3 represents a hydrogen atom, a halogen atom, a cyan group, an alkyl group, an alkyl group, v-ru;!4 Hetero u, alkoxy group, acylamino group, sulfonamido group, alkoxycarbonylamino group, ureido group, alkylamino group, anilino group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group or alkylthio group can also be P , Q may be taken together to form a phenyl ring.

Was.

To explain in more detail, A1% A2 may be the same or different, and each represents a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 2λ carbon atoms, such as a methyl group,
Ethyl group, butyl group, octyl group,! - ebulhexyl group, halogen atom, water group, cyan group, aryl group, carbonyl group, alkoxy group, aryloxy group,
Acylamino group, sulfonamide group, imide group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arifrethio group, alkylsulfonyl group,
Arylsulfonyl group, carbamoyl group, Su/l/7
7 molar group, alkyloxy-carbonylamino group, aryloxycarbonylamino group, ureido group, acyl group, alkyl group substituted with an alkylamino group or arylamino group, etc.), aryl group (preferably carbon number 6 to 32 aryl groups, such as phenyl groups, naphthyl groups, and the optionally substituted aryl groups mentioned above for the alkyl groups, to heterocyclic groups (for example, 2-pyridyl groups,
λ-quinolyl group, cobenzothiazolyl group, cofuryl group, copyrimidinyl group, etc.), acyl group (e.g. acetyl group, butanoyl group, hetesanoyl group, trifluoroacetyl group, hetafluorobutanoyl group, benzoyl group) , naphthonyl group, pentafluorocarbonyl group, pentachlorophenyl group, 2-7 carbonyl group, 2-quinolinecarbonyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, hexanesulfonyl group, benzenesulfonyl group, naphthalenesulfonyl group) , and the optionally substituted alkali/sulfonyl group, arylsulfonyl group, etc. mentioned above for the alkyl group) carbamoyl group (e.g. N-methylcarbamoyl group, N-dodecylcarbamoyl group, N,N-diethylcarbamoyl group, N -phenylcarbamoyl group, and N-alkylcarbamoyl group which may be substituted with the substituents mentioned above for the alkyl group, N,N-dialkylcarbamoyl'M, N-7lylcarbamoyl group, NlN-diarylcarbamoyl group, ), sulfamoyl group (e.g., N-methylsulfamoyl group, N, -n-octylsulfamoyl group, N
-Phenylsulfamoyl group, N,N-diethylsulfamoyl group, and the substituents mentioned above for the alkyl group. , N-arylsulfamoyl group, N,N-diarylsulfamoyl L, etc.), alkoxycarbonyl group (e.g., t,
Methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, 2-ethylhexyloxy7
carbonyl group, alkoxycarbonyl group which may be substituted with the substituent mentioned above for the alkyl group, etc.)
, and both A and A2 are never hydrogen atoms.

In addition, for a j-membered or 6-membered ring formed with a nitrogen atom by bonding 80 and A2 to each other, for example, an aromatic heterocyclic group containing a nitrogen atom and constituting a 6π or l0rc dragon system (for example, /-pyrrolyl group, l-imidazolyl group,
l-pyrazolyl group, l(' + 2+ gate riazolyl group), /-(/.

λ, 3-triazolyl group), /-(1,2,3゜hiro-tetrazolyl group), /-(l, 2,3.j-tetrazolyl group), l-indolyl group, 2-isoindolyl group, l-
benzimidazolyl group, /-benzo) IJ thiazolyl group and the above aromatic heterocyclic group ((, halogen atom, cyano group, nitro group, alkyl group, aryl group, carbonyl group, alkoxy group, aryloxy group, acylamino group, sulfone Amide group, imide group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group,
Substituted with an arylthio group, an alkyl-sulfonyl group, an arylsulfonyl group, a carbamoyl group, a sulfamoylated group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a ureido group, an acyl group, an alkylamino group, or an arylamino group. aromatic heterocyclic groups, etc.), saturated or unsaturated heterocyclic groups that do not form an aromatic ring that combines nitrogen atoms (for example, /-pyrrolidinyl group, l-piperidinyl group, N-morpholinyl i, N
-(/, 2,3.IA-tetrahydroquinolyl group, l-
pyrrolinyl group, l-imidazolinyl group, /-pyrazolidinyl group, suinindonyl group, /-indolinyl group,
and a heterocyclic group which may be substituted with the substituent mentioned above for the aromatic heterocyclic group on the above saturated or unsaturated heterocyclic group, etc., a cyclic imide group (for example, N-succinimide group, N-phthalimide group, /-N-hydantoinyl group, 3-N-2,≠~dioxooxazolidinyl group, ≠-N-urazolyl group, etc., and the above-mentioned imide group, the aromatic heterocycle imido group which may be substituted with the substituents mentioned above), 2-, N-/, / -dioquino-3-(,2H)-oxo-/, cobenzisothiazolyl group (saccharin), Co-N-/, /-dioxo-3-(,2H)-ox7-/, 2-benzisothiazolyl group, 〇-, which may have a substituent as described above for the aromatic heterocyclic group 1 or -N-, and R3 and R4 are hydrogen atoms and may have a substituent as described above for the aromatic heterocyclic group. Also R3. R4 may form a condensed ring (for example, preferable groups include 2(/H)-pyridone group, 7thaladion group, etc.) and or co, and R3 and R4 are hydrogen atoms or the above aromatic heterocyclic group. By the way, it may have the substituents mentioned above. Also R3. R4 may form a fused ring.

For example, preferred groups include λ-okine-/-pyrrolidinyl group, co-oxo-7-piperidinyl group, etc.), and these A1. The substituent of A2 may include a hydroxyphenylsulfonyl group or a hydroxyphenylsulfoxy group.

R1 is an alkyl group (preferably an argyl group having 1 to 32 carbon atoms, such as a methyl group, a benzyl group, a dodecyl group, a beta-cyanomotyl group, etc.), an aryl group (preferably an argyl group having 1 to 32 carbon atoms), The aryl group represents a phenyl group or a naphthyl group, and may be substituted with a halogen atom, an alkyl group, an alkoxy group, a cyano group, an acylamino group, a sulfonamido group, or an alkoxycarbonyl group, such as x, a, g-A-dichlorophenyl group, λ,
! , -cyclohirohiro-methoxyphenyl group, 2. A-cyclo-t-methylphenyl group, 2-chloro-≠.

1, -dimethylphenyl group, λ, z-dichlorophenyl group, etc.), heterocyclic group (heterocyclic group having 1 to 32 carbon atoms, such as copyridinyl group, λ-pyrimidyl group, λ-
/, 3. (j-) riazinyl group, 2-benzooxacylyl group, 2-benzothiazolyl group, etc.), and hydroxytubonylsulfonyl iti may be combined with a hydroxyphenylsulfoxy group as a substituent of R1. R
2 is an acylamino group (e.g., acetamido group, benzamide group, (J-n-pentadecylphenoxy)acetamide group, 3-[α-(2, Hiroji-tert-amylphenoxy)butyramide]benzamide, etc.), 3-[α-
(4L-Hydroxy-3-1-butylphenoxy)dodecanamide]benzamide, etc.] still has a ureido group (
For example, N-methylureido group, N-dodecylureido group, N.

N-dioctylureido group, phenylureido group, N-
(3-[α~(2,4L-di-te'rt-amylphenoxy)butylamido]phenyl)ureido group, etc.), and the substituent of these R2 is a hydroxyphenylsulfonyl group or a hydroxyphenylsulfoxy group. You can. R3 is a hydrogen atom, a halogen atom (for example,
Chlorine atom, bromine atom, @), cyan group, alkyl group (e.g. methyl group, propyl group, hexadecyl group, 3-(
3-pentadecylphenoxy)propyl l,j-(λ,
I/-di-tert-amylphenoxy)propyl group,
λ-[α-(j-tert-butyl-v-hydroxyphenoxy)tetradecanamidoethyl) group, )rifluoromethyl group, etc.), aryl group (e.g., phenyl group,
α- or β-naphthyl group, goomethylphenyl group,
, 2, s-dichlorophenyl group, Ku[α-(2,
4L-di-tert-amylfe/'xy)butyramide] phenyl group, etc.), heterocyclic groups (e.g., 2-pyridyl group, 2-chenyl group, coquinolyl group, etc.), alkoxy groups (e.g., methoxy group, propyl group, etc.) Oxy group, dodecyloxy group, 2-dodecyloxyethyl group, benzyloxy7 group, ge, 4t, gu, 3..3, 2, 2-
(beptafluorobutyloxy, etc.), acylamino groups (e.g., acetamido group, benzamide group, 3-(3
-pentadecylphenoxy)butyramide group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, octane sulfonamide group,
gumethylinzenesulfonamide group, '4), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonyl d(nylamino group, etc.), ureido group (e.g., N-methylureido group,
N-phenylureido group, N,N-dibutylureido group, N-(3-[α-(,!,4/--di-tert-amylphenoxy)butyramido]phenyl)ureido group, etc.), alkylamino group ( For example, methylamine thread,
diethylamine group, n-dodecylamino u, %), anilino group (e.g., phenylamino group, cochroro!
-Tetradecanamide fer;.

Ruamino group, a-(α-(3-tert-butyl-≠-
(hydroxyphenoxy)tetradecane atado]anilino group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, dodecyloxycarbonyl group, etc.)
, carbamoyl group (e.g. N-methylcarbamoyl group, N-phenylcar/rmoyl group, etc.), sulfamoyl group (e.g. N-methylsulfamoyl group, N,
N-dimethylsulfamoyl group, N-methyl-N-dodecylsulfamoyl group, etc.) or alkylthio group (e.g. methylthio group, hexylthio group, dodecylthio group, etc.), and these R3 substituents are hydroxy It may also refer to a phenylsulfonyl group or a hydroxyphenylsulfoxy group.

Also, the above A, A2. At least one of R□, R2, and R3 contains a hydroxyphenylsulfonyl group or a hydroxyphenylsulfoxy group.

l ≠ l j / t 7 767- l ♂ ■ O CF2CF2CF3 1 ri 0 , 2G H H 0 CF2CF2CF3 ti -〇〇 insult Senmachi Kabu 2- can be synthesized by a known method, that is, U.S. Patent No. 11,211/ , No. 161, II, 237.2
No. 77, same≠, 220, ψ70, Intermediate.

07t, No. 533, same φ, o4Lo, r3z, same≠
, 30/, No. 236, Tokuko Shoj4-Sansan, Hiroshi No. 22,
Tokukai Akira! /-3. Ko3ko issue and Tokukai Sho! ? −≠20≠
It can be synthesized by a combination of the methods described in No.

Synthesis Example 1 Synthesis of coupler 1 Already known intermediate, 1-(co,≠,A-1)chlorophenyl)-3-(co-chloro-12-tro-a-2)-
≠-(3,!-dimethyl-l, 2゜≠-triazole-l
-yl)-s-oxo-2-pyrazoline, 53 g under a nitrogen stream, acetic acid! θOml.

It was suspended in water and heated on a steam bath. next! 0
Gradually add reduced iron from Step 9, and wait 20 minutes after addition. The mixture was stirred vigorously at 00 to 100 s'C. The reaction solution, which had become homogeneous and had lost its yellow color due to nitro groups, was rapidly cooled with water, and ion sodium acetate was added thereto.

After stirring for 1 hour at room temperature, the already known acid chloride, α-[
After gradually adding 9 drops of ≠-(≠-benzyloxyphenylsulfonyl)phenoxy]dodecanoyl chloride, J-,4I, the reaction solution was heated to ≠θ°~5o0C, and 1
Stir for hours. Then /, jl ethyl acetate and joorn
1 of water was added to the reaction solution, and after stirring well, the insoluble matter was filtered through Cegiite base. The p solution was washed with dilute aqueous hydrochloric acid solution and saturated saline in that order, and anhydrous sodium sulfate was added and dried. The solvent was removed. 7. Dissolve the residual oil solution in Ksooml's tetrahydrochloride without purification. After adding 10% palladium-carbon of Jll, in autoclave ≠θ°~
Hydrogenation was carried out for 6 hours at Hiro's 'C. After the reaction was completed, the catalyst was removed and the solvent was distilled off under reduced pressure.

The residual oil solution was purified with a silica gel column to obtain the target product 13ji as a powder. The elemental analysis values agreed with the theoretical values.

Synthesis Example 2 Synthesis of Coupler 2 Already known intermediate, /-(,2,≠,monotrichlorophenyl)-J-(α-[Hiro-(≠-indyloxyphenylsulfonyl)phenoxycotetradecanamide)
703 g of benzamide-φ-promo-oxocopyrazoline and 279 to 200 g of pyrazole were suspended in sulfolane, and the mixture was heated and stirred at an internal temperature of t0 to rz0c under a nitrogen stream.

After heating and stirring for μ hours, ethyl acetate (21) was gradually added while cooling. Next, the ethyl acetate solution was thoroughly washed with water, and anhydrous sodium sulfate was added to dry it.

After removing the solvent, the residue is purified by column to obtain the desired intermediate,
/-(2,φ, monotrichlorophenyl)-3-(α-
(4-(II-penzyloxyphenylsulfonyl)
phenoxycotetradecanamide)benzamide-4<
-(/-pyrazolyl)-! -Oquine-2-pyrazoline was obtained as a tip. This was hydrogenated and debenzylated in the same manner as in Synthesis Example 1 to obtain the desired coupler as a powder.

The elemental analysis values agreed with the theoretical values.

Next, a more detailed explanation will be given with reference to examples.

Example-1 The coupler +1)/l' of the present invention was replaced with dibutyl phthalate/
Sodium dodecylbenzenesulfonate was dissolved in jmJ and 10-ethyl acetate with heating. /gtttr/θ%
The mixture was mixed with 100 rnl of an aqueous gelatin solution and stirred and mixed using a homogenizer rotating at high speed at jOoC to obtain a coupler emulsified dispersion. This dispersion and chlorinated silver emulsion/J2fl(
A 2% aqueous solution lj- of λ-hydroxy-4Z, 4-dichloro-5-triazine Na salt and a 5% aqueous solution Aml of saponin were processed, and a silver amount of 19 Sample A was prepared by applying a gelatin protective layer with a dry film thickness of /μ on top. Samples B to F were prepared in the same manner as Sample A, as shown in Table 1, except that the molar amount of coupler applied and the amount of silver applied were adjusted to be the same as Sample A.

Samples AF were subjected to stepwise exposure for sensitometry, and then subjected to the following development treatment.

Process Temperature Time Development color development
3r0C 3 minutes water washing #1 minute bleach-fixing I 1 minute 30 seconds water washing 31r 0C 1 minute color developing solution composition was as follows.

Cp-/benzyl alcohol -diethylene glycol-
Development Crude μmAmino-3-methyl-N-N-niga-N-β-hydroxyethylaniso-sulfate 3.19 Sodium sulfite 2f1 Hydroxylamine sulfur 8m 39 Charcoal string Potassium
! Add 0fi water
/1 Ri I-I (Moshi ni j) / 0, 2CD
-2C1) -J -/jml -lr ml -l ≠-amino-3-methyl-N-ethyl
-N-β (methanesulfonamide) ethylaniline sulfate zg sg cog -29 3fl 3f130fi
309/l
/1 10, J / 0, λ The white fixer composition is as follows: Ethylenediamine-Hiroshi-6ff-λ-sodium salt 2,9 Ethylenediamine-≠-acetic acid 32 iron salt ≠o! ? Add sodium sulfite 3g ammonium thiotioate 709 water
/! pH, g, tVc adjustment Measure the transmitted light density of each sample obtained in this way,
Table 1 shows the results of determining the maximum degree of elasticity Dmax and γ.

From this result, Sample A contains the uninvented coupler.

Both B and C exhibit good color development, but comparative samples E and F have small Dmax and γ, indicating low color development.

In particular, CD-,2, which contains a common relatively active color developing agent.
Comparing CD-j and CD-j, the comparison sample shows a significant decrease in color development with CD-2, which does not contain benzyl alcohol, while the sample of the present invention has CD-co,! :The difference in CD-3 is small.<(It can be seen that the color is sufficiently developed even without dil alcohol.

Next, the amount of the coupler used in the color sensitive material of the present invention and the components other than the coupler of the present invention used in the color sensitive material of the present invention will be described.

There is no particular restriction on the amount of uninvented Kab 2- and other couplers used, but silver 1 in the silver halide emulsion layer.
For mole, 2X/θ-3 mol to j×l0-1 mol,
In particular, it is preferably 1xlO-2 mol to jxio'' mol.

The coupler can be introduced into the silver halide emulsion layer by a known method, such as the method described in US Patent No. 3λλ, No. 027. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl heptathalate, etc.), phosphoric acid esters (ginenyl phosphate,
trinoenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl laurylamide), fatty acids esters (e.g. dibutoxyethyl succinate),
Trimesic acid esters, etc., or boiling point of about 30 to ty
o0c organic solvents, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl fropionate,
Secondary butyl alcohol, methyl isobutyl ketone, β-
After being dissolved in ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

As the yellow coloring coupler, known open-chain ketomethylene couplers can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is disclosed in U.S. Patent 2. Za7ta, No. 057, 3, u
A! ;+'! ; θ6, 3゜Hiro OK, 19ψ, 3,331.133, J,! ;12.322
No. 3.723.072, No. 3. Zari l, μ Hiroj No., West German Patent/, J Hiro 7゜g6g, West German Application Publication 2, 2
/ri, No. 717, same λ, 2ru/, 3.1. / issue, same 2.
Hiroshi/≠, No. 006, British Patent/, 4A2J, O'20, Special Publication No. Sho si51-7O7, Japanese Patent Publication No. Sho 11772613
No.3, same ψg-731≠7, same J/-/, 02t3
No., yo-1g≠1, 30-/233 Hiro 2,
Same 30-/30. Hiroshi≠No.2, same! /-2/za, No. 27,
Same so-gVAjO, same j2-, 2≠2hiro, same 3
2-//1219, etc.

As magenta light color couplers, pyrazolone compounds,
Interzolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are advantageous. Specific examples of magenta color-forming couplers that can be used include U.S. Pat.
No. r, 3,042. A53, 3. /Core, 2t No. 3, 3//.

No. 41.7, 3. ≠l ri, 3ri 1, 3.51, ≠λ ri, 3,331, 3/ri, 3゜jεko,
3 Coco No. 3, 1. /J,! 1O1s No. 3, 1
311-, RiOza No. 31za5'/, ≠Hiroj No., West German Patent/, I10. ll-4'1, West German patent application (
OL8) 2. IAoza, No. 66j, same λ, ≠17°24! J issue, same 2. IAII, YjY No. 2. Hiroλμ
, ≠ No. 67, Special Public Akihiro 0-AOj/No., Special Public Akihiro! ;l-
No. 20f2A, “J2-!Zari, No. 22, μter/
2ri! No. 13Ir, No. 4'5'-71AO27, No. 3
0-/j'F331. Same issue! 2-Hiroko/, No. 21, No. 9-7u021, No. Q-1.0.233, No. 3
These are those described in No. 1-261ψ, No. 13-4312λ, etc.

A phenol compound, a naphthol compound, etc. can be used as the cyan-almost color cazoler. The specific sequence is U.S. Pat.
No. 272, 2. Gua≠, Kota No. 3, Same 2. j co/, rior number, same, zari j.

No. 121, 3,0311. r9.2, 3,311
, Gua wo issue, same 3,113g, 31! No. 3゜da 74
, No. 163, 3. jza 3,27/issue, 3.39/,
No. 313, same J, 7t7. Hiro1 No. 1, same p, oo≠, riλri No., West German patent application (OLS) λ, gl≠, ? No. 30, same λ, ≠! Hiroshi, No. 322, JP-A-1-49131
No. j/-21,0344, No. &f-jOjjt, No. j/-/174121, No. 3.2-&ri62, λ-ta. It is described in No. 232.

Colored couplers include, for example, U.S. Patent J,
Hiro7 & , jtl, No. 0, same, :z, tai, ri□j
No. 3.03≠, ♂ri No. 2, Tokko Akira≠Hiroshi-2014, No. JJ'-22, 3J! No. 4A2-1/JO4c
No., Intermediate≠-3,2 Hiro J/No., Tokukaisho! 1-2tθ31
/- issue details lips, same! Those described in Koμ, 2i2i, West German Patent Application (OLS) J, ≠it, 52 can be used.

As a DIR coupler, for example, U.S. Pat.
7.16≠No., J, l, /7. ．． 2ri No. 7, same 3.7
No. 01.713, No. 3,720,3g, No. J, A
32.3jAj issue, Wi Germany% Permission MA (OLS)
Ko, 4L/4t, θot, same J, 4tJ'+, jo1
No. 4'j4', No. 322, British Patent No. 33. ≠
! ≠ issue, JP-A-52-62t2 ≠ issue, intermediary turf 223
Letters listed in No. 3j and Special Publication Shoj/-/A/No. 3 can be used.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases all of the development inhibitor during development; for example, as described in US Pat. No. 3.2, 7. See≠! No. 3, J 79
, J 25', West German% Permit a (OLS) λ
, g/7. ri l≠ issue, JP-A-12-/j27/ issue, same j
Those described in No. '3-ta/It can be used.

Two or more of the above couplers can be contained in the same layer.

The same compound may be contained in two or more different layers.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an aryl group (e.g., those described in U.S. Pat. No. 3,333.7), Hiro-thiacylidone compounds (e.g., U.S. Pat. , 3.3j.

tr1), benzophenone compounds (e.g., those described in JP-A No. 6-27111), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3.7-03.103)
No. J, 707, J7j No. 1c), butadiene compounds (for example, US Pat.

O≠j, those described in No.
(described in item j) can be used. Furthermore, U.S. Patent No. 3.4L Tata, 7A, No. 2, JP-A-Sho 54A-arsJ
Those described in No. s 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 ultraviolet absorbers may be mordanted in specific layers.

The photographic emulsion used in the present invention is P, C1afkide.
Written by Chimie et Physique Photo
ogrsphique (published by Paul Monte1,
/ri 1967), GJ'.

Photographic Emuls by Duffin
ion Chemistry (The Focal P
ress (S/ri 1966), V, L, Zeli
Making and Co by kman et al.
ating Photographic Emulsio
n (Published by The Focal Press, lit≠
It can be adjusted using the method described in 2010). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof.

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

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

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

Two or more types of silver halide emulsions formed separately may be mixed and used.

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

Gelatin is advantageously used as a binder or retention colloid in photographic emulsions, but other hydrophilic colloids can also be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, and 8Ci.

Enzyme-treated gelatin as described in Phot, Japan, A/A, PJO (/ri A4) may be used, and gelatin hydrolysates and enzymatically decomposed products may be used in the photographic emulsion used in the present invention. Antifoggants and various compounds can be added during the manufacturing process, storage, or photographic processing of photosensitive materials. Namely, azoles such as benzothiazolium salts, nitroimidazole, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazole ψ, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-mercaptotetrazole)
mercaptopyrimidines: mercaptotriazine collection; thioketo compounds such as oxadolinthione; azaindenes, such as triazaindene,
Tetraazaindene A (especially ≠-hydroxy substituted (/
, J, Ja, 7) Tetraazaindene @), pentaazaindene; known as antifoggants or stabilizers such as benzenethiosulfonic acid, henzenesulfonic acid, benzenesulfonic acid amide, etc. In addition, many compounds can be added. For example, US Patent 3. Rijl
, No. 4'74', 3. r2. Rihiro No. 7, Tokuko Shoj
Those described in λ-, zt, and tto issues can be used.

For the purpose of increasing sensitivity, increasing contrast, or promoting development, the photographic emulsion layer of the uninvented photographic light-sensitive material contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomol 7-oliys, and class ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic emulsions used in the invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex melonanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nucleus, etc.; Nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benz Oxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, nandothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoli/nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -one nucleus, thiohydantoin nucleus, cochoxazolidine-2
．． J-A member heteroartic ring nuclei such as Hiro-dione nucleus, thiazolidine-2,≠-dione nucleus, rhodanine nucleus, and thiobarbyl acid group can be applied.

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

Along with the sensitizing dye, the emulsion may contain a dye which itself does not have a sensitizing effect or a substance which does not absorb visible light in a negative manner and exhibits supersensitization.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. 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.

In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These may be water-soluble,
A water-insoluble brightener may also be used in the form of a dispersion.

When carrying out the invention, the following known anti-fading agents can be used in combination, and the color image stabilizers used in the invention can be used alone or in combination of two or more. Known anti-fading agents include, for example, US Pat.

1.13, λ, A7j, 3/g, 70i,
iri No. 7, 2,701/-, 7/3, λ.

721, tjY No. 2,732,300, λ,
733.7 Aj No. x, 'yio, roi No. 2.
Hydroquinone derivatives described in R/L, No. 021, British Patent I, 3t3゜ri No. 21, etc., US Patent No. 3. ≠j7
．． No. 07, 3.0 tons.

Gallic acid derivatives described in US Pat. No. 262, etc., US Patent No. 2.
73! , No. 761, 3, ! ,'? r, 90
No. 9, Special Public Sho ≠ Tar No. 20277, 12-At, 23
p-alkoxyphenols described in US Pat. No. 3. ≠No. 32,300, 3, 173.

oro issue, 3,57≠, 627, 3,7t≠, 3
No. 37, JP-A No. 32-33633, same taco/4'7
Gu3≠ issue, same! p- described in r2-132223
Oxyphenol derivatives, U.S. Pat. No. 3,700, μ
j! There are bisphenols listed in this issue.

The photosensitive material made using the present invention may contain, as a color antifoggant, a hydroquinone derivative, an amine phenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc., specific examples of which are disclosed in the U.S. Pat. Su, 3AO, 2
No. 0, No. 2, 33t.

3.27, same 2. ≠03,7 No.1, same No.2. ≠lf,
l, /3 issue, same 2, t7j, 3/IA issue, same 2゜7
01, / No. 7, No. 2.70≠, No. 713, No. 2.72
1, Atri No., No. 73.2,300, No. 2.7
3ta, 71. j number, JP-A-Sho j0-tack rt number, same jO
-Ta λri tri, same evening θ-ta 3ri 2g, same! 0-/1
No. 0337, same! 2-/≠No. 623j, special public show 1O-2
It is described in the specification of No. 31r13.

The invention is also applicable to multilayer, multicolor photographic materials that accommodate at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but other combinations may be used in some cases. .

For photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. Further, the processing temperature is usually selected between /J0C and jθ0C, but may be lower than /Ir'c or higher than zooc. Depending on the purpose,
Development processing to form a silver image (black and white photographic processing), or
Any color photographic process consisting of a development process to form a dye image can be applied.

Color developers generally consist of an alkaline water bath containing a color developing agent. The main color development system is a known primary aromatic amine developer, such as phenylenediamines (Kuriehiro-amino-N, N-diethylaniline, 3-methyl-≠
-amino-N, N-diethylaniline, j-amino-N
-ethyl-N-β-human “”xyethylaniline, 3-
Methyl-7-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-≠-amino-N-ethyl-N-β-methanesulfamide ethylaniline, μmamino-3-methyl-N-ethyl-N -β-methoxyethylaniline, etc.) can be used.

In addition, Photo-gr by L, F, A, Mason
apbic Processing Chemistry
try (For, published by al Press, 1st year A6)
PcojA~22, U.S. Patent λ, lli3. ois issue,
Same 2゜r'? J,, 3tQ issue, % Kaisho*r-641! Those described in RI No. 33 may also be used.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors such as bromides, iodides, and anticapri agents; You can use preventive agents etc. Also, if necessary, water softeners, preservatives such as hydroxylamine,
Containers such as benzyl alcohol and diethylene glycol
development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as l-phenyl-3-pyrazolidone, viscosity imparting agents. agent, US patent≠.

Polycarboxylic acid-based chelating agent described in θ13.723, West German Publication (OLS), z, g2. It may also contain antioxidants as described in No. z and SO.

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

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleaching agent, iron (m),
Compounds of polyvalent metals such as cobalt (■), chromium (■), and hook (II), peracids, quinones, and 2)n compounds are used. For example, Felina: / compound, dichromium mortar, iron (m) -! or copal) (m), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,! ,3
-Aminopolycarboxylic acids such as diamino-2-propatoltetraacetic acid or complex salts of monoacid such as citric acid, tartaric acid, malic acid; persulfates, permanganates; nitronephenol, etc. can be used.

Of these, Felician Northern 18 ethylenediaminetetraacetate + TII) sodium and ethylenediaminetetraacetate iron (TII) ammonium are particularly useful.

Ethylenediaminetetraacetic acid iron (m) complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fixing. Furthermore, the bleach-fixing solution includes U.S. Pat. Nickel silver accelerators described in λda/, No. 744, Tokuko Sho PS-TSOT No., Tokko Akihiro J-Rza 3 No. 3, etc., Tokuko Sho J
In addition to the thiol compounds described in No. t3-6373λ, various additives can also be added.

Procedural amendment (side) July 27, 1920, Mr. Commissioner of the Japan Patent Office 1, Indication of the case, Showa SR, Patent Application No. j≠7≠3
No. 2, Name of the invention)・Silver halogenide color photographic light-sensitive material 3, Relationship with the person making the amendment Case 1 Patent applicant Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 4; Date of amendment order: Showa SR (Month to Day) 5, Subject of amendment: Specification 6, Contents of amendment: Engraving of the specification (no change in content)

Claims (1)

[Scope of Claims] A halogenated coupler containing a magenta color-forming coupler represented by the following general formula (I) and having at least 7 hydroxyphenylsulfonyl groups or 7 hydroxyphenylsulfokyl groups in the molecule: Silver color photo W
& original material. Represents a group bonded to position 1, Ao and A2 may be the same or different, and each represents a hydrogen atom, an alkyl group, an aryl group, a Peter group, an acyl group, a sulfonyl group, a carbamoyl group, a sulciamoyl group, and an alkoxy group. It represents a carbonyl group or an aryloxycarbonyl group, and A1 and A2 are not both hydrogen atoms. Furthermore, A□ and A2 may be bonded to each other to form a j-negative or t-membered ring with the nitrogen atom. This j negative or 6-membered ring may further be fused with a benzene ring or a heterocycle. C+)up represents a magenta image-forming coupler.