JPH04368939A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance image storage stability and color reproducibility by incorporating a specified malondianilide type yellow dye-forming coupler and a specified compound. CONSTITUTION:A blue-sensitive silver halide emulsifier layer contains the malondianilide type yellow dye-forming coupler represented by formula I or II and further at least one of the compound represented by formula III. In formulae I-III, each of X1 and X2 is alkyl, aryl, or a heterocyclic group: X3 is an organic group necessary for forming an N-containing heterocyclic group together with >N-; Y is aryl or a heterocyclic group; Z is a group to be released by coupling with the oxidation product of a developing agent; each of Y5 and Y6 is a nonmetallic atomic group necessary for forming an N-containing heterocyclic group; each of R6 and R8 is an aliphatic group optionally interrupted by an S atom; and R7 is H or lower alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to color photographic materials.
In particular, it is important to improve the storage stability of photosensitive materials and image preservation.
Silver halide color with improved properties and excellent color reproducibility
It relates to photographic materials. [Prior Art] Dye for silver halide color photographic light-sensitive material
Image formation is generally done using cyan coupler or magenta coupler.
- aromatic primary amine system in the presence of yellow coupler
This is done by color development using a developing agent. Silver halide in the color photographic light-sensitive material exposed at that time
The particles are reduced by the developing agent, and at the same time the developing agent
The oxidation product of the active ingredient undergoes a coupling reaction with the coupler.
Generates cyan, magenta, and yellow pigments to produce color
Form a photographic image. Among these, yellow coupler
as benzoylacetanilide or pivaloyl
Acetanilides are often used, but these
The color image of the puller has poor storage stability in high temperature and humidity.
It's a minute. Furthermore, the image obtained from the above yellow coupler is
Yellow pigment has unfavorable absorption in the green region.
This has the problem of reducing color reproducibility.
It was hoped that this would be resolved. [Problems to be Solved by the Invention] The purpose of the present invention is to
Preservability of materials and retention of yellow images under high temperature and humidity
Silver halide with improved compatibility and color reproducibility
Our objective is to provide color photographic materials. [Means for Solving the Problem] The present inventor has solved the above problem.
As a result of various studies to decide, the following color photo was created.
We have found that the problem can be solved using photosensitive materials. on support
one or more blue-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers, respectively.
It has a red-sensitive silver halide layer and a red-sensitive silver halide layer.
In silver halide color photographic light-sensitive materials, the blue-sensitive
The silver halide emulsion layer has the formula (1) shown in the following chemical formula (4) or the chemical formula (5).
Malondianilide type yellow color represented by formula (2) shown below
containing at least one elementary-forming coupler, and the halogen
The silver oxide color photographic light-sensitive material has the formula (A) shown in the following chemical formula 6.
characterized by containing at least one compound represented by
A silver halide color photographic light-sensitive material. ##STR00004## [0006] (In formulas (1) and (2), X1 and X2
each represents an alkyl group, an aryl group or a heterocyclic group;
, X3 is an organic group which together with >N- forms a nitrogen-containing heterocyclic group.
represents a machine residue, and Y represents an aryl group or a heterocyclic group.
, Z indicates that the coupler represented by the formula reacts with the oxidized developing agent.
represents a group that leaves when [0007] (In formula (A), Y5 and Y6 each represent a pin.
loline, indoline, thiazoline, thiazole, benzo
Thiazole, naphthothiazole, selenazole, benzo
selenazole, naphthoselenazole, oxazole,
zuoxazole, naphthoxazole, imidazole
, benzimidazole, pyridine and quinoline.
The non-containing elements necessary to form a nitrogen-containing heterocyclic nucleus selected from the group
Represents a group of metal atoms, and these heterocyclic nuclei contain halogen atoms.
child, lower alkyl group, lower alkoxy group, phenoxy group
, the phenyl group may be substituted. R6 and R8 are
Each may be substituted, and the carbon chain may be an oxygen atom or an ion.
represents an aliphatic group which may be interrupted by a U atom, R6
or at least one of R8 is a hydroxyl group, a carboxyl group,
The above resin having either a xyl group or a sulfo group
Represents an aliphatic group. R7 is a hydrogen atom or lower alkyl
). First, as shown in formulas (1) and (2)
Let's talk about couplers in detail. X1 and X2 are
When representing an alkyl group, the number of carbon atoms is 1 to 30, preferably 1
~20 linear, branched, cyclic, saturated, unsaturated, substituted or
is an unsubstituted alkyl group. Examples of alkyl groups are
Methyl, ethyl, propyl, butyl, cyclopropyl,
Allyl, t-octyl, i-butyl, dodecyl, 2-h
Examples include xyldecyl. X1 and X2 are complex
When representing a ring group, it has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
Heteroatoms such as nitrogen, oxygen or sulfur
Contains at least one yellow atom, preferably 3 to 12, preferably
5- or 6-membered ring, saturated or unsaturated, substituted or
is an unsubstituted monocyclic or fused ring heterocyclic group. multiple
Examples of bare ring groups include 3-pyrrolidinyl, 1,2,4-
triazol-3-yl, 2-pyridyl, 4-pyrimidine
Nyl, 3-pyrazolyl, 2-pyrrolyl, 2,4-dioxyl
So-1,3-imidazolidin-5-yl or pyranyl
Examples include. [0009] When X1 and X2 represent an aryl group,
and a substitution having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, or
Represents an unsubstituted aryl group. An example of an aryl group is
Typical examples are phenyl and naphthyl. X3 is>N- and
When representing a nitrogen-containing heterocyclic group forming a
a hetero atom having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms;
In addition to nitrogen atoms, for example, oxygen atoms or sulfur atoms
may contain a 3- to 12-membered ring, preferably a 5- or 6-membered ring.
Member ring, substituted or unsubstituted, saturated or unsaturated
, a monocyclic or fused ring heterocyclic group. This heterocyclic group
Examples include pyrrolidino, piperidino, morpholino,
1-piperazinyl, 1-indolinyl, 1,2,3,4
-tetrahydroquinolin-1-yl, 1-imidazolidi
Nyl, 1-pyrazolyl, 1-pyrrolinyl, 1-pyrazolyl
Dinyl, 2,3-dihydro-1-indazolyl, 2-y
Soindolinyl, 1-indolyl, 1-pyrrolyl, 4-
Thiazin-S,S-dioxo-4-yl or benzio
Xazin-4-yl is mentioned. [0010] X1 and X2 have a substituent
When representing an alkyl, aryl or heterocyclic group,
and a nitrogen-containing heterocycle formed by X3 together with >N-
When a group has substituents, examples of those substituents include
These include: Halogen atoms (e.g. fluorine atoms)
child, chlor atom), alkoxycarbonyl group (carbon number 2
~30, preferably 2-20. For example, methoxycarbony
dodecyloxycarbonyl, hexadecyloxycarbonyl
carbonyl), acylamino group (2 to 30 carbon atoms, preferably
2-20. For example, acetamide, tetradecanamide
2-(2,4-di-t-amylphenoxy)butane
amide, benzamide), sulfonamide group (1 carbon number
~30, preferably 1-20. For example, methanesulfona
mido, dodecane sulfonamide, hexadecyl sulfone
amide, benzenesulfonamide), carbamoyl group (
1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. For example, N-buty
carbamoyl, N,N-diethylcarbamoyl), N
-Sulfonylcarbamoyl group (1 to 30 carbon atoms, preferably
1-20. For example, N-mesylcarbamoyl, N-do
decylsulfonylcarbamoyl), sulfamoyl group (
1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. For example, N-buty
Rusulfamoyl, N-dodecylsulfamoyl, N-
Hexadecylsulfamoyl, N-3-(2,4-di-
t-amylphenoxy)butylsulfamoyl, N,N
-diethylsulfamoyl), alkoxy group (1 carbon number
~30, preferably 1-20. For example, methoxy, hexa
decyloxy, isopropoxy), aryloxy group (
6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. For example, fenoki
cy, 4-methoxyphenoxy, 3-t-butyl-4-h
droxyphenoxy, naphthoxy), aryloxyca
Rubonyl group (7 to 21 carbon atoms, preferably 7 to 11 carbon atoms, e.g.
(e.g., phenoxycarbonyl), N-acylsulfamoy
group (2 to 30 carbon atoms, preferably 2 to 20 carbon atoms; for example, N
-Propanoylsulfamoyl, N-tetradecanoyl
sulfamoyl), sulfonyl group (1 to 30 carbon atoms, preferably
Preferably 1-20. For example, methanesulfonyl, octane
Sulfonyl, 4-hydroxyphenylsulfonyl, dode
cansulfonyl), alkoxycarbonylamino group (charcoal
Prime number 1-30, preferably 1-20. For example, ethoxyca
(rubonylamino), cyano group, nitro group, carboxyl
group, hydroxyl group, sulfo group, alkylthio group (carbon
Number 1-30, preferably 1-20. For example, methylthio
dodecylthio, dodecylcarbamoylmethylthio),
Reid group (1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, e.g.
(N-phenylureido, N-hexadecylureido)
, aryl group (6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, e.g. phenyl, naphthyl, 4-methoxyphenyl),
Heterocyclic group (1 to 20 carbon atoms, preferably 1 to 10 carbon atoms)
Examples of nitrogen atoms include nitrogen atoms, oxygen atoms, or sulfur atoms.
containing at least one child from 3 to 12, preferably as many as 5
or a 6-membered ring, monocyclic or fused ring. For example, 2-pyri
Zyl, 3-pyrazolyl, 1-pyrrolyl, 2,4-dioxyl
So-1,3-imidazolidin-1-yl, 2-benzo
xazolyl, morpholino, indolyl), alkyl group (
Straight chain, branched, having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms,
cyclic, saturated, unsaturated, e.g. methyl, ethyl, isopropylene
Pyl, cyclopropyl, t-pentyl, t-octyl,
cyclopentyl, t-butyl, s-butyl, dodecyl,
2-hexyldecyl), acyl group (1 to 30 carbon atoms, preferably
Preferably 2-20. For example, acetyl, benzoyl),
Syloxy group (2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, e.g. propanoyloxy, tetradecanoyloxy)
, arylthio group (6 to 20 carbon atoms, preferably 6 to 1 carbon atoms)
0. For example, phenylthio, naphthylthio), sulfamo
ylamino group (0 to 30 carbon atoms, preferably 0 to 20 carbon atoms. For example, N-butylsulfamoylamino, N-dodecyl
Sulfamoylamino, N-phenylsulfamoyla
mino) or N-sulfonylsulfamoyl group (carbon
Number 1-30, preferably 1-20. For example, N-mesilus
Rufamoyl, N-ethanesulfonylsulfamoyl
, N-dodecanesulfonylsulfamoyl, N-hexa
(decanesulfonylsulfamoyl). Up
The above substituents may further have a substituent. its substituents
Examples include the substituents listed here. above
Among these, preferred substituents include alkoxy groups and halogen groups.
child, alkoxycarbonyl group, acyloxy group, acyl
Amino group, sulfonyl group, carbamoyl group, sulfamo group
yl group, sulfonamide group, nitro group, alkyl group or
is an aryl group. In formulas (1) and (2), Y is ary
When representing a group, the number of carbon atoms is 6 to 20, preferably 6 to 10
is a substituted or unsubstituted aryl group. For example, Feni
Typical examples are ru and naphthyl groups. Formula (1
) and (2), when Y represents a heterocyclic group, X1
Or the same as explained when X2 represents a heterocyclic group
It is the meaning. The above Y is a substituted aryl group or a substituted heterocycle
When representing a group, as an example of a substituent, for example, the above-mentioned X1 is
The substituents listed as examples when having a substituent are
It will be done. Preferred examples of substituents for Y include
One of the substituents is a halogen atom, an alkoxycarbonyl atom,
group, sulfamoyl group, carbamoyl group, sulfonyl group
group, N-sulfonylsulfamoyl group, N-acylsulf
Famoyl group, alkoxy group, acylamino group, N-su
sulfonylcarbamoyl group, sulfonamide group or alkali
When it is a kill group. There are few particularly preferable examples for Y.
At least one substituent is a phenyl group in the ortho position.
Ru. In the formulas (1) and (2), Z represents
Examples of groups include conventionally known coupling-off groups.
It may be either. A preferable Z is a nitrogen atom
Nitrogen-containing heterocyclic group, aryl bonded to the coupling position at
Oxy group, arylthio group, heterocyclic oxy group, heterocyclic group
o group, acyloxy group, carbamoyloxy group, alkyloxy group,
Examples include a ruthio group or a halogen atom. These separations
Degrouping involves removing a non-photographically useful group or a photographically useful group or
precursors (e.g. development inhibitors, development accelerators, desilvering accelerators)
, fogging agent, dye, hardener, coupler, developing agent oxidation
body scavengers, fluorescent dyes, developing agents or electron transfer
agent) may be used. Z is a photographically useful group
In such cases, conventionally known methods are useful. For example, the United States
Patent No. 4248962, Patent No. 4409323, Patent No. 44
No. 38193, No. 4421845, No. 4618571
No. 4652516, No. 4861701, No. 47
No. 82012, No. 4857440, No. 4847185
No. 4477563, No. 4438193, No. 46
No. 28024, No. 4618571, No. 4741994
European Published Patent No. 193389A, 348
Photographic property as described in No. 139A or No. 272573A
a starting group or a leaving group to release it (e.g. tie
ming group) is used. [0013] Z is bonded to the coupling position through the nitrogen atom
When representing a nitrogen-containing heterocyclic group, it preferably has 1 to 1 carbon atoms.
5, preferably 1 to 10, 5- or 6-membered ring substitutions
or unsubstituted, saturated or unsaturated, monocyclic or
is a fused ring heterocyclic group. Nitrogen atoms as heteroatoms
In addition to children, it may also contain oxygen atoms or sulfur atoms. multiple
Preferred specific examples of the bare ring group include 1-pyrazolyl, 1
-imidazolyl, pyrrolino, 1,2,4-triazole
-2-yl, 1,2,3-triazol-1-yl,
Benzotriazolyl, benzimidazolyl, imidazolidi
ion-2,4-dione-3-yl, oxazolidine-2,
4-dione-3-yl, 1,2,4-triazolidine-
3,5-dione-4-yl, imidazolidine-2,4,
5-trion-3-yl, 2-imidazolinone-1-y
3,5-dioxomorpholino or 1-indazoly
For example, When these heterocyclic groups have a substituent
As the substituent, the group represented by the above-mentioned X1 group is
The substituents listed as optional substituents are examples.
can be mentioned. As a preferable substituent, one of the substituents is
Alkyl group, alkoxy group, halogen atom, alkoxy
Carbonyl group, aryloxycarbonyl group, alkyl group
Thio group, acylamino group, sulfonamide group, aryl
group, nitro group, carbamoyl group, cyano group or sulfonate group.
When it is a nyl group. When Z represents an aromatic oxy group, preferably
is a substituted or unsubstituted aromatic oxy group having 6 to 10 carbon atoms
It is. Particularly preferably substituted or unsubstituted phenoxy
It is the basis. When having a substituent, examples of the substituent are:
The following are the substituents that the group represented by X1 may have:
Examples include the substituents listed above. Favorite among them
At least one substituent is an electron-withdrawing substituent.
Examples include sulfonyl
group, alkoxycarbonyl group, sulfamoyl group, halo
Gen atom, carbamoyl group, nitro group, cyano group or
Examples include acyl groups. When Z represents an aromatic thio group,
Preferably substituted or unsubstituted aromatic having 6 to 10 carbon atoms
It is a thio group. Particularly preferably substituted or unsubstituted
It is a nylthio group. When having a substituent, examples of the substituent and
is a substituent that the group represented by X1 above may have.
Examples include the substituents listed in . the
Among these, preferred substituents include at least one substituent.
, alkyl group, alkoxy group, sulfonyl group, alkoxy
Cycarbonyl group, sulfamoyl group, halogen atom, carbon
When it is a rubamoyl group or a nitro group. [0015] When Z represents a heterocyclic oxy group, a heterocyclic group
The moiety is a heterocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
Examples of nitrogen atoms include nitrogen atoms, oxygen atoms, or sulfur atoms.
containing at least one child from 3 to 12, preferably as many as 5
or a 6-membered ring, substituted or unsubstituted, saturated or
It is an unsaturated, monocyclic or fused ring heterocyclic group. complex
Examples of ring oxy groups include pyridyloxy, pyrazoli
and furyloxy group. replacement
When having a group, examples of the substituent include the group shown in X1 above.
The substituents listed as substituents that the group may have are
An example of this is: Among them, the preferred substituent is
If one of the substituents is an alkyl group, an aryl group, or a carboxyl group,
xyl group, alkoxy group, halogen atom, alkoxy group
carbonyl group, aryloxycarbonyl group, alkyl group
o group, acylamino group, sulfonamide group, nitro group,
When it is a carbamoyl group or a sulfonyl group
. When Z represents a heterocyclic thio group, the heterocyclic group
The moiety is a hetero group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
Atoms such as nitrogen atoms, oxygen atoms or sulfur atoms
3 to 12, preferably 5 or more.
or a 6-membered ring, substituted or unsubstituted, saturated or unsubstituted.
It is a saturated, monocyclic or fused ring heterocyclic group. heterocycle
Examples of thio groups include tetrazolylthio group, 1,3,4
-thiadiazolylthio group, 1,3,4-oxadiazoli
ruthio group, 1,3,4-triazolylthio group, benzyl
midazolylthio group, benzothiazolylthio group, or 2
-pyridylthio group. When having a substituent,
Examples of substituents include the group represented by X1 above.
The substituents listed as good substituents are given as examples.
It will be done. Among them, preferred substituents include a small number of substituents.
At least one is an alkyl group, aryl group, or carboxyl group
group, alkoxy group, halogen atom, alkoxycarbonyl
group, aryloxycarbonyl group, alkylthio group,
Acylamino group, sulfonamide group, nitro group, carba
When it is a moyl group, a heterocyclic group or a sulfonyl group,
be. When Z represents an acyloxy group, preferably
is a monocyclic or fused ring having 6 to 10 carbon atoms, substituted or
or an unsubstituted aromatic acyloxy group, or a group having 2 or more carbon atoms.
30 preferably 2 to 20 substituted or unsubstituted aliphatic
It is an acyloxy group. When these have substituents,
Examples of substituents include the group represented by X1 above.
The substituents listed as good substituents are given as examples.
It will be done. When Z represents a carbamoyloxy group, the number of carbon atoms
1 to 30, preferably 1 to 20, aliphatic, aromatic,
Bare ring, substituted or unsubstituted carbamoyloxy group
Ru. For example, N,N-diethylcarbamoyloxy, N-
Phenylcarbamoyloxy, 1-imidazolylcarbo
Nyloxy or 1-pyrrolocarbonyloxy are mentioned.
It will be done. When these have a substituent, examples of the substituent include
is a substituent that the group represented by X1 above may have.
Examples include the substituents listed above. Z is Al
When representing a kylthio group, the number of carbon atoms is 1 to 30, preferably 1
~20 linear, branched, cyclic, saturated, unsaturated, substituted
is an unsubstituted alkylthio group. have a substituent
When, as an example of the substituent, the group represented by X1 is
The substituents listed as optional substituents are examples.
can be mentioned. Next, expressed by equations (1) and (2),
Particularly preferred ranges of couplers are described below. The group represented by X1 in formula (1) is preferably a
It is a rukyl group. Particularly preferable is an alkali having 1 to 10 carbon atoms.
It is a kill group. Indicated by Y in formulas (1) and (2)
The group is preferably an aromatic group. Especially preferably
A phenyl group having at least one substituent at the ortho position
be. The explanation of the substituents is as follows when Y is an aromatic group.
Examples of suitable substituents include those described above. preferred
The same applies to the explanation of substituents. In equations (1) and (2)
The group represented by Z is preferably a 5- to 6-membered nitrogen group.
Nitrogen-containing heterocyclic group bonded to the coupling position at the atom, aromatic
Group oxy group, 5-6 membered heterocyclic oxy group, or 5-6
Examples include a membered heterocyclic thio group. Equations (1) and (2)
Preferred couplers are the formulas (7 to 9) shown below.
3), (4) or (5). [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] In the formulas (3) to (5), Z is as explained in the formula (1).
, X4 represents an alkyl group, and X
5 represents an alkyl group or an aromatic group, and Ar is an or
represents a phenyl group having at least one substituent in the
and X6 is nitrogen-containing with -C(R1 R2)-N<
Organic residues forming a heterocyclic group (single ring or fused ring)
and X7 is -C(R3)=C(R4)-N<
Both form a nitrogen-containing heterocyclic group (single ring or fused ring)
Represents an organic residue, R1, R2, R3 and R4 are
Represents a hydrogen atom or a substituent. Formulas (3) to (5) Smell
Details of the groups represented by X4 to X7, Ar and Z
For explanation and preferred ranges, formula (1) and (
Explanation to the extent applicable in the explanation given in 2)
It has the same meaning as . R1 to R4 represent substituents
When, the substituents that X1 may have are listed as
An example is something like this. Among the above formulas, particularly preferred couplers are formula (4) or
This is a coupler represented by (5). In formulas (1) to (5)
Couplers shown are X1 to X7, Y, Ar, R1
〜R4 and the group represented by Z are divalent or
Dimers or more linked to each other through the above groups
forming multimers (e.g. telomers or polymers) of
Good too. In this case, the carbon atom number range shown in each substituent above is
It may be outside the scope of the regulations. Shown by formulas (1) to (5)
It is preferable that the coupler used is a diffusion-resistant coupler.
This is an example. Diffusion-resistant type means that the molecules are immobilized in the added layer.
In order to
It is a coupler that Usually, the total carbon number is 8 to 30,
Preferably 10 to 20 alkyl groups or a total of 4 to 20 carbon atoms
An aryl group with 20 substituents is used. these
The diffusion-resistant group may be substituted anywhere in the molecule, and
You may have more than one. Chemical formula 10 to Chemical formula 30 shown below
Specific examples of yellow couplers represented by formulas (1) to (5)
However, the present invention is not limited thereto. [Formula 10] [Formula 11] [Formula 11] [Formula 12] [Formula 13] [Formula 13] [Formula 14] [Formula 14] [Formula 15] [Formula 16] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image Y-56, Y-57, and compound shown in 28
In Y-58 shown in 29, "}" is a phenyl ring
The above substituent is at either the 5th or 6th position of the phenyl ring
It means to combine. The present invention represented by general formulas (1) to (5)
The yellow couplers are shown in the following chemical formulas 31 to 34.
It can be synthesized using the wasu route. Synthesis Example-1 [Chemical 31] Synthesis of Intermediate B Compound A 357.5 g (3.0 mol), Compound B 396
．． 3 g (3.0 mol) was added to 1.2 liters of ethyl acetate and di
It was dissolved in 0.6 liters of methylformamide. stir
while dicyclohexylcarbodiimide 631g (3
．． A solution of 0.06 mol) in acetonitrile (400 ml) was added to 1
It was added dropwise at 5-35°C. React at 20-30℃ for 2 hours.
After that, the precipitated dicyclohexyl urea was filtered off. Filtrate
Add 500 ml of ethyl acetate and 1 liter of water, and remove the aqueous layer.
Removed. Next, the organic layer was washed twice with 1 liter of water.
. After drying the organic layer with anhydrous sodium sulfate, ethyl acetate was added.
The oil was distilled off under reduced pressure, and 692 g (9
8.9%) was obtained. Intermediate A 692g (2.97mol)
Dissolve in 3 liters of ethyl alcohol and stir while stirring.
430g of 30% sodium hydroxide aqueous solution at 75-80℃
was dripped. After dropping, react at the same temperature for 30 minutes.
The precipitated crystals were filtered. (Yield 658g) This crystal
was suspended in 5 liters of water, and added with concentrated hydrochloric acid at 40 to 50°C.
ml was added dropwise with stirring. Stir at the same temperature for 1 hour.
After that, the crystals were filtered to obtain 579 g (95%) of Intermediate B.
Ta. (Decomposition point: 127°C) Synthesis of Intermediate D 45.1 g (0.22 mol) of Intermediate B, Compound C86.
6g (0.2mol) in 400ml of ethyl acetate and dimethyl
Dissolved in 200 ml of acetamide. While stirring,
Cyclohexylcarbodiimide 66g (0.32mol)
acetonitrile (100 ml) solution at 15-30℃
dripped. After reacting at 20-30℃ for 2 hours, precipitation
The cyclohexylurea was filtered out. Add 4 ethyl acetate to the filtrate.
After adding 00ml and 600ml of water and removing the aqueous layer,
The machine layer was washed twice with water. Dry the organic layer with anhydrous sodium sulfate.
After drying, ethyl acetate was distilled off under reduced pressure to obtain 162g of oil.
Obtained. This oil was mixed with 100 ml of ethyl acetate and 30 ml of n-hexane.
Crystallized from 0 ml, 108 g (87.1
%)Obtained. (Melting point 132-134°C) Elemental content of intermediate D
The analytical values are shown in Table 1 below. [Table 1] 49.6 g (0.08 mol) of synthetic intermediate D of exemplary coupler Y-7 was added to dichloromethane.
It was dissolved in 300ml. Add sulfuryl chloride 11 to this solution.
．． While stirring 4g (0.084 mol) at 10-15℃
dripped. After reacting at the same temperature for 30 minutes, the reaction mixture
Drop 200g of 5% sodium bicarbonate aqueous solution onto the object.
Ta. After separating the organic layer, wash it with 200 ml of water and dry it.
Dry with sodium sulfate. Dichloromethane is distilled off under reduced pressure
47g of oil was obtained. Add 47g of this oil to acetonitrile.
Dissolve in 200 ml of tolyl and add 28.4 g of compound D to this.
(0.22 mol) and 22.2 g (0.22 mol) of triethylamine.
22 mol) was added with stirring. 4 o'clock at 40-50℃
After reacting for a while, it was poured into 300ml of water and the precipitated oil was
The material was extracted with 300 ml of ethyl acetate. Add organic layer to 5% water
After washing with 200g of sodium oxide aqueous solution, wash twice more.
It was washed with 300 ml of water. The organic layer was made acidic with dilute hydrochloric acid.
Thereafter, the mixture was washed twice with water and concentrated under reduced pressure to obtain a residue. (Yield 70
g) The obtained oily substance was mixed with 50 ml of ethyl acetate and n-hexane.
Crystallized with 100 ml of mixed solvent, the exemplary coupler Y-
47.8g (80%) of 7 was obtained. (Melting point 145-147
℃) Table 2 below shows the elemental analysis values of exemplary coupler Y-7.
Expressed in [Table 2] Synthesis Example-2 [Chemical 32] Synthesis of Intermediate E 90.3 g (0.44 mol) of Intermediate B, Compound E187
g (0.4 mol) in 500 ml of ethyl acetate and dimethyl fluoride.
It was dissolved in 300 ml of Lumamide. While stirring,
131.9 g (0.64 mole) of chlorhexylcarbodiimide
15-30 mL of acetonitrile (200 ml) solution
It was added dropwise at ℃. After reacting at 20-30°C for 2 hours, analysis
Dicyclohexylurea released was filtered. Add acetic acid to the filtrate.
Added 500ml of chill and 600ml of water and removed the aqueous layer.
Afterwards, the organic layer was washed twice with water. The organic layer was treated with anhydrous sodium sulfate.
After drying with a vacuum cleaner, ethyl acetate was distilled off under reduced pressure, and the oil was
81g was obtained. Heat this with 1.5 liters of n-hexane
The solution was dissolved and insoluble matter was filtered out. n-hexane solution
After cooling with water, the precipitated intermediate E was collected by filtration. Yield 243.4
g (93%) Elemental analysis of intermediate E, melting point 103-105°C
The values are shown in Table 3 below. [Table 3] 39.3 g (0.06 mol) of synthetic intermediate E of exemplary coupler Y-6 was added to dichloromethane.
It was dissolved in 200ml. Add 8% of sulfuryl chloride to this solution.
7g (0.064 mol) at 10-15℃ while stirring
dripped. After reacting at the same temperature for 30 minutes, the reaction mixture
200g of 4% sodium bicarbonate aqueous solution was added dropwise to
. After separating the organic layer, wash it with 200ml of water, and add anhydrous sulfuric acid.
Dried with sodium. Dichloromethane was distilled off under reduced pressure,
41.3g of oil was obtained. 41.3 g of this oil was mixed with 1 part of acetonitrile.
00ml, dissolved in 200ml of dimethylacetamide,
Compound D20.8g (0.16mol) and triethylamine
16.2 g of water were added with stirring. 3 at 30-40℃
After reacting for an hour, pour into 400ml of water and precipitate oil.
The resulting product was extracted with 300 ml of ethyl acetate. 2% organic layer
After washing with 300g of sodium hydroxide aqueous solution,
Washed twice with water. After acidifying the organic layer with dilute hydrochloric acid, wash twice with water.
The residue was concentrated under reduced pressure to obtain 42 g of a residue. Add this to methanol
Exemplary coupler Y-6 was crystallized in 200 ml.
8g (85%) obtained. (Melting point 110-112°C) Examples
The elemental analysis values of Puller Y-6 are shown in Table 4 below. [Table 4] Synthesis Example-3 [Chemical Formula 33] Synthesis of Intermediate F 104.7 g (0.51 mol) of Intermediate B, Compound E18
7.5 g (0.5 mol) was added to 1 liter of ethyl acetate and dimethyl
It was dissolved in 400 ml of chillformamide. while stirring
, dicyclohexylcarbodiimide 107.3g (0.
525 mol) in dimethylformamide (100 ml)
The liquid was added dropwise at 15-30°C. Incubate for 1 hour at 20-30℃
After reacting, add 500ml of ethyl acetate and
The mixture was heated at ℃ and dicyclohexylurea was filtered off. To the filtrate
Add 500ml of water and remove the water layer, then wash twice with water.
did. After drying the organic layer with anhydrous sodium sulfate, acetic acid
Ethyl was distilled off under reduced pressure to obtain 290 g of an oily substance. This oily
Add the substance with 1 liter of ethyl acetate and 2 liters of methanol.
Heat it, filter out the insoluble matter, cool the filtrate with water, and the intermediate
Crystals of Form F precipitated and were filtered. Yield 267g (9
5%) The elemental analysis values of Intermediate F with a melting point of 163-164℃ are as follows.
It is shown in Table 5 below. [Table 5] Synthesis of Intermediate G 114.0 g (0.2 mol) of Intermediate F was dissolved in dichloromethane.
It was dissolved in 500ml. Add this solution to sulfuryl chloride 28
．． 4g (0.21 mol) at 10-15℃ while stirring
dripped. After reacting at the same temperature for 30 minutes, the reaction mixture
500g of 6% sodium bicarbonate aqueous solution was added dropwise to
. After separating the organic layer, it was washed with 500 ml of water, and washed with anhydrous sulfuric acid.
Dried with sodium. Dichloromethane is distilled off under reduced pressure
Intermediate G precipitated as crystals and was filtered out (yield
108.6g (91%)). 29.8 g (0.05 mol) of synthetic intermediate G of exemplary coupler Y-12 was added in dimethylform.
Dissolved in 80 ml of amide, 12.9 g of compound D (0.1
mol) and then 10.1 g (0.0 mol) of triethylamine.
10 mol) was added dropwise while stirring at 20 to 30°C. 4
After reacting at 0 to 45°C for 1 hour, 300 m of ethyl acetate was added.
1 and 200 ml of water. The organic layer was treated with 2% sodium hydroxide.
After washing twice with 400g of lium aqueous solution, wash once more.
did. The organic layer was made acidic with dilute hydrochloric acid, washed twice with water, and concentrated under reduced pressure.
34g of residue was obtained. Add this to 50 ml of ethyl acetate, n
-Crystallize with a mixed solvent of 150 ml of hexane, and
19g of Puller Y-12 was obtained. These crystals are mixed with ethyl acetate/
120 ml of mixed solvent with n-hexane = 1/3 vol ratio
15 g (43.5
%)Obtained. (Melting point 135-136°C) Exemplary coupler Y-
The elemental analysis values of the 12 samples are shown in Table 6 below. [Table 6] Synthesis Example-4 [Formula 34] 27.0 g (0.15 mol) of synthetic compound G of exemplary coupler Y-49, triethylamine
15.2 g (0.15 mol) of
It was dissolved in 50ml. 29.8 g of intermediate G to this mixture.
(0.05 mol) of dimethylformamide (30 ml)
The solution was added dropwise while stirring. Incubate at 30-40℃ for 4 hours.
After reacting, add 400 ml of ethyl acetate and 300 ml of water.
It was. The organic layer was washed with 400 g of 2% aqueous sodium hydroxide solution.
After that, it was washed with water two more times. The organic layer was made acidic with dilute hydrochloric acid.
Thereafter, it was washed twice with water and dried over anhydrous sodium sulfate. acetic acid
Ethyl was distilled off under reduced pressure to obtain 54 g of a residue. Add this to acetic acid.
Chill/methanol (1/2 vol ratio) mixed solvent 300
Example coupler Y-49 was filtered. The obtained crystals were mixed with ethyl acetate/methanol (1/2 vol ratio).
) Recrystallized from 200 ml of mixed solvent to obtain example coupler Y-4.
28.8g (77.8%) of 9 was obtained. Melting point 190-19
The table below shows the elemental analysis values of the 1°C exemplary coupler Y-49.
7. [Table 7] Couplers represented by formula (1) or (2) in the present invention
- is 0.001 mol to 1 mol of silver in the emulsion layer.
2 mol, preferably 0.01 mol to 0.5 mol
It is generally used within a range. On the other hand, the yellow coupler obtained from the present invention
The yellow pigment used is benzoyl, which has traditionally been used.
Acetanilide or pivaloylacetanilide?
The preferable green area for the yellow dye obtained from
Highly saturated yellow is preferred due to reduced absorption.
It can be reproduced. However, it is required for photosensitive materials.
The requirement is to reduce sensitivity changes during storage while maintaining performance.
It was by no means satisfactory. this request
In order to satisfy the above formula (A), the compound represented by formula (A) is
It was necessary to contain at least one kind. In the above formula (A), Y5 and Y6 are
, preferably benzothiazole, naphthothiazole,
Zoselenazole, Naphthoselenazole, Benzoxa
From sol, naphthoxazole, benzimidazole
necessary to form a nitrogen-containing heterocyclic nucleus selected from the group
Represents a group of nonmetallic atoms, and these heterocyclic nuclei contain halogens.
atom, alkyl group having 1 to 8 carbon atoms, alkyl group having 1 to 8 carbon atoms
The koxy group and phenyl group may be substituted. Also,
R6 and R8 represent an alkyl group having 1 to 8 carbon atoms;
, R6 or R8 is hydroxyl
group, carboxyl group or sulfo group. Shown below
Specific examples of compounds represented by formula (A) in formulas 35 to 42
However, it is of course not limited to these. [Chemical 35] [Chemical 36] [Chemical 36] [Chemical 37] [Chemical 38] [Chemical 39] embedded image The compound represented by formula (A) is used in a spectrally sensitizing amount.
However, specifically, 5 x 10-7 moles per mole of silver halide.
2 x 10-2 mol, preferably 5 x 10-6 mol
1 x 10-2 mol, particularly preferably 1 x 10-5 mol
Contained in a silver halide photographic emulsion at a ratio of 5 x 10-3 mol.
be possessed. The sensitizing dye used in the present invention is directly applied to the emulsion.
can be dispersed inside. In addition, these can be used in suitable solvents.
, for example, methyl alcohol, ethyl alcohol,
Pill alcohol, methylcellosolve, JP-A-48-97
15, halogenated atom described in U.S. Pat. No. 3,756,830
alcohol, acetone, water, pyridine or
It is dissolved in a mixed solvent and added to the emulsion in the form of a solution.
You can also As another method of adding
4185, U.S. Pat. No. 3,822,135, U.S. Patent No. 3,6
No. 60,101, No. 2,912,343, No. 2,99
No. 6,287, No. 3,429,835, No. 3,469
, No. 987, No. 3,658,546, No. 3,822,
The method described in No. 135 can be used. Doi again
The method described in Patent Application No. 2,104,283, U.S. Pat.
The method described in Patent No. 3,649,286 can also be used.
Wear. The above sensitizing dye is also coated on a suitable support.
It may be uniformly dispersed in the silver halide emulsion beforehand, but of course
It can be dispersed during any step in the preparation of silver halide emulsions.
can. The light-sensitive material of the present invention has a blue-sensitive material on a support.
layer, green-sensitive layer, and red-sensitive layer.
It is sufficient if at least one layer is provided, silver halide milk
There are no particular restrictions on the number or order of the agent layer and non-photosensitive layer.
stomach. Typically, a substantially color-sensitive
Multiple silver halide emulsions with the same but different sensitivities
halogenated with at least one photosensitive layer consisting of
It is a silver photographic light-sensitive material, and the photosensitive layer has blue light, green light,
and a unit photosensitive layer sensitive to either red light.
Yes, in multilayer silver halide color photographic materials.
Generally, the unit photosensitive layers are arranged in order of red sensitivity from the support side.
A chromatic layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order. However, even if the above installation order is reversed depending on the purpose,
Installation where different photosensitive layers are sandwiched within the same color sensitive layer
The order can be taken. Between the above silver halide photosensitive layers and
In addition, non-photosensitive layers such as various intermediate layers are provided on the top and bottom layers.
You can leave it. For example, Japanese Patent Application Laid-Open No. 61-437
No. 48, No. 59-113438, No. 59-11344
No. 0, No. 61-20037, No. 61-20038
Contains couplers and DIR compounds as described in the
It may contain color mixing inhibitors as is commonly used.
It's okay to stay. Multiple halogens forming each unit photosensitive layer
The silver emulsion layer is described in West German Patent No. 1,121,470.
or as described in British Patent No. 923,045.
A two-layer structure consisting of a high-speed emulsion layer and a low-speed emulsion layer is preferably used.
be able to. Usually, the sensitivity increases sequentially toward the support.
It is preferable to arrange them so that each halogenated
A non-photosensitive layer may be provided between the silver emulsion layers. Also, for example, JP-A No. 57-112751, JP-A No. 62-2
No. 00350, No. 62-206541, No. 62-20
The side remote from the support as described in No. 6543
A low-sensitivity emulsion layer is installed on the side, and a high-sensitivity emulsion layer is installed on the side closer to the support.
You may. As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL
)/High-sensitivity red-sensitive layer (RH)/Low-sensitivity red-sensitive layer (R
L) or BH/BL/GL/GH/RH/RL
or BH/BL/GH/GL/RL/RH
etc. can be installed. Also, special public service 55-3493
As stated in Publication No. 2, the furthest from the support
Arranged in the order of blue-sensitive layer/GH/RH/GL/RL from the side
You can also. Also, JP-A No. 56-25738,
As described in the publication No. 62-63936, support
Blue photosensitive layer from the side farthest from the body/GL/RL/GH/
They can also be arranged in the order of RH. Also, special public service 1977-1
As described in Japanese Patent No. 5495, the upper layer is the most photosensitive.
High-strength silver halide emulsion layer, lower density in the middle layer
Light intensity silver halide emulsion layer, the lower layer is more light sensitive than the middle layer
A low-strength silver halide emulsion layer is placed and directed toward the support.
Consisting of three layers with different photosensitivity, each with sequentially lower photosensitivity.
Examples include arrays that are These three different photosensitivity
Even if it is composed of layers, JP-A-59-202464
As described in the publication, in the same color-sensitive layer,
medium-sensitivity emulsion layer/high-sensitivity emulsion layer from the side away from the support.
/low-sensitivity emulsion layer. In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer.
They may be arranged in any order. Also, if there are 4 or more layers
However, the arrangement may be changed as described above. Improve color reproducibility
No. 4,663,271;
No. 05,744, No. 4,707,436, JP-A-62
-160448 and 63-89850
Main photosensitive layers such as BL, GL, RL and spectral sensitivity distribution
A donor layer (CL) with different interlayer effects is placed adjacent to the main photosensitive layer.
Alternatively, it is preferable to arrange them close to each other. as above
Depending on the purpose of each photosensitive material, various layer configurations and
Arrays can be selected. [0068] Photographic milk of the photographic light-sensitive material used in the present invention
The preferred amount of silver halide contained in the agent layer is about 30 mol%.
Silver iodobromide, silver iodochloride, including the following silver iodides:
Silver is iodochlorobromide. Particularly preferred is about 2 mol%.
Silver iodobromide containing up to about 10 mol% silver iodide
Silver is iodochlorobromide. Silver halide grains in photographic emulsion
Children are regular crystals like cubes, octahedrons, and tetradecahedrons.
Those with irregular crystal shapes such as spherical or plate-like
crystal defects such as twin planes, or
may be a combination thereof. The grain size of silver halide is approximately
Even fine particles of 0.2 μm or less have a projected area diameter of approximately 10 μm.
Large-sized grains up to m are acceptable, and polydisperse emulsions
It may also be a monodisperse emulsion. Silver halide photographic emulsion that can be used in the present invention
For example, Research Disclosure (RD) No.
．． 17643 (December 1978), pp. 22-23,
“I. Emulsion preparation
tion and types)”, and the same No.
．． 18716 (November 1979), 648 pages, same N
o. 307105 (November 1989), 863-8
65 pages, and “Physics and Chemistry of Photography” by Grafkide, P.
Published by P. Glafkides, Chim
ie etPhysique Photograp
Paul Montel, 1967),
"Photographic Emulsion Chemistry" by Duffin, published by Focal Press (
G. F. Duffin, Photographic
Emulsion Chemistry (Focal
Press, 1966)), Zelikman et al.
"Preparation and Coating of Emulsions", published by Focal Press (V.L.
Zelikman et al. ,Making
and Coating Photography
ic Emulsion, Focal Press
, 1964).
can. For example, US Pat. No. 3,574,628
, No. 3,655,394 and British Patent No. 1,41
Monodisperse emulsions described in No. 3,748 are also preferred. Also
, tabular grains with an aspect ratio of about 3 or more are also included.
Can be used for inventions. Tabular grains are described, for example, by Gatoff, F.
graphic science and engineering
Gutoff, Photographic Sc.
engineering), 1st
4, pp. 248-257 (1970); U.S. Patent No. 4,
No. 434,226, No. 4,414,310, No. 4
, No. 433,048, No. 4,439,520 and
The method described in British Patent No. 2,112,157
It can be simply prepared. Even if the crystal structure is uniform
, even if the inside and outside have different halogen compositions.
Often, it may have a layered structure. Also, epitaxy
Silver halides of different compositions are joined by mechanical joining.
Halogens such as Rodan silver and lead oxide may also be used.
It may be bonded with a compound other than silver germide. Also seeds
Mixtures of particles of different crystalline forms may also be used. Emulsion of the above
Although it is a surface latent image type in which latent images are mainly formed on the surface, particles
Even if it is an internal latent image type that forms inside, it can be used both on the surface and inside.
Any type with a latent image may be used, but it may be a negative type emulsion.
It is necessary to Among the internal latent image types, JP-A-63-
Core/shell type internal latent image type emulsion described in No. 264740
It may be. This core/shell type internal latent image emulsion
The preparation method is described in JP-A-59-133542.
There is. The thickness of the shell of this emulsion is determined by development processing, etc.
Although different, 3 to 40 nm is preferable, and 5 to 20 nm is particularly preferable.
preferred. Silver halide emulsions are usually subjected to physical ripening, chemical
Use those that have been subjected to chemical ripening and spectral sensitization. This way
Additives used in the eel process are research disclosures.
Jar No. 17643, same No. 18716 and
Same No. 307105, and the applicable
The locations are summarized in the table below. The photosensitive material of the present invention includes
Grain size and grain size distribution of photosensitive silver halide emulsions,
At least one characteristic of halogen composition, particle shape, and sensitivity
Two or more types of emulsions with different properties are mixed in the same layer.
can be used. U.S. Patent No. 4,082,553
Silver halide grains coated with the grain surface described in , USA
Patent No. 4,626,498, JP 59-21485
Silver halide grains with the insides of the grains covered, as described in No. 2;
Colloidal silver is added to the photosensitive silver halide emulsion layer and/or
Preferred for use in substantially non-photosensitive hydrophilic colloid layers.
Wear. Silver halide grains covered inside or on the surface of grains
Child refers to any part of the photosensitive material, regardless of whether it is an unexposed area or an exposed area.
silver halide grains that can be developed in a non-imagewise manner.
Say something. Halogen inside or on the surface of the particle
The method for preparing silver oxide particles is described in U.S. Pat. No. 4,626,498.
, JP-A-59-214852. particle
core/shell type silver halide grains with internally fogged
The silver halide that forms the inner core has the same halogen composition.
or have a different halogen composition.
. As silver halide inside or on the surface of grains
is silver chloride, silver chlorobromide, silver iodobromide, or silver chloroiodobromide.
can also be used. These capped halogens
There is no particular limitation on the grain size of silver oxide grains, but the average
The particle size is 0.01 to 0.75 μm, especially 0.
．． 05 to 0.6 μm is preferable. Also, regarding the particle shape,
There is no particular limitation on the particles, and regular particles may be used.
Dispersed emulsions may be used, but monodisperse (weight of silver halide grains)
or at least 95% of the particles are ±40% of the average particle size.
% or less). [0072] In the present invention, non-photosensitive fine grain silver halide
It is preferable to use Non-photosensitive fine particle halogenation
Silver is a material that is not sensitive during imagewise exposure to obtain dye images.
Not exposed to light and virtually undeveloped in its development process
It is a silver halide fine grain and has not been fogged in advance.
It is preferable not to have it. Fine grain silver halide contains silver bromide.
The content is 0 to 100 mol%, and silver chloride or
and/or silver iodide. Preferably iodized
It contains 0.5 to 10 mol% of silver. Particulate matter
Silver halide has an average grain size (average diameter equivalent to a circle of projected area).
value) is preferably 0.01 to 0.5 μm, and preferably 0.02 to 0.5 μm.
0.2 μm is more preferable. Fine grain silver halide is
It can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains is optically sensitized.
There is no need for spectral sensitization. however,
Before adding this to the coating solution,
Sol type, azaindene type, benzothiazolium type, etc.
or known compounds such as mercapto compounds or zinc compounds.
It is preferable to add a stabilizer. This fine particle
The layer containing silver halide particles preferably contains colloidal silver.
can be set. The coating silver amount of the photosensitive material of the present invention is 6
．． 0g/m2 or less is preferable, 4.5g/m2 or less
is most preferred. Known photographic additives that can be used in the present invention
As stated in the three research disclosures above,
The relevant information is shown in the table below. Additive type RD17643 RD
18716 RD307105 1. chemical sensitization
Agent page 23 page 648 right
Column 866 pages 2. Sensitivity enhancer
648 pages
Right column 3. spectral sensitizer, 2
Pages 3-24 Page 648 Right column 86
Pages 6-868 Super sensitizer
~Page 649, right column 4.
Brightener page 24
Page 647 right column Page 868 5.
Antifoggant Pages 24-25 Page 649 Right
Column pages 868-870 Stabilizer 6. Light absorber, pages 25-26
Page 649 right column Page 873 F
filter
~Page 650 left column Dyes, ultraviolet absorbers 7. Stain inhibitor page 25 right column 6
Page 50 left column to right column Page 872 8. dye image cheap
Fixing agent page 25 page 650 left column
872 pages 9. Hardener
Page 26 Page 651 Left column
Pages 874-875 10. binder
Page 26 Page 651 Left column
Pages 873-874 11. plasticizer,
Page 27 Page 650 Right column
Page 876 Lubricants 12. Coating aids, pages 26-27
Page 650 right column Pages 875-876 Table
Surfactant 13. Static inhibitor page 27
Page 650, right column, pages 876-877 14. Ma
protective agent
878-8
Page 79. [0074] In addition, photographic properties due to formaldehyde gas
In order to prevent deterioration of performance, U.S. Patent No. 4,411,9
Forms described in No. 87 and No. 4,435,503
Compounds that can be immobilized by reacting with aldehydes are used as photosensitive materials
It is preferable to add. The photosensitive material of the present invention is
Permit No. 4,740,454, No. 4,788,132
, JP-A-62-18539, JP-A-1-283551
It is preferable to contain the mercapto compound described in
stomach. The photosensitive material of the present invention is described in JP-A No. 1-106052.
It is unrelated to the amount of developed silver produced by the development process as stated.
Do not use fogging agents, development accelerators, silver halide solvents or the like.
It is preferable to contain a compound that releases these precursors.
Yes. International publication WO88/047 in the photosensitive material of the present invention
No. 94, by the method described in Special Publication No. 1-502912.
dispersed dyes or European Patent No. 317,308A;
U.S. Patent No. 4,420,555, JP 1-2593
It is preferable to contain the dye described in No. 58. Various color couplers can be used in the present invention.
, a specific example is the research disclosure mentioned above.
No. 17643, VII-C to G, and the same No. 3
No. 07105, VII-C to G
It is. As a yellow coupler, for example, U.S. Patent No. 3,93
No. 3,501, No. 4,022,620, No. 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 No. 3,973,968, U.S. Patent No. 4,314,
No. 023, No. 4,511,649, European Patent No. 24
Those described in No. 9,473A are preferably used in combination.
can. 5-pyrazolone as magenta coupler
and pyrazoloazole type compounds are preferred, for example
, U.S. Pat. No. 4,310,619, U.S. Pat. No. 4,351,
No. 897, European Patent No. 73,636, U.S. Patent No. 3,
No. 061,432, No. 3,725,067, Reser
Chi Disclosure No. 24220 (1984
(June), Japanese Patent Publication No. 60-33552, Research D.
Closer No. 24230 (June 1984)
, JP-A-60-43659, JP-A-61-72238,
No. 60-35730, No. 55-118034, No. 6
No. 0-185951, U.S. Patent No. 4,500,630
, No. 4,540,654, No. 4,556,630
The one described in International Publication No. WO88/04795 is
preferred. As cyan couplers, phenolic and
and naphthol couplers, such as those described in U.S. Patent No.
No. 4,052,212, No. 4,146,396, No. 4,146,396, No. 4,146,396, No.
No. 4,228,233, No. 4,296,200,
Same No. 2,369,929, Same No. 2,801,171
, No. 2,772,162, No. 2,895,826
No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,1
No. 73, West German Patent Publication No. 3,329,729,
No. 121,365A, No. 249,453A, U.S.
National Patent No. 3,446,622, National Patent No. 4,333,99
No. 9, No. 4,775,616, No. 4,451,5
No. 59, No. 4,427,767, No. 4,690,
No. 889, No. 4,254,212, No. 4,296
, No. 199, and JP-A-61-42658.
preferable. Furthermore, JP-A-64-553, JP-A-64-5
No. 54, No. 64-555, No. 64-556
Pyrazoloazole couplers and U.S. Patent No. 4,818
, No. 672 is also used.
be able to. References to polymerized dye-forming couplers
Examples include, for example, U.S. Pat. No. 3,451,820;
No. 4,080,211, No. 4,367,282, No. 4,080,211, No. 4,367,282, No.
No. 4,409,320, No. 4,576,910,
British Patent No. 2,102,137, European Patent No. 341,
No. 188A. Couplers whose coloring dyes have appropriate diffusivity
As U.S. Patent No. 4,366,237, British Patent No.
No. 2,125,570, European Patent No. 96,570,
As described in West German Patent (Publication) No. 3,234,533
is preferred. Color to correct unnecessary absorption of coloring pigments
The code coupler is a research disclosure
No. Section VII-G of 17643, No. 3071
Section VII-G of 05, U.S. Patent No. 4,163,670
, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,
No. 929, No. 4,138,258, British Patent No. 1,
146,368 is preferred. Also, the United States
During the coupling described in Patent No. 4,774,181
The emitted fluorescent dye corrects unnecessary absorption of the coloring dye.
couplers described in U.S. Pat. No. 4,777,120.
A dye precursor that can react with a developing agent to form a dye
It is also preferred to use couplers having - groups as leaving groups.
Yes. Coupling releases photographically useful residues
Compounds that can also be preferably used in the present invention. Development suppression
The drug-releasing DIR coupler is the aforementioned RD17643.
, VII-F and the same No. 307105, VII-
The patent described in Section F, JP-A-57-151944,
No. 57-154234, No. 60-184248, No. 60-184248, No.
No. 63-37346, No. 63-37350, US Patent
No. 4,248,962, No. 4,782,012
Those described are preferred. For example, RD No. 11
449, 24241, JP-A-61-201247
The described bleach accelerator releasing couplers can be treated with bleaching ability.
It is effective in shortening the process time, especially in the flattening process mentioned above.
When added to photosensitive materials using plate-like silver halide grains
The effect is great. The nucleating agent may appear on the image during development.
A British patent for a coupler that releases a development accelerator
No. 2,097,140, No. 2,131,188,
JP-A-59-157638, JP-A No. 59-170840
Those described in are preferred. Also, JP-A-60-1070
No. 29, No. 60-252340, JP-A-1-4494
No. 0, the oxidized form of the developing agent described in No. 1-45687;
For example, fogging agents, development accelerators, etc.
, compounds that release silver halide solvents are also preferred. Other materials that can be used in the photosensitive material of the present invention
Examples of compounds that can be used include, for example, U.S. Patent No. 4,130,
Competitive couplers such as those described in U.S. Pat.
No. 283,472, No. 4,338,393, No. 4
, 310,618, e.g.
Publication No. 60-185950, JP-A No. 62-24252
DIR redox compound releasing couplers described in DIR
Coupler-emitting coupler, DIR coupler-emitting redox
compound or DIR redox releasing redox compound
, European Patent No. 173,302A, European Patent No. 313,308
A coupler that releases a dye that restores color after separation as described in item A;
For example, Riggan as described in U.S. Pat. No. 4,555,477.
A red-emitting coupler, disclosed in JP-A-63-75747
Ico dye-releasing couplers, U.S. Pat. No. 4,774,
Examples include couplers that emit fluorescent dyes as described in No. 181.
It will be done. The couplers used in the present invention include various known couplers.
It can be introduced into photosensitive materials by a dispersion method. Oil droplet dispersion method
Examples of high boiling point solvents used in
No. 22,027. Used for oil droplet dispersion method
High-boiling organic solvents with a boiling point of 175°C or higher at normal pressure
Specific examples include phthalate esters (e.g.
Luphthalate, dicyclohexyl phthalate, di-2-
Ethylhexyl phthalate, decyl phthalate, bis(
2,4-di-t-amylphenyl) phthalate, bis(
2,4-di-t-amyl phenyl) isophthalate, bicarbonate
(1,1-diethylpropyl)phthalate), phosphoric acid
or esters of phosphonic acids (e.g. triphenylphonate).
sphate, tricresyl phosphate, 2-ethyl phosphate
xyl diphenyl phosphate, tricyclohexyl phosphate
Sphate, tri-2-ethylhexyl phosphate,
Tridodecyl phosphate, tributoxyethyl phosph
ate, trichloropropyl phosphate, di-2-
tylhexylphenylphosphonate), benzoic acid ester
(e.g. 2-ethylhexylbenzoate, dodecyl)
Rubenzoate, 2-ethylhexyl-p-hydroxy
benzoate), amides (e.g. N,N-diethyld),
Decanamide, N,N-diethyl laurylamide, N-
(tetradecylpyrrolidone), alcohols or phenolics
alcohols (e.g. isostearyl alcohol, 2,4-di
-tert-amylphenol), aliphatic carboxylic acid ester
Steles (e.g. bis(2-ethylhexyl) sebaque)
, dioctyl azelate, glycerol tributylate
Isostearyl lactate, trioctyl citre
), aniline derivatives (e.g. N,N-dibutyl-2-
butoxy-5-tert-octylaniline), hydrocarbon
elements (e.g. paraffin, dodecylbenzene, diisopropylene)
(ropyrunaphthalene), etc. Also with auxiliary solvent
For example, the boiling point is about 30°C or higher, preferably 50°C.
Organic solvents with a temperature of about 160°C or less can be used, and a typical example is
For example, ethyl acetate, butyl acetate, ethyl propionate.
methyl ethyl ketone, cyclohexanone, 2-ethyl
Examples include xyethyl acetate and dimethylformamide.
It will be done. Latex dispersion process, effects and impregnation
Specific examples of TEX include, for example, U.S. Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230. Cyan, magenta, yellow in the present invention
-The coupler dispersion has a boiling point of 15 in the ratio expressed by the following formula:
A high boiling point organic solvent of 0° C. or higher may be included. 0≦High boiling point organic solvent (weight)/Coupler (weight)≦1.
0 This ratio is more preferable than the requirements for improving sharpness and film strength.
0.7 or less, more preferably 0.5 or less
. In addition, the high boiling point organic solvent in the above formula is co-emulsified.
refers to something that [0080] The color photosensitive material of the present invention contains fenethyl
alcohol, JP-A No. 63-257747, No. 62-
Described in No. 272248 and JP-A No. 1-80941
1,2-benzisothiazolin-3-one, n-butyl
p-hydroxybenzoate, phenol, 4-
Chlor-3,5-dimethylphenol, 2-phenoxy
Ethanol, 2-(4-thiazolyl)benzimidazole
It is preferable to add various preservatives or antifungal agents such as
Delicious. The present invention can be applied to various color photosensitive materials.
Can be done. Color negative film for general use or movies
, color reversal film for slides or television;
Color paper, color positive film and color reversal
A typical example is paper. main departure
Suitable supports which can obviously be used include, for example, the above-mentioned RD
No. 17643, page 28, same No. 18716-6
From the right column on page 47 to the left column on page 648, and No. 307
105, page 879. Photosensitive material of the present invention
is the total thickness of all the hydrophilic colloid layers on the side with the emulsion layer.
It is preferable that the sum is 28 μm or less, and 23 μm
The following is more preferable, 18 μm or less is even more preferable,
Particularly preferred is 16 μm or less. Also, membrane swelling rate T1/
2 is preferably 30 seconds or less, more preferably 20 seconds or less
stomach. Film thickness was measured at 25°C and 55% relative humidity (2 days).
The membrane swelling rate T1/2 means the specified film thickness.
can be measured according to methods known in the art.
Ru. For example, according to A. Green et al.
Photographic Science and Engineering
Alling (Photogr. Sci. & Eng.), 1
Suelome of the type described in Volume 9, No. 2, pp. 124-129
T1 can be measured by using a swell meter.
/2 is when processed with color developer at 30℃ for 3 minutes and 15 seconds.
The saturated film thickness is defined as 90% of the maximum swelling film thickness reached.
Defined as the time required to reach 1/2 of the thickness. Membrane swelling rate
Degree T1/2 is gelatin as binder and hardener.
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 based on the conditions mentioned earlier.
From the maximum swelling film thickness below, the formula: (maximum swelling film thickness - film thickness)
/ Can be calculated according to film thickness. The light-sensitive material of the present invention is an emulsion
On the side opposite to the side with the layer, the total dry film thickness is 2 μm to 2
A 0 μm hydrophilic colloid layer (referred to as back layer) is provided.
It is preferable that This back layer contains the aforementioned light absorbing material.
, filter dyes, ultraviolet absorbers, static inhibitors,
Hardeners, binders, plasticizers, lubricants, coating aids, surfaces
It is preferable to contain an activator or the like. This back layer
The swelling rate is preferably 150 to 500%. [0081] The color photographic material according to the present invention
RD No. mentioned above. 17643, pages 28-29, same No.
．． 18716, page 651 left column to right column, and the same No.
Normal person listed on pages 880-881 of 307105
It can be developed by a method. Photosensitive material of the present invention
The color developing solution used for developing the material is preferably an aromatic one.
Alkaline whose main ingredient is a primary amine color developing agent.
It is an aqueous solution. As this color developing agent, aminophere
Nol-based compounds are also useful, but p-phenylenediamine
Preferably used are compounds such as
For example, 3-methyl-4-amino-N,N-diethylanily
3-methyl-4-amino-N-ethyl-N-β-h
Droxyethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylanili
3-methyl-4-amino-N-ethyl-β-methoxy
Ethylaniline and their sulfates, hydrochlorides or
Examples include p-toluenesulfonate. Among these
, especially 3-methyl-4-amino-N-ethyl-N-β
-Hydroxyethylaniline sulfate is preferred. these
Two or more of these compounds can also be used in combination depending on the purpose. Color developing solutions include, for example, alkali metal carbonates and borates.
or pH buffering agents such as phosphates, chloride salts, bromide
salts, iodide salts, benzimidazoles, benzothiazo
development inhibitors such as polymers or mercapto compounds.
It generally contains antifoggants or antifoggants. needed again
Depending on hydroxylamine, diethyl hydroxyl
Min, sulfite, N,N-biscarboxymethylhydra
Hydrazines such as gin, phenyl semicarbazides,
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
Imparting agent, aminopolycarboxylic acid, aminopolyphosphonic acid
, alkylphosphonic acids, and phosphonocarboxylic acids.
Various chelating agents such as
Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, hydroxyethylimine
Nodiacetic acid, 1-hydroxyethylidene-1,1-diphos
Phonic acid, nitrilo-N,N,N-trimethylenephosphone
Acid, ethylenediamine-N,N,N,N-tetramethylene
phosphonic acid, ethylenediamine-di(o-hydroxy
phenylacetic acid) and their salts as representative examples.
I can do it. [0082] When performing inversion processing, it is usually black and white.
After imaging, color development is performed. This black and white developer contains
Dihydroxybenzenes such as hydroquinone, 1-phenylene
3-pyrazolidones such as nyl-3-pyrazolidone or
is an aminophenol such as N-methyl-p-aminophenol.
Known black and white developing agents such as nols may be used alone or in combination.
Can be used together. These color developing solutions and
The pH of black and white developer is generally 9 to 12.
. In addition, the amount of replenishment of these developing solutions depends on the color photo being processed.
It depends on the photosensitive material, but generally 1 square meter of photosensitive material
3 liters or less, and bromide ions in the replenisher
500ml or more by reducing the concentration.
It can also be lowered. Process to reduce replenishment amount
Evaporation of the liquid is reduced by reducing the contact area with the air in the tank.
It is preferable to prevent oxidation and air oxidation. Photo taken in the treatment tank
The contact area between the real processing liquid and air is determined by the aperture ratio defined below.
It can be expressed as That is, aperture ratio = (contact area of processing liquid and air (cm2))/(
Capacity of treatment liquid (cm3)) 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 bleaching, bleach-fixing, fixing, water washing, and stabilization
It is preferable to apply it in the process. Also, in the developer
By using measures to reduce the accumulation of bromide ions in
It is also possible to reduce the amount of replenishment. Color development processing time is
, usually set between 2 to 5 minutes, with high temperature and high pH,
Furthermore, by using a high concentration of color developing agent,
It is also possible to reduce processing time. The photographic emulsion layer after color development is usually bleached.
be done. The bleaching process may be carried out simultaneously with the fixing process.
(bleach-fixing treatment) and may be carried out separately. Further treatment
In order to speed up processing, bleach-fixing treatment is performed after bleaching.
It may be a physical method. Furthermore, it is treated with two continuous bleach-fixing baths.
processing, fixing before bleach-fixing, or
may be bleached after bleach-fixing depending on the purpose.
Can be implemented. Examples of bleaching agents include iron (III).
Which polyvalent metal compounds, peracids, quinones, nitro compounds
things are used. Iron (III) is a typical bleaching agent.
organic complex salts, such as ethylenediaminetetraacetic acid, diethyl
triaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
Methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid
, glycol ether diamine tetraacetic acid, etc.
Ricarboxylic acids or citric acid, tartaric acid, malic acid
Any complex salt can be used. Of these, ethylene
Diaminetetraacetic acid iron (III) complex salt, and 1,3-dia
Iron(III) complex salt of minopropane tetraacetate
Minopolycarboxylic acid iron (III) complex salts are rapidly processed and cyclic
This is preferable from the viewpoint of preventing environmental pollution. In addition, aminopolycarboxylic acid iron (III) complex salts can be bleached.
It is particularly useful in both bleach-fix solutions and bleach-fix solutions. Using these aminopolycarboxylic acid iron (III) complex salts,
The pH of the bleach or bleach-fix solution used is usually 4.0 to 8.
However, to speed up the process, process at a lower pH.
You can also do that. Bleach solutions, bleach-fix solutions and their prebaths include
, a bleach accelerator can be used if necessary. Specific examples of useful bleach accelerators are described in
For example, U.S. Patent No. 3,893,858,
No. 1,290,812, No. 2,059,988
, JP-A-53-32736, JP-A No. 53-57831,
No. 53-37418, No. 53-72623, No. 53
-95630, 53-95631, 53-10
No. 4232, No. 53-124424, No. 53-141
No. 623, No. 53-28426, Research Disk
Roger No. No. 17129 (July 1978)
Compounds having a mercapto group or disulfide group as described
thiazolidine described in JP-A-50-140129
Derivatives: Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-208
No. 32, No. 53-32735, U.S. Patent No. 3,706
, 561; West German Patent No. 1,1
No. 27,715 and JP-A-58-16235.
Compound salt; West German Patent No. 966,410, West German Patent No. 2,748
, 430;
Polyamine compound described in No. 1988-8836; other special
No. 49-40943, No. 49-59644, No. 5
No. 3-94927, No. 54-35727, No. 55-2
Compounds described in No. 6506 and No. 58-163940; odor
Compound ions etc. can be used. Among them, mercapto group and
It appears that compounds with disulfide groups have a large promoting effect.
preferred in this respect, particularly U.S. Pat. No. 3,893,858;
West German Patent No. 1,290,812, JP-A-53-956
The compounds described in No. 30 are preferred. Additionally, U.S. Patent No. 4
, 552,834 are also preferred. these
A bleach accelerator may be added to the light-sensitive material. for photography
These bleaches are accelerated when bleach-fixing color photosensitive materials.
agents are particularly effective. Bleach and bleach-fix solutions contain the above compounds.
In addition to compounds, organic acids are used to prevent bleach stains.
It is preferable to have it. Particularly preferred organic acids are
A compound with a separation constant (pKa) of 2 to 5, specifically
For example, acetic acid, propionic acid, hydroxyacetic acid are preferred.
. Examples of fixing agents used in fixing solutions and bleach-fixing solutions include
Thiosulfates, thiocyanates, thioether compounds
, thioureas, and large amounts of iodide salts.
, the use of thiosulfate is common, especially thiosulfate
Ammonium is the most widely used. Also, thiosulfate
and thiocyanates, thioether compounds, and thioureas.
Any combination is preferred. As a preservative for fixing solutions and bleach-fixing solutions.
Sulfites, bisulfites, carbonyl bisulfites
or sulfur as described in European Patent No. 294769A.
Preferred are phosphoric acid compounds. In addition, it can be used as a fixer or bleach-fixer.
For the purpose of stabilizing the liquid, various aminopolycarboxylic acids and
The addition of organic phosphonic acids is preferred. In the present invention,
The fixer or bleach-fixer contains pKa for pH adjustment.
is 6.0 to 9.0, preferably imidazole
, 1-methylimidazole, 1-ethylimidazole,
Imidazole such as 2-methylimidazole at 0.1
It is preferable to add up to 10 mol/liter. [0085] The total time of the desilvering process is determined by the time when desilvering failure occurs.
It is preferable that the length be as short as possible. The preferred time is 1 minute to 3 minutes.
minutes, more preferably 1 to 2 minutes. Also, the processing temperature is
The temperature is 25°C to 50°C, preferably 35°C to 45°C. good
In the desired temperature range, the desilvering rate increases and the processing speed increases.
The occurrence of stains after treatment is effectively prevented. In the desilvering process
It is preferable that the agitation is as strong as possible.
stomach. As a specific method for strengthening stirring, see Japanese Patent Application Laid-open No. 62-1.
A jet of processing liquid on the emulsion surface of the photosensitive material described in No. 83460
The method of colliding the
A method of increasing the stirring effect using a transfer means, and a method of increasing the stirring effect by using a
While touching the wiper blade and the emulsion surface,
By moving the optical material and creating turbulence on the emulsion surface
How to improve the stirring effect and the circulation flow rate of the entire processing liquid
One example is how to increase the This method of improving stirring
The step is whether it is bleach, bleach-fix, or fixer.
It is valid. Improving stirring is achieved by adding bleach and fixing agents into the emulsion film.
It is thought that this will speed up the supply of silver and, as a result, increase the speed of desilvering.
It will be done. In addition, the above-mentioned means for improving agitation uses a bleach accelerator.
It is more effective when used, and the promoting effect is significantly increased.
To eliminate the fixation inhibiting effect caused by bleaching agents and bleaching accelerators.
Can be done. The automatic developing machine used for the photosensitive material of the present invention is
, JP-A-60-191257, JP-A No. 60-19125
No. 8, photosensitive material transportation described in No. 60-191259.
It is preferable to have means. The above-mentioned Japanese Patent Application Publication No. 1986-
As described in No. 191257, such conveyance means
The carry-over of processing liquid from the pre-bath to the post-bath can be significantly reduced.
Highly effective in preventing performance deterioration of physical fluids. This kind of effect
This reduces the processing time in each process and reduces the amount of processing solution replenishment.
It is particularly effective in reducing Silver halide color photographic material of the present invention
It is best to carry out a water washing and/or stabilization process after desilvering.
Common. The amount of water used in the washing process is determined by the characteristics of the photosensitive material.
(for example, depending on the material used, such as couplers), the purpose, and even the water
Replenishment of washing water temperature, number of washing tanks (number of stages), countercurrent flow, forward flow, etc.
It can be set in a wide range depending on the method and various other conditions. Of these, the number of washing tanks and water volume in the multi-stage countercurrent method
The relationship is Journal of the Soc.
iety of Motion Picture
and Television Engine
ers, Volume 64, p. 248-253 (May 1955
You can obtain it using the method described in the monthly issue). Said literature
According to the multi-stage countercurrent method described in , the amount of washing water is significantly reduced.
However, due to the increased residence time of water in the tank,
, bacteria propagate, and the resulting floating matter attaches to the photosensitive material.
Problems such as wearing the clothes may occur. Processing of the color photosensitive material of the present invention
As a solution to this problem, the
Calcium ions and magnets described in No. 2-288838
Using extremely effective methods to reduce sium ions
I can do it. Also, the model described in Japanese Patent Application Laid-Open No. 57-8542
Sothiazolone compounds, thiabendazoles, chlorinated
Chlorine-based disinfectants such as sodium socyanurate, and other
Benzotriazole, etc., “Chemistry of Antibacterial and Antifungal Agents” by Hiroshi Horiguchi
(1986) “Sterilization of Microorganisms” edited by Sankyo Publishing, Society of Hygiene Technology
, Sterilization, Anti-mold Technology” (1982) Industrial Technology Society, Japan Defense
Listed in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by the Society of Antifungal and Antifungal Agents
Fungicides can also be used. Processing of the photosensitive material of the present invention
The pH of the washing water in the process is 4 to 9, preferably 5.
~8. Washing water temperature and washing time also depend on the characteristics of the photosensitive material.
Various settings can be made depending on the application, etc., but in general, the temperature is 15 to 45°C.
20 seconds to 10 minutes, preferably 30 seconds to 5 minutes at 25-40°C
A range of minutes is selected. Furthermore, the photosensitive material of the present invention
Instead of washing with water, it can also be treated directly with a stabilizing solution.
Ru. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-8
No. 543, No. 58-148344, No. 60-2203
All known methods described in No. 45 can be used.
. In addition, following the water washing treatment, further stabilization treatment may be performed.
An example of this is the final production of color photosensitive materials for photography.
Contains dye stabilizers and surfactants, used as baths
One example is a stabilizing bath. As a dye stabilizer
For example, alcohols such as formalin and glutaraldehyde
Rudehydes, N-methylol compounds, hexamethylenete
Mention tolamin or aldehyde sulfite adducts
Can be done. Various chelating agents and antifungal agents are also added to this stable bath.
You can also get it. [0087] The water washing and/or stabilizing solution replenishment
The bar flow liquid is not reused in other processes such as desilvering process.
You can also In processing using automatic processing machines etc.
, if each of the above treatment liquids is concentrated by evaporation, water
It is preferable to correct the concentration by adding The silver halide color photosensitive material of the present invention has
Contains a color developing agent for the purpose of simplifying and speeding up processing.
It's okay. In order to incorporate various preforms of color developing agents,
Preferably, a cursor is used. For example, U.S. Patent No.
Indoaniline compounds described in No. 342,597;
No. 3,342,599, Research Disclosure
No. 14850 and the same No. 15159
Schiff base type compound, No. Al described in 13924
Dole compounds, described in U.S. Pat. No. 3,719,492
Metal salt complex, ureta described in JP-A-53-135628
Examples include ion-based compounds. Halogenation of the present invention
For silver color photosensitive materials, color development may be accelerated if necessary.
Various 1-phenyl-3-pyrazolidones are used for the purpose of
It may be built-in. Typical compounds are disclosed in JP-A-56-
No. 64339, No. 57-144547, and No. 58
-115438. Each in the present invention
The seed treatment liquid is used at 10°C to 50°C. Normally
A temperature of 33°C to 38°C is standard, but higher temperatures can be used.
to accelerate the processing and shorten the processing time, or conversely to lower the temperature
to achieve improved image quality and safety of processing solutions.
Can be done. Further, the silver halide photosensitive material of the present invention can be used for example.
For example, U.S. Patent No. 4,500,626, JP-A-60-1
No. 33449, No. 59-218443, No. 61-23
No. 8056, described in European Patent No. 210,660A2.
It can also be applied to heat-developable photosensitive materials. [Example] The present invention will be specifically explained below with reference to an example.
However, it is not limited to this. Preparation of Sample 101 Cellulose triacetate with a thickness of 127 μm and undercoated.
A multilayer film consisting of each layer with the following composition is formed on the film support.
A color sensitive material was prepared and designated as Sample 101. The number is m2
Represents the amount added per unit. The effect of the added compound is
It is not limited to the uses listed. 1st layer: antihalation layer black colloidal silver
0.20g
gelatin
1.9 g
UV absorber U-1
0.04g
UV absorber U-2
0.1 g ultraviolet light
Absorbent U-3
0.1 g UV absorber
U-4
0.1 g UV absorber U-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g High boiling point organic solvent Oil-1
0.1
g Microcrystalline solid dispersion of dye E-1
0.1 g 2nd layer: medium
Interlayer gelatin
0.40
g Compound Cpd-D
5
mg Compound Cpd-L
5
mg Compound Cpd-M
3
mg High boiling point organic solvent Oil-3
0.1 g
Dye D-4
0.4 mg
3rd layer: Intermediate layer Fine grain silver iodobromide emulsion with covered surface and interior
(Average particle size 0.06 μm, coefficient of variation 18%,
AgI content 1 mol%)
Silver amount
0.05g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4 g 4th layer: low red sensitivity
Emulsion layer Emulsion A
Silver amount 0.1
g Emulsion B
Silver amount 0.4
g Gelatin
0.
8g coupler-C-1
0.1
5g coupler-C-2
0.05g
Coupler-C-9
0.05g
Compound Cpd-D
10mg
High boiling point organic solvent Oil-2
0.1 g 5th layer: Medium sensitivity red
Sensitive emulsion layer Emulsion B
Silver amount 0.2
g Emulsion C
Silver amount 0.3
g Gelatin
0.
8g coupler-C-1
0.2
g Coupler-C-2
0.05
g Coupler-C-3
0.2 g
High boiling point organic solvent Oil-2
0.1 g 6th layer: High sensation
Red-sensitive emulsion layer Emulsion D
Silver amount 0.4
g Gelatin
1.1
g Coupler-C-1
0.3
g Coupler-C-3
0.7
g Additive P-1
0.1
g7th layer: middle layer gelatin
0.6
g Additive M-1
0.3
g Color mixing prevention agent Cpd-K
2.6 mg
UV absorber U-1
0.1 g
UV absorber U-6
0.1 g Dye D
-1
0.02g compound
Cpd-D
5 mg compound
Product Cpd-L
5 mg
Compound Cpd-M
5 mg 8th layer:
Intermediate layer Silver iodobromide emulsion with covered surface and interior
(Average particle size 0.06 μm, coefficient of variation 16%, AgI
content 0.3 mol%)
Silver amount
0.02g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 g Additive P-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2 g Color mixture prevention agent Cp
d-N
0.1 g Color mixing prevention agent Cpd-A
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 g 9th layer: Low sensitivity green-sensitive emulsion layer Emulsion E
Silver amount 0.25g
Emulsion F
Silver amount 0.15g
gelatin
0.5
g Coupler-C-7
0.05g
Coupler-C-8
0.20g
Compound Cpd-B
0.03g
Compound Cpd-D
10 mg
Compound Cpd-E
0.02g Compound C
pd-F
0.02g Compound Cpd-
G
0.02g Compound Cpd-H
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g High boiling point organic solvent Oil-1
0.1
g High boiling point organic solvent Oil-2
0.1 g 10th layer
: Medium-sensitivity green-sensitive emulsion layer Emulsion G
Silver amount 0.4
g Gelatin
0.6
g Coupler-C-7
0.2
g Coupler-C-8
0.1
g Compound Cpd-B
0.03g
Compound Cpd-E
0.02g
Compound Cpd-F
0.02g Compound C
pd-G
0.05g Compound Cpd-
H
0.05g High boiling point organic solvent Oil
-2 0
．． 01g 11th layer: Highly sensitive green-sensitive emulsion layer Emulsion H
Silver amount 0.5
g Gelatin
1.0
g Coupler-C-4
0.3
g Coupler-C-8
0.1
g Compound Cpd-B
0.08g
Compound Cpd-E
0.02g
Compound Cpd-F
0.02g Compound C
pd-G
0.02g Compound Cpd-
H
0.02g High boiling point organic solvent Oil
-1 0
．． 02g High boiling point organic solvent Oil-2
0.02g 12th
Layer: Middle layer gelatin
0.6
g Dye D-1
0.0
2g Dye D-2
0.0
5g Dye D-3
0.0
1g 13th layer: Yellow filter layer Yellow colloidal silver
Silver amount 0.07g
gelatin
1.1 g
Color mixing prevention agent Cpd-A
0.01g High boiling point
Organic solvent Oil-1
0.01g Dye E-2 microcrystalline solid
Body dispersion 0.0
5g 14th layer: Middle layer gelatin
0.6
g15th layer: low-speed blue-sensitive emulsion layer Emulsion I
Silver amount 0.4
g Emulsion J
Silver amount 0.2
g Gelatin
0.
8g Coupler-C-5
0.2
g Coupler-C-10
0.4
g16th layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion K
Silver amount 0.4
g Gelatin
0.9
g Coupler-C-5
0.3
g Coupler-C-6
0.1
g Coupler-C-10
0.1 gth
17th layer: High sensitivity blue sensitive emulsion layer Emulsion L
Silver amount 0.4
g Gelatin
1.2
g Coupler-C-6
0.6
g Coupler-C-10
0.1 g
18th layer: 1st protective layer gelatin
0.7
g Ultraviolet absorber U-1
0.04g
UV absorber U-2
0.01g ultraviolet
Line absorber U-3
0.03g UV absorber
U-4
0.03g UV absorber U-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g UV absorber U-6
0.
05g High boiling point organic solvent Oil-1
0.02g
Formalin scavenger Cpd-C
0.2 g formalin scavenger
- Cpd-I 0.4 g
Dye D-3
0.05g
Compound Cpd-N
0.02g 19th layer
:Second protective layer colloidal silver
Silver amount 0.1 mg
Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1
mole%)
Silver amount
0.1 g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4 g 20th layer: 3rd protective layer gelatin
0.4
g Polymethyl methacrylate (average particle size 1.
5 μm) 0.1 g Methyl methacrylate
4:6 copolymer of acrylic acid and acrylic acid (average particle
diameter 1.5μm)
0.1 g silicone oil
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03g Surfactant W-1
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0 mg Surfactant W-2
0
．． 03g In addition to the above composition, all emulsion layers contain additives.
Additives F-1 to F-8 were added. Furthermore, each layer has the above
In addition to the composition, gelatin hardener H-1 and for coating and emulsification
Surfactant W-3, W-4, W-5, W-6, W-7
Added. Furthermore, phenol, 1,2 as a preservative and anti-mold agent.
-benzisothiazolin-3-one, 2-phenoxyene
Tanol and phenethyl alcohol were added. Table 8 below
Table A shown in Table A shows the grains of emulsions A to L used in Sample 101 above.
The structure, composition, and size of the emulsions are shown in Table B shown in Tables 9 and 10.
The type, amount, and method of addition of the sensitizing dye to be added are shown. [Table 8] [Table 9] [Table 10] The following chemical formulas 43 to 58 show the structures of the compounds used in the above sample preparation.
It shows the structure. [Chemical 43] [Chemical 44] [Chemical 44] [Chemical 49] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image [Chemical Formula 57] [Chemical Formula 58] Production of Samples 102 to 113 In the production of sample 101, the additives were added to the 15th, 16th, and 17th layers.
The type of sensitizing dye to be added and the sensitizing dye added to the 15th, 16th and 17th layers.
The yellow coupler types shown in Table C are shown in Table 11 below.
Samples 102 to 113 were prepared by replacing
. Replacement was carried out in equimolar amounts. [Table 11] Samples 101 to 113 obtained in the above manner were
1/2 through a continuous wedge using an 800°K white light source.
After exposing for 50 seconds, develop according to the following steps.
It was. The samples were incubated at 55°C and 50% relative humidity for 3 days.
After that, the same exposure and processing as above was performed. At this time, each
The yellow color is 1.0 higher than the minimum density.
Calculate the relative sensitivity from the exposure amount, and change the sensitivity with and without incubation.
The storage stability of the photosensitive materials was evaluated. Also, the above processing
The sample was stored at 70°C and 70% relative humidity for 3 days.
, low density in the area where the yellow color density is 2.0 immediately after processing
I measured the bottom. In addition, samples 101 to 113 had yellow-green and
Color reproducibility was achieved by photographing an orange subject and performing the above processing.
compared. These results are shown in Table C. From Table C, the samples of the present invention have good color image storage stability and
It is clear that the color reproducibility is improved.
be. [0111]
[Processing process] Processing process
Time Temperature Tank capacity
Replenishment amount Black and white development 6 minutes
38℃ 12 liters 2.2 liters
liter/m2 First flush 2〃
38〃 4〃
7.5 Inversion 2
〃 38〃 4 〃
1.1 Color development 6
38 〃 12 〃 2
．． 2 Adjustment 2
38〃 4〃
1.1 Bleaching 6
〃 38〃 12 〃
0.22 Fixed 4
38〃 8〃
1.1 〃 Second washing 4〃
38 〃 8 〃 7
．． 5 Stable 1
25〃 2〃
1.1 The composition after each treatment was as follows
. [0112] Black and white development
mother
Liquid Replenisher Nitrilo-N,N
, N-trimethylenephosphonic acid
・5sodium salt
2.0g 2.0g
sodium sulfite
30g 30
g Hydroquinone monosulfonic acid
Rium 20 g 20 g
potassium carbonate
33g
33 g 1-phenyl-4-
Methyl-4-hydroxy methyl
Ru-3-pyrazolidone 2
．． 0g 2.0g Potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
2.5g 1.4g
potassium thiocyanate
1.2g 1.2g
potassium iodide
2.0mg
…add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml 1000ml
pH
9.60 9
．． 60 pH is hydrochloric acid or potassium hydroxide.
Adjusted with Rium. Inversion liquid
mother
Liquid replenisher Nitrilo-N,
N,N-trimethylenephosphonic acid
・5sodium salt
3.0g Same as mother liquor
Stannous chloride dihydrate
1.0g p
-aminophenol
0.1g sodium hydroxide
Mu
8 g glacial acetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 15 ml water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH
　　　　　　　　　　　　　　　　　　　　　　　　　
6.00p
H was adjusted with hydrochloric acid or sodium hydroxide. Color developer
mother
Liquid Replenisher Nitrilo-N, N,
N-trimethylenephosphonic acid
・5sodium salt
2.0g 2.0g
sodium sulfite
7.0g 7.0g
Trisodium phosphate dodecahydrate
36 g 36
g potassium bromide
1.0g
… Potassium iodide
　　　　　　　　　　　　　　　　　　　　　　　　　
90 mg...Hydroxy acid
Sodium
3.0g 3.0g
Citrazic acid
1.5g
1.5g N-ethyl (β-methanesulfate)
(honamidoethyl) -3-methyl
-4-aminoaniline sulfate 11 g
11 g 3,6-dithia-1,8-o
Cutanediol 1.0g 1.0g
add water
1000ml
1000ml pH
　　　　　　　　　　　　　　　　　　　　　　　　　
11.80 12.00
pH was adjusted with hydrochloric acid or potassium hydroxide. [0115] Conditioning liquid
mother
Liquid Replenisher Ethylenediamine
Tetraacetic acid, disodium salt,
dihydrate salt
8.0g Same as mother liquor
sodium sulfite
12g
1-thioglycerin
0.4ml Sorbi
Tan ester (compound shown in chemical formula 59 below)
0.1g [0116] [Chemical formula 59] Add water
1000ml
pH
6.2
0 pH is hydrochloric acid or sodium hydroxide
Adjusted with um. 0117 Bleach solution
mother
Liquid Replenisher Ethylenediamine
Tetraacetic acid, disodium salt,
dihydrate salt
2.0g 4.0g
Ethylenediaminetetraacetic acid/Fe(III)
/ Ammonium dihydrate salt
120g
240g potassium bromide
1
00g 200g Ammonium nitrate
Umu
10g 20g
add water
1000ml 1
000ml pH
　　　　　　　　　　　　　　　　　　　　　　　　　
5.70 5.50
pH was adjusted with hydrochloric acid or sodium hydroxide. Fixing liquid
mother
Solution Replenisher Sodium thiosulfate
Umu
8.0g in mother liquor
sodium sulfate
5.0g same
sodium bisulfite
5.0g water
In addition
1000ml
pH
6.50
The pH was adjusted with hydrochloric acid or aqueous ammonia. [0119]

Claims (1)

[Claims] Claim 1. A silver halide color photographic light-sensitive material comprising one or more blue-sensitive silver halide emulsion layers, one or more green-sensitive silver halide layers, and one or more red-sensitive silver halide layers on a support, wherein the blue-sensitive silver halide emulsion layer is provided on a support. The silver halide emulsion layer has the following formula 1
The silver halide color photographic light-sensitive material contains at least one malondianilide type yellow dye-forming coupler represented by the formula (1) shown below or the formula (2) shown below, and the silver halide color photographic light-sensitive material has the formula shown below (3). A silver halide color photographic material containing at least one compound represented by (A). [Formula 1] [Formula 2] (In formulas (1) and (2), X1 and X2
each represents an alkyl group, an aryl group or a heterocyclic group, X3 represents an organic residue forming a nitrogen-containing heterocyclic group together with >N-, Y represents an aryl group or a heterocyclic group, and Z is (Represents a group that leaves when the coupler shown reacts with an oxidized developing agent) [Formula 3] (In formula (A), Y5 and Y6 are pyrroline, indoline, thiazoline, thiazole, benzothiazole, naphthothiazole, and selenazole, respectively) , represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocyclic nucleus selected from the group consisting of benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxazole, imidazole, benzimidazole, pyridine, and quinoline, These heterocyclic nuclei may be substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group, or a phenyl group. R6 and R8 may each be substituted, and the carbon chain is an oxygen atom or a sulfur atom. represents an optionally interrupted aliphatic group, R6
Alternatively, at least one of R8 represents the aliphatic group having any one of a hydroxyl group, a carboxyl group, and a sulfo group. R7 represents a hydrogen atom or a lower alkyl group)