JPS6319654A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an improved sharpness by incorporating a prescribed amount of a plane plate like silver halide emulsion to the titled material, and also by incorporating one kind of the compd. capable of cleaving a developing controller by reacting a compd. cleaved after reacting with the oxidant of an developing agent, with the oxidant of an another 1mol of the developing agent, to the titled material. CONSTITUTION:The plane-like silver halide emulsion in which at least 50% the total project area of the silver halide emulsion powder is the mean aspect ratio of >=(5:1), is incorporated to the titled emulsion. The titled material contains at least one kind of the compd. capable of cleaving the developing controller by reacting the compd. cleaved after reacting it with the oxidant of the developing agent, with the oxidant of the another one molecule of the developing agent. Said plane like silver halide powder has a particle diameter having >=5 times the thickness of the powder, and the diameter of said powder is 0.2-20mu, preferably, 0.3-10.0mu. The usable plane like silver halide powder is exemplified by preferably, a silver iodobromide contg. <=15mol% silver bromide and silver iodide respectively or a silver chloroiodobromide having <=50mol% silver chloride and <=2mol% silver iodide, and silver chlorobromide. Thus, the titled material having improved image quality and stability of the processing solution is obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and in particular, a silver halide color photograph for photographing which has excellent sharpness and granularity and excellent brown color reproducibility. It relates to photosensitive materials.

f) Prior Art) In recent years, silver halide photosensitive materials, especially photographic photosensitive materials, have become highly sensitive, such as ultra-high sensitivity photosensitive materials typified by ISO/400 films and /10. There is a growing demand for a photosensitive material that has high image quality and high sharpness that can be used even with large magnification magnifications suitable for cameras with small formats such as disks.

The main technology to meet these demands is to use tabular silver halide grains whose diameter-to-thickness ratio (C, ct ratio) is greater than tnia (for example, as disclosed in JP-A-Sho! I). -//Jri No. 341) is known.

However, when tabular silver halide grains are used.

It became clear that the glabellar effect, which is important for improving image quality, decreased and nine-color reproduction deteriorated. In order to overcome this drawback, the use of a compound that releases a diffusible development inhibitor in conjunction with the tabular silver halide grains has been proposed in JP-A-Sho! Tar 1
It was proposed in 2RITA No. 2 and J/-14TTSZ.

However, these methods are still insufficient in improving color reproducibility.

Furthermore, it has become clear that although the use of tabular silver halide grains improves the sharpness in the high frequency range, there is a problem in that the sharpness in the low frequency range deteriorates significantly.

On the other hand, compounds similar to the compounds of the present invention are % Kaisho AO-
/1! ? jO, No. 77-//1136, etc., but the use of these compounds alone was not sufficient to improve the sharpness.

(Object of the Invention) The object of the present invention is, firstly, to provide a photosensitive material with excellent sharpness, and thirdly, to provide a photosensitive material with improved color reproducibility. An object of the present invention is to provide a photosensitive material with high sensitivity and excellent graininess.

(Structure of the Invention) These objects of the present invention are to provide a silver halide photographic material having a silver halide emulsion layer on a support. θ is the average aspect ratio! = At least one of the compounds that contains a tabular halogenated emulsion of 7 or more and that cleaves after the reaction with the oxidized developing agent reacts with another molecule of the oxidized developing agent. This is achieved by a silver halogenide color photographic light-sensitive material characterized by containing seeds.

The compound cleaved after the reaction with the oxidized developing agent of the present invention reacts with another molecule of the oxidized developing agent, resulting in the formation of:
The compound that inhibits cleavage is represented by the general formula [1].

1'-j'' formula (1) % formula % In the formula, A(1) represents a group that reacts with the oxidized developing agent to release T' Generates a phenomenon suppressant through a reaction with the portraited body,
(Represents.

Among the compounds represented by the general formula (+1), preferred compounds are represented by the following general formula (n).

General formula (11) A(]j+) vI3 (L 2 ) W l)
1 out of 1 formula.・＼）Small development crude drug V Reaction with infertility storage V Koyori (1 Tsukasa 1v-r-1-(L 2-) 1.-1) T
cleave and represent -, Ii) jj Q from A,
<After a B (L 21 w I) ' Represents the cleavage of the former t-A-(Ll)v yo IJ (2) represents J (7) which cleaves, Ll represents 8 (8 which cleaves DI after being cleaved from B, DJ represents present (elephant suppression cutting), and (2) and ~ (2) represent O or /.

The compound represented by the general formula (11) is present (Illustration 4 to 1)
The reaction process to release 1 is shown in the following equation 100)
Fusane, Ru.

A-(L]')v-B(L2)WDTj2fL+)
-n-(L21w-T)T -B-(L2)1. -DT
In the formula, A, Ll, B, L2. DI, v and W represent the same meaning as explained in the general formula (■), and To
represents the 1st phantom main medicine corrected form.

In the above reaction formula, (L2)1 from B-(L2)w”
．． -The reactions that produce DI characterize the most significant effects of the present invention. That is, this reaction is To and B (L2), v-
1) It is a secondary reaction with T. In other words, the reaction rate depends on the concentration of each. Therefore, where TO occurs in many machines, B-(L2) -DI is (L2)
Generate two-DI immediately. In contrast, in places where only 1 TO occurs, B-(L2)w-D
I slowly produces (L2)w-1)T. Such a reaction process, in combination with the above reaction process, effectively exhibits the action of DI.

Next, the compound represented by the general formula (Ill) will be explained in detail.

In general formula (11), A specifically represents a coupler residue or a redox group.

When A represents a coupler residue, known ones can be used. For example, yellow coupler residues (e.g. open chain ketomethylene type coupler residues), magenta coupler residues (e.g. yo-pyrazolone type, pyrazoloimidazole type, pyrazolotriazole type coupler groups), cyan coupler residues (e.g. phenol type coupler residues), , naphthol type, etc.), and colorless coupler shallow parts (e.g., indanone type, acetophenone type, etc. coupler residues) or U.S. Pat. Examples include coupler residues described in 7j No. 7j, 7j Q, /7/, 7j No. 3, 1, 22 O, and 23 Da.

When A represents an oxidation-reduction group, the following general formula (l
it).

General formula (1) A, -P-(X=Y). -Q-A2 In the formula, P and Q are each independently an oxygen atom or jL
Represents an unsubstituted or unsubstituted imino group, and at least /+ of X and Y of n1 is -(Ll) -B+L2)
1. -1') represents methine J, (with T as a substituent, in which X and Y represent substituted or unsubstituted methine groups or nitrogen atoms, n
represents an integer from / to 3, and represents n+fl's X, n! I
Y in IA represents the same or different things A1
and A2 each represent a hydrogen atom or a group that can be removed by an alkali. Here P%X.

Any two substituents of Y, Q%A, and A2 are 2u
It also includes the case where they are linked as ifi & to form a cyclic structure. For example (x=y). forms a benzene ring, a pyridine ring, etc.

The group represented by L2 in general formula (II) may or may not be used in the present invention. It is selected as appropriate depending on the purpose. Examples of the groups represented by Ll and L2 include the following known linking groups.

(1) Ant that uses +11 hemiacetal cleavage reaction.

For example, U.S. Pat.
It is a group represented by the following general formula and is described in the 1μ/μr number and the same 1.0-2tI/μr data number. Here, the red seal represents the left side vc bond - 1θ in general formula (1), and the 10 mark represents the position of the position bonded to the right jjllll in general formula (1). R1 and R1 represent a hydrogen atom or a substituent, tii/ or -2, and when 1 is co, two R;

and R2 may be the same or different (t
Also included is a case where one of %R1%R2 and R3 is linked to form a cyclic structure.

Specifically, the following groups may be mentioned.

Rice-0CR-4-+ 10-3CH2-10-
10 -5CH-44+-〇CH-Mirai 4- S CH-
Half-baked (2) Intramolecular nucleophilicity (1 reaction is used to cause a cleavage reaction.

For example, the tie bang and LI% described in 1911 US Patent No. ψ, 211-♂, 762 can be mentioned. It can be expressed by the following general formula.

ms -N u -L i n k -E-Future
(T-1) In the formula, the red stamp is 11 on the left in general formula (1).
+1 Represents the position where VC is bonded, and the American red stamp is the general formula (1
), Nu represents a nucleophilic group, such as an oxygen atom or a sulfur atom, and E represents an electrophilic group that undergoes nucleophilic attack from Nu to form a bond with the half-liquid. It is a cleavable group, and Link represents a connecting group that sterically associates Nu and E so that they can undergo an intramolecular nucleophilic reaction.

Specific examples of the group represented by (T--2) are as follows.

O2 to 02
COOC4H9020H3 Rice-〇 Rice-8COOC)
13 +-0 to N02C (3) A group that causes an opening reaction using a reaction along a conjugated system.

For example, IZI U.S. Pat. No. 323 or 1
．． It is a group described in μ-7, rvj and represented by the following general formula.

IR2 In the formula, red seal, rice red seal, R1, R2 and t are (T-/)
Same meaning as explained above 1 Represents vermilion. Specifically, the following groups may be mentioned.

N02 COOCH3cooc41 (9 - wood 〇 rice - 〇cooH5
O2CI13t? 2 (,1) Noiri that utilizes the cleavage reaction caused by the removal of water from the ester.

For example, in West German Publication↑〒Revision No. 2, 4jA, No. 315, there is a concatenation J, % with 8self, l.(), and the following groups are mentioned.

In the formula, the red stamp and the one-point stamp have the same meaning as explained for (T-/).

In general formula (I, the section represented by B is A-
(Ll), a group that becomes a coupler after further cleavage or A-
It is a group that becomes a redox group after being cleaved from (L+)v. For example, in the case of a phenol type coupler, the group serving as a coupler is a group that is bonded to A-(Ls)v at an oxygen atom other than a hydrogen atom of a hydroxyl group. In the case of a yo-pyrazolone type coupler, it is bonded to A(L+)v at an oxygen atom obtained by removing a hydrogen atom from a hydroxyl group of the tautomerized type of yo-hydrocypyrazole. In these examples, A(Ll)v
Yo Q g Ecstasy 7 First time using a phenolic coupler or! −
Pyran°ron 7 (2 couplers) has (Ll)1.-DT at their coupling position.

When B represents a group serving as a redox group, it is preferably represented by the general formula (B-/).

General formula CB-/) Rice-1)-(X'=Y')n-q-A2 In the formula,
The red seal has the ti position that combines with A-(L,), A2, P%Q and n1i general formula (Illlv
The same sound as explained above, representing the ending, n1lJl
of Y′ and Y′ (both /d is (Ll) Yer DI
represents a methine group having as a substituent, and other Y'
and Y' represents a substituted or unsubstituted methine group or nitrogen atom. Here, any λ FUfl groups of A2, P%Q%
It also includes cases where it forms.

In the general formula CI, DI is specifically a tetrazolylthio group, a benzimidazolylthio group, a benzothiadiazolylthio group, a benzoxazolylthio group, an ininoζ riazolyl group, a penzoindazolyl group, a triazolylthio group,
Imidazolylthio group, thiadiazolylthio(, deoether lt-substituted triazolyl group (for example, U.S. Patent No. 4)
, J7, No. 114, etc., or oxadiazolyl, 1, etc., may have an appropriate substituent. Typical substituents include the following examples. In the example below, the total number of carbon atoms is preferably 20 or less. ...Rogen atom, aliphatic group, nitro group, acylamino group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, imide group, sulfonamide group, aliphatic oxy group, aromatic oxy group, aminoya, imino group, ano group, aromatic group, anluoquine group, sulfonyloquine group, aliphatic thio group, aromatic thio group, aromatic oxy/sulfonyl group, aliphatic oxine sulfonyl group, aliphatic oxinecarbonylamino group, aromatic Examples include group oxycarbonylamino groups, aliphatic carbonyl groups, 11 monocyclic carbonyl groups, heterocyclic carbonyl groups, sulfonyl groups, acyl groups, ranido groups, heterocyclic groups, hydroquinyl groups, etc. +

General formula (II)+, ノ~, “l s Bs ”
2 and DJ, the general formula (1
This application i1 also includes polymerization in which a bond is connected in addition to the bond represented by 1). The effect of the present invention can be obtained even if this second bond is not cut when τ is cut. Examples of such a bond are as follows.

The compound represented by the general formula (II) of the present invention also includes a polymeric platform. That is, the following general formula (P-1
) is a monomer compound 4''!F, and is a polymer having a repeating unit represented by the general formula (P-1), or an aromatic wrp/, post-amine gapping agent base.・
A small group (also known as 7) that does not have the ability to couple with χ
of ethylene J, % y, (3/, [is a copolymer with II). Here, the monomers are copolymerized simultaneously with 21 monomers and t't You can leave it there.

General formula (P-■) C) I 2=C+A 2・Hea 1A3Se 廿A, SuriQ
2'' General formula (P-co) +CH2-(,:su(A2←-→A3ner→A1-Q1) In the formula, R is a hydrogen atom, a lower alkyl having carbon number/-4Z, or a chlorine atom. The expression %A+ is -CONH-1-1
NHCOINH-1-NHCOO-1-COO-1-S
O2-1-CO-1-N l-I To C0-1-802 11-1-~5o2-1-OCO-1-OCONII
-1-S-1-Nll- or -〇-, A2 is -
c ON +-+- or -COO-, A3 is an empty group having 7 to 70 carbon atoms; a substituted or substituted alkylene group;
It represents an aralkylene group or -f1 or tA arylene group, and the alkylene group may be a straight chain or a branched chain.

(Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and denlumethylene; examples of aralkylene groups include benzylidene; examples of arylene groups include phenylene, naphthylene, etc.)Q) Well, Represents a compound residue represented by the general formula (1), and may be bonded to any one of A, LI, B, and L2.

1, C and k represent O or /; D, 1,'', t
, ; and k are never VCOs at one time.

Here, the alkylene group represented by A3 is acetoquine group 1 (or arylene group is aryl J,
”: I Mi (phenyl)) 4), nitroya, hydroxyl group, nano, sulfo group, alkoxy/% (171, for example, methquine group), aryloquine group (for example, 1 silicate, phenyl 7 group), anluoquine group (for example, acetoquine group) ), azilamino group (e.g. acetylamino group), sulfonamide') k (e.g. methanesulfona is a do group), sulfamoyl group (e.g. methylsulfamoyl j!), halogen atom (e.g. fluorine, chlorine, sodium bromine) , a carboxy group, a carbamoyl group (e.g., methylcarbamoyl group), an alkoxycarnyl group (e.g., methoxycarnyl group), and a sulfonyl group (e.g., methylsulfonyl group).There are two or more of these +# substituents. The times may be the same or different.

Next, non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic-rich amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid, and derivatives of these acrylic acids. Examples include esters or amides, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, and vinylpyridines. More than one kind of the non-chromic ethylene-like monomers used here can be used at the same time.

Next, more preferable ranges among the compounds of the present invention will be explained.

Preferred examples of A in general formula (1) or (It) IC are the following general formulas (Cp-/), (Cp-λ), (Cp
-J), (Cp-4'), (C,p-'-t), (Cp
-11, (Cp-7), (Cpr) or (Cp-ta)
This is when the coupler is shallow as expressed by . These couplers are preferred because of their high coupling speed.

General formula (Cp-/) General formula (Cp-2) General formula (Cp-J) General formula (Cp-4') General formula (C
p-j) General formula (Cp-6) General formula (Cp-7
) H General formula (Cp-1) General formula (Cp-ta) In the above formula, the free bond derived from the coupling stand represents the bonding position of the campling leaving group.

In the above formula, 1151 ・152% +153,
fls4 ・rt55 %R56% R57, nss
, +159 , R60, r (61, R62 or R
If 63 contains a diffusion-resistant group, it means that the total number of carbon atoms is! to tIO1 is preferably selected to be 10 to 30, and in cases other than U, the total number of carbon atoms is preferably /j or less.

Any of the above-mentioned substituents represents a divalent group at the 4-unit of a bis-type, telomer-type or polymer-type coupler, and connects a repeating unit or the like. In this case, the range of carbon numbers may be outside the specified range.

KR51 to f163, d and eVc will be explained in detail below. In the following, R41 represents an aliphatic group, an aromatic group, or a heterocyclic group, R42 represents an aromatic atom group or an atomous ring group, and R43, R44, and R45 represent a hydrogen atom, an aliphatic group, or an aromatic group. Hole or heterocycle7. (Represents.

It 51 has the same meaning as 1141. R
52 and +153 have the same meaning as R42 and =I respectively.
−) Ding.

R54 is the same as 1141, Ishiro C0N
- group, L3R43 rt43R44 144NGO- group or he=C- group. I(ss
represents a group having the same meaning as R41. R56 and 157
each has the same meaning as the R43 group, R4, S- group, R43
0-parrot, rt, +, COf'J- group, 1111N-
The group R43R43 R38 represents a group having the same meaning as 141. rt59
is a group with the same meaning as rt41, 114. C0N- group, ■ R43NS02N- group, R41〇- group, R4]S-8,
... rt44 R,, 5 Gen Ii child also i"l, rl 41N- group.

d represents O not t43 and 3. When d is plural, R59 of multiple 1 yen represents the same replacement waste or different replacements. Also, each R
59 may be linked together to form a ring structure. IyI of the 11′1IIi group to form a cyclic structure
I represents an integer of ¥43 to 1, and g represents an integer of 0 to -, respectively.

R6Q represents the base of R4, which has a Japanese meaning.

rt61 represents a group having the same meaning as R41. R62
is a group with the same meaning as T141, 114ICONH→,
1R45 R44R45 represents a rogen atom or an R41N- group. R63 represents a group having the same meaning as Tt41, an R430so 2- group, a halogen JToyo group, a nitro group, an ano group, or an R43C〇- group. e is 0 to μ
represents an integer. When there are multiple amounts of rL62 or R63, each represents the same or different thing.

In the above-mentioned dimension, aliphatic is an internal phase having carbon atoms of /~32, preferably /-2,2, or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic carbon. It is an elementary group. Typical 1γ groups include methyl group, ethyl group, propyl group, inopropyl group, butyl group, (1)-butyl group, (i)-butyl group, (t)-amyl group, hexyl group, /chlorohequinyl group. , coethylhequinyl group, octyl group, /, /, 3. J-Tetramethylbutyl group, decyl group, dodecyl group, hexypdenyl or octade/
Examples include ru groups.

The aromatic group has t-coO carbon atoms, preferably a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group.

A heterocyclic group is a heterocyclic group having 1 to 7 carbon atoms, preferably 7 to 7 carbon atoms, and the hetero atom selected from a nitrogen atom, an oxygen atom, or a sulfur atom, preferably a 3-membered or ! It is a heterocyclic group with substituted or unsubstituted ring members.

? 'A typical example of WA ring 1 & is 2-pyridyl koto,
t-pyridyl) l;, 2-chenyl group, 2-furyl group,
λ-imita "zolyl group, pyrazinyl group, i-pyrimidinyl) 1(, /-imidazolyl group, /-indolyl 11(
, phthalimide bracket, /, 3. ≠-Thiadiazoruko f Ruhr, 14. -<sonooxane-2-yl group, 2-quinolyl group, 1μm dioquine/, 3-imidazolidine-y-yl8, 224m dioquine-7,3
Examples include -imidazolidin-3-ylno-1(, succinimide group, phthalimide group, /, J, ≠-triazol-2-yl group or /-pyrazolyl group).

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include: rogene atom, R470- group, R46S- group.

Examples include n47 114 s n, 7oso2- group, cyano group or nitro group. Here, n46 represents an aliphatic group, aromatic group, or heterocyclic group, and R49 represents an aliphatic group, aromatic group, heterocyclic group, or hydrogen atom, respectively.Aliphatic group , aromatic or heterocyclic group have the same meanings as defined above.

Next, preferred ranges of rt51 to R63% d and e will be explained.

R51Vi aliphatic or aromatic groups are preferred.

It52, R53 and R55 are preferably aromatic groups. R54 is preferably an r(4,CONH- group, or an R4,- group. R56 and R57 is a t5 group,
410-group or rt41s- group is preferred. R58
is preferably an aliphatic group or an aromatic group. General formula (Cp-
In G), 1159 is preferably a chlorine atom, an aliphatic group or a T14, (?0NH- group. d is preferably 1 or 2. R60 is preferably an aromatic group. General formula (
R59tri1'(4,C0NN-
Groups are preferred. In the general formula (Cp-7), (1 is preferably /. R61 is preferably a fat, a radical, or an aromatic paper. In the general formula (Cp-J') vc, e is preferably Q or /. As R62 is 114, 0CONII- no shu, n41CONH-hei, or R41sO2~■-
These groups are preferably substituted in the j-position of the naphthol ring. As R63, R4, C0NH-containing (, r(
4l So 2NH- group, R41NSO2- group,
R4,5o2- group, 141-CO- group, nitro group or cyano group are preferred.

Next, typical examples of R51 to R63 will be explained.

R51 is tl)-butyl group, ψ-methoxyphenyl group, phenyl moiety, j-(λ-(2,Hiro-di-t-amylphenoquine)butanamido)phenyl)l,'I-octadecyloxyphenyl group, or Examples include methyl groups. R52 and R53 are fdj-chloro-j-dodecyloxycarbonylphenyl group 1,2-chloro-j
-hexadecylsulfonamidophenyl group, Cochrolow 1-tetradecanamidophenyl group, Cochrolow 5
-(4!-(co,q-di-t-amylphenoquine)butanamido)phenyl group, cochrolow 5-(-1(J,
u-di-t-amylphenoquine)butanamido) phenyl group, 2-methoxyphenyl group, cometquine-j-tetradecyloxylponylphenyl group, cochrolow-(/-ethoxycarbonylethquinecarbonyl)phenyl group, λ- Pyridyl group, λ-chloro monooctyloxycarbonylphenyl group, 2. II-dichlorophenyl X, u-/Florol-(l-dodecyloxylponylethoxyruzenyl)phenyl group, cochlorophenyl group or 2-ethoxyphenyl group are included.

As R54, 3-(ko(ko).

U-) -t-amylphenoquine)butanamido)benzamide group, 3-(≠-(2,q-di-monoamylphenoxy)butanamido)benzamide group, %1. l-chloro-j-tetradecanamide anilino group, j-(,2
, &-di-1-amylphenoxyacetamide) benzamide group, cochloro-g-(co(3-1-butyl-q-hydroquinphenoquine)tetradecanamide) Anilino, (,2,2-dimethylpropanimide 11(
, 2-(J--<ntadecylphenoquine)phthanamide, pyrrolidino group, or N,N-dibutylamino group. 1155 includes λ, μ, 4-trichlorophenyl, 1. Il, 2-chlorophenyl scraps, co.

j-dichlorophenyl group, 2.3-dichlorophenyl group, 2. A-dichloro-≠-methquin phenyl group, gu(2-(co,q-di-t-amylphenoquine)butanamide) phenyl group or 2. Otsu-shifu o o-II
-) l-thanesulfonylphenyl group is a preferred example. R56 is a methyl group, an ethyl group, an inpropyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a 3-phenylureido group, a 3-butylureido group,
or 3-(2,≠-di-t-amylphenoquine)propylno, r,. l”t57 is j
-(2, Hiro-di-1-amylphenoquine)propyl group,
3-(4'-1-2-1nige-(l-hydroxyphenylsulfonyl)phenoquincotetradecanamido)phenyl]propyl), r, , methoxy group, Etquin J,
I,, methylthio group, ethylthio group, methyl group, /-methyl-r-1r-octyl-oquinolj-(U-octyloxy-!;-(/, /, 3.3-tetramethylbutyl-l)phenyl Sulfonamido] phenylsulfonamido)ethyl M, j (II-(g-)"tecyloquinphenylsulfonamido)phenyl)propyl group, /,
/-dimethyl-2-(2-octyl-oquinojt-(/
, /, 3.3-tetramethylbutyl) phenylsulfonamido) ethyl group, or dodenruthio group. Rss Tehanochlorophenyl group, pentafluorophenyl group, heptafluoropropyl L/-(,!
.

q-di-1-amylphenoxy)propyl group, 3-(,
! , 44-di-t-amylphenoxy)propyl group, co-, l-di-1-amylmethyl group, or furyl group. rt59 includes a chloro atom, a methyl group, an ethyl group, a propyl group, a butyl group, an inpropyl-containing (,no(co,Il-di-t-amylphenoquine)butanamide group, and a no(co,tA-di-1-amylphenoquine) group. ) hexaneamide group, --(j, 4(-di-t-octylphenoxy)octaneamide group, 2-(nochlorophenoxy)tetradecanamide group, co9.2-dimethylpro-
ξn7mi)"M, -2-+ 4'-(≠-hydroquinphenylsulfonyl)phenoquine)tetradecanamide group, or 2-(no(2,guzi-t-amylphenoxyacetamido)phenoxy)butanamide group Examples of R60 include gucyanophenyl group, 2-cyanophenyl group, ≠-butylsulfonylphenyl group, μm
Propylsulfonylphenyl/L'M% 4'-x Toxycarbonylphenyl group, ≠-N,N-diethylsulfamoylphenyl group, 3,t-dichlorophenyl group or 3-methoxycarbonylphenyl group.

R61 is a dode/l group, hexadecyl group, cyclohexyl group, butyl group, 3-(2, Hiro-di-t-amylphenoquine)propyl group, Hiro-(29 μm 9 μm sheet t-
amylphenoquinyl group, 3-dodenruoquinebropyl group, notetradeneruoquine/phenyl group)5. , t-i thylg, 2-(,2-hexyldecyloxy)phenyl group,
No methoxy! Examples include -dodenyloxylponylphenyl group, 2-butquinphenyl group and /-naphthyl group.

R62 is an inbutyloxy/carbonylamino group,
Etquin carbonyl ξ group, phenylsulfonylamino group, methanesulfonamide group, butanesulfonamide x, <z-methylbenzenesulfonamide group, benzamide group, trifluoroacetamide group, 3-phenylureido group, butoxy7carponylamino group , or the acetamide group is removed. R63 is J, 44-di-t-amylphenoquine acetamide group,' (2,
"-di-t-amylphenoxy)butanamide group, hexade/rusulfonate ξdo group, N-methyl-he-octadecylsulfamoyl group, N-dioctylsulfamoyl group, dodecyloxine-rbo'nyl group, chloro atom , a furan atom, a nitro group, a n-ano group, a ~-3-(2,gudi-t-amylphenoxy)propylsulfamoyl group, a methanesulfonyl group, or a hexadenesulfonyl group.

Preferred clauses will be described below when A in the general formula (11) is represented by the general formula (Ill 1).

P) J and Q are substituted or absent! When representing the imino form of δ, it is preferably an imino group substituted with a sulfonyl group or an a/r group.

At this time, P and Q are expressed as follows.

General formula (N-/) General formula (N-2) here represents the bonding position with US-India Fi, A + straddling A2,
The Yoshi sign represents the position where it bonds with one of the free bonds in -(X=Y0-).

In the formula, the group represented by G is a linear or branched, chain or cyclic, saturated or unsubstituted, @-substituted or unsubstituted aliphatic 'IIM(+'' (e.g. methyl group, ethyl group, benzyl group, phenoxybutyl group, inpropyl group, etc.), C6-/Q substituted, habitual or unsubstituted aromatic groups (e.g. evaphenyl group, ≠-methylphenyl group, l -naphthyl group, heatdecyloxyphenyl group, etc.), or an 1- to 7-membered heterocyclic group selected from a nitrogen atom, sulfur atom, or oxygen atom (for example, -1-pyridyl group, l-phenyl-
U-imidazolyl group, nofuryl group, benzothenyl group, etc.) are preferred examples.

A! When A2 represents a group that can be removed by an alkali (hereinafter referred to as a precursor group), it is preferably a group that can be removed by hydrolysis such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxacyl group, or a sulfonyl group. U.S. Pat. No. U, OO.

A type of precursor group that utilizes the reverse Michael reaction described in No. 022, and a type that utilizes an anion generated after a ring cleavage reaction as an intramolecular nucleophilic group as described in U.S. Patent Nos. ψ, 3/θ, and 6/2. precursor group.

US Patent Hawk J, A74! , 4 (No. 7r, same J, 932
゜ago issue or 3. Polygonum 3,1. Precursor group in which the anion described in No. t/ issues transfers electrons through a conjugated system and thereby causes a cleavage reaction, US Patent ≠, 3341
．． 200, or US Pat. rruj, mμ, ulo, tie
Precursor groups using imidomethyl groups as described in No.

In general formula (III), preferably P represents an oxygen atom and A2 represents a hydrogen atom.

More preferably, in general formula (III), X and Y are methine groups with -(LI+IB+L29DT as fillers), except for the case where the other X and Y are substituted or unreplaced methine groups. It's time.

Among the groups represented by the general formula (III), particularly preferred are those represented by the following general formula (IV) or (V).
do.

General formula (1v) -A2 General formula (V) , -4゛i ~, A2 In the formula, the red stamp represents the bonding position of +L 1 + 78 + L 2), -DI, P = Q s A t and A2
represents the same meaning as explained in general formula (1), R represents a substituent, and q represents 0. Represents an integer from / to 3. When q is 2 or more, two or more R's may be the same or different (and two R's may be ++ on adjacent carbons)
When filled with T substituents, each becomes 2iTff+ groups, and when the cyclic meaning is lost, it also contains n-r.

At that time, it becomes a benzene condensed ring, for example, naphthalene,
Benzonorbornene 4 chroman, indole 1 negative, hung thiophenes, quinolines, benzofuran f, J
j, J-dihydrobenzofuran, kidney beans, or indene 1, which may further have 7 or more substituents. Examples of preferred substituents when these condensed rings have substituents, and preferred examples of R when R does not form a condensed ring are listed below. That is, fatty groups (e.g. methyl group, ethyl group, allyl group, benzyl group, dodenyl group),
fenoquinecarbonylphenyl group), halogen atom (e.g. chloro atom, bromo atom), alkoxy group (e.g. methquine group, hexadenluoquine group), alkylthio group (e.g. methylthio group, dodecylthio group, benzylthio, IF:), arylthio group (e.g. phenoxy group, hiro-(-octylphenoquine d, 2.IA-di-t-amylphenoquine group), arylthio group (e.g. phenylthio group, μm dodenruoquine phenylthio group), carbamoyl group (e.g. - Ethercarbamoyl group, ~-propylcarbamoyl 71''% hexadecyl group, ~-t-butylcarbamoyl group, N-J-(
j,4j-di-1-amylphenoquine)propylcarbamoyl group, hemethyl-he-octadecyl27/l/bamoyl group), alkoxycarbonyl group (e.g. methquinecarbonyl group, coneanoethquinecarbonyl group, ethquinecarbonyl group, Doden Luokin Force Lubonil 4, J
-(2,4L-di-t-amyldiphenol)propoquine carbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, kunonylphenoxycarbonyl group), sulfonyl group (e.g. evamethanesulfonyl group, benzenesulfonyl group) group, p-toluenesulfonyl group)
, sulfamoyl group (e.g. heprobil sulfamoyl group, N-methyl-he-octadesol sulfamoyl J
%, N-phenylsulfamoyl group, Heddensulfamoyl group), acylamino group (e.g. acetamido group, benzamide group, tetradecaneamide group, 4!-(
J, 4(-di-t-amylphenoquine)butanamide group, λ-(,2,4<-di-amylphenoxy)butanamide group, 2-(2,lI-di-t-amylphenoxy)tetradecanamide (group), sulfonate (for example, methanesulfonamide group, benzenesulfonamide group, hexade/rusulfonamide group), a/l group (for example, acetyl group, benzoyl group, myristoyl group)
lumitoyl group), nitrone group, alkoxy group (e.g. acetamido, benzoyloxy group, lauryloxy group), ureido group (e.g. 3-phenylureido Lj-(
≠-cyanophenyl group), nitro group, cyan group, atomcyclic group (heterocyclic group with tl- to t-membered ring selected from nitrogen atom, oxygen atom, or sulfur atom as hetero atom. For example, -furyl group, 2-pyridyl group, /-imidazolyl group, /-morpholino group), hydroquine group, carbonyl group, alkoxycarbonylamino group (e.g. methoxycarbonylamino group, phenoxy/carbonylamino group, dodefluoroquine carbonyl group) ), sulfo group, amine group, arylamino group (1>II: anilino group, ≠-methquinecarbonylanilino group, n-fatty amino group (e.g., N-diethylamino group, dodecylamino group), sulfinyl) ,'q f Examples: j-habenzenesulfinyl group, propylsulfinyl group), sulfamoylamino group (e.g. 3-phenylsulfamoyl group), thioanyl group (e.g. thiobenzoyl group)
, a thioureido group (e.g. 3-phenylthioureido group), a heterocyclic thio group (e.g. thiadiazolylthio8), an imide group (e.g. sufnonimide, phthalimide, octadecenylimide group) or a heterocyclic amino group (e.g. (μmm imidazolylamino group, l-pyridylamino group), etc.

When there is an aliphatic group in the partial structure of the above-mentioned dermatological group, the number of carbon atoms is 1 to 32, preferably /-20, chain or cyclic, linear or branched, saturated or unstructured, substituted or :S is an aliphatic group.

When there is an aromatic group moiety in the partial structure of the abbreviated group listed above, the number of carbon atoms is 6 to IO, preferably i, substituted or tQFH)? It is a phenyl group.

The general formula (11r: represented by B''''C in IIIC) is preferably represented by the general formula (T3-/).

In the general formula 1-/), P preferably represents an oxygen atom, and Q is preferably an oxygen atom or an atom. The red seal here is (X'-Y'). The red seal at the end represents the bond that connects with A2.

In the formula, G has the same meaning as explained in the general formulas (N-/) and (N-2).

Further, when the group represented by B in general formula (III) is represented by the following general formula (B--2) or (B-j), it is particularly preferable in view of the effects of the present invention.

General formula (B-j) Rice $ -A2 General formula (l3-J) In the Rice Jume style, Shinu represents the bond that connects with A- (Ll), -, and Rice Shuin represents - (L2). -DT represents a bond bonded to R, q, Q and A2 have the same meaning as explained in general formula (fV) or (V).

Preferred examples of R in general formulas (B-2) and (B--?-) include the following examples.

In the following example, the number of carbon atoms is preferably /j or less. fatty groups (e.g. methyl group, ethyl group), alkoxy^(
(e.g. methoxy group, ethoxy group), alkylthio f&
(e.g. methylthio group, ethylthio group), alkoxycarbonyl group (e.g. methoxycarbonyl group, propoquine carbonyl group), aryloxycarbonyl group (e.g. fenoquine carbonyl group), carbamoyl group (e.g. N-
propylcarbamoyl group, N-t-7'ylcarbamoyl group, N-ethylcarbamoyl group), sulfonamide group (e.g. methanesulfonamide group), acylamino group (
Examples include acetamido group), heterocyclic thio group (eg, tetrazolylthio group), hydroxyl group, or aromatic group.

A preferred example is when V and W are both O in general formula (U).

The group represented by A in general formula (II) is particularly preferably a coupler residue.

More preferred embodiments of the present invention N are described below.

Particularly preferred DT in general formula (II) is a compound that has development inhibiting properties when cleaved as DI,
It is a development inhibitor that has the property of decomposing (or changing) into chemical compounds that do not substantially affect photographic properties after flowing out into the color developing solution.

For example, U.S. Pat.
O-2/♂16≠ψ, same to-ko 2/, 7jO, same 40-233. OtsujO issue, or 6/-//, 717
Examples include development inhibitors described in No. 3, preferably those having the following general formulas (D-/), (D-2), (D-j), (D-
μ), (D-j), (1)-1), (D-7), (D
-fl, (D-ta), (I)-10) or (I)-/
/).

3-Y ■ t, 3-y 1'' Rice-He/N Moxibustion N Hehe In the formula, the red stamp represents the position where it is bonded to A+L 1) -B-(L2) two in general formula (II).

■ X represents a hydrogen atom or a substituent, dbal or co, LJ represents a group containing a chemical bond that is cleaved in the chemical solution, Y represents a group that exhibits a chemical bond that suppresses the chemical reaction, It is one group and represents an aliphatic group, an aromatic group, or a heterocyclic group.

The above ring 1-element suppression m11 reduction is A-(LJ)v-8-(L
2)1. - The development inhibitor that is more cleaved (diffuses through the photographic layer while showing an effect of suppressing color development, and partially flows out into the processing solution for color development. The development inhibitor that flows out into the processing solution is generally contained in the processing solution. Reacts with hydroxyl ions or hydroxylamine, etc., and rapidly decomposes (e.g., hydrolysis of ester bonds) in the chemical moiety contained in LJ, i.e., the group represented by Y is cleaved, resulting in highly water-soluble compounds. This results in a compound with low anti-elephant activity, and eventually the anti-inflammatory effect is substantially eliminated.

A preferred example of X is a hydrogen atom, but it may also represent a substituent (substituents include aliphatic groups (e.g. methyl group, ethyl group), acylamino groups (e.g. acetamido group, propionamide group), alkoxy groups ( For example, methoxy group,
Typical examples include a /S rogene atom (eg, chloro atom, bromo atom), a nitro group, or a sulfonamide group (eg, methanesulfonamide group).

The linking group represented by LJ contains a chemical bond that is cleaved in the reaction solution. Such chemical bonds include the examples listed in the table below. These are cleaved by nucleophilic reagents such as hydroquine ion or hydroxylamine, which are components in the color developer, respectively.

The chemical bonding mode shown in the above table is connected directly to the heterocyclic moiety constituting the development inhibitor or via an alkylene group or (and) a phenylene group, and directly connected to Y. When connecting via an alkylene group or a phenylene group, the two intervening groups may contain an ether bond, an amide bond, a carbonyl group, a thioether bond, a sulfone group, a sulfonamide bond, and a urea bond.

When Y represents an aliphatic group, it is a saturated or unsaturated, linear or branched, chain or cyclic, substituted or non-II-substituted hydrocarbon group having 1-coO1 carbon atoms, preferably /-10;
Particularly preferred is a hydrocarbon group having a substituent.

When Y represents an aromatic group, it is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

When Y represents a heterocyclic group, a V member containing a sulfur atom, an oxygen atom or a nitrogen atom as a heteroatom or! It is an atom ring group of @ ring.

Examples of the heterocycle include a pyridyl group, an imidazolyl group, a furyl group, a pyrazolyl group, an oxasilyl group, a thiazolyl group, a thiadiazolyl group, a triazolyl group, a diazolidinyl group, and a diazinyl crystal.

When the aliphatic hydrocarbon group, aromatic group, and heterocyclic group have a substituent, the substituent includes a rogone atom, a nitro group, an alkoxy group having 10 carbon atoms, and 6 to 10 carbon atoms.
7 arylox groups, an alkanesulfonyl group with a carbon number of /~IO, an arylsulfonyl group with a carbon number of A-10, an alkanamide group with a carbon number of l~IO, an anilino group, a benzamide group, an alkylcarbamoyl group with a carbon number of e21-7o,
Carbamoyl group, arylcarbamoyl group having 6 to 10 carbon atoms, alkylsulfonamide group having 7 to IO carbon atoms, arylsulfonamide group having 6 to 10 carbon atoms, 1 to 1 carbon atoms
IO alkylthio group, arylthio group having z to 10 carbon atoms, phthalimide group, succinimide group, imidazolyl group, /, 2. lI-triazolyl group, pyrazolyl group,
(nztriazolyl group, furyl group, benzthiazolyl group, alkylamino group with carbon number/~10, carbon number/~IO
Alkanoyl group, hanzoyl group, alkanoyloxy group having 1 to 10 carbon atoms, benzoyloxy group, carbon number 1-
j perfluoroalkyl group, cyano group, tetrazolyl group, hydroxy group, mercapto group, amino group, number of carbon atoms/
-10 sulfamoyl group, C6-10 arylsulfamoyl group, morpholino group, C-10 aryl group, pyrrolidinyl group, ureido group, urethane group,
Alkoxycarbonyl group having 7 to IQ carbon atoms, t to IQ carbon atoms
Examples include an aryloxycarbonyl group of IO, an imidazolidinyl group, and an alkylidene amino group having 1 to 10 carbon atoms.

(Compound Examples) Specific examples of the compounds of the present invention are listed below, but the invention is not limited thereto.

H (4') OH (ri2H5 (') OH (ri) CH2C○2CTh-, taat'-+vC2)45 C2H5 I-1 C2)1゜(''') .H SaH2CO□(ΣI (/ 6) OH station 2H5 te 2H5 (it) H 2H5 (,201 0H tsu4H9 (ko 3) "CH2C02CH2CO2C4H9 2H5 bu) 0 days (2t) 2H5 0 days 3 da) C02CH2C days 2CN (3t) (#/) To H )(COCH2CH2COOCH2CH2CNC3H
1, (t) (j4)
(sr) CH3 α ○C)13 (bl) (t3) C6HI3 (6ri) CO2C+8837 (7j) (7t) ()l) (7ri) (r+21 (rB) (rψ) (rri(r+) (171 (J (rB ′ri) (ri0) ZH5 (ri/) to = he (tada) (riri C2 day 5 (ri7) C2 day 5 ′==N, 1″ (10t) (#)71 (10r) ■ 2H5 (10ri) C2H5 OH (iti) N=A typical synthesis example is shown below, but other compounds can be synthesized in the same way.

Synthesis example (]) Synthesis of exemplified compound (1) It was synthesized using the following synthetic route.

OHOH OH OH OH Exemplary Compound (4') ■First Step (Synthesis of Compound 3) Compound No. 12.9. caustic potash/ri, and water io
ml was added to 7 ooml of toluene and heated under reflux for 7 hours under a nitrogen atmosphere, and the water was distilled off azeotropically with the toluene. 0ml of N,N-dimethylformamide was added to the residue, heated to 1000C, and 37g of the compound was added.

After reacting at 1000C for 1 hour, the mixture was cooled to room temperature, ethyl acetate was added thereto, and the mixture was transferred to a separating funnel and washed with water. The ethyl acetate layer was taken and the solvent 6 was distilled off under reduced pressure to obtain 53 g of an oily residue containing 3 as the main component.

■Second technique (synthesis of compound l) 3 obtained above! 3g of ethanol and 1 part of water
Dissolved in a mixed solvent with 20ml uog of monohypotassium hydroxide
added. The mixture was heated under reflux for μ hours, neutralized with hydrochloric acid, extracted with ethyl acetate and water, the ethyl acetate layer was taken, and the solvent was distilled off to obtain an oily residue G31 containing Da as the main component.

■Kasanko (synthesis of compound) Dissolve u3fl of ≠ obtained above in ethyl acetate JOOml,
t of hebutafluorobutanoic anhydride! Pi was added dropwise at room temperature. After 30 minutes of reaction, water was removed and the mixture was washed with water in a liquid separation oven. After removing the oil layer and distilling off the solvent, column chromatography was performed to isolate and purify the target product using the cross-section method. Nlicagel was used as a packing material, and chloroform containing 1% and 2% ethanol was used as an eluent. Hiro 7. ! 9 oily j was obtained.

■Second step (synthesis of combination)! r, tA7g, Chichigi, 31. ．． 3g and 10m acetic acid
1 was added to a mixed solvent of uoml of water and uomt of Improper Tools and heated under reflux for 7 hours. The hot mouth fluid was concentrated to about half. By taking the precipitated crystals,
4419 was obtained.

■Jth step (synthesis of compound 7) B, μ19 was added to 00ml of acetonitrile and heated under reflux. 2♂g of 2-(co,≠-di-t-amylphenoxy)butanoyl chloride was added dropwise.

After refluxing for 30 minutes, the mixture was cooled to room temperature, ethyl acetate was added, and the mixture was washed with water using a branched funnel. By removing the oil layer, distilling off the soot under reduced pressure, and recrystallizing it from acetonitrile, 7
I got it.

■The second step (combination of compound r 55.) 7. AO9 was added to dichloromethane jooml.

Boron tribromide, 3≠, cooled to −70°C.

sg was added dropwise. After simmering for 20 minutes at -z'C or lower, an aqueous solution of sodium carbonate was added until the aqueous layer became neutral. It was transferred to a separatory funnel and washed with water. The oil layer was taken and the solvent was distilled off under reduced pressure. The residue was re-crystallized from acetonitrile to obtain g of 4Zj, λ.

■Step 7 (Example [Synthesis of compound (1)) 2%
Add 2g of acetonitrile to acetonitrile (,2)
j'C), a solution containing /-phenyltetranyl-j-sulfenyl chloride λ0, -29'x in chloroform was added dropwise. Ethyl acetate was added and the mixture was transferred to a separatory funnel and washed with water. The oil layer was taken and the solvent was distilled off.

Recrystallized from a mixed solvent of hexane and ethyl acetate, 143
．． 3 g of exemplified r-H compound (1) was obtained.

Synthesis example (2) Synthesis of exemplified compound (, 2♂) Synthesis example (])
■ In the seventh step, l-phenyltetrazolyl-! −
Synthesis was carried out in the same manner as in Synthesis Example (]), except that 26.7 g of /-ethoxycarnymethquinecarbonylmethyl-y-sulfenyl chloride was used in place of sulfenyl chloride, 20°JJ. However, a mixed solvent of hexane and chloroform was used as the packing solvent.

Synthesis Example (3) Synthesis of Exemplary Compound (30) Synthesis was carried out by the following synthetic route.

0tl
0fI0H H H G H Example 1 Compound (30) ■First step (synthesis of compound 10) Ri (J, Am Chem Soc, It%aAO
(.

(Synthesized by the method described in /93)), /177
．． 7fi, potassium hydroxide, -μ, B and water ismt
was added to toluene/l and heated under reflux for 7 hours at 7IO. Water and toluene were distilled off azeotropically. Shallow 1 ml, N-dimethylformamide JOOml, 70 g, cuprous chloride 0
．． 3g was added and reacted at 1xo0c for t hours. After cooling to room temperature, 12 me of hydrochloric acid, water/jOml and sooml of methanol were added.

By sampling the precipitated crystals, IO was obtained.

■Second step (synthesis of compound l/) IO 31. 300ml of ethanol and 100ml of water
In addition to the mixed solvent of No. 1, nitrogen gas was passed through the mixture. 3/1 Ifj of potassium hydroxide was added to this solution, and the mixture was heated under reflux for 6 hours. The mixture was cooled to room temperature and neutralized by adding hydrochloric acid. Oml of ethyl acetate was added, and the mixture was transferred to a separating funnel and washed with water. The oil layer was separated and the solvent was distilled off under reduced pressure. Remainder/f (ψA, -2p
) was used in the next step for the entire image.

■Third step (synthesis of compound 12) 4tt and 2g of the compound l/l obtained in step ■ were added to ethyl acetate r
00ml. 177.Jg of hebutafluorobutanoic anhydride was added dropwise at room temperature. After reacting at that temperature for UO minutes, carbonic acid and IJum water were added to neutralize. The oil layer was collected using a separatory funnel and washed with water. The oil surface was separated, the solvent was distilled off under reduced pressure, and chloroform was added to the residue to precipitate crystals. By removing this and concentrating to zero liquid, compound 1
I2°39 of 2 was obtained. This was used in the next process of making money.

■No. 1 step (synthesis of compound/3) Compound/co obtained above '9s reduced iron j3
g, ammonium chloride 3g, acetic acid Jml isopro, o
It was added to a mixed 4 medium of 2rOrnl of alcohol and ≠Oml of water and heated at a high rate of flow for an hour. The filtrate was concentrated under reduced pressure while hot. When crystals precipitated, the concentration was stopped and the mixture was cooled and stretched. By dividing the precipitated crystals into zero, 4t! Compound 13 with r, 29 was obtained.

■Jth step (synthesis of compound/l) gt and xg of compound/3 are acetonitrile jOomlv
c Add 2?(2,≠-G-t-acylfenoquine)butanoyl chloride under heated stream. , 3I was added dropwise. 3
After reacting for 0 minutes under reflux, the mixture was cooled to room temperature, ethyl acetate was added, and the mixture was washed with water. The oil layer was separated and the solvent was distilled off under reduced pressure. The remaining liquid was recrystallized from ethyl acetate and n-hexane/q! , 4.7. I got p.

■6th step (synthesis of compound /!) /q! A.7. ! 7 is tetrahydro 7 run λ! Omg
, thionyl chloride≠2. ugy dripped. After reacting for 30 minutes -10
Cooled to 0C. Add propylamine to this solution, 67.7
9 was added dropwise while keeping the temperature below 00C. 30 minutes @
After the reaction was carried out at 30°C, ethyl acetate was added and the mixture was washed with water. The oil layer was separated and the solvent was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of ethyl acetate and hexane to obtain /j of ≠5.29.

■ 7th step (synthesis of compound 16) /J paste 5.2g with methanol 3oomt and hydrochloric acid lrm
The mixture was added to a mixed solvent of 300 ml and heated to reflux for 1 hour. After cooling to room temperature, add water and take the precipitated crystals to obtain I1 of -r, tg.
Synthesis of 30)/Part 21, All was added to 600ml of tetrahydrofuran and cooled to -70°C to obtain aluminum chloride.

tg was added. In this c liquid, l-phenyltetrazolyl-
Yo-Sulfenylcro IJ)"f, r 'l'r
A dichloromethane solution containing 0 mt was added dropwise. 30
After reacting at -100C for minutes, ethyl acetate and water were added. The oil layer was separated using a separatory funnel and washed with water. Remove the oil layer and reduce the pressure! The solvent d was distilled off, and the residue /& was recrystallized from a mixed solvent of hexane and ethanol to obtain the desired exemplary compound (30).

Synthesis Example (4) Synthesis of Exemplified Compound (3/) In step ① of Synthesis Example (3), instead of l-phenyltetrazolyl-y-sulfenyl chloride Ir, 2g / + , rg
of! −(≠−methoxyl〆nylphenoquiquinluponylmethylthio)−/, j.

A pond using μm thiadiazolyl-λ-sulfenyl chloride was synthesized in the same manner as in Synthesis Example (3).

Synthesis Example (5) Synthesis of Exemplary Compound (73) α-Chloro-α
-pensoyl-2-rero-octadecyloxylponylacetanilide, 30.21/, j-(/-(
λ-(Honanophenoquinecarbonyl)ethylcotetrazolyl-yo-thio l-3. ≠, j-trihydroquine benzoic acid pucopyl ester, 21t, 3g and potassium carbonate, 6°I, N,N-dimethylformamide,! Om
Add to a mixed solvent of 100ml of toluene and 100ml of toluene and add 2
Allowed time to react. After the chamber was cooled to a fine state, it was transferred to a separatory funnel, washed with water, diluted hydrochloric acid, and further washed with water, and the oil layer was dried over sodium succinate. After distilling off the solvent under reduced pressure, the residue was recrystallized from ethyl acetate and n-hexane to obtain the desired exemplary compound (73).

The compound represented by the general formula (1) of the present invention can be added to a photosensitive silver halide emulsion layer or a layer adjacent thereto in a light-sensitive material. ], and the amount added is /X10-/
X/(17mol/m iJ, good tL<1tJx
lO-rxto-'mol/m2, more preferably /x
It is 10-5 to 2×i o ”-' mol/m.

The compound represented by the general formula (N) of the present invention can be added in the same manner as for ordinary couplers, as described below.

In the tabular silver halide emulsion used in the present invention, one average spectrum ratio means the average value of the ratio of the diameter to the thickness of the silver halide grains.

That is, it is the average value of the diameter of each individual silver halide grain divided by the thickness. Here, the diameter refers to the diameter of a circle having an area equal to the projected area of one grain when the silver halide emulsion is observed using a microscope or an electron microscope. Therefore, when the average asquit ratio is S; or more, it means that the diameter of this circle is three times or more the thickness of the particle.

The diameter of one grain of the tabular silver halide grains used in the silver halide emulsion of the present invention is 3 times or more the grain thickness, preferably j to 30 times, more preferably j-/j times, particularly preferably is j-10 times. Further, the proportion of tabular silver halide grains in the projected area of all silver halide grains is at least the jO coefficient, preferably at least 704%, particularly preferably at least tj%.

By using such an emulsion, a silver halide photographic material having a sharpness superior to that of K can be obtained. The reason why the sharpness is excellent is that the light scattering by the emulsion layer using such an emulsion is extremely small compared to the conventional emulsion layer.

This can be easily confirmed by experimental methods routinely used by those skilled in the art. Although it is not clear why the light scattering of the emulsion layer using a tabular silver halide emulsion is small.

This is thought to be because the main plane of the tabular silver halide emulsion is oriented parallel to the support surface.

Further, the diameter of the tabular halogenated steel particles is 0.2 to 0.0μ, preferably 0.7 to 10.0μ, particularly preferably 0.4! ~3.0μ. The thickness of the particles is preferably 0. jμ or less. Here, the diameter of a tabular halogenated particle is defined as r! of a circle with an area equal to the projected area of one particle. Refers to the diameter. Also.

Grain thickness is expressed by the distance between the two parallel planes that make up the tabular halogenated grain.

In the present invention, more preferred tabular silver halide grains have a grain diameter of 0.3 μm or more and 10.0 μm or less, a single grain thickness of 0.3 μm or less, and an average (diameter/thickness) of 1 or more and 10.0 μm or less. It is as follows.

If it exceeds this range, it is undesirable because the photosensitive material may be bent, tightly rolled up, or the photographic performance may be affected when it comes into contact with a harsh object. More preferably, a silver halide photographic emulsion in which grains each having a diameter of 0.4 cm or more and 7.0 μm or less and an average C diameter/thickness of 3 or more occupy 114 or more of the total projected area of all silver halide grains. This is the case.

The tabular silver halide grains used in the present invention include chloride,
Any of bromide complex, silver chlorobromide, silver iodobromide, silver chloroiodobromide may be used; Brominated steel is more preferred, and the composition distribution in the mixed halogenated steel may be uniform or localized.

Further, the particle size distribution may be narrow or wide.

The tabular silver halide emulsion used in the present invention is:

Reports by Cugnac, Chateau and Duffin
Author-Photographic Emulsion C
hemistry''lr Published by Focal Press. New York/9A t [pp. 4-72, and A, P, H, Trivelli.

Edited by W, F, Smith ``Pbot, Jour
nal' 10 (/tag θ year), page 2rs, but JP-A-Shojlr-//Jri No. 27, zr
-/1Jyar issue, same! It can be easily prepared by referring to the method described in No. 1-1272.2/.

For example, seed crystals containing tabular grains of 0.4 or more by weight are formed in an atmosphere with a relatively high pAg value of pBr of 1.3 or less, and silver and halogen solutions are simultaneously added while maintaining the pBr value at the same level. It is obtained by growing seed crystals. During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of parent crystal nuclei.

The size of tabular silver halide grains is determined by temperature control, selection of solvent type and quality, and silver salt used during grain growth.

It can be adjusted by controlling the rate of addition of the halide and the like.

During the production of tabular silver halide grains of the present invention.

By using a silver halide solvent as necessary, grain size, grain shape (diameter/thickness ratio, etc.) - grain size distribution, and grain growth rate can be controlled. The amount of solvent used is io -i, o of the reaction solution'.
A weight range of 4 is preferred, and a weight range of 10 −10 weight is particularly preferred.

In the present invention, as the amount of solvent used increases, the particle size distribution becomes monodisperse and the growth rate can be accelerated, but the thickness of the particles also tends to increase as the amount of solvent used increases.

In the present invention, known silver monohalide solvents can be used. Examples of frequently used silver halide solvents include ammonia, thioethers, thioureas-thiocyanate salts, and thiazolinthiones. Regarding thioethers, U.S. Pat.
, 27/, /j7, 3.37μ, 421, 3.7ri 0.317, and the like. Regarding thioureas, see Japanese Patent Application Laid-Open No. 2003-33330.

No. 1j-77737, U.S. Patent No. 2,22 regarding thiocyanate salt, λ64L No. 2゜4C4Cr
,! ! No. 4c, No. J, 320. OtY issue.

Regarding thiazolinthions, JP-A-33-1 Dag 3
You can refer to each issue No. 12.

In the process of forming or physically ripening silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. may coexist. .

When producing the tabular silver halide grains used in the present invention, a silver salt solution (e.g., AgNO3 aqueous solution) and a halide solution (e.g., KBr) are added to accelerate grain growth.
A method of increasing the addition rate and addition amount of the aqueous solution (aqueous solution) and increasing the addition degree is preferably used.

Regarding these methods - for example British Patent No. 1゜33j
, R2j, U.S. Patent No. 3. tJO, No. 737, No. 3
, No. 472,900 - Hiroshi Dodai, 2ILL Ko, ≠≠! issue,
t￥F Kaisho 13-/Hiroko 3 Kota issue, sameyoyo-/, tl/
You can refer to the description in No. 2, etc.

The tabular silver halide grains of the present invention can be chemically sensitized if necessary. Chemically sensitized K is, for example, H
, F r i e s e r ed.”DieGrundl
Agen der Photography
enProzesse mit Silberha
"Logeniden" (Akademische V
erlagsgesellschaft.

/ri tr year) t7! Page~73! The method described on page can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reduction sensitization method using noble metal compounds (e.g., total complex salts, hydrazine derivatives, formamidine sulfinic acid-silane compounds);
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as r, Pd, etc. can be used alone or in combination.

These specific examples are described in U.S. Patent No. 1 for monosulfur sensitization.
, 37≠, tag≠ issue, interval λ, 27g.

Tag No. 7, same No. 2. 10. Atri No. - Same No. ko.

No. 721.661, No. J, AjJ, No. 916, etc. - U.S. Pat. Da/Ri, Ri No. 7, Same No. 2. 13. U.S. Patent No. 2.3 Tade, 01 regarding noble metal sensitization methods such as tOri No., Oj≠, μjt No.
No. 3, same No. 2. l/-'It.

No. 040, British Patent No. 411.041, and other specifications.

Particularly from the viewpoint of lead content, the tabular silver halide grains of the present invention are preferably gold sensitized, sulfur sensitized, or a combination thereof.

The tabular silver halide grains of the present invention can be spectrally sensitized with methine dyes or the like, if necessary. In addition to the above-mentioned improvement in sharpness, the tabular silver halide grains of the present invention also have a high spectral velocity. 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 those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Useful sensitizing dyes include, for example, German Patent No. 929.
No. 010, U.S. Patent No. 093,7≠, U.S. Patent No.
! No. 03.774, No. 03.774, No. 001, No. 2, 32, No. J, 614. ri No. 39, ri No. 3.67, tri No. 7, ri No. 44,021. J≠ri issue,
British Patent No. 1゜Coμco, ZRR-Special Publication Showairi-1 7μO
Examples include those described in JO issue.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of one-strong color sensitization.

A typical example is U.S. Patent No. 2. try, z<ri issue, same@ko, ri issue 77.229, same number 3.397. Oto issue, same issue J! 22. OjJ No. 3. ! Core, Jda No. 1,
Same No. J, t/7. Kota No. 3, same No. J, jiff,? Au
No. J, 4A6. lll0, $3.672. z
yr No. 3.672, lJt No. J, ro11
．． No. t09, No. 026,707, British Patent No. 1
I3μ≠.

21/ issue, special public Shogu 3-data 3bu issue, 13-/237
! No., JP-A No. 32-10-923-J No. 1 tot
It is described in the IT issue.

The photographic emulsion used in the present invention has the following properties: 1. To prevent fogging during the manufacturing process, storage, and photographic processing of light-sensitive materials; Or for the purpose of stabilizing photographic performance.

Various compounds can be included. Azoles 1 such as benzothiazolium salts, nitroimidazoles, triazoles, benzotrizoles, benzimidazoles (especially nitro- or halogen translocators); heterocyclic mercapto compounds, such as mercaptothiazoles.

Mercapto (nzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles).

Mercaptotetrazoles (especially 7-phenyl-!-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxadorinthion; Azaindenes, such as triazaindene-substituted (/, J, 3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acids; and other antifoggants or stabilizers. Many compounds can be added.

For more detailed examples of these and how to use them, see, for example, U.S. Patent No. 3. P! μ, Hiro 7 μ issue, same No. 3.
Riko, Tag No. 7, Hiroshi Dodai, Ono/.

Each specification of λda, or Tokko Sho J'Kono ZrAAO
The description in the publication can be referred to.

The tabular emulsion of the present invention may be contained in any layer other than the protective layer and the antihalation layer in the light-sensitive material, but the layer containing the compound represented by general formula (I) and/or
Or, one color may be contained in a layer having a different color sensitivity from this layer and/or a color sensitive layer that is substantially the same as the layer between the layer and a layer having a different color sensitivity. This is particularly preferred for improving reproducibility.

In addition to the above-mentioned tabular emulsion, the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver bromide and iodobromide.

Silver halogenide may also be used. Preferred silver halides are silver iodobromide or silver iodochlorobromide, containing less than about 30 moles of silver iodide. Particularly preferred is about λ molar coefficient to about uj
Silver iodobromide containing silver iodide in molar z-t.

Silver halide grains in photographic emulsions are cubic, hedral,
It may be a so-called regular particle with a regular crystalline structure such as a tetradecahedron, a particle with an irregular crystalline shape such as a spherical shape, a particle with twin planes, any crystal defects, or a combination thereof. good.

The grain size of the silver halide may be fine grains of less than about 0.1 micron or large grains with a projected area diameter of up to about 10 microns, monodisperse emulsions with a narrow distribution or polydisperse with a wide distribution. An emulsion may also be used.

Silver halide photographic emulsions that can be used in the present invention are:

It can be produced by a known method - for example, Research Disclosure (RD), 116/71eμ3 (11/71, November 2005), pp. 22-23, 1st, emulsion production (Emulsin
preparation and types)
' and ibid., I6/17/l (November 1279).

The method described on page 4 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimie et Phy
siquePhotographique Paul
Montel, /ri67), “Photographic Emulsion Chemistry” by Du Huynh, published by Focal Press (G, F, Duf
fin, Photographic Emulsio
n Chemistry (Focal Press
.

/9tt), “Production and Coating of Photographic Emulsions” by Zelikman et al.
, published by Focal Press (V, L, Zelikma
Net al, Making and Coat
ingPhotographic Emulsion
, Focal Press.

iyt≠). That is, any of the acidic method-neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method of keeping the pAg in the liquid phase produced by the halogenated steel constant, ie, the so-called Chondrald double jet method, can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

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

The above-mentioned silver halide emulsion consisting of regular grains can be obtained by controlling pAg and pH during the formation of one grain. For more information, please see Photographic Science and Engineering.
5science and Engineering]
Volume 7j ~/lj page (/IAJ); Journal
Of Photographic Science (Journal
ofPhotographic 5science
l, /+2 volumes, +2≠-~koj/page (/9+th), US Patent No. J, 4jj-032≠ and British Patent Nos. 1, 4
It is described in No. L13,74tt.

A representative example of a monodispersed emulsion is an emulsion in which silver halide grains have an average grain diameter larger than about 0.11 microns, and at least about 1% by weight of the silver halide grains are within ±≠θ of the average grain diameter. . The silver halide grains have an average grain diameter of about 0.21-J microns and contain at least about 11 silver halide grains in an amount of at least about 2.
Emulsions such as those within the range of 0.0 to 0.0 mm can be used in the present invention.

A method for producing such an emulsion is described in U.S. Patent No. 3. ! 7≠.

tJt No. J, 633. Jri No. 4 and British Patent No. 1. μ73.7μ is described in the issue.

Also, JP-A-Sho≠, r-rtoo issue, same j/-32O27-same! /-13097 No. 33-/, No. 37/33,
same! Boku → Zama, No. 27, same tU-Tatahiro No. 19, same! l
Monodisperse emulsions such as those described in No. -37tJj and No. ♂-l Tata No. 3r can also be preferably used in the present invention.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are covered by the British patent @/, 0 core, /
≠No. 6, U.S. Patent No. J, Jol, No. 041, Dohiro, ←
t'1.1177 and patent application No. 11-21/-1 Hirot.
It is disclosed in the following issue.

Furthermore, silver halides having different compositions may be joined by epitaxial joining.
It may be bonded with a compound other than silver halide, such as lead oxide. These emulsion grains are described in U.S. Pat.
3j3, British Patent No. 031.7? No.-, U.S. Patent No. μ, 389, AJJ No., same! , 391. Ifi7r issue, same reference.

≠JJ,! 0/No., same μ, Hiro 6J, 017, same J, t
it, No. 26, 3. r! Ko, No. 067.

Tokukai Akira! Tar/1λ! It is disclosed in ≠θ, etc.

Also, mixtures of particles of various crystal forms may be used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure & 176≠
3 and A/J'7/&, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and the locations listed are shown in the table below.

l Chemical sensitizer, page 23 tdar page right column λ
Sensitivity enhancer Same as above 3 Spectral sensitizer 1 strength 23~λda page Tar page right column~Color sensitizer
6th page right column ≠ Brightener Koda page! Antifoggant 2μ~! Page 1 page right column and stabilizer t light absorber, 2j-26 page t μ page right column~
Luther dye, purple Page 120 left margin line absorber 7 Stain inhibitor Page 21 right column Page 410 left to right column
Binder Copper page Same as above/l Plasticizer - Lubricant page 27 Page 410 right column/2 Coating aid -
Surface Pages 26-27 Same as above Activator 13 Static inhibitor Core page Same as above Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (RD
) Ya/764L3, ■-C-GK described in the patent. As dye-forming couplers, couplers that provide the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development are important, and specific examples of diffusion-resistant, reference equivalent or 2-equivalent couplers are the RD/7A dazzling mentioned above. 3. In addition to the couplers described in the patents described in Sections 1-C and D, the following can be preferably used in the present invention.

Yellow couplers that can be used in the present invention include:

A typical example is a hydrophobic acylacetamide coupler having a pallast group. A specific example is US Patent No. 2. 〇7. J/θ No. 2゜17! , No. 017 and No. 3. It is described in Kotz, rot issue, etc.

The use of a two-cap yellow coupler is preferred for the present invention and is described in U.S. Pat. Reference 17.
Takowo No. 3I No. 33,101 and Hiroshi No. 0
22゜1.20, etc., or Japanese Patent Publication No. 1073, U.S. Pat.
No. 1-RD/1rOj3 (/979 Gu month).

British Patent No. 1,4A2j,020, West German Application No. 2
No. 1219,917, No. 2,261.34/, No. 32, J17 and No. 2 1133.11
A representative example of this is the nitrogen atom separation type yellow coupler described in No. 2. The .alpha.-piparoylacetanilide coupler has excellent color fastness, particularly light fastness, while the .alpha.-benzoylacetanilide coupler provides a high color density.

Magenta couplers that can be used in the present invention include:

Examples include hydrophobic indacylon or cyanoacetyl couplers having a ballast group, preferably Vis-pyrazolone and pyrazoloazole couplers. The j-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamine group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. No. - Same @2.31A3,703
No. 2,400,711, No. 2. Or, 17
3, same No. j, 042,633, same No. 3. /ta j, r
Pj No. and J, 93t, 0/! It is written in the number etc. As a leaving group for a two-equivalent pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. The IJ-ruthio group described in IrR No. 7 is particularly preferred. A pyrazolone coupler having a pallast group as described in European Patent No. 73.63≦ provides a high color density. As a pyrazoloazole coupler, U.S. Patent No. 3゜θ
ti, tt3 pyrazo-described zimidazoles, preferably US Pat. No. 3.7.2! , pyrazolo (j,/-c) [/.

Ko, Hiroshi] Triazoles, Research Disclosure Coμ Coco 0 (Month 19114) and JP-A-Sho tO-
Examples include pyrazolotetrazoles described in No. 33!12 and pyrazolo pyrazoles described in Research Disclosure 2ax3o (lqrtx, June 2013) and JP-A No. 33!12. U.S. Patent No. μ, in terms of low yellow side absorption and light fastness of the coloring dye! 00
．． The imidazo CI, J-b) pyrazoles described in US Patent No. t3θ are preferred. The pyrazolo(/, r-b)C/, co, Hiro] triazole described in No. ≠0.12≠ is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic, diffusion-resistant naphthol and phenolic couplers, such as those described in U.S. Patent No. J, ≠7μ.

193, preferably the naphthol couplers described in U.S. Patent No. ≠, O! KO, KO/KO No. - Same No. GU.

Typical examples include the oxygen atom dissociating type di-St naphthol couplers described in 1lit, No. 4<, 2.2F, 233 and 2.2F, 6,200. Specific examples of sweet phenolic couplers are described in U.S. Pat. No. 2,349. No. 222, No. 2, 70/, /7
/ No. U, 772. /6-No. 2,193,1
21. It is written in the number etc. Couplers capable of forming cyan dyes that are robust to humidity and temperature are used in the present invention, exemplified by U.S. Pat. No. 3,772,002. A phenolic cyan coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus described in US Pat. ≠.

/26,396 No. μ, 33 μ, 0 Tsuno No.

1I, 327. /7J7! West German Patent Publication No. 3゜32
No. 9.71P and European Patent f, /2/, El.

U.S. Patent No. 3. ≠4t6゜422, same No.≠, JJJ, ri9q, same No.≠.

μ! /, No. 619 and No. 4127.767, etc., which have a phenylureido group at the no position and! It is a phenolic coupler with an acylamino group in the - position. European Patent No. 11/.

The cyan coupler described in No. t2 tk, in which naphthol is substituted with a sulfonamide group, an amide group, etc. at the j-position, also has excellent fastness of the twisted colored image and can be preferably used in the present invention.

In order to correct unnecessary absorption of color pigments, it is preferable to perform masking by using a colored coupler in combination with a color photosensitive material for photographing. The yellow-colored magenta couplers described in U.S. Pat. 31, Jjr and British Patent No. 1
．． Typical examples include the magenta-colored cyan couplers described in No. 1, No. 1, No. 1, No. 1, JTR, and the like. Other colored couplers include the aforementioned RD/74μ3. It is described in sections ① to G.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
US Patent No. 4! , JG4,237 and British Patent No. Co, /2! Specific examples of magenta couplers are given in EP 2A, 770 and German Published Application No. 3.
231. ! Specific examples of No. JJ KH yellow, magenta or cyan couplers are described.

Dye-forming couplers and special couplers listed above.

A dimer or higher polymer may also be formed. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. II
-! /, No. 120 and No. a, oro.

It is described in issue 2//. Specific examples of polymerized magenta couplers are given in British Patent No. 1, 102. No. 73 and U.S. Patent No. 44. It is described in JA7,212.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler that releases the development inhibitor is the aforementioned RD774ψ3, ■
The patent couplers listed in Sections .-F. are useful.

A preferred combination with the present invention is JP-A-7-
/! Developer deactivated type represented by No./941'1; U.S. Pat.
The timing type represented by No. 112Jμ; the reaction type represented by Japanese Patent Application Sho J Day No. 3243-3; particularly preferred are the timing type represented by Japanese Patent Application Sho J De No. 3243-3; 7-7j/ributsu≠ issue, same! t-co1
7de 3J issue, Tokugan Sho J Turf jμ7≠ issue, same! 9-r Coco 14 issue, same jter! rλ21v issue and the same J Tata Ohiro 3 issue, etc., present Rin liquid deactivation type DIR coupler and special application Sho! This is a reactive DIR coupler described in No. 9-3-413 and the like.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent No. 2,097゜l≠O; /, 3/
, No. 111. Couplers that release a nucleating agent that has an adsorption effect on silver halide are preferable for @, and specific examples thereof are given in JP-A-Sho! tar1syt3
r and J Day/701 Hiroo, etc.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers C, such as U.S. Pat.
30. ≠ couplers described in No. 27, etc.), multi-equivalent couplers C, such as those described in U.S. Pat.

21rJ, tLt No. 72, 4 (, 331, J'PJ
Couplers listed in No. 1, No. 11, Sio, Bu No. 11, etc.)

Examples include dye-releasing couplers C which recover color after separation (for example, the coupler described in European Patent Publication No. 173,30λ).

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of tyz"c or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or water is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Pat.
No. 2,027, etc.

Dispersion may involve phase inversion - and if necessary, co-solvents may be removed or reduced by distillation, noodle washing or ultrafiltration before use for coating.

Specific examples of latex dispersion process steps, effects, and latex for impregnation can be found in U.S. Pat.

No. 274c and No. 274c, J Hiro 1. It is written in Ko No. 30, etc.

Suitable supports that can be used in the present invention include, for example.

The aforementioned RD, page 21 of A/7j≠3 and the same, B/1
7/ It is written from the right column of page 7 of A to the left column of page jllff.

The color photographic light-sensitive material according to the present invention includes the above-mentioned RD-A
z 7A 4t3 pages 2t to λ and the same, Tomb/17/
Development processing can be carried out by the usual methods described in the left column to right column of tsi of 1.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phinidine diamine compounds are preferably used, representative examples of which include 3-methyl-μm amino-N,N-diethylaniline, 3 -Methyl-≠-amino-N-ethyl-N-
β-Hydroxylethylaniline, 3-methyl-amino-N-ethyl-N-β-methanesulfone-3-methyl-≠-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-toluenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates - development inhibitors or antifoggants such as bromide-iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it contains agents such as agents. Also, if necessary, preservatives such as hydroxylamine or sulfites, organic solvents such as triethanolamine, diethylene glycol, etc.
Development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, and adjuvants such as phenyl-3-pyrazolidone. Developing agents, viscosity imparting agents, various rice chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids,
Antioxidants such as those described in West German Patent Application (OLS) No. 62, No. 30 may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, l-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as amine phenols such as methyl-p-aminophenol can be used alone or in combination.

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

The bleaching treatment may be carried out simultaneously with the fixing treatment or may be carried out separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleach-fixing process is carried out after the Zhaobai process. Examples of bleaching agents used include compounds of polyvalent metals such as iron (I [11), cobalt (III)-chromium (M), and copper (II)), peracids, quinones, and nitrone compounds. Typical bleaching agents as ferricyanide; dichromate; iron (I
I[) or organic complex salts of cobalt(III) 1 such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, /, -? -Diamino 2-
Aminopolycarboxylic acids such as prono2noltetraacetic acid, salts of organic acids such as citric acid, tartaric acid-malic acid; per(ilff acid salts; manganates; nitrosophels, etc.) can also be used. Among them, ethylenediaminetetraacetate iron(III) salt, diethylenetriaminepentaacetate iron(III) salt, and persulfate ring are preferable from the viewpoint of rapid processing and environmental pollution. In addition, iron ethylenediaminetetraacetate (
I[I3 complex salts are particularly useful in both stand-alone bleach solutions and total bleach-fix solutions.

For bleach solutions, bleach-fix solutions and their pre-baths.

A bleach accelerator can be used if necessary.

Specific examples of useful bleach accelerators are described in U.S. Patent No. 3. ! 93. r! No. R - West German Patent No. 1
,2ri 0,1/2 issue, same co, O! Di.

QTR issue, Tokukai Sho! No. 3-327Jt, JJ-171
rJI, J711/I, j3-buj73,
Same jJ-7J No. 23, Same j3-2! No. 630, Same! 3
-Ta j4J/No., jJ-1011λ3 No., same! rJ
-/Kou4A2Q, same! 3-7μ/No. 123, Sameta 3
- Kotdako wo issue, Research Disclosure 417
Compounds having a mercapto group or a disulfide group described in No. 122 (July 1971); #Kaisho! 0-/
1,000 azolidine derivatives as described in Daoix No. 9; λ No., same, tJ-3273! No. 3.7 at, z
Thiourea derivatives described in No. TI; West German patent WCL, 12
7.71j issue, @ Kaisho! Iodide described in If-/Ako No. 33; West German Patent No. 944.4c10, 2.7φF,
! Polyethylene oxides described in JO issue;
Polyamine compound described in No. 47-4134; Others @
Kaisho≠tar4Iλμ3≠, same IA? -7? 4444
! Same issue! 3-? ≠Octopus No. 7 - Same! ≠-3, No. 727,
Same j! - Kotj No. 04 and No. 1? The compounds described in No. -/63 ao and iodine and bromine ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferable because they have a large promoting effect. US Patent No. J, 193. Iyoj No. 1, West German Patent No. 1゜290.11
No. 2, JP-A No. 13-9r & 30 are preferred. Additionally, U.S. Patent No. ψ.

j12. Compounds described in No. tau are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleaching and fixing color light-sensitive materials for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of thioether compounds, and large amounts of iodides, but thiosulfuric acid sulfate is commonly used. As the preservative for the bleach-fix solution and the fix solution, bisulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent sedimentation, water softeners such as turnip acid, aminopolycarboxylic acid, organic minopolyphosphonic acid, and organic phosphoric acid, and sterilization to prevent the growth of bacteria, algae, and mold are recommended. If necessary, additives such as anti-peking agents, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants to prevent drying load and unevenness, and various hardening agents can be added. . Or Photographic Science and Engineering magazine by West (L, E, Wesl
, Phot, Sci.

Eng, ), Volume 31111~J! Compounds described in Tabezi (L. Jt.) and the like may be added. The addition of chelating agents and anti-piping agents is particularly effective.

In the rinsing process, it is common to use counter-current flushing in more than one tank to save water. In addition, instead of the water washing process, JP-A-7
-r may be subjected to a multistage countercurrent stabilization treatment process as described in No. 113. In the case of wood grains, a two-tank countercurrent tower is required. In addition to the above-mentioned additives, various nutritional compounds are added to the stabilizing bath for the purpose of stabilizing images. Various buffering agents (e.g., borates, metaborates, borax, phosphorous salts, carbonates, potassium hydroxide, sodium hydroxide) to adjust the membrane pH (e.g., pi(J)).

Typical examples include aldehydes such as ammonia water, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. Others - Chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (benzisothiazolinone, isothiazolone, ≠- Various additives such as thiazoline bensimitasol, ), rogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be used, and may be used for the same or different purposes. Two or more of these compounds may be used in combination.

In addition, ammonium chloride,
Ammonium nitrate, ammonium sulfate.

It is preferable to add various ammonium salts such as ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

In addition, the above-mentioned stabilization step and washing step (water-saving treatment) K can be replaced with the 1-washing-stabilization step after fixing, which is normally carried out in color photosensitive materials for photography. In this case, when the amount of magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to IO minutes, preferably λO seconds or more! It's a minute.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For this purpose, it is preferable to use various precursors of color developing agents.

For example, indoaniline compounds described in US Pat. No. 3.31, 597, US Pat. No. 3.3,! Wata issue, Research Disclosure 14trlO issue and the same/! /
! Schiff base-type compounds described in US Pat. No. 3.7/2, aldol compounds described in US Pat.

Including the urethane-based compounds described in JP-A Sho! j j -/ j j j , J', JP-A Sho! 6-Otsu 13
J No. 16-/A/33, J Otsu-j No. 9232.

same! t-17r4 (- issue, jt-137311 issue, jj-IJ73J- issue, jt-tJ7Jt issue, ta
-rri73! No., same, tG-4/137-same! T-!
≠Ko 30, same t4-104 ≠1.

The same jA-10723, the same j7-ta7!31 and the same j7-1314! Examples include various salt-type precursors described in No. 1, etc.

The silver halide color light-sensitive material of the present invention may optionally contain one type of l-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are JP-A No. 6-6μ33, J7-/≠≠Jμ7, and JP-A No. 17-2/l/μ7-Sho! r-#0jJi No. 31-3063, same! r-10133, same 5r-
sot3μ issue, same! r-,tO! Jj issue and 11-
/1juJI issue etc.

Each pond treatment solution in the present invention is used at 1o0cNto0c. A temperature of 33°C or JIoC is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. Can be done. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 225770 or US Pat.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

(Example) The present invention will be explained below in detail with reference to Examples, but the present invention is not limited thereto.

Example / Inert gelatin 3 oy, potassium bromide tt - distilled water lt
Stir the aqueous solution in which is dissolved at 7!0C, and add the aqueous solution in which nitric acid steel J and 0ri are dissolved 3! After adding an aqueous solution 3j in which potassium bromide j, , 2 and potassium monoiodide O0rrr were added at a flow rate of 70τ/min for 30 seconds, the pAg was increased by 10K and ripened for 30 minutes to form a type 1 emulsion. was prepared.

Next, silver nitrate l≠j? A predetermined amount of an aqueous solution/l of dissolved potassium bromide and an aqueous solution of a mixture of potassium bromide and potassium iodide are added in equimolar amounts at a predetermined temperature and a predetermined pAg at an addition rate close to the exfoliation growth rate to form a flat core emulsion. was prepared.

Furthermore, the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a composition different from that used in preparing the core emulsion were added in equimolar amounts at a rate close to the critical growth rate to wrinkle the core. Inverted core/shell type silver bromide tabular emulsions A to D were prepared.

Aspect ratio adjustment is performed during core and shell preparation l)A
It was obtained by selecting g. The results are shown in Table 1-1.

Table 1-7 1) For every 1,000 emulsion grains J, measure the aspect ratio of each individual grain, select grains whose total projected area is equivalent to JO4s from grains with larger aspect ratios, and Average aspect ratio.

2) Similarly to 1), the aspect ratio of particles corresponding to rj of the total projected area is the average value of the ect ratio.

Next, each layer having the composition shown below was coated on the undercoated cellulose triacetate film support to prepare a multilayer color photosensitive material 10/.

C Photosensitive Layer Composition) The numbers corresponding to each component indicate the coating amount expressed in units of f/FF12, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes and couplers, the coating amounts are expressed in moles per mole of silver halide in the same layer.

(Sample 1O11 1st layer; antihalation layer black colloidal silver
・・・・・・・・・Silver o, ir gelatin・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・o,tt.

Second layer; middle layer! -G-t- is tadecylhydroquinone・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 0. /rC-/ ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.07C-J ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.02 [J
-／ ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・o
, orU-ko ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・o、orHBS-／ ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・ 0.10HBS-1 ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・0.02 gelatin・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
.../, 0μ Third layer; First red-sensitive emulsion layer Silver iodobromide emulsion f Silver iodide 6 mol ratio.

Average particle size o, rμ)・・・・・・・・・・・・・・・
・・・・・・Silver O, SO sensitizing dye■・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・t, 9Xl
O-5 sensitizing dye ■・・・・・・・・・・・・・・・
・・・・・・・・・・・・Harxio-5 sensitizing dye■
・・・・・・・・・・・・・・・・・・・・・・・・
...3. /X10-4 sensitizing dye ■・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・ II
-,0X10-5C-ko・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...0. /4IAHBS-/ ・・・・・・・・・
·····················river···
・・ o, oozC-IO・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・ o
, oor gelatin ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・／、
20th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion C silver iodide! I'm sorry.

Average particle size o, rzμ)・・・・・・・・・・・・・・・
...Silver/, l! -1, -6---10 for sensitizing dye
,−0,−,1,,,,,z,t x t o −
s-sensitizing dye ■・・・・・・・・・・・・・・・・・・
・・・・・・・・・8≠X / 0-5 sensitizing dye■
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・−・3×10-4 sensitizing dye W・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・J,
0xlO-5C-ko ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
... o, ot.

C-3・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ o, oo
rC-io ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0.0
0μHBS-2・・・・・・・φ・・・・・・・・・
・・・・・・・・・・・・・・・・・・ o, ooz gelatin・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・1. jθ jth layer; 3rd red-sensitive emulsion layer silver iodobromide emulsion (silver iodide 10 molar width, average grain size i, zμ)・・・・・・・・・・・・・・・・・・
·····Silver/, ! 00 sensitizer■・・・・・・・・・
・・・・・・・・・・・・・・・・・・Yo,≠×
10-5 sensitizing dye ■・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・1. μX10-5 sensitizing dye■・・・・・・・・・・・・・・・・・・・・・
......-8 Hiro x 10-4 sensitizing dye ■...
・・・・・・・・・・・・・・・・・・・・・・・・
J, /Xl0-5C-t ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・ 0.0/koC-J ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 0.003C-Reference ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 0.00≠HBS-/ ・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 0.3 Nogelatin・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ l, 63 6th layer; middle layer gelatin・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ /, O1s
7th layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide t mole - average grain size o, rμ)
・Silver 0. JJ-sensitizing dye■・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・3.0X10-
5 Sensitizing dye■・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・／、0XlO-4 sensitizing dye ■・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・J, Ixlo-4C-A ・・・・・・・・・
river························
......o, ia.

C-7・・・・・・・・・・・・・・・・・・・・・
・River・・・・・・・・・・・・・・・0.02IC-
7. River・・・・・・・・・・・・・・・・・・
・・River・・・・・・・・・・0,030C-?・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・o, o! H8B-/
・・・・River・・・・・・・・・River・・・・・・・・・
・・・・・・・・・0.20 gelatin ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...0.70 rth layer: second green-sensitive emulsion layer silver iodobromide emulsion (silver iodide 1 mol % - average grain size o, rrμ) ... river ......・・・
・Silver 0.7! Sensitizing dye■・・・・・・・・・・・・・・・
River・・・・・・・・・・・・・1X10-5 sensitizing dye ■・・・・・・・・・・・・・・・・−
......-7,0X10-5 sensitizing dye■...
・・・・・・・・・・・・・・・・・・・・・・・・
Ko, AX10-4C-4・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...o, oko/C-?・・・・・・・・・・・・・・・
··················river······
・・o、ooaC-/ ・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...0. 002C-7・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・ 0. 003H8B-/・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 0. /! Gelatin ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
... o, t.

3rd layer; 3rd green-sensitive emulsion layer Emulsion A・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・Silver/0. r
O sensitizing dye■・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・j, JXlo-5 sensitizing dye ■・
・・・・・・・・・・・・・・・・・・・・・・・・
...r, oxio-s sensitizing dye ■...
・・・・・・・・・・・・・・・・・・・・・・・・3.0
xlO-4C-A ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・0.0//C-/ ・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・o、ooiHBS-2・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
O0t Tagelatin ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・7.7μ 1st O layer; Yellow filter layer Yellow colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・・・・・・Silver 0.0! Ko,! -G-t- is tadecylhydroquinone・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.03 Gelatin・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・Ooori! 1st/Layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (6 moles of silver iodide).

Average particle size o, tμ)・・・・・・・・・・・・・・・
・・・・・・＠0.2≠Sensitizing dye■・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・j, JXl
o-4C-9・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・θ,
-7C-?・・・・・・・・・・・・・・・・・・・・・
・River・・・・・・・・・・・・・・・・・・Q, 00
! HBS-／・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ O, ko r
gelatin·····················
・・・・・・・・・・・・・・・・・・／、Cor No. 12
Layer: λth blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide iomol).

Average particle size i, oμ)・・・・・・・・・・・・・・・
・・Cleft O0 μj sensitizing dye ■・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・Co, /X/Q-4
C-9・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・o、oqr
HBS-／・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.03 Gelatin・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・River・・・O1≠ 13th layer: 3rd
Blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 70 mol width).

Average particle size 1. ♂μ)・・・・・・・・・・・・・・・
・・Silver 0.77 sensitizing dye～■・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・2.2×7O−
4C-9・・・・・・・・・・・・・・・・・・
・・・・・・・・・River・・・・・・・・・0.03AH
BS-／・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.07 Gelatin・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.62 1st ≠ layer; first protective layer silver iodobromide [per mole of silver iodide.

Average particle size 0.07μ)・・・・・・・・・・・・・・・
・・・・・・Silver 0. ! U-／・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0. /IU-ko・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0. /7HBS-/ ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・O first layer; second protective layer polymethyl methacrylate particles C diameter approximately i, z μm)・・・・・・・・・・・・O
3! ≠S-／ ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...0. /jS-ko・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...0. Oj gelatin・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...0.72 In addition to the above composition, gelatin hardener H-7 and a surfactant were added to each layer.

Samples 102 to 10 were prepared in the same manner except that Emulsion A in the second layer of Sample 10 was replaced with Emulsion B to Emulsion 2.

(Sample IO!~l/ko) C-r of the 7th layer and the 7th layer of sample 101-10≠,
C-tto, p times moles and compounds of the invention <30
)/, replace sample 10 with 7 times the mole! ~10r and 10~/l samples were prepared.

Samples 10/~// obtained in this manner were exposed to uniform blue light, and then exposed to image quizzes with green light. When the following development process was performed, the result was as shown in Figure 1. A characteristic curve for magenta color images and a characteristic curve for yellow color images were obtained. Here, ΔDB indicates the degree of suppression that the uniformly covered back photosensitive emulsion layer receives when the green-sensitive emulsion layer is developed from point cA in the unexposed area to point cA in the exposed area). That is, in FIG. 1, curve 1 represents a characteristic curve for a magenta color image of a green-sensitive emulsion, and curve 1 represents a yellow image density of a blue-sensitive layer uniformly exposed to blue light.

Point A is the capri part of the magenta image, point B is the magenta density part,
It represents the exposure amount part that gives O.

The density difference (a-b) between the yellow density (a) at point A in the unexposed area and the yellow density (b) at the same point B was expressed as ΔDB and was used as a measure of one-color reproducibility (color turbidity). .

Measurement of MTF value is based on The Theory of Pho.
tographic Process Jr.
edd (published by Matsuku Millan, written by Mies). Relative sensitivity was calculated from magenta density values of samples processed by imagewise exposure using white light.

On the other hand, the emulsion-coated side of the sample was turned inside, and the sample was bent for 70 seconds to an angle of ≠θ degrees, and then exposed to white light.

Thereafter, the same development process was performed, and the optical densities of the folded portion and the unfolded portion were measured, and the density abnormality at the time of folding was determined based on the magnitude of the difference in density.

Color development processing was carried out at 3t0C according to the following processing steps.

Color development 3 minutes/j seconds Bleach white for minutes 30 seconds Water Wash λ minutes 10 seconds Fixed Arrival Part 20 seconds Water Wash 3 minutes lj seconds Stability 1 minute oj seconds The composition of the processing solution used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid/091-hydroxyethylidene-l.

l-Diphosphonic acid λ, 01i' Sodium sulfite p, or potassium carbonate
30.09 Potassium Bromide
1. Potassium iodide
i, 31#9 hydroxylamine sulfate
Ko, ≠t#-(N-ethyl-N-β-hydroxyethylamino)-kotathylaniline sulfate Da, j? Add water /, 0tpH10.0 Bleach solution ethylenediaminetetraacetic acid ferric ammonium salt ioo, or ethylenediaminetetraacetic acid disodium salt 10. Of ammonium bromide ljθ, ot ammonium nitrate IO, t)? add water
/, 01 pHa, O Fixer Ethylenediaminetetraacetic acid disodium trilam salt /, 07 Sodium sulfite μ, O Ammonium tathiosulfate aqueous solution (70%) / 73.0ml Sodium bisulfite ≠, t? Add water /, 07. .

pH 4,4 Stabilized liquid formalin (≠O bond) 2.0 ml polyoxyethylene-p-monononylphenyl ether (average m 10'j, 0.39 water added /, O2 clear from Table 1-J As shown, the sample /10-//λ of the present invention has very high sharpness expressed by the KMTF value without a decrease in sensitivity, and also has a high value of ΔD, which represents one-color reproducibility.

In contrast, one sample to which the DIR compound of the present invention is not used
With i-ior, sharpness and single-color reproducibility are greatly inferior.1 Even when the DIR compound of the present invention is used, high sharpness cannot be obtained when using an emulsion with an average aspect ratio of less than j:l. I can't do it.

Example λ Inert gelatin J Ot, potassium bromide 4t, distilled water/
Stir an aqueous solution containing l- with jOoC and add silver nitrate j, 0? 3jcc of an aqueous solution containing 3. -2, potassium iodide O.

Dill? Each aqueous solution Jjcc/'10C
pAgt-10K after 15 seconds of addition at a flow rate of C/min.
The mixture was raised and aged for 30 minutes to prepare an emulsion.

Next, a predetermined amount of an aqueous solution of silver nitrate/Hirojf/4 and an equimolar amount of an aqueous solution of a mixture of potassium bromide and potassium iodide were added at a predetermined temperature, a predetermined pAg, and an addition rate close to the critical growth rate. A flat core emulsion was prepared.

Continuing further.

Adding the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a composition different from that used in preparing the core emulsion in equimolar amounts at a rate close to the critical growth rate;
Core/shell type silver bromide tabular emulsion E-F that coats the core
was prepared.

The aspect ratio can be adjusted by adjusting pAg during core and shell preparation.
obtained by selecting.

Table 1-1 1) The average surface area in Tables 1-7 was determined in the same manner as in 1).

2) The mean ratios in Tables 1-7 were determined in the same manner as in 2).

Next, each layer having the composition shown below was coated on a transparent support to prepare a multilayer color photosensitive material. The results are shown in Table 1-3.

f Photosensitive layer composition) Numbers corresponding to each component are shown using the same notation method as shown in Example 1.

(Sample 0/) 1st layer: Antihalation layer black colloidal silver・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・Scissors 0. /! U-1...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0. jU-2...
・・・・・・・・・－・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・O、koHBS-j・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0. μ gelatin...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・1. jth layer, 2nd layer: middle layer C-7・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0.
10C-j ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・00l12, j-di-t-octylhydroquinone・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.0jHBS-/
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.10 gelatin・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・／, 10 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion f Silver iodide! Mole size, coefficient of variation regarding particle size/7% monodisperse average particle size O6qμ emulsion)...O, もC-l
Ko························
・・・・・・・・・・・・・・・0.3j(:'-/j
・・・・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.37C-j ・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.12('-7o・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.0j2HBS-j・・・・・・
···················river·····
... 0. JO sensitized raw material...
・・・・・・・・・・・・・・・・・・ 11.3X1
Same as 0-4 ■・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 1. ≠X / 0-5 same I
[[・・・・・・・・・・・・・・・・・・・・・・・・
...... Ko, J×l0-4 same IV...
・・・・・・・・・・・・・・・River・・・・・・・・・ ,3
．． 0×10-5 gelatin・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・／、
10th μ layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (coefficient of variation with respect to silver iodide 6 molar ratio 1 grain size/44 monodisperse average grain size/, 0 μ emulsion) Sensitizing dye processing・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ Il, jXlo-4 same I [...
·················river·······
・ i, zxio-5 sensitizing dye ■... River...
・・・・・・・・・・・・・・・・・・・JXlO-
4 Same ■ ・・・River・・・・・・・・・・・・・・・
・・・・・・・・・ Ko, O×105C-μ ・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・River・・・0.07IC-j ・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・o, Ohiro! HBS-/
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・o, oi.

gelatin·····················
・・・・・・・・・・・・・・・・・・0.10th! Layer: Middle layer! -G-t-octylhydroquinone ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・River...O0/2HBS-/
········river··············
・・・・・・・・・・・・0.20 Seratin ・・・・・・
Yu・・・・・・・・・・River・・・River・・・・・・River・
・/, 0 6th layer: 1st green-sensitive emulsion layer Emulsion E ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0. Sensitizing dye V・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 0x10-5 same ■ ・・
・・・・・・・・・・・・・・・・・・・・・・・・
...3.0xIO-4 same ■ ...River...
・・・・・・・・・・・・−・・・・・・ r, 0X1
0-4C-A・・・・・・・・・River・・・・・・・・・
・・・・・・・・・・・・・・・・・・・River・0.27
C-l ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・117. 0
72C-7・・・・・・・・・・・・・・・・・・
River・・・・・・・・・・・・・・・・・・0. /
2cmr ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・o,
oi.

HBS-／・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0. l! gelatin······················
・・・・・・・・・・・・・・・・・・0.70 7th layer:
λ green-sensitive emulsion layer Silver iodobromide emulsion (silver iodobromide 7 molar width - coefficient of variation with respect to grain size it <, average grain size O6 μ) ...
・・・・・・0.10 sensitizing dye ■・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・lt, 0X1
0-5 same ■ ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 1. jXlo-4 same
■ ・・・・・・・・・・・・・・・・・・・・・・・・
...... 3.0x10-4C-A ...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.07IC-/ ・・
・・・・・・・・・・・・・・・・・・・・・・・・
・River・・・・・・・・・・・・0.02IC-7・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・o, oitHBS-2・River・・・・・・・・・・・・・・・・・・・・・・・・
Out... o, i.

gelatin·····················
・・・・・・・・・・・・・・・・・・0,9/1st layer: Intermediate layer, J-T-octylhydroquinone ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・o、orHBS-2
・・・Yu・・・・・・・・・・・・・・・・・・
・・・・・・・・・o, i.

gelatin·····················
・・・・・・・・・・・・・・・・・・ 0.70 Second layer: Emulsion layer Silver iodobromide (silver iodide μmolar coefficient - coefficient of variation regarding grain size / average grain size at j4 0, lμ emulsion)・・・・・・・・・・・・・・・・・・
...O, aO sensitizing dye X...
・・・・・・・・・・・・・・・・・・j, 0×1O−
4C-t・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0.
0! IC-/da ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0.0
2! HBS-／・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0. /! l
-2・・・・・・・・・・・・・・・・・・・・・
・・・・・・ψ・彎・・・・・・ 0. /! gelatin··
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0. AO io layer: yellow filter layer yellow colloidal silver・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0. I! 2, J--G-t-
Octylhydroquinone・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0. ItHBS-
/ ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.20 Gelatin・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・o, t.

11th layer: 1st blue-sensitive emulsion layer Emulsion E ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・O0≠Sensitizing dye X■・・・・・・・・・・・・・・・・・・・
......ri, OX/Q-4C-?・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・／、l0C-t ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・o, os.

HBS-／・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・o, or.

Gelatin・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・／、! 1st co-layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (emulsion with an average grain size of 0.7μ with a coefficient of variation with respect to silver iodide 2 molar width 1 grain size/94) Sensitizing dye...・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・HajtX10-4C-9・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0. J/HBS-/
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・o, i, x gelatin・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・o, rr 73rd layer: Intermediate layer TJ-/ ・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・(1
17,12U-λ ・・・・・・・・・・・・・・・
・・・・・・River・・・・・・・・・・・・・・・・・・0
．． ItHBS-J・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0.12 Gelatin ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.7j 1st μ layer:
Holding layer silver iodobromide emulsion (silver iodide emulsion, average grain size o, or μ with a coefficient of variation regarding grain size of 104 r)
......O0/! Polymethyl methacrylate particles (diameter/, jμ) 3-/ ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・ o、
orS-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0. /! gelatin················
・・・・・・・・・・・・・・・・・・・・・・・・0.
10 In addition to the above composition, a surfactant and a gelatin hardening agent H-t were added to each layer.

(Sample-〇2-2041 The DIR compound in the third layer and first red-sensitive emulsion layer of sample coi was
-t u-C-t z, (x)(3ol (py)
Samples 202 to 202 were prepared in the same manner except that K was replaced.

sample 207 to sample 204) The first green-sensitive emulsion layer and the third layer of sample 20/-204
Samples 207 to 12 were prepared in the same manner except that Emulsion E in the first red-sensitive emulsion layer was replaced with Emulsion F in HP.

C sample λ73~col≠) 6th layer, 1st green-sensitive emulsion layer and 11th layer of sample λ7.2 @
l Instead of emulsion F in the blue-sensitive emulsion layer, use emulsion F and emulsion E by weight! A sample 2/J was prepared by replacing the mixture with a mixture of O and O. Furthermore, a sample 4L was prepared by replacing emulsion F with a mixture of emulsion F and emulsion E each containing 2j'L 714 in a weight ratio.

Samples 2/3 to 214 here! The average aspect ratios of the emulsions used are shown in Table 1-2.

Table 1-2 1) The average surface area of Table /-/ was determined in the same manner as for the cross ratio of 1.

f) The average aspect ratio of table /-/ was determined in the same manner as 1゜.

These samples were subjected to the same test as in Example 1.

The results obtained are shown in Table 2-3. These samples gave almost the same sensitivity and gradation. The RM
S values were measured using ILtIrμ diameter.

As for photographic performance, sensitivity and gradation were generally the same for Samples 20/-Kolhiro.

As is clear from Table 2-3, sample 2/0- of the present invention
5-j /≠ is the RMS value - for the comparative example KO/~λO
Excellent in MTF value and ΔDB'. In particular, it can be seen that it is significantly superior to the samples CoOIN, 203, 207 to Co0 using the DIR compounds C-/o, C-t 4t, and C-iz. In addition, samples 2/3 and 2/3, in which the average particle density ratio of emulsion grains was gradually decreased with respect to sample 2/3,
μ, 20t has a deteriorated RMS-MTF value.

Structure of the compound used in Example 1-2 -i U-CoC-λ C-J C-≠ -t -j Average molecular weight 30,000 α cr (U.S. Patent No. 4(,4(77,163) Coupler described in JP-A No. 1989-/2914c A/-1IIAJj)
C-// (Coupler described in U.S. Patent No. 3.27.!jμ) C-/2 (1) (, :5H11 ( '-/≠ (@Kaisho J-7-/!Ko 23≠ No.-Doyoter/29rltY, same t/-/1it3jt) N(J2 C-/yo (U.S. Patent No. Coupler included in μ, Kou, R, No. 222, JP-A No. 12, Rμ, No. J/-/μ63j) ate HBS-co didutyl phthalate HBS-j) li-n-hexyl phosphate H-t
CH2=CH-802-CH2=CH-CH2CH
2=CH802-CH2-CONH-CH2 sensitizing dye■ S-/S-2HB
S-/)+) Cresyl phosphate HBS-co Didutyl phthalate HBS-J) IJ -n-hexyl phosphate H-/ CH2=CH802CH2C0NHCH
2CH2=CH-802-CH2-CONH-CH22
H5 2H5 (CH214SO3Na Sensitizing dye

[Brief explanation of drawings]

FIG. 7 represents the characteristic curve. l represents the characteristic curve of the magenta color image of the green-sensitive layer, and λ represents the yellow color image density of the blue-sensitive layer due to uniform blue exposure. 3 represents the theoretical yellow density line of the blue sensitive layer upon uniform blue exposure. Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment dated 1985, April 1, 1985; Case description: 1932, Application No. 16≠GWata No. 2; Name of the invention: Silver logenide color photographic image source. Material 3
, Relationship with the case of the person making the amendment Patent applicant'4. Subject of amendment The statement in column 5 of [Detailed Description of the Invention] of the description and the section of ``Detailed Description of the Invention'' of the description of contents of the amendment is amended as follows. /) Correct "aspect only" in the second line of page 102 to "aspect ratio." 2) Daiichi Hiro! Between the 2nd and 7th lines of the page [Gelatin...................................0, J
Insert Oj. July 1986''￥OLl

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, at least 50% of the total projected area of the silver halide emulsion grains contains a tabular silver halide emulsion having an average aspect ratio of 5:1 or more. , and containing at least one compound that cleaves a development inhibitor when the compound cleaved after reaction with an oxidized developing agent reacts with another molecule of an oxidized developing agent. Photographic material.