JPH04212152A - Color image forming method - Google Patents

Abstract

PURPOSE:To form a cyan color image having sharp absorption form and an improved hue by processing a silver halide color photographic sensitive material having a layer contg. a specified cyan coupler with a specified color developing soln. CONSTITUTION:A silver halide color photographic sensitive material having at least one layer contg. a cyan coupler represented by formula I is developed with a color developing soln. contg. a color developing agent represented by formula II. In the formula I, R<1> is alkyl, alkenyl, etc., R<2> is 4-30C alkyl or alkenyl, R<3> is aryl and Z is H or a group releasable by coupling. In the formula II, R<4> is methyl, etc., each of R<5> and R<6> is methyl or ethyl, L is methylene or ethylene and n is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color image forming method.
More specifically, silver halide color photography.
Color image forming method for color development processing of true photosensitive materials
and, more specifically, specific cyancaps
silver halide photographic light-sensitive materials containing color
-Color images developed with a color developer containing a developer
The present invention relates to an image forming method. [Prior Art] Silver halide color photographic materials are usually
, a yellow coupler that produces a yellow color, maze
Magenta coupler and cyan coloring (reddish-purple)
The above three primary colors of cyan coupler that develops a blue-green color
Oxidation of aromatic primary amine color developers in the presence of
The above coupler undergoes a coupling reaction with the body.
Yellow dye, magenta dye and cyan dye respectively.
It is designed to produce color images.
be. [0003] In recent years, color photographic light-sensitive materials have improved with the advancement of technology.
Both have greatly improved performance. In particular, color reproducibility and
Remarkable progress has been made in improving the fastness of existing color images. Meanwhile, the demand for simple and rapid processing of color photosensitive materials is also increasing.
, photosensitive materials must be suitable for simple or rapid processing.
being sought after. In other words, it is suitable for short-term development processing,
A photosensitive material with little variation in finish due to processing conditions.
development is required. [0004] In response to these demands, yellow sub-absorbent
Pyrazoloazole-based pigments that form magenta pigments with little
Development of couplers and anti-fading technology for various image dyes
Steady progress has been made in the development of
It's coming. However, in terms of color reproduction, yellow
The reproducibility in the green area is still not sufficient.
. Cyan of silver halide color photographic light-sensitive materials
Couplers have traditionally been used, for example, in U.S. Pat.
, No. 531, No. 3,772,002, No. 4,56
2-amidophenol disclosed in No. 0,630 etc.
type cyan couplers, e.g. U.S. Pat. No. 4,333,99
2-ureidophenol type shea disclosed in No. 9 etc.
coupler, or e.g. U.S. Pat. No. 3,002,83
The naphthol type cyan coupler disclosed in No. 6 etc.
It was used and is still widely used today. These shea
Among couplers, especially the above-mentioned 2-amidophenol type
The cyan coupler is the polar of the cyan dye produced from it.
Since the large absorption wavelength is relatively short,
It is used in photosensitive materials for photosensitive materials, and in particular, the
Phenolic cyan coupler or naphthol cyan coupler
The coupler has the same maximum absorption wavelength at a relatively long wavelength.
Since then, it has been used particularly in negative photosensitive materials. By the way, silver halide color photographic materials
Cyan couplers used in materials have various performance requirements.
has been done. For example, the cyan coupler and an aromatic primary
Through coupling reaction with oxidized amine color developer
The hue of the cyan dye produced is good, and the cup
that the ring reaction proceeds at a good rate;
The cyan image formed by the graying reaction is also sensitive to light.
Robust against heat and moisture
In addition, the cyan coupler is used for silver halide color photography.
After the material is manufactured, it is disassembled to produce yellow, red, magenta, cyan, etc.
For example, it does not generate stains.
In order to improve the required performance,
Research continues. [0007] In particular, the preform that forms the final positive image
Cyan couplers for color photosensitive materials for prints have the above-mentioned performance characteristics.
is strictly required. This is because negative photosensitive materials are directly
Since it is not intended for viewing, for example, the color of cyan dye
Masking using colored couplers is possible even if the phase is not good.
Take corrective measures such as printing or color correction during printing.
I can do it. In contrast, color photosensitive materials for printing are directly
Since it is intended for viewing, please take the above correction measures.
If the hue of the cyan dye is not good, the image may differ from the subject.
Color prints with poor color reproducibility
I can only get images. [0008] In this way, cyan coupler is used for printing.
For use with color photosensitive materials, it is better to use
Even more demanding performance is required, especially when it comes to the hue of cyan dyes.
, that is, the maximum absorption wavelength is appropriate and the absorption type is sharp.
Improves the color reproduction of color prints
The above is essential. However, conventional color photosensitive printing
2-amide phenol couplers used in materials and
Produced from p-phenylenediamine color developing agent.
The dye has high sub-absorption in the yellow part and magenta.
It also had the disadvantage of high partial absorption. Therefore conventionally
Improved color reproduction as long as phenolic couplers are used.
had its limits. Dyeing with phenolic couplers
As a technique for improving the absorption characteristics of
Naphtholka with a special structure as described in No. 88,532
A technique using agglomerated pullers is known, but it is not sufficient.
performance is not achieved. In addition, if the treatment was performed for a short period of time,
There is a problem that the stability of the finished product is not sufficient.
. Problems to be Solved by the Invention Therefore, the first aspect of the present invention
The purpose of this is to have a maximum absorption wavelength of 630 to 650 nm.
, and the absorption shape is sharp, that is, the hue is improved.
An object of the present invention is to provide a method for forming a cyan coupler image.
Ru. A second object of the present invention is to achieve the above object.
To provide a color image forming method for color printing.
It is in. The third object of the present invention is to maximize the cyan dye.
The absorption wavelength is significantly shifted to a shorter wavelength, and the absorption type is shifted.
The object of the present invention is to provide a means for improving the hue by sharpening the hue. A fourth object of the present invention is to provide a method suitable for short-time processing.
An object of the present invention is to provide a color image forming method. [Means for solving the problem] The above object is achieved by the following general formula
The layer containing the cyan coupler represented by (I) is reduced.
At least one layer of silver halide color photographic light-sensitive material
A developer containing a color developer represented by the following general formula (D)
A color image type characterized by processing with a color developer
This was achieved using a method of construction. General formula (I) [Formula 3] (wherein, R1 is an alkyl group, an alkenyl group, or a
Represents a chloroalkyl group. R2 has a total number of carbon atoms of 4 to 3
0 alkyl, alkenyl or cycloalkyl groups
represents. R3 represents an aryl group. Z is a hydrogen atom
Alternatively, it represents a coupling-off group. ) General formula (D) [Chemical formula 3] (wherein, R4 is a hydrogen atom, a halogen atom, or
represents a methyl group. R5 and R6 are methyl groups or
represents an ethyl group. L is methylene group or ethylene group
represents. n is 1 or 2. ) Preferable cyan dyes for photosensitive materials for printing
The maximum absorption wavelength is between 630 and 650 nm.
, preferred maximum absorption wavelength of cyan dye for negative photosensitive materials
There is a large difference between 670 and 700 nm.
to give preferable maximum absorption wavelength to photosensitive materials for printing.
The use of cyan couplers in negative photosensitive materials, and vice versa.
Cyan provides a preferable maximum absorption wavelength for negative photosensitive materials.
It is also practical to use couplers in photosensitive materials for printing.
was considered impossible. On the other hand, the photosensitive material for printing is subjected to color development processing.
The color developer used when printing contains a sulfate in the dialkylamino
4-amino-3-methyl-N-ethyl group having a phonamido group
Chil-N-(β-methanesulfonamidoethyl)anili
is commonly used. On the other hand, negative photosensitive materials
Dialkylamide is used as a color developer during color development processing.
4-amino-3-methyl having a hydroxy group in the
-N-ethyl-N-(β-hydroxyethyl)aniline
is commonly used. Contains the same cyan coupler
The above-mentioned color development processing solution for printing the color photosensitive material with
Developed with the negative color developing solution mentioned above.
The maximum absorption wavelength of the cyan dye produced compared to the case where
A shortening of the wavelength is observed, but the degree of shortening is generally 5 to 15
It was nm. Therefore, by taking advantage of this fact,
− Amidophenol type cyan coupler is used as a negative photosensitive material
It can also be used as a 2-ureidophenol.
Cyan coupler type and naphthol type cyan coupler.
It is virtually impossible to use it in photosensitive materials for printing.
It was considered. [0017] Also, produced from cyan coupler for printing
The sharpening of the absorption form of the cyan dye
4-amino-
3-Methyl-N-ethyl-(β-methanesulfonamide
Coloring photosensitive materials for printing containing ethyl aniline
This cannot be achieved by color development using a developing solution.
there were. That is, a coupler containing the same cyan coupler
Even if a color-sensitive material is developed with the above-mentioned color developing solution for printing,
, compared to the case of developing with the above-mentioned negative color developer,
The absorption form of the cyan dye obtained does not change substantially.
It was. Therefore, in this respect as well, it is preferable for negative photosensitive materials.
Even if it is a desirable cyan coupler, it can be used as a photosensitive material for printing.
It is considered virtually impossible to use it favorably for
there was. [0019] We have prepared a specific 2
-Silver halide color containing ureido cyan coupler
- A photographic light-sensitive material with a specific color represented by the general formula (D)
Conventionally, when processing with a color developing solution containing a developing agent,
What is not well known is that the maximum absorption wavelength is 40 to 50 nm.
The wavelength is also shortened to give a value of 630 to 650, and the absorption type
is greatly sharpened, especially the half-width on the half-value side on the short wavelength side.
Preferred cyan dye for printing sensitive materials that can be reduced to 54 nm or less
The present invention was accomplished by discovering that . This book
Annealing dyes are conventionally known dyes for printed photosensitive materials.
than the absorption form of the cyan dye produced from the uncoupler.
It could have been made even sharper. By the way, if a sulfonyl group is added to the 5-position ballast part,
For example, the 2-ureido cyan coupler having
No. 4,775,616, JP 2-13942, JP
The general formula of the present invention is disclosed in No. 2-125252.
Some of the cyan couplers represented by (I) have these characteristics.
It is specifically disclosed in the patent specification. however,
In these specifications, 4-amino-3-methyl-N-ethyl
Net containing Ru-(β-hydroxylethyl)aniline
Only the specific aspects of developing with a color developer for moths are described.
is not listed, and as mentioned above, it is expressed by the general formula (D).
Developed with a color developer containing a color developer that is washed away.
Then, as mentioned above, the maximum absorption wavelength becomes uniquely large and short.
The wavelength becomes shorter and the absorption shape becomes sharper.
No suggestion of unexpected effects based on conventional knowledge
It has not been. [0021] On the other hand, 5
2-ureidosia having a sulfonyl group in the ballast position
cyan coupler is disclosed, and the cyan coupler is further disclosed.
A photosensitive material containing 4-amino-3-methyl-N-ethyl
Chil-N-(β-methanesulfonamidoethyl)anili
Developing with a printing color developer containing
Although specific examples of 2-ureido of the present application are shown,
Cyan couplers are not specifically mentioned and as mentioned above
The maximum absorption wavelength is specifically large and shortened, and the absorption type
This is not predicted based on conventional knowledge that the
There is no suggestion of any unexpected effects. [0022] A color developer represented by the general formula (D)
When developed with a color developing solution containing
Conventionally, the wavelength becomes shorter and the absorption shape becomes sharper.
The unknown effect is that the 5-position ballast has a sulfonyl group.
It is not common for 2-ureido cyan couplers to
, as represented by general formula (I), the 5-position ballast group is
It is specifically expressed when it has a certain structure. [0023] Below, the present invention represented by general formula (I)
The cyan coupler will be explained in detail. General formula (I
), R1 is preferably the total number of carbon atoms (hereinafter C
linear chain of 1 to 30 (more preferably 6 to 24)
or branched alkyl group, C2-30 (more preferred)
Preferably 6 to 24) linear or branched alkenes
group, or C number 3 to 30 (more preferably 6 to 24)
represents a 3- to 12-membered cycloalkyl group, these are substituted with
Substituents (e.g. halogen atoms, hydroxyl groups, carboxyl groups)
Syl group, sulfo group, cyano group, nitro group, amino group, a
alkyl group, alkenyl group, alkynyl group, cycloalkyl group
group, aryl group, alkoxy group, aryloxy group,
Alkylthio group, arylthio group, alkylsulfonyl
group, arylsulfonyl group, acyl group, acyloxy group
, alkoxycarbonyl group, aryloxycarbonyl group
group, carbonamide group, sulfonamide group, carbamoy
group, sulfamoyl group, ureido group, alkoxyl group
Bonylamino group, sulfamoylamino group, alkoxy
Sulfonyl group, imide group or heterocyclic group, or above substituent group
A) may be substituted. R1 is even better
Preferably a linear or branched unsubstituted alkyl group,
or a substituent (e.g., alkoxy group, alkylthio group)
group, aryloxy group, arylthio group, alkylsulf
Honyl group, arylsulfonyl group, aryl group, alco
Oxycarbonyl group, epoxy group, cyano group or halogen
an alkyl group [e.g. n-octyl, n
-decyl, n-dodecyl, n-hexadecyl, 2-ethyl
hexyl, 3,5,5-trimethylhexyl, 3,5
, 5-trimethylhexyl, 2-ethyl-4-methylpene
undecyl, 2-hexyldecyl, 2-heptylundecyl
, 2-octyldodecyl, 2,4,6-trimethylhep
Chil, 2,4,6,8-tetramethylnonyl, benzyl
, 2-phenethyl, 3-(t-octylphenoxy)
Lopyru, 3-(2,4-di-t-pentylphenoxy)
Propyl, 2-(4-biphenyloxy)ethyl, 3-
Dodecyloxypropyl, 2-dodecylthioethyl, 9
, 10-epoxyoctadecyl, dodecyloxycarbo
nylmethyl, 2-(2-naphthyloxy)ethyl], none
Substitution or substituents (e.g. halogen atoms, aryl groups)
, alkoxy group, alkylthio group, aryloxy group,
arylthio group or alkoxycarbonyl group)
alkenyl groups [e.g. allyl, 10-undecenyl,
oleyl, citronellyl, cinnamyl], unsubstituted or
is a substituent (halogen atom, alkyl group, cycloalkyl
group, aryl group, alkoxy group or aryloxy group
) having a cycloalkyl group [e.g. cyclopentyl,
Cyclohexyl, 3,5-dimethylcyclohexyl, 4
-t-butylcyclohexyl], particularly preferably
The above linear or branched unsubstituted alkyl group or
is a substituted alkyl group. R2 is a C number of 4 to 30 (more preferably 4
-20, particularly preferably 4-10) linear or branched
Chain alkyl group, C number 4 to 30 (more preferably 4 to 30)
24 linear or branched alkenyl groups, or C
cycloalkyl of number 4 to 30 (more preferably 4 to 24)
represents a group selected from the above substituent group A.
It may be substituted with a substituent. R2 is more preferred
is a linear or branched unsubstituted alkyl group, or
is a substituent (e.g., alkoxy group, alkylthio group,
lyloxy group, arylthio group, alkylsulfonyl
group, allylsulfonyl group, aryl group, alkoxyl group
(bonyl group, epoxy group, cyano group or halogen atom)
an alkyl group [e.g. n-butyl, i-butyl,
n-amyl, i-amyl, t-amyl, n-hexyl,
n-heptyl, n-octyl, n-decyl, n-dodecyl
n-hexadecyl, 2-ethylhexyl, 3,5,
5-trimethylhexyl, 3,5,5-trimethylhexyl
sil, 2-ethyl-4-methylpentyl, 2-hexyl
Decyl, 2-heptylundecyl, 2-octyldodecyl
2,4,6-trimethylheptyl, 2,4,6,8
-tetramethylnonyl, benzyl, 2-phenethyl, 3
-(t-octylphenoxy)propyl, 3-(2,4
-di-t-pentylphenoxy)propyl, 2-(4-
biphenyloxy)ethyl, 3-dodecyloxypropyl
2-dodecylthioethyl, 9,10-epoxyoc
Tadecyl, dodecyloxycarbonylmethyl, 2-(2
-naphthyloxy)ethyl], unsubstituted or substituted (
For example, halogen atoms, aryl groups, alkoxy groups,
Kylthio group, aryloxy group, arylthio group or
an alkenyl group [e.g.
Allyl, 10-undecenyl, oleyl, citronelli
cinnamyl], unsubstituted or substituted (halogen base),
child, alkyl group, cycloalkyl group, aryl group, alkyl group,
4- to 12-membered carbonyloxy group or aryloxy group)
cycloalkyl group [e.g. cyclopentyl, cyclohexyl]
xyl, 3,5-dimethylcyclohexyl, 4-t-butyl
tylcyclohexyl], particularly preferably the above-mentioned
Straight chain or branched unsubstituted alkyl group or substituted
It is an alkyl group. In general formula (I), R3 is preferably
is an aryl group having 6 to 36 carbon atoms, more preferably 6 to 15 carbon atoms
is substituted with a substituent selected from the above substituent group A.
It may be a fused ring or a fused ring. Here, preferred
As a substituent, a halogen atom (F, Cl, Br, I),
Cyano groups, nitro groups, acyl groups (e.g. acetyl, benzene)
zoyl), alkyl groups (e.g. methyl, t-butyl,
(lifluoromethyl, trichloromethyl), alkoxy group
(e.g. methoxy, ethoxy, butoxy, trifluoro
methoxy), alkylsulfonyl groups (e.g. methylsulfonyl),
Honyl, propylsulfonyl, butylsulfonyl, ben
dilsulfonyl), arylsulfonyl (e.g. phenylsulfonyl), arylsulfonyl (e.g.
Rusulfonyl, p-tolylsulfonyl, p-chlorophene
(nylsulfonyl), alkoxycarbonyl groups (e.g.
(toxycarbonyl, butoxycarbonyl), sulfona
Mido groups (e.g. methanesulfonamide, trifluoromethane)
tansulfonamide, toluenesulfonamide), cal
Bamoyl group (e.g. N,N-dimethylcarbamoyl, N
-phenylcarbamoyl) or sulfamoyl group (e.g.
For example, N,N-diethylsulfamoyl, N-phenyls
rufamoyl). R3 is preferably halo
Gen atom, cyano group, sulfonamide group, alkyl sulfate
Honyl group, arylsulfonyl group and trifluoromethyl group
a group having at least one substituent selected from the group consisting of
phenyl group, more preferably 4-cyanophenyl,
4-cyano-3-halogenophenyl, 3-cyano-4-
Halogenophenyl, 4-alkylsulfonylphenyl,
4-alkylsulfonyl-3-halogenophenyl, 4-
Alkylsulfonyl-3-alkoxyphenyl, 3-a
Rukoxy-4-alkylsulfonylphenyl, 3,4-
Dihalogenophenyl, 4-halogenophenyl, 3,4,
5-trihalogenophenyl, 3,4-dicyanophenyl
, 3-cyano-4,5-dihalogenophenyl, 4-tri
Fluoromethylphenyl or 3-sulfonamide phenylene
particularly preferably 4-cyanophenyl, 3-
Cyano-4-halogenophenyl, 4-cyano-3-halo
Genophenyl, 3,4-dicyanophenyl or 4-a
rukylsulfonylphenyl, most preferably 4
-cyanophenyl. In general formula (I), Z is water
elementary atoms or coupling-off groups (including leaving atoms;
(same as below). Preferred as a coupling-off group
or halogen atom, alkoxy group, aryloxy group or
or an alkylthio group, particularly preferably a chlorine atom,
A group represented by the following general formula (II) or a group represented by the following general formula (
III) is a group represented by: General formula (II) [Formula 5] (wherein, R12 is a halogen atom, a cyano group, a nitro group,
Alkyl group, alkoxy group, alkylthio group, alkyl
Sulfonyl group, arylsulfonyl group, carbonamide
group, sulfonamide group, alkoxycarbonyl group, carbonyl group,
Bamoyl group, sulfamoyl group or carboxyl group
, m represents an integer from 0 to 5. Here, when m is plural, R
12 may be the same or different. ) General formula (III) [Formula 6] (wherein, R13 and R14 are each a hydrogen atom or 1
A valent group, Y is -CO-, -SO-, SO2 - or
-(O)P(R16)-, R15 and R16 are respectively
hydroxyl group, alkyl group, aryl group, alkoxy
cy group, alkenyloxy group, aryloxy group, or
a substituted or unsubstituted amino group, p represents an integer of 1 to 6;
Was. Here, when p is plural, -C(R13)(R14
)- may be the same or different. ) In the general formula (II), R12 is preferably
or halogen atoms, alkyl groups (e.g. methyl, t-butyl
t-octyl, pentadecyl), alkoxy group (
For example, methoxy, n-butoxy, n-octyloxy,
benzyloxy, methoxyethoxy), carbonamide
groups (e.g. acetamide, 3-carboxypropanamide)
) or sulfonamide groups (e.g. methanesulfonate)
Mido, toluenesulfonamide, p-dodecyloxybe
(benzenesulfonamide), particularly preferably alkylene
or alkoxy group. m is preferably 0 to 2
, more preferably an integer of 0 or 1. In the general formula (III), R13 and
/or when R14 represents a monovalent group, preferably
Alkyl groups (e.g. methyl, ethyl, n-butyl, ethyl
xy, carbonylmethyl, benzyl, n-decyl, n-
dodecyl), aryl groups (e.g. phenyl, 4-chloro
phenyl, 4-methoxyphenyl), acyl groups (e.g.
acetyl, decanoyl, benzoyl, bivaloyl) and
is a carbamoyl group (e.g. N-ethylcarbamoyl, N
-phenylcarbamoyl), and R13 and R14 are
More preferably a hydrogen atom, an alkyl group or an aryl group
It is the basis. In general formula (III), Y is preferably -CO- or
or -SO2-, more preferably -CO-
be. In general formula (III), R15 is preferably
Alkyl group, alkoxy group, alkenyloxy group, ali
is an oxy group or a substituted or unsubstituted amino group.
, more preferably an alkoxy group or a substituted or unsubstituted
It is a substituted amino group. In general formula (III), p is
Preferably it represents an integer of 1 to 3, more preferably 1. [0030] Below, R1-SO in general formula (I)
A specific example of 2 -C(R2)HCONH- is shown below. [Chemical 7] [Chemical 8] [0032] Specific examples of R3 in the general formula (I) are as follows.
Give an example. [Chemical 9] [Chemical 10] Specific examples of Z in general formula (I) are shown below.
show. [Chemical 11] [Chemical 12] [Chemical 13] [Chemical 14] In addition, when Z is a coupling-off group, photographically useful
Contains no groups (e.g. development inhibitor residues, dye residues)
is preferable. Next, typical examples of the coupler of the present invention will be described.
Examples are shown, but the present invention is not limited thereto. [Chemical 15] [Chemical 16] [Chemical 16] [Chemical 17] [Chemical 18] [Chemical 19] 2-Ureido represented by the general formula (I)
The phenol type cyan coupler is published by Special Publication No. 63-11656.
and U.S. Pat. No. 4,775,616.
It can be manufactured according to the following. Below, the method for synthesizing the coupler of the present invention will be described.
Specifically shown. Synthesis Example 1 Invention Coupler Example C-2
Synthesis of Intermediate 2 Synthesis of Intermediate 2 In a 2 liter three-necked flask equipped with a stirrer, n-hexyl was added.
Sadecyl mercaptan (commercial reagent) 130g (0.5
mol), α-bromocaproic acid ethyl ester 123g
(0.55 mol) and 500 ml of ethyl alcohol.
Then add 93% caustic soda at room temperature under a nitrogen stream while stirring.
25.9g (0.55mol) was dissolved in 100ml of water.
The solution was added dropwise. After dropping, stir for 4 hours and then let stand overnight.
Ta. Next, 500 ml of tetrahydrofuran, methylalcohol
200 ml of coal and 43.0 g of 93% caustic soda (1
．． 0 mol) and stirred at room temperature for 1 hour, white crystals were formed.
It precipitated. Dissolve by heating, neutralize with hydrochloric acid, and then add ethyl acetate.
Extracted with. After dehydration with anhydrous sodium sulfate, the solvent is distilled off.
and recrystallized with n-hexane to obtain white crystals 16 of intermediate 2.
9 g (yield 90%) was obtained. Synthesis of Intermediate 3 Intermediate 2 was placed in a 1 liter three-necked flask equipped with a stirrer.
55.9 g (0.15 mol), 230 ml of acetic acid and
Add 0.6g of sodium tungstate and stir at room temperature.
42.5g (0.375mol) of 31% hydrogen peroxide solution
was dripped. The reaction system became clear and dissolved with an exotherm. the
When stirring was continued, the product precipitated over the entire surface. heating melting
After dissolving and filtering out insoluble matter, add 300 ml of acetonitrile.
and cooled. The precipitated crystals were collected by filtration and diluted with acetonitrile.
After washing, 49.4 g of white crystals of intermediate 3 (yield 81%) were obtained.
) was obtained. Synthesis of Intermediate 4 Calcium chloride 200 ml equipped with drying tube and stirrer
12.2 g of intermediate 3 (0.030 g
mol), methylene pre-dried with molecular sieves
Add 100 ml of chloride, and stir at room temperature.
Add 5.2 ml (0.060 mol) of zaryl chloride dropwise.
Ta. Then, add 1 ml of N,N-dimethylformamide.
When heated, foaming was observed. Stir for 1 hour at room temperature.
After that, insoluble matter was filtered off, and the solvent was distilled off to form a colorless oil.
12.0 g (yield 95%) of Intermediate 4 was obtained. child
When left to stand, it turned into white crystals. Synthesis of Intermediate 5 1 liter three-necked flask equipped with a stirrer and a reflux condenser
4-chloro-5-nitro-2-aminophenol 5
6.6g (0.3 mol), N-(p-cyanophenyl)
Phenyl carbamate 71.5g (0.3 mol), immi
2.4 g (0.03 mol) of dazole and acetonitrile
600 ml was added and stirred under heating and reflux for 3 hours. room temperature
After cooling to
48.5 g of yellow crystals of Intermediate 5 (yield:
49%). Synthesis of Intermediate 6 and Inventive Coupler Example C-21 Electromagnetic Stirring
200ml three spout equipped with stirring device and hydrogen gas supply device
10.0 g (0.03 mol) of intermediate 5 in the flask,
and 200 ml of N,N-dimethylacetamide were added,
It was dissolved at 40°C. To this, 10% palladium carbon
Add 1.0 g of catalyst and hydrogenate at normal pressure while stirring at 40°C.
Ta. The reaction was completed after 10 hours and intermediate 6 was produced.
was confirmed by thin layer chromatography. this reaction
Add 12.1 g (0.03 mol) of intermediate 4 to the solution.
Ta. After stirring for 1 hour, the catalyst was filtered off and vinegar was added.
After extraction with ethyl acid and washing with dilute hydrochloric acid, chloroform monoacetic acid was added.
Column chroma using ethyl (mixing ratio 3:1) as a developing solvent
A white solid of the present coupler example C-21 was obtained by toography.
10.5 g (yield 51%) was obtained. DI-EI mass spec
vector: parent peak not observed, fragment peak m/
e=570, 544, 158, 144, 118, etc. this
supported the objective structure. [Table 1] [0054] The silver halide photographic light-sensitive material of the present invention
A cyan coupler represented by general formula (I) is placed on the support.
It has at least one layer containing. Cyanka of the present invention
The layer containing the puller is a hydrophilic colloid on the support.
It suffices if it is a hard layer. Common color photosensitive materials have a support
Blue-sensitive silver halide emulsion layer on top, green-sensitive silver halide emulsion layer
at least one silver halide emulsion layer and a red-sensitive silver halide emulsion layer.
It can be configured by coating in this order, but it is different from this.
It may be in any order. In addition, infrared-sensitive halogen
A silver oxide emulsion is used instead of at least one of the photosensitive emulsion layers described above.
It can be used for. These photosensitive emulsion layers include
Silver halide emulsions sensitive to each wavelength range and
Color caps that form pigments that have a complementary color relationship with the emitted light.
By containing color, subtractive color reproduction can be performed.
Wear. However, the color developed by the photosensitive emulsion layer and color coupler
A phase may also be a configuration that does not have the above correspondence.
. Hydrophilic properties on supports containing cyan couplers of the invention
These colloidal layers are sensitive to visible or infrared regions.
silver halide emulsion layer or its adjacent layer with
Ru. In order to achieve the object of the present invention, it is preferable that photosensitive
A silver halide emulsion layer, more preferably a red-sensitive halide emulsion layer.
This is a silver germide emulsion layer. The amount of the cyan coupler of the present invention added is 1 m
0.002 to 5 mmol per 2, preferably 0.01
~2 mmol. In the photosensitive material of the present invention, the general formula
The cyan coupler represented by (I) may be used alone.
You may use a mixture of two or more types. Also, the general formula (I
) may be used in combination with cyan couplers other than cyan couplers. However, in this case, the cyancapacitor represented by general formula (I)
The proportion of cyan coupler in total is 50 mol%.
It is preferable that the amount is 75 mol% or more.
Even more preferred. The cyan coupler of the present invention can be prepared from various known materials.
Dispersion methods, such as U.S. Pat. No. 2,322,027,
Oil-in-water dispersion method described in U.S. Pat. No. 4,199,363
No. 2,541,274, West German Patent Application No. 2,541,274,
No. 2,541,230, Special Publication No. 53-41091 and
and the polymer content described in European Patent Publication No. 029104 etc.
Dispersion method, PCT International Publication No. W088/00723 details
By the dispersion method using an organic solvent soluble polymer described in the book
Can be introduced into photosensitive materials. Dispersion medium for such couplers and
Dielectric constant (25℃) 2-20 (preferably 2-5)
, a high boiling point organic solvent with a refractive index (25°C) of 1.5 to 1.7;
and/or insoluble polymeric compounds are preferably used.
. The cyan coupler of the present invention includes phthalic acid.
Ester-based (e.g. dibutyl phthalate, dioctyl
phthalates), aliphatic esters (e.g. succinic acid di-
butoxyethyl) and chlorinated paraffinic high boiling point organic
Solvents are preferred. As a high boiling point organic solvent, preferably the following
The high boiling point organic solvent represented by the general formulas (A) to (E) is
used. [Image Omitted] (In the formula, W1, W2, W3 are each substituted or
is an unsubstituted alkyl group, cycloalkyl group, alkenyl
group, aryl group or heterocyclic group, W4 is W
1, OW1 or S-W1, and n is 1.
is an S integer of I to 5, and when n is 2 or more, W4 is mutually
may be the same or different, and in general formula (E)
, W1 and W2 may form a condensed ring. ) Among these, general formulas (B) and (C)
Particular preference is given to the high-boiling organic solvents shown. Used in the present invention
The high boiling point organic solvents mentioned above are those having general formulas (A) to (E) or below.
Water with a melting point below 100℃ and a boiling point above 140℃ even outdoors.
It is an immiscible compound and can be used if it is a good solvent for the coupler.
Wear. The melting point of the high boiling point organic solvent is preferably 80°C or lower.
be. The boiling point of the high boiling point organic solvent is preferably 160°C or higher.
and more preferably 170°C or higher. these
For details on high boiling point organic solvents, see JP-A-62-21
5272 Publication Specification, page 137 lower right column to page 144 right
It is listed in the upper column. [0060] These couplers also have the above-mentioned high boiling point.
Loadable latex in the presence or absence of organic solvents
polymers (e.g. U.S. Pat. No. 4,203,716)
or water-insoluble and organic solvent-soluble porous.
Dissolve in reamer and emulsify and disperse in hydrophilic colloid aqueous solution.
can be done. Preferably International Publication WO88/007
The homopolymer described on pages 12 to 30 of Specification No. 23 or
Copolymers are used, especially acrylamide-based polymers.
The use of is preferred from the viewpoint of color image stabilization and the like. The cyan coupler of the present invention is a high boiling point organic solvent.
(If necessary, a low boiling point organic solvent may be used in combination.)
Silver halide milk is dissolved and emulsified and dispersed in gelatin aqueous solution.
It is preferable to add it to the agent. High-boiling organic solvents are couplers
0 to 2.0 times, preferably 0 to 1.0 times, by weight.
Can be used in 0x amount. The cyan coupler of the present invention
0 to 0.1 times the amount of high-boiling organic solvent compared to cyan coupler
Can be stably dispersed even in medium. [0062] The cyan coupler of the present invention can be used, for example, for color
paper, color reversal paper, direct positive color photosensitive material
Applicable to film, color positive film, color reversal film, etc.
can. Among them, color photosensitive materials having a reflective support (
For example, color paper, color reversal paper) or positive painting
Image-forming color photosensitive materials (e.g. direct positive color photosensitive materials)
Optical materials, color positive films, color reversal films)
It is preferable to apply
Application to optical materials is preferred. Silver halide emulsion used in the present invention
Silver iodobromide, silver iodochlorobromide, silver bromide, silver chlorobromide, chloride
It may be of any halogen composition such as silver. Preferred c
The fluorine composition varies depending on the type of photosensitive material used.
Silver chlorobromide emulsions are mainly used for color paper, etc.
Photosensitive materials for photography such as lane negative film contain iodobromide.
Silver emulsions, direct positive color photosensitive materials, etc. do not contain silver bromide or salt.
A silver bromide emulsion is used. In addition, the color is suitable for rapid processing.
- Paper photosensitive materials contain so-called high silver chloride content.
High silver chloride emulsions are preferably used. In the present invention, in particular, substantially no silver iodide is used.
It is preferable to use silver chlorobromide or silver chloride that does not contain
It can be used in many ways. "Substantially contains silver iodide"
"No" means that the silver iodide content is 1 mol% or less, preferably
It means 0.2 mol% or less. 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 difference in composition, mixed crystals are formed and the boundaries are unclear.
It is also possible to actively create continuous structural changes.
It may be something. Regarding the halogen composition of these silver chlorobromide emulsions,
The chloride content is usually 90 mol% or more, and 95 mol% or more.
% or more is preferable. Silver chloride should be 90 mol% or more.
Improves color development during rapid processing, or reduces color mixing.
It should be improved. These high silver chloride emulsions
As mentioned above, the silver bromide localized phase can be layered or non-layered.
Structures inside and/or on the surface of silver halide grains
It is preferable to use a wooden one. The halogen composition of the above localized phase is
Preferably, the silver oxide content is at least 10 mol%.
More preferably, it exceeds 20 mol%. and
, these localized phases are located inside the particle, at the edges of the particle surface, and at the core.
corner or surface, but one preferred
A good example is epitaxial growth on the corners of particles.
I can list some things that I did. On the other hand, the sensitivity when the photosensitive material is subjected to pressure
Silver chloride content is 90 mol% or more in order to suppress the decline as much as possible.
Even in high silver chloride emulsions, the halogen composition within the grains is
It is also preferred to use particles of small uniform structure in the fabric.
be exposed. In addition, the developing processing solution can be adjusted without causing fluctuations during continuous processing.
The silver chloride content of silver halide emulsions is
It is also effective to further increase the coverage rate. In such a case
has a silver chloride content of 98 mol% to 100 mol%.
Emulsions of substantially pure silver chloride, such as those described above, are also preferably used. Contained in the silver halide emulsion used in the present invention
Average size of silver halide grains (projected area of grains, etc.)
The particle size is determined by the diameter of the circular circle, and the number average is taken.
) is preferably 0.1 μm to 2 μm. Also, that
These particle size distributions are determined by the coefficient of variation (standard deviation of particle size).
difference divided by average particle size) 20% or less, preferably
A so-called monodisperse material having a concentration of 15% or less is preferable. child
When using the above monodispersed milk to obtain a wide latitude,
Blending agents in the same layer or applying multiple layers
This is also preferably done. Silver halide grains contained in the photographic emulsion layer
Shapes are regular like cubes, tetradecahedrons or octahedrons
regular Something with a crystalline shape, spherical,
Irregular, such as plate-like
Those that have crystalline forms or those that have composite forms of these
can be used. It also has various crystal forms.
It may also consist of a mixture of materials. The present invention
Among these, particles with the above-mentioned regular crystal shape
50% or more, preferably 70% or more, more preferably
The content is preferably 90% or more. The silver halide emulsion used in the present invention is:
So-called surface latent image where the latent image is mainly formed on the particle surface.
A type emulsion, or latent image, is formed primarily inside the grains.
Which type of so-called internal latent image emulsion is used?
It's okay. 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
and types), and the same magazine No. 18716(
(November 1979), p. 648, Grafkide, “Photography”
"Physics and Chemistry", published by Paul Montell (P. Glafk)
ides Chemie et Physique P
photographique, Paul Monte
L, 1967), Duffin, “Photographic Emulsion Chemistry”, F.
Published by Local Press (G. F. Duffin, P.
photographic emulsion Che
mistry (Focal Press, 1966)
), “Manufacture and Coating of Photographic Emulsions” by Zelikman, Focus
Published by Le Press (V. L. Zeliman et al.
al. ,Makingand Coating Pho
tographic Emulsion, Focal
Press, 1964) etc.
It can be prepared by U.S. Patent No. 3,574,62
No. 8, No. 3,655,394 and British Patent No. 1,41
Monodisperse emulsions such as those described in No. 3,748 are also preferred. Also, tabular grains with an aspect ratio of about 5 or more
can also be used in the present invention. The silver halide emulsion used in the present invention is:
Usually, those that have undergone physical ripening, chemical ripening, and spectral sensitization.
use. The silver halide emulsion used in the present invention is
In the process of agent particle formation or physical ripening, various polyvalent
Metal ion impurities can be introduced. to use
Examples of compounds include cadmium, zinc, lead, copper, and thallium.
salts such as aluminum, or group VIII elements such as iron and ruthenium.
Taenium, rhodium, palladium, osmium, iridium
Examples include salts or complex salts such as aluminum, platinum, etc.
. In particular, the Group VIII elements mentioned above can be preferably used.
Ru. The amount of these compounds added varies widely depending on the purpose.
is preferably 10-9 to 10-2 mol relative to silver halide.
Yes. Silver halide emulsion used in the present invention
Additives used in physical ripening, chemical ripening and spectral sensitization processes
is Research Disclosure No. 17643,
Same No. 18716 and the same No. Listed in 30715
The relevant sections are summarized in the table below. To the present invention
Known photographic additives that can be used are also included in the above three research studies.
・Listed in the disclosure and related to the table below
We have shown the locations where it is written. Additive type RD1764
3 RD18716
RD307105 1 Chemical sensitizer
23 pages 648 pages
Right column page 866 2
Sensitivity enhancer
Page 648 right column
3 spectral sensitizer,
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
Supersensitizer 2
Pages 3 to 24 Page 648 right column to Page 649 right column
Pages 866-868 4 Brightener
24 pages 647 pages
Right column page 868 5
antifoggant,
　　　　　　　　　　　　　　　　　　　　　　　　　
stabilizer
pages 24-25 6
Page 49, right column, pages 866-870
6 Light absorbers, fi
　　　　　　　　　　　　　　　　　　　　　　　　　
Luther dyeing
fee,
　　　　　　　　　　　　　　　　　　　　　　　　　
UV absorber
Pages 25-26 Page 649 right column - Page 650 left column
Page 873 7 Stain inhibitor
Page 25 right column Page 650 left column ~
Right column page 872 8 Dye image
Stabilizer page 25
Page 650 left column Page 872
9 Hardener
Page 26 Page 651 Left column
Pages 874-875 10 Binder
26 pages
Page 651 left column 873-874
Page 11 Plasticizer, lubricant Page 27
Page 650 right column
Page 876 12 Coating aid, surface
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
Activator 2
Pages 6-27 Page 650 Right column
Pages 875-876 13 Static inhibitor
Page 27 Page 650 Right
Column 876-877 page 14
matting agent
　　　　　　　　　　　　　　　　　　　　　　　　　
Pages 878-879
In order to prevent deterioration of photographic performance due to rudehyde gas,
U.S. Patent No. 4,411,987 and U.S. Patent No. 4,435,5
Fixed by reacting with formaldehyde described in No. 03
It is also possible to add to the photosensitive material a compound that can be converted into [0076] The present invention uses various color couplers in combination.
A specific example of this can be found in the research study mentioned above.
Closure (RD) No. 17643, VII-C~
G and the same No. 307105, described in VII-C to G
described in the patent issued by [0077] Preferably used in combination with the cyan coupler of the present invention.
Cyan coupler, magenta coupler and yellow coupler
The puller has the following general formula (C-I), (C-II), (M
-I), (M-II) and (Y)
. However, for cyan couplers, the general formula (I) is
It is preferable to use the compound in an amount of 50 mol% or more. [Formula 27] [Formula 28] [Formula 28] [Formula 29] [Formula 30] [Formula 31] [Formula 31] )smell
R1, R2 and R4 are substituted or unsubstituted
represents an aliphatic, aromatic or heterocyclic group, R3, R5
and R6 is a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group.
represents an aromatic group or an acylamino group, R3 is R2
A nonmetal that forms a nitrogen-containing 5- or 6-membered ring with
It may also represent a group of atoms. Y1 and Y2 are hydrogen atoms or
or released during the coupling reaction with the oxidized form of the developing agent.
Represents a glutinous group. n represents 0 or 1. As R5 in general formula (C-II)
is preferably an aliphatic group, for example, a methyl group,
Ethyl group, propyl group, butyl group, pentadecyl group, t
ert-butyl group, cyclohexyl group, cyclohexyl
Methyl group, phenylthiomethyl group, dodecyloxyphene
Nylthiomethyl group, butanamidomethyl group, methoxymethyl group
Examples include chill group. The above general formula (C-I) or (C-II)
A preferred example of a cyan coupler represented by is as follows.
be. In general formula (C-I), preferable R1 is ali
halogen atom, alkyl group,
Alkoxy group, aryloxy group, acylamino group, alkoxy group, aryloxy group, acylamino group,
Syl group, carbamoyl group, sulfonamide group, sulfa group
Moyl group, sulfonyl group, sulfamide group, oxycal group
Must be an aryl group substituted with a bonyl group or cyano group
is even more preferable. In general formula (C-I), R3 and
When R2 does not form a ring, R2 is preferably substituted
or an unsubstituted alkyl group or aryl group, especially
Preferred is a substituted aryloxy-substituted alkyl group.
, R3 is preferably a hydrogen atom. Preferred R4 in general formula (C-II)
is a substituted or unsubstituted alkyl group, and is particularly preferred.
or a substituted aryloxy-substituted alkyl group. Preferred R5 in general formula (C-II)
is an alkyl group having 2 to 15 carbon atoms, and is an alkyl group having 1 or more carbon atoms.
It is a methyl group with a substituent, and the substituent is an aryl group.
ruthio group, alkylthio group, acylamino group, aryl
Oxy groups and alkyloxy groups are preferred. General formula (C-
In II), R5 is an alkyl group having 2 to 15 carbon atoms;
More preferably, an alkyl group having 2 to 4 carbon atoms
It is particularly preferable that Preferred R6 in general formula (C-II)
are hydrogen atoms, halogen atoms, chlorine atoms and fluorine atoms.
Elementary atoms are particularly preferred. General formulas (C-I) and (C-I
Preferred Y1 and Y2 in I) are each water
Elementary atoms, halogen atoms, alkoxy groups, aryloxy
group, acyloxy group, and sulfonamide group. In general formula (M-I), R7 and R
9 represents an aryl group, R8 is a hydrogen atom, an aliphatic group
or aromatic acyl group, aliphatic or aromatic group.
represents a sulfonyl group, and Y3 represents a hydrogen atom or a leaving group.
represent. R7 and R9 are aryl groups (preferably phenyl groups)
) are the permissible substituents for substituent R1.
When there are two or more substituents
may be the same or different. R8 is preferably water
an elementary atom, an aliphatic acyl group or a sulfonyl group,
Particularly preferred is a hydrogen atom. Preferred Y3 is io
Iu, a type that leaves with either oxygen or nitrogen atoms
For example, U.S. Patent No. 4,351,897 and
It is described in International Publication WO/88/04795.
The sulfur atom detachment type is particularly preferred. In general formula (M-II), R10 is water
Represents an elementary atom or a substituent. Y4 is a hydrogen atom or
Represents a leaving group, especially a halogen atom or an arylthio group.
preferable. Za, Zb and Zc methine, substituted methine, =
Represents N- or -NH-, with Za-Zb bond and Zb-Z
One of the c bonds is a double bond and the other is a single bond.
Ru. If the Zb-Zc bond is a carbon-carbon double bond,
Including cases where it is part of an aromatic ring. R10 or Y4
When a dimer or more multimer is formed with Za, Z
When b or Zc is a substituted methine, the substituted methine
This includes the case where a dimer or more multimer is formed with the molecule. general formula
Pyrazoloazole coupler represented by (M-II)
Among these, the yellow side absorption of the coloring dye is low and the light fastness is excellent.
The imitation described in U.S. Pat. No. 4,500,630 in terms of
Dazo[1,2-b]pyrazoles are preferred, and U.S. Pat.
Pyrazolo [1,5-b as described in No. 4,540,654
][1,2,4]triazole is particularly preferred. [0091] Others described in Japanese Patent Application Laid-open No. 61-65245
A branched alkyl group such as
Directly linked to the 2, 3 or 6 position of pyrazolotriazole
Puller, as described in JP-A No. 61-65246.
Pyrazolotriazole containing a sulfonamide group in the molecule
Coupler, described in JP-A-61-147254
Alkoxyphenylsulfonamide ballast groups such as
Motsu pyrazolotriazole coupler and European patent (published)
No. 226,849 and No. 294,785.
A pin having an alkoxy group or an aryloxy group at the 6-position such as
The use of lazolotriazole couplers is preferred. In the general formula (Y), R11 is halogen
atom, alkoxy group, trifluoromethyl group or ali
R12 represents a hydrogen atom, a halogen atom or a
represents an alkoxy group. A is -NHCOR13,
-NHSO2-R13, -SO2NHR13, -CO
OR13 represents -SO2N(R13)(R14)
vinegar. However, R13 and R14 are an alkyl group and an alkyl group, respectively.
Represents a lyl group or an acyl group. Y5 represents a leaving group
Was. As substituents for R12, R13, and R14, R1
are the same as the substituents allowed for leaving group Y5
is preferably either an oxygen atom or a nitrogen atom
A type that leaves a nitrogen atom, and a nitrogen atom split type is particularly preferable.
stomach. General formulas (C-I), (C-II), (M-
I), (M-II) and (Y) couplers
Specific examples are listed below. Shea of general formula (I) of the present invention
The coupler is represented by the general formula (M-I) or (M-II).
magenta coupler represented by general formula (Y), and i
Preferably used in combination with yellow couplers. In particular, these three types are applied to the photosensitive layer provided on the reflective support.
Combine couplers to achieve unprecedented color reproducibility.
Can be done. The magenta coupler in this case is a photosensitive halide.
Usually 0.003 to 3.0 mole per mole of silver halide
mol, preferably 0.015 to 1.5 mol.
However, the amount of coating per square meter is 0.01.
and 5 mmol, preferably 0.1 to 2 mmol.
It is le. [0095] The yellow coupler is also a photosensitive halogen
Usually used from 0.01 to 4.0 mol per mol of silveride.
and preferably used from 0.05 to 2.0 mol, and
Coating amount per square meter is 0.02 to 8.0
mmol, preferably 0.2 to 3.0 mmol
It is le. Moreover, general formula (M-II) is preferably the following:
Particularly preferred are compounds represented by the following formula. embedded image In general formulas (M-IIa) and (M-IIb), R10
, Y4 is R10 in general formula (M-II), Y4
is synonymous with R15 represents a hydrogen atom or a substituent. 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 [0104] [0104] [0105] [0105] [0106] [Table 2] [0107] [Table 3] [0108] [Table 4] [0109] [Table 5] [0110] [Table 6] ] Table 7 Table 8 Table 8 Standard use of color couplers that can be used together
The amount is 0.001 to 1 mole per mole of photosensitive silver halide.
preferably in the range of 0 for yellow couplers.
．． 01-0.5 mol, 0.00 for magenta coupler
3-0.3 mol, cyan coupler 0.002-0.
It is 3 moles. [0119] Can be used in the photosensitive material of the present invention
In addition to the above-mentioned RD magazine, additives are also available in European Patent No. 337,4.
Oxonol dye described in No. 90A2, European Patent No. 277
Color image storage improving compound described in No. 589, JP-A-63-2
Antifungal agent described in No. 71247, JP-A-62-215272
No. 2-33144, European Patent No. 355,66
Silver halide emulsion described in No. 0, silver halide solvent, chemistry
Sensitizer, spectral sensitizer, emulsion stabilizer, development accelerator, color
Couplers, color enhancers, ultraviolet absorbers, anti-fading agents, high
Boiling point or low boiling point organic solvent, hardener, developing agent precursor
agents, development inhibitors, release compounds, dyes, antifade agents,
Conditioning agent, anti-stain agent, surfactant, antistatic agent,
Coating aids, lubricants, anti-adhesion agents, binders, thickeners,
Examples include polymer latex, matting agents, etc.
Ru. We also discuss dispersion methods for photographic additives, supports, sensitive material layers, and structures.
These include the following: [0120] The support used in the present invention is usually
Cellulose nitrate used in photographic materials
Transparent film such as film or polyethylene terephthalate
Lumens and reflective supports can be used. For the purpose of this invention
Therefore, it is more preferable to use a reflective support. [0121] "" which can be preferably used in the present invention
"Reflective support" is a silver halide emulsion layer that increases reflectivity.
This refers to something that sharpens the pigment image formed on the
Una reflective support has titanium oxide and zinc oxide on the support.
, calcium carbonate, calcium sulfate, etc.
Those coated with a hydrophobic resin containing dispersed materials or those coated with light-reflecting substances.
Contains those using dispersed hydrophobic resin as a support.
will be included. For example, baryta paper; polyethylene coated paper;
Lipropylene synthetic paper; with a reflective layer or reflective material
A transparent support (e.g. glass plate, polyethylene
Nterephthalate, cellulose triacetate or nitrate cell
Polyester film, polyamide film for loin etc.
film, polycarbonate film, polystyrene film
, vinyl chloride resin, etc.). Next, color development represented by general formula (D)
Explain the medicine in detail. R4 is hydrogen atom, halogen
R4 is a halogen atom or a methyl group, and R4 is a halogen atom.
When a fluorine atom, chlorine atom, bromine atom or iodine atom
It is an elementary atom. R4 is preferably a methyl group. R5 and R6 are methyl group or ethyl
group, R5 is an ethyl group, and R6 is a methyl group
It is. L is a methylene group or an ethylene group, preferably an ethylene group.
It is a tyrene group. Next, color development represented by general formula (D)
Specific examples of drugs are shown. [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted]
-1 color developer. Represented by general formula (D)
Aromatic primary amines are described in British Patent No. 651,749;
No. 651,909, U.S. Patent No. 2,566,271
No., Journal of the American
Chemical Society 73 3100 (
1951) (Journal of the American
Chemical Society Magazine Volume 73 310
Preferably produced by the method described in Page 0 (1951)
can. The color developer of the present invention is represented by the general formula (D).
Compounds that are mixed with sulfates, hydrochlorides, sulfites, p-tol
It may also be a salt such as an ensulfonate. The power of the present invention
The amount of color developer to be used is the preferred amount per 1 liter of color developer.
Preferably about 0.1 g to about 20 g, more preferably about
Concentrations range from 0.5 g to about 10 g. Color developer of the present invention
is mainly composed of a color developer represented by the above general formula (D).
It is an alkaline aqueous solution containing a Furthermore, the effects of the present invention
Other aromatic primary amine groups may be used as long as they do not interfere with
An imaging agent may be used in combination. [0130] The color developing solution contains alkali metal carbonates,
pH buffering agents such as borates or phosphates; chloride salts
, aminetetraacetic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, nitrilo-N,N,N-trimethylenepho
Sulfonic acid, ethylenediamine-N,N,N,N-tetra
methylenephosphonic acid and their salts): 4,4'-dia
Fluorescent compounds such as mino-2,2-disulfostilbene compounds
Photobrightener; alkylsulfonic acid, arylsulfonic acid,
Various interfaces such as aliphatic carboxylic acids and aromatic carboxylic acids
Activators and the like can be added. [0131] Color developing solutions for printing materials mainly include
benzyl alcohol to increase the rate of pigment formation.
and diethylene glycol as its auxiliary solvent.
has been used. However, benzyl alcohol
This is undesirable as it causes high BOD of wastewater. For this reason
In recent years, in this industry, benzyl amines have been replaced with color developing solutions.
Progress is being made in the direction of eliminating lucor. [0132] However, the removal of benzyl alcohol
Required in the industry to slow down color development
This is contradictory to the direction of speeding up. Techniques to solve this
As a technique, silver chloride emulsion and benzyl alcohol were introduced.
A technology has been developed to reduce the concentration of sulfite ions from the removed processing liquid.
It has become possible to achieve both environmental conservation and speed-up. [0133] In carrying out the present invention, substantially
Use a color developer that does not contain diyl alcohol.
is preferred. Here, it is preferable that it does not substantially contain
is 2 ml/liter or less, more preferably 0.5 ml
Benzyl alcohol concentration of less than /liter, the most
Preferably does not contain any benzyl alcohol
It is. [0134] The color developing solution used in the present invention is sulfite
More preferably, it does not substantially contain ions. sulfur
Acid ions act as preservatives for color developers and at the same time
In addition, silver halide dissolving action and reaction with oxidized color developer
Accordingly, it has the effect of lowering the dye formation efficiency. This way
These effects are the reason for the increased variation in photographic properties that accompanies continuous processing.
This is presumed to be one of the causes. Here, it means that it does not substantially contain
, preferably 3.0 x 10-3 mol/liter or less
sulfate ion concentration, most preferably sulfite ion.
It must not contain at all. However, in the present invention
, a process in which the developing agent is concentrated before being mixed into the working solution.
A very small amount of sulfite ion is used to prevent oxidation in the agent kit.
are excluded. [0135] The color developer used in the present invention is sulfite
Preferably, it is substantially free of ions, but further
More preferably, it does not substantially contain hydroxylamine.
Delicious. This is because hydroxylamine is a preservative in the developer.
At the same time, it also has silver developing activity and is a hydrocarbon.
Fluctuations in the concentration of xylamine greatly affect photographic properties
This is because it is thought that. Hydroxylamine here
Preferably, the content is substantially free of 5.0×1
At hydroxylamine concentrations below 0-3 mol/liter
most preferably contains no hydroxylamine.
There is no such thing. The developer used in the present invention is
JP-A-1-9 instead of droxylamine or sulfite ion
No. 7953, No. 1-186939, No. 1-18694
No. 0, hydroxylamine described in No. 1-187557
derivatives, or organic preservatives such as hydrazine derivatives.
It is more preferable to contain it. [0136] In the present invention, chlorine ion is added to the color developer.
3.5 x 10-2 to 1.5 x 10-1 mol/liter
Contains 100% polyester for quick development, color development, and anti-fogging properties.
preferred. Particularly preferably 4 x 10-2 to 1 x 1
It is 0-1 mol/liter. Also, in color developer
Bromine ion from 3.0 x 10-5 to 1.0 x 10-3 mol
/ liter contains rapid developability, color development, sensitivity,
This is preferable from the viewpoint of preventing fogging. More preferably 5.0
x10-5 to 5 x 10-4 mol/liter. here
In this case, chloride and bromide ions are added directly to the developer.
may be eluted from the photosensitive material into the developer during processing.
Good too. When added directly to the color developer, chlorine
Sodium chloride, potassium chloride as ion supply substances
, ammonium chloride, lithium chloride, nickel chloride, salt
Magnesium chloride, manganese chloride, calcium chloride, chloride
Examples include cadmium, but the preferred one is salt.
sodium chloride and potassium chloride. Also, in the developer
It may also be supplied from an added optical brightener. [0138] Sodium bromide is used as a bromide ion supply material.
potassium bromide, ammonium bromide, lithium bromide
, calcium bromide, magnesium bromide, manganese bromide,
Nickel Bromide, Cadmium Bromide, Cerium Bromide, Ta Bromide
Among them, potassium bromide is preferred.
Lium, sodium bromide. [0139] When eluted from the photosensitive material during the development process,
Both chloride and bromide ions may be supplied from the emulsion.
However, it may be supplied from a source other than the emulsion. Color development of the present invention
The pH of the liquid is preferably 9-12, preferably 9-11.
0 is more preferable. [0140] The color photosensitive material of the present invention has a color forming material of the present invention.
The absorption spectrum is sharp and the hue is good due to the developer.
, and can obtain cyan dye images with high color density.
. Generally, the color photosensitive material of the present invention is desilvered after color development.
Processed and washed with water. A bleaching solution is used in the desilvering process.
Instead of a bleaching process and a fixing process using a fixer solution,
A bleach-fixing process using a white fixer can also be performed.
The bleaching process, fixing process, and bleach-fixing process are optional.
May be combined in this order. An inexpensive alternative to the water washing process
A stabilization process may be performed, or the stabilization process may be performed after a water washing process.
You may perform the process. In combination with these processing steps
, a pre-hardening process, its neutralization process, a stop-fixing process,
A postdural treatment process, adjustment process, reinforcing process, etc. may be performed.
. An intermediate washing step may be optionally provided between the above steps.
. [0141] In addition, as a color reversal development process, general
Specifically, black and white development process, water washing or rinsing process,
A reversal process and a color development process are performed. Reversal treatment
For the treatment process, an inversion bath containing a fogging agent was used.
Alternatively, a light reversal process may be used. In addition, the above fogging agent
It is also possible to omit the reversal process by incorporating the color developer into the color developing solution.
stomach. Processing steps and color development formulations other than the developing agent of the present invention.
Regarding other processing liquids, etc., please refer to the above-mentioned RD magazine and
No. 62-215272, Japanese Patent Application Publication No. 2-33144, European
Also described in State Patent No. 355,660A2
Can be used. [Example] The effects of the present invention will be specifically explained by examples.
However, the present invention is not limited thereto. Example 1 Primed cellulose triacetate support
A monochromatic color consisting of two layers, an emulsion layer and a protective layer, is formed on the carrier.
A photosensitive material was prepared with the composition shown below. The numbers are
Items other than puller were expressed in units of g/m2. (Ha
Regarding silver halogenide, the value is expressed in terms of silver) 01
44] Emulsion layer Silver chlorobromide emulsion (silver chloride 80 mol%, average grain size
0.3μm)
Silver
0.8 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.2 Coupler (see Table 1)
mol/m2 unit
0.001 dibutyl phthalate
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3 [0145] Protective layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.9 Polymethyl methacrylate grains
Child (diameter 1.5μm) 0.4
Sodium 1-oxy-3,5-dichloro-s-triazine
0.04 0146] Each sample was measured with a sensitometer (Fuji
Photo Film Co., Ltd., FWH type, light source color temperature 32
00°K) and a three-color separation filter for sensitometry.
Red gradation exposure was given through a router. Exposure at this time
The exposure time is 0.1 seconds and the exposure amount is 250CMS.
I went to sea urchin. After exposure, the sample undergoes the following processing steps and
Processing is performed using an automatic processor using a processing solution composition.
It was. 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 Sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0g potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
30g
N-ethyl-N-(β-methanesulfone
amidoethyl)
-3-methyl-4-aminoaniline sulfate
4.5g hydro
xylamine sulfate
3.0g Fluorescence increase
Whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical)
Add 1.0g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH
(25℃)
10.25
Bleach-fix water
　　　　　　　　　　　　　　　　　　　　　　　　　
400ml ammonium thiosulfate (
70%)
150ml sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
18g ethylenediamine
Iron (III) ammonium tetraacetate
55g Ethylenediaminetetraacetic acid dibasic acid
thorium
Add 5g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
6.70 Washing water a
On-exchange water (calcium, magnesium 3ppm each)
Below) The color density of the cyan coloring sample obtained in this way is 1.
The absorption spectrum of the part was measured. (with an integrating sphere attached)
UV-visible spectrophotometer UV-260 model manufactured by Shimadzu Corporation
) The long wave side shape of the absorption form of cyan dye is cyan.
Absorption sharpness is not important to the hue of the image.
is the half-width on the short wavelength side, that is, the absorbance at the maximum absorption wavelength.
Short wavelength side that gives 1/2 absorbance and maximum absorption wave
The evaluation was based on the wavelength difference from the long wavelength. Next, the color of the present invention in the color developer is
-Developer N-ethyl-N-(β-methanesulfonamide
ethyl)-3-methyl-4-aminoaniline sulfate (this
color developer A) instead of 4.5g, use a negative color developer.
color developer 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)aniline (color development
Using 3.0 g of drug B), perform exactly the same operation as above.
The absorption spectrum of the colored cyan dye was evaluated. Conclusion
The results are shown in Table 9, Table 10, and Table 11. [Table 9] [Table 10] [Table 11] [Chemical 50] [Chemical 51] [Chemical 52] [Chemical 52] [Chemical 52] [Chemical 52] [Chemical 52]
naphthol type cyan coupler (comparison coupler (ix)
)) and 2-ureido cyan coupler (comparison coupler (v
ii) Color photosensitive material containing color developer B
When developed with a negative color developer containing
The maximum absorption wavelength of the dye is a long wavelength exceeding 680 mn.
Also, the absorption shape is not sharp (No. 42, 38
). This photosensitive material is used to develop color for printing containing color developer A.
When processed with a developer, the maximum absorption wavelength of cyan dye becomes short.
Although wavelength shift is observed, it is about 10 nm, and absorption
There is virtually no sharpening of the shape. (No. 4
1, 37) or U.S. Pat. No. 4,775,616, esp.
JP-A No. 2-13942, JP-A No. 2-125252, and
The 5th position disclosed in Special Publication No. 63-11656
2-ureidosia with ballast group containing sulfonyl group
coupler (comparison coupler (iii), (iv), (
v) and (vi)).
When developed with a negative color developer containing developer B (No.
30, 32, 34, 36), has a long wavelength, and has an absorption type of N.
o. It is sharper than 42 and 38, and is a photosensitive material for negatives.
It shows improved absorption properties as a material. But long
Then, print this color photosensitive material containing color developer A.
Even if developed with a color developing solution, the absorption of cyan dye is high.
15 nm, and sharpening of the absorption type was observed.
These 2-ureido cyan couplers are
It does not give a hue that can be used as a cyan coupler for
(No. 29, 31, 33, 35). On the other hand, the specific sulfonyl group-containing
2-ureidocyan having a ballast group at the 5-position with the structure
The coupler is for printing containing the color developer A of the present invention.
When developed with a color developer (No. 1, 3, 5, 7,
9, 11, 13, 15, 17, 19, 21, 23) Development
Compare the results when developed with a negative color developer containing Drug B.
The maximum absorption wavelength of cyan dye is as short as 40-50 nm.
Preferred wavelength for printing from 630 to 650 nm
In addition, the absorption type has a half-width value on the short wavelength side of 10 to 15.
nm has also been sharpened, making it easier to use conventional printing shears.
Coupler comparison coupler (viii), No. 39) Yo
It also provides an even better cyan dye for printing.
I understand. Furthermore, No. 1, 3, 5, 7, 9, 11, 13,
15, 17, 19, 23 as No. 25, 27, 29, 3
As is clear from the comparison with 1 and 36, the general formula (I)
, 2-urei in which R2 has a total number of carbon atoms of 4 or more
Color photographic materials containing docyan couplers, especially one
Color developer containing a color developer represented by general formula (D)
By developing with
It can be seen that the above effects can be obtained. Especially when
Comparative coupler (i) (No. 1) was compared with puller example 1 (No. 1).
25) or comparison coupler (ii) (No. 27)
It can be understood more clearly when compared. Example 2 Next, an example of accelerated development processing will be shown. On subbed cellulose triacetate support
A photosensitive material consisting of an emulsion layer and a protective layer (sample 101 to
115) was prepared with the composition shown below. Indicates the amount of coating
Values are in moles/m2 for couplers;
The values other than 100% were expressed in units of g/m2. (Halo
Regarding silver genenide, it is shown as a value in terms of silver) 0159
] First layer (emulsion layer) Silver chlorobromide emulsion (see Table 2)
silver 0.22
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.9 Cyan coupler (see table 2)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.001 dibutyl phthalate
　　　　　　　　　　　　　　　　　　　　　　　　　
0.3 Second layer (middle layer)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4 Third layer (yellow coupler layer)
)
gelachi
hmm
　　　　　　　　　　　　　　　　　　　　　　　　　
1.9 Yellow coupler EXY-1
　　　　　　　　　　　　　　　　　　　　　　　　　
0.001 dibutyl phthalate
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0 protective layer gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.9 Polymethyl methacrylate grains
Child (diameter 1.5μm) 0.41-
Sodium oxy-3,5-dichloro-s-triazine
0.04 [0160] [Chemical formula 53] [0161] The color photosensitive material thus prepared (
Samples 201 to 214) were passed through a continuous density optical wedge.
After exposure, the following color development process was performed. Kara
-Development treatment (temperature: 35°C) The composition of each solution is shown below. color developer water
　　　　　　　　　　　　　　　　　　　　　　　　　
800ml ethylenediamine-N,N,
N,N-tetramethylene phosphonic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
1.5g potassium bromide
Mu
0.015
g triethanolamine
8
．． 0g sodium chloride
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4g potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
25g N-ethyl-N-(β
-methanesulfonamidoethyl)-3-methyl
-4-aminoaniline sulfate
5.0g N,N-bis(carboxyme)
Chill) hydrazine 5.5
g Fluorescent brightener (WHITEX 4B
, manufactured by Sumitomo Chemical) 1.0g
add water
100
0ml pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
10.05 Bleach-fix water
　　　　　　　　　　　　　　　　　　　　　　　　　
400ml ammonium thiosulfate aqueous solution
(70%) 10
0ml sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
17g ethylenediaminetetraacetic acid (III)
Ammonium 55g
Ethylenediaminetetraacetic acid disodium
5g Bromide
ammonium
40g
add water
100
0ml pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
6.0 Rinse liquid ion exchange water (calcium, magnesium 3pp each
m or less) 0165 Samples 201, 203, 205, 207, 2
The color development time for 09, 211, and 213 is 80 seconds.
The time for other samples was 40 seconds. Shape of colored sample obtained after treatment
Measure the density of green and yellow, and give the density of cyan as 1.5.
Find the yellow density at the exposure amount and express it in DY.
Ta. The results are shown in Table 12. [Table 12] [Image Omitted] According to Table 12, the capacitors of the general formula (I) of the present invention
It can be seen that the DY is lower when using the In particular, chloride
Comparative samples with a silver content of 90% were processed for a short time.
In samples 202 and 214, the increase in DY was large, whereas
However, in the sample using the coupler of the present invention, the DY increased significantly.
You can see that it is very small. This means that the general formula (I
) coupler in combination with an emulsion with a silver chloride content of 90% or more
It can be seen that when used together, an increase in color mixture can be prevented. Example 3 The silver chlorobromide emulsion of Example 1 was mixed with silver chloride.
98 mol%, and the coupler was changed as shown in Table 13.
, Samples 301 to 307 were created. This sample 301-3
07 was subjected to image exposure and then passed through the processing of Example 2. At this time, the color development time was 30 seconds. The resulting color development
Measure the absorption spectrum of the sample using the spectrometer mentioned above.
Samples with absorbance of 1.0 at λmax
Find the absorbance at 470 nm in the absorption spectrum of
It was designated as A470. This sample was heated at 80℃ and 70%RH.
The increase in absorbance at 470 nm was calculated as ΔA4.
Expressed in 70. The larger ΔA470 is, the more muddy the color becomes.
represents large. [Table 13] From the results in Table 13, it is clear that the coupler of the present invention
It has been found that color turbidity during storage of color images is improved when
Ru. Among the couplers of the present invention, C-31 is a comparative coupler.
It was also found that the color was muddy, although not to a great extent. This effect
The result is that R2 of the structure of general formula (I) is compared with C-13.
This is due to the partial structure of R2, and the number of carbon atoms in R2 is 12.
It turns out that less than 1 is sufficient. Example 4 A roller was applied to the surface of a paper support laminated on both sides with polyethylene.
After the sodium discharge treatment, the sodium dodecylbenzelsulfonate
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 201 was produced. Prepare the coating liquid as follows.
Manufactured. First layer coating solution preparation Yellow coupler (ExY) 19.1g and color image stability
agent (Cpd-1) 4.4g and color image stabilizer (Cpd
-7) 0.7g, 27.2cc of ethyl acetate and solvent (
Solv-3) and (Solv-7) respectively
4.1g was added and dissolved, and this solution was diluted with 10% dodecyl bene.
10% gelatin containing 8 cc of sodium zensulfonate
Prepare emulsified dispersion A by emulsifying and dispersing in 185 cc of aqueous solution.
did. On the other hand, silver chlorobromide emulsion A (cubic, average grain size
0.88μm large size emulsion A and 0.70μm small size emulsion
A 3:7 mixture (silver molar ratio) with Emulsion A. Particle size
The coefficient of variation of the fabric is 0.08 and 0.10, respectively, for each size.
In both emulsions, 0.3 mol% of brominating agent is localized on a part of the grain surface.
(containing) was prepared. This emulsion has the blue sensitivity enhancement shown below.
For large size emulsion A, the sensitive dyes A and B are per mole of silver.
, 2.0 x 10-4 mol, respectively, and small size emulsion A
2.5 x 10-4 mol was added to
There is. In addition, chemical ripening of this emulsion is performed using a sulfur sensitizer and gold sensitizer.
It was done by adding the agent. The above emulsified dispersion A and its salty odor
Mix and dissolve Silver Fide Emulsion A to obtain the composition shown below.
A first layer coating solution was prepared. [0172] The coating liquid 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
1-oxy-3,5-dichloro-s-triazine
Thorium salt was used. In addition, each layer contains Cpd-10 and C
The total amount of pd-11 was 25.0 mg/m2, respectively.
It was added at a concentration of 50.0 mg/m2. The silver chlorobromide emulsion in each photosensitive emulsion layer contains the following:
Spectral sensitizing dyes were used. [For large size emulsion A, per mole of silver halide]
2.0 x 10-4 mol each, and for small size emulsion A
(2.5 x 10-4 mol, respectively) Sensitizing dye C for green-blue sensitive emulsion layer (For large size emulsion B, per mol of silver halide)
4.0 x 10-4 mol each, for small size emulsion B
, 5.6 x 10-4 mol) and sensitizing color for green-sensitive emulsion layer
Element D [Chemical formula 57] (per mole of silver halide, for large size emulsion B
7.0 x 10-5 mol, and for small size emulsion B
, 1.0×10-5 mol) Sensitizing dye E for red-sensitive emulsion layer
0.9 x 10-4 mol each, also for small size emulsion C
(1.1 x 10-4 mol) For the red-sensitive emulsion layer, the following compound was added.
Added 2.6 x 10-3 mol per mol of silver halide.
Ta. [Chemical formula 59] [0177] Also, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer,
For the emulsion layer, 1-(5-methylureidophenyl)-
5-methylcaptotetrazole and silver halide respectively
8.5 x 10-5 mol, 7.7 x 10-4 mol per mol
2.5 x 10-4 mol was added. Also, blue-sensitive emulsion
4-hydroxy-6-methyl for the green-sensitive emulsion layer and the green-sensitive emulsion layer.
-1, 3, 3a, 7-tetradesignden
1 x 10-4 mol and 2 x 10-4 mol per mol of silver halide
4 mol was added. Also, to prevent irritation
Add the following dyes (the amount in parentheses indicates the coating amount) to the emulsion layer.
added. embedded image (Layer structure) The composition of each layer is shown below. numbers
represents the coating amount (g/m2). Silver halide emulsion is silver
Represents the converted coating amount. Support polyethylene laminate paper (white pigment (TiO2) and polyethylene on the first layer side)
First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A described above
　　　　　　　　　　　　　　　　　　　　　　　　　
0.30 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.86 Yellow coupler (
ExY)
0.82 Color image stability
agent (Cpd-1)
0.
19 Solvent (Solv-3)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.18 Solvent (Solv-7)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.18
Color image stabilizer (Cpd-7)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.06 0182 Second layer (color mixing prevention layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.99 Color mixing prevention agent (Cpd-2)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.08 Solvent (So
lv-1)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16 Solvent (Solv-4)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.08 Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ
m large size emulsion B and 0.39 μm small size emulsion
A 1:3 mixture (Ag molar ratio) of Emulsion B and Emulsion B. grain
The coefficient of variation of the child size distribution is 0.10 and
0.08, each size emulsion is AgBr 0.
(8 mol% was localized on a part of the particle surface)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.12
gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.24 Magenta coupler (ExM)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.23 Color image stabilizer (Cpd-
2)
0.03
Color image stabilizer (Cpd-3)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16 Color image stabilizer (Cpd-4
)
0.02
Color image stabilizer (Cpd-9)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 Solvent (Solv-2)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40
0184 Fourth layer (ultraviolet absorbing layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.58 Ultraviolet absorber (UV-1)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.47 Color mixing prevention agent (
Cpd-5)
0.05
Solvent (Solv-5)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.24 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
1:4 mixture with Emulsion C (Ag molar ratio). grain
The coefficient of variation of the child size distribution is 0.09 and 0.11.
, AgBr 0.8 mol% for each size emulsion
localized on a part of the particle surface)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.23 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.34
Cyan coupler C-1
0.001 (mol
/m2) Color image stabilizer (Cpd-2)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03 Color image stabilizer (Cpd-4
)
0.02 Color image stability
Fixing agent (Cpd-6)
0
．． 18 Color image stabilizer (Cpd-7)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40 Color image stabilizer (Cpd-8)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.05 Solvent (S
olv-6)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.14 0186 Sixth layer (ultraviolet absorption layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.53 Ultraviolet absorber (UV-1)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16 Color mixing prevention agent (
Cpd-5)
0.02
Solvent (Solv-5)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.08 0187 Seventh layer (protective layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.33 Polyvinyl alcohol acrylic
Lyle modified copolymer (degree of modification 17%)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 Fluid PA
ruffin
0.
03 [0188] Cyan coupler C-1 of sample 201
C-2, C-3, C-4, C-10, C-15, C-1
7, C-19, C-27, C-28, C-29, C-3
Samples 201 to 212 were created in the same manner except that the value was changed to 0.
did. [Chemical 61] [Chemical 62] [Chemical 62] [Chemical 67] Each sample was colored red using a continuous tone wedge.
gave exposure. After exposure, the sample is transferred to a paper processing machine.
2 of the tank capacity for color development in the next processing step.
Continuous processing (running test) is carried out until double replenishment
did. Treatment process Temperature Time
Refill amount* Tank capacity Color development
35℃ 45 seconds 161ml
17 liters
Bleach fixing 30-35℃ 45
seconds 215ml 17 liters
Rinse ■ 3
0~35℃ 20 seconds -
10 liters
■ 30~35℃ 20 seconds
- 10 liters
Rinse■ 30-35℃
20 seconds 350ml 10 liters
Tor drying 70-80℃
60 seconds
*
The amount of replenishment is per 1 m2 of photosensitive material (rinse
→■ A 3-tank countercurrent system was adopted. )0197] Various places
The composition of the physical solution is as follows. color developer
tank liquid
replenisher water
800ml
800ml ethylene di
Amine-N,N,N,N-
　　　　　　　　　　　　　　　　　　　　　　　　　
Tetramethylene phosphonic acid
2.0g 2.0g
potassium bromide
0.015g -
triethanolamine
8.0g
12.0g Sodium chloride
1.4
g - potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
25g 25g N-ethyl-N
-(β-methanesulfone amidoethyl)-3-
Methyl-4-aminoaniline sulfate
5.0g
7.0g N,N-bis(carboxymethyl)hydrogen
Do Jin
5.5g
7.0g Fluorescent brightener (WHITEX 4B
,
manufactured by Sumitomo Chemical)
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0g 2.0g Add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml 1000ml pH
(25℃)
10.05 10.45 0198 Bleach-fix solution (tank solution and replenisher solution are the same) Water
　　　　　　　　　　　　　　　　　　　　　　　　　
400ml
Ammonium thiosulfate (70%)
100ml sodium sulfite
Mu
17g ethylenediamine
Tetraacetic acid (III) ammonium
55g Disodium ethylenediaminetetraacetate
5g bromide
ammonium
Add 40g water
Yes
1000ml
pH (25℃)
6.00199] Lin
solution (tank solution and replenishment solution are the same), ion exchange water (calcium
(3 ppm or less each) [0200] The sample colored cyan in this way was
The hue of the cyan dye was evaluated in the same manner as in Example 1. present invention
Multilayer color photographic paper made using cyan coupler
A sample is developed with a color developer containing the color developer of the present invention.
The processed samples 201 to 212 are preferred for color photographic paper.
Gives a cyan hue. Effect of the invention: Specific ballast represented by general formula (I)
A 2-ureido cyan coupler having a to group at the 5-position is
Contains a specific color developer represented by general formula (D)
By developing with a color developing solution, it becomes photosensitive for printing.
The material has a preferable maximum absorption wavelength and is an absorptive type.
A cyan image with a sharp and desirable hue can be obtained. therefore
, it is possible to obtain color prints with good color reproducibility. [C4]

Claims (2)

[Claims] Claim 1: A silver halide color photographic light-sensitive material having at least one layer containing a cyan coupler represented by the following general formula (I) is processed into a color developing solution containing a color developer represented by the following general formula (D). A color image forming method characterized by performing a development process. General formula (I) [Formula 1] (In the formula, R1 represents an alkyl group, an alkenyl group, or a cycloalkyl group. R2 has a total number of carbon atoms of 4 to 3.
0 alkyl group, alkenyl group or cycloalkyl group. R3 represents an aryl group. Z represents a hydrogen atom or a coupling-off group. ) General formula (D) [Formula 2] (In the formula, R4 represents a hydrogen atom, a halogen atom, or a methyl group. R5 and R6 represent a methyl group or an ethyl group. L represents a methylene group or an ethylene group. n is 1 or 2.) 2. Color image formation according to claim 1, wherein at least one silver halide emulsion layer of the silver halide color photographic light-sensitive material contains silver halide containing 90 mol % or more of silver chloride. Method.