JPH04218042A - Yellow dye forming coupler and silver halide color photosensitive material containing same - Google Patents

Abstract

PURPOSE:To provide the yellow dye forming coupler superior in color development performance and spectral absorption characteristics of a yellow image produced by color development, and to provide the silver halide color photosensitive material containing the coupler. CONSTITUTION:The silver halide color photosensitive material contains the acylacetoamide type yellow dye forming coupler, and its acyl group is represented by general formula (I) in which R1 is a monovalent group, and Q is a nonmetallic atomic group necessary to form a 3- or 5-membered hydrocarbon ring or 3- or 5-membered hetero ring containing a hetero atom together with the carbon atom, and R1 is not H and does not form a ring together with Q.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to a novel acylacetaminyl
De-type yellow dye-forming coupler and halide containing the same
This invention relates to silver halide color photographic materials. [0002] Silver halide color photographic light-sensitive materials are
Oxidation is prevented by color development after exposing the material to light.
Aromatic primary amine developer and dye-forming coupler (hereinafter referred to as
A color image is created by the reaction of the lower coupler).
It is formed. Generally, this method uses a subtractive color method.
A color reproduction method is used to reproduce blue, green, and red.
Yellow, magenta and cyan are complementary colors.
A color image is formed. No for forming yellow color image.
Low dye-forming coupler (hereinafter referred to as yellow coupler)
As acylacetamide couplers and malondianili
A magenta coupler is used to form a magenta color image.
5-pyrazolone coupler and pyrazolotria as
Sol couplers etc. are used to form cyan images.
Phenol couplers and naphthol couplers as pullers
are commonly used. Yellow color obtained from these couplers
dye, magenta dye, and cyan dye are absorbed by the dye.
For radiation that is complementary to the radiation that is contained
in the color-sensitive silver halide emulsion layer or its adjacent layer.
It is generally formed by By the way, Yellow Ka
benzoylacetani, especially for image forming.
For lido couplers and pivaloylacetanilide couplers
Typical acylacetamide couplers are commonly used.
It is being The former is generally an aromatic primary amine during development.
It has high coupling activity with the oxidized developer and is
High sensitivity is required because the yellow dye has a large molecular extinction coefficient.
Color photosensitive materials for photography, especially color negatives
The latter is mainly used for film, and the latter is a yellow dye component.
It is mainly used for color paper because of its excellent light absorption characteristics and fastness.
Used for par and color reversal films. However, benzoylacetanilide-type caps
For color development, aromatic primary amine development is used during color development.
It has high coupling reactivity with the oxidized form of the drug and is
The yellow azomethine dye has a large molecular extinction coefficient.
The disadvantage is that the spectral absorption characteristics of the yellow image are inferior.
For pivaloylacetanilide couplers, yellow
Although the image has excellent spectral absorption characteristics, the aroma during color development
Coupling reactivity of group primary amine developers with oxidized products
is low, and the molecular absorption of the yellow azomethine dye produced is low.
The drawback was that the optical coefficient was small. [0005] Here, the high coupling reaction of the coupler
The high molecular extinction coefficient of the dye produced leads to high sensitivity,
Enables high gamma value and high color density, so-called high
Provides strong color development. In addition, the superiority in yellow color images
The spectral absorption characteristic is, for example, the cutoff on the long wavelength side of spectral absorption.
This means that the absorption characteristics are good and there is little unnecessary absorption in the green area.
do. Therefore, the best of both worlds: high color development (capturing).
High coupling reactivity of dyes and large molecular absorption of dyes
An image with excellent spectral absorption characteristics for color images (light coefficient) and color images.
The development of a yellow coupler was desired. Acyl of acylacetanilide type coupler
Based on U.S. Pat. No. Re 27,848, Pivalo et al.
yl group, 7,7-dimethylnorbornane-1-carboni
group, 1-methylcyclohexane-1-carbonyl group, etc.
However, in Japanese Patent Application Laid-open No. 47-26133, cyclopropane
1-carbonyl group, cyclohexane-1-carbonyl group
etc. are disclosed. However, these couplers
Poor coupling reactivity or molecular extinction coefficient of the dye
is small, or the spectral absorption characteristics of the color image are poor.
It was inferior in some respect. [0007] Problems to be Solved by the Invention: Recent photographic materials
has higher sensitivity, higher image quality, and better toughness than before.
It is even more strongly demanded. Therefore, it has excellent color development,
The development of couplers with excellent spectral absorption characteristics for color images is now underway.
It was highly desired. However, the conventional
As mentioned above, the yellow coupler meets all of these requirements.
It was difficult to meet all requirements. Therefore, the first object of the present invention is to improve color development.
Yellow coupler and halogenated coupler containing it
The purpose of the present invention is to provide a silver color photographic material. of the present invention
The second purpose is to improve the yellow image produced by color development.
A yellow coupler with excellent spectral absorption characteristics and a yellow coupler containing this.
To provide a silver halide color photographic light-sensitive material having
It is in. [Means for Solving the Problems] The above objects of the present invention are as follows.
Yellow coupler (1) and silver halide (2)
This is achieved using color photographic materials. (1) Acyl group
is represented by the following general formula (I).
Ruacetamide-type yellow dye-forming coupler. General formula (I) [Formula 2] (wherein, R1 represents a monovalent group, Q together with C,
3-5 membered hydrocarbon ring or selected from N, O, S, P
3-5 membered ring having at least one heteroatom in the ring
Represents a group of nonmetallic atoms necessary to form a heterocycle. However, R1 is not a hydrogen atom, and Q and
They do not combine to form a ring. ) (2) At least one layer of halogen on the support
silver emulsion layer and a yellow dye-forming coupler.
In silver halide color photographic materials, the yellow color
At least one of the elementary-forming couplers is yellow as described in item 1.
Silver halide characterized by being a dye-forming coupler
Color photographic material. [0012] Below, the acylacetamide type i
I will explain the yellow coupler in detail. The reed of the present invention
The ruacetamide type yellow coupler is preferably one of the following:
It is represented by general formula (II). Formula (II) [Formula (II), R1 and Q are each represented by
are the same as R1 and Q, and R' and R'' are respectively
Each independently represents a hydrogen atom, an alkyl group, an aryl group, or a hetero
Represents a ring group. Here, R' and R'' are combined with each other and N
They may form a ring together. X is a hydrogen atom or
Indicates a coupling-off group. ) Acylacetamide type yellow pigment of the present invention
The puller is more preferably represented by the following general formula (Y).
be done. [0015] Formula (Y) [0016] In formula (Y), R1 is a monovalent group other than hydrogen.
Q is a 3- to 5-membered hydrocarbon ring or
At least one heterogen selected from N, S, O, P
necessary to form a 3- to 5-membered heterocycle containing a child in the ring.
R2 is a hydrogen atom, a halogen atom (F
, Cl, Br, I. The same applies to the description of formula (Y) below. ), alkoxy group, aryloxy group, alkyl group or
an amino group, R3 is a group that can be substituted on the benzene ring,
X is a hydrogen atom or an oxidized product of an aromatic primary amine developer
A group that can be separated by a coupling reaction (hereinafter referred to as a leaving group)
), and l represents an integer from 0 to 4, respectively. just
When there are multiple R3s, the R3s may be the same or different.
Good too. [0017] Here, as an example of R3, a halogen atom,
Alkyl group, aryl group, alkoxy group, arylox
cy group, alkoxycarbonyl group, aryloxycarbo
Nyl group, carbonamide group, sulfonamide group, carba
Moyl group, sulfamoyl group, alkylsulfonyl group,
Ureido group, sulfamoylamino group, alkoxylic
Bonylamino group, alkoxysulfonyl group, nitro group,
Heterocyclic group, cyano group, acyl group, acyloxy group, alkyl
Kylsulfonyloxy group, arylsulfonyloxy group
An example of a leaving group is a nitrogen atom with coupling activity.
Heterocyclic group, aryloxy group, aryl group bonded to
o group, acyloxy group, alkylsulfonyloxy group,
Arylsulfonyloxy group, heterocyclic oxy group, halogen
There is an atom. [0018] When the substituent in formula (Y) is an alkyl group,
or contains an alkyl group, unless otherwise specified.
The alkyl group can be linear, branched or cyclic, substituted.
an alkyl group that may contain unsaturated bonds even if
(e.g. methyl, isopropyl, t-butyl, cyclo
Pentyl, t-pentyl, cyclohexyl, 2-ethyl
hexyl, 1,1,3,3-tetramethylbutyl, dode
syl, hexadecyl, allyl, 3-cyclohexenyl,
Oleyl, benzyl, trifluoromethyl, hydroxy
Methylmethoxyethyl, ethoxycarbonylmethyl, fluoride
phenoxyethyl). [0019] The substituent in formula (Y) is an aryl group.
or contains an aryl group, unless otherwise specified.
The aryl group is an optionally substituted monocyclic or fused ring.
aryl groups (e.g. phenyl, 1-naphthyl, p-t)
Lyle, o-tolyl, p-chlorophenyl, 4-methoxy
Phenyl, 8-quinolyl, 4-hexadecyloxyphene
nil, pentafluorophenyl, p-hydroxyphenyl
p-cyanophenyl, 3-pentadecylphenyl,
2,4-di-t-pentylphenyl, p-methanesulfonate
(3,4-dichlorophenyl)
do. [0020] The substituent in formula (Y) is a heterocyclic group or
or a heterocyclic group, unless otherwise specified, the heterocyclic group
is at least selected from O, N, S, P, Se, Te.
3- to 8-membered substituted ring containing one heteroatom
Good monocyclic or fused ring heterocyclic groups (e.g. 2-fur
2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1
-imidazolyl, 1-benzotriazolyl, 2-benzo
triariazolyl, succinimide, phthalimide, 1
-benzyl-2,4-imidazolidinedione-3-yl
) means. [0021] Hereinafter, preferably used in formula (Y)
The substituents are explained below. In formula (Y), R1 is
Preferably a halogen atom, a cyano group, or both
Total number of carbon atoms that may be substituted (hereinafter abbreviated as C number) 1 to 3
0 monovalent groups (e.g. alkyl groups, alkoxy groups) or
is a monovalent group having 6 to 30 carbon atoms (e.g. aryl group, aryl group,
(aloxy group), and its substituents include, for example, halo
Gen atom, alkyl group, alkoxy group, nitro group, amino
- group, carbonamide group, sulfonamide group, acyl group
There is. R1 may be a so-called ballast group. In formula (Y), Q is preferably together with C.
Any of 3 to 5 members may be substituted with C number 3 to 3
0 hydrocarbon rings or at least one N, S, O, P
A complex having 2 to 30 carbon atoms containing a heteroatom selected from
Represents a group of nonmetallic atoms necessary to form a ring. Also,
Even if the ring formed by Q and C contains an unsaturated bond within the ring,
good. Cyclopropane is an example of a ring formed by Q together with C.
ring, cyclobutane ring, cyclopentane ring, cycloprope
ring, cyclobutene ring, cyclopentene ring, oxetane ring
ring, oxolane ring, 1,3-dioxolane ring, thietane
ring, thiolane ring, and pyrrolidine ring. As an example of a substituent
halogen atom, hydroxyl group, alkyl group, aryl
group, acyl group, alkoxy group, aryloxy group,
Ano group, alkoxycarbonyl group, alkylthio group, a
It has a lylthio group. In formula (Y), R2 is preferably halo
Gen atom, any of which may be substituted, C number 1-3
0 alkoxy group, C6-30 aryloxy group,
C1-30 alkyl group or C0-30 amino
represents a group, and its substituents include, for example, a halogen atom.
children, alkyl groups, alkoxy groups, and aryloxy groups.
Ru. In formula (Y), R3 is preferably H
rogene atom, any of which may be substituted, C number 1-30
Alkyl group, C6-30 aryl group, C1-3
0 alkoxy group, C2-30 alkoxycarbonyl group
group, C7-30 aryloxycarbonyl group, C
Carbon amide group having 1 to 30 carbon atoms, sulfo group having 1 to 30 carbon atoms
amide group, carbamoyl group with 1 to 30 carbon atoms, 0 to 30 carbon atoms
30 sulfamoyl groups, C1-30 alkyl sulfur
Honyl group, C6-30 arylsulfonyl group, C number
1 to 30 ureido group, sulfamoyl having 0 to 30 carbon atoms
Amino group, C2-30 alkoxycarbonylamino
group, C1-30 heterocyclic group, C1-30 acyl group
, C1-30 alkylsulfonyloxy group, C6
~30 arylsulfonyloxy groups;
Examples of substituents include halogen atoms, alkyl groups, and aryl groups.
group, heterocyclic group, alkoxy group, aryloxy group,
Heterocyclic oxy group, alkylthio group, arylthio group,
Barocyclic thio group, alkylsulfonyl group, arylsulfony group
group, acyl group, carbonamide group, sulfonamide group
, carbamoyl group, sulfamoyl group, alkoxylic
Bonylamino group, sulfamoylamino group, ureido group
, cyano group, nitro group, acyloxy group, alkoxy group
Rubonyl group, aryloxycarbonyl group, alkyl group
Contains sulfonyloxy group and arylsulfonyloxy group
. In formula (Y), l is preferably 1 or
represents an integer of 2, and the substitution position of R3 is preferably the meta or para position with respect to [Image Omitted]. In formula (Y)
and X is preferably a nitrogen atom in the coupling active position.
Represents a bonding heterocyclic group or aryloxy group. When X represents a heterocyclic group, X is preferably
is a 5- to 7-membered monocyclic or fused ring which may be substituted
is a heterocyclic group such as succinimide,
rheinimide, phthalimide, diglycolimide, pi
role, pyrazole, imidazole, 1,2,4-tri
Azole, tetrazole, indole, indazole,
Benzimidazole, benzotriazole, imidazoli
Dine-2,4-dione, oxazolidine-2,4-dio
thiazolidine-2,4-dione, imidazolidine-
2-one, oxazolidin-2-one, thiazolidine-
2-one, benzimidazolin-2-one, benziox
sazolin-2-one, benzothiazolin-2-one, 2
-pyrrolin-5-one, 2-imidazolin-5-one,
Indoline-2,3-dione, 2,6-dioxypurine
, parabanic acid, 1,2,4-triazolidine-3,5-
Dione, 2-pyridone, 4-pyridone, 2-pyrimidone
, 6-pyridazone-2-pyrazone, 2-amino-1,3
, 4-thiazolidine, 2-imino-1,3,4-thiazo
lysin-4-one, etc., and these heterocycles are substituted.
You can leave it there. Examples of these heterocyclic substituents include:
Halogen atom, hydroxyl group, nitro group, cyano group,
carboxyl group, sulfo group, alkyl group, aryl group,
Alkoxy group, aryloxy group, alkylthio group,
Rylthio group, alkylsulfonyl group, arylsulfonyl group
Nyl group, alkoxycarbonyl group, aryloxycar
Bonyl group, acyl group, acyloxy group, amino group, carbonyl group,
Bonamide group, sulfonamide group, carbamoyl group,
Rufamoyl group, ureido group, alkoxycarbonyl group
There are mino groups and sulfamoylamino groups. X is aryl
When representing an oxy group, X preferably has 6 to 30 carbon atoms.
represents an aryloxy group, and when the above X is a heterocycle
may be substituted with a group selected from the substituent groups listed in
stomach. As a substituent for the aryloxy group, a halogen atom
, cyano group, nitro group, carboxyl group, trifluoro
Methyl group, alkoxycarbonyl group, carbonamide group
, sulfonamide group, carbamoyl group, sulfamoyl
group, alkylsulfonyl group, arylsulfonyl group, or
or cyano group is preferred. Next, particularly preferably used in formula (Y)
The following substituents are explained below. R1 is particularly preferably
is a halogen atom or an alkyl group, most preferably
It is a methyl group. Q is particularly preferably a ring formed together with C.
is a group of non-metals that form a 3- to 5-membered hydrocarbon ring, e.g.
For example, [Chemical 6]. R represents a halogen atom, hydrogen atom, or alkyl group
(However, multiple Rs may be the same or different.) Q most preferably forms a three-membered ring together with C. [Chemical 7] R2 is particularly preferably a chlorine atom or a fluorine atom.
elementary atoms, C1-6 alkyl groups (e.g. methyl,
Lifluoromethyl, ethyl, isopropyl, t-butyl
), C1-8 alkoxy groups (e.g. methoxy, ethoxy
(oxy, methoxyethoxy, butoxy), or C number 6~
24 aryloxy groups (e.g. phenoxy group, p-to
(lyloxy, p-methoxyphenoxy) and the most preferred
or chlorine atom, methoxy group or trifluoromethyl
It is the basis. R3 is particularly preferably a halogen atom
, alkoxy group, alkoxycarbonyl group, aryl group
Oxycarbonyl group, carbonamide group, sulfonamide
group, carbamoyl group or sulfamoyl group and most
Preferably an alkoxy group, an alkoxycarbonyl group, or a carbonyl group.
It is a carbonamide group or a sulfonamide group. [0030] X is particularly preferably represented by the following formula (Y-1) or
It is a group represented by (Y-2). Formula (Y-1) In formula (Y-1), Z represents the following formula. where R4, R5, R8, and R9
is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group
, aryloxy group, alkylthio group, arylthio group
, alkylsulfonyl group, arylsulfonyl group or
represents an amino group, R6 and R7 are hydrogen atoms,
alkyl group, aryl group, alkylsulfonyl group, aryl group, aryl group, alkyl sulfonyl group, aryl group,
Represents a sulfonyl group or an alkoxycarbonyl group.
, R10 and R11 are hydrogen atoms, alkyl groups or alkyl groups.
Represents a lyl group. R10 and R11 are combined with each other to form a base.
A ring may be formed. R4 and R5, R5 and
R6, R6 and R7 or R4 and R8 are connected to each other.
Combined to form a ring (e.g. cyclobutane, cyclohexane, cyclo
loheptane, cyclohexene, pyrrolidine, piperidine
) may be formed. Among the heterocyclic groups represented by formula (Y-1),
Particularly preferred is the formula (Y-1) in which Z is [Chemical formula 1
0] is a heterocyclic group. Complex represented by formula (Y-1)
The number of carbon atoms in the ring group is 2 to 30, preferably 4 to 20, more preferably
Preferably it is 5-16. [0034] Formula (Y-2) [Image Omitted] In formula (Y-2), R12 and R1
At least one of 3 is a halogen atom, a cyano group, or a nitro group.
group, trifluoromethyl group, carboxyl group, alkoxy group
Cycarbonyl group, carbonamide group, sulfonamide group
, carbamoyl group, sulfamoyl group, alkyl sulfo
Selected from nyl group, arylsulfonyl group or acyl group
and the other is a hydrogen atom, an alkyl group, or
It may also be an alkoxy group. R14 is R12 or R
Represents a group with the same meaning as 13, and m represents an integer from 0 to 2.
. The number of carbon atoms in the aryloxy group represented by formula (Y-2) is
6-30 preferably 6-24, more preferably 6-1
It is 5. The coupler represented by formula (Y) has a substituent
Dimers or
or more multimers may be formed. In this case, before
If the number of carbon atoms is outside the specified range for each substituent,
It's okay to be. Specifics of each substituent in formula (Y) are shown below.
Give an example. ■Examples of the [Formula 13] group formed by R1 and Q together with C are shown below. [Formula 14] [Formula 15] [Formula 15] [Formula 16] [Formula 17] [Formula 17] [Formula 18] [Formula 18] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] [Chemical 28] [Chemical 29] [Chemical 29] [Chemical 30] [Chemical 30] [Chemical 31] [Chemical 32] [Chemical 32] [0056] [Chemical 33] [Chemical 34] [Chemical 34] [0058] 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 embedded image embedded image 49] [Chemical 50] [Chemical 50] [Chemical 51] [Chemical 52] [Chemical 52] [Chemical 52] [Chemical 53] [Chemical 54] [Chemical 54] [0078] The compounds of the present invention represented by the formula (Y) Yellow mosquito
Puller can be synthesized by the following synthetic route. ##STR55## Here, compound a is described in J. Chem. Soc.
．． (C), 1968, 2548, J. Am. Chem.
Soc. , 1934, 56, 2710, Synthes
is, 1971, 258, J. Org. Chem. ,1
978, 43, 1729, CA, 1960, 66, 18
It is synthesized by the method described in 533y et al. Compound b was synthesized using thionyl chloride, oxali
Solvent-free or methylene chloride using dichlorochloride etc.
, chloroform, carbon tetrachloride, dichloroethane, toluene
N,N-dimethylformamide, N,N-dimethyl
Performed by reaction in a solvent such as acetamide
. The reaction temperature is usually -20°C to 150°C, preferably -1
It is 0°C to 80°C. Compound c converts ethyl acetoacetate into magnesium
Make an anion using mumethoxide etc. and add b into it.
It is synthesized by adding. The reaction can be carried out without solvent or with
Reaction temperature using trahydrofuran, ethyl ether, etc.
is usually -20°C to 60°C, preferably -10°C to 30°C
It is. Compound d is compound c and ammonia as base
Water, NaHCO3 aqueous solution, sodium hydroxide aqueous solution, etc.
with no solvent or methanol, ethanol, acetic acid.
Synthesized by reaction in a solvent such as tonitrile
It will be done. The reaction temperature is usually -20°C to 50°C, preferably -
The temperature is 10°C to 30°C. Compound e is obtained by reacting compounds d and g without a solvent.
It is synthesized by The reaction temperature is usually 100~
The temperature is 150°C, preferably 100 to 120°C. X
is not H, the leaving group X after chlorination or bromination
and synthesize compound f. Compound e is dichloroethane
carbon, carbon tetrachloride, chloroform, methylene chloride, tetra
Sulfuryl chloride, N-chloro in a solvent such as hydrofuran
Either chloro-substituted with succinimide, etc., or bromine,
Bromo-substituted product with N-bromosuccinimide etc.
. At this time, the reaction temperature is -20°C to 70°C, preferably -
The temperature is 10°C to 50°C. Next, the chloro- or bromo-substituted product is separated.
The deradical proton adduct H-X and methylene chloride, chloro
Form, tetrahydrofuran, acetone, acetonitrile
dioxane, N-methylpyrrolidone, N,N'-di
Methylimidazolidin-2-one, N,N-dimethylphos
In solvents such as lumamide, N,N-dimethylacetamide, etc.
, reaction temperature -20°C to 150°C, preferably -10°C to
By reacting at 100°C, the coupler f of the present invention
can be obtained. At this time, triethylamine, N-
Ethylmorpholine, tetramethylguanidine, potassium carbonate
Bases such as um, sodium hydroxide, sodium bicarbonate, etc.
may also be used. Examples of the synthesis of the couplers of the present invention are shown below. Synthesis Example 1 Synthesis of Exemplary Compound Y-30 Gotkis,
D. etal, J. Am. Chem. Soc. ,193
1 synthesized by the method described in 4,56,2710
- 25 g of methylcyclopropanecarboxylic acid, methylene chloride
100 ml of N,N-dimethylformamide, 1 ml of N,N-dimethylformamide
Add 38.1 g of oxalyl chloride to the mixture at room temperature.
The solution was added dropwise over 30 minutes. After dropping, react at room temperature for 2 hours.
Aspirator methylene chloride under vacuum, excess oxalyl
1-Methylcyclopropyropropylene by removing the chloride
An oil of pancarbonyl chloride was obtained. A mixture of 6 g of magnesium and 2 ml of carbon tetrachloride
Pour 100ml of methanol into the mixture at room temperature for 30 minutes.
After heating and refluxing for 2 hours, 3-oxobutane
Add 32.6 g of ethyl chloride dropwise over 30 minutes while heating under reflux.
do. After dropping, heat under reflux for another 2 hours to remove methanol.
Completely distill off under reduced pressure using a pyrator. Tetrahydrofuran
Add 100 ml to the reaction mixture and disperse at room temperature.
Add 1-methylcyclopropanecarbonyl chloride dropwise
do. After reacting for 30 minutes, the reaction solution was mixed with 300 ml of ethyl acetate,
Extract with dilute sulfuric acid water, wash with water, and then add the organic layer to anhydrous sodium sulfate.
After drying, the solvent was distilled off to give 2-(1-methylcyclopropylene).
Oil of ethyl pancarbonyl-3-oxobutanoate
55.3g was obtained. 2-(1-methylcyclopropanecarbonyl)
55 g of ethyl)-3-oxobutanoate, 1 ethanol
Stir 60 ml of the solution at room temperature and add 30% ammonia into it.
Add 60 ml of water dropwise over 10 minutes. 1 hour after that
Stir, extract with 300 ml of ethyl acetate and diluted hydrochloric acid, and neutralize.
, After washing with water, dry the organic layer with anhydrous sodium sulfate and remove the solvent.
(1-methylcyclopropanecarbonyl) vinegar by distilling off
43 g of ethyl acid oil was obtained. (1-methylcyclopropanecarbonyl)
34 g of ethyl acetate and N-(3-amino-4-chlorophene)
Nyl)-2-(2,4-di-t-pentylphenoxy)
Add 44.5 g of butanamide at an internal temperature of 100 to 120°C.
Heat to reflux under vacuum using a spirator. Reaction solution after 4 hours reaction
column chromatography using a mixed solvent of n-hexane and ethyl acetate.
49g of Exemplified Compound Y-30 was purified from tomatoes and turned into a viscous oil.
obtained as. The structure of the compound is determined by MS spectrum, NMR
Confirmed by spectrum and elemental analysis. Synthesis Example 2 Synthesis of Exemplified Compound Y-1 22.8 g of Exemplified Compound Y-30 was mixed with 30 g of methylene chloride.
Dissolve 5.4 g of sulfuryl chloride in 0 ml and cool on ice for 10 minutes.
Drip over time. After reacting for 30 minutes, wash the reaction solution thoroughly with water.
After drying over anhydrous sodium sulfate, it was concentrated to obtain Exemplified Compound Y-3.
0 chloride was obtained. 1-benzyl-5-ethoxyhydan
Toin 18.7g, triethylamine 11.2ml, N
, N-dimethylformamide in a solution of 50 ml first.
The chloride of the synthesized exemplary compound Y-30 was converted into N,N-dimethylene.
Dissolved in 50ml of formaldehyde for 30 minutes.
Add dropwise at room temperature. After reaction at 40°C for 4 hours, the reaction solution was
Extract with 300 ml of ethyl acetate, wash with water, and add 2% triethyl acetate.
Wash with 300 ml of Min aqueous solution, then with dilute hydrochloric acid water.
Neutralize. After drying the organic layer with anhydrous sodium sulfate,
The oil obtained by distilling off the solvent was diluted with n-hexane and ethyl acetate.
It was crystallized from a mixed solvent of The precipitated crystals were filtered and n-
Wash with a mixed solvent of hexane and ethyl acetate, then dry.
22.8 g of crystals of Exemplified Compound Y-1 were obtained. transformation
The structure of the compound is determined by MS spectrum, NMR spectrum, and elements.
Confirmed by analysis. The melting point is 132-133℃.
It was. Synthesis Example 3 Synthesis of Exemplary Compound Y-43 Cyclohexyl
Organic Synthe using alcohol as raw material
Synthesized by the method described in Ses, Vol 46, 72
32 g of 1-methylcyclopentanecarboxylic acid was synthesized.
Instead of 1-methylcyclopropanecarboxylic acid in Example 1
Using the same procedure as in Synthesis Example 1, N-
2-chloro-5-(2-(2,4-di-t-pentylph)
phenoxy)butanamido)phenyl]-2-(1-methy
Add 50 g of (cyclopentane carbonyl) acetamide to the
Obtained as amorphous material. Then this N-[2-chloro
Rho-5-(2-(2,4-di-t-pentylphenoxy)
)butanamido)phenyl]-2-(1-methylcyclo
Synthesis example of 23.9g of pentanecarbonyl)acetamide
Using the same reaction mixture as a raw material instead of Exemplified Compound 30 in 2.
After the treatment, the obtained oil was mixed with n-hexane,
Illustrated by column chromatographic purification using a mixed solvent of ethyl acetate.
26.5 g of compound Y-43 was obtained as a viscous oil. The structure of the compound is determined by MS spectrum, NMR spectrum and
This was confirmed by elemental analysis. Obtained from exemplified compound Y-31 of the present invention
Obtained from dye A and pivaloylacetanilide type coupler
Spectral absorption spectrum and fraction of dye B in ethyl acetate
The extinction coefficients were compared. Dye A has better spectroscopy than dye B
Shows absorption spectral characteristics and approximately 30% higher molecular extinction coefficient.
(Figure 1). ##STR56## The method of the present invention uses a color developer.
It can be applied to any treatment process. for example
Color paper, color reversal paper, color positive
color negative film, color reversal film, color
- Can be applied to the processing of direct positive photosensitive materials, etc.
. The silver halide emulsion of the light-sensitive material used in the present invention is
Any halogen such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride, etc.
It can also be used with a composition of The halogen composition of the emulsion differs between grains.
However, the halogen composition between particles must be the same.
When using emulsions with
is easy. In addition, halogens inside silver halide emulsion grains
Regarding the gene composition distribution, which part of the silver halide grain is
Particles with a so-called uniform structure that have very equal composition,
The core inside the silver halide grain and the surrounding core
The difference in halogen composition between the shell (single layer or multiple layers)
Particles with a so-called layered structure, or inside particles
has a non-layered surface with different halogen compositions.
Structure (if it is on the particle surface, the edges and corners of the particle)
particles with a structure in which parts of different compositions are joined on a surface)
can be selected and used as appropriate. To obtain high sensitivity
, it is better to use either of the latter two than particles with a homogeneous structure.
is advantageous, and is also preferable from the viewpoint of pressure resistance. Halogen
When the silver oxide grains have the above-mentioned structure, halogen
The boundary between parts with different gene compositions is a clear boundary.
Even if there is, a mixed crystal is formed due to the composition difference and the boundary is unclear.
It is okay to have continuous structural changes.
It may be something that The halogen composition depends on the type of photosensitive material to which it is applied.
For example, prints such as color paper, etc.
Silver chlorobromide emulsions are mainly used as lint materials.
- In photographic materials such as negatives, iodobromide is the main
A silver emulsion system is used. In addition, photosensitive materials suitable for rapid processing
A so-called high-silver chloride emulsion with a high silver chloride content is preferred as a material.
commonly used. The silver chloride content of these high silver chloride emulsions is
90 mol% or more is preferable, and 95 mol% or more is more preferable.
Delicious. In such high silver chloride emulsions, silver bromide
The halogen phase can be layered or non-layered as mentioned above.
It is preferable to have a structure inside and/or on the surface of the silver grain.
Delicious. The halogen composition of the above localized phase depends on the silver bromide content.
preferably at least 10 mol%, preferably 20 mol%
More preferably, it exceeds 1%. And these stations
The existing phase is inside the particle, on the edge, corner or on the particle surface.
can be on a surface, but as one preferred example
, those with epitaxial growth on the corners of the particles are listed.
can be given. Average of silver halide grains used in the present invention
Particle size (in the case of spherical or near-spherical particles, the particle size
For cubic particles, the edge length is the particle size.
It is expressed as an average based on the projected area. Also for average particles
Expressed in ball terms. ) is 2μm or less and 0.1μm or more
Although preferred, particularly preferred is 1.5 μm or less and 0.1
It is 5 μm or more. Particle size distribution can be narrow or wide
Either is fine, but depending on the grain size distribution curve of the silver halide emulsion
The standard deviation value divided by the average particle size (rate of variation)
) is within 20%, particularly preferably within 15%.
Monodisperse silver halide emulsions are preferably used in the present invention.
Yes. In addition, in order to satisfy the target gradation of photosensitive materials,
grains in the emulsion layer having substantially the same color sensitivity.
Two or more types of monodispersed silver halide emulsions with different sizes (monodispersed silver halide emulsions)
As for dispersibility, it is preferable to have the above-mentioned fluctuation rate)
can be mixed in the same layer or applied in separate layers.
. Furthermore, two or more types of polydisperse silver halide emulsions or single
Mixing or layering combinations of dispersed emulsions and polydispersed emulsions
It can also be used as [0101] The shape of the silver halide grains used in the present invention is
Regular shapes such as cubes, octahedrons, rhombidodecahedrons, and dodecahedrons
(regular) having a crystalline substance or
It may be a coexistence of these, or it may have a spherical shape or other irregularities.
Even those with irregular crystalline bodies
It may also have a composite form of these crystal forms.
. Also, tabular grains may be used. Silver halide photographic emulsion that can be used in the present invention
For example, Research Disclosure (RD) No.
．． 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types)” and the same No. 187
16 (November 1979), p. 648, by Grafkide, “
"Physics and Chemistry of Photography", published by Paul Montell (P.Gla.
fkides, Chemie et Physiqu
e Photographique, Paul Mo
Ntel, 1967), Duffin, “Photographic Emulsion Chemistry”
”, Focal Press (G.F. Duffin)
, Photographic Emulsion C
hemistry (Focal Press, 196
6)), “Production and Coating of Photographic Emulsions” by Zelikman et al.
Published by Local Press (V. L. Zelikman
et al. , Making and Coatin
g Photographic Emulsion,
Focal Press, 1964) etc.
It can be prepared using the same method. [0103] US Pat. No. 3,574,628, 3,
655,394 and British Patent No. 1,413,748
Monodisperse emulsions described in et al. are also preferred. Also, aspen
Tabular grains having an ect ratio of about 5 or more can also be used in the present invention.
Can be used. Tabular grains are described by Gatoff, Photography.
Guto Science and Engineering
ff, Photographic Science
and Engineering), Volume 14, 248
~257 pages (1970); U.S. Patent No. 4,434,2
No. 26, No. 4,414,310, No. 4,433,04
No. 8, No. 4,439,520 and British Patent No. 2,11
It can be easily prepared by the method described in No. 2,157 etc.
I can do that. [0104] Even if the crystal structure is uniform, there are internal and external parts.
may be composed of different halogen compositions, and have a layered structure.
It may also be formed by epitaxial bonding.
Silver halides of different compositions may be bonded together,
In addition, other than silver halides, such as Rodan silver and lead oxide,
It may be conjugated with a compound. Also, grains of various crystal shapes
Mixtures of children may also be used. Silver halide emulsions are usually subjected to physical ripening, chemical
Use those that have been subjected to chemical ripening and spectral sensitization. like this
The additives used in this process are listed in the research disk mentioned above.
Roger No. 17643 and the same No. in 18716
The relevant sections are summarized in the table below. Known photographic additives that can be used in the present invention
As stated in the above two research disclosures,
The relevant information is shown in the table below. Additive type R
D17643 RD18716
1 Chemical sensitizer
23 pages
Page 648 right column
2 Sensitivity enhancer
same
Top 3 Spectral sensitizer,
Supersensitizer pages 23-24 6
Page 48 right column to page 649 right column 4 Brightener
24
page
5 Antifoggants and stabilizers
pages 24-25 64
Page 9 right column 6 Light absorber,
Filter dyeing pages 25-26
Page 649 right column to page 650 left column Price, purple
External ray absorber 7 Anti-stain agent
Page 25 right column Page 650 left column to right column
8 Dye image stabilizer
25 pages
9 hard
Film agent
Page 26 Page 651 Left column
10 Binder
26 pages
Same as above 1
1 Plasticizer, lubricant
Page 27 Page 650 Right column
12 Coating aids, surfactants
pages 26-27
Same as above 13 Static inhibitor
Page 27 Same
Above: Photographs taken with formaldehyde gas
To prevent performance degradation, U.S. Patent No. 4,411,
987 and 4,435,503.
Compounds that can be immobilized by reacting with maldehyde are used as photosensitive materials.
It is preferable to add it to the ingredients. This invention is available in various colors.
Couplers can be used, examples of which are given in the previous reference.
Search Disclosure (RD) No. 17643
, described in the patents listed in VII-C to G
. [0108] Ingredients that can be used in combination with the yellow coupler of the present invention
As a yellow coupler, for example, U.S. Pat. No. 3,933
, No. 501, No. 4,022,620, No. 4,32
No. 6,024, No. 4,401,752, No. 4,2
No. 48,961, Special Publication No. 58-10739, British Patent
No. 1,425,020, No. 1,476,760,
U.S. Patent No. 3,973,968, U.S. Patent No. 4,314,0
No. 23, No. 4,511,649, European Patent No. 249
, No. 473A, etc., and contains 50 mol% or less
Can be used together. 5-pyrazolone as magenta coupler
and pyrazoloazole compounds are preferred;
Permit No. 4,310,619, No. 4,351,897
, European Patent No. 73,636, US Patent No. 3,061,
No. 432, No. 3,725,067, Research D.
Closer No. 24220 (June 1984),
JP-A-60-33552, Research Disclosure
Char No. 24230 (June 1984), Japanese Patent Application Publication No. 1986
-43659, 61-72238, 60-35
No. 730, No. 55-118034, No. 60-1859
No. 51, U.S. Patent No. 4,500,630, U.S. Patent No. 4,5
No. 40,654, No. 4,556,630, International Publication
Particularly preferred are those described in WO88/04795 etc.
. As cyan couplers, phenolic and
U.S. Patent No. 4,0
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2
, No. 369,929, No. 2,801,171, No. 369,929, No. 2,801,171, No.
No. 2,772,162, No. 2,895,826, No. 2,895,826, No. 2,895,826, No.
No. 3,772,002, No. 3,758,308,
Same No. 4,334,011, Same No. 4,327,173
, West German Patent Publication No. 3,329,729, European Patent No. 1
No. 21,365A, No. 249,453A, U.S. Patent
No. 3,446,622, No. 4,333,999,
Same No. 4,775,616, Same No. 4,451,559
, No. 4,427,767, No. 4,690,889
No. 4,254,212, No. 4,296,19
No. 9, JP-A No. 61-42658, etc. are preferred.
Yes. [0111] Color for correcting unnecessary absorption of coloring dye
The code coupler is Research Disclosure No.
．． Section VII-G of 17643, U.S. Patent No. 4,163
, No. 670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4
, No. 004,929, No. 4,138,258, United Kingdom
Preferred are those described in Patent No. 1,146,368. Also, the cup described in U.S. Pat. No. 4,774,181
The fluorescent dye released during the ring eliminates unnecessary absorption of the coloring dye.
A coupler that corrects the loss of energy and U.S. Pat. No. 4,777,12
A dye capable of forming a dye by reacting with a developing agent described in No. 0
Using a coupler with a precursor group as a leaving group
It is also preferable. A cap with suitable coloring pigment diffusibility.
U.S. Pat. No. 4,366,237;
Patent No. 2,125,570, European Patent No. 96,570
, as described in West German Patent (Publication) No. 3,234,533.
is preferable. Typical of polymerized dye-forming couplers
Examples are U.S. Pat. Nos. 3,451,820 and 4,080.
, No. 211, No. 4,367,282, No. 4,40
No. 9,320, No. 4,576,910, British Patent 2
, No. 102, 137, etc. Photographically useful residues associated with coupling
Couplers that release
. DIR couplers that release development inhibitors are the aforementioned RD
17643, patent listed in Section VII-F, JP-A-Sho
No. 57-151944, No. 57-154234, No. 6
No. 0-184248, No. 63-37346, No. 63-
No. 37350, U.S. Pat. No. 4,248,962, U.S. Pat.
, 782,012 is preferred. Nucleating agent or development accelerator in image form during development
As a coupler that releases an agent, British Patent No. 2,097
, No. 140, No. 2,131,188, JP-A-59-
Those described in No. 157638 and No. 59-170840
is preferred. Other materials that can be used in the photosensitive material of the present invention
A possible coupler is U.S. Patent No. 4,130,42.
Competitive couplers such as those described in U.S. Pat. No. 4,283, et al.
No. 472, No. 4,338,393, No. 4,310
, 618, etc., JP-A-60-1
D described in No. 85950, JP-A No. 62-24252, etc.
IR redox compound releasing coupler, DIR coupler releasing
Out coupler, DIR coupler releasing redox compound
DIR redox releasing redox compound, European patent
Described in No. 173,302A and No. 313,308A
R. D. N
o. 11449, same No. 24241, JP-A-61-2
Bleach accelerator releasing couplers described in US Pat. No. 01247, etc.
The ligand release mechanism described in Patent No. 4,553,477 etc.
Leuco dye described in JP-A No. 63-75747
U.S. Pat. No. 4,774,181
Examples include couplers that emit fluorescent dyes as described in . [0116] The couplers used in the present invention include various known couplers.
It can be introduced into photosensitive materials by a dispersion method. Oil droplet dispersion method
Examples of high boiling point organic solvents used in
No. 2,027, etc. In addition, polymer content
The process, effects, and implications of latex dispersion as one of the dispersion methods
Specific examples of latex for dipping are shown in U.S. Patent No. 4,199,
No. 363, West German Patent Application (OLS) No. 2,541,27
No. 4 and No. 2,541,230, etc., organic solvents can be used.
For dispersion methods using soluble polymers, see PCT Application No. J
It is described in the specification of P87/00492. [0117] The organic solvent used in the above-mentioned oil-in-water dispersion method
As a medium, for example, phthalic acid alkyl ester (dibutyl ester)
tylphthalate, dioctyl phthalate, etc.)
Stell (diphenyl phosphate, triphenyl phosphate)
Sphate, tricresyl phosphate, dioctyl
butyl phosphate), citric acid esters (e.g.
cetyl tributyl citrate), benzoic acid ester (e.g.
octyl benzoate), alkylamides (e.g. diethyl amide),
fatty acid esters (e.g. dibutylamide), fatty acid esters (e.g.
xyethyl succinate, diethyl azelate), tri
Mesinate esters (e.g. tributyl trimesate)
or an organic solvent with a boiling point of about 30°C to 150°C, e.g.
Lower alkyl acetates such as ethyl acetate and butyl acetate
ethyl propionate, secondary butyl alcohol, methyl
lysobutyl ketone, β-ethoxyethyl acetate,
Methyl cellosolve acetate or the like may be used in combination. The yellow coupler of the present invention is usually used in
1 x 10-3 mol per mol of silver halide in the layer
1 mol, preferably 1 x 10-2 mol to 8 x 10-1 mol
It can be used within a range of files. Moreover, the coupler of the present invention
- can also be used with other types of yellow couplers.
Ru. The additive layer of the yellow coupler of the present invention can be any halogen.
It may be a silver emulsion layer or a non-photosensitive layer, but preferably
Blue-sensitive silver halide emulsion layer or adjacent non-sensitive layer
It is a photosensitive layer. Used in blue-sensitive silver halide emulsion layer
In this case, the amount of silver is preferably 0.1 to 10 g/m2.
Ru. In addition, when used in a non-photosensitive layer, the present invention
The amount of yellow coupler used is preferably 0.1 to 2 mm.
le/m2. [0119] The standard amount of color coupler used is
0.001 to 2 mol per mol of silver halide
and preferably 0.0 for yellow couplers.
1 to 1.5 mole, 0.003 for magenta coupler
to 1.0 mol, and 0.002 for cyan couplers
The amount is between 1.0 mol and 1.0 mol. [0120] The color photosensitive material of the present invention contains
No. 3-257747, No. 62-272248, and special
1,2-benzisothiae described in Kaihei 1-80941
Zolin-3-one, n-butyl, p-hydroxybenzo
ate, phenol, 4-chloro-3,5-dimethylphthalate
phenol, 2-phenoxyethanol, 2-(4-thia
Various preservatives such as zolyl) benzimidazole or
It is preferable to add a fungicide. [0121] The photographic material used in the present invention is a conventional photographic material.
plastic film (cellulose nitrate,
cellulose acetate, polyethylene terephthalate, etc.),
A flexible support such as paper or a rigid support such as glass
applied to the body. For more information on supports and coating methods, please see
Research Disclosure Volume 176 Item
17643 Section XV (p.27) Section XVII (p.
28) (December 1978 issue). Main departure
Photosensitive materials made using light are used as color fog preventive agents.
, hydroquinone derivatives, aminophenoxy derivatives,
Contains edible acid derivatives, ascorbic acid derivatives, etc.
Good too. [0122] The photosensitive material of the present invention contains various anti-fading agents.
can be used. i.e. cyan, magenta and
As an organic anti-fade agent for yellow and/or yellow images,
Hydroquinones, 6-hydroxychromans, 5-hydro
Roxycoumarans, spirochromans, p-alkoxy
Hinder based on phenols and bisphenols
Dophenols, gallic acid derivatives, methylene dioxybe
enzymes, aminophenols, hindered amines and
and silylation of the phenolic hydroxyl groups of these compounds.
Typical examples are rkylated ether or ester derivatives.
It is mentioned as. Also, (bissalicylaldoxima
g) Nickel complex and (bis-N,N-dialkyl dithi)
(Ocarbamato) Metal complexes such as nickel complexes, etc.
can also be used. Specific examples of organic anti-fade agents are listed in the following patents:
It is stated in the specification. Hydroquinones are disclosed in US Pat. No. 2,360.
, No. 290, No. 2,418,613, No. 2,67
No. 5,314, No. 2,701,197, No. 2,7
No. 28,659, No. 2,732,300, No. 2,
No. 735,765, No. 3,982,944, No. 4
, 430,425, British Patent No. 1,363,921
, U.S. Patent No. 2,710,801, U.S. Patent No. 2,816,
028 etc., 6-hydroxychromans, 5-hydro
Roxycoumarans and spirochromans are covered by U.S. Patent No. 3,
No. 432,300, No. 3,573,050, No. 3
, No. 574,627, No. 3,698,909, No. 3,698,909, No. 3,698,909, No.
No. 3,764,337, JP-A-52-152225, etc.
However, spiroindanes are disclosed in U.S. Patent No. 4,360,58.
No. 9, p-alkoxyphenols are disclosed in U.S. Patent No. 2,
No. 735,765, British Patent No. 2,066,975;
JP 59-10539, JP 57-19765
etc., hindered phenols are disclosed in U.S. Patent No. 3,70.
No. 0,455, JP-A-52-72224, U.S. Patent No.
No. 4,228,235, Special Publication No. 52-6623, etc.
, gallic acid derivatives, methylenedioxybenzenes, amino acids
Nophenols are each covered by U.S. Patent No. 3,457,07.
No. 9, No. 4,332,886, Special Publication No. 56-211
No. 44, etc., and hindered amines are disclosed in U.S. Patent Nos. 3 and 3.
No. 36,135, No. 4,268,593, British Patent
No. 1,326,889, No. 1,354,313,
No. 1,410,846, Special Publication No. 51-1420,
JP-A-58-114036, JP-A No. 59-53846
, No. 59-78344, etc., metal complexes are disclosed in U.S. patents.
No. 4,050,938, No. 4,241,155,
British Patent No. 2,027,731(A) etc.
Are listed. These compounds each correspond to
Usually 5 to 100% by weight of color coupler.
By co-emulsifying with the photosensitive layer and adding it to the photosensitive layer, it is possible to achieve the desired purpose.
can be achieved. Cyan dye image heat and especially light
In order to prevent deterioration due to
UV absorbers can be introduced into the layers on both sides adjacent to this layer.
more effective. [0124] As a UV absorber, substituted with an aryl group
benzotriazole compounds (e.g., U.S. Pat.
, 533,794), 4-thiazolidone
compounds (e.g., U.S. Pat. No. 3,314,794;
3,352,681), benzophenone
Compounds (e.g. those described in JP-A-46-2784)
, cinnamate ester compounds (e.g. U.S. Pat. No. 3,70
No. 5,805 and No. 3,707,375
), butadiene compounds (U.S. Pat. No. 4,045,229
) or benzoxidol compounds
(For example, as described in U.S. Pat. No. 3,700,455)
) can be used. UV-absorbing couplers (e.g.
For example, α-naphthol cyan dye-forming couplers),
A UV-absorbing polymer or the like may also be used. these
The ultraviolet absorber may be mordanted in a particular layer. Among them, benzotriazo substituted with the above aryl group
A metal compound is preferred. [0125] What can be used in the emulsion layer of the light-sensitive material of the present invention?
Gelatin can be used as a binder or protective colloid.
Although it is advantageous to use other hydrophilic colloid monomers,
Can be used with gelatin or gelatin. present invention
Gelatin is processed using acid even if it is lime-treated.
It doesn't matter which one is processed. Made of gelatin
For more information on the law, see Arthur Weiss, The Macromolecule
La Chemistry of Gelatin (Academic)
Press, published in 1964). [0126] Color development used in the development process of the photosensitive material of the present invention
The developer is preferably an aromatic primary amine color developer.
It is an alkaline aqueous solution containing medicine as its main ingredient. This color development
Aminophenol compounds are also useful as image agents.
However, p-phenylenediamine compounds are preferably used.
A typical example is 3-methyl-4-amino-N
, N-diethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline, 3-methane
Thyl-4-amino-N-ethyl-N-β-methanesulfo
amidoethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methoxyethylaniline and these
sulfate, hydrochloride or p-toluenesulfonate of
Can be mentioned. Two or more of these compounds may be used in combination depending on the purpose.
You can also. [0127] The color developing solution contains alkali metal carbonates,
pH buffering agents such as borates or phosphates, bromide salts
, iodide salts, benzimidazoles, benzothiazoles
or development inhibitors such as mercapto compounds or
It generally contains antifoggants and the like. needed again
Depending on hydroxylamine, diethyl hydroxyl
Min, sulfites, hydrazines, phenyl semicarbazi
compounds, triethanolamine, catechol sulfonic acids
, triethylenediamine (1,4-diazabicyclo[2
, 2, 2] octane), various preservatives such as 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, sodium boron hydride
fogging agents such as 1-phenyl-3-pyrazolidone
Auxiliary developing agents, tackifying agents, aminopolycarbohydrates such as
acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonic acid,
Various chelating agents such as sulfonocarboxylic acids,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Ethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid
Acetic acid, hydroxyethyliminodiacetic acid, 1-hydroxy
Ethylidene-1,1-diphosphonic acid, nitrilo-N,N
, N-trimethylenephosphonic acid, ethylenediamine-N
, N, N', N'-tetramethylenephosphonic acid, ethylene
diamine-di(o-hydroxyphenylacetic acid) and its
Representative examples include these salts. [0128] 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
is an aminophenol such as N-methyl-p-aminophenol.
Known black and white developing agents such as nols may be used alone or in combination.
Can be used together. [0129] The pH of these color developing solutions and black and white developing solutions
It is generally between 9 and 12. Also, these developments
The amount of liquid to be refilled depends on the color photographic material being processed.
, generally less than 3 liters per square meter of photosensitive material.
Yes, it is recommended to reduce the bromide ion concentration in the replenisher.
The volume can also be reduced to 500 ml or less. Refill amount
In order to reduce the
It is preferable to prevent liquid evaporation and air oxidation by
Delicious. There are also ways to prevent the accumulation of bromide ions in the developer.
The replenishment amount can also be reduced by using stages. The photographic emulsion layer after color development is usually bleached.
It will be done. Bleaching treatment may be performed simultaneously with fixing treatment (
Bleach-fixing treatment) may be carried out separately. Further processing
In order to speed up the process, a bleach-fixing process is applied after bleaching.
It could even be a law. Furthermore, it is processed in two consecutive bleach-fixing baths.
fixing before bleach-fixing, or
Depending on the purpose, bleaching may be optionally performed after bleach-fixing.
Can be implemented. Examples of bleaching agents include iron(III),
Cobalt (III), chromium (VI), copper (II), etc.
Which polyvalent metal compounds, peracids, quinones, nitro compounds
objects etc. are used. Felician is a typical bleaching agent.
compound; dichromate; iron(III) or cobalt
Organic complex salts of (III), such as ethylenediaminetetraacetic acid
acid, diethylenetriaminepentaacetic acid, cyclohexanedia
Minetetraacetic acid, methyliminodiacetic acid, 1,3-diaminoprol
Ropane tetraacetic acid, glycol ether diamine tetraacetic acid, etc.
Which aminopolycarboxylic acids or citric acid, tartaric acid
, complex salts such as malic acid; persulfates; bromates; permanga
salts; nitrobenzenes, etc. can be used. Of these, ethylenediaminetetraacetate iron(III) complex
Aminopolycarboxylic acid iron (III) complexes including salts
Salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution.
Delicious. In addition, aminopolycarboxylic acid iron(III) complex
Salt is especially useful in both bleach and bleach-fix solutions.
It is. These iron(III) aminopolycarboxylic acids
The pH of bleach or bleach-fix solutions using complex salts is usually 5.5.
~8, but for faster processing, lower pH
It can also be processed with 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. 1
, No. 290,812, JP-A-53-95630, Lisa
Disclosure No. No. 17129 (197
mercapto group or disulfide group described in
Compounds having a do bond; in JP-A-50-140129
Thiazolidine derivatives described; U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; JP-A-58-1623
Iodide salt described in No. 5; West German Patent No. 2,748,430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; Bromide ion
etc. can be used. Among them, mercapto group or disulf
Compounds having a do group are preferable from the viewpoint of having a large promoting effect.
In particular, U.S. Patent No. 3,893,858 and West German Patent No.
No. 1,290,812, described in JP-A No. 53-95630.
The compounds listed above are preferred. Additionally, U.S. Patent No. 4,552
, 834 are also preferred. these bleaching
A promoter may be added to the light-sensitive material. Color feeling for photography
These bleach accelerators are especially useful when bleach-fixing photomaterials.
It is valid. [0132] As a fixing agent, thiosulfate and thiocyanic acid are used.
Salts, thioether compounds, thioureas, large amounts of iodides
Although salts can be mentioned, thiosulfates are generally used.
ammonium thiosulfate is the most widely used
can. Preservatives for bleach-fix solutions include sulfite and bicarbonate.
Sulfates or carbonyl bisulfite adducts are preferred. 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.
(depending on the materials used, such as couplers), usage, and even
Compensation for flushing water temperature, number of flushing tanks (number of stages), countercurrent flow, forward flow, etc.
Can be set in a wide range depending on charging method and various other conditions
. Of these, the number of water washing tanks and water volume in the multi-stage countercurrent method
The relationship between the Journal of the Society
y of Motion Picture and T
elevision Engineers Volume 64,
p. 248-253 (May 1955 issue)
And you can ask for it. According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of flushing water can be significantly reduced,
Due to the increased residence time, bacteria multiplied and produced
Problems such as floating objects adhering to the photosensitive material arise. The present invention
It is difficult to solve such problems in the processing of color photosensitive materials.
As a solution, the cal
How to reduce sium ions and magnesium ions
It can be used very effectively. Also, JP-A-57-
Isothiazolone compounds and cyaben described in No. 8542
Dazoles, salts of chlorinated sodium isocyanurate, etc.
Basic fungicides, other benzotriazole, etc., written by Hiroshi Horiguchi.
“Chemistry of antibacterial and antifungal agents” (1986) Sankyo Publishing, Hygiene Technology
"Sterilization, sterilization, and anti-mold technology of microorganisms" (1982)
“Encyclopedia of Antibacterial and Antifungal Agents” edited by the Society of Industrial Engineers and the Japan Society of Antibacterial and Antifungal Agents (
It is also possible to use the fungicides described in (1986). [0135] Washing water in processing the photosensitive material of the present invention
The pH is 4-9, preferably 5-8. washing with water
Water temperature and water washing time can also be set in various ways depending on the characteristics of the photosensitive material, application, etc.
However, it is generally heated at 15 to 45°C for 20 seconds to 10 minutes, preferably
Preferably, a temperature range of 30 seconds to 5 minutes at 25 to 40°C is selected.
Ru. Furthermore, in the photosensitive material of the present invention, instead of the above-mentioned washing with water,
It is also possible to work directly with a stabilizing solution. like this
In the stabilization treatment, Japanese Patent Application Laid-open No. 57-8543 and No. 5
Publication No. 8-14834 and No. 60-220345
All known methods can be used. In addition, the water washing
Treatment may be followed by further stabilization treatment.
For example, it is used as the final bath for color photosensitive materials for photography.
Stabilized baths containing formalin and surfactants are listed below.
be able to. This stable bath also contains various chelating agents and antifungal agents.
You can also add of the above water washing and/or stabilizing solution.
Overflow liquid from replenishment is used in other processes such as desilvering process.
It can also be reused. [0136] The silver halide color photosensitive material of the present invention has
Contains a color developing agent for the purpose of simplifying and speeding up processing.
It's okay. In order to incorporate various preforms of color developing agents,
Preferably, a cursor is used. For example, U.S. Patent No.
Indoaniline compounds described in No. 342,597;
No. 3,342,599, Research Disclosure
Schiff base formation described in No. 14850 and No. 15159
compound, aldol compound described in No. 13924, U.S. Pat.
Metal complex described in Patent No. 3,719,492, JP-A-53
- List the urethane compounds described in No. 135628
I can do it. The silver halide color photosensitive material of the present invention must be
If necessary, various 1-frames may be added for the purpose of promoting color development.
Phenyl-3-pyrazolidones may also be incorporated. typical
Compounds are disclosed in JP-A-56-64339 and JP-A-57-144.
Described in No. 547 and No. 58-115438, etc.
There is. The various processing solutions used in the present invention are kept at a temperature of 10°C to 50°C.
used. Normally, the standard temperature is between 33°C and 38°C.
However, the process is accelerated by increasing the temperature and the processing time is shortened.
or conversely, lower the temperature to improve image quality and stabilize the processing solution.
Improved sexual performance can be achieved. Also, the section on photosensitive materials
The edge described in West German Patent No. 2,226,770 for silver
treatment using root intensification or hydrogen peroxide intensification.
Good too. [0137] Sulfites and hydroxide are used as preservatives for the processing solution.
Roxylamine and the like can be used. Also, this
Organic preservatives can also be included instead of these preservatives.
. Organic preservatives are processing solutions for color photographic materials.
Aromatic primary amine color developing agent
refers to all organic compounds that reduce the rate of deterioration of That is, Kara
- Has the function of preventing oxidation of the developing agent due to air, etc.
Among them, hydroxylamine-induced
Conductors (excluding hydroxylamines), hydroxamic acids
hydrazines, hydrazides, phenols, α-
Hydroxyketones, α-aminoketones, sugars, mono
Amines, diamines, polyamines, quaternary ammonium
salts, nitroxy radicals, alcohols, oxy
Particularly important are compounds, diamide compounds, and fused amines.
It is an effective organic preservative. These are
No. 96, JP-A-52-143020, JP-A No. 63-423
No. 5, No. 63-30845, No. 63-21647,
No. 63-44655, No. 63-53551, No. 63
-43140, 63-56654, 63-58
No. 346, No. 63-43138, No. 63-14604
No. 1, No. 63-44657, No. 63-44656,
U.S. Patent Nos. 3,615,503 and 2,494,90
No. 3, JP-A No. 1-97953, JP-A No. 1-186939
, No. 1-186940, No. 1-187557, No. 2
-306244, etc. Other preservatives
JP-A-57-44148 and JP-A-57-537
Various metals described in No. 49, JP-A-59-180588
Salicylic acids described in JP-A No. 63-239447,
JP-A-63-128340, JP-A-1-186939
Amines such as those described in No. 1 and No. 1-187557
, alkanolamines described in JP-A-54-3532
, polyethyleneimine described in JP-A No. 56-94349
aromatic polymers described in U.S. Patent No. 3,746,544, etc.
A rehydroxy compound or the like may be used if necessary. Special
Alkanolamines such as triethanolamine
, N,N-diethylhydroxylamine and N,N-di(
Dialkyl such as sulfoethyl) hydroxylamine
Hydroxylamine, N,N-bis(carboxymethyl
) hydrazine derivatives like hydrazine (hydrazine
except. ) or the addition of aromatic polyhydroxy compounds
preferable. In particular, dialkylhydroxylamines and/or
Or using hydrazine derivatives and alkanolamines together
This improves the stability of color developers and improves the stability of color developers.
This is more preferable from the viewpoint of improving stability during continuous processing. [Example] The present invention will be explained in more detail with reference to an example.
. Example 1 Comparative coupler, YC-1 8.25g
Weigh out 30% of trioctyl phosphate as a high-boiling organic solvent.
．． Add 3g and further add 25ml of ethyl acetate to dissolve.
did. Add this solution to 280g of 10% gelatin aqueous solution.
Additionally, 1.0 g of dodecylbenzenesulfonic acid
Sodium was added and emulsified and dispersed. Add salt to this emulsified dispersion.
136g of silver bromide emulsion (silver 65.4g/kg emulsion, silver bromide
70 mol%), and then 10% gelatin aqueous solution 2
30 g and 320 ml of water were added. Finally, as a hardening agent
, 1-oxy-3,5-dichloro-s-triazine
Added 0.8g of thorium, and the amount of coated silver was 0.865g/
Triacetylcellulose primed to m2
Sample 101 was prepared by coating on a film base. At this time, 1.55 g of protective layer was added on top of this coating layer.
/m2 gelatin layer was provided. Comparative couplers, YC-2-6, and the present invention
Coupler is added so that the amount of coupler applied is equimolar.
Samples 102 to 114 were prepared by coating according to the method described above. Next
This is the evaluation method for samples prepared in
Light meter (manufactured by Fuji Photo Film Co., Ltd., FWH type, light source)
Color temperature: 3200°K) for sensitometry
gradation exposure was given. The exposure at this time is 0.1 seconds.
This was done so that the exposure amount was 250 CMS. end of exposure
For completed samples, use the following treatment process and treatment liquid composition.
The film was then processed using an automatic processor. The composition of each treatment liquid is as follows. Color developer water
　　　　　　　　　　　　　　　　　　　　　　　　　
800ml diethylenetri
amine pentaacetic acid
1.0g nit
Lilotriacetic acid
2.0
g benzyl alcohol
　　　　　　　　　　　　　　　　　　　　　　　　　
15ml diethylene glycol
call
10ml
sodium sulfite
2
．． 0g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0g carbonic acid
potassium
　　　　　　　　　　　　　　　　　　　　　　　　　
30g N-ethyl-N-(β-methane
Sulfonamido ethyl)-3-methyl-4-a
Minoaniline sulfate 4.5g
hydroxylamine sulfate
3.
0g Fluorescent brightener (WHITEX 4
B, Sumitomo Chemical) 1.0
g Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH (25
℃)
10.25 0
141] Bleach-fix solution water
　　　　　　　　　　　　　　　　　　　　　　　　　
400ml ammonium thiosulfate
Ni (70%)
150ml sodium sulfite
Rium
18g
Iron(III) ethylenediaminetetraacetate A
Ammonium 55g
Ethylenediaminetetraacetic acid disodium
5g
add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH (2
5℃)
6.70 0
142] Sensitometry of the obtained sample in the blue region
From the curve, calculate its maximum color development Dmax and 1/ of Dmax.
The slope γ of a close game at a density of 2 was read. these
Table 1 shows the table. As is clear from Table 1
, the coupler of the present invention has a significant Dmax compared to the comparative example.
Very big. In addition, the coupler of the present invention has a large γ value and has high activity.
It shows that it is a sexual coupler. In particular, the best of the present invention
Y-1, Y-9, Y-4 are also preferred coupler structures.
7. Y-8 is a coupler with even better performance
I can say that. The following are the models used for comparison in Examples 1 to 9.
The structure of the puller is shown. [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] YC-1 YC-2 Research Disclosure
No. 18053 Compound 14 YC-3 Acyl described in U.S. Patent No. 3,265,506
Base YC-4 Same as above YC-5 Same as above YC-6 Same as above YC-7 Research Disclosure
Magazine No. 18053 Compound 1 YC-8 YC-9 described in JP-A-63-43144
Described in US Pat. No. 3,933,501 [Table 1] Next, the maximum density color was developed in the above sample.
The transmission and absorption spectrum in the film state was measured using
Established. The results are shown in Table 2. Here λmax is
This is the wavelength that gives maximum absorbance. Also Δλ0.5 and
λ0.1 are 1/2 and 1/1 of the maximum concentration, respectively.
The long wavelength that gives a concentration of 0 and the wave that gives a maximum concentration
This is the difference in length. The smaller these values, the more absorption on the long wavelength side.
This shows that the absorption waveform is sharp and favorable for color reproduction.
vinegar. The couplers of the invention are similar to the corresponding comparative couplers.
(with only the acyl moiety replaced) on the shorter wavelength side.
Shows absorption peaks. Also, Δλ0.5 and λ0.1 are
It shows a small value compared to the corresponding comparison coupler. these
The characteristic is that the absorption of undesirable magenta into the yellow area is reduced.
This means that it has favorable characteristics in terms of color reproduction.
I can do it. [0151] From the above, the coupler of the present invention is expensive.
It has activity, high absorbance, and excellent hue.
It can be said that it is a revolutionary coupler. [Table 2] Example 2 The following was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown in Figure 1 was prepared. The coating liquid is
It was prepared as follows. Preparation of first layer coating solution 12.1 g of yellow coupler (YC-1) and
4.4 g of purple image stabilizer (Cpd-1) and color image stabilizer (
Cpd-7) 0.7g with 27.2cc of ethyl acetate and
Add and dissolve 4.8 g of solvent (Solv-3), and this solution
8cc of 10% sodium dodecylbenzenesulfonate
Emulsified and dispersed in 185cc of 10% gelatin aqueous solution containing
Ta. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.88
A 3:7 mixture of μm and 0.70 μm (silver
molar ratio). The coefficient of variation of particle size distribution is 0.08 and 0.08.
10. In each emulsion, 0.2 mol% of silver bromide was localized on the grain surface.
(contains) contains the following blue-sensitive sensitizing dyes per mole of silver.
For size emulsions, 2.0 x 10-4 mol each
In addition, for small size emulsions, 2.5×
After adding 10-4 mol, sulfur sensitization was performed.
Ta. The above emulsified dispersion and this emulsion were mixed and dissolved, and the following
A first layer coating solution was prepared to have the following composition. [0155] The coating solution for the second to seventh layers is also applied as the first layer.
It was prepared in the same way as the liquid. As a gelatin hardening agent for each layer
is 1-oxy-3,5-dichloro-s-triazid
The sodium salt was used. As a spectral sensitizing dye for each layer
I used the one listed below. Blue-sensitive emulsion layer [For large size emulsions, per mole of silver halide]
2.0 x 10-4 mol each, also for small size emulsions
(2.5 x 10-4 mol each) Green-sensitive emulsion layer [Chemical 62] (per mol of silver halide, for large emulsion
4.0 x 10-4 mol, 5.6 for small size emulsions
x 10-4 mol) and [Formula 63] (per mol of silver halide, for large emulsions)
7.0 x 10-5 mol, or 1 for small size emulsions
．． 0x10-5 mol) Red-sensitive emulsion layer [Formula 64] (per mol of silver halide, for large emulsions
0.9 x 10-4 mol, or 1 for small size emulsions
．． 1 x 10-4 mol) [0159] For the red-sensitive emulsion layer, the following compound was added.
Added 2.6 x 10-3 mol per mol of silver halide.
Ta. ##STR65## Also, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer,
For the emulsion layer, 1-(5-methylureidophenyl)-
5-mercaptotetrazole to 1 silver halide each
8.5 x 10-5 mol, 7.7 x 10-4 mol per mole
2.5 x 10-4 mol was added. Irradiation
To prevent this, the following dyes were added to the emulsion layer. [Image Omitted] and [Image Omitted] (Layer structure) The composition of each layer is shown below. numbers
represents the coating amount (g/m2). Silver halide emulsions are silver convertible.
Represents the calculated coating amount. For silver halide emulsions, coating amounts are shown in terms of silver.
Was. Support polyethylene laminate paper [first layer side polyethylene
Contains white pigment (TiO2) and blue dye (ulmarine)]
First layer (blue-sensitive layer) The silver chlorobromide emulsion
0.
30 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.86
Yellow coupler (YC-1)
0.52
Color image stabilizer (Cpd-1)
0.1
9 Solvent (Solv-3)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.21 Color image stabilizer (
Cpd-7)
0.06 0166 Second layer (color mixing prevention layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.99 Color mixing prevention agent (Cpd
-5)
0.08 Solvent (
Solv-1)
0.16
Solvent (Solv-4)
0
．． 08 [0167] Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ
1:3 mixture of 0.39μm and 0.39μm
Compound (Ag molar ratio). Variation coefficient of particle size distribution
The numbers are 0.10 and 0.08, each emulsion is AgBr.
0.8 mol% was locally contained on the particle surface.
) 0.12
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.24 Magenta coupler (ExM)
0.2
0 Color image stabilizer (Cpd-2)
0.03
Color image stabilizer (Cpd-3)
0.15 color
Image stabilizer (Cpd-4)
0.02 Color image stability
Fixing agent (Cpd-9)
0.02 Solvent (So
lv-2)
0.40 0168 Fourth layer (ultraviolet absorption layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.58 Ultraviolet absorber (UV-1)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.47 Color mixing inhibitor (Cpd-5
)
0.05 Solvent (So
lv-5)
0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.58μ
m's
A 1:4 mixture of A and 0.45 μm (A
g molar ratio). The coefficient of variation of particle size distribution is 0.
09 and 0.11, each emulsion had AgBr 0.
(6 mol% was locally contained on a part of the particle surface)
0.2
3 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.34
Cyan coupler (ExC)
0.32
Color image stabilizer (Cpd-6)
0.
17 Color image stabilizer (Cpd-7)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40 Color image stabilizer (C
pd-8)
0.04 melt
Solv-6
0.15 01
70] Sixth layer (ultraviolet absorption layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.53 Ultraviolet absorber (UV-1)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16 Color mixing inhibitor (Cpd-5
)
0.02 Solvent (Solv-5
)
0.08 0171
] Seventh layer (protective layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.33 Polyvinyl alcohol acrylic
Lyle modified copolymer
(denaturation degree 17%)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 Liquid paraffy
hmm
0.03
embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] [Chemical 75] [Chemical 76] Comparative couplers YC-2 to 4 and the present invention
Coupler is added so that the amount of coupler applied is equimolar.
Samples 202 to 212 were prepared by coating according to the method described above. [0182] Next, the processing method for these samples will be described.
. First, measure each sample using a sensitometer (manufactured by Fuji Photo Film Co., Ltd.).
, FWH type, light source color temperature 3200°K),
Provides gradation exposure for 3-color separation filter for cytometry
Ta. The exposure at this time is. 250CM with 0.1 seconds exposure time
The exposure amount was set to S. Sample after exposure
The paper processing machine is used to produce color in the next processing step.
Continuous processing (run-time) until twice the statue tank capacity is refilled.
A testing test was conducted. Treatment process temperature time
Refill fluid* Tank capacity
-Development 35℃ 45 seconds
161ml 17 liters
Bleach fixing 30-35℃ 45 seconds
215ml 17 liters
Rinse■ 30-35℃ 20 seconds
- 10 liters
Rinse■ 30-35℃ 20 seconds
- 10 liters
Rinse■ 30-35℃ 20 seconds
350ml 10 liters dry
Drying 70-80℃ 60 seconds * Replenishment
The amount is per 1 m2 of photosensitive material (3 ton of rinse → →
A counter-current method was used. ) The composition of each treatment solution is as follows.
Ru. Color developer
tank liquid
replenisher water
800m
l 800ml Ethylenediamine-N, N
,N,N-
Tetramethylene phosphone
acid 1.5g
2.0g triethanolamine
8.0g 12
．． 0g sodium chloride
1.4g potassium carbonate
Umu
25g 25g
N-ethyl-N-(β-methanesulfone
　　　　　　　　　　　　　　　　　　　　　　　　　
(amidoethyl)-3-methyl-4-
　　　　　　　　　　　　　　　　　　　　　　　　　
Aminoaniline sulfate
5.0g
7.0g N,N-bis(carboxymethyl)
　　　　　　　　　　　　　　　　　　　　　　　　　
hydrazine
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0g 7.0g Fluorescent brightener (WH
ITEX 4B,
　　　　　　　　　　　　　　　　　　　　　　　　　
(manufactured by Sumitomo Chemical)
1.0g 2.0g
add water
1000ml 1000
ml pH (25℃)
10.05 10
．． 45 Bleach-fix solution (tank solution and replenisher solution are the same)
　　　　　　　　　　　　　　　　　　　　　　　　　
water
　　　　　　　　　　　　　　　　　　　　　　　　　
400ml ammonium thiosulfate (
70%)
100ml sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
17g ethylenediaminetetraacetic acid iron (III
) Ammonium 55g
Ethylenediaminetetraacetic acid disodium
5g ammonium bromide
Mu
Add 40g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH (
25℃)
6.0 0
185] Rinse solution (tank solution and refill solution are the same) ion exchanger
Water change (calcium and magnesium each less than 3 ppm)
) Evaluation was performed using the maximum color density Dmax. Also, sodium sulfite is a competing compound in the color developer.
Decrease in Dmax when 0.5g/liter of
was set as ΔDmax. These values are shown in Table 3. table
3, it is clear that the coupler of the present invention is superior to the comparative example.
All have high Dmax and can be said to have high color development. Also,
Highly active with small concentration drop when competitive compounds are added
It can be said that it is a coupler. Such couplers are
It is possible to provide a stable finish even when the composition changes.
It can be said that it is an excellent coupler. In particular, the best of the present invention
Y-1, Y-9, and Y also fall within the range of preferred couplers.
-47 and Y-8 show particularly excellent performance. [Table 3] Example 3 Weighed out 15.0 g of coupler YC-7 for comparison, and
Add 5.0g of organic solvent and tricresyl phosphate,
Furthermore, add 15 ml of ethyl acetate to dissolve the solution.
Contains 1.5g of sodium dodecylbenzenesulfonate
The mixture was emulsified and dispersed in 200 g of a 10 wt % gelatin aqueous solution. child
The total amount of the emulsified dispersion was added to 310 g of silver iodobromide emulsion (70.0 g of silver iodobromide emulsion).
0 g/kg emulsion, silver iodide content 10 mol%) and coated.
Apply an undercoat layer so that the amount of silver on the cloth is 1.61g/m2.
This application was applied onto a triacetate film base.
As a protective layer on top of the gelatin layer, the dry film thickness is 1.0.
A sample 301 was prepared by providing the sample 301 so as to have a diameter of μ. In addition,
As a latin hardener, 1,2-bis(vinylsulfonyl
(acetamido)ethane was used. [0189] The color photographic light-sensitive material as described above is exposed to light.
Thereafter, it was treated as described below. Next, the composition of the treatment liquid will be described. (Color developer)
(
Unit g) Diethylenetriaminepentaacetic acid
1
．． 0 1-hydroxyethylidene-
1,1-diphosphonic acid 3.0
sodium sulfite
4.
0 potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
30.0 Bromide
potassium
1.
4 Potassium iodide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5mg hydroxylamide
sulfate
2.4 4
-[N-ethyl-N-β-hydroxy ethyla
[Mino]2-methylaniline sulfate
4.5 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter
pH
　　　　　　　　　　　　　　　　　　　　　　　　　
10.05 0191 (Bleach solution)
　　　　　　　　　　　　　　　　　　　　　　　　　
(Unit g) Ferric ammonium ethylenediaminetetraacetic acid
Nium dihydrate 120.0 Ethylenedia
Minetetraacetic acid disodium salt
10.0 Ammonium Bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
100.0 Ammonium nitrate
nium
10.0
bleach accelerator
　　　　　　　　　　　　　　　　　　　　　　　　　
0.005 mol [Chemical formula 77] Ammonia water (27%)
15.0m
l add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
6.3 (Bleach-fix solution)
(
Unit g) Ferric ammonium ethylenediaminetetraacetic acid
Mu dihydrate salt
　　　　　　　　　　　　　　　　　　　　　　　　　
50.0 Ethylenediami
Tetraacetic acid disodium salt
5.0 Ammonium sulfite
nium
12.0
Ammonium thiosulfate aqueous solution (70%)
240.0ml Anmo
Near water (27%)
6.0ml water
plus
1.0li
pH
　　　　　　　　　　　　　　　　　　　　　　　　　
7.2 0193 (Washing liquid) Water supply
H-type strongly acidic cation exchange resin (Rohm and Haas)
Amberlite IR-120B) and OH type anio
filled with exchange resin (Amberlite IR-400).
Water is passed through a mixed bed column to remove calcium and magnesium.
Treat the ion concentration to 3 mg/liter or less, and then
Sodium chloride isocyanurate 20mg/liter and
0.15 g/liter of sodium sulfate was added. this
The pH of the liquid is in the range of 6.5 to 7.5. (Stabilizing liquid)
　　　　　　　　　　　　　　　　　　　　　　　　　
(Unit: g) Formalin (37%)
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0ml polyoxyethylene-p-
Monononylphenyl ether (average degree of polymerization 10
)
0.3 Ethylenediaminetetraacetic acid disodium
Salt 0.0
5 Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 liter pH
　　　　　　　　　　　　　　　　　　　　　　　　　
5.8 to 8.0 [0195] Above and above
The outer coupler and the coupler of the present invention have a coating amount of coupler
Sample 302 was applied using the above method so that the amount of
~309 was produced. The results obtained are shown in Table 4. Book
The coupler of the invention is a pivaloyl type coupler YC-9,
Provides significantly higher color density compared to YC-2 and YC-3
. In addition, benzoyl type, which was conventionally thought to have high color density,
Provides even higher color density compared to coupler YC-7.
It can be seen that it is an excellent coupler. Table 4 Example 4 On a subbed cellulose triacetate film support,
Multilayer color is created by coating each layer with the composition shown below.
Sample 401, which is a photosensitive material, was prepared. (Photosensitive layer composition)
The numbers corresponding to each component are coatings expressed in g/m2.
For silver halide, the coating amount is expressed in terms of silver.
show. However, for sensitizing dyes, halogenation in the same layer
The amount of coating per mole of silver is shown in moles. (Sample 401) First layer (antihalation layer) Black colloidal silver
Silver
0.18 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.40 Second layer (middle layer) 2,5-di-t-pentadecylhydroquinone
0.18 EX-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0
．． 07 EX-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 EX-12
　　　　　　　　　　　　　　　　　　　　　　　　　
0.002
U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.06 U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.08 U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 HBS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.04 [0200] Third layer (first red-sensitive emulsion layer) Emulsion A
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.25 Emulsion B
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.25 Sensitized color
Elementary I
6.9×
10-5 Sensitizing dye II
　　　　　　　　　　　　　　　　　　　　　　　　　
1.8×10-5 Sensitizing dye III
　　　　　　　　　　　　　　　　　　　　　　　　　
3.1×10-4
EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.035 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020 U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070 U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050 U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.060 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.8
7. Fourth layer (second red-sensitive emulsion layer) Emulsion G
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 1.0 Sensitizing dye I
　　　　　　　　　　　　　　　　　　　　　　　　　
5.1×10-5 Sensitizing dye I
I
1.4×1
0-5 Sensitizing dye III
　　　　　　　　　　　　　　　　　　　　　　　　　
2.3×10-4 EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.400
EX-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
0.015 U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070 U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.050 U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
0.070 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.30 0202 Fifth layer (third red-sensitive emulsion layer) Emulsion D
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 1.60 Sensitizing dye I
　　　　　　　　　　　　　　　　　　　　　　　　　
5.4×10-5 sensitizing dye
II
1.4×
10-5 Sensitizing dye III
　　　　　　　　　　　　　　　　　　　　　　　　　
2.4×10-4 EX-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.010
EX-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.080 EX-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.097H
BS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.22 HBS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.63
0203 6th layer (middle layer) EX-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.040 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020 Zera
Chin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.80 [0204] Seventh layer (first green-sensitive emulsion layer) Emulsion A
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.15 Emulsion B
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.15 Sensitized color
Basic V
3.0×
10-5 Sensitizing dye VI
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0×10-4 Sensitizing dye VII
　　　　　　　　　　　　　　　　　　　　　　　　　
3.8×10-4
EX-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.260 EX-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.021EX
-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.030 EX-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.025 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
100 HBS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.010 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.63 0
205] 8th layer (second green-sensitive emulsion layer) Emulsion C
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.45 Sensitizing dye V
　　　　　　　　　　　　　　　　　　　　　　　　　
2.1×10-5 sensitizing dye
VI
7.0×
10-5 Sensitizing dye VII
　　　　　　　　　　　　　　　　　　　　　　　　　
2.6×10-4 EX-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.094
EX-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.018 EX-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.026H
BS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.160 HBS-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.008 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.
50 Layer 9 (Third green-sensitive emulsion layer) Emulsion E
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 1.2 Sensitizing dye V
　　　　　　　　　　　　　　　　　　　　　　　　　
3.5×10-5 Sensitizing dye V
I
8.0×1
0-5 Sensitizing dye VII
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0×10-4 EX-13
　　　　　　　　　　　　　　　　　　　　　　　　　
0.015
EX-11
　　　　　　　　　　　　　　　　　　　　　　　　　
0.100 EX-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.025 HBS-
1
0
．． 25 HBS-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.54 02
07 Layer 10 (yellow filter layer) Yellow colloidal silver
Silver
0.05 EX-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.08 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.95 [0208] Eleventh layer (first blue-sensitive emulsion layer) Emulsion A
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.08 Emulsion B
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.07 Emulsion F
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver
0.07 Sensitizing dye VIII
　　　　　　　　　　　　　　　　　　　　　　　　　
3.5×10-4 EX-9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.72
1 EX-8
　　　　　　　　　　　　　　　　　　　　　　　　　
0.042 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.28 Zera
Chin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.10 12th layer (second blue-sensitive emulsion layer) Emulsion G
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.45 Sensitizing dye VIII
　　　　　　　　　　　　　　　　　　　　　　　　　
2.1×10-4 EX-
9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.154 EX-10
　　　　　　　　　　　　　　　　　　　　　　　　　
0.007 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.78 [0210] 13th layer (third blue-sensitive emulsion layer) Emulsion H
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.77 Sensitizing dye VIII
　　　　　　　　　　　　　　　　　　　　　　　　　
2.2×10-4 EX-
9
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.07 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.69 [
14th layer (first protective layer) Emulsion I
　　　　　　　　　　　　　　　　　　　　　　　　　
Silver 0.20 U-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.11 U-
5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 HBS-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0
0212 15th layer (second protective layer) Polymethyl methacrylate particles (diameter approximately 1.5
μm) 0.54 S-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2
0 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.200213 Each layer has the above components.
In addition to the ingredients, gelatin hardening agent H-1 and surfactant are added.
Ta. The composition and physical properties of the emulsion used in this example are shown in Table 5 below.
The structural formula of the compound shown is shown below. [Table 5] [Formula 78] [Formula 78] [Formula 79] [Formula 80] [Formula 80] [Formula 81] [Formula 81] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] Noi
Yellow coupler Ex-9 (YC-7) is shown in Table 6.
Samples 402 to 404 were replaced with couplers of the present invention.
was created. Furthermore, the first and second samples of samples 402 to 404
Table 6 shows only the coating amount without changing the composition of the and third blue-sensitive emulsion layer.
Change it as shown in the image so that the gradation of each layer is almost the same.
Samples 405 to 407 were prepared. The above sample
After wedge exposure with white light, the method described in Example 3
processed. Check the yellow color density of the processed sample.
The measured results are shown in Table 6. [Table 6] [0228] From Table 6, the couplers of the present invention have the same coating amount.
It can be seen that it gives a high color density. Also sample 405~
407, the same concentration as sample 401 was obtained.
The amount of coupler coating required to obtain the comparative coupler YC-
It can be seen that it requires less than 7. this is economical
Not only is it profitable, but it also makes it possible to make the emulsion layer thinner.
This reduces undesirable light scattering in the gelatin film.
It is possible to improve the sharpness of the image.
Noh. [0229] Actually, samples 401 and 405 to 407
, print a pattern for MTF measurement with white light and develop it.
After treatment, a spatial frequency of 25 cycles/mm was measured using red light.
The MTF value was measured. The results are shown in Table 7. [Table 7] [0231] As is clear from Table 7, the couplers of the present invention
gives a higher MTF value than the comparison coupler when using
, it can be seen that sharpness has improved. That's all
The coupler of the present invention provides high color density and improves the sensitivity of photosensitive materials.
An excellent coupler that can improve sharpness.
I can say that there is. Example 5 Preparation of Sample 501 Cellulose triacetate film with a thickness of 127 μm coated with an undercoat.
A multilayer color effect consisting of each layer with the following composition on a film support.
An optical material was produced and designated as sample 501. Numbers are per m2
represents the amount of addition. The effects of the added compounds are not listed.
It is not limited to other uses. 1st layer: antihalation layer black colloidal silver
0
．． 25g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.9g UV absorber U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.04g UV absorber U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1g UV absorber U-
3
0.1g UV absorption
Agent U-4
0.1g ultraviolet
Line absorber U-6
0.1g
High boiling point organic solvent Oil-1
0.1g [
0234 Second layer: middle layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40g Dye D-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4mg 0235 Third layer: Intermediate layer Fine grain silver iodobromide emulsion with covered surface and interior
(Average particle size 0.06 μm, coefficient of variation 18%, A
gI content 1 mol%)
Silver amount 0.05g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4g
4th layer: low sensitivity red-sensitive emulsion layer Emulsion A
Silver amount
0.2g Emulsion B
Silver amount
0.3g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.8g Coupler C-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15g coupler
-C-2
0.05g
Coupler C-9
0.
05g Compound Cpd-D
　　　　　　　　　　　　　　　　　　　　　　　　　
10mg High boiling point organic solvent Oil-2
0
．． 1g 5th layer: Medium red-sensitive emulsion layer Emulsion B
Silver amount
0.2g Emulsion C
Silver amount
0.3g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.8g Coupler C-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2g coupler
C-2
0.05g
Coupler C-3
0.2
g High boiling point organic solvent Oil-2
0.1g [
6th layer: Highly sensitive red-sensitive emulsion layer Emulsion D
Silver amount
0.4g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.1g Coupler C-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.7g Coupler C-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3g Additive P-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1g 023
9] 7th layer: middle layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.6g Additive M-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3g Color mixing prevention agent Cpd-K
　　　　　　　　　　　　　　　　　　　　　　　　　
2.6mg UV absorber U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1g UV absorber U-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1g Dye D-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g [0240] 8th layer: Intermediate layer Silver iodobromide emulsion covered on the surface and inside (
Average particle size 0.06 μm, coefficient of variation 16%,
AgI content 0.3 mol%) Silver
Amount 0.02g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0g attached
Addition P-1
0.2
g Color mixing prevention agent Cpd-J
0.1
g Color mixing prevention agent Cpd-A
0.1
g0241 Layer 9: Low-sensitivity green-sensitive emulsion layer Emulsion E
Silver amount
0.3g Emulsion F
Silver amount
0.1g Emulsion G
Silver
Amount 0.1g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.5g cup
Ra C-7
0.35g
Compound Cpd-B
0.
03g Compound Cpd-E
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g Compound Cpd-F
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g Compound Cpd-G
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g Compound Cpd-H
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02g Compound Cpd-D
　　　　　　　　　　　　　　　　　　　　　　　　　
10mg high boiling point organic solution
Medium Oil-1
0.1g High boiling point organic solvent O
il-2
0.1g 0242 Layer 10: Medium-sensitivity green-sensitive emulsion layer Emulsion G
Silver amount
0.3g Emulsion H
Silver amount
0.1g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.6g Coupler C-7
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3g Compound C
pd-B
0.03g
Compound Cpd-E
0.02g
Compound Cpd-F
0.
02g Compound Cpd-G
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g Compound Cpd-H
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g High boiling point organic solvent Oil-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01g 0243 Layer 11: Highly sensitive green-sensitive emulsion layer Emulsion 1
Silver amount
0.5g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0g Coupler C-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4g Compound Cpd-B
　　　　　　　　　　　　　　　　　　　　　　　　　
0.08g Compound Cpd
-E
0.02g compound
Cpd-F
0.02g
Compound Cpd-G
0.02
g Compound Cpd-H
0
．． 02g High boiling point organic solvent Oil-1
0.
02g High boiling point organic solvent Oil-2
0.0
2g 0244 12th layer: middle layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.6g Dye D-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g Dye D-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1g Dye D-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.07g 0
245] Layer 13: Yellow filter layer Yellow colloidal silver
Silver amount 0.1
g Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.1g Color mixing prevention agent Cpd-A
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01g High boiling point organic solvent Oil-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01g 0246 14th layer: Middle layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.6g 15th layer: Low-speed blue-sensitive emulsion layer Emulsion J
Silver amount
0.4g Emulsion K
Silver amount
0.1g Emulsion L
Silver
Amount 0.1g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.8g cup
Ra C-5
0.4g [
16th layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L
Silver amount
0.1g Emulsion M
Silver amount
0.4g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.9g Coupler C-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.20g coupler
-C-6
0.25g [
17th layer: High sensitivity blue-sensitive emulsion layer Emulsion N
Silver amount
0.4g gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.2g coupler C-6
　　　　　　　　　　　　　　　　　　　　　　　　　
0.7g 0250 18th layer: 1st protective layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.7g UV absorber U-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.04g UV absorber U-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.01g UV absorber U-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.04g UV absorber U-4
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03g UV absorber U-5
　　　　　　　　　　　　　　　　　　　　　　　　　
0.04g UV absorber U
-6
0.05g High boiling point organic
Solvent Oil-1
0.02g formalinth
Cavenger Cpd-C
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2g Cpd-I
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4g Dye D-3
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05g 0251 Layer 19: Second protective layer Colloidal silver
Silver amount 0
．． 1mg fine grain silver iodobromide emulsion (average grain size 0.06μ
m, AgI content 1 mol%)
Silver amount 0.1g
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4g 0252 Layer 20: Third protective layer Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4g polymethyl methacrylate (average particle size
1.5μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1g Methyl methacrylate
4:6 copolymer of carbonate and acrylic acid (average particle size
diameter 1.5μ)
0.1g silicone oil
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03g Surfactant W-1
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0mg Surfactant W-2
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03g 0253
In addition to the above composition, additive F-1 was added to all emulsion layers.
~F-8 was added. In addition to the above composition, each layer also contains
Gelatin hardening agent H-1 and surfactant for coating and emulsification
W-3 and W-4 were added. Furthermore, as a preservative and anti-mold agent
Phenol, 1,2-benzisothiazolin-3-one
, 2-phenoxyethanol, phenethyl alcohol
Added. The silver iodobromide emulsion used for sample 501 was as follows:
It is. [Table 8] [Table 9] [Formula 89] [Formula 90] [Formula 90] [Formula 91] [Formula 91] [Formula 93] [Formula 94] [Formula 94] [Formula 95] [Formula 95] [Formula 95] [Formula 95] [Formula 100] ] [Chemical 101] [Chemical 102] [Chemical 102] [Chemical 103] [Chemical 104] [Chemical 104] Other comparative examples and the couplers of the present invention are the above.
Low-speed blue-sensitive emulsion layer, medium-speed blue-sensitive emulsion layer and high-speed blue-sensitive emulsion layer as described below.
Equimolar coating amount of yellow coupler in blue-sensitive emulsion layer
It was created by replacing it so that Produced in this way
After exposing the sample to gradation light, it is processed through the steps shown below.
Ta. Treatment process Treatment process Time Temperature
1 development 6 minutes 38℃ water
Wash 2 minutes 38cm
Transfer 2 minutes 38〃Color development
Statue 6 minutes 38th tone
Adjustment 2 minutes 38〃drift
White 6 minutes 38〃set
Arrive 4 minutes 38〃Wed.
Wash 4 minutes 38 yen
Dry at room temperature for 1 minute
The composition of the drying treatment liquid used is as follows. 0274 First developer water
　　　　　　　　　　　　　　　　　　　　　　　　　
700ml Nitrilo-N,N,N-
Trimethylene phosphonic acid pentasodium salt
　　　　　　　　　　　　　　　　　　　　　　　　　
2g sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
20g Hyde
Rokinone monosulfonate
30g sodium carbonate
Thorium (monohydrate)
30g
1-phenyl-4-methyl-4-hydroxy
Methyl-3-pyrazolidone
2
g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
2.5g potassium thiocyanate
　　　　　　　　　　　　　　　　　　　　　　　　　
1.2g Potassium iodide
(0.1% solution)
2ml
add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml 0275 Inversion liquid water
　　　　　　　　　　　　　　　　　　　　　　　　　
700ml Nitrilo-N,N,
N-trimethylenephosphonic acid
pentasodium salt
　　　　　　　　　　　　　　　　　　　　　　　　　
3g salt
Stannous chemical (dihydrate)
　　　　　　　　　　　　　　　　　　　　　　　　　
1g p-aminophenol
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1g sodium hydroxide
　　　　　　　　　　　　　　　　　　　　　　　　　
8g glacial acetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
15
Add ml water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml 0276 Color developer water
　　　　　　　　　　　　　　　　　　　　　　　　　
700ml Nitrilo-N,N,
N-trimethylenephosphonic acid
pentasodium salt
　　　　　　　　　　　　　　　　　　　　　　　　　
3g sub
sodium sulfate
　　　　　　　　　　　　　　　　　　　　　　　　　
7g Sodium triphosphate (decahydrate)
　　　　　　　　　　　　　　　　　　　　　　　　　
36g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1g potassium iodide (0.
1% solution)
90ml sodium hydroxide
Rium
3
g Citrazic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5g N-ethyl-N-(β-methane
Sulfonamido ethyl)-3-methyl-4-a
Mino aniline sulfate
　　　　　　　　　　　　　　　　　　　　　　　　　
11g 3,6-dithia
Octane-1,8-diol
Add 1g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml 027
7] Adjustment liquid water
　　　　　　　　　　　　　　　　　　　　　　　　　
700ml sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
12g Echi
Sodium diaminetetraacetate (dihydrate)
8g Thioglycerin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.4ml
glacial acetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 3ml water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml 02
78] Bleach solution water
　　　　　　　　　　　　　　　　　　　　　　　　　
800ml ethylenediamine tetra
Sodium acetate (dihydrate)
2g Iron (I) ethylenediaminetetraacetate
II) Ammonium (dihydrate) 120g
potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 100g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml 0279 Fixer water
　　　　　　　　　　　　　　　　　　　　　　　　　
800ml sodium thiosulfate
　　　　　　　　　　　　　　　　　　　　　　　　　
80.0g sodium sulfite
Rium
5.0g
sodium bisulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 5.0g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml Stabilizing liquid water
　　　　　　　　　　　　　　　　　　　　　　　　　
800ml formalin (37 layers)
amount%)
5.0ml Fuji Driou
(Surfactant manufactured by Fujifilm Co., Ltd.)
Add 5.0ml water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml 0281 Results
It is shown in Table 10. The coupler of the present invention has more color than the comparative example.
It has a high concentration and can be said to be an excellent coupler. [Table 10] Example 6 A paper support laminated on both sides with polyethylene was coated with the following material.
A color photographic material coated in layers from layer 1 to layer 12.
Created. Titanium foam is applied to the first layer of polyethylene.
ion as a white pigment, and a small amount of ultramarine as a bluish dye.
Including. (Photosensitive layer composition) Below are the components and g/m2 unit.
Indicates the amount of application indicated. Regarding silver halide, silver
Shows the converted coating amount. 1st layer (gelatin layer) Gelatin
…1.3
0 2nd layer (antihalation layer) Black colloidal silver
…0.10
gelatin
…0.70th
3 layers (low sensitivity red sensitive layer) Spectral sensitization with red sensitizing dyes (ExS-1, 2, 3)
silver chloride iodobromide EM1 (silver chloride 1 mol%, iodide)
4 mol% silver, average particle size 0.3μ, particle size distribution
10%, cubic, core iodity type core shell)
…0.06 Red sensitizing dye (ExS-1, 2
, 3) spectrally sensitized silver iodobromide EM2 (iodide
Silver 5 mol%, average particle size 0.45μ, particle size
20% cloth, flat plate (aspect ratio = 5))
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
...1.00 Cyan coupler (ExC-1)
…0.14
Uncoupler (ExC-2)
…0.07 Anti-fading agent (Cpd-
2, 3, 4, 9 equivalents) …0.12
Coupler dispersion medium (Cpd-5)
…0.03 Coupler solvent (So
lv-1, 2, 3) ...0.0
60284 4th layer (high sensitivity red-sensitive layer) Spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3)
silver iodobromide EM3 (silver iodide 6 mol%, average grain
Grain size 0.75μ, particle size distribution 25%, flat plate (A
Spectral ratio = 8, core iodine))
...0.15 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
…1.00 Cyan coupler
-(ExC-1)
...0.20 Cyan coupler (ExC-2)
…0.10
Antifading agent (Cpd-2, 3, 4, 9 equivalents)
...0.15 Coupler dispersion medium (Cpd-5)
...0.03
Coupler solvent (Solv-1, 2, 3)
…0.100285 5th layer (middle layer) Magenta colloid silver
…0.02 Zera
Chin
…1.00 mixed
Color inhibitor (Cpd-6, 7)
…0.08 Color mixing inhibitor solvent (So
lv-4, 5) ...0.1
6 Polymer latex (Cpd-8)
…0.100286 6th layer (low sensitivity green sensitive layer) Salt iodine spectrally sensitized with green sensitizing dye (ExS-3)
Silver bromide EM4 (silver chloride 1 mol%, silver iodide 2.5
Mol%, average particle size 0.28μ, particle size distribution 1
2%, cubic, core iodide type core shell))
...0.04 Green sensitizing dye (ExS-3
) spectrally sensitized silver iodobromide EM5 (silver iodide 2.8
Mol%, average particle size 0.45μ, particle size min.
12% cloth, flat plate (aspect ratio = 5))
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.06 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.80 Magenta coupler (ExM-
1) ...0.10
Antifading agent (Cpd-9)
…0.10 Stain protection
inhibitor (Cpd-10)
...0.01 Stain inhibitor (Cpd-11)
…0.001
Stain inhibitor (Cpd-12)
…0.01 Coupler dispersion medium (C
pd-5)
...0.05 Coupler solvent (Solv-4, 6)
…0.15 0287 7th layer (high sensitivity green sensitive layer) Iodor spectral sensitized with green sensitizing dye (ExS-3)
Silver oxide EM6 (silver iodide 3.5 mol%, average grain size
size 0.9μ, particle size distribution 23%, flat plate (aspect
ratio = 9, homogeneous iodide type)
...0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.80 Mazen
Ta coupler (ExM-1)
...0.10 Anti-fading agent (Cpd-9)
…0
．． 10 Stain inhibitor (Cpd-10)
…0.01 Stain protection
inhibitor (Cpd-11)
...0.001 Stain inhibitor (Cpd-12
)...0.01
Coupler dispersion medium (Cpd-5)
...0.05 coupler solvent (S
olv-4,6)...
0.15 0288 8th layer (yellow filter layer) Yellow colloidal silver
…0.20 Zera
Chin
…1.00 mixed
Color inhibitor (Cpd-7)
...0.06 Color mixing inhibitor solvent (
Solv-4, 5) ...0
．． 15 Polymer latex (Cpd-8)
...0.100289] 9th layer (low sensitivity blue sensitive layer) Spectrally sensitized with blue sensitizing dye (ExS-5, 6)
Silver chloroiodobromide EM7 (silver chloride 2 mol%, silver iodide 2
．． 5 mol%, average particle size 0.35μ, particle size
Cloth 8%, cubic, core iodine type core shell))
...0.07 Blue sensitizing dye (ExS-5,
Silver iodobromide EM8 (silver iodobromide) spectrally sensitized with
2.5 mol%, average particle size 0.45μ, particle size
16% distribution, flat plate (aspect ratio = 6))
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.50 Yellow coupler (ExY-1)
…0.20 Ste
Inhibitor (Cpd-11)
...0.001 Antifading agent (Cpd-6
)
...0.10 Coupler dispersion medium (Cpd-5)
…0.05 kap
Solv-2
...0.050290] 10th layer (high sensitivity blue sensitive layer) Spectral sensitized with blue sensitizing dye (ExS-5, 6)
Silver iodobromide EM9 (silver iodide 2.5 mol%, average grain
particle size 1.2μ, particle size distribution 21%, flat plate (as
Pect ratio = 14))
…0.25 Zera
Chin
…1.00 i
Yellow coupler (ExY-1)
…0.40 Stain inhibitor (Cpd
-11) ...0.
002 Anti-fading agent (Cpd-6)
…0.10 kap
lar dispersion medium (Cpd-5)
...0.15 coupler solvent (Solv
-2) …0
．． 100291 Layer 11 (ultraviolet absorbing layer) Gelatin
…1.5
0 Ultraviolet absorber (Cpd-1, 3, 13)
...1.00 Color mixing prevention agent (Cpd-
6, 14) …0
．． 06 Dispersion medium (Cpd-5) Ultraviolet absorber solvent (Solv-1, 2)
…0.15 Irradiation prevention dyeing
Fee (Cpd-15, 16) …0.02 Irajie
tion prevention dye (Cpd-17, 18)...0.0
2 12th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0
．． 2μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.07 Modified poval
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.02 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
...1.50 Gelatin hardening agent (H-1)
…0.
17 [0293] Furthermore, in each layer, as an emulsification and dispersion aid,
Alkanol XC (Dupont) and Alkylbe
sodium sulfonate as a coating aid.
Acid ester and Magefac F-120 (Dainippon Co., Ltd.
(manufactured by Ink Co., Ltd.) was used. silver halide or colloid
The silver-containing layer contains (Cpd-19, 20,
21) was used. The compounds used in the examples 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 Solv-1 Di(2-ethylhexyl
) Phthalate Solv-2 Trinonyl phosphate Solv-3
Di(3-methylhexyl) phthalate Solv-4
Tricresyl phosphate Solv-5 Djibouti
Luphthalate Solv-6 Trioctyl phosphate H-1
1,2 bis(vinylsulfonylacetamide)
d) Ethane 0305 (Emulsion A) Monodisperse with (100) crystal habit
Preparation of emulsion pBr was added to an aqueous gelatin solution kept at 70°C.
containing silver nitrate aqueous solution and KBr, KI while keeping the temperature at 4.5.
Add an aqueous solution using a double jet to obtain (100) crystal habit.
A monodisperse emulsion (edge length 0.68 μm) was prepared. Next
Divide this core emulsion into three parts and apply different conditions as follows.
to form a shell, and the final particle size was set to 0.7 μm, A
The gI content was 3 mol%. [0306] Sodium thiasulfate and chloroauric acid are added to the above core.
Potassium was added to perform chemical sensitization. Then core formation
The shell was precipitated under similar conditions. coupler for comparison
and the couplers of the present invention have a low sensitivity blue sensitive layer and a high sensitivity blue sensitive layer.
Make equimolar amounts of yellow coupler ExY-1 in the sensitive layer.
It was made by replacing sea urchin with sea urchin. These samples are shown below.
It was processed and evaluated according to the method. [0307] Processing step first development (black and white development) 38°C
Wash with water for 75 seconds
38℃ 90 seconds inversion exposure
100Lux or more 6
Color development for 0 seconds or more 38
℃ Wash with water for 135 seconds
38℃ 45
Second bleach fixing 38℃
Wash with water for 120 seconds
Dry at 38℃ for 135 seconds
Drying Processing solution composition (first developer) Nitrilo-N,N,N-trimethylenephosphone
　　　　　　　　　　　　　　　　　　　　　　　　　
Acid/pentasodium salt
0.
6g diethylenetriaminepentaacetic acid, pentasodium salt
4.0g sulfite
potassium
30.0
g Potassium thiocyanate
　　　　　　　　　　　　　　　　　　　　　　　　　
1.2g potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
35.0g hydroquinone monosulfate
Honate potassium salt 2
5.0g diethylene glycol
　　　　　　　　　　　　　　　　　　　　　　　　　
15.0ml 1-phenyl-4-hydroxymeth
Thyl-4-methyl-3-pyrazolidone
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
0.5g Potassium iodide
Umu
5.
Add 0mg water
　　　　　　　　　　　　　　　　　　　　　　　　　
1 liter
　　　　　　　　　　　　　　　　　　　　　　　　　
(pH 9.70)
(Color developer) Benzyl alcohol
1
5.0ml diethylene glycol
　　　　　　　　　　　　　　　　　　　　　　　　　
12.0ml 3,6-dithia-1,8-oc
Tandiol 0
．． 2g Nitrilo-N,N,N-trimethylenephosphor
hmm
Acid/pentasodium salt
　　　　　　　　　　　　　　　　　　　　　　　　　
0.5g diethylenetriaminepentaacetic acid, pentatrisodium
Umu salt 2.0g
sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
2.0g potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
25.0g Hydroxylamine sulfate
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0g N-ethyl-N-(β
-methanesulfonamidoethyl)
-3-methyl-4-aminoanili
Sulfate 5.0
g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
0.5g potassium iodide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0mg water
plus
　　　　　　　　　　　　　　　　　　　　　　　　　
1 liter
　　　　　　　　　　　　　　　　　　　　　　　　　
(pH 10.40) (Bleach-fix solution) 2-mercapto-1,3,4-triazole
1.0g ethylene
Diaminetetraacetic acid, disodium salt, dihydrate salt
5.0g Ethylenediaminetetraacetic acid/F
e(III)・Anmo
nium monohydrate
　　　　　　　　　　　　　　　　　　　　　　　　　
80.0g sodium sulfite
Rium
15.0g
Sodium thiosulfate (700g/liter liquid)
160.0ml glacial acetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
5.0
Add ml water
　　　　　　　　　　　　　　　　　　　　　　　　　
1 liter
　　　　　　　　　　　　　　　　　　　　　　　　　
(pH6.50)
[0311] In this case as well, the same result as shown in Example 1 is obtained.
The fruit was obtained. Example 7 Paper support laminated on both sides with polyethylene (thickness 10
0 micron) on the front side, apply the following 1st to 14th layers on the back side.
Color photographic effect with layer 15 to layer 16 applied on the sides
Created optical materials. The polyethylene on the first layer coating side is acidic.
Titanium chloride (4 g/m2) was used as a white pigment, and a trace amount (
Contains 0.003g/m2) of ultramarine as a blue tinting dye.
(The chromaticity of the surface of the support is 8 in L*, a*, b* system.
8.0, -0.20, -0.75). (Photosensitive layer composition) The components and coating amount (g/
m2 unit). Regarding silver halide, it is expressed in silver equivalent.
Indicates the amount of coating. The emulsion used in each layer was the emulsion EM used in the post-surgery process.
Made according to method 1. However, the emulsion in the 14th layer is on the surface.
A Lippmann emulsion without chemical sensitization was used. 0313 First layer (antihalation layer) Black colloidal silver
…0.10
gelatin
…0.70 [
0314 Second layer (middle layer) Gelatin
…0.7
0315 3rd layer (low sensitivity red sensitive layer) Spectral sensitization with red sensitizing dyes (ExS-1, 2, 3)
silver bromide (average grain size 0.25μ, grain
Size distribution [coefficient of variation] 8%, octahedral)
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.04
Spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3)
Silver chlorobromide (silver chloride 5 mol%, average particle size 0
．． 40μ, size distribution 10%, octahedron)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.08
gelatin
…1.00
Cyan coupler (ExC-1, 2, 3 1:1:0.
2)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.30 Antifading agent (Cpd-1, 2, 3,
4 equivalents) …0.18 Stain prevention
agent (Cpd-5)
...0.003 Coupler dispersion medium (Cpd-6)
...0.03
Coupler solvent (Solv-1, 2, 3 equivalents)
...0.12 0316] 4th layer (high sensitivity red-sensitive layer) Spectral sensitization with red sensitizing dyes (ExS-1, 2, 3)
silver bromide (average grain size 0.60μ, grain
Size distribution 15%, octahedron) …0.14 gelati
hmm
…1.00 Shea
Coupler (ExC-1, 2, 3 1:1:0.2)
　　　　　　　　　　　　　　　　　　　　　　　　　
…
0.30 Antifading agent (Cpd-1, 2, 3, 4 equivalents
)...0.18 Coupler dispersion medium (C
pd-6)
…0.03 Coupler solvent (Solv-1, 2, 3, etc.)
amount) ...0.12 0317] 5th layer (middle layer) Gelatin
…1.0
0 Color mixing prevention agent (Cpd-7)
…0.08 Color mixing prevention
Agent solvent (Solv-4, 5 equivalents)
...0.16 Polymer latex (Cpd-8)
...0.100318] 6th layer (low sensitivity green sensitive layer) Bromide spectrally sensitized with green sensitizing dye (ExS-4)
Silver (average particle size 0.25μ,
Particle size distribution 8%, octahedral) ...0.04
Salt odor spectrally sensitized with green sensitizing dye (ExS-4)
Silver chloride (silver chloride 5 mol%, average particle size 0.4
0μ, size distribution 10%, octahedral)
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.06 Zera
Chin
…0.80 ma
Zenta coupler (ExM-1, 2, 3 equivalent)
...0.11 Antifading agent (Equivalent amount of Cpd-9, 26
) …0.15 Stain prevention
inhibitor (Cpd-10, 11, 12, 13 in 10:7:7
:1 ratio)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.025 Coupler dispersion medium (Cpd-
6) ...0.
05 Coupler solvent (Solv-4, 6 equivalents)
...0.15 0319] 7th layer (high sensitivity green sensitive layer) Bromide spectrally sensitized with green sensitizing dye (ExS-4)
Silver (average particle size 0.65μ, particle size
16% cloth, octahedron) …0.10 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.80 Magenta
Coupler (ExM-1, 2, 3 equivalents)...0
．． 11 Anti-fading agent (Cpd-9, 26 equivalents)
…0.15 Stain inhibitor
(Cpd-10, 11, 12, 13 at 10:7:7:1
(by comparison)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.025 Coupler dispersion medium (Cpd-6)
…0.05
Coupler solvent (Solv-4, 6 equivalents)
...0.150320] 8th layer (middle layer
) Same as 5th layer 0321 9th layer (yellow filter layer) Yellow colloidal silver (particle size 100A)
...0.12 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.70 Color mixing prevention agent (Cpd-7)
…
0.03 Color mixing inhibitor solvent (Solv-4, 5 equivalents)
…0.10 Polymer latex
(Cpd-8)...
0.07 0322] 10th layer (middle layer) Same as 5th layer
11th layer (low sensitivity blue sensitive layer) Spectrally sensitized with blue sensitizing dyes (ExS-5, 6)
Silver bromide (average particle size 0.40μ, particles
Size distribution 8%, octahedron) …0.07
Salt odor spectrally sensitized with blue sensitizing dye (ExS-5, 6)
Silver chloride (silver chloride 8 mol%, average particle size 0.6
0μ, particle size distribution 11%, octahedral)
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.14
gelatin
...0.80
Yellow coupler (ExY-1, 2 equivalent)
...0.35 Anti-fading agent (Cpd-14)
…0.
10 Stain inhibitor (Cpd-5, 15 in 1:5 ratio)
)...0.007 Coupler dispersion medium (Cpd-6
)...0.0
5 Coupler solvent (Solv-2)
...0.100324] 12th layer (high sensitivity blue sensitive layer) Spectrally sensitized with blue sensitizing dye (ExS-5, 6)
Silver bromide (average particle size 0.85μ, particles
Size distribution 18%, octahedral) ...0.15 ze
latin
...0.60
Yellow coupler (ExY-1, 2 equivalent)
...0.30 Anti-fading agent (Cpd-14)
...0.1
0 Stain inhibitor (Cpd-5, 15 in a 1:5 ratio)
)...0.007 Coupler dispersion medium (Cpd-6)
…0.05
Coupler solvent (Solv-2)
...0.100325] 13th layer (ultraviolet absorption layer) Gelatin
…1.0
0 UV absorber (Cpd-2, 4, 16 equivalent)
...0.50 Color mixing prevention agent (Cpd-7,
17 equivalents) …0.03
Dispersion medium (Cpd-6)
…0.02 Ultraviolet absorption
Collecting solvent (Solv-2, 7 equivalents)...
0.08 Anti-irradiation dye (Cpd-18
, 19, 20, 21, 27 at 10: 10:13
:15:20 ratio)
...0.050326] 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0
．． 1μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.03 Polyvinyl alcohol acrylic
Modified copolymer (molecular weight 50,000)
…0.0
1 Polymethyl methacrylate particles (average particle size
2.4μ) and silicon oxide (average particle size 5μ)
) equivalent amount
...0.05 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
...1.80 Gelatin hardening agent (H-1, H-2
Equivalent amount) …0.18 0327
] 15th layer (back layer) Gelatin
…2.5
0 UV absorber (Cpd-2, 4, 16 equivalent)
...0.50 Dye (Cpd-18, 19
, 20, 21, 27 in equal amounts)
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.060328 16th layer (back protective layer) Polymethyl methacrylate particles (average particle size 2
．． 4μ) and silicon oxide (average particle size 5μ)
Equal amount
...0.05 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
...2.00 Gelatin hardening agent (H-1, H-2, etc.)
amount)...0.140329]
How to make emulsion EM-1: Stir an aqueous solution of potassium bromide and silver nitrate into an aqueous gelatin solution.
They were added at the same time at 75°C for 15 minutes with thorough stirring,
Octahedral silver bromide grains with an average grain size of 0.35 μm were obtained. this
0.3 g of 3,4-dimethyl-1,
3-thiazoline-2-thione was added. silver in this emulsion
6 mg sodium thiosulfate and 7 mg chloride per mole
Add gold acid (tetrahydrate) sequentially and heat at 75°C for 80 minutes.
A chemical sensitization treatment was carried out. The particles obtained in this way
As a core, it grows further in the same precipitation environment as the first time.
Finally, an octahedral monodisperse core with an average particle size of 0.7μ/
A shell silver bromide emulsion was obtained. The coefficient of variation of particle size is approximately 1
It was 0%. This emulsion contains 1.5 mg per mole of silver.
Sodium thiosulfate and 1.5 mg chloroauric acid (tetrahydrate)
was added and heated at 60℃ for 60 minutes to perform chemical sensitization treatment.
An internal latent image type silver halide emulsion was obtained. Each photosensitive layer contains ExZK-1 as a nucleating agent.
and ExZK-2 to silver halide at 10-3, respectively.
, 10-2% by weight, and 1% Cpd-22 as a nucleation accelerator.
0-2% by weight was used. Furthermore, each layer contains an emulsifying and dispersing agent.
Alkanol XC (Dupont) and alkyl
Sodium benzenesulfonate is used as a coating aid.
Citric acid ester and Magefac F-120 (Dainippon
(manufactured by Ink Co., Ltd.) was used. Silver halide and colloidal silver containing layers contain stabilizers (
Cpd-23, 24, 25) was used. Sample this sample
The number was set to 101. The compounds used in the examples 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 embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image
Solv-2 trinonyl phosphate Solv-3
Di(3-methylhexyl) phthalate Solv-4
Tricresyl phosphate Solv-5 Djibouti
Luphthalate Solv-6 Trioctyl phosphate Solv-
7 Di(2-ethylhexyl) phthalate H-1
1,2-bis(vinylsulfonylacetamido)ethane
H-2 4,6-dichloro-2-hydroxy-1,3
,5-triazine Na salt ExZK-1 7-(3-E
Toxythiocarbonylaminobenzamide)-9-
Methyl-10-propagy
Ru-1,2,3,4-tetrahydroa
Clidinium trifluoromethane
Sulfonate ExZK-2 2-[4-{3-[3-
{3-[5-{3-[2-chloro-5-
(1-dodecyloxycarbonyl
Toxicarbonyl) Phenyl
[lucarbamoyl]-4-hydroxy-1-nafthi
Lucio Teto Lazo
l-1-yl]phenyl}ureido]benzenesulfone
amide}phenyl]
-1-Formylhydrazine 0344 Comparative coupler
- and the couplers of the present invention have a low sensitivity blue sensitive layer and a high sensitivity blue sensitive layer.
Yellow couplers ExY-1 and ExY-2 in the blue-sensitive layer
It was prepared by replacing them in equimolar amounts. these
The samples were processed and evaluated by the method shown below. More than
The silver halide color photographic light-sensitive material created in this way is
After imagewise exposure, use the method described below using an automatic processor.
Until the cumulative amount of liquid refilled becomes three times the tank capacity.
Processed continuously. [0345] Treatment process Time Temperature Mother
Liquid tank capacity Replenishment amount Color development 135 seconds
38℃ 15 liters 300m
l/m2 Bleach fixing 40 seconds 33℃
3 liters 300ml/m2
Washing with water (1) 40 seconds
33℃ 3 liters - water
Washing (2) 40 seconds 33℃
3 liters 320ml/m2
Drying 30 seconds 80℃
[0346] The washing water replenishment method is to replenish the washing bath (2).
Then, transfer the overflow liquid from the washing bath (2) to the washing bath (1).
A so-called countercurrent replenishment method was used. At this time, the photosensitive material
Transfer of the bleach-fix solution from the bleach-fix bath to the washing bath (1)
The amount of infiltration is 35ml/m2, and the bleach-fixing solution must be brought in.
The ratio of the amount of washing water replenished to the amount of washing water was 9.1 times. [0347] The composition of each treatment liquid was as follows. Color developer
　　　　　　　　　　　　　　　　　　　　　　　　　
Mother liquor Replenisher D-sorbitol
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15g 0.20g
Sodium naphthalene sulfonate/formalin condensation
Compound 0.15g 0.20g
Tyle diamine tetrakis methylene phosphonic acid
1.5g 1.5g diethylene
glycol
12.0ml 16.0
ml benzyl alcohol
13.
5ml 18.0ml Potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
0.80g -
benzotriazole
0.003
g 0.004g Sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
2.4g 3.2g N,
N-bis(carboxymethyl)hydrazine
6.0g 8.0g D-Gluco
base
2.0g
2.4g triethanolamine
6.
0g 8.0g N-ethyl-N-(β-
methanesulfonamidoethyl)
-3-methyl-4-aminoaniline
Sulfate 6.4g
8.5g potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
30.0g 25.0g Optical brightener (di
aminostilbene series)
1.0g 1.2g Add water
hand
1000ml 10
00ml pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
10.50 11.00 0348 Bleach-fix solution
　　　　　　　　　　　　　　　　　　　　　　　　　
Mother liquor Replenisher Ethylenediamine 4 vinegar
Acid, disodium, dihydrate 4.0g
Same as mother liquor Ethylenediaminetetraacetic acid/Fe(
III)・Ammonium・2
water salt
70.0g
Ammonium thiosulfate (700g/liter)
180ml Sodium p-toluenesulfinate
Thorium 20.0
g Sodium bisulfite
20.0g
5-Mercapto-1,3,4-triazole
0.5g ammonium nitrate
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 10.0g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH (25
℃)
6.200349] Washing with water
Water (both mother liquor and replenisher) tap water is exchanged with H-type strongly acidic cations.
Replacement resin (Amberlite IR- manufactured by Rohm and Haas)
120B) and OH type anion exchange resin (Amberla
Water was passed through a mixed bed column packed with IR-400).
Calcium and magnesium ion concentration 3mg/litre
treated with dichlorinated isocyanurate followed by sodium chloride.
Lithium 20mg/liter and sodium sulfate 1.5g/
liter was added. The pH of this solution is between 6.5 and 7.5.
It was within range. In this case, the same as shown in Example 1
The results were obtained. Example 8 Weighed 9.15 g of a comparative coupler (ExY-1),
10.0 g of tricresyl phosphate as a high boiling point organic solvent.
Add 20ml of ethyl acetate and heat to dissolve.
Ta. Add this solution to 250g of 10% gelatin solution.
, and 1.2 g of sodium dodecylbenzenesulfonate.
was added and emulsified and dispersed. [0351] 75.7 g of silver chlorobromide emulsion was added to the above emulsified dispersion.
(silver 64.9g/kg emulsion, silver bromide 70 mol%) was added.
, further 300 g of 10% gelatin aqueous solution and 153 g of water
ml was added. Finally, 1-oxy-3,5 as a hardening agent.
- Added 1.0 g of sodium dichloro-5-triazate.
Add so that the amount of coupler applied is 1 mmol/m2.
coated on a triacetylcellulose support primed with
Sample 801 was prepared. At that time, on top of this coating layer
A 1.66g/m2 gelatin layer is provided as a protective layer.
I got it. Other comparative couplers and couplers of the invention
Prepare an emulsified dispersion so that the applied amount is equimolar, and
It was applied using the same method. Pass the above sample through an optical wedge
It was exposed to white light and processed as follows. [0353] [0354] Color developer water
　　　　　　　　　　　　　　　　　　　　　　　　　
700ml ethylenediaminetetraacetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0g 1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt
4.0g triethanol
amine
12.0g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5g potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
27.0g Fluorescent brightener (W
HITEX 4B (manufactured by Sumitomo Chemical)
1.0g sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1g disodium-N,N
-bis(sulfonate) hydroxylamine
　　　　　　　　　　　　　　　　　　　　　　　　　
10.0g N-ethyl-N-(β-methane
Sulfonamido ethyl)-3-methyl-4-a
Minoaniline sulfate 5.0g Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH (25
℃)
10.050355 Bleach-fix water
　　　　　　　　　　　　　　　　　　　　　　　　　
600ml ammonium thiosulfate (700g
/liter) 100ml Ethi
Amnium iron(III) diaminetetraacetate
55g ethylenediaminetetraacetic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
5g ammonium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
40g nitric acid (67%)
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 30g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH (25℃) (
(with acetic acid and aqueous ammonia) 5.
8 [0356] [0357] Measurement of yellow color density of treated sample
Table 11 shows the maximum color density Dmax. [Table 11] Next, the spectral absorption spectrum of the above samples 801 to 804
The spectrum was measured and shown in FIG. From Table 11, the method of the present invention
Puller Y-1 gives higher color density than the comparative couplers.
I understand that it can be done. Also, as can be seen from Figure 2, the comparative
ExY-2 has a silica in the molecule similar to the coupler of the present invention.
Although it has a chloropropane ring, its spectral characteristics are that its absorbance is
Although it increases slightly, it is clearly unfavorable absorption on the long wavelength side.
have. On the other hand, cyclo with a methyl group at the 1-position
ExY-3, which has a hexyl ring structure, has spectral properties of pivaloy.
It is almost the same as the double type coupler (ExY-1), but the absorbance is different.
It is decreasing slightly. However, the coupler Y-1 of the present invention exhibits light absorption.
Not only does the wavelength increase significantly, but also the absorption on the long wavelength side is cut off.
It can be seen that this has been significantly improved. Cap of the present invention
The fact that RA Y-1 has such excellent properties means that
, as is clear from FIG. 2, a known cap with a similar structure
From the analogy of ExY-2 and ExY-3,
It is difficult to predict. Example 9 A roller was applied to the surface of a paper support laminated on both sides with polyethylene.
After the sodium discharge treatment, dodecylbenzenesulfonate sodium
A gelatin undercoat layer containing thorium is provided, and various photocoating layers are applied.
Multilayer color prints with the layer structure shown below by applying true constituent layers
Paper (sample 901) was produced. Apply the coating liquid as follows.
It was prepared using First layer coating solution preparation Yellow coupler (ExY-1) 15.4 g, color image stability
agent (Cpd-1) 4.8g, color image stabilizer (Cpd-7)
1.3g, color image stabilizer (Cpd-9) 1.0g, and
Ethyl acetate 25.0 to 0.3 g of stabilizer (Cpd-12)
cc and solvent (Solv-3) and (Solv-7
), add and dissolve 3.8 g of each, and add this solution to 10%
10 containing 8 cc of sodium decylbenzenesulfonate
% gelatin aqueous solution and emulsify and disperse it.
Product A was prepared. On the other hand, silver chlorobromide emulsion A (cubic, average
Large size emulsion A with grain size of 0.88μm and 0.70μm
3:7 mixture (silver molar ratio) with m small size A. particle rhinoceros
The coefficient of variation of the size distribution is 0.08 and 0.10, respectively.
Both emulsions contain 0.3 mol% silver bromide on a part of the grain surface.
(containing) was prepared. This emulsion has the blue sensitivity shown below.
Sensitizing dyes A and B per mole of silver for large size emulsion A
Add 2.0 x 10-4 mol to each
For emulsion A, 2.5 x 10-4 mol was added, respectively.
has been added. In addition, chemical ripening of this emulsion is performed using a sulfur sensitizer.
This was done with the addition of a gold sensitizer. The above emulsified dispersion A and
This silver chlorobromide emulsion A was mixed and dissolved to obtain the composition shown below.
The first coating solution was prepared as follows. 0363 The coating liquid for the second to seventh layers is also applied as the first layer.
It was prepared in the same manner as the liquid. As a gelatin hardening agent for each layer
In this case, H-1 and H-2 were used. In addition, each layer has Cpd-
The total amount of 10 and Cpd-11 was 25.0 mg/m each.
2 and 50.0 mg/m2. each
The following spectral sensitizing dyes are used in the silver chlorobromide emulsion in the light-sensitive emulsion layer.
Each was used. embedded image (per mole of silver halide, for large size emulsion A)
are 2.0 x 10-4 mol each, and for small size emulsion A.
2.5 x 10-4 mol) Sensitizing dye C for green-sensitive emulsion layer [Formula 129] (per mol of silver halide, for large size emulsion B)
is 4.0 x 10-4 mol, and 5 for small size emulsion B.
．． 6 x 10-4 mol) and sensitizing dye for green-sensitive emulsion layer
D [Chemical formula 130] (per mole of silver halide, for large size emulsion B)
is 7.0 x 10-5 mol, 1 for small size emulsion B
．． 0x10-5 mol) 0366] Sensitizing dye E for red-sensitive emulsion layer [Formula 131] (per 1 mol of silver halide, for large size emulsion C)
is 0.9 x 10-4 mol, 1 for small size emulsion C
．． 1 x 10-4 mol) [0367] For the red-sensitive emulsion layer, the following compound was added.
Added 2.6 x 10-3 mol per mol of silver halide.
Ta. ##STR132## Also, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer,
For the emulsion layer, 1-(5-methylureidophenyl)-
5-mercaptotetrazole to 1 silver halide each
8.5 x 10-5 mol, 7.7 x 10-4 mol per mole
2.5 x 10-4 mol was added. [0370] Also, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer,
, 4-hydroxy-6-methyl-1,3,3a,7-te
trazaindene per mole of silver halide,
1 x 10-4 mol and 2 x 10-4 mol were added. Also,
The following dyes (colors) are added to the emulsion layer to prevent irradiation.
The amount in parentheses indicates the coating amount). embedded image (Layer structure) The composition of each layer is shown below. numbers
represents the coating amount (g/m2). Silver halide emulsions are converted into silver.
Represents the calculated coating amount. Support polyethylene laminate paper [white pigment (TiO2) and blue polyethylene on the first layer side]
Contains taste dye (ulmarine blue)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A described above
　　　　　　　　　　　　　　　　　　　　　　　　　
0.26 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.54 Yellow mosquito
Puller (ExY-1)
0.48 Color image stability
agent (Cpd-1)
0.15
Solvent (Solv-3)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.12 Solvent (Solv-7)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.12 Color image stabilizer (Cpd-7)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.04 Color image stabilizer (Cpd
-9)
0.03 Color image stabilizer
(Cpd-12)
0.01 037
5] Second layer (color mixing prevention layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.99 Color mixing prevention agent (Cpd-5
)
0.08 Solvent
-1)
0.16 melt
Solv-4
0
．． 080376 Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ
Large size emulsion B of m and small size emulsion of 0.39μm
1:3 mixture with agent B (Ag molar ratio). particle size distribution
The coefficient of variation is 0.10 and 0.88, respectively, for each size breast.
Also, 0.8 mol% of AgBr was applied to a part of the particle surface.
(contained)
0.12 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.24 Magenta Taka
Puller (ExM)
0.23 Color image
Stabilizer (Cpd-2)
0.03
Color image stabilizer (Cpd-3)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15 Color image stabilizer (Cpd-4)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 Color image stabilizer (Cpd-9)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 Solvent (Solv-2)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40 0377 Fourth layer (ultraviolet absorption layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.58 Ultraviolet absorber (UV-1
)
0.47 Color mixing prevention agent (C
pd-5)
0.05 Solvent (
Solv-5)
0.2
4. Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0.58μ
m large size emulsion C and 0.45 μm small size emulsion C
(Ag molar ratio). Changes in particle size distribution
The dynamic coefficient is 0.09 and 0.11, AgB for each size emulsion.
0.6 mol% of r was locally contained in a part of the particle surface.
)
0.23 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.34
Uncoupler (ExC)
0.3
2 Color image stabilizer (Cpd-2)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03 Color image stabilizer (Cpd-4)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 Color image stabilizer (Cpd-6)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16 Color image stabilizer (Cpd-
7)
0.40 Color image stabilizer (
Cpd-8)
0.05 solvent
(Solv-6)
0.
14 0379 Sixth layer (ultraviolet absorption layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.53 Ultraviolet absorber (UV-1
)
0.16 Color mixing prevention agent (C
pd-5)
0.02 Solvent (
Solv-5)
0.0
80380 Seventh layer (protective layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.33 Polyvinyl alcohol
Acrylic modified copolymer (degree of modification 17%) 0.17
liquid paraffin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03 140 [0388] [0389] Next, yellow coupler for comparison of sample 901
The type and amount of coating were changed as shown in Table 12, and the sample
902 to 913 were produced. However, at this time the coupler
The molar ratio of coating amount of silver halide and silver halide is constant (sample 901 and
Adjusted so that it is the same). [0390] First, each sample was measured using a sensitometer (Fuji Photo Film).
Co., Ltd., FWH type, light source color temperature 3200°K)
The gradation of the three-color separation filter used for sensitometry
gave exposure. The exposure at this time was 2 with an exposure time of 0.1 seconds.
The exposure amount was set to 50 CMS. [0391] After the exposure, the sample is processed by a paper processing machine.
Using the following processing steps and processing solution composition,
Continuous processing until twice the capacity of the color developing tank is refilled.
A running test) was conducted. 0392 Treatment process Temperature Time
Refill fluid* Tank capacity color
Image 35℃ 45 seconds 16
1ml 17 liters bleach fixing 30~3
5℃ 45 seconds 215ml 17li
Thorough rinse■ 30-35℃ 20 seconds
- 10 liter rinse
■ 30~35℃ 20 seconds
- 10 liter rinse■ 3
0~35℃ 20 seconds 350ml
10 liters dry 70-80℃
60 seconds * Replenishment amount is per 1 m2 of photosensitive material (rinsing
A three-tank countercurrent flow system was adopted from ■→■. ) The composition of each treatment liquid is as follows. color developer
tank liquid
replenisher water
80
0ml 800ml Ethylenediamine-N, N
,N,N-tetramethylenephosphonic acid
1.5g 2
．． 0g potassium bromide
0.015g
reethanolamine
8.0g 12.0g Chloride
sodium
1.4g potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
25g 25g N-ethyl
-N-(β-methanesulfone amidoethyl)-
3-Methyl-4-aminoaniline sulfate
5.0g
7.0g N,N-bis(carboxymethyl
) Hydrazine 4.0g 5.0g N
,N-di(sulfoethyl)hydroxylamine
・1Na
4.0g 5.0g Fluorescence
Brightener (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0g
Add 2.0g water
1
000ml 1000ml pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
10.05 10.45 0394 Bleach-fix solution
(Tank fluid and refill fluid are the same) Water
　　　　　　　　　　　　　　　　　　　　　　　　　
400
ml ammonium thiosulfate (70%)
100
ml sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
17g ethylenediaminetetraacetic acid iron (I
II) Ammonium
55g
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
Ethylenediaminetetraacetic acid disodium
　　　　　　　　　　　　　　　　　　　　　　　　　
5g ammonium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 40g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH (25
℃)
6
．． 00395 Rinse liquid (tank liquid and refill liquid are the same)
Ion exchange water (calcium, magnesium 3pp each)
m or less) Yellow color density for each processed sample
Measurements were made. The maximum concentration among the results obtained at this time
are shown in Table 12. [0396] As is clear from Table 12, the same application cup
When compared in terms of the amount of color, the coupler of the present invention has no
Both give higher color density than known comparative couplers.
I understand that. In particular, Y- having the preferred structure of the present invention
1, Y-53, and Y-56 are better. Further, coupler Y-1 of the present invention was used.
Compare the color density of sample 904 with coupler ExY-
If you want to obtain it with 1, coupler and silver halide emulsion.
The amount of application must be increased by approximately 1.3 times. However,
Therefore, the coupler of the present invention is preferable from the viewpoint of resource saving.
It can be seen that [0398] Comparative coupler ExY-2 is also
Although the color density is a little high among the colors, this sample
is visually orange, which is the preferred hue for color reproduction.
It is difficult to say. Based on the above, the capacitor of the present invention
Color gives high color density and is also favorable for color reproduction.
It can be said that it is a new and excellent coupler. [Table 12] [Effect of the invention] The yellow coupler of the present invention has excellent coloring properties.
It has excellent spectral absorption characteristics for yellow images. of the present invention
Silver halide color photographic materials are yellow like this.
Contains a coupler and coats the emulsion layer on the support.
Can be made into thin layers and provides high quality photographic images with good color reproducibility
be able to.

[Brief explanation of the drawing]

FIG. 1 is a diagram comparing the spectral absorption spectra in ethyl acetate of Dye A obtained from the yellow dye-forming coupler of the present invention and Dye B obtained from a conventional pivaloylacetanilide type coupler. The horizontal axis shows wavelength (nm), and the vertical axis shows relative absorbance.

FIG. 2 Comparative yellow dye-forming coupler ExY- with the dye obtained from yellow dye-forming coupler Y-1 of the present invention.
FIG. 1 is a diagram comparing the spectral absorption spectra of dyes obtained from ExY-2 or ExY-3.

Claims (2)

[Claims] 1. An acylacetamide type yellow dye-forming coupler, wherein the acyl group is represented by the following general formula (I). General formula (I) [Chemical formula 1] (In the formula, R1 represents a monovalent group. Q together with C,
Represents a group of nonmetallic atoms necessary to form a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle having at least one heteroatom selected from N, O, S, and P in the ring. However, R1 is not a hydrogen atom and does not combine with Q to form a ring. ) 2. A silver halide color photographic material containing the yellow dye-forming coupler according to claim 1 in at least one layer.