JPH0480750A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure superior sharpness, color reproducibility and suitability to an automatic printer by incorporating a yellow colored cyan coupler into a nonphotosensitive layer. CONSTITUTION:This silver halide color photographic sensitive material has one or more blue-sensitive silver halide emulsion layers, one or more green- sensitive silver halide emulsion layers, one or more red-sensitive silver halide emulsion layers and one or more nonphotosensitive layers close to the red- sensitive silver halide emulsion layers and the nonphotosensitive layers contain a yellow colored cyan coupler. This coupler is a cyan coupler having its absorption max. in the visible absorption region between 400nm and 500nm and forming a cyan dye having its absorption max. in the visible absorption region between 630nm and 750nm by coupling with the oxidized body of an arom. prim. amine developing agent. Superior color reproducibility, sharpness and suitability to an automatic printer are ensured.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, in particular, it contains a yellow-colored cyan coupler in a non-light-sensitive layer close to a red-sensitive emulsion layer to improve sharpness and color reproducibility. The present invention also relates to a color photosensitive material for photographing that has excellent suitability for auto printers. (Prior Art) As a means for improving color reproducibility and sharpness, it is often recommended to use so-called DIR compounds described in, for example, JP-A-54-145135, JP-A-56114-946, and JP-A-57-151944. Are known. f
Although these compounds have improved the interlayer effect and edge effect, and improved color reproducibility and sharpness to some extent, these compounds do not release enough development inhibitors to suppress the development. There are problems such as not being able to obtain the glabellar effect or edge effect, and the desired glabellar effect not being obtained if the angry light layer that should be suppressed is not properly developed, so it is necessary to provide a sufficient effect in the entire hazy light area. I couldn't do 1. Moreover, in order to obtain this effect, the sensitivity of the added color-sensitive layer and the adjacent color-sensitive layer is lowered. On the other hand, it has been found that an effect similar to the interlayer effect from the red-sensitive emulsion layer to the blue-sensitive layer in terms of photographic performance can be obtained by using a yellow-colored cyan coupler in the red-sensitive emulsion layer. 1986-221748, Japanese Patent Application Publication No. 1319744, and West German Patent Publication No. 3815469
However, the method described in these patents, that is, the addition of these yellow-colored cyan couplers to the emulsion layer alone did not have sufficient effects. In addition, conventionally known yellow colored cyan couplers had problems such as the yellow dye having a small molecular extinction coefficient and low coupling activity. Furthermore, it was disclosed in Japanese Patent Application Laid-Open No. 51-13 that a diffusion-resistant colored coupler was used in the non-photosensitive layer between the green photosensitive layer and the red photosensitive layer.
No. 5535 describes the use of a diffusion-resistant colored coupler in the non-photosensitive layer between the red photosensitive layer and the support.
No. 117631, but these colored couplers are limited to those exhibiting a red color before coupling, and the structure is different from that of the present invention, so that the effects of the present invention cannot be obtained. . In addition, because the spectral absorption of the coloring dye of the yellow coupler used in conjunction with the hue of conventional colored couplers is not compatible, there are problems such as insufficient suitability for printing with various automatic printers used in the fabric lab. was there. (tJ, ff to be solved by the invention) The first object of the present invention is to provide a photosensitive material with excellent color reproducibility,
The second objective is to provide a sensitive material with excellent sharpness, and the third objective is to provide a photosensitive material with excellent sharpness.
The second objective is to provide a photosensitive material with excellent printability on an auto printer, and the fourth objective is to provide a photosensitive material with high sensitivity. (Problems to be Solved by the Invention) These objects of the present invention have been achieved by the following color photographic material. At least one layer each of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a non-photosensitive layer adjacent to the red-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material, which is characterized in that the above-mentioned non-light-sensitive layer contains a yellow-colored cyan coupler. / / / / / / / / Next, the yellow colored cyan coupler of the present invention will be explained. In the present invention, the yellow color tone uncoupler means that the maximum absorption in the visible absorption region of the coupler is 400 nm.
m to 500 nm, and is a cyan coupler that couples with an oxidized aromatic primary amine developing agent to form a cyan dye having an absorption maximum in the visible absorption region between 630 nm and 750 nm. say. Among the yellow-colored cyan couplers of the present invention, a water-soluble 6-hydroxy-2-pyridon-5-ylazo group, a water-soluble pyrazolone-4-ylazo group, and a water-soluble pyrazolone-4-ylazo group, a water-soluble 2-7-nylaminophenyl azo group or a water-soluble 2-
A cyan coupler capable of releasing a compound residue containing a sulfonamidophenylazo group is preferably used. The yellow colored cyan coupler of the present invention is preferably represented by the following general formulas (CI) to (CIV). General formula (CI) General formula (Cm) General formula (CI[[) General formula (CIV) R. R1゜R. General formula (C

In [) to (CI'tr'), cp is
Uncoupler residue (T is attached to its coupling position)
), T is the timing group, and k is an integer of 0 or 1.
, X includes N, 0, or S, so that (T)
, and represents a divalent linking group that connects with Q, where Q is
Represents an arylene group or a divalent heterocyclic group. In the general formula (cr), R1 and R1 are independently hydrogen atoms.
child, carboxyl group, sulfo group, cyano group, alkyl group
, cycloalkyl group, aryl group, heterocyclic group, carbamo
yl group, sulfamoyl group, carbonamide group, sulfamoyl group,
amide group or alkylsulfonyl group, R1 is hydrogen
atoms, alkyl groups, cycloalkyl groups, aryl groups or
each represents a heterocyclic group. However, T, X, Q, R
At least one of R2 or R1 is a water-soluble group (e.g.
Hydroxyl, carboxyl, sulfo, amino, amino
moniramil, phosphono, phosphino, hydroxysulfo
Niluoquin). It is well known that can take the following tautomeric structure.
These tautomer structures also have the general formula (
CI). (When RS is a hydrogen atom) ■1 Ho Ho (When R. is a hydrogen atom) (When R. is a hydrogen atom) (When Rr is a hydrogen atom) In general formula (CII), R4 is an acyl group or a sulfo group.
R3 is a substitutable group, " is an integer from 0 to 4.
represents a number. When j is an integer greater than or equal to 2, R4 is the same.
may also be different. However, T, X, Q, R4 or
At least one of R1 is a water-soluble group (e.g. hydroxy
syl, carboxyl, sulfo, phosphono, phosphino,
Hydroquine sulfonyloxy, amino, ammoniamil
) shall be included. In general formulas (CIO) and (CCV), R7 is water
Elementary atom, carphoquinol group, sulfo group, Noah 2 group, al
Kyl group, nocroalkyl group, aryl group, alkoxy group
, cycloalkyloquino group, aryloxy group, heterocycle
group, carbamoyl group, sulfamoyl group, carbonamide
do group, sulfonamido group, or alkylsulfonyl
, R1° is a hydrogen atom, an alkyl group, a cycloalkyl group,
Each represents an aryl group or a heterocyclic group. However, T
, XQ, R, or R1゜
Water-soluble groups (e.g. hydroxyl, carboxyl, sulfonate)
, phosphono, phosphino, hydroquinesulfonyloxy
, amino, ammoniamil). Rt. IQ They are isomers and are the same compound. Compounds represented by general formulas (C1) to (CIV) below
will be explained in more detail. The coupler residue represented by Cp is a known cyan coupler.
- residues (e.g. phenol type, naphthol type, etc.)
can be lost. Preferred examples of Cp include the following general formula (Cp6), (
Coupler residue represented by Cp-7) or (Cp-8)
can be mentioned. General formula (Cp-6) General formula (Cp General formula (Cp (Rss)) Free bond derived from the coupling position in the above formula
The hand represents the attachment position of the coupling-off group. In the above formula, R5b R5ZI R531R54 or
If R5S contains a diffusion-resistant group, it means that the total number of carbon atoms is
8 to 40, preferably 10 to 30
selected, otherwise the total number of carbons is 15 or less
preferable. Bis-type, telomeric-type or polymer-type caps
In the case of R, any of the above substituents represents a divalent group.
and concatenate repeating units. In this case the number of carbons
The range may be outside the specified range. In the following, R41 represents an aliphatic group, an aromatic group or a heterocyclic group.
, R4□ represents an aromatic group or a heterocyclic group, and R4
:l + R44 and Ras are hydrogen atoms, aliphatic groups,
Represents an aromatic group or a heterocyclic group. Below are R5I, R52, Rsz, R54, Rss
, d and e will be explained in detail. R51 has the same meaning as R4z. R52 and R41
Groups with the same meaning, R, C0N- group, R,,0CON- group, R4*
R4goR4,50□ N-group, R
,3NCON- group, R43R44R45 R110- group, R,, S- group, halogen atom, or R
, , represents an N-group. d represents O to 3. When d is plural, the plural R52s are the same substituent or different
represents a substituent. Also, each R52 is a divalent group.
may be connected to form a cyclic structure. A typical example of a divalent group for forming a cyclic structure is R4. Here f is O to 4
and g is an integer from 0 to 2, respectively. R23
represents a group having the same meaning as R4I. Ra4 is the same as R41
A group with the same meaning as Ra1, R55 is a group with the same meaning as Ra1, R,,0
CONH- group, R,,50,NH- group, RaxN CO
N- group, R4, NSO2N- group, Raa Ras
Raa Ra5R, 30- group, R,
, S- group, halogen atom or R=IN- group
. When there are multiple R5S, each R4 represents the same thing or different things. In the above, aliphatic group has 1 to 32 carbon atoms, preferably
1 to 22 saturated or unsaturated, chain or cyclic, straight chain or
or a branched, substituted or unsubstituted aliphatic hydrocarbon group
. Typical examples include methyl, ethyl, propyl, and
Sopropyl, butyl, (1) butyl, (i) butyl, (
1) Amino, hexyl, cyclohexyl, 2-ethylhexyl
xyl, octyl, 1.1,3.3-tetramethylbuty
decyl, dodecyl, hexadecyl, or octadeyl
One example is Sill. An aromatic group has 6 to 20 carbon atoms, preferably substituted or
Unsubstituted phenyl group, or substituted or unsubstituted naphyl group
It is a chill group. A heterocyclic group is a heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms.
Is it a nitrogen atom, an oxygen atom, or a sulfur atom as an elementary atom?
or preferably a 3- to 8-membered ring substitution selected from
is an unsubstituted heterocyclic group. Representative examples of heterocyclic groups include 2-pyridyl and 2-thienyl.
2-furyl, 1,3.4-thiadiazol-2-y
2,4-dioxo-1,3 imidazolidine-5-y
1,2,4-)lyazol-2-yl or 1-pyru
Examples include lazolyl. The aliphatic hydrocarbon group, aromatic group and heterocyclic group are substituted
Typical substituents include halogen atoms
, R4, 〇- group, R,, S- group, R,, C0N- group, R
,,NC〇- group, R,60CONR4*R4@Ra7 group, R,,5O2N- group, R,,NSO□- group, Raq
Ram R5-3ot- group, R4? ○C〇- group, R,, NC0N
- group, a group having the same meaning as R44, an R2HRaq group, an ano group, or a nido group. Here Ra
h represents an aliphatic group, an aromatic group, or a heterocyclic group, and R
a1, R4l1 and Raq are an aliphatic group and an aromatic group, respectively.
, represents a heterocyclic group or a hydrogen atom. aliphatic group, aromatic group
radical or heterocyclic group has the same meaning as previously defined;
be. In general formula (Cp-6), Rs+ is an aliphatic group or
Aromatic groups are preferred. RSz is a chloro atom, an aliphatic group or
or R,, CONH- group is preferable. d is 1 or 2
preferable. R5j is preferably an aromatic group. In general formula (Cp-7), R5□ is R,,C0NH
- groups are preferred. d is preferably 1. R54 is preferably an aliphatic group or an aromatic group. In general formula (Cp-8), e is preferably 0 or 1.
stomach. R5S is R,, OCONH- group, R,, C0
NH- group or R,,SO□hH- group are preferable.
The preferred substitution position is the 5-position of the naphthol ring. The timing group represented by T is a coupler and an aromatic primary
CP and oxidized product of amine developer and cambling reaction
is a group whose bond with X is cleaved after the bond of is cleaved,
Coupling reactivity adjustment, coupler stabilization, X or less
It is used for various purposes such as adjusting the release timing of Ta
Examples of the iming group include the following known groups. In the following, * mark is Cp, ** mark is X, or * mark is
CP and ** are combined with Q, respectively. (T-1) (T-2) CH. (T (T (R (T-5) 0iN\ba** (T *-0CHz (TC) In the formula, Ro. represents a group that can be substituted on the Hensen ring, and R
11 has the same meaning as explained for R4, and R,
□ represents a hydrogen atom or a substituent. t is 0 to 4
As a substituent for R8° and R12, which represents an integer, R
48, halogen atom, R430-R= 35-1R4z
(R-4) NC0-1R4ffOOC-R4,SO
,-1R,3(R,,)NSO□R4,CON (R,
)-1R,,SC2N (R,z)R,,C0-1R
,,COO-1R,,SO-,Nitro,R,,(R,,
)NCON (R,s) -, cyan, R4,0CON
(R-z)-1R430SO2R,, (R,,)N R43(R-) N S Oz N (R-s)-5
or k is an integer of O or 1, but generally k is O
In other words, it is preferable that Cp and χ bond directly.
stomach. X is a divalent bond with (T)k or more through N, O or S
is a linking group of -〇--S O000 II 11 II
ll0C-, -0CO--0C3--0CNHOSO
□--030, NH- or N combined with (T) or more
Heterocyclic groups (e.g. pyrrolidine, piperidine, morphol)
piperazine, pyrrole, pyrazole, imidazole
, 1.2.1-triazole, benzotriazole, su
Funonimide, phthalimide, oxazolidine-2,4
-dione, imidapridine-2,4-dione, 1.2.
Derived from 4-triacylidine-3,5-dione etc.
groups) or these groups and alkylene groups (e.g. methylene
, ethylene, propylene), cycloalkylene groups (e.g.
(1,4-chlorohequinlene), arylene group (e.g.
0-phenylene, P-phenylene), divalent heterocyclic group (
For example, 4) derived from pyridine, thiophene, etc.
-c. soz --coo--CONH 3○2NH--3O□O--NHCONH3Oh -
--NHCONH NH30, NH--NHCOO-, etc. composite linking group
is preferred. X is more preferably represented by the general formula (It)
I will be forgotten. General formula (I[) *X+ (L Xz);-**General formula (
In n), * indicates the bonding position with (T)k or more, **
is the bonding position with Q or below, X is 10- or -5-
, L is an alkylene group, X2 is a single bond, -O--5-1
-CO SO, --〇C--CO--NHC II II II o 0 0 -CNH---3O□ NH--NH5O2I SOx O05Oz QC○CNH- -NHC○ NHCNH NH30□ NH ocs--sc. 11]1OSOzNH or -NH3O□, m represents an integer of 0 to 3. The total number of carbon atoms in X (hereinafter referred to as the number of C)
) is preferably 0 to 12, more preferably 0 to 8.
be. The most preferable X is 0CH2CH20-
It is. Q represents an arylene group or a divalent heterocyclic group. Q is
In the case of an arylene group, even if the arylene group is a condensed ring,
Substituents (e.g. halogen atoms, hydroxyl, carboxy
Ru, sulfo, nitro, cyano, amino, ammonium,
Phosphono, phosphino, alkyl, cycloalkyl, a
Reel, carbonamide, sulfonamide, alkoxy
, aryloxy, acyl, sulfonyl, carboxyl
, carbamoyl, sulfamoyl).
, C number is preferably 6 to 15, more preferably 6 to 10
It is. When Q is a divalent heterocyclic group, the number of heterocyclic groups is small.
and one N, O, S, P, Se or Te
A 3- to 8-membered ring containing a heteroatom selected from
or a 5- to 7-membered monocyclic or fused ring heterocyclic group (e.g.
Pyridine, thiophene, furan, pyrrole, pyrazole
, imidazole, thiazole, oxazole, penzothi
Azur, benzoxazole, benzofuran, benzo
Thiophene, 13.4-thiadiazole, indole,
a group derived from quinoline etc.), and a substituent (Q
Even if has the same substituent as in the case of an arylene group)
The number of C is preferably 2 to 15, more preferably 2 to 15.
It is 10. Q is the most preferable and therefore the most preferable in the present invention.
Preferable. When R,, R, or R1 is an alkyl group, the alkyl
Regardless of whether the group is linear or branched, it has unsaturated bonds.
substituent (e.g. halogen atom,
Hydroxyl, carboxyl, sulfo, phosphono, phospho
fino, cyano, alkoxy, aryl, alkoxyca
rubonyl, amino, ammoniamil, acyl, carvone
amides, sulfonamides, carbamoyls, sulfamoyls
or sulfonyl). When R,, R, or R1 is a cycloalkyl group,
A cycloalkyl group is a 3- to 8-membered cycloalkyl group.
Even if it has a crosslinking group or contains an unsaturated bond,
, substituent (R+, Rz or R:I is an alkyl group)
Same as substituents. ). When R,, R, or R1 is an aryl group, aryl
Even if the group is a fused ring, the substituent (RR2 or R3 is
In addition to substituents for alkyl groups, alkyl, cycloal
There are kills, etc. ). When R,, R, or R3 is a heterocyclic group, a heterocyclic group
is at least one N, S, O, PSe or
3- to 8-membered (preferably) containing a heteroatom selected from Te in the ring
Preferably a 5- to 7-membered) monocyclic or condensed ring heterocyclic group (
For example imidazolyl, thienyl, pyrazolyl, thiazolyl
pyrinol, quinolinyl), and the substituent (R+
, same as one substituent when Rz or R1 is an aryl group)
It may have. Here, the carboxyl group replaces the carboxylade group with the sulfonate group.
The group is sulfonate M, and the phosphino group is phosphinate.
and the phosphono group contains the phosphonate group, respectively.
At this time, the counterions are Lj゛Na'', K', and ammonium.
Mu et al. R1 is preferably a hydrogen atom, a carboxyl group, or a C number of 1 to
10 alkyl groups (e.g. methyl, t-butyl, carbomethane)
methyl, 2-sulfomethyl, carboxinmethyl, 2-cal
Boquin methyl, 2-hydroxymethyl, Hensyl, ethyl
methyl, isopropyl) or C6-12 aryl group
(e.g. phenyl, 4-methoxyphenyl, 4-sulfonate)
phenyl), particularly preferably a hydrogen atom or a methyl group
or a carboxyl group. R2 is preferably a cyano group, a carboxyl group, or a C number of 1 to
10 carbamoyl groups, C number O-10 sulfamoyl
group, sulfo group, alkyl group having 1 to 10 carbon atoms (e.g. methyl
sulfonyl group, sulfomethyl), sulfonyl group having 1 to 10 carbon atoms (e.g.
For example, methylsulfonyl, phenylsulfonyl), C number 1
~10 carbonamide groups (e.g. acetamide, hemp)
zamide) or a sulfonamide group having 1 to 10 carbon atoms (e.g.
(e.g. methanesulfonamide, toluenesulfonamide)
and particularly preferably a cyano group, a carbamoyl group or
is a carboxyl group. R3 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms
(e.g. methyl, sulfomethyl, carboquinomethyl, 2
-sulfomethyl, 2-carboxymethyl, ethyl, n-
butyl, hensyl, 4-sulfohensyl) or C number 6
~15 aryl groups (e.g. evaphenyl, 4-carboxy
Phenyl, 3-carboxyphenyl, 4-methoxyphenyl
24-dicarboxyphenyl, 2-sulfophenyl
, 3-sulfophenyl, 4-sulfophenyl, 2.4-
disulfophenyl, 25-disulfophenyl),
More preferably a C1-7 alkyl group or a C6-7 alkyl group
10 aryl groups. R4 is specifically anru represented by general formula (III)
group or a sulfonyl group represented by the general formula. General formula (Ill) R,, C- (I ○ General formula (IV) R,,502 When RII is an alkyl group, the alkyl group is linear, branched
Even if it is branched or contains unsaturated bonds,
Often substituents (e.g. halogen atoms, hydroxyl, carbon
Luboxyl, sulfo, phosphono, phosphino, cyano,
Alkoxy, aryl, alkoxycarbonyl, amine
, ammoniamil, anol, carbonamide, sulfone
amido, carbamoyl, sulfamoyl, sulfonyl)
It may have. When R11 is a 7-chloroalkyl group, /chloroalkyl
The group is a 3- to 8-membered 7-chloroalkyl group, and is a bridging group.
Even if it has an unsaturated bond, the substituent (
R,, has the same substituent when it is an alkyl group)
It's okay. When R11 is an aryl group, the aryl group is a condensed ring.
Even if there is a substituent (substituent when R11 is an alkyl group)
In addition, there are alkyl, cycloalkyl, etc.)
You can leave it there. When R11 is a heterocyclic group, the heterocyclic group has at least one
selected from N, S, ○ P, Se or Te
3 to 8 members (preferably 5 to 7 members) containing a beta atom in the ring
) monocyclic or fused heterocyclic groups (e.g. imidazolytic
ru, thienyl, biraduryl, thiazolyl, pyridyl, ki
(nonlinyl), where the substituent (R,, is an aryl group)
may have the same substituents). Here, the carboxyl group is carboxylade I, sulfonate
The group is a sulfonate group, and the phosphino group is a phosphinate group.
and the phosphono group contains the phosphonate group, respectively.
At this time, the counter ions are LiNa', K'', and ammonium.
etc. RII is preferably an alkyl group having 1 to 10 carbon atoms (e.g.
Methyl, carboquinomethyl, sulfoethyl, cyanoe
cycloalkyl group having 5 to 8 carbon atoms (e.g. cyclo
hexyl, 2-carboxycyclohexyl), or
Allyl group having 6 to 10 carbon atoms (phenyl, 1-naphthyl, 4
-sulfophenyl), particularly preferably C number 1-
It is an alkyl group with 3 carbon atoms and an aryl group with 6 carbon atoms. R5 is a substitutable group, preferably an electron donating group
Yes, particularly preferably −NR, □R1+ or 10R
It is 34. The preferred substitution position is the 4-position. R1
□, R1 and Rla are hydrogen atoms, alkyl groups,
It is a loalkyl group, an aryl group or a heterocyclic group. Furthermore, a ring may be formed between RI2 and R13, and
The nitrogen heterocycle used is preferably an alicyclic one. J represents an integer from 0 to 4, preferably 1 or
2, particularly preferably 1. When R1 or R1゜ is an alkyl group, the alkyl group is
Whether linear or branched, it contains unsaturated bonds.
substituents (e.g. halogen atoms, hydrocarbon atoms).
xyl, carboxyl, sulfo, phosphono, phosphino
, cyano, alcoquino, aryl, alcoquine carboni
amino, ammoniamil, acyl, carbonamide
, sulfonamide, carbamoyl, sulfamoyl, sulphate
sulfonyl). When R9 or R3゜ is a cycloalkyl group, cycloalkyl group
A loalkyl group is a 3- to 8-membered cycloalkyl group,
, even if it has a crosslinking group or an unsaturated bond,
Substituent (substituent when R9 or R1゜ is an alkyl group)
). When R7 or R3゜ is an aryl group, the aryl group
Even if the substituent (R or RIG is a fused ring),
In addition to substituents for kyl groups, alkyl, cycloalkyl
). When R1 or R3゜ is a heterocyclic group, the heterocyclic group is
At least one N, S, 0. From P Se or Te
3- to 8-membered (preferably
5-7 membered) monocyclic or condensed ring heterocyclic group (e.g.
midazolyl, thienyl, pyrazolyl, thiazolyl, pyryl
zyl, quinolinyl) V with one substituent (Rq or R
IO has the same substituent as the aryl group)
Good too. Here, the carboxyl group replaces the carboxylade group with the sulfonate group.
The group is a sulfonate group, and the phosphino group is a phosphinate group.
and the phosphono group contains the phosphonate group, respectively.
At this time, the counterions are L1゛Na'', Ni', and ammonium.
Mu et al. R9 is preferably a cyano group, a carboxyl group, or a C number of 1 to
10 carbamoyl groups, C2-10 alkoxylic
Bonyl group, C7-11 aryloxycarbonyl group
, C number 0-10 sulfamoyl group, sulfo group, C number 1
~10 alkyl groups (e.g. methyl, carboxymethyl
, sulfomethyl), C1-10 sulfonyl group (e.g.
methylsulfonyl, phenylsulfonyl), C number 1~
10 carbonamide groups (e.g. acetamide, henz
amide), C1-10 sulfonamide group (e.g.
tansulfonamide, toluenesulfonamide), alkaline
Kyloxy group (e.g. methoxy, ethoxy) or ali
and phenoxy groups, particularly preferred
or cyano group, carbamoyl group, alkoxycarbonyl
group, carboxyl group. R3゜ is preferably a hydrogen atom, and C number is preferably an alkyl group having 1 to 12 carbon atoms.
groups (e.g. methyl, sulfomethyl, carboxymethyl
, ethyl, 2-sulfoethyl, 2carboxyethyl, 3
-Sulfopropyl, 3-carboxypropyl, 5-sulfopropyl
Hopentyl, 5-carboxypentyl, 4-sulfoben
Zyl) or C6-15 aryl group (e.g. phenyl) or C6-15 aryl group (e.g.
ru, 4-carboxyphenyl, 3-carboxyphenyl,
2.4-dicarboxyphenyl, 4-sulfophenyl,
3-sulfophenyl, 25-disulfophenyl, 2.4
-disulfophenyl), more preferably C number 1-
7 alkyl group or C6-10 aryl group
. Below = cp in general formulas (C1) to (C~'), R1
A specific example of 0 IG is shown below. (Example of Cp) CH CH CH CH CH CH Cm Hl, (n) CH CH CH CH. (i) C, Hq OCN CH C,H CH CH H CH CzHs CH -Hs Ch H+z(n) nA (Example of X) -O-, -3-, -OCH, -2-OCH2CHz -
OCHz CHz○-, -0CH2CH2CH20-1
〇(CH2CH20) z , 0CHz CHz
S-〇CH2CH2NHCO-, -0CH2CH2N
H5○20CH2CH25o2-, -0CH2CH2Q
C○OCH, CH, C0--3CH2CONH-3CH
, COO-3-○CHCONH-. CH3 10CHHz CHz O20,-,-0COOCHz
CH, 0CHZ CHCHzCO□HCo2H -OCR,CHO-. 0CRCH,0- CO□H CO□H -OCR,CHS- QC) (, CHO Co, H Oz Na (Example of Q) So, K SO: +Na and OOH Ro. H CH. CH, CH3 0zNa O2H 3O□ Na Urn CN C0□CzHs CO2C2H5 03Na CO□H CHzCHzSOxNa CI(2CO□H CHzCHzSOJa CHzCHzSOzNa CHzCHzSOzNa CO 2C2H R1゜CO□H 0xNa so, Na Specific examples of the yellow color tone uncoupler of the present invention are shown below.
However, it is not limited to these. (YC ■) (YC-2) (YC-3) (YC H (YC (YC (YC (YC-8) (YC-9) 〈;ν (YC (YC-11) (YC-12) LJ ( VC (YC-14) (YC-15) (YC (VC (YC H CHz CHz SOx Na (YC H (YC (YC-23) H CH2CH2S○, Na CH2CH25o1Na O3Na (YC (YC-25) C6H+3(n) C○○I'' (YC 00H z Hs (YC (YC-29) C6H1,3(n) wa (YC (YC (YC (YC (YC (YC-38) (YC-39) H NtiUIJl,, 1- 13 (YC-41) H (YC H OChHl 3 CI (30C6) + 1:1 (YC Kano (YC CH CH, OC, H CHJ C6H13 (YC CH CHxOC6H13 (YC-46) CH CH30CJ12 (YC CH (YC-48) ) CH2CH3 (YC (YC O3Na (YC CH2Co, H (YC-54) CHz CHz SOz Na Yellow colored compound represented by the general formula (CI) of the present invention
Couplers are generally 6-hydroxy-2-pyridone and couplers.
Aromatic diazonium salts or heterocyclic diazonium salts containing
Synthesized by diazo coupling reaction with zonium salt
be able to. The former, θ-hydroxy-2-pyridones, are talin.
"Heterocyclic Compounds - Pyridine and its Derivatives" edited by Sberg
Classes - Part 3” (Interscience Publishing, 1962
), Journal of the American ``Chemical
Society (J. Am, Chem, Soc,) 1943, 65 volumes,
449 pages, Journal on the Chemical Technology
- and biotechnology (J, Chem,
Tech. Biotechnol, ) 1986, Volume 36, 41
Page 0, Tetrahedron 1
966, Vol. 22, p. 445, Special Publication No. 1987-52827
, West German Patent No. 2,162,612, West German Patent No. 2.349.7
No. 09, No. 2,902,486, U.S. Patent No. 3,763
．． It can be synthesized by the method described in No. 170 and the like. The latter diazonium salt is disclosed in U.S. Patent No. 4.004929.
, No. 4,138,258, Japanese Patent Publication No. 6172244,
Synthesized by the method described in No. 61-273543 etc.
be able to. 6-hydroxy-2-pyridones and dia
The diazo coupling reaction with zonium salt is performed using methanol,
Ethanol, methyl cellosolve, acetic acid, N,N-dimethy
Formamide, N,N-dimethylacetamide, Tet
Solvents such as lahydrofuran, dioxane, water, etc. or these
It can be carried out in a mixed solvent of. At this time, as a base
Sodium acetate, potassium acetate, sodium carbonate, charcoal
acid potassium, sodium bicarbonate, sodium hydroxide,
Potassium hydroxide, pyridine, triethylamine, tetra
Methylurea, tetramethylguanidine, etc. can be used.
can. The reaction temperature is usually -78°C to 60°C, preferably 20°C.
℃~30''C. Examples of synthesis of the yellow colored coupler of the present invention are shown below.
vinegar. Kasumi 110γ1 ditaurine 125.2g and potassium hydroxide 66g
Add 500 mf of alcohol, heat and stir, and add methyl cyanoacetate.
110 g of the solution was added dropwise over about 1 hour. After heating under reflux for 5 hours, it was left to stand overnight, and the precipitated crystals were filtered.
The crystals of compound a are removed by washing with ethanol and drying.
202.6g of crystals were obtained. ■ Enterprise ■ 11.5g of Jinkai compound a and 3.5g of potassium carbonate and 11g of water
．． Add 5ml and heat on a steam bath while stirring.
7.8 g of ethyl cetoacetate was added dropwise, and the mixture was further stirred for 7 hours.
Ta. After cooling, add 9.2 mf of concentrated hydrochloric acid and stir.
Crystals precipitated. Filter, wash with methanol and dry.
As a result, 10.4 g of crystals of the compound Su were obtained. Kapu-YC-mu by the synthetic method described in U.S. Pat. No. 4,138,258.
1 g of the compound ClO, synthesized by
Dissolved in Muamide 60mf and Methyl Cellosolve 60ml
4.3 ml of concentrated hydrochloric acid was added to the water-cooled solution, and then sulfurous acid was added.
A solution of 1.84 g of sodium in 5 mf of water was added dropwise, and the diazo
A solution of Nium was prepared. Next, compound b7゜8g and acetic acid
8.2 g of sodium, 60 ml of methyl cellosolve and water
Add 20 m2 of the diazonium while stirring under water cooling.
After adding the solution 6 drops, stir for another 1 hour and then at room temperature for 2 hours.
The mixture was stirred and the precipitated crystals were filtered. After washing with water and drying, remove the crystals.
Dispersed in 500ml of methanol and heated under reflux for 1 hour.
It got cold. The crystals were filtered, washed with methanol, and dried.
Red crystals of the desired exemplary coupler (YC-1)
13.6g was obtained. The melting point of this compound is 269-272'C (decomposition).
, the structure is 'HNMR spectrum, mass spectrum and original
Confirmed by elementary analysis. In addition, this compound in methanol
The maximum absorption wavelength of is 457.7 nm, and the molecular extinction coefficient is 41.
300, good as a yellow colored coupler.
The spectral absorption characteristics were shown. (Synthesis Example 2) Synthesis of Exemplary Coupler (VC-3) JP-A No. 6
Compound synthesized by the synthesis method described in No. 2 85242
75m of N,N-dimethylformamide to 19.2g of product d
Add 1 and 75 ml of methyl cellosolve, dissolve, and cool with water.
5. Add concentrated hydrochloric acid while stirring. 6m+4! and then add
0 drops of a solution of 25 g of sodium nitrate in 5 ml of water
After stirring for 1 hour, stir at room temperature for another 1 hour to dissolve the diazonium solution.
A liquid was prepared. Add 1 g of compound blo and 10.7 g of sodium acetate.
Circelosolve 75mj! Add 26mj2 of water and
The diazonium solution was added dropwise while stirring under cooling.
After dropping for 1 hour, stir at room temperature for another 2 hours to remove the precipitated crystals.
The crystals were filtered. Next, the crystal is 200m/! of methanol
A solution of 2.2 g of thorium hydroxide in 10 ml of water
was added dropwise and stirred for 3 hours. Neutralized with concentrated hydrochloric acid and precipitated
The crystals were washed with water and methanol, and then dried. The resulting crude
The crystals were purified using hot methanol as in Synthesis Example 1.
The desired exemplary coupler (YC3) is converted to 14.
I got 8g. The melting point of this compound is 246-251℃ (decomposition
), and the structure is 'HNMR spectrum, mass spectrum
Confirmed by sample and elemental analysis. In addition, the methano
The maximum absorption wavelength in the glass is 457.6 nm, and the molecular absorption coefficient
The number is 42,700, and it is a yellow colored coupler.
It showed good spectral absorption characteristics. = O Kasumi Jυ口 ≧ 137.1 g of anthranilic acid to 600 m of acetonitrile
Add 92゜5g of diketene to the mixture under heat and stir for about 1 hour.
It dripped in between. After heating under reflux for 1 hour, cool to room temperature and precipitate.
The crystals were filtered, washed with acetonitrile, and dried.
200.5 g of crystals of compound e were obtained. Clasp 1 raw gold cinnabar compound e199. Ig, ethyl cyanoacetate 89°2g,
Add 344 g of 28% sodium methoxide to 0.0 g of methanol.
91 and reacted for 8 hours at 120°C in an autoclave.
Ta. -After standing overnight, the reaction mixture was concentrated under reduced pressure and 700ml of water was added.
j! was added and acidified with 230 ml of concentrated hydrochloric acid. precipitation
The resulting crystals were collected by filtration, and the resulting crude crystals were dissolved in ethyl acetate and acetate.
Compound f, 152 was prepared by heating and washing with a mixed solvent of tonitrile.
I got g. Synthesis of Exemplary Coupler (YC-28) Following the synthesis method described in U.S. Pat. No. 4,138,258.
Compound g, 13.0 g, synthesized as above was heated with N. Dissolved in 40ml of N-dimethylformamide and concentrated on a water-cooled system.
Add 4.5 mj2 of hydrochloric acid, then 1.5 mj2 of sodium nitrite.
Add 48g of water 5mf solution dropwise to prepare diazonium solution.
I arranged it. Next, compound f6. Og and 8g sodium acetate
20mj of N,N-dimethylformamide! and water 15
ml of the diazonium solution and stirred under water cooling.
was dripped. After the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. acidify with hydrochloric acid,
After extraction with ethyl acetate and washing with water, concentrate under reduced pressure.
The condensate was recrystallized from a mixed solvent of ethyl acetate and methanol.
13 g of yellow crystals of the exemplary coupler (YC-28) were obtained. The melting point of this coupler (YC28) is 154-6°C.
, the structure is 'HNMR spectrum, mass spectrum and original
Confirmed by elementary analysis. In addition, this compound in methanol
Maximum absorption wavelength is 458.2 nm, molecular extinction coefficient is 428
00, which is good as a yellow colored coupler.
It showed light absorption characteristics. (Synthesis Example 4) Synthesis of Exemplary Coupler YC 42 Exemplary Coupler YC (1) Synthesis of Compound 3 1445.5 g of phenyl ester and isopropanol
290.1g of amine to 60C1d of acetonitrile! During,
The mixture was heated under reflux for 2 hours. After cooling with water, the precipitated crystals are collected by filtration and dried.
After drying, 3342 g of the compound was obtained. mp, 162-5℃ (2) Synthesis of compound 5 3341 g of hydroxyl compound and 2-hexyldecanoyl
Add 231g of loride to 880ml of acetonitrile for 2 hours.
After heating under reflux and cooling with water, the precipitated crystals are collected by filtration, dried and combined.
5,437 g of the product was obtained. mp, 97-100°C (3) Synthesis of compound 6 5370 g of nitro compound, 6 g of 10% Pd-C catalyst, ethyl acetate
Place Chill 11 in an autoclave and soak in water at 50℃ for 3 hours.
Attached. After the reduction, the catalyst is filtered off and the filtrate is reduced under reduced pressure.
The residue obtained by condensation was crystallized with n-hexane to precipitate
The crystals were collected by filtration and dried to obtain 7327 g of an amine compound. mp
, 95-7°C (4) 720.8 g of the synthetic amine compound of exemplary coupler YC-42 was added to dimethylformamide 601.
After dissolving, concentrated hydrochloric acid 7.6- was added under water cooling. Further sub
Add an aqueous solution of 2.7 g of sodium nitrate and 1 (ld) water for 20 minutes.
The solution was added dropwise, and stirring was continued for 30 minutes to prepare a diazo solution. Meanwhile, add 79.7 g of pyridone and 13 g of sodium acetate to 3 O of water.
-, dimethylformamide 30-, and heated.
After dissolving, cool with water and add the above diazo while stirring at 10°C or less.
The liquid was added slowly. After continuing stirring for another 15 minutes,
It was extracted with ethyl acetate and washed with water three times. Reduce organic layer
It was compressed under 4 pressure, and the residue was crystallized with methanol and ethyl acetate.
The resulting crystals were collected by filtration and dried to give example coupler YC-42.
1.2 g was obtained. mp, 1179℃ Yellow color represented by general formulas (C■) to (CCV)
The decyan coupler is published in Japanese Patent Publication No. 58-6939,
No. 1-197563 and represented by the general formula (CI)
The coupler synthesis method is based on the method described in the patents etc. mentioned above.
can be synthesized. In the present invention, the general formula (CI) and the He-IG formula (C
The yellow colored cyan coupler represented by II) is
Even more preferably used and represented by general 2 (CI)
is particularly preferably used. The yellow-colored cyan coupler of the present invention is red-sensitive.
It is added to the non-light sensitive layer adjacent to the emulsion layer. close here
means directly adjacent or another non-photosensitive layer.
Indicates that it is installed in one layer. Here, the non-photosensitive layer includes halogen that has not been chemically sensitized.
Silver emulsion, fine grain silver halide emulsion, colloidal silver grains
Coupler, dye, color mixing inhibitor, ultraviolet absorber, hydrophilic
or lipophilic polymers and high boiling point solvents.
May have. Yellow-colored cyan coupler-containing non-photosensitive layer
It is fine as long as it is close to the photosensitive emulsion layer, but to improve sharpness
From the viewpoint of
Proximity or simultaneous proximity to red-sensitive emulsion layer and support
is preferable, from the viewpoint of increasing sensitivity and improving color reproducibility.
, red-sensitive, especially adjacent to the most sensitive red-sensitive emulsion layer.
It is preferable that L! As for you, yellow color
Red cyan coupler has the highest sensitivity red photosensitive milk i! FI layer and
Added to the adjacent non-photosensitive layer at the same time as the low-speed green-sensitive emulsion layer.
added. The highest sensitivity red-sensitive emulsion layer and the lowest (or intermediate)
) Added to the adjacent non-photosensitive layer at the same time as the red-sensitive emulsion layer.
added. or a low-sensitivity blue-sensitive layer adjacent to and supporting the blue-sensitive layer.
It is added to the non-photosensitive layer adjacent to the carrier. The total amount added to the sensitive material is 0.005 to 030 g/distance
and preferably 0.02 to 0.20 g/rd, etc.
The amount is preferably 0.03 to 0.15 g/ba. The method of adding the yellow colored cyan coupler of the present invention is
Add it in the same way as a regular coupler as described below.
is possible. The light-sensitive material of the present invention has a blue-sensitizing layer on a support, a green-sensitizing layer, and a green-sensitizing layer on a support.
layer, at least one silver halide emulsion layer of the red-sensitive layer
It is sufficient if the silver halide emulsion layer and the non-silver halide emulsion layer are
There is no particular restriction on the number of photosensitive layers and the layer order; typical
For example, on a support, the color sensitivity is substantially the same.
consists of multiple silver halide emulsion layers with different sensitivities.
Silver halide photographic material having at least one photosensitive layer
The photosensitive layer is sensitive to blue light, green light, and red light.
It is a unit photosensitive layer that has color sensitivity to any one of the
In silver halide color photographic materials, the unit is generally
The arrangement of the photosensitive layers is from the support side to the red sensitive layer and the green sensitive layer.
The chromatic layer is placed in this order, followed by the blue-chromatic layer. However, depending on the purpose
Even if the above installation order is reversed, the same color-sensitive layer
The order of placement may be such that different photosensitive layers are sandwiched between them. Between the above silver halide photosensitive layers and the top and bottom layers
may be provided with a non-photosensitive layer other than the one according to the present invention. The intermediate layer of the present invention and the above-mentioned intermediate layer include Jikai No. 8,
No. 59-113440, No. 61-20037, No. 61
A coupler as described in -20038, D
IR compounds etc. may be included and are commonly used.
The sea urchin may contain a color mixing inhibitor. The multiple silver halide emulsion layers constituting each unit photosensitive layer are
, West German Patent No. 1,121,470 or British Patent No.
No. 923,045, the high speed emulsion layer, the low
A two-layer structure of sensitive emulsion layers can be preferably used. Usually, the arrangement is such that the photosensitivity gradually decreases toward the support.
It is preferable that the halogen emulsion layers
A photosensitive layer may be provided.
No. 112751, No. 62200350, No. 62-20
Described in No. 6541, No. 62-206543, etc.
A low-speed emulsion layer is placed on the side far from the support, and a low-speed emulsion layer is placed close to the support.
A high-sensitivity emulsion layer may be provided on the opposite side. As a specific example, from the side farthest from the support, low sensitivity blue light
Color layer (BL) / High sensitivity blue sensitive layer (BH) / High sensitivity
Green photosensitive layer (GH) / Low sensitivity blue photosensitive layer (GL) / High
High-sensitivity red-sensitive layer (RH) /low-sensitivity red-sensitive layer (R1,
) page 11, or 81 (/BL/GL/GH/R11
/l? In the order of L, or BH/BL/GH/GL/R1,
/RH, etc. It is also stated in Japanese Patent Publication No. 55-34932.
From the side farthest from the support, the blue-sensitive layer/Gll/
They can also be arranged in the order of R+(/GL/Ill.
JP-A-56-25738 and JP-A-62-63936
on the side farthest from the support, as specified in the specification.
Blue photosensitive layer/GL/RL/Gll/l? Arranged in one ton of H
You can also queue. It is also stated in the Japanese Patent Publication No. 49-15495.
The upper layer is the silver halide emulsion layer with the highest sensitivity, and the middle layer is the silver halide emulsion layer with the highest sensitivity.
A silver halide emulsion layer with a lower sensitivity than that, the lower layer
A silver halide emulsion layer with lower sensitivity than the middle layer is placed.
The photosensitivity gradually decreases toward the support.
Mention may be made of an arrangement consisting of three different layers. like this
Even if it is composed of three layers with different photosensitivity,
As described in specification No. 59-202464,
- Medium sensitivity from the side far from the support in the color-sensitive layer
The layers are arranged in the following order: emulsion layer/high-temperature emulsion layer/low-temperature emulsion layer.
Good too. In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Or low-speed emulsion N/medium-speed emulsion layer/high-speed emulsion layer.
They may be arranged in any order. Also, if there are 4 or more layers, please change the arrangement as above.
stomach. As mentioned above, there are various types depending on the purpose of each photosensitive material.
You can choose the layer structure and arrangement. Contained in the photographic emulsion layer of the photographic photosensitive material used in the present invention
The preferred silver halide contains less than about 30 mole percent iodide.
Silver-containing silver iodobromide, silver iodochloride, or iodosalt odor
It is chemical silver. Preferred for vF is about 2 mol% to about 10
Silver iodobromide or iodide salts containing up to mol% silver iodide
It is silver bromide. Silver halide grains in photographic emulsions are cubic, octahedral, and decahedral.
Those with regular crystals such as tetrahedrons, spherical, plate-shaped
crystals with irregular crystal shapes, such as crystals with twin planes,
It may be one with crystal defects or a composite form thereof.
. The grain size of silver halide is fine particles of approximately 0.2 microns or less.
However, the projected area diameter is about 10 microns.
It may be a polydisperse emulsion or a monodisperse emulsion. Silver halide photographic emulsions that can be used in the present invention include, for example,
Search Disclosure (RD) Nα17643
(December 1978), pp. 22-23, “1. Emulsion production
(Emulsion preparation and
types)”, # and the same Ni118716 (
November 1979), 648 pages, 307105
(November 1989), pp. 863-865, and
Graphic “Physics and Chemistry of Photography”, Paul Montell
Published by P, Glafkides, Chemie et al.
Ph1sique Photographique,
Paul Montel, 1967), Duffin,
"Photographic Emulsion Chemistry", published by Focal Press (G, F, D
uffinPhotographic Emulsio
n Chemistry (Focal Press1
966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, published by Focal Press (V, L, Zelikma
Netal、Making and Coatin
g Photographic Emulsion,
Focal Press, 1964) etc.
It can be prepared using the same method. U.S. Patent Nos. 3,574,628 and 3,655,39
No. 4 and British Patent No. L413.748, etc.
Also preferred are monodispersed emulsions. Also, tabular grains with an aspect ratio of about 3 or more
can also be used in the present invention. Tabular grains are
graphic science and engineering
Gutoff, Photographic Sci.
ence and Engineering), No.
14, pp. 248-257 (1970); U.S. Patent No. 4
, 434,226, 4,414.310, 4,
433.048, 4,439.520 and UK
It can be easily done by the method described in Patent No. 2.112.157 etc.
It can be simply prepared. Even if the crystal structure is -like, it is a halo whose inside and outside are different.
It may have a layered structure.
Also, epitaxial junctions can have different compositions.
silver halide may be bonded, and for example silver halide may be bonded.
Bonding with compounds other than silver halide such as silver oxide and lead oxide
may also contain mixtures of particles of various crystalline forms.
May be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface.
However, even with the internal latent image type formed inside the particle, the surface and internal
Any type with a latent image may be used, but negative type
It is necessary that the emulsion is Of the internal latent image types,
Core/shell type interior described in Kaisho 63-264740
This core/shell type internal latent emulsion may be a latent image type emulsion.
The method for preparing image-type emulsions is described in JP-A-59-133542.
Are listed. The shell thickness of this emulsion varies depending on the development process, etc.
is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.
Yes. Silver halide emulsions are typically subjected to physical ripening, chemical ripening and
Use one that has been spectrally sensitized. used in such processes.
The additives used are Research Disclosure 1!1
117643, same N[L 18716 and same 307
105, and the relevant parts are shown in the table below.
I stopped it. The light-sensitive material of the present invention includes grains of a light-sensitive silver halide emulsion.
size, particle size distribution, halogen composition, particle shape,
Two or more types of emulsions that differ in at least one characteristic of sensitivity
can be used mixed in the same layer. The particle surface described in U.S. Pat. No. 4,082,553
Blurred Silver Halide Grains, U.S. Pat. No. 4.626.4
Inside the particle described in No. 98 and JP-A No. 59-214852
Silver halide particles and colloidal silver are
a silver halide emulsion layer and/or a substantially non-light-sensitive parent layer;
It can be preferably used in an aqueous colloid layer. What is a silver halide grain with a puffed interior or surface?
, -like (
silver halide grains that can be developed (non-imagewise)
say. Silver halide grains with thickened interior or surface
The method for preparing the eggs is described in U.S. Pat. No. 4,626,498,
It is described in No. 59-214852. Core with puffed inside of grain/nonyl type silver halide grain
The silver halide that forms the inner core of the child is the same halogen
Whether it has a different composition or a different halogen composition.
good. Silver halide coated inside or on the surface of the grain
Silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide
A deviation can also be used. these covered ha
There is no particular limitation on the grain size of silver halide grains, but
The average particle size is 0.01 to 0.75 μ■, especially
A value of 0.05 to 0.6 μm is preferable. Also, regarding the particle shape,
There are no particular limitations on the particles, and regular particles may be used.
Polydisperse emulsions may be used, but monodisperse emulsions (silver halide grains
At least 95% of the amount or number of particles is ±4 of the average particle size
(having a particle size within 0%) is preferable.
. The present invention includes the use of non-photosensitive fine grain silver halide.
The non-photosensitive fine grain silver halide, which is preferably
During imagewise exposure to obtain an image, it is not exposed to light;
Silver halide that is not substantially developed during the development process.
It is fine particles and is preferably not fogged beforehand.
Delicious. Fine-grain silver halide has a silver bromide content of 0 to 100 moles.
silver chloride and/or silver iodide as required.
may contain silver iodide, preferably 0.5 to 10 moles of silver iodide.
%. Fine-grain silver halide has an average grain size (circle equivalent straight line of projected area)
A layer with an average diameter (+fi) of 0.01 to 0.5μ is preferable.
, 0.02 to 0.2μ■ are more preferable. Fine-grain silver halide is the same as ordinary photosensitive silver halide.
It can be prepared in various ways. In this case, the silver halide grains
The surface need not be optically enhanced or spectrally sensitized.
is also unnecessary. However, before adding this to the coating solution,
Standing, rough triazole type, azaindene type,
Inzothiadurium or mercapto compounds or
It is possible to add a known stabilizer such as a zinc compound.
Preferably, this fine-grain silver halide grain-containing layer is coated with a colloid.
It is possible to preferably contain silver. The coating silver amount of the photosensitive material of the present invention is preferably 6.0 g/bore or less.
Most preferably, the amount is 4.5 g/bo or less. Known photographic additives that can be used in the present invention also include the above three additives.
It is stated in the research disclosure and below.
The relevant entries are shown in the table below. Prevents deterioration of photographic performance due to formaldehyde gas
In order to prevent
, No. 435, 503.
Accordingly, a compound that can be immobilized is added to the photosensitive material.
is preferred. U.S. Patent No. 4,740.454 for the photosensitive material of the present invention
, No. 4.788,132, JP-A-62-18539
Mercapto compounds described in JP-A No. 1283551
It is preferable to contain. The photosensitive material of the present invention is described in JP-A No. 1-106052.
, regardless of the amount of developed silver produced during the development process.
Blurring agents, development accelerators, silver halide solvents or the like
It is preferable to contain a compound that releases a precursor of
. International Publication No. 088104794 for the photosensitive material of the present invention
, dispersed by the method described in Special Table of Contents No. 11-502912.
EP 317.308A, U.S. Pat.
, No. 420,555, described in JP-A No. 1-259358
It is preferable to contain a dye of. Various color couplers can be used in the present invention.
A specific example is the aforementioned Research Disclosure Koji.
17643, ■-C-C2 and Nα307105
, ■-C-G. As a yellow coupler, for example, U.S. Patent Box 3.93
3.501, 4.022,620, 4.3
No. 26.024, No. 4.401,752, No. 4.
No. 248.961, Special Publication No. 58-10739, British Special Publication No.
No. 1,425,020, No. 1.476.760
, U.S. Patent Box 3,973,968, U.S. Patent No. 4.314,
No. 023, No. 4,511.649, European Patent No. 24
No. 9,473A, etc. are preferred. As magenta couplers, 5-pyrazolone and pyrazo
Loazole compounds are preferred, US Patent Box 4.31
No. 0.619, No. 4.351,897, European Patent No.
No. 73,636, U.S. Patent Box 3,061,432,
No. 3725.067, Research Disclosure
No. 24220 (June 1984), Japanese Patent Application Publication No. 1983
-33552, Research Disclosure 24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 60-35730, No. 61-72238, No. 60-35730, No.
No. 55-118034, No. 60-185951, United States
Patent Box No. 4500.630, Patent Box No. 4.540.654
, No. 4,556.630, International Publication-088104
Particularly preferred are those described in No. 795 and the like. As cyan couplers, phenolic and naphthol
U.S. Patent Box 4.052.212
No. 4,146,396, No. 4,228.23
No. 3, No. 4.296,200, No. 2,369.9
No. 29, No. 2,801, No. 171, No. 2,772.
No. 162, No. 2,895,826, No. 3,772
．． No. 002, No. 3.758.308, No. 4.33
No. 4.011, No. 4.327,173, West German Patent Publication
Patent No. 3゜329.729, European Patent No. 121.365
No. A, No. 249°453A, U.S. Patent Box 3,446
, No. 622, No. 4,333.999, No. 4,77
No. 5,616, No. 4.451,559, No. 4.4
No. 27.767, No. 4,690.889, No. 4.
No. 254212, No. 4.296.199, Japanese Unexamined Patent Publication No. 6
1-42658 and the like are preferred. moreover,
JP-A-64-553, JP-A-64-554, JP-A-64-5
55, pyrazoloazole compounds described in 64-556.
puller, or the model described in U.S. Patent Box 4°818,672.
Midazole couplers can also be used. A typical example of a polymerized dye-forming coupler is
Permit No. 3.451,820, No. 4,080,211
, No. 4,367.282, No. 4.409.320
No. 4.576910, British Patent No. 2.102.1
No. 37, European Patent No. 341188A, etc.
Ru. As a coupler whose coloring dye has an appropriate diffusivity, American
National Patent No. 4,366.237, British Patent No. 2,125
．． 570, European Patent No. 96,570, West German Patent (Public Patent)
3,234,533 is preferred. Colored coupler to correct unnecessary absorption of color pigments
In addition to the yellow colored cyan coupler of the present invention,
is Research Disclosure Seed 17643■-
Section G, ■-G section of the same seed 307105, U.S. Patent No. 4.1
No. 63,670, Special Publication No. 57-39413, U.S. Patent
No. 4,004,929, No. 4,138,258,
Preference is given to those described in British Patent No. 1,146,368.
stomach. Also, the model described in U.S. Pat. No. 4,774,181
The fluorescent dye released during coupling can prevent the coloring dye from dissipating.
Couplers that correct absorption requirements and U.S. Pat. No. 4,777.
Can react with the developing agent described in No. 120 to form a dye
Using a coupler that has a dye precursor group as a leaving group
It is also preferable to be there. Releases photographically useful residues upon calf pulling
Compounds can also be preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned RD
17643, ■-F term and same stone 307105, ■-F
The patent described in JP-A No. 57-151944,
No. 57-154234, No. 60484248, No. 63
-37346, 63-37350, U.S. Patent 4,
Described in No. 248,962 and No. 4,782,012
Preferably. Releases nucleating agent or development accelerator in image form during development
As a coupler, British Patent No. 2.097.140,
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred. Also, JP-A-60-107029, JP-A No. 60-2523
No. 40, Japanese Patent Publication No. 144940, Japanese Patent Publication No. 1-45687
Due to the oxidation-reduction reaction with the oxidized form of the described developing agent, fog is formed.
Chemicals that release oxidizing agents, development accelerators, silver halide solvents, etc.
Compounds are also preferred. Other compounds that can be used in the photosensitive material of the present invention
As described in U.S. Patent No. 4.130.427 etc.
Competitive coupler, U.S. Pat. No. 4,283,472;
No. 4,338.393, No. 4,310.618, etc.
The multi-equivalent coupler described in JP-A-60-185950,
DIR redox described in JP-A-6224252 etc.
compound releasing coupler, DIR coupler releasing coupler, DI
R coupler releasing redox compound or DIR redon
Oxus-releasing redox compound, European Patent No. 173°302
No. A, the color is restored after detachment as described in No. 313,308A.
Dye-releasing coupler, R, D, 11449, 2
4241, bleaching described in JP-A No. 61-201247, etc.
Facilitated release coupler, U.S. Pat. No. 4,555,477
Ligand-releasing coupler described in JP-A-63-757
The leuco dye-releasing coupler described in No. 47, U.S. Pat.
No. 4774, 181, which emits fluorescent dyes.
Examples include puller. The couplers used in the present invention can be obtained by various known dispersion methods.
can be introduced into light-sensitive materials. An example of a high boiling point solvent used in the oil-in-water dispersion method is a U.S. patent.
No. 2,322,027, etc. The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high-boiling organic solvents include phthalate es
esters (dibutyl tucrate, synchrohexyl phthalate)
di-2-ethylhexyl phthalate, decylphthalate
rate, bis(2,4-di-t-amyl phenyl) phthalate
bis(2,4-di-t-amyl phenyl) isophtha
Bis(1,1-diethylpropyl)phthalate
etc.), esters of phosphoric or phosphonic acids (trif
phenyl phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexane
Xyl phosphate, tri-2-ethylhexyl phthalate
-t, tridodecyl phosphate, tributoxyethyl
Phosphate, trichloropropyl phosphate, di
2-ethylhexol phenyl phosphonitrate, etc.),
! I, aromatic acid esters (2-ethylhexylhensche
do, dodecyl hennate, 2-ethylhexyl-p-
hydroxyhenzoate, etc.), amides (N,N-di
Ethyldodecaneamide, N,N diethyl laurylamide
, N-tetradenlepyrrolitone, etc.), alcohols or
or phenols (isostearyl alcohol, 2,4
-g-tert-amylphenol, etc.), aliphatic carbon
Rubonic acid esters (bis(2-ethylhexyl)cetate)
Vacate, dioctyl azelate, glycerol trib
thyrate, isostearyl lactate, trioctyl lactate
trate, etc.), aniline derivatives (N,N-dibutyl 2
-butoxy-5-tert-octylaniline, etc.),
Hydrocarbons (paraffin, dodenruhenzen, diisopropylene)
(e.g., lopylnaphthalene). In addition, as an auxiliary solvent, it is preferable that the boiling point is about 30°C or higher.
or use organic solvents at temperatures above 50°C and below approximately 160°C.
Typical examples include ethyl acetate, butyl acetate, and
Ethyl pionate, methyl ethyl ketone, cyclohexano
2-ethoxyethyl acetate, dimethylforma
Examples include mido. Latex dispersion process, effects and latex for impregnation
Specific examples include U.S. Patent No. 4.199.363,
Patent No. 11 (OLS) No. 2.541.274 and
No. 2541.230, etc. The color photosensitive material of the present invention contains phenethyl alcohol.
JP 63-257747, JP 62-272248
and the 1,2-base described in JP-A No. 1-80941.
nisothiaprin-3-one, n-butyl p-hydro
Roxybenzoate, phenol, 4-chloro-3,5
-dimethylphenol, 2-phenoxyethanol, 2
- Various preservatives such as (4thiazolyl)benzimidazole
In other words, it is preferable to add an antifungal agent. The present invention can be applied to various color photosensitive materials.
. General purpose or movie color negative film, slide
Color reversal film for cards or televisions, color base
paper, color positive film and color reversal paper
etc. can be cited as representative examples. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, same Nα18716
From page 647 right column to page 648 left column and fellow 30710
5, page 879. The photosensitive material of the present invention has a total hydrophilic color on the side having the emulsion layer.
It is preferable that the total thickness of the id layer is 28μ or less.
The thickness is more preferably 23μ or less, and even more preferably 18μ or less.
Preferably, 16μ or less is particularly preferable, and the membrane swelling rate is
Degree TI/□ is preferably 30 seconds or less, more preferably 20 seconds or less.
preferable. The film thickness is measured at 25°C and 55% vN humidity (
2 days), and the membrane swelling rate Tl/2 is
, measured according to techniques known in the art.
For example, Knee Green (A, Green
) et al. Photographic Science &
Engineering (Photogr, Sci, Eng,
), Vol. 19, No. 2, pp. 124-129.
Measured by using a swellometer (swelling membrane)
TI/□ is processed at 30°C for 13 minutes and 15 seconds with color developer.
The saturated film thickness is 90% of the maximum swollen film thickness reached when
It is defined as the time it takes to reach 1/2 of the saturated film thickness.
. The membrane swelling rate TI/□ is determined by gelatin as a binder.
Adding a hardening agent or changing the aging conditions after application
It can be adjusted by In addition, the swelling rate is
150-400% is preferred. The swelling rate is as mentioned earlier.
From the maximum swollen film thickness under the conditions, the formula: (maximum swollen film thickness
- film thickness)/film thickness. The photosensitive material of the present invention has a dry layer on the side opposite to the side having the emulsion layer.
The total dry film thickness is 2 μ- to 20 μ-〇 Hydrophilic colloid layer (
It is preferable to provide a bank layer (referred to as a bank layer). this bag
The layers include the aforementioned light absorbers, filter dyes, and UV absorbers.
agent, anti-static agent, hardening agent, binder, plasticizer,
It is preferable to include lubricants, coating aids, surfactants, etc.
Delicious. The swelling rate of this hack layer is preferably 150 to 500%.
Delicious. The color photographic material according to the present invention includes the above-mentioned RD,
Chen 17643, pages 28-29, same N11l 18716
651 left column to right column, and 880 of fellow friend 307105
Develop by the usual method described on page 881.
can be done. The color developing solution used in the development of the photosensitive material of the present invention is preferably
Preferably, the main ingredient is an aromatic primary amine color developing agent.
It is an alkaline aqueous solution. As this color developing agent
Aminophenol compounds are also useful;
Preferably, phenylenediamine compounds are used;
As a table example, 3methyl-4-amino-N,N-diethyla
Nilin, 3-methyl-4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino
-N-ethyl-Nβ-methanesulfonamidoethylani
Phosphorus, 3-methyl-4-amino-N-ethyl-β-meth
Xyethylaniline and their g#i salts, hydrochloride
Examples include p-toluenesulfonate. these
In particular, 3-methyl-4-amino-N-ethyl-
Nβ-hydroxyethylaniline sulfate is preferred;
Two or more of these compounds can be used in combination depending on the purpose.
Ru. The color developer is an alkali metal carbonate, borate or
are pH buffering agents such as phosphates, chloride salts, bromide salts,
Iodide salts, benzimidazoles, hendithiazoles
or development inhibitors or carbons such as mercapto compounds.
It generally contains anti-bleeding agents. Also, if necessary
hydroxylamine, diethylhydroxylamine
N, N-biscarboxymethylhydra
Hydrazines like gin, phenyl semical hands,
Such as triethanolamine, catechol sulfonic acids
Various preservatives, ethylene glycol, diethylene glycol
Organic solvents such as alcohol, benzyl alcohol, polyethylene
such as glycols, quaternary ammonium salts, and amines.
Development accelerators, dye-forming couplers, competitive couplers, 1-F
Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity
Granting side, aminopolycarboxylic acid, aminopolyphosphonic acid
, alkylphosphonic acids, and phosphonocarboxylic acids.
Various chelating agents such as
Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, hydroxyethyl imide
Nodiacetic acid, 1-hydroquinethylidene-1,1-diphos
Phonic acid, nitrilo-N,N,N-trimethylenephosphone
Acid, ethylenediamine-N,N,N,N tetramethylene
Phosphonic acid, ethylene diamine di(0-hydroxyphene)
Typical examples include nylacetic acid) and their salts.
can. Also, when performing reversal processing, black and white development is usually performed.
Color development is performed. This black and white developer contains hydroquinone.
dihydroxyhenzenes such as l-phenyl-3-phenyl
3-pyrazolidones such as lazolidone or N-methyl
-aminophenols such as p-aminephenol, etc.
Using known black and white developing agents alone or in combination
can be done. The p)I of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that Also, replenish these developing solutions.
The amount depends on the color photographic material being processed, but generally
32 or less per square meter of photosensitive material, and the replenisher
By reducing the bromide ion concentration in
It can also be set to 0d or less. When reducing replenishment amount
By reducing the contact area with the air in the treatment tank
It is preferable to prevent evaporation of the liquid and air oxidation. The contact area between the photographic processing solution and air in the processing tank is determined as follows:
It can be expressed by the aperture ratio. That is, the above aperture ratio is preferably 0.1 or less;
It is preferably 0.001 to 0.05. in this way
One way to reduce the aperture ratio is to use photographic processing liquid in the processing tank.
In addition to providing a shield such as a floating lid on the surface,
Method using a movable lid described in No. 033, JP-A-63
The slit development treatment method described in No.-216050
can be mentioned. Reducing the aperture ratio increases color development
Not only the development and black and white development processes, but also the subsequent processes,
For example, all processes such as bleaching, bleach-fixing, fixing, washing, stabilization, etc.
It is preferable to apply it in all steps. Also, developing
We decided to use a method to suppress the accumulation of bromide ions in the liquid.
It is also possible to further reduce the amount of replenishment. The time for color development processing is usually set between 2 and 5 minutes.
However, a high temperature cylinder of 9H and a high concentration of color developing agent are used.
By doing so, you can further reduce processing time.
Ru. After color development, the photographic milking layer is usually bleached. Bleaching treatment may be carried out simultaneously with fixing treatment.
fusing treatment), which may be carried out separately, and which is more rapid in processing.
In order to achieve
Good too. Further treatment with two consecutive bleach-fix baths
and fixing before bleach-fixing or bleach-fixing.
Depending on the purpose, bleaching treatment can be carried out after coloring treatment.
Ru. On the bleaching side, for example, polyvalent gold such as iron (Ili)
Compounds of the genus, peracids, quinones, nitro compounds, etc. are used.
It will be done. As a typical bleaching side, iron (I[I) is IR complexed.
salts, e.g. ethylenediaminetetraacetic acid, diethylenetria
aminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyl
midazole, 1,3-diaminopropanetetraacetic acid, glyco
Aminopolycarboxylate such as ether diamine tetraacetic acid, etc.
Citric acids or complex salts of citric acid, tartaric acid, malic acid, etc.
etc. can be used. Of these, ethylenedia
Iron(III) mintetraacetate complex salt, and L3-diaminopro
Aminopolycarboxylic compounds including iron (old) pantetraacetic acid complex salts
Iron phosphate (I[[) complex salts are suitable for rapid processing and prevention of environmental pollution.
Further preferred are aminopolycarboxylic acid iron (III
) Complex salts are particularly important in both bleach and bleach-fix solutions.
Useful. These iron aminopolycarboxylic acids (I[[
) p of a bleach or bleach-fix solution using a complex salt. is usually 4.0 to 8, but may be further increased to speed up processing.
It can also be treated at low pH. Bleach solution, bleach-fix solution, and their pre-baths may contain
bleach accelerators can be used. Specific examples of useful bleach accelerators are described in
Yes: U.S. Patent No. 3,893.858, West German Patent No. 1
, No. 290.812, No. 2,059,988, JP-A-Sho
No. 53-32736, No. 53-57831, No. 53-
37. H8 No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53-124424, No. 53-141623
, No. 53-28426, Research Disclosure
-Mel written in No. 17129 (July 1978) etc.
Compounds with capto or disulfide groups; JP-A-Sho
Thiazolidine derivatives described in No. 50-140129;
Publication No. 45-8506, Japanese Unexamined Patent Publication No. 52-20832, same
No. 53-32735, U.S. Patent No. 3.706.561
Thiourea derivatives described in West German Patent No. 1.127,71
No. 5, iodide salt rubber described in JP-A No. 58-16.235
West German Patent No. 966.410, West German Patent No. 2,748.430
Polyoxine ethylene compounds described in Japanese Patent Publication No. 45-8
Polyamine compound described in No. 836; Other times opened in 1977-
No. 40,943, No. 49-59.644, No. 53-9
No. 4.927, No. 54-35.727, No. 55-26
．． Compounds described in No. 506 and No. 58-163.940:
Bromide ion etc. can be used. Among them, mercapto group
or compounds with disulfide groups have a large promoting effect.
Preferred from this point of view, especially U.S. Pat. No. 3,893,858
, West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 53-95
．． No. 630 is preferred; furthermore, the compounds described in U.S. Pat.
Also preferred are the compounds described in No. 4,552,834. child
These bleach accelerators may be added to the photosensitive material, and are used for side shadows.
These bleaches are accelerated when bleach-fixing color photosensitive materials.
agents are particularly effective. In addition to the above compounds, bleach and bleach-fix solutions contain bleaching steps.
It is preferable to contain organic acid for the purpose of preventing oxidation.
A particularly preferred organic acid has an acid dissociation constant (pKa) of 2.
~5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Thio-g is a fixing agent used in fixing solutions and bleach-fixing solutions.
Acid salts, thiocyanates, thioether compounds, thiouria
These include a large amount of iodide salts, etc., but thio
The use of sulfates is common, especially ammonium thiosulfate.
system is the most widely used. In addition, thiogates and thiogates
Combination use of anates, thioether compounds, thiourea, etc.
is also preferable. As a preservative for fixer and bleach-fixer,
Sulfates, bisulfites, carbonyl bisulfite adducts or
is the sulfine oxidation described in European Patent No. 294769A.
A compound is preferred. In addition, the fixer and bleach-fixer contain
various aminopolycarboxylic acids and organic phosphors for the purpose of
Addition of fonic acids is preferred. In the present invention, the fixing solution or bleach-fixing solution includes pH adjustment.
Compounds with pKa of 6.0 to 9.0, preferably
is imidazole, 1-methylimidazole, 1ethyl
Imidazo such as imidazole, 2-methylimidazole
It is preferable to add 0.1 to 10 mol/l of alcohols.
. The total time for the desilvering process should be short as long as derailment failure does not occur.
It is preferable. The preferred time is 1 minute to 3 minutes, more preferably
Preferably, it is 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C to 45°C. Like
In the new temperature range, the desilvering rate increases and the processing speed increases.
Later occurrence of sting is effectively prevented. In the desilvering process, stirring is strengthened as much as possible.
As a specific method of strengthening stirring, it is preferable to
On the emulsion side of the light-sensitive material described in 1983-183460
A method of colliding jets of processing liquid, and Japanese Patent Application Laid-Open No. 62-183
Method of increasing stirring effect using rotating means of No. 461, further
The wiper blade installed in the liquid contacts the emulsion surface.
turbulent flow on the emulsion surface by moving the photosensitive material while
A method to improve the stirring effect by
Examples include methods of increasing the amount of W1 perfusion in the body. This way
This means of improving agitation can be used to improve the agitation of bleach, bleach-fix, and fixer solutions.
It is effective even in the case of misalignment and improves stirring.
Speeds up the supply of bleach and fixing agents, resulting in higher desilvering speeds.
It is considered that the Further, the above-mentioned stirring improving means includes:
More effective when using bleach accelerator, accelerating effect
or inhibit the fixation effect of bleach accelerators.
It can be resolved. The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
-191259.
It is preferable that
As stated in the issue, such conveyance means can be used to transfer from the pre-bath to the post-bath.
・It can significantly reduce the amount of processing liquid brought in, improving the performance of processing liquid.
Highly effective in preventing deterioration. This kind of effect applies to each process.
It is particularly useful for shortening processing time and reducing the amount of processing solution replenishment required.
It is effective. The silver halide color photographic light-sensitive material of the present invention is subjected to desilvering treatment.
After that, it is common to undergo a water washing and/or stabilization process. The amount of water used in the washing process is determined by the characteristics of the photosensitive material (e.g.
(depending on the materials used), usage, washing water temperature, washing
Number of tanks (number of stages), replenishment methods such as counterflow, forward flow, etc.
It can be set over a wide range depending on various conditions. Of these, many
The relationship between the number of washing tanks and the amount of water in the stage counterflow method is Jo
Urnal of the 5ociety of M
tion Picture and Te1evis
ion Engineers Volume 64, P, 248~
253 (May 1955 issue).
be able to. According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be increased.
The residence time of water in the tank may be increased.
As a result, bacteria proliferate and the resulting suspended matter becomes photosensitive.
6. Color sensitization of the present invention that causes problems such as adhesion to materials
In material processing, these problems can be solved by
Calcium ion described in JP-A No. 62-288.838
A highly effective method to reduce ions,
It can be used for. Also, JP-A-57-8.542
Inthiazolone compounds and thiabendazole listed in the issue
chlorine-based sterilization such as chlorinated sodium isocyanurate
Horiguchi's antibacterial and antifungal agents, such as benzotriazole, etc.
Chemistry of Agents J (1986) Tool Publishing, Hygiene Technology Extra Line
“Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Society of Industrial Engineers, Japan Antibacterial and Mildew Society Line “Encyclopedia of Antibacterial and Antifungal” (
It is also possible to use the fungicides described in (1986). The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. Washing water temperature, during washing
Although the time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.,
Generally, at 15-45°C for 20 seconds to 10 minutes, preferably
A range of 30 seconds to 5 minutes at 25-40°C is selected. Change
In addition, the photosensitive material of the present invention can be directly washed with a stabilizing solution instead of washing with water.
It can also be processed by In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
No. 3, No. 58-14834, No. 60-220345
All known methods described in can be used. In addition, when further stabilization treatment is performed following the water washing treatment,
An example of this is the final bath of color photosensitive materials for photography.
Contains dye stabilizers and surfactants, used as
One example is a stabilizing bath. As a dye stabilizer
, aldehydes such as formalin and glutaraldehyde
, N-methylol compound, hexamethylenetetramine
Examples include aldehyde sulfite adducts.
Ru. Various cow-rate agents and anti-mold agents can also be added to this stabilizing bath.
can. Oats ＼Flo due to the above-mentioned water washing and/or replenishment of the stabilizing solution.
- The liquid can be reused in other processes such as desilvering.
can. In processing using an automatic processor etc., each of the above processing solutions
Due to the nuclear power plant, i! ! If you want to make m, add water! shrinkage
It is preferable to correct it. The silver halide color light-sensitive material of the present invention has simplification of processing.
Also, a color developing agent may be incorporated for the purpose of speeding up the process. Inside
For storage, various precursors of color developing agents are used.
It is preferable to be there. For example, U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure Seed 14.85
0 and 15.159 of the same. F base type compound, aldolization as described in No. 13.924
metal salt complexes described in U.S. Pat. No. 3,719,492
urethane compounds described in JP-A-53-135628
I can name things. The silver halide color photosensitive material of the present invention may be prepared as necessary.
, various 1-phenyl-3-
It is also possible to incorporate birapritons. Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438, etc.
It is listed. Various processing solutions in the present invention are kept at 10°C to 50°C.
Normally, the standard temperature is 33°C to 38°C.
However, higher temperatures can be used to accelerate the process and shorten the process time.
Reduce the temperature or conversely lower the temperature to improve image quality and stabilize the processing solution.
Qualitative improvements can be achieved. Further, the silver halide photosensitive material of the present invention is disclosed in US Patent No. 4.
No. 500.626, JP-A No. 60-133449, No. 5
No. 9-218443, No. 61-238056, European Special
The heat development process described in 210.66OA2 etc.
It can also be applied to optical materials. (Example) Below, the present invention will be explained in more detail with reference to Examples.
However, the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material consisting of each layer with the composition shown below.
Sample 101, which is a sample, was prepared. (Composition of photosensitive layer) The coating amount is g/g for silver halide and colloidal silver.
The amount of silver in m and also the amount of Cabra additive and Zera
For Chin, the amount expressed in g/r+ (units) and sensitized
Regarding dyes, the amount per mole of silver halide in the same station is
Expressed in moles. 1st layer, anti-oxidation layer Black colloidal silver gelatin V-1 V-2 pd-1 pd-2 olv-1 olv-2 2nd layer, intermediate layer Fine grain silver iodobromide (Ag 11.0 mol% , equivalent sphere diameter 0.0
7μm) Silver coating amount 0.15 W & coating amount 0.20 2.20 0, ■1 4.0X10 1.9X10 0.30 1.2X10 Gelatin 1.00 xC-4 pd-3 3rd layer: 1st red Silver iodobromide emulsion (Ag 15.0 mol%, surface height Agl type, equivalent sphere diameter 0.9 μm, variation in equivalent sphere diameter)
Coefficient 21%, tabular grains, diameter/thickness ratio 7.5) Silver coating amount Silver iodobromide emulsion (Ag 1 4.0 mol%, internal height Agl
type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 18%, dodecahedral particles) 6.0X10 2.0X10 0.42 Gelatin xS-I xS-2 xS-3 EχC-I EχC-3 xC -4 W & coating IO, 40 1,90 4,5X 10-'mol 1.5 X 10-'mol 4.0 32 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Ag + 3.5 mol%, internal high Agl type, equivalent sphere diameter 1.0 μm, variation in equivalent sphere diameter
Coefficient 25%, plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0.85 Gelatin 0.91E x
S -13,0xlO-'Mole Ex S -21,
0X10-'mol Ex S-33,0XiO-'mol
5olv-10,10 5th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion (AgI 11.3 mol% , internal height Ag
L type, equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere diameter 28%
, plate-shaped particles, diameter/thickness ratio 6. O) Silver coating it 1.50 Gelatin 1.20E x
S-12,0X10-'MoleExS-26,0XIF5MoleExS-32,0X10-'-ExC-28
,5xlO-2 EχC-57,3X10-" 5olv-10,12 Solv-20,12 6th layer: Intermediate layer gelatin 0,50Cp
d -42,0X10"" S o I v -1s, oxlo-" 7th layer: 1st green
Sensitive emulsion layer Silver iodobromide emulsion (Ag + 5.0 mol%, surface height Agl type, equivalent sphere diameter 0.9 μm, variation in equivalent sphere diameter
Coefficient 21%, tabular grains, diameter/thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μm, equivalent sphere diameter Fluctuation
Coefficient 18%, dodecahedral particles) W & coating amount 0.16 Gelatin 1.20E x
S -4s, oxto-'mol Ex S -52,
0x10-'mol Ex S -61,0xlO-'mol
LE ExM-10,50 ExM-20,10 ExM-53,5X10-” 5olv-10,20 S o Iv-33,0XIO-” 8th layer: 2nd green
Sensitive emulsion layer Silver iodobromide emulsion (Ag + 8.5 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, variation in equivalent sphere diameter
Coefficient 25%, plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0457 Gelatin 0.45E x
S -43,5xto-'mol Ex S -51,4
xlO-'molE x S-67,0X10-'mol
ExM-10,12 ExM-27,lX10-'EχM-33,5xlO-" 5olv-10,15 S o lv-31,0X10-" 9th layer: Intermediate
Layered gelatin 0.50S o
I v -12,oxio-! 10th layer: 3rd green emulsion
Layered silver iodobromide emulsion (Ag1 11.3 mol%, internal high Agl
Mold, equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1.30 Gelatin 1.20E x
S -42,0 x 10-'mol Ex S -58,
0x10-'mol Ex-6s, oxto-5mol
Le ExM-44,5X10-" Ex M-610XIO-2 Ex C-24,5X10-" Cp d-51,0X10"" 5olv-10,25 11th layer: Yellow filter layer gelatin 0゜50Cp
d -65,2X10-" 5olv-10,12 12th layer; middle layer gelatin 0.45cp
d-30,10 13th layer: First blue emulsion layer Silver iodobromide emulsion (Ag 12 mol%, uniform-Agl type, equivalent sphere diameter 0.55/l/m, equivalent sphere diameter
Coefficient of variation of 25%, tabular grains, diameter/thickness ratio 7.0) Silver coating amount 0.20 Gelatin 1.00ExS
7 3.0X10-''mol Ex
Y -10,60 EχY-22,3
L type, equivalent sphere diameter 1.07/m, coefficient of variation of equivalent sphere diameter 16
%, octahedral particles) Silver-coated M019 Gelatin 0.3. '5E
x S -72,0X10”'Mole ExY-10,22 S o I v -17,0X10-2 15th layer: Intermediate
Layer fine grain silver iodobromide (Ag 12 mol%, uniform-Agl type, equivalent sphere diameter 0.13 μm) Silver coating amount 0
．． 20 Gelatin 0.36 16th layer
・Third blue-sensitive emulsion layer silver iodobromide emulsion (Ag1 14.0 mol%, internal high AgI
Mold, equivalent sphere diameter 1.7 μm, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 5.0) Silver coating I L55 Gelatin 1. OOE x
S -81,5xlO-'mol E x Y -10,
21 S o l v -17,0X10-” 17th layer: 1st
Protective layer gelatin Jl-1 V-2 olv-1 olv-2 18th layer: 2nd protective layer fine grain silver chloride (equivalent sphere diameter 1.80 0.13 0.21 1.0X10-" 1, OX 10-" 0.07μm) Silver coating amount 0.36 Gelatin 0.70 B-1 (diameter 1.5μm) 2.0X10-
2B-2 (diameter 1.5μm) 0.15B
-33,0xlO-” W-12,0xlO-” H-10,35 Cpd-71,00 This sample contains 1,2-henzisothiazoline=3-o
(average 200 ppm relative to gelatin), n-butyl
Ru-p-hydrokinchenshade (1'J'r1.00
0 ppm), and 2-phenoquinoethanol (
Approximately 10,000 ppIll) was added. moreover
B-4, B-5, W-2, W-3, F-1, F-2, F
3, F-4, F-5, F-6, F-7, F-8, F9,
F-10, F-11, F-12, F-13 and iron salts,
Contains lead salts, gold salts, platinum salts, iridium salts, and rhodium salts
has been done. U V xC 0 (i) C4HqOCNH I) xC H (n)C+zHzs xC xC H xC xM xM-2 xM-3 xM (II- ExM-5 ExM − 4 p d-5 Pd H JH C6HI+ pd H3 olv olv olv xS xS-2 xS-3 xS xS xS-6 xS-7 (CHz) ash? (CH,) , 5O3H-N (C2H5) 3xS-8 (1 -Flz): +1038・NL zH5 saw n=2
~4 C)+2=CH3O□-CL C0NHHz CH2=CH3O□-GHz CONH-CI(. Yellow colored cyan of the present invention
Coupler (YC-42) was added at 0.040g/n.
Sample 102 was produced. Addition of (YC-42) is as follows.
After melting the oil phase and aqueous phase separately, mix them together and prepare for household use.
This was done as an emulsion that was emulsified with a mixer. (Oil phase) Coupler of the present invention (VC-42) 20.0gcpa
-410,0g 5olv-140,0g Ethyl acetate 150M1 (water
phase) Beef bone gelatin 100gW-21
,0g W to 3 1. 0g water
1000d (trial
Samples 103 to 110) No. 6N (YC-42) of sample 102 was
Samples 103 to 110 were prepared by replacing the puller with equimolar amounts.
did. These samples were exposed to red imagewise light and subjected to the following color development process.
I did it. Dew that gives cyan density (Capri + 0°2)
The logarithm of the reciprocal of the light amount was determined as the relative sensitivity. Also cyan
Yellow density to yellow density (Capri + 2.0)
Table 1 shows the value that eliminates the low capri density as color turbidity.
Ta. Also, expose and develop the MTF measurement pattern with white light,
25 cycles/yellow and cyan color image M in Tsuru
T F (+fi was measured. The MTF value is The
Theory of the Photography
c Process 3rded, (Ma, Cumilla
The method was followed as described in Mies, published by John Co., Ltd. Process Processing time Color development 3 minutes 15 seconds Bleach 45 seconds Bleach-fixing [1145 seconds Bleach-fixing +21 45 seconds Water washing +1 + 20 seconds Processing method Processing temperature □ 41 38℃ 3 (ld 47! 38℃ □ 21 Washing with water (2120 seconds 38℃ 30m 21 amps
Constant 20 seconds 38℃ 2 (1wi
21 Drying 1 minute 55℃ Main replenishment amount
is the amount per 35m width and 1m length for each process of bleaching, fixing and washing.
The process is countercurrent from (2) to ill, and
All overflow of the bleaching solution is led to bleach-fixing (2).
I entered. In addition, the amount of bleach-fix solution brought into the washing process in the above treatment
was 2i per meter length of the photosensitive material having a width of 35 mm. (Color developer) Mother solution (g) Replenisher (g) Die
Cilenttriamine 5゜06. 〇Sodium pentaacetic acid sulfite 4.0 5.0 Potassium carbonate
Lium 30.0 37.0 Potassium Bromide
1.3 0.5 potassium iodide
1.2■ Hydroxylamine sulfur 2.0 3.6-acid 4-[N-ethyl-N-4,76,2 β-hydroxyethylamine] -2-Methylaniline sulfate was added to pH (bleaching solution) 13 -Diaminopropane tetranodic acid ferric ammonium hydrate - 1.3-Diaminopropane tetraacetic acid Ammonium bromide Ammonium nitrate Ammonia water (27%) Acetic acid (98%) Add water (p) ((Bleach-fix solution) Ethylenediamine tetra Ammonium ferric acid 1.01 10.00 Mother liquor (g) 144.0 2.8 84.0 17.5 1O80 51,1 1, Ol 4.3 Mother liquor (g) 50.0 1, Ol 10, 1 5 Replenishment solution (g) 206.0 4.0 120.0 25.0 1.8 73.0 3.4 Replenishment solution (g) Munihydrate ethylenediamine 5.0 25.0 Acid disodium salt Ammonium sulfate 12.0 20.0 Thiosulfate
Ammonium acid 290.0 m 320.0 d
Aqueous solution (700g/β) Aqueous ammonia (27%) 6. (llR115,0
TR1 Add water l, Q f
1.01 pH 6,88,0 (Washing water) Mother liquor, replenisher Common tap water
Amberlight IR-120B) manufactured by
Basic anion exchange resin (Amberlite IRA-4
Calcium and
and magnesium ion concentration to 3/1 or less, and continued.
Sodium isocyanurate dichloride 20μ/l and sulfur
150 μl/l of sodium acid was added. The pH of this solution was in the range of 6.5-7.5. (Stable solution) Mother solution and replenisher common formalin (37%) Surfactant (C+.H!, -o-4:C) lzcH, OF2゜H]
Add ethylene glycol water and adjust the pH to 5° Table 1 (From Table 1, the sample of the present invention has high sensitivity and less color turbidity.
It is clear that it is excellent in contrast as expressed by MTF.
It is clear. Example 2 (Sample 201) Sample 20 except for the fifth layer (YC-42) of sample 101
It was set to 1. (Sample 202) 0.010 g/n in the second layer of sample 201 (and the third layer
0.025g/r4 (VC-43) was added to the sample.
It was set to 202. (Sample 203) Equal moles of (VC-43) and (YC-45) in sample 202
I replaced it with test 14203. These samples were sliced into a 35m wide piece, and 135 size pieces were
Photosensitive material 201.202 processed by Rhone 24-shot processing
．． 203 was produced. These photosensitive materials have an RSO sensitivity of 64
Canon EO3 with each setting condition of 00.1600.400
At -630, a half-length portrait of a human figure and a color chain made by Makhes.
I put the camera in and took the picture. Also, commercially available Super HG-4
00 + SO sensitivity setting 1600.400.50 settings
The same subject was photographed and the following color development was performed. The color development process is as follows at 38℃ using an automatic processor.
processed. Color development Bleach for 2 minutes and 45 seconds Bleach fix for 1 minute Wash with water for 3 minutes and 15 seconds ■ Wash with water for 40 seconds ■ Stable for 1 minute Dry for 40 seconds (50℃)
) 1 minute 15 seconds In the above treatment process, water washing ■ and ■ are in the direction from ■ to ■.
The method was washed with running water. Next, the composition of each treatment liquid will be described. The replenishment amount of each processing solution is based on the amount of color development per 1-color photosensitive material.
is 1200m, all others are 800m including water washing, or
The amount of pre-bath carried into the water washing process is 50 per color photosensitive material.
-It was. (Color developing solution) Mother solution replenisher Diethylenetriamine Pentose acid 1-Hydroxyethylidene 1.1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N β-hydroxyethylamino) -2-Methylaniline sulfate solution added 1.0g 2.0g 4.0g 30.0g 1.4g 1.3■ 4.5g 1.01 pH 10.0 (Bleach solution) Common to mother liquor and replenisher ethylenediaminetetraacetic acid Ferric ammonium salt Ethylenediaminetetraacetic acid disodium 1,1 g 2.2 g 4.4 g 32.0 g 0.7 g 5.0 g 1, OA' 10.05 1 20,0 g Lithium salt Ammonium sulfate Ammonium bromide bleach accelerator 10,0 g 10,0 g 100,0 g 5XIO-'Mole Add ammonia water pH 6.3 Add water
1.07! (bleach-fix solution)
Common to mother liquor and replenisher: ethylenediaminetetraacetic acid ferric ammonium salt 50.0 g
Didiaminetetraacetic acid disodium salt 5.0g sulfite
Sodium 12.0 g Thiog acid
Ammonia aqueous solution (70%) 240d ammonia
Add water pH7.3 Add water
1. Of (washing water) Calcium ion 32/1, Magnesium ion 7.
Tap water containing 3■/1 with H-swelling acidic cation exchange resin
In a column filled with OH type strongly basic anion exchange resin
Water passes through, calcium ion 1.2 / 1, magnesium
Isocyanine dichloride is added to water treated with ions of 0.4■/1.
Sodium chlorate was added at 20 μm per 11 days. (Stable solution) Common formalin for mother solution and replenisher solution (37% w/v) 2.
Od polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g ethylene
diaminetetraacetic acid di-sodium salt 0.05 g water
In addition, 11 pH 5.8 (drying) The drying temperature was 50°C. Auto printer FAP-3500 manufactured by Fuji Film Co., Ltd.
Macbesca with Sanjo print of Super HG-400
The B, G, and R concentrations of Larch Ecker's Neutral 5 are
It was set to be 0.75±0.02. under this condition
Photosensitive materials 201 to 203 were printed. In the print
Fuji Color Paper HG was used. These samples
Kuhes Color Checker density was measured on paper. In addition, color turbidity and MTF value were measured using the same method as in Example 1.
Established. However, the color development described above was used. From Table 2, samples 302 and 303 of the present invention, similar to 301,
Color variations on automated printers for developed samples with various exposures
There is less color reproduction, which is expressed by color turbidity compared to sample 301.
It is clear that the sharpness expressed by MTF is excellent.
It is. Example 3 Yellow color of the present invention was applied to the fourth layer of samples 101 to 110.
Docyan coupler (YC-43) at 0015g/m
A sample was prepared by adding 0.010 g/m of (YC-42) to the 5th layer.
301 to 310 were prepared and evaluated in the same manner as in Example 1.
As a result, samples 302 to 309 of the present invention were compared to sample 301.
．． 3) Higher sensitivity and less color turbidity compared to 0, from Nya to Pune
He was also good at speed. Patent applicant: Fuji Photo Film Co., Ltd. Month f? Day

Claims (4)

[Claims] (1) At least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, one red-sensitive silver halide emulsion layer, and at least one non-photosensitive layer adjacent to the red-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material having at least one layer, characterized in that the non-light-sensitive layer contains a yellow-colored cyan coupler. (2) Claim (1) characterized in that the non-light-sensitive layer containing a yellow-colored cyan coupler is simultaneously adjacent to the red-sensitive silver halide emulsion layer and the green-sensitive emulsion layer.
The silver halide color photographic light-sensitive material described in . (3) A silver halide color photograph according to claim (1), characterized in that the non-light-sensitive layer containing a yellow-colored cyan coupler is adjacent to the red-sensitive silver halide emulsion layer and the support at the same time. photosensitive material. (4) The yellow colored cyan coupler is the first aromatic
Due to the coupling reaction with the oxidized product of grade amine developing agent,
Water-soluble 6-hydroxy-2-pyridon-5-ylazo group, water-soluble pyrazolone-4-ylazo group, water-soluble 2
Claim (1) characterized in that the cyan coupler is capable of releasing a compound residue containing a -acylaminophenylazo group or a water-soluble 2-sulfonamide phenylazo group.
The silver halide color photographic light-sensitive material described in (3) above.