JPH04277740A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the image fastness after processing and to lessen the fluctuation in photographic performance as well as to improve image quality in the preservation of the photosensitive material by incorporating specific couplers into the above photosensitive material. CONSTITUTION:This photosensitive material contains the couplers expressed by formula 1 and formula II and contains the coupler expressed by formula III. In the formulas I, II, X1 and X2 respectively denote an alkyl group, aryl group or heterocyclic group; X3 denotes a residual org. group forming a nitrogenous heterocyclic group together with >N-; Y denotes an aryl group or heterocyclic group; Z denotes the group which is eliminated when the couplers expressed by the formulas I, II react with the oxidant of a developing agent. In the formula III, M and Q denote a group which can be substd. with a benzene ring; L denotes a hydrogen atom, halogen atom or aliphat. oxy group; m denotes 0 to 5 integer; n denotes 0 to 4 integer; X denotes the group which can be eliminated by coupling reaction with the oxidant of an arom. primary amine developing agent.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to silver halide color photography.
This is related to photosensitive materials, and for more details, how to preserve photosensitive materials.
Small fluctuations in photographic performance during processing, color image preservation after processing, and color
Regarding silver halide color photographic materials with improved reproducibility.
It is something to do. [Prior Art] Silver halide color photographic materials (hereinafter referred to as
(abbreviated simply as photosensitive material), especially color photosensitive material for photography
is highly sensitive and prevents changes in photographic performance during storage of photosensitive materials.
There is no movement, and the image quality of the resulting color image (color reproducibility, sharpness,
There is a demand for photosensitive materials with excellent graininess) and color image storage properties.
Ru. In the subtractive color method, yellow forms a color photographic image.
- Couplers include benzoylacetanilide and
Acyl acetate represented by pivaloylacetanilide series
Amide couplers are commonly used. The former is general
Cup with oxidized aromatic primary amine developer during development.
High ring activity and molecular absorption of the yellow dye produced.
The optical coefficient is slightly larger than the latter, so high sensitivity is required.
It is mainly used for color photosensitive materials for photography, and the latter is
Mainly because the spectral absorption characteristics and fastness of rho dyes are superior to the former.
It is used as color paper and color reversal type.
ing. However, benzoylacetanilide-type caps
Aromatic primary amine developer during color development
has high coupling reactivity with the oxidant of
The molecular extinction coefficient of rho dye is pivaloylacetanilide type
Spectrum of a yellow image of something much larger than the coupler
It also has the drawbacks of poor absorption characteristics and poor color image fastness.
have Here, the coupler's high coupling reactivity and
The large molecular extinction coefficient of the dyes that make up the
It enables high color density and so-called high color development.
bring. It also has excellent spectral absorption in yellow images.
For example, the absorption concentration on the long wavelength side of spectral absorption is low.
, means absorption characteristics with less unnecessary absorption in the green region. did
Therefore, high emission due to the high molecular extinction coefficient of the produced dye
Gives color density, excellent spectral absorption properties of color images, excellent color
It is desirable to develop a yellow coupler that combines image robustness.
It was. On the other hand, another yellow coupler of the present invention
For example, malondiamide couplers related to
It is described in French Patent No. 1,558,452,
The coupler disclosed in the patent has an oxygen atom at the active position.
So-called O-eliminating couplers, which have a group that leaves via
and is mainly composed of diffusive couplers. In addition, malondiamide couplers can be used as functional couplers.
For example, development inhibitor releasing (DIR) couplers are disclosed in JP-A No.
No. 52-69624, No. 52-82424, No. 57
-151944, described in JP-A No. 2-250053.
However, JP-A-52-82424 and JP-A No. 57-15
No. 1944 does not disclose any specific compounds. Inside this
JP-A No. 52-69624 describes specific effects.
There is no description. In addition, the caps described in each of the above-mentioned patents
Regarding color, the color development property, storage stability of light-sensitive materials, and color image fastness are
It turned out that she had a problem with her sexuality. Problem to be Solved by the Invention Therefore, the object of the present invention is to
The first target is silver halide color, which has excellent image fastness after processing.
The purpose of the present invention is to provide color photographic materials. The second is photosensitive material
Halogenation reduces fluctuations in photographic performance during storage of materials
The purpose of the present invention is to provide a silver color photographic material. The third is painting
Providing improved quality silver halide color photographic materials
It's about doing. [Means for solving the problem] The above problem is solved as follows.
This problem was solved using the following methods. i.e. less on the support
Both have one photosensitive silver halide emulsion layer.
In silver oxide color photographic light-sensitive materials, general formula (I) and /
or contains a coupler represented by general formula (II),
and contains a coupler represented by general formula (A)
By means of silver halide color photographic light-sensitive materials characterized by
I was able to achieve it. . General formula (I) [Chemical formula (I)] [Chemical formula 5] [Chemical formula 5] In the formula, X1 and X2 each represent an alkyl
group, aryl group or heterocyclic group, and X3 is >N-
represents an organic residue that forms a nitrogen-containing heterocyclic group with Y
represents an aryl group or a heterocyclic group, and Z is represented by the general formula
When the coupler is reacted with the oxidized developing agent, it is released.
represents a group. General formula (A) [Chemical formula 6] In general formula (A), M and Q are benzene.
Groups (including atoms) that can be substituted on the ring, L is a hydrogen atom,
rogene atom or aliphatic oxy group, m is an integer of 0 to 5
, n is an integer from 0 to 4, X is aromatic primary amine development
Represents a group that can be separated by a coupling reaction with a drug oxidant.
vinegar. However, when m is plural, (M) m may be the same but different.
Similarly, when n is plural, (Q)n is the same.
They may be the same or different. Also, M, Q, L or X
Becomes a divalent to tetravalent linking group and is represented by general formula (A)
It may be a dimer to a tetramer of yellow couplers. [0011] Below, general formula (I) and general formula (II)
The coupler represented by is described in detail. [0012] When X1 and X2 represent an alkyl group,
straight chain, fractional, having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms
Branched, cyclic, saturated, unsaturated, substituted or unsubstituted alkyl
It is the basis. Examples of alkyl groups are methyl, ethyl,
lopyl, butyl, cyclopropyl, allyl, t-octyl
, i-butyl, dodecyl, 2-hexyldecyl.
It will be done. When X1 and X2 represent a heterocyclic group, carbon
As a number of 1 to 20, preferably 1 to 10, heteroatoms
For example, at least a nitrogen atom, an oxygen atom or a sulfur atom.
3- to 12-, preferably 5- or 6-membered ring containing one or more members
saturated or unsaturated, substituted or unsubstituted, monocyclic
Or it is a fused ring heterocyclic group. As an example of a heterocyclic group
is 3-pyrrolidinyl, 1,2,4-triazole-3
-yl, 2-pyridyl, 4-pyrimidinyl, 3-pyrazo
Lyle, 2-pyrrolyl, 2,4-dioxo-1,3-imie
Examples include dazolidin-5-yl or pyranyl.
. When X1 and X2 represent an aryl group, the number of carbon atoms
6 to 20, preferably 6 to 10 substituted or unsubstituted atoms
Represents a lyl group. Examples of aryl groups are phenyl, sodium
Phthyl is a typical example. If X3 forms with >N-
When representing a nitrogen-containing heterocyclic group, the heterocyclic group has 1 to 1 carbon atoms.
20, preferably 1 to 15 nitrogen atoms as heteroatoms
In addition to atoms, it may also contain, for example, oxygen atoms or sulfur atoms.
a 3- to 12-membered ring, preferably a 5- or 6-membered ring;
Substituted or unsubstituted, saturated or unsaturated, monocyclic
is a fused ring heterocyclic group. As an example of this heterocyclic group
is pyrrolidino, piperidino, morpholino, 1-pipera
Dinyl, 1-indolinyl, 1,2,3,4-tetrahy
Doroquinolin-1-yl, 1-imidazolidinyl, 1-
Pyrazolyl, 1-pyrrolinyl, 1-pyrazolidinyl, 2
, 3-dihydro-1-indazolyl, 2-isoindoly
Nyl, 1-indolyl, 1-pyrrolyl, 4-thiazine-
s. s-dioxo-4-yl or benzoxazine-
4-yl is mentioned. [0013] 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
do, 2-(2,4-di-t-amylphenoxy), buta
sulfonamide, benzamide), sulfonamide group (carbon number
1-30, preferably 1-20. For example, methanesulfone
amide, dodecane sulfonamide, hexadecyl sulfonamide
(benzenesulfonamide, benzenesulfonamide), carbamoyl group
(1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. For example, N-butyl
tylcarbamoyl, N,N-diethylcarbamoyl),
N-sulfonylcarbamoyl group (1 to 30 carbon atoms, preferably
Or 1-20. For example, N-mesylcarbamoyl, N-
dodecylsulfonylcarbamoyl), sulfamoyl group
(1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. For example, N-butyl
Tylsulfamoyl, N-dodecylsulfamoyl, N
-hexadecylsulfamoyl, N-3-(2,4-di
-t-amylphenoxy)butylsulfamoyl, N,
N-diethylsulfamoyl), alkoxy group (number of carbon atoms
1-30, preferably 1-20. For example, methoxy, hexa
sadecyloxy, isopropoxy), aryloxy group
(6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. For example, phenol
xy, 4-methoxyphenoxy, 3-t-butyl-4-
hydroxyphenoxy, naphthoxy), aryloxy
Carbonyl group (7 to 21 carbon atoms, preferably 7 to 11 carbon atoms, e.g. phenoxycarbonyl), N-acylsulfamo
yl group (2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, e.g.
N-propanoylsulfamoyl, N-tetradecanoy
rusulfamoyl), sulfonyl group (1 to 30 carbon atoms,
Preferably 1-20. For example, methanesulfonyl, octa
sulfonyl, 4-hydroxyphenylsulfonyl,
decanesulfonyl), alkoxycarbonylamino group (
1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. For example, ethoxy
carbonylamino), cyano group, nitro group, carboxy
group, hydroxyl group, sulfo group, alkylthio group (carbon
Prime number 1-30, preferably 1-20. For example, methylthio
, dodecylthio, dodecylcarbamoylmethylthio),
Ureido group (1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, e.g.
For example, 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)
eg nitrogen atom, oxygen atom or sulfur as a telo atom
Contains at least one atom, 3 to 12, preferably 5
Or a 6-membered ring, single ring or fused ring. For example, 2-pin
Lysyl, 3-pyrazolyl, 1-pyrrolyl, 2,4-dio
xo-1,3-imidazolidin-1-yl, 2-benz
oxazolyl, morpholino, indolyl), alkyl group
(C 1 to 30, preferably 1 to 20, linear, branched)
, cyclic, saturated, unsaturated. For example, methyl, ethyl, isopropyl
Lopyl, cyclopropyl, t-pentyl, t-octyl
, cyclopentyl, t-butyl, s-butyl, dodecyl
, 2-hexyldecyl), acyl group (1 to 30 carbon atoms,
Preferably 2-20. e.g. acetyl, benzoyl),
Acyloxy group (2 to 30 carbon atoms, preferably 2 to 20 carbon atoms)
. For example, propanoyloxy, tetradecanoyloxy
), arylthio group (6 to 20 carbon atoms, preferably 6 to 20 carbon atoms)
10. For example, phenylthio, naphthylthio), sulfa
Moylamino group (carbon number 0-30, preferably 0-20
. For example, N-butylsulfamoylamino, N-dodecyl
Rusulfamoylamino, N-phenylsulfamoyl
amino) or N-sulfonylsulfamoyl group (carbon
Prime number 1-30, preferably 1-20. For example, N-methyl
Sulfamoyl, N-ethanesulfonylsulfamoy
N-dodecanesulfonylsulfamoyl, N-hexyl
sadecanesulfonylsulfamoyl). Up
The above substituents may further have a substituent. its substituents
Examples include the substituents listed here. Among the above, preferable substituents include alkyl
Oxy group, halogen atom, alkoxycarbonyl group, acyl group
oxy group, acylamino group, sulfonyl group, carbamo group
yl group, sulfamoyl group, sulfonamide group, nitro
group, alkyl group or aryl group. general formula
When Y represents an aryl group in (I) and (II)
and a substitution having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, or
It is an unsubstituted aryl group. For example, phenyl and sodium
A typical example is the phthyl group. General formula (I) and
In (II), when Y represents a heterocyclic group, X1 or
has the same meaning as explained when X2 represents a heterocyclic group.
be. When the above Y represents a substituted aryl group or a substituted heterocyclic group
Examples of substituents include, for example, X1 has a substituent.
Examples of such substituents include the substituents listed above. Y is
Preferred examples of substituents include
One is a halogen atom, an alkoxycarbonyl group, a sulfur atom,
amoyl group, carbamoyl group, sulfonyl group, N-sulfonyl group
Honylsulfamoyl group, N-acylsulfamoyl group
, alkoxy group, acylamino group, N-sulfonyl group
Bamoyl group, sulfonamide group or alkyl group
It's time. In general formulas (I) and (II), Z is
The groups shown include conventionally known coupling and dissociation groups.
It may be either degrouping. A preferable Z is nitrogen.
A nitrogen-containing heterocyclic group that is bonded to the coupling position with an elementary atom,
aryloxy group, arylthio group, heterocyclic oxy group,
Barocyclic thio group, acyloxy group, carbamoyloxy group,
Examples include an alkylthio group or a halogen atom. this
These leaving groups may be non-photographically useful groups or photographically useful groups.
or its precursors (e.g. development inhibitors, development accelerators, desilvering agents)
Accelerator, fogging agent, dye, hardener, coupler, developer
Drug oxidant scavengers, fluorescent dyes, developing agents or electrolytes
It may be any of the following. Z is a photographically useful group
When this is the case, conventionally known methods are useful. example
U.S. Pat. No. 4,248,962, U.S. Pat. No. 4,409,323,
No. 4438193, No. 4421845, No. 4618
No. 571, No. 4652516, No. 4861701,
No. 4782012, No. 4857440, No. 4847
No. 185, No. 4477563, No. 4438193,
No. 4628024, No. 4618571, No. 4741
No. 994, European Published Patent No. 193389A,
Photographic properties described in 348139A or 272573A
A useful group or a leaving group to release it (e.g. Ta
iming group) is used. Z is the coupling position and nitrogen
When representing a nitrogen-containing heterocyclic group bonded through atoms, preferably
, 5 or 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms
6-membered ring, substituted or unsubstituted, saturated or unsaturated
is a monocyclic or fused ring heterocyclic group. heteroatom
contains oxygen or sulfur atoms in addition to nitrogen atoms.
You can. Preferred specific examples of the heterocyclic group include 1-
Pyrazolyl, 1-imidazolyl, pyrolino, 1,2,4
-triazol-2-yl, 1,2,3-triazole
-3-yl, benzotriazolyl, benzimidazolyl
, imidazolidine-2,4-dion-3-yl, oxa
Zolidin-2,4-dion-3-yl, 1,2,4-t
Lyazolidine-3,5-dione-4-yl, 2-imida
Zolinon-1-yl, 3,5-dioxomorpholino or
Examples include 1-imidazolyl. These heterocyclic groups
When having a substituent, the substituent is
The substituents listed as optional substituents for the group represented by
Examples include substituents. As a preferred substituent
One of the substituents is an alkyl group, an alkoxy group, or a halogen group.
Atom, alkoxycarbonyl group, aryloxycarbo
Nyl group, alkylthio group, acylamino group, sulfona group
Mido group, aryl group, nitro group, carbamoyl group, and
is a sulfonyl 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, carboxyl group, carbamoyl group, nitro group
, a cyano group or an acyl group. Z is aromatic
When representing an o group, it is preferably substituted with 6 to 10 carbon atoms or
is an unsubstituted aromatic thio group. Particularly preferably replacement or
It is an unsubstituted phenylthio group. Having a substituent
Examples of substituents include the group represented by X1 above.
Examples of substituents listed as permissible substituents are
Can be mentioned. Among them, the preferred substituents include at least
One substituent is an alkyl group, an alkoxy group, or a sulfonate group.
Nyl group, alkoxycarbonyl group, sulfamoyl group,
Is a halogen atom, carbamoyl group, or nitro group
It's time. [0017] 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 number of carbon atoms in the heterocyclic group is
1 to 20, preferably 1 to 10, heteroatoms such as
For example, at least a nitrogen atom, an oxygen atom or a sulfur atom
containing one or more 3- to 12-, preferably 5- or 6-membered rings
, substituted or unsubstituted, saturated or unsaturated, monocyclic
Or it is a fused ring heterocyclic group. Examples of heterocyclic thio groups
is a tetrazolylthio group, 1,3,4-thiadiazo
Lylthio group, 1,3,4-oxadiazolylthio group, 1
, 3,4-triazolylthio group, benzimidazolylthio group
O group, benzothiazolylthio group, or 2-pyridylthio group
O group is mentioned. 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
is an alkyl group, an aryl group, a carboxyl group, an alkyl group
cy group, halogen atom, alkoxycarbonyl group, aryl
oxycarbonyl group, alkylthio group, acylamino
group, sulfonamide group, nitro group, carbamoyl group,
When it is a terocyclic group or a sulfonyl group. 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, the compounds represented by general formulas (I) and (II)
Particularly preferred ranges of couplers are described below.
. The group represented by X1 in general formula (I) is preferably
is an alkyl group. Particularly preferably having 1 to 10 carbon atoms
It is an alkyl group. In general formulas (I) and (II)
The group represented by Y is preferably an aromatic group. especially
Preferably, the fluorophore has at least one substituent in the ortho position.
It is a phenyl group. The explanation of the substituent is that Y is an aromatic group.
The substituents that may be present include those described above.
Ru. The description of preferred substituents is also the same. General formula (I) and
The group represented by Z in (II) and (II) preferably has 5 to
A 6-membered nitrogen-containing compound bonded to the coupling position by a nitrogen atom.
Barocyclic group, aromatic oxy group, 5- to 6-membered heterocyclic oxy group,
Or a 5- to 6-membered heterocyclic thio group can be mentioned. In general formulas (I) and (II), preferred
The new coupler has the following general formula (III), (IV) or
is indicated by (V). General formula (III) [0021] [Formula 7] General formula (IV) [0022] [Formula 8] General formula (V) [Formula 9] [Formula 9] In the formula, Z is as explained in the general formula (I) I did it
, X4 represents an alkyl group, and X5
represents an alkyl group or an aromatic group, and Ar is at the ortho position.
represents a phenyl group having at least one substituent,
X6 is a nitrogen-containing complex with -C(R1 R2)-N<
Represents an organic residue that forms a bare ring group (single ring or fused ring)
, X7 is -C(R3)=C(R4)-N<
An organic compound that forms a nitrogen-containing heterocyclic group (single ring or fused ring)
Represents a residue, R1, R2, R3 and R4 are water
Represents an elementary atom or a substituent. General formula (III) ~(V
), a group represented by X4 to X7, Ar and Z
For a detailed explanation and preferred range of, please refer to the general formula (
In the explanations given in I) and (II),
It has the same meaning as explained in the box. R1 to R4
When represents a substituent, the substitution that X1 may have
Examples include those listed as groups. the above
Among the general formulas, particularly preferred couplers are those of the general formula (IV)
Or a coupler represented by (V). Couplers represented by general formulas (I) to (V)
are X1 to X7, Y, Ar, R1 to R4 and
Through a divalent or higher group in the group represented by Z
Dimers or multimers that bind to each other (e.g.
polymers or polymers) may also be formed. this place
In this case, the range of carbon atoms shown in each substituent above is
It may be outside the specified range. Represented by general formulas (I) to (V)
Preferably, the coupler is a diffusion-resistant coupler.
It is. Diffusion-resistant type means that molecules are immobilized in the added layer.
, a coupler that has a group in the molecule that increases the molecular weight sufficiently
-It is about. Usually 8 to 30 total carbon atoms, preferably
Substitution with 10-20 alkyl groups or 4-20 total carbon atoms
An aryl group having a group is used. These diffusion-resistant groups
may be substituted anywhere in the molecule, or multiple
may have. Shown below by general formulas (I) to (V)
A specific example of the yellow coupler shown in FIG.
It is not limited to these. [Formula 10] [Formula 11] [Formula 11] [Formula 12] [Formula 12] [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 ] [Chemical 24] [Chemical 25] The yellow coupler of the present invention can be used in light-sensitive materials.
Added to the photosensitive silver halide emulsion layer or its adjacent layer
It is preferable to add it to the photosensitive silver halide emulsion layer.
It is particularly preferable to do so. The total amount added to the sensitive material is
When the leaving group Z contains a photographically useful group component, 0.
0001 to 0.80 g/m2, preferably 0.0
005 to 0.50 g/m2, more preferably 0.02 to
It is 0.30g/m2. In addition, the leaving group Z is a photographically useful group.
If no component is included, the amount added is 0.001~
1.20g/m2, preferably 0.01-1.0
More preferably 0.10 to 0.80 g/m
It is 2. The yellow coupler of the present invention is commonly used as described below.
It can be added in the same way as conventional couplers. Synthesis Example (1) Synthesis of Exemplary Coupler (1)
It was synthesized by ##STR26## Step ■N,N-dimethylformamide 10
In a mixed solvent of 0 ml and acetonitrile 100 ml (
3.5 g of a) and 13 g of 2 were dissolved. In this solution,
N,N'-dicyclohexylcarbodiimide 6 at room temperature
40 ml of an acetonitrile solution in which g was dissolved was added dropwise. After 2 hours of reaction, N,N'-dicyclohexyl urine was precipitated.
I separated the basics. Pour the filtrate into 500ml of water and add ethyl acetate.
Extracted with 500 ml of water. Transfer to a separatory funnel and wash with water.
After that, the oil layer was separated. The solvent was distilled off under reduced pressure and the residue was
was added to crystallize. 16.1 g of (c) was obtained. Step ① 16 g of (c) was mixed with 1 part of dichloromethane.
Mixed to 50 ml. Dichlorometh containing 4.8g of bromine
10 ml of the solution was added dropwise under ice cooling (5°C to 10°C). After reacting for 10 minutes, the mixture was transferred to a separatory funnel and washed with water. oil
The layer (including (d)) was removed and this solution was used in the next step. 8.2 g of step ■(e) and 8.8 g of triethylamine
ml to 160 ml of N,N-dimethylformamide.
Ta. Add the dichloromethane solution of 4 obtained above to this solution in the room.
It was added dropwise while still warm. After reacting for 1 hour, add 500ml of ethyl acetate.
It was then transferred to a separatory funnel and washed with water. Again after neutralizing with dilute hydrochloric acid
Washed with water. The oil layer was separated and the solvent was distilled off under reduced pressure. Residue
was separated and purified by column chromatography. Mitsuru
Silica gel as a buffer and ethyl acetate/hexyl as an eluent.
Xane (1/1) was used. A file containing the compound of interest
The filtration is collected and the solvent is distilled off under reduced pressure.
16.3 g of exemplary coupler (1) in the form of a wedge was obtained. Synthesis Example (2) Synthesis of Exemplary Coupler (2)
Synthesis was performed in the same manner as in Synthesis Example (1). However, the above (b
) in place of (f), and in place of (e), (g) in equal moles.
Do the same for the desired example coupler, substituting the quantity
-(2) 15.4 g of wax-like product was obtained. Synthesis Example (3) Synthesis of Exemplary Coupler (6) The following scheme
It was synthesized by the reaction shown in the following figure. ##STR28## Add to 50 ml of N,N-dimethylformamide
4.42 g of compound (i) and triethylamine 1.
87 g was added and stirred for 10 minutes. In this solution at room temperature,
Dissolve 6.23 g of compound (h) in 20 ml of methylene chloride.
The dissolved solution was added dropwise over 15 minutes. 1 hour at room temperature
After the reaction, pour the reaction solution onto water and extract with ethyl acetate.
did. Dry the organic layer over magnesium sulfate and remove the desiccant.
It was filtered off, and the solvent was distilled off under reduced pressure. Silica gel column chromatography
The desired exemplary coupler (6) was purified by
4.7 g was obtained as a white powder. Next, the coupler represented by the general formula (A)
will be explained in more detail. As an example of M and Q
Halogen atom (fluorine, chlorine, bromine), carbon number 1-20
aliphatic group having 6 to 20 carbon atoms, aromatic group having 1 to 2 carbon atoms
0 aliphatic oxy group, aromatic oxy group having 6 to 20 carbon atoms
, carbon amide group having 2 to 24 carbon atoms, 0 to 20 carbon atoms
sulfonamide group, carbamoyl group having 1 to 24 carbon atoms
, sulfamoyl group having 0 to 20 carbon atoms, 2 to 20 carbon atoms
acyloxy group, aliphatic oxycal having 2 to 20 carbon atoms
Bonyl group, substituted amino group having 2 to 24 carbon atoms, 1 to 24 carbon atoms
24 aliphatic thio groups, ureido groups having 0 to 20 carbon atoms, carbon
Prime number 0 to 20 sulfamoylamino group, cyano group, carbon
aliphatic oxycarbonylamino group with a prime number of 2 to 20, carbon
Imide group with 4 to 20 carbon atoms, aliphatic sulfonate with 1 to 20 carbon atoms
Nyl group, aromatic sulfonyl group having 6 to 20 carbon atoms, number of carbon atoms
1 to 20 heterocyclic groups, etc. L is hydrogen atom, halogen
Atom (fluorine, chlorine, bromine) or having 1 to 24 carbon atoms
It is an aliphatic oxy group. X is an aromatic primary amine developer
It is a group that can be separated by a coupling reaction with an oxidant.
, details are expressed by the following general formulas [B], [C] and [D].
I will be forgotten. General formula [B] -O-R' General formula [C] -S-R'' General formula [D] [Chemical formula 29] [0052] In the general formula [B], R' has 2 to 3 carbon atoms.
0 aromatic group, heterocyclic group having 1 to 28 carbon atoms, 2 to 28 carbon atoms
28 acyl group, aliphatic sulfonyl group having 1 to 24 carbon atoms
Or it is an aromatic sulfonyl group having 6 to 24 carbon atoms. one
In the general formula [C], R'' is an aliphatic group having 1 to 30 carbon atoms,
Aromatic group having 6 to 30 carbon atoms or complex group having 1 to 28 carbon atoms
Represents a ring group. In general formula [D], Y and Q are single
Necessary to form a ring or fused 5- to 7-membered heterocycle
represents a group of nonmetallic atoms. complex formed by Q and Y
Examples of rings include pyrrole, pyrazole, imidazole,
1,2,4-triazole, tetrazole, indole
, indazole, benzimidazole, benzotriazo
alcohol, tetraazaindene, succinimide, phthalic acid
imide, saccharin, oxazolidine-2,4-dione
, imidazolidine-2,4-dione, thiazolidine-2
, 4-dione, urazole, parabanic acid, maleimide
do, 2-pyridone, 4-pyridone, 6-pyridazone, 6
-pyrimidone, 2-pyrazone, 1,3,5-triazine
-2-one, 1,2,4-triazin-6-one, 1,
3,4-triazin-6-one, 2-oxazolone, 2
-thiazolone, 2-imidazolone, 3-isoxazolone
5-tetrazolone, 1,2,4-triazo-5-o
These may be substituted and their substituents
Examples include halogen atoms, hydroxyl groups, nitro groups, and
Ano group, hydroxy group, aliphatic group, aromatic group, heterocyclic group
, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic
aromatic thio group, aliphatic oxycarbonyl group, carbonamide
do group, sulfonamide group, carbamoyl group, sulfamo group
yl group, ureido group, sulfamoylamino group, aliphatic group
Examples include oxycarbonylamino groups and substituted amino groups. In the present invention, aliphatic groups are linear, branched,
Chain or cyclic alkyl group, alkenyl group or alkyl group
Represents a quinyl group, which may be substituted. aliphatic group
Examples include methyl, ethyl, isopropyl, n-butyl,
t-butyl, t-amyl, n-hexyl, cyclohexy
n-octyl, 2-ethylhexyl, n-decyl,
n-dodecyl, n-tetradecyl, n-hexadecyl,
2-hexyldecyl, n-octadecyl, allyl, ben
Zyl, phenethyl, undecenyl, octadecenyl, to
Lifluoromethyl, chloroethyl, cyanoethyl, 1-
(Ethoxycarbonyl)ethyl, methoxyethyl, buto
xyethyl, 3-dodecyloxypropyl, phenoxy
There are ethyl etc. In the present invention, a heterocyclic group refers to a substituted or
is an unsubstituted monocyclic or condensed ring heterocyclic group, e.g.
For example, in addition to groups derived from the compounds listed above as [Chemical formula 30]
2-furyl, 2-chenyl, 2-pyridyl, 3-pyridyl
Zyl, 4-pyridyl, 2-quinolyl, oxazole-2
-yl, thiazol-2-yl, benzoxazole-
2-yl, benzothiazol-2-yl, 1,3,4-
Thiadiazol-2-yl, 1,3,4-oxadiazole
There are 2-yl and the like. What is an aromatic group in the present invention?
Substituted or unsubstituted monocyclic or fused ring aryl group
Yes, examples include phenyl, tolyl, 4-chlorophenyl
, 4-methoxyphenyl, 1-naphthyl, 2-naphthyl
, 4-t-butylphenoxy and the like. Next, the general formula (
Examples of preferred substituents in the coupler represented by A)
state. M is preferably an aliphatic group (methyl, ethyl,
n-propyl, t-butyl, etc.), aliphatic oxy groups (meth
xy, ethoxy, n-butoxy, n-dodecyloxy, etc.
), halogen atoms (fluorine, chlorine, bromine), carbon atoms
Mido group (acetamide, n-butanamide, n-tetra
(decaneamide, benzamide, etc.) or sulfonamide
group (methylsulfonamide), n-butylsulfonamide
do, n-octylsulfonamide, n-dodecylsulfonamide
amide, toluene sulfonamide, etc.). L is preferably a chlorine atom or an aliphatic oxy group (methoxy group).
cy, ethoxy, methoxyethoxy, n-octyloxy
, 2-ethylhexyloxy, n-tetradecyloxy
etc.). Q is preferably a substituent listed in M above
In addition to the aliphatic oxycarbonyl group (methoxycarbonyl group)
, ethoxycarbonyl, n-butoxycarbonyl, n
-hexyloxycarbonyl, 2-ethylhexyloxy
Cycarbonyl, 1-(ethoxycarbonyl)ethyloxy
Cycarbonyl, 3-dodecyloxypropyloxycal
Bonyl, n-decyloxycarbonyl, n-dodecyloxycarbonyl
(oxycarbonyl, phenethyloxycarbonyl, etc.)
is a carbamoyl group (dimethylcarbamoyl, dibutylcarbamoyl)
Rubamoyl, dihexylcarbamoyl, di-2-ethyl
hexylcarbamoyl, n-dodecylcarbamoyl, etc.)
It is. m is preferably 0 to 2, and n is preferably
It is 0-2. X is preferably R in general formula [B]
' is an aromatic group (4-methoxycarbonylphenol)
xy, 4-methylsulfonylphenoxy, 4-cyanof
phenoxy, 4-dimethylsulfamoylphenoxy, 2
-acetamido-4-ethoxycarbonylphenoxy,
4-Ethoxycarbonyl-2-methylsulfonamide
phenoxy, etc.) or a group represented by the general formula [D]
, among the latter, a group represented by the following general formula [E] is further
preferable. General formula [E] [Chemical formula 31] In general formula [E], V is substituted or unsubstituted.
Represents a substituted methylene group or a substituted or unsubstituted imino group.
I, W is an oxygen atom, a sulfur atom, substituted or unsubstituted
Represents a methylene group or an unsubstituted imino group. However, V
When it is an imino group, W can be either an oxygen atom or a sulfur atom.
do not have. As an example of the group represented by the general formula [E], succinic acid
imide, phthalic acid imide, 1-methyl-imidazolidine
-2,4-dione-3-yl, 1-benzyl-imidazo
Lysine-2,4-dion-3-yl, 5-ethoxy-1
-methylimidazolidine-2,4-dione-3-yl,
5-Methoxy-1-methylimidazolidine-2,4-di
On-3-yl, 5,5-dimethyloxazolidine-2
,4-dion-3-yl,thiazolidine-2,4-dio
-3-yl, 1-benzyl-2-phenyltriazoli
Dine-3,5-dion-4-yl, 1-n-propyl-
2-phenyltriazolidine-3,5-dione-4-y
5-ethoxy-1-benzyl-imidazolidine-2
, 4-dione-3-yl, etc. Represented by general formula (A)
The yellow coupler has its substituents M, Q, L or
Either of X becomes a divalent to tetravalent linking group, and yellow color
Although it may be a dimer or tetramer of the platinum, it may be a monomer or a tetramer.
mer is preferred. Here, the compound represented by the general formula (A)
When the low coupler is a dimer to a tetramer, M, Q, L or X
The carbon number ranges listed above do not apply. less than
Yellow represented by general formula (A) used in the present invention
Specific examples of couplers used in the present invention are shown below.
is not limited to these. 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 [0066] The above-mentioned items preferably used in the present invention
Yellow couplers are synthesized by conventionally known methods. For example, U.S. Patent Nos. 3,227,554 and 3,408,
No. 194, No. 3,415,652, No. 3,447,9
No. 28, No. 4,401,752, British Patent No. 1,040
, No. 710, JP-A-47-26133, JP-A No. 47-37
No. 736, No. 48-733147, No. 48-9443
No. 2, No. 48-68834, No. 48-68835,
No. 48-68836, No. 50-34232, No. 51
-50734, 51-102636, 55-5
No. 98, No. 55-161239, No. 56-95237
No. 56-161543, No. 56-153343
, No. 59-174839 and No. 60-35730.
It can be synthesized by the synthesis method described in the specification. [0067] The group represented by the general formula (A) of the present invention
A puller is a light-sensitive silver halide emulsion layer in a light-sensitive material.
It is preferable to add the photosensitive halogen to the adjacent layer.
It is particularly preferred to add it to the silver germide emulsion layer. That feeling
The total amount added to the optical material is 1 x 10-3 to 1.20 g/m
2, preferably 1 x 10-2 to 1.00 g/m2
and more preferably 1 x 10-1 to 0.80 g/m
It is 2. In addition, it is added to the photosensitive silver halide emulsion layer.
In this case, when converted to 1 mole of silver halide, it is 1×1
0-3 to 2 mol, preferably 1 x 10-2 to 1 mol
more preferably 2×10−2 to 5×10−1
It can be used in a molar range. Represented by general formula (A)
The coupler is sensitized with a high-boiling organic solvent as described below.
It can be added to optical materials. The aforementioned general formula (I)
and/or a coupler represented by general formula (II)
Couplers represented by general formula (A) are used together in the same layer.
When mixing, the mixing ratio can be chosen arbitrarily. child
is represented by general formula (I) and/or general formula (II)
When the coupler used is a functional coupler and when the coupler is a non-functional coupler.
This is because the mixing ratio differs depending on the case. In the present invention, the general formula (I) and/or
Or a coupler represented by the general formula (II) and the general formula (
Adding the coupler represented by A) to the constituent layers of the photosensitive material
Various known techniques can be applied to
. Oil-in-water dispersion, commonly known as oil protection method
After dissolving in a solvent, it can be added by the interfacial
Emulsify and disperse in an aqueous gelatin solution containing an activator. Alright
water or gelatin in coupler solution containing surfactant.
By adding aqueous solution of
good. For example, described in U.S. Patent No. 2,322,027, etc.
The oil-in-water dispersion method uses high boiling points of approximately 175°C or higher at normal pressure.
Boiling point organic solvents such as phthalates, phosphates
Benzoic acid esters, fatty acid esters, amides
phenols, alcohols, carboxylic acids, N,
N-dialkylanilines, hydrocarbons, oligomers, etc.
Insulator polymers and/or boiling point of about 30℃ to normal pressure
Organic solvents with a low boiling point of about 160°C, such as esters (e.g.
Ethyl acetate, butyl acetate, ethylpropio
nate, β-ethoxyethyl acetate, methyl celloso
(rube acetate), alcohols (e.g. secondary
butyl alcohol), ketones (e.g. methyl isobutyl
ketone, methyl ethyl ketone, cyclohexanone),
Amides (e.g. dimethylformamide, N-methylpiamide)
lolidone), ethers (e.g. tetrahydrofuran,
Lipophilic photographic organic compounds were dissolved with dioxane) etc.
It is then emulsified and dispersed in hydrophilic colloids such as gelatin. In addition
, distillation, noodle washing or limited
After removing the low boiling point organic solvent by methods such as external filtration,
May be mixed with photographic emulsion. In the present invention, the above-mentioned
In addition to high-boiling organic solvents such as plasticizers, water-insoluble
High-boiling point organic solvents also include high-molecular compounds. child
High boiling point organic solvents such as
It can be in any form such as dielectric constant (
(25°C) in the range of 2 to 20, preferably in the range of 3 to 15.
The refractive index (25°C) is 1.30 to 1.7.
0, preferably in the range of 1.35 to 1.60
It is an organic solvent. The above-mentioned high boiling point organic solvents are preferably
It is represented by the following formulas [S-1] to [S-9]. Formula [S-1] [Chemical formula 39] [Chemical formula 39] Formula [S-2] [Chemical formula 40] [Chemical formula 40] Formula [S-3] (Ar-COO)b -
R7 Formula [S-4] (R8 -COO
)c -R9 Formula [S-5] R1
0-(COO-R11)d Formula [S-6] [0073] [Formula 41] [0074] Formula [S-7] 0075] [Formula 42] [0076] Formula [S-8] 0077] Formula [S-9] -(A1) a1 -(
A2) a2 ---(An) an-0079]
In formula [S-1], R1, R2 and R3 are
Each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
represents a group. In formula [S-2], R4 and R5
each independently represents an alkyl group, a cycloalkyl group, or
represents an aryl group, R6 is a halogen atom (F, Cl
, Br, the same applies below I), alkyl group, alkoxy group, a
Represents a lyloxy group or an alkoxycarbonyl group
, a represents an integer from 0 to 3. When a is plural, plural R
6 may be the same or different. In formula [S-3]
, Ar represents an aryl group, and b represents an integer from 1 to 6.
I, R7 is a b-valent hydrocarbon group or an ether bond.
Represents hydrocarbon groups bonded to each other. In formula [S-4]
and R8 represents an alkyl group or a cycloalkyl group.
, c represents an integer of 1 to 6, and R9 is a c-valent hydrocarbon.
Hydrocarbon groups bonded to each other through elementary or ether bonds
represent In formula [S-5], d represents an integer from 2 to 6.
and R10 is a d-valent hydrocarbon group (excluding aromatic groups)
), and R11 is an alkyl group, a cycloalkyl group or
or represents an aryl group. In formula [S-6], R12
, R13 and R14 are each independently an alkyl group,
Represents a loalkyl group or an aryl group. R12 and R1
3 or R13 and R14 combine with each other to form a ring
You can stay there. In formula [S-7], R15 is an alkyl group
, cycloalkyl group, alkoxycarbonyl group, alkyl
sulfonyl group, arylsulfonyl group, aryl group or
or a cyano group, and R16 is a halogen atom or an alkyl atom.
group, cycloalkyl group, aryl group, alkoxy group or
or an aryloxy group, and e represents an integer of 0 to 3.
Was. When e is plural, the plural R16s may be the same or different.
You can stay there. In formula [S-8], R17 and R18 are
Each independently represents an alkyl group, a cycloalkyl group, or an alkyl group.
Represents a lyl group, R19 is a halogen atom, an alkyl group
, cycloalkyl group, aryl group, alkoxy group or
represents an aryloxy group, f represents an integer of 0 to 4
. When f is multiple, multiple R19s may be the same or different.
Good too. In formula [S-9], A1, A2,...
, An are different non-chromogenic ethylene-like monomers.
represents the polymerized unit given by a1, a2, ・
..., an represents the weight fraction of each polymerized unit.
, n represents an integer from 1 to 30. used in the present invention
Specific examples of high boiling point organic solvents are shown below. 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
Examples of compounds other than those mentioned above and/or these high boiling point organic solvents
A method for synthesizing the medium is described, for example, in U.S. Pat. No. 2,322,027.
, No. 2,533,514, No. 2,772,163
No. 2,835,579, No. 3,676,13
No. 7, No. 3,912,515, No. 3,936,3
No. 03, No. 4,080,209, No. 4,127,
No. 413, No. 4,193,802, No. 4,239
, No. 851, No. 4,278,757, No. 4,36
No. 3,873, No. 4,483,918, No. 4,7
No. 45,049, European Patent No. 276,319A, JP
No. 48-47335, No. 51-149028, No. 6
No. 1-84641, No. 62-118345, No. 62-
No. 247364, No. 63-167357, No. 64-6
No. 8745, JP-A No. 1-101543, etc.
There is. In the present invention, the above-mentioned high boiling point organic solvents are the same.
General formula (I) and/or general formula (I) contained in the layer
A coupler represented by I) and a coupler represented by the general formula (A)
Used at a weight ratio of 1.0 or less to the total weight of the coupler
It will be done. This weight ratio is preferably 0.01 to 0.50.
be. More preferably, it is in the range of 0.05 to 0.35.
. The weight ratio of high boiling point organic solvent to the above couplers is:
By reducing the weight ratio, the lower layer (support side
In addition to the advantages of improving the image quality of
This generally reduces the fastness of color images and increases the quality of light-sensitive materials.
Although the photographic performance fluctuates greatly during storage, the capacitor of the present invention
This method has the advantage of reducing the degree of deterioration in
do. These high boiling point organic solvents are used in combination of two or more types.
It may also be used in combination with high boiling point organic solvents other than those mentioned above.
You can also. 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. deer
However, even if the above installation order is reversed depending on the purpose, the same
The installation order is such that different photosensitive layers are sandwiched between color-sensitive layers.
You can get it. Between and at the top of the silver halide photosensitive layer above.
Non-photosensitive layers such as various intermediate layers are provided on the top and bottom layers.
Good too. The intermediate layer includes Japanese Patent Application Laid-open No. 61-43748,
No. 59-113438, No. 59-113440,
In the specifications of No. 61-20037 and No. 61-20038
Contains couplers, DIR compounds, etc. as described
It may contain a color mixing inhibitor as is commonly used.
You can stay there. Multiple halogens forming each unit photosensitive layer
The silver oxide emulsion layer is 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-sensitivity emulsion layer and a low-sensitivity emulsion layer is preferably used.
can be done. Typically, the photosensitivity is sequential towards the support.
It is preferable to arrange them so that each halogen
A non-photosensitive layer may be provided between the emulsion layers. Ma
JP-A-57-112751, JP-A No. 62-200
No. 350, No. 62-206541, No. 62-2065
The side away from the support as described in No. 43, etc.
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 (
RL) or BH/BL/GL/GH/RH/R
In order of L or BH/BL/GH/GL/RL/RH
They can be installed in any order. Also, Tokuko Sho 55-34
As described in Publication No. 932, from the support
From the farthest side, the blue-sensitive layer/GH/RH/GL/RL.
It can also be arranged in Also, JP-A-56-25738
No. 62-63936.
From the side farthest from the support, the blue-sensitive layer/GL/RL
They can also be arranged in the order of /GH/RH. Also Tokko Akira
49-15495, the upper layer is
The most sensitive silver halide emulsion layer, with the middle layer more
A silver halide emulsion layer with lower sensitivity, the lower layer is more sensitive than the middle layer.
Furthermore, a silver halide emulsion layer with low photosensitivity is placed on the support.
Three layers with different photosensitivity, with the photosensitivity decreasing sequentially toward
An example is an array consisting of . This kind of sensitivity
Even if it is composed of three different layers, JP-A-59-20
As described in the specification of No. 2464, the same color sensitivity
Medium-sensitivity emulsion layer/
They may be arranged in the order of high-speed emulsion layer/low-speed 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. In addition, 4 or more layers
In this case, the arrangement may be changed as described above. Improved color reproducibility
No. 4,663,271;
No. 4,705,744, No. 4,707,436
, JP-A No. 62-160448, No. 63-8985
The main feeling of BL, GL, RL etc. described in the specification of No. 0
A multilayer effect donor layer (CL) with a different spectral sensitivity distribution from the optical layer
) may be arranged adjacent to or close to the main photosensitive layer.
preferable. As mentioned above, depending on the purpose of each photosensitive material,
Various layer configurations and arrangements can be selected accordingly. [0087] 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.
It can be large-sized particles up to m, or it can be a polydisperse emulsion.
A monodispersed emulsion may be used. Silver halide that can be used in the present invention
Photographic emulsions are, for example, Research Disclosure (R
D) No. 17643 (December 1978), 22
~pages 23, “I. Emulsion Preparation”
parity and types)” and
No. 18716 (November 1979), 648
Page, same No. 307105 (November 1989), 86
pp. 3 to 865, and “Physics of Photography” by Grafkide.
"Chemistry", published by Paul Montell (P. Glafkides)
, Chemieet Phisique Photo
graphique, Paul Montel, 1
967), “Photographic Emulsion Chemistry” by Duffin, Focalp.
Published by Ressha (G.F. Duffin, Photograp
hic Emulsion Chemistry (F
ocal Press, 1966)), Zelikman et al.
Author: “Production and Coating of Photographic Emulsions”, published by Focal Press (
V. L. Zelikman et al. , Ma
King and Coating Photogra
phic Emulsion, Focal Pres
s, 1964) and others.
can do. [0088] US Pat. No. 3,574,628,
No. 3,655,394 and British Patent No. 1,413,
Monodispersed emulsions such as those described in No. 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 by Gatoff, Photog
Rough Science and Engineering (
Gutoff, Photographic Science
CE and Engineering), Volume 14
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 etc.
Can be more easily prepared. The crystal structure is uniform
However, the inside and outside may have different halogen compositions.
It may have a layered structure, or it may have an epitaxial structure.
Silver halides of different compositions are connected by taxial bonding.
For example, Rodan silver, lead oxide, etc.
may be bonded with a compound other than silver halide. Also, mixtures of particles of various crystal forms may be used. the above
The emulsion is a surface latent image type in which a latent image is mainly formed on the surface.
Even with the internal latent image type formed inside the particle, both the surface and the inside
Any type of breast that has a latent image may be used, but negative type breasts may be used.
It is necessary to be a drug. Among the internal latent image types, JP-A-Sho
63-264740
It may also be an image-type emulsion. This core/shell type internal latent image
The method for preparing the type emulsion is described in JP-A-59-133542.
Are listed. The shell thickness of this emulsion is determined by the development process.
etc., but preferably 3 to 40 nm, and 5 to 2 nm.
0 nm is particularly 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 the same
No. 307105, and the relevant part
are summarized in the table below. The photosensitive material of the present invention has photosensitive
Grain size, grain size distribution, halo of silver halide emulsions
at least one of the following characteristics: particle composition, particle shape, and sensitivity.
Mixing two or more different emulsions in the same layer
can be done. U.S. Patent No. 4,082,553
Silver halide grains coated with the grain surface described above, US Pat.
Patent No. 4,626,498, JP 59-2148
Silver halide grains whose interiors are covered as described in No. 52
, colloidal silver is added to a photosensitive silver halide emulsion layer and/or
or a substantially non-photosensitive hydrophilic colloid layer.
Can be used. Halogenation inside or on the surface of the particle
Silver particles refer to both unexposed and exposed areas of photosensitive materials.
, silver halide that can be developed uniformly (non-imagewise)
Refers to particles. particles inside or on the surface.
A method for preparing silver halide grains is described in U.S. Patent No. 4,626,
No. 498, as described in JP-A No. 59-214852.
There is. Core/shell type halogen with fogged inside of particle
The silver halide that forms the inner core of silver grains is
Those with a halogen composition or those with a different halogen composition
It's okay. Halogen inside or on the surface of the particle
Silver oxides include silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiobromide.
Any silver can be used. these head coverings
There are no special limitations on the grain size of silver halide grains.
However, the average particle size is 0.01 to 0.75 μm.
, particularly preferably 0.05 to 0.6 μm. Also, the particle shape
There is no particular limitation on the shape, and regular particles may be used.
Polydisperse emulsions may also be used, but monodisperse emulsions (silver halide emulsions) may be used.
At least 95% of the weight or number of particles is an average particle
The particle size must be within ±40% of the particle diameter.
preferable. [0090] 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-grained silver halide is made from silver bromide.
The content is 0 to 100 mol%, and salt is added as necessary.
It may contain silver oxide and/or silver iodide. preferably
contains 0.5 to 10 mol% of silver iodide. Fine-grain silver halide has an average grain size (circle equivalent straight line of projected area)
The average diameter) is preferably 0.01 to 0.5 μm, and 0.01 to 0.5 μm.
．． 02 to 0.2 μm is more preferable. Fine particle halogen
Silver halide is prepared in the same way as ordinary photosensitive silver halide.
Can be manufactured. In this case, the surface of the silver halide grains is optically
does not need to be sensitized spectrally or spectral sensitization
. However, before adding this to the coating solution,
Humidity triazole series, azaindene series, benzothiazoli
um-based or mercapto-based compounds or zinc compounds
It is preferable to add a known stabilizer such as. child
Colloidal silver is preferably used in the layer containing fine silver halide grains.
It can be contained in various ways. Application of the photosensitive material of the present invention
The amount of silver is preferably 6.0 g/m2 or less, and 4.5 g/m
2 or less is most preferable. 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
RD18716 RD30
7105 1. Chemical sensitizer page 23
Page 648 right column
866 pages 2. Sensitivity enhancer
648 page right column
3. spectral sensitizer, 2
Pages 3-24 Page 648 Right column
Pages 866-868 Supersensitizer
~649 pages
Right column 4. brightener
Page 24 Page 647 Right column
868 pages 5. Anti-fogging
Pages 24-25 Page 649 Right column
Pages 868-870 Agents, stabilizers 6. Light absorber, pages 25-26
Page 649 right column 87
Page 3 Filter
~Page 650 left column
Dyes, UV absorbers 7. Stain page 25 right column
Page 650 left column 87
Page 2 Inhibitor
~Right column
8. Dye image 25 pages
Page 650 left column
Page 872 Stabilizers 9. Hardener page 26
Page 651 left column 874~
875 pages 10. Binder 26 pages
Page 651 left column 87
Pages 3-874 11. plasticizer, 2
Page 7 650 page right column
Page 876 Lubricants 12. Coating aids, pages 26-27
Page 650 right column 875-8
Page 76 Surfactant
　　　　　　　　　　　　　　　　　　　　　　　　　
13. Statistic
Page 27 Page 650 Right column
Pages 876-877 Inhibitor 14. matte agent
　　　　　　　　　　　　　　　　　　　　　　　　　
Pages 878-879 [0092] Also, formalde
In order to prevent deterioration of photographic performance due to hydrogen gas,
Patent No. 4,411,987 and Patent No. 4,435,50
Immobilization by reaction with formaldehyde described in No. 3
It is preferable to add a compound capable of forming a photosensitive material to a photosensitive material. Book
U.S. Patent No. 4,740,454 for the photosensitive material of the invention
, No. 4,788,132, JP-A-62-1853
No. 9, mercapto conversion described in JP-A No. 1-283551
It is preferable to contain a compound. The photosensitive material of the present invention
, by the development process described in JP-A No. 1-106052.
fogging agent, development acceleration, regardless of the amount of developed silver produced.
silver halide solvents or their precursors.
It is preferable to contain a compound. Photosensitive material of the present invention
In, International Publication No. WO88/04794, Special Publication Hei 1-50
Dye or E dispersed by the method described in No. 2912
P 317,308A, U.S. Patent 4,420,5
Contains the dye described in No. 55 and JP-A No. 1-259358.
It is preferable to let The present invention includes various color couplers.
can be used, specific examples of which can be found in the research mentioned above.
・Disclosure No. 17643, VII-C
~G, and the same No. 307105, VII-C~
It is described in the patent described in G. yellow coupler
In addition to the above-mentioned couplers, for example, U.S. Pat.
No. 933,501, No. 4,022,620, No. 933,501, No. 4,022,620, No.
No. 4,326,024, No. 4,401,752
, No. 4,248,961, Special Publication No. 58-107
39, British Patent No. 1,425,020, British Patent No.
No. 1,476,760, U.S. Patent No. 3,973,96
No. 8, No. 4,314,023, No. 4,511,
No. 649, European Patent No. 249,473A, etc.
Those described are preferred. 5-pyrazolone as magenta coupler
and pyrazoloazole compounds are preferred;
Permit No. 4,310,619, No. 4,351,89
No. 7, European Patent No. 73,636, US Patent No. 3,
No. 061,432, No. 3,725,067,
Research Disclosure No. 24220 (19
June 1984), JP-A No. 60-33552, Research
Disclosure No. 24230 (June 1984
), JP-A-60-43659, JP-A-61-72238
, No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Patent No. 4,500,6
No. 30, No. 4,540,654, No. 4, 5
No. 56,630, International Publication WO88/04795, etc.
Those described are particularly preferred. As a cyan coupler,
Examples include phenolic and naphthol couplers,
National Patent No. 4,052,212, National Patent No. 4,146,
No. 396, No. 4,228,233, No. 4,29
No. 6,200, No. 2,369,929, No. 2
, No. 801,171, No. 2,772,162, No. 801,171, No. 2,772,162, No.
No. 2,895,826, No. 3,772,002
No. 3,758,308, No. 4,334,
No. 011, No. 4,327,173, West German Patent Publication
No. 3,329,729, European Patent No. 121,36
No. 5A, No. 249,453A, U.S. Patent No. 3
, No. 446,622, No. 4,333,999, No. 4,333,999, No. 4,333,999, No.
No. 4,775,616, No. 4,451,559
No. 4,427,767, No. 4,690,
No. 889, No. 4,254, 212, No. 4,
No. 296,199, JP-A No. 61-42658, etc.
Those described are preferred. Furthermore, JP-A No. 64-553
, No. 64-554, No. 64-555, No. 64-55
The pyrazoloazole couplers described in No. 6 and U.S. Pat.
Imidazole couplers described in No. 4,818,672
- can also be used. polymerized pigment formation
A typical example of a coupler is U.S. Pat. No. 3,451,820.
No. 4,080,211, No. 4,367,
No. 282, No. 4,409,320, No. 4, 5
No. 76,910, British Patent No. 2,102,137
, European Patent No. 341,188A, etc. 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
No. 3,234,533, West German Patent Publication No. 3,234,533.
The one listed is preferred. To correct unnecessary absorption of coloring dyes.
The colored coupler is from Research Disclosure.
Char No. Section VII-G of 17643, No. 30
Section VII-G of 7105, U.S. Pat. No. 4,163,
No. 670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4
, No. 004,929, No. 4,138,258, English
Preferably, the one described in National Patent No. 1,146,368
. Also, the method described in U.S. Patent No. 4,774,181
The fluorescent dye released during coupling can prevent the coloring dye from dissipating.
Couplers that correct absorption requirements and U.S. Patent No. 4,777
, No. 120, which reacts with the developing agent to form a dye.
A coupler having a dye precursor group as a leaving group
It is also preferable to use Photography along with the coupling
Compounds that release useful residues are also preferably used in the present invention.
Can be used. The DIR coupler releasing the development inhibitor is
RD 17643, Section VII-F and No. 3
07105, patent listed in Section VII-F, JP-A-Sho
No. 57-151944, No. 57-154234, No. 57-154234, No. 57-151944, No. 57-154234, No.
No. 60-184248, No. 63-37346, No. 6
No. 3-37350, U.S. Patent No. 4,248,962,
4,782,012 is preferred. R. D. No. 11449, 24241, JP-A-6
Bleach accelerator releasing coupler described in No. 1-201247 etc.
- is useful in reducing the time of processing steps with bleaching capabilities.
This is particularly effective when using the tabular silver halide grains mentioned above.
It has a great effect when added to photosensitive materials.
A nucleating agent or development accelerator is released in an image form during development.
British Patent No. 2,097,140
No. 2,131,188, JP-A-59-157
No. 638 and No. 59-170840.
preferable. Also, Japanese Patent Application Laid-open No. 60-107029,
No. 60-252340, JP-A No. 1-44940, same.
Oxidation-reduction with the oxidized product of the developing agent described in No. 1-45687
Depending on the original reaction, fogging agents, development accelerators, silver halide
Also preferred are compounds that release solvents and the like. Other materials that can be used in the photosensitive material of the present invention
Compounds that can be used include U.S. Patent No. 4,130,427.
Competitive coupler described in U.S. Pat. No. 4,283, et al.
No. 472, No. 4,338,393, No. 4,3
10,618 etc., JP-A-60
-185950, JP-A No. 62-24252, etc.
DIR redox compound releasing coupler, DIR cap
DIR-emitting couplers, DIR coupler-emitting redox compounds
Redox compound or DIR redox releasing redox compound, European
State Patent No. 173,302A, State Patent No. 313,308A
Couplers that release dyes that recolor after separation as described in US
Ligand release described in Patent No. 4,555,477 etc.
Coupler, leuco color described in JP-A-63-75747
U.S. Patent No. 4,774,181
Examples include couplers that emit fluorescent dyes as described in the issue.
Ru. The coupler used in the present invention is the above-mentioned water coupler.
In addition to the medium oil droplet dispersion method, various known dispersion methods can be used to prepare photosensitive materials.
It can be introduced into the fee. For example, the process and effects of latex dispersion method
and specific examples of latex for impregnation are given in U.S. Pat.
, No. 199,363, West German Patent Application (OLS) No. 2,
No. 541,274 and No. 2,541,230.
It is written in which. [0097] The color photosensitive material of the present invention contains fenethyl
Alcohol and JP-A No. 63-257747, 62
-272248 and JP-A No. 1-80941
1,2-benzisothiazolin-3-one, n-
Butyl p-hydroxybenzoate, phenol,
4-chloro-3,5-dimethylphenol, 2-phene
Noxyethanol, 2-(4-thiazolyl)benzimine
Adding various preservatives or fungicides such as dazol
is preferable. The present invention can be applied to various color photosensitive materials.
can be done. Color negative for general use or movie use
Color reversal film for film, slides or television
color paper, color positive film, and color
-Reverse paper can be cited as a typical example.
. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No. 17643, page 28, No. 18716
From the right column of page 647 to the left column of page 648, and the same No. 3
07105, page 879. of the present invention
The photosensitive material consists of the entire hydrophilic colloid layer on the side with the emulsion layer.
It is preferable that the total film thickness is 28 μm or less, and 2
3 μm or less is more preferable, and 18 μm or less is even more preferable.
The thickness is particularly preferably 16 μm or less. Also, the membrane swelling rate
Degree T1/2 is preferably 30 seconds or less, preferably 20 seconds or less.
More preferable. Film thickness was measured at 25°C and 55% relative humidity (2 days).
The membrane swelling rate T1/2 means the membrane thickness
It can be measured according to a known method in the field. For example, A. Green et al.
Photographic Science and Engineering
(Photogr.Sci.Eng.), 19 volumes,
2, pp. 124-129
- (swelling meter), it can be measured and T1/
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
The speed T1/2 is the hardness of gelatin as a binder.
Adding agents or changing the aging conditions after application
It can be adjusted by Also, the swelling rate is 1
50-400% is preferred. The swelling rate is as mentioned earlier.
From the maximum swollen film thickness under the conditions, the formula: (maximum swollen film thickness -
It can be calculated according to (film thickness)/film thickness. The photosensitive material of the present invention is
, the total dry film thickness is 2μ on the side opposite to the side with the emulsion layer.
m ~ 20μm hydrophilic colloid layer (referred to as back layer)
It is preferable to provide one. This back layer contains the aforementioned light absorber, filter dye,
UV absorbers, anti-static agents, hardeners, binders
, plasticizers, lubricants, coating aids, surfactants, etc.
It is preferable that The swelling rate of this back layer is 150-5
00% is preferred. [0098] The color photographic material according to the present invention
The mentioned RD. No. 17643, pages 28-29, No.
651 left column to right column of 18716, and the same No. 30
7105, pages 880-881
It can be developed by any method. Photosensitivity of the present invention
The color developing solution used for developing the material is preferably aromatic.
Alkali whose main component is a group primary amine color developing agent
It is a liquid aqueous solution. As this color developing agent, aminoph
Although phenolic compounds are also useful, p-phenylenedia
Mine-based compounds are preferably used, and typical examples include
3-methyl-4-amino-N,N diethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 3-methyl-4-ami
No-N-ethyl-N-β-methanesulfonamide
Thylaniline, 3-methyl-4-amino-N-ethyl
Ru-β-methoxyethylaniline and their sulfuric acids
salt, hydrochloride or p-toluenesulfonate.
can be lost. Among these, 3-methyl-4-a
Mino-N-ethyl-N-β-hydroxyethyl acetate
Niline sulfate is preferred. These compounds are used depending on the purpose.
Two or more types can also be used together. Color developer is alkaline
p such as metal carbonates, borates or phosphates.
H buffer, chloride salt, bromide salt, iodide salt, benzimide
Dazoles, benzothiazoles or mercaptization
Contains development inhibitors or antifoggants such as compounds
is common. In addition, if necessary, hydroxyl
amine, diethylhydroxylamine, sulfite, N,N
-Hydrazines such as biscarboxymethylhydrazine
, phenyl semicarbazides, triethanolamine,
Various preservatives such as catechol sulfonic acids, ethylene
Recalls, organic solvents such as diethylene glycol,
alcohol, polyethylene glycol, quaternary alcohol
Development accelerators such as monium salts, amines, and dye-forming agents.
puller, competitive coupler, 1-phenyl-3-pyrazolide
Auxiliary developing agents such as
Bonic acid, aminopolyphosphonic acid, alkylphosphonic acid,
Various chelating agents such as phosphonocarboxylic acids
, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid,
diethylenetriaminepentaacetic acid, cyclohexanediamine
Tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxy
siethylidene-1,1-diphosphonic acid, nitrilo-N
, N,N-trimethylenephosphonic acid, ethylenediamine
-N,N,N,N- Tetramethylenephosphonic acid, ethyl
Diamine-di(o-hydroxyphenylacetic acid)
and their salts are representative examples. [0099] Also, 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 amino acids such as N-methyl-p-aminophenol.
Known black and white developing agents such as phenols are used alone or
Can be used in combination. These color developers
The pH of the black and white developer is generally 9 to 12.
be. Also, the amount of replenishment of these developers depends on the color being processed.
It depends on the photosensitive material, but generally one square meter of photosensitive material
bromide ion concentration in the replenisher.
By reducing the concentration, the volume can be reduced to 500ml or less.
You can also. When reducing the amount of replenishment, the treatment tank
Evaporation of liquid by reducing the contact area with air,
Preferably, air oxidation is prevented. Photo studio in the processing tank
The contact area between the physical liquid and air is expressed by the aperture ratio defined below.
I can do it. In other words, aperture ratio = [processing liquid and air
Contact area (cm2) ÷ [Capacity of processing liquid (cm3)
] The above aperture ratio is preferably 0.1 or less,
More preferably, it is 0.001 to 0.05. This way
One way to reduce the open area ratio of sea urchins is to use photo processing in the processing tank.
In addition to installing a shield such as a floating lid on the liquid surface,
- Method using a movable lid described in No. 82033, JP-A-82033
Slit development process described in No. 63-216050
I can list the methods. reducing the aperture ratio
is used not only for both the color development and black and white development processes, but also for the subsequent
Various processes, such as bleaching, bleach-fixing, fixing, washing, stabilization
It is preferable to apply it to all steps such as. Ma
In addition, measures are taken to suppress the accumulation of bromide ions in the developer.
By doing so, the amount of replenishment can also be reduced. color development
The processing time is usually set between 2 to 5 minutes, but
Use a high pH and a high concentration of color developing agent.
Accordingly, it is possible to further shorten the processing time. The photographic emulsion layer after color development is usually bleached.
It will be done. The bleaching process may be carried out simultaneously with the fixing process.
(Bleach-fixing treatment) may be carried out separately. further processing
In order to speed up the process, bleach-fixing treatment is applied after bleaching.
It may be a method. Furthermore, it is processed in two continuous bleach-fixing baths.
fixing before bleach-fixing, or
Bleaching after bleach-fixing may also be carried out depending on the purpose.
It can be done. Examples of bleaching agents include iron (III), etc.
Compounds of polyvalent metals, peracids, quinones, nitro compounds
etc. 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 etc. can be used. Of these, Ethi
diaminetetraacetic acid iron (III) complex salt, and 1,3-
Including diaminopropane tetraacetic acid iron (III) complex salts
Aminopolycarboxylic acid iron(III) complex salts can be rapidly processed.
This is preferable from the viewpoint of preventing environmental pollution. Furthermore, Aminopoly
Carboxylic acid iron (III) complex salts can be used in bleaching solutions as well.
It is also particularly useful in white fixers. These aminopo
Bleaching solution or bleach using recarboxylic acid iron(III) complex salt
The pH of white fixer is usually 4.0 to 8, but
It is also possible to process at lower pH for speed. Bleach solution, bleach-fix solution and their pre-baths
, a bleach accelerator can be used if necessary. Specific examples of useful bleach accelerators are described in
Yes: U.S. Patent No. 3,893,858, West German Patent No.
No. 1,290,812, No. 2,059,988,
JP-A No. 53-32736, JP-A No. 53-57831, JP-A No. 53-57831,
No. 53-37418, No. 53-72623, No. 53-
No. 95630, No. 53-95631, No. 53-104
No. 232, No. 53-124424, No. 53-14
No. 1623, No. 53-28426, Research D.
Closer No. No. 17129 (July 1978)
having a mercapto group or disulfide group as described in
Compound; thia described in JP-A-50-140129
Zolidine derivative; Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 1973
No. 2-20832, No. 53-32735, U.S. Patent No.
Thiourea derivatives described in No. 3,706,561; West Germany
Patent No. 1,127,715, JP-A-58-16-2
Iodide salt described in No. 35; West German Patent No. 966,410
No. 2,748,430
Thyrene compounds; poly described in Japanese Patent Publication No. 45-8836
Amine compounds; other JP-A No. 49-40,943;
No. 49-59,644, No. 53-94,927
, No. 54-35,727, No. 55-26,506
No. 58-163,940; Bromide I
On, etc. can be used. Among them, mercapto group or dis
Compounds with a ruphide group are preferred because they have a large promoting effect.
Specifically, U.S. Pat. No. 3,893,858, West Germany
Patent No. 1,290,812, JP-A-53-95,6
The compounds described in No. 30 are preferred. Additionally, U.S. Patent No.
Also preferred are the compounds described in No. 4,552,834. child
These bleach accelerators may be added to the photosensitive 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
Acetic acid, propionic acid, hydroxyacetic acid, etc. are preferred. Thiosulfur is a fixing agent used in fixers and bleach-fixers.
Acid salts, thiocyanates, thioether compounds, thiouria
These include a large amount of iodide salts, etc., but thio
The use of sulfates is common, especially ammonium thiosulfate.
system is the most widely used. Also, thiosulfate and thiosulfate
Combination use of anates, thioether compounds, thiourea, etc.
is also preferable. As a preservative for fixer and bleach-fixer,
Sulfates, bisulfites, carbonyl bisulfite adducts or
is the sulfinic acid described in European Patent No. 294769A
Compounds are preferred. Furthermore, the fixing solution and bleach-fixing solution contain
For stabilization purposes, various aminopolycarboxylic acids and organic
The addition of sulfonic acids is preferred. In the present invention, the fixer
Or the bleach-fix solution has a pKa of 6 for pH adjustment.
．． 0 to 9.0 compounds, preferably imidazole, 1
-Methylimidazole, 1-ethylimidazole, 2-
0.1 to 1 imidazole such as methylimidazole
It is preferable to add 0 mol/l. [0102] 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 25°C to 50°C, preferably 35°C to 45°C. In the preferred temperature range, the desilvering rate increases and
The generation of stains after treatment is effectively prevented. For the desilvering process
It is preferable that the agitation is as strong as possible.
Yes. A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62-18
A jet of processing liquid is applied to the emulsion surface of the photosensitive material described in No. 3460.
The collision method and the issue of JP-A No. 62-183461
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, the circulation flow rate of the entire processing liquid
One method is 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
, Japanese Patent Publication No. 60-191257, No. 60-1912
No. 58, photosensitive material transportation described in No. 60-191259.
It is preferable to have a feeding means. The above-mentioned Japanese Patent Publication No. 6
As described in No. 0-191257, such conveyor
The stage can significantly reduce the carry-over of processing liquid from the front bath to the rear bath.
, is highly effective in preventing performance deterioration of the processing liquid. like this
The effect is a reduction in processing time in each process and a reduction in the amount of processing solution refilled.
It is particularly effective in reducing Silver halide color photographic material of the present invention
After desilvering, it is easier to go through a water washing and/or stabilization process.
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
Relationship is Jour-al of the Society
y of Motion Picture and T
ele-vision Engineers 64th
Volume, P. 248-253 (May 1955 issue)
You can find it using the method listed below. Many of the documents mentioned above
According to the stage counterflow method, the amount of washing water can be significantly reduced, but
Due to the increased residence time of water in the tank, bacteria
The bacteria may propagate and the resulting floating matter may adhere to the photosensitive material.
A problem arises. In processing the color photosensitive material of the present invention
, as a solution to this problem, Japanese Patent Application Laid-Open No. 62-288
, No. 838, the calcium ions and magnesium ions described in
It is possible to use extremely effective methods to reduce
Ru. Also, isothiae described in JP-A No. 57-8,542
Zolone compounds, thiabendazoles, chlorinated isocyanates
Chlorine-based disinfectants such as sodium nurate, and other benzoate
Riazor et al., Hiroshi Horiguchi, “Chemistry of antibacterial and fungicidal agents” (198
6th year) Sankyo Publishing, Hygiene Technology Society, ed. “Sterilization and sterilization of microorganisms,
Anti-mold technology” (1982) Society of Industrial Engineers, Japan Anti-bacterial and anti-mold science
Disinfectants listed in the Society's "Encyclopedia of Antibacterial and Antifungal Agents" (1986)
You can also use In processing the photosensitive material of the present invention
The pH of the washing water is 4 to 9, preferably 5 to 8.
be. Washing water temperature, washing time, characteristics of photosensitive materials, uses, etc.
Various settings can be made, but generally the temperature is 15 to 45°C for 20 seconds.
~10 minutes, preferably in the range of 30 seconds to 5 minutes at 25-40°C
The box is selected. Furthermore, the photosensitive material of the present invention can be washed with water as described above.
Alternatively, it is also possible to work directly with the stabilizing solution. child
In the stabilization treatment, JP-A-57-8543
No. 58-14834, No. 60-220345
All known methods described in this issue can be used. Ma
In addition, following the water washing treatment, a further stabilization treatment may be performed.
An example of this is the final bath for color photosensitive materials for photography.
Contains dye stabilizers and surfactants used as
One example is a stable bath. As a dye stabilizer,
aldehydes such as formalin and glutaraldehyde,
N-methylol compound, hexamethylenetetramine
Examples include aldehyde sulfite adducts.
. Various chelating agents and antifungal agents can also be added to this stable bath.
Can also be done. [0104] O
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 Halogen of the present invention
Silver oxide color light-sensitive materials have the potential to simplify and speed up processing.
A color developing agent may be incorporated therein. In order to incorporate
It is preferable to use various precursors of color developing agents.
stomach. For example, the example described in U.S. Pat. No. 3,342,597
Ndoaniline compound, No. 3,342,599,
Research Disclosure No. 14,850 and
Same No. Schiff base type compound described in 15,159
, aldol compound described in No. 13,924, US Pat.
Metal salt complex described in No. 3,719,492, JP-A-5
The urethane compounds described in No. 3-135628 are listed below.
be able to. The silver halide color photosensitive material of the present invention can be prepared as necessary.
, various 1-phenyl-3 for the purpose of promoting color development.
- Pyrazolidones may be incorporated. A typical compound is
JP-A-56-64339, JP-A No. 57-144547,
and No. 58-115438. Book
Various processing solutions in the invention are used at 10°C to 50°C.
be done. Normally, the standard temperature is between 33°C and 38°C.
, accelerate the process by increasing the temperature and shorten the process time.
Conversely, it lowers the temperature to improve image quality and stability of the processing solution.
can be achieved. Moreover, the silver halide of the present invention
The photosensitive material is U.S. Patent No. 4,500,626, Japanese Patent Application Publication No. Sho
No. 60-133449, No. 59-218443,
No. 61-238056, European Patent 210,660A
It can also be applied to heat-developable photosensitive materials described in No. 2, etc.
Wear. [Example] The present invention will be explained in more detail with reference to Examples below.
However, the present invention is not limited to these.
. Example 1 On a subbed cellulose triacetate film support, an undercoat was applied.
Create a color photosensitive material consisting of each layer with the composition shown below.
Manufactured. Regarding the coating amount for each layer composition, please refer to the halogen
The amount of silver expressed in units of [g/m2] is measured by the coupler.
-, gelatin, etc. are expressed in units of [g/m2].
Indicate quantity. 1st layer (low sensitivity emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI
Type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter
12%, octahedral particles) Silver coated
Amount 0.41 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
2.65
Coupler of the present invention (Y-1)
0
．． 90 Comparison coupler (a)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 S-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
50 2nd layer (high sensitivity emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high Ag
Type I, equivalent sphere diameter 1.3 μm, variation of equivalent sphere diameter
Several 20%, normal crystal, twin mixed grain, diameter/thickness ratio 5.5
)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount 0.52 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
2.00 Coupler of the present invention (Y-1)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.12 S-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.06th
3 layers (protective layer) gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.32 In addition, the production of the above photosensitive materials
The following surfactants are used to prepare coupler dispersions during production.
agent was used. [0107] Furthermore, during coating, the following surfactant is added to the gel.
The following hardener was used as the latin hardener. [Chemical formula 50] [Chemical formula 51] The sample prepared as above was designated as 101.
do. Next, from sample 102 onwards, the first and second layer caps are
Change S as shown in Table 1, replace equimolar amounts, and S
-8/Adjust the coupler weight ratio to 0.5.
Samples 101 to 119 were produced. These prepared samples are
After processing it to a width of 35mm and applying white light wedge exposure.
Using an automatic processor, accumulate the color developer using the method described below.
Separately until the volume of replenishment becomes three times the volume of the mother liquor tank.
Processing was carried out after the sample had been imagewise exposed. However, in the prepared sample 119, precipitation of coupler was observed,
Although the above treatment was applied, the performance cannot be evaluated due to poor color development.
Therefore, it was excluded. Treatment method Step Treatment time Treatment temperature
Replenishment amount
Ink capacity color development 3 minutes 15 seconds
38℃ 33ml
20l bleach
6 minutes 30 seconds 38℃
25ml
Wash with 40l water 2 minutes 10 seconds
24℃ 1200ml
20l fixed
4 minutes 20 seconds 38℃
25ml
30l water washing (1) 1 minute 05 seconds
24℃ (2) empty (1)
Counter-current piping method 10L water washing (2)
1 minute 00 seconds 24℃
1200ml
10l stable 1 minute 05 seconds
38℃ 25ml
10l dry
4 minutes 20 seconds 55℃
The amount of replenishment is per 35mm width and 1m length [0113]Next
The composition of the treatment liquid is shown in . (color developer)
Mother liquor (g)
Replenisher (g) Diethylenetriaminepentaacetic acid
1
．． 0 1.1 1-hydroxyethylidene
-1,1-diphosphonic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0 3.2 Sodium sulfite
thorium
4.0 4.4
potassium carbonate
30.0
37.0 Potassium Bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4 0.7 Potassium iodide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5mg - Hi
Droxylamine sulfate
2.4 2.8
4-[N-ethyl-N-β-hydroxyethyl
Ruamino]-2-methylaniline sulfate
4.5 5.5 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0l 1.0l
pH
10.05
10.10 (Bleach solution)
Mother liquor (g)
Replenisher (g) Ethylenediaminetetraacetic acid
Ferric sodium trihydrate
　　　　　　　　　　　　　　　　　　　　　　　　　
100.0 120.0 Ethylenediamine
Tetraacetic acid disodium salt 10.
0 10.0 Ammonium bromide
1
40.0 160.0 Ammonium nitrate
　　　　　　　　　　　　　　　　　　　　　　　　　
30.0 35.0 Ammonia water (2
7%)
6.5ml 4.0ml Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0l 1.0l
pH
　　　　　　　　　　　　　　　　　　　　　　　　　
6.0 5.7 (Fixer)
Mother liquor (g)
Replenisher (g) Ethylenediaminetetraacetic acid
Disodium salt 0.5
0.7 Sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0 8.0 Sodium bisulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0 5.5 Thiosulfate
Ammonium aqueous solution (70%) 170
．． 0ml 200.0ml Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0l 1.0l pH
　　　　　　　　　　　　　　　　　　　　　　　　　
6.7
6.6 (Stabilizer)
Mother liquor (g)
Replenisher (g) Formalin (37%)
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0ml 3.0ml Polyoxyethylene
Ren-p-monononylphenyl ether (average
Degree of polymerization 10)
0.3 0.45 Ethylenediaminetetraacetic acid
Disodium salt 0.05
0.08 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0l 1.0l pH
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0-8.0 5.0-
8.0 [0117] The sample obtained after treatment was exposed to blue light.
Measure the density, obtain its characteristic curve, and find the best photographic performance.
The logarithm of the reciprocal of the exposure that gives a density of small density + 0.2 is
This value was determined as sensitivity (S). Furthermore, from this sensitivity point
The density value (D) at a high exposure amount of logE=1.5 is
For reading and sensitivity, each test is based on sample 101.
Determine the sensitivity difference (△S) between sample 1 and the sample 1 for the concentration value.
The percentage (D%) was calculated based on the value of 01.
. In addition, the treated sample was tested at 80℃ and 70%RH.
Store for a period when there is a significant difference between the materials, and store under high temperature and high humidity.
The fastness of the color image was examined, and the color image survival rate (%) was determined at an initial density of 1.5.
I asked about 0. Next, the concentration of the processed sample
Measurement is done with green light, yellow density is minimum density + 1.5
The density measured in green light at an exposure that gives a density of
Read the value and calculate the concentration difference (with respect to sample 101)
△DG) was calculated. On the other hand, prepare two sets for each sample.
One set was stored at 50℃ and 40%RH for 7 days.
The other set was stored at 5°C and exposed to white light under the same conditions.
Apply exposure and perform the above processing at the same time, using the method described above.
The reciprocal of the exposure amount that gives the minimum density + 1.0 density according to
Find the logarithm of and calculate the difference (△ST) in the same sample.
did. These results are summarized in Table 1 and
It is shown in Table 2. [Table 1] [Table 2] Comparative couplers and reference couplers in Tables 1 and 2
The structural formula of RA is shown below. [Chemical formula 52] [Chemical formula 53] As is clear from the results in Tables 1 and 2,
Comparative coupler (a) and reference coupler in the first layer and second layer, respectively.
puller (b), reference coupler (c), the above general of the present invention
A coupler represented by formula (I) and the above general formula (A)
The constituent elements of the present invention were verified in the samples prepared using different methods.
The sample satisfies the sensitivity, color density, color fastness, and length.
The sample was found to have excellent absorbance on the wavelength side and storage stability of the sensitive material.
This can be seen from mutual comparison. However, in the present invention, the cap
It is essential that the polymer has a diffusion-resistant hydrophobic group in its molecule.
This can be easily seen from sample 119. especially
, even in a sample that satisfies the constituent requirements of the present invention.
Samples using the coupler represented by the general formula (I)
Coupler mother of couplers (b) and (c) cited by Hou
Compared to a sample using a coupler with a diffusive nucleus, the above performance is
It turns out it's better. Example 2 Sample 101 of Example 1 was basically used for the first and second layers.
Change the coupler shown in Table 3 and Table 4,
Equimolar amounts were substituted, and the S-8/total coupler weight ratio was changed in the same way.
A sample was prepared by adjusting the value to 0.5. These trials
The material was subjected to the same treatment as in Example 1, and its performance was the same.
It was evaluated according to the method. The results are summarized in Tables 3 and 4.
Samples 101 and 118 of Example 1 are shown for comparison.
The results are also shown. [Table 3] [Table 4] [Table 4] From the above table, samples satisfying the constituent requirements of the present invention
are photographic properties, color image fastness, spectral absorption characteristics of color images, and preservation of sensitive materials.
It is clear that it has excellent durability. In the configuration of the present invention
Even if represented by the general formula (I) and general formula (II),
Comparing the couplers represented by the general formula (II),
The coupler is higher than the coupler represented by the general formula (I).
Samples 118 and 201-2 have excellent properties as described above.
This can be seen from the comparison between 03 and samples 204 to 207. moreover,
In non-functional couplers, the leaving group becomes active via the N atom.
The coupler bonded to the
(Samples 207, 209-21
1 and samples 208, 212), bonding to the active site via N atoms.
Couplers that have a leaving group that is attached to them have the above-mentioned properties.
It is also clear that he is excellent at Noh. Also, expressed by general formula (A)
Good results can be obtained even if the coupler is changed.
I know what I can do. Example 3 Based on sample 101 prepared in Example 1, Tables 5 and 6 were prepared.
By changing the couplers in the first and second layers as shown, etc.
Replace the molar amount and further change the weight ratio of S-8/total coupler
A sample was prepared with the change. These samples are 35mm wide.
The sample is cut and separately subjected to imagewise exposure, then processed and color developed.
The cumulative replenishment amount of liquid is three times the mother liquid tank capacity.
After performing the running process until the
The following treatments were carried out. Processing process and
The composition of the treatment liquid is shown below. Processing process Processing time
Processing temperature Refill amount* Tank
Capacity Color development 3 minutes 05 seconds
38.0℃ 600ml
5 l bleach
50 seconds 38.0℃
140ml 3
l Bleach fixing 50 seconds
38.0℃ -
3 l fixation
50 seconds 38.0℃
420ml 3
l Wash with water for 30 seconds
38.0℃ 980
ml 2 l stable (
1) 20 seconds 38.0
℃ −
2 l Stable (2) 2
0 seconds 38.0℃ 5
60ml 2 l dry
Drying 1 minute 6
0 °C *The amount of replenishment is the amount per 1 m2 of photosensitive material Washing with water
The water flow is countercurrent from (2) to (1), and the washing water
All of the overflow liquid was introduced into the fixing bath. bleach fixing
Refill the bath at the top of the automatic processor's bleach tank and at the bleach-fix tank.
Connect the bottom and top of the fixing tank to the bottom of the bleach-fixing tank with a pipe.
connection and the supply of replenisher to the bleach tank and fixer tank.
so that all overflow liquid flows into the bleach-fix bath.
I did it. In addition, the amount of developer brought into the bleaching process, the amount of bleaching solution
Amount brought into the bleach-fixing process, amount of bleach-fix solution brought into the fixing process
and the amount of fixer brought into the water washing process of the photosensitive material.
65ml, 50ml, 50ml per 1m2 of water
, 50ml. Also, crossover time yes
The deviation is also 5 seconds, and this time is included in the processing time of the previous process.
be done. The composition of the treatment liquid is shown below. (color developer)
Mother liquor (g)
Replenisher (g) Diethylenetriaminepentaacetic acid
2
．． 0 2.2 1-hydroxyethylidene
-1,1-diphosphonic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
3.3 3.3 Sulfur
acid sodium
3.9 5
．． 2 Potassium carbonate
37.5
39.0 Potassium Bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4 0.4 Potassium iodide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.3mg -
hydroxylamine sulfate
2.4 3.3
2-Methyl-4-[N-ethyl-N-(β-hy-
(Droxyethyl)amino]aniline sulfate
4.5 6.0 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0l 1.0l
pH
10.0
5 10.15 (Bleach solution)
Mother liquor (g)
Replenisher (g) 1,3-propylenedia
Ferric ammonium mintetraacetate monohydrate
　　　　　　　　　　　　　　　　　　　　　　　　　
144.0 206.0 Ammonium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
84.0 120.0 Ammonium nitrate
Mu
17.5 25.0 Hydro
xyacetic acid
63.0 90.0
acetic acid
54
．． 2 80.0 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0l 1.0l pH [ammo
Adjust with near water]
3.80 3.60 0132] (bleaching
Fixer solution mother solution) 15 pairs of the above bleaching solution mother solution and the following fixer solution mother solution
Mixed liquid of 85 (Fixer)
Mother liquor (g)
Replenisher (g) Ammonium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
19.0 57.0 Ammonium thiosulfate
Aqueous solution (700g/l) 280ml
840ml imidazole
　　　　　　　　　　　　　　　　　　　　　　　　　
28.5 85.5 Ethylenediamine tetra
acetic acid
12.5 37.5 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0l 1.0l p
H [Adjusted with aqueous ammonia and acetic acid]
7.40 7.45 0134](
Washing water) Common tap water for mother liquor and replenisher is H-type strongly acidic.
Cation exchange resin (Amberla manufactured by Rohm and Haas)
IR-120B) and OH type strong basic anion exchange
A mixture filled with resin (Amberlite IRA-400)
Water is passed through a bed type column to remove calcium and magnesium ions.
treatment to reduce the concentration of carbon dioxide to 3 mg/l or less, followed by
Sodium annulate 20mg/l and sodium sulfate 1
50 mg/l was added. The pH of this solution is 6.5-7.
It was in the range of 5. (Stable solution) Common to mother solution and replenisher solution
(
Unit: g) Formalin (37%)
　　　　　　　　　　　　　　　　　　　　　　　　　
1.2ml p-toluene sulfy
Sodium phosphate
0.3g polyoxyethylene
-p-monononylphenyl ether (average polymerization
degree 10)
0.
2 Ethylenediaminetetraacetic acid disodium salt
0.0
5 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0l pH
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
7.2 [0136] The sample obtained by the treatment was
Photographic properties, color image retention rate, and aging of sample in Example 1
Stability (ΔST) was determined according to a similar method. However
Regarding photographic properties, S-8/Coupler between the same couplers
Comparisons were made using the sample with the highest weight ratio as the standard. Result is
A summary is shown in Tables 5 and 6. [Table 5] [Table 6] [Table 6] From Tables 5 and 6, samples 305 to 3 of the present invention
14 is the weight ratio of high boiling point organic solvent (S-8)/total coupler
Even if the value is reduced, the variation in photographic properties is small and the color image fastness is
The degree of oxidation is small, and there is also little change in shelf life.
Is it a comparison with comparative samples 301-304 and 101?
It is clear that Furthermore, in the present invention, mixed use
In the case where the general formula (I) and general formula (II) of the present invention are
The higher the ratio of couplers represented, the better.
is the pair of samples 305-309 and samples 310-314.
This can be easily determined from the ratio. Example 4 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material consisting of each layer with the composition shown below.
A sample 401 was prepared as a sample. (Composition of photosensitive layer) The coating amount is silver halide and colloid.
For silver, the amount expressed in g/m2 of silver, also in caps.
in g/m2 for fillers, additives and gelatin.
For sensitizing dyes, halogen in the same layer.
It is expressed as the number of moles per mole of silveride. 1st layer (antihalation layer) Black colloidal silver
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.90
ExM-1
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-3 2nd layer (middle layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
2.10 UV-1
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-
2 UV-2
　　　　　　　　　　　　　　　　　　　　　　　　　
6.0×10-2 UV-3
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-2
ExF-1
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0×10-3 S-6
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-2th
3 layers (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, spherical phase
Equivalent diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 29%, normal crystal,
Twinned mixed particles, diameter/thickness ratio 2.5)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount
0.50 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.50 ExS
-1
1.
0x10-4 ExS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-4 ExS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×1
0-5 ExC-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.11 ExC-3
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.11 ExC-4
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-2 ExC-7
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-
2 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-3 4th layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, spherical phase
Equivalent diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal
, twinned mixed particles, diameter/thickness ratio 1.0)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount
0.85 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
2.00Ex
S-1
1
．． 0x10-4 ExS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-4 ExS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×
10-5 ExC-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16 ExC-2
　　　　　　　　　　　　　　　　　　　　　　　　　
8.0×1
0-2 ExC-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 ExC-7
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5×10
-2 Comparison coupler (b)
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-2 ExY-1
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-2 Cpd
-10
1.0
×10-4 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 5th layer (high
Sensitive red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type
, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, dual
Crystal mixed particles, diameter/thickness ratio 2.0)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount
0.70 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.60 ExS-
1
1.0
×10-4 ExS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-4 ExS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10
-5 ExC-5
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-2 ExC-6
　　　　　　　　　　　　　　　　　　　　　　　　　
8.0×10-2
ExC-7
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5×10-2 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15
S-6
　　　　　　　　　　　　　　　　　　　　　　　　　
8.0×10-2 6th layer (middle layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.10 P-2
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 Cpd-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Cpd-4
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-2 7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, spherical phase
Equivalent diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 28%, normal crystal,
Twinned mixed particles, diameter/thickness ratio 2.5)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount
0.30 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.50 ExS
-4
5.
0x10-4 ExS-5
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-4 ExS-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3×1
0-4 ExM-1
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-2 ExM-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
20 Comparison coupler (b)
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-2 S-23
　　　　　　　　　　　　　　　　　　　　　　　　　
7.0×10-3 S-
1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 8th layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, spherical phase
Equivalent diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal
, twinned mixed particles, diameter/thickness ratio 4.0)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount
0.70 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00Ex
S-4
5
．． 0x10-4 ExS-5
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-4 ExS-6
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×
10-5 ExM-1
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-2 ExM-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0
．． 25 ExM-3
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5×10-2 Comparison coupler (b)
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0×10-2 S-
23
　　　　　　　　　　　　　　　　　　　　　　　　　
9.0×10-3 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 9th
Layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere
Equivalent diameter 0.7μm, coefficient of variation of sphere equivalent diameter 30%, normal crystal
, twinned mixed particles, diameter/thickness ratio 2.0)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount
0.50 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.90Ex
S-4
2
．． 0x10-4 ExS-5
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-4 ExS-6
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×
10-5 ExS-7
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-4 ExM-1
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-
2 ExM-4
　　　　　　　　　　　　　　　　　　　　　　　　　
3.9×10-2 ExM-5
　　　　　　　　　　　　　　　　　　　　　　　　　
2.6×10-2
Cpd-2
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-2 Cpd-9
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-4 Cpd
-10
2.0
×10-4 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 S-6
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10−2 10th layer (yellow filter layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.90 yellow colloid
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0×10-2
Cpd-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
15 11th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type,
Equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 15%, 8 surfaces
body particles)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount 0.40 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
1.00 ExS-8
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-4 Comparison coupler
-(b)
9.0×10-2
Coupler (Y-1)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.90 Cpd-2
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-2 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.30 12th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere
Equivalent diameter 1.3μm, coefficient of variation of sphere equivalent diameter 25%, normal crystal
, twinned mixed grains, diameter/thickness ratio 4.5)
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver coating amount
0.50 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.60Ex
S-8
1
．． 0x10-4 coupler (Y-1)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.12 Cpd-2
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10
-3 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0×10−2 [0144] Thirteenth layer (first protective layer) Fine grain silver iodobromide (average grain size 0.07 μm, AgI
1 mol%) 0.20 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.80 UV-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 UV-3
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 UV-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20S
-3
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0×10-2 P-2
　　　　　　　　　　　　　　　　　　　　　　　　　
9.0×10-2 1st
4 layers (second protective layer) gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.90 B-1 (diameter 1.5
μm)
0.10 B-2
(1.5μm in diameter)
0.1
0 B-3
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0×10-2 H-1
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40 Furthermore, storage stability, processability, pressure resistance, anti-mold and anti-bacterial properties
In order to improve the properties, antistatic properties, and coating properties, the following
Cpd-3, Cpd-5, Cpd-6, Cpd-7, C
pd-8, P-1, W-1, W-2, W-3 were added
. In addition to the above, n-butyl-p-hydroxybenzoate
was added. Furthermore, B-4, F-1, F-4, F-
5, F-6, F-7, F-8, F-9, F-10, F-
11, and iron salts, lead salts, gold salts, platinum salts, iridium
Contains salts and rhodium salts. Next, used in the present invention
The chemical structural formula or chemical name of the compound is shown below. 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 embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] Following the preparation of sample 401, a red-sensitive emulsion layer was prepared.
the fourth layer, the seventh and eighth layers of the green-sensitive emulsion layer, and the blue-sensitive emulsion layer.
Comparative coupler (b) of the 11th and 12th layers of ExY-
1, Y-1, etc. as shown in Table 7, and make the respective equivalent models.
Samples were prepared by replacing the amount of water. At this time, the blue-sensitive emulsion layer
For the 11th and 12th layers, S-1/total coupler weight ratio
was adjusted to 1/3. The obtained sample is Example 3
The process described in Example 1 was carried out, and yellow
- Photographic properties of color images (△S, D (%)), yellow color images and
The color image retention rate of the zenta color image was determined. Furthermore, yellow color
The graininess that gives the minimum image density + 0.5 is
Measure the RMS value with a 48 μm diameter aperture.
As for the sharpness, the yellow color image was determined using the conventional MTF method.
(25 cycles/mm). These results
A summary is shown in Table 7. [Table 7] [0161] As is clear from Table 7, the constituent elements of the present invention
Samples 402 to 404 that meet the conditions have both sensitivity and color density.
It exhibits excellent photographic properties and excellent color image fastness.
. Furthermore, graininess and sharpness also showed good results, improving image quality.
It can be seen that it has excellent effects as well. In addition, the present invention
Represented by the general formula (I) and/or general formula (II)
The compound shown in the green-sensitive emulsion layer was replaced with the comparative coupler (b).
It was also found that the color image fastness improved when used. In addition, the graininess and sharpness of magenta color images were also found in samples 401 and 4.
Samples 403 and 404 are better than 02.
was also confirmed. Effect of the invention: Having at least one photosensitive emulsion layer
In silver halide color photographic materials, the general formula (I
) and/or a coupler represented by general formula (II)
Contains a coupler represented by general formula (A)
A photosensitive material having at least one photosensitive emulsion layer is
It has high sensitivity and color density, and exhibits excellent photographic performance.
The optical material has good storage stability over time, and the color images obtained are long-wavelength.
It shows good color reproducibility with little absorption on the long side, and has no graininess or brightness.
It also has excellent sharpness. From these results, high color development
The storage stability of the photosensitive material is also good, and the color image fastness and
Providing silver halide color photographic materials with excellent color and image quality
can do.

Claims (2)

[Claims] Claim 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, comprising a compound of general formula (I) and/or general formula (II).
A silver halide color photographic light-sensitive material characterized by containing a coupler represented by formula (A). General formula (I) [Formula 1] General formula (II) [Formula 2] In the formula, X1 and X2 each represent an alkyl group, an aryl group or a heterocyclic group, and X3 represents a nitrogen-containing heterocyclic group together with >N-. represents an organic residue to be formed, Y represents an aryl group or a heterocyclic group, and Z represents a group that leaves when the coupler represented by the general formula reacts with an oxidized developing agent. General formula (A) [Chemical formula 3] In general formula (A), M and Q are groups (including atoms) that can be substituted on the benzene ring, L is a hydrogen atom, a halogen atom, or an aliphatic oxy group, and m is 0 ~5 integer, n is 0~
4 is an integer, and X represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. However, m
When n is plural, (M)m may be the same or different; similarly, when n is plural, (Q)n may be the same or different. Further, M, Q, L or X may serve as a divalent to tetravalent linking group to form a dimer to tetramer of the yellow coupler represented by the general formula (A). [Claim 2] General formula (I) and/or contained in the same layer
Or a coupler represented by the general formula (II) and the general formula (
2. The silver halide color photographic material according to claim 1, wherein the ratio of the total weight of the high boiling point organic solvent in the same layer to the total weight of the coupler represented by A) is 1.0 or less.