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Claims  |
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What is claimed is:
1. A processing method of an image-wise exposed silver halide color
photographic light-sensitive material comprising a replenishing process to
replenish a color developer-replenisher to a color developer being used
for said processing, wherein said silver halide color photographic
material comprises at least one emulsion layer comprising a core-shell
structural silver halide grain containing not less than 3 mol% of silver
iodide and a magenta coupler represented by the following general formula
[I], and said color developer replenisher contains 0 to
3.0.times.10.sup.-3 mol of bromide per liter and a replenishing volume of
said color developer-replenisher to be replenished to said color developer
is 0.5 to 9 ml per 100 cm.sup.2 of said silver halide color photographic
light-sensitive material:
##STR69##
wherein, Z represents a group of non-metallic atoms necessary to form a
nitrogen-containing heterocyclic ring;
X represents a hydrogen atom or a substituent which is, upon a reaction
with an oxidation product of a color developing agent, capable of being
released from the coupler residue;
and R represents a hydrogen atom, substituent.
2. The processing method of claim 1, wherein said color developer contains
a chelating agent represented by the general formula [XII], [XIII] or
[XIV]:
[XII] A--COOM
[XIII] B--PO.sub.3 M.sub.2
##STR70##
wherein, A and B represent a monovalent atom, or a monovalent inorganic or
organic group;
D represents a group of non-metallic atoms necessary to complete an
aromatic ring or a heterocyclic ring;
and M represents a hydrogen atom or an alkali metal atom.
3. The processing method of claim 2, wherein said color developer
replenisher contains 0 to 2.0.times.10.sup.-3 mol of a bromide.
4. The processing method of claim 1, wherein said magenta coupler is
represented by the general formula [VIII]:
##STR71##
wherein, Z.sub.1, X, R, represent the same atoms or groups represented by
Z, X, R of the formula [I], respectively.
5. The processing method of claim 4, wherein said magenta coupler is
represented by the general formula [II]:
##STR72##
wherein, R represents the same atoms or groups represented by R of the
formula [I];
X is the same as X of the formula [I];
and R.sub.2 represents a substituent.
6. The silver halide photographic material of claim 1, wherein said R
represents a hydrogen atom, a halogen atom or a monovalent group selected
from the group consisting of an alkyl group, a cycloalkyl group, an
alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a
heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a
phosphonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, a
residue of spiro compounds, a residue of bridged hydrocarbons, an alkoxy
group, an aryloxy group, a heterocycloxy group, a siloxy group, an acyloxy
group, a carbamoyloxy group, an amino group, an acylamino group, a
sulfonamido group, an imido group, a ureido group, a sulfamoylamino group,
an alkoxycarbonylamino group, an aryloxycarbonylamino group, an
alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an
arylthio group, and a heterocyclic group.
7. The processing method of claim 6, wherein said R is represented by the
general formula [IX]:
##STR73##
wherein, said R.sub.9, R.sub.10 and R.sub.11 represent a hydrogen atom, a
halogen atom or a group selected from the group consisting of a halogen
atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl
group, an alkynyl group, an aryl group, a heterocyclic group, an acyl
group, a sulfonyl group, a sulfinyl group, a phosphonyl group, a carbamoyl
group, a sulfamoyl group, a cyano group, a residue of spiro compounds, a
residue of bridged hydrocarbons, an alkoxy group, an aryloxy group, a
heterocycloxy group, a cyloxy group, an acyloxy group, a carbamoyloxy
group, an amino group, an acylamino group, a sulfonamido group, an imido
group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino
group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an
aryloxycarbonyl group, an alkylthio group, an arylthio group, and a
heterocyclic group, respectively, provided that at least two of R.sub.9,
R.sub.10 and R.sub.11 shall not be hydrogen atoms.
8. The processing method of claim 7, wherein two of said R.sub.9, R.sub.10
and R.sub.11 are alkyl groups, respectively.
9. The processing method of claim 7, wherein two of said R.sub.9, R.sub.10
and R.sub.11 form a saturated or unsaturated ring.
10. The processing method of claim 9, wherein one of said R.sub.9, R.sub.10
and R.sub.11 is a hydrogen atom and group represented remaining two of
them form a cycloalkyl ring with the carbon atoms combined with said two
groups.
11. The processing method of claim 5, wherein R.sub.2 is represented by the
general formula [X]:
[X] --R.sup.1 --SO.sub.2 --R.sup.2
wherein,
R.sup.1 represents an alkylene group,
and R.sup.2 represents an alkyl group, a cycloalkyl group or an aryl group.
12. The processing method of claim 1, wherein said color developer contains
a chelating agent represented by the general formula [XV]:
[XV] M.sub.m P.sub.m O.sub.3m
wherein,
M represents a hydrogen atom or an alkali metal atom,
and m represents an integer of 3 to 6.
13. The processing method of claim 2, wherein said chelating agent
represented by the general formula [XII] is represented by the general
formula [XVII]:
[XVII] A.sub.1 --R.sub.21 --Z--R.sub.22 --COOH
wherein,
Z represents .dbd.N--R.sub.27 --A.sub.6 or .dbd.N--A.sub.6,
A.sub.2 and A.sub.6 independently represents a hydrogen atom, --OH, --COOM,
or --PO.sub.3 M.sub.2,
R.sub.21, R.sub.22 and R.sub.27 independently represents a substituted or
unsubstituted alkylene group;
and M is the same as M of the general formula [XII].
14. The processing method of claim 1, wherein said color developer contains
a chelating agent represented by the general formula [XXII]:
##STR74##
wherein, R.sub.34 represents a group selected from the group consisting of
an alkyl group containing 1 to 12 carbon atoms, an alkoxy group containing
1 to 12 carbon atoms, a monoalkylamino group containing 1 to 12 carbon
atoms, a dialkylamino group containing 2 to 12 carbon atoms, an amino
group, an allyloxy group containing 1 to 24 carbon atoms, an arylamino
group containing 6 to 24 carbon atoms, and an amyloxy group;
Q.sub.1, Q.sub.2 and Q.sub.3 independently represent a group selected from
the group consisting of --OH, an alkoxy group containing 1 to 24 carbon
atoms, an aralkyloxy group containing 1 to 24 carbon atoms, an alkoxy
group containing 1 to 24 carbon atoms, --OM' (M' is a cation), an amino
group, a morpholino group, a cyclic amino group, an alkylamino group, a
dialkylamino group, an arylamino group and an alkyloxy group.
15. The processing method of claim 2, wherein said chelating agent
represented by the general formula [XIV] is represented by the general
formula [XXIII]:
##STR75##
wherein, R.sub.35 and R.sub.36 independently represent a hydrogen atom, a
halogen atom or a group selected from the group consisting of a sulfonic
acid group, an alkyl group containing 1 to 7 carbon atoms, --OR.sub.39,
--COOR.sub.40,
##STR76##
and a phenyl group in which R.sub.39, R.sub.40, R.sub.41, and R.sub.42
independently represent a hydrogen atom or an alkyl group containing 1 to
18 carbon atoms.
16. The processing method of claim 2, wherein said chelating agent
represented by the general formula [XIV] is represented by the general
formula [XXV]:
##STR77##
wherein, R.sub.43 and R.sub.44 independently represent a hydrogen atom, a
halogen atom or a sulfonic acid group.
17. The processing method of claim 1, wherein said color developer contains
a chelating agent represented by the general formula [XXVI]:
##STR78##
wherein, R.sub.49 and R.sub.50 independently represent a hydrogen atom or
a group selected from the group consisting of a phosphoric acid group, a
carbonic acid group --CH.sub.2 COOH, --CH.sub.2 PO.sub.3 H.sub.2, and
their salts,
X.sub.10 represents a hydroxy group or its salts;
W.sub.10, Z.sub.10 and Y.sub.10 independently represent a hydrogen atom, a
halogen atom or a group selected from the group consisting of a hydroxy
group, a cyano group, a carbonic acid group, a phosphoric acid group, a
sulfonic acid group, and their salts, an alkoxy group, and an alkyl group;
m.sub.1 represents an integer of 0 or 1;
n.sub.1 represents an integer of 1 to 4;
I.sub.1 represents an integer of 1 or 2;
p.sub.1 represents an integer of 0 to 3;
and q.sub.1 represents an integer of 0 to 2.
18. The processing method of claim 2, wherein a content of said chelating
agent in said color developer is within the range of 1.times.10.sup.-4 to
1 mol/l.
19. The processing method of claim 1, wherein a content of silver iodide in
a core of said core-shell structural silver halide grain is within the
range of 0.5 to 10 mol%.
20. The processing method of claim 1, wherein a shell of said core-shell
structural silver halide grain consists of silver bromide or silver
bromoiodide.
21. The processing method of claim 4, wherein said R represents a hydrogen
atom, a halogen atom or a monovalent group selected from the group
consisting of an alkyl group, a cycloalkyl group, an alkenyl group, a
cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, a
carbamoyl group, a sulfamoyl group a cyano group, a residue of spiro
compounds, a residue of bridged hydrocarbons, an alkoxy group, an aryloxy
group, a heterocycloxy group, a siloxy group, an acyloxy group, a
carbamoyloxy group, an amino group, an acylamino group, a sulfonamido
group, an imido group, a ureido group, a sulfamoylamino group, an
alkoxycarbonylamino group, an aryloxycarbonylamino group, an
alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an
arylthio group, and a heterocyclic group.
22. The silver halide photographic material of claim 5, wherein said R
represents a hydrogen atom, a halogen atom or a monovalent group selected
from the group consisting of an alkyl group, a cycloalkyl group, an
alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a
heterocyclic group, a sulfonyl group, a sulfinyl group, a phosphonyl
group, a carbamoyl group, a sulfamoyl group a cyano group a residue of
spiro compounds, a residue of bridged hydrocarbons, an alkoxy group, an
aryloxy group, a heterocycloxy group, a siloxy group, an acyloxy group, a
carbamoyloxy group, an amino group, an acylamino group, a sulfonamido
group, an imido group, a ureido group, a sulfamoylamino group, an
alkoxycarbonylamino group, an aryloxycarbonylamino group, an
alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an
arylthio group, and a heterocyclic group.
23. The process method of claim 4, wherin said R is represented by the
general formula [IX]:
##STR79##
wherein, said R.sub.9, R.sub.10 and R.sub.11 represent a hydrogen atom, a
halogen atom or a group selected from the group consisting of a halogen
atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl
group, an alkynyl group, an aryl group, a heterocyclic group, an acyl
group, a sulfonyl group, a sulfinyl group, a phosphonyl group, a carbamoyl
group, a sulfamoyl group, a cyano group, a residue of spiro compounds, a
residue fo bridged hydrocarbons, an alkoxy group, an aryloxy group, a
heterocycloxy group, a cyloxy group, an acyloxy group, a carbamoyloxy
group, an amino group, an acylamino group, a sulfonamido group, an imido
group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino
group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an
aryloxycarbonyl group, an alkylthio group, an arylthio group, and a
heterocyclic group, respectively, provided that at least two of R.sub.9,
R.sub.10 and R.sub.11 shall not be hydrogen atoms.
24. The process method of claim 5, wherein said R is represented by the
general formula [IX]:
##STR80##
wherein, said R.sub.9, R.sub.10 and R.sub.11 represent a hydrogen atom, a
halogen atom or a group selected from the group consisting of a halogen
atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl
group, an alkynyl group, an aryl group, a heterocyclic group, an acyl
group, a sulfonyl group, a sulfinyl group, a phosphonyl group, a carbamoyl
group, a sulfamoyl group, a cyano group, a residue of spiro compounds, a
residue of bridged hydrocarbons, an alkoxy group, an aryloxy group, a
heterocycloxy group, a cyloxy group, an acyloxy group, a carbamoyloxy
group, an amino group, an acylamino group, a sulfonamido group, an imido
group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino
group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an
aryloxycarbonyl group, an alkylthio group, an arylthio group, and a
heterocyclic group, respectively, provided that at least two of R.sub.9,
R.sub.10 and R.sub.11 shall not be hydrogen atoms.
25. The processing method of claim 2, wherein said chelating agent
represented by the general formula [XXIV]:
##STR81##
wherein, R.sub.37 and R.sub.38 independently represent a hydrogen atom, a
halogen atom or a group selected from the group consisting of a sulfonic
acid group, an alkyl group containing 1 to 7 carbon atoms, --OR.sub.39,
--COOR.sub.40,
##STR82##
and a phenyl group in which R.sub.39, R.sub.40, R.sub.41, and R.sub.42
independently represent a hydrogen atom or an alkyl group containing 1 to
18 carbon atoms.
26. The processing method of claim 1, wherein said color developer contains
a chelating agent represented by the general formula [XVI]:
[XVI] M.sub.n+2 P.sub.n O.sub.3n+1
wherein, M represents a hydrogen atom or an alkali metal atom and n
represents an integer of 2 to 20.
27. The processing method of claim 1, wherein said color developer contains
a chelating agent represented by the general formula [XIX]:
[XIX] R.sub.28 --N (CH.sub.2 PO.sub.3 M.sub.2).sub.2
wherein,
R.sub.28 represents a group selected from the group consisting of a lower
class alkyl group, an aryl group, an alalkyl group, or a
nitrogen-containing six membered heterocyclic group, --OH, --OR and
--COOM;
and M represents a hydrogen atom or an alkali metal atom.
28. The processing method of claim 1, wherein said color developer contains
a chelating agent represented by the general formula [XX]:
##STR83##
wherein, R.sub.29, R.sub.30 and R.sub.31 represent a hydrogen atom or a
lower class alkyl group, which may have --OH, --COOM, or --PO.sub.3
M.sub.2 as a substituent;
B.sub.1, B.sub.2 and B.sub.3 independently represent a hydrogen atom or a
group selected from the group consisting of --OH, --COOM, --PO.sub.3
M.sub.2 and --NJ.sub.2 in which J represents a hydrogen atom, a lower
class alkyl group, --C.sub.2 H.sub.4 OH or PO.sub.3 M.sub.2 and M
represents a hydrogen or an alkali metal atom
and m' and n' represents an integer of 0 or 1, respectively.
29. The processing method of claim 1, wherein said color developer contains
a chelating agent represented by the general formula [XXI]:
##STR84##
wherein, R.sub.32 and R.sub.33 represent a hydrogen atom, an alkali metal
atom or a group selected from the group consisting of an alkyl group, an
alkenyl group, and a cycloalkyl group, each containing 1 to 12 carbon
atoms,
and M represents a hydrogen atom or an alkali metal atom.
30. The processing method of claim 1, wherein said color developer contains
a chelating agent represented by the general formula [XVIII]:
##STR85##
wherein, E represents a group selected from the group consisting of an
alkylene group, a cycloalkylene group, a phenylene group, --R.sub.27
--OR.sub.27 --, --R.sub.27 --OR.sub.27 OR.sub.27 --, and R.sub.27 Z.sub.2
R.sub.27 --, in which Z.sub.2 represents >N--R.sub.27 --A.sub.6 or
>N--A.sub.6 ;
A.sub.2, A.sub.3, A.sub.4, A.sub.5 and A.sub.6 independently represent a
hydrogen atom, --OH, --COOM, or --PO.sub.3 M.sub.2,
R.sub.24, R.sub.25, R.sub.26 and R.sub.27, independently represent a
substituted or unsubstituted alkylene group,
and M represents a hydrogen atom or an alkali metal atom. |
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Claims |
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Description |
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BACKGROUND OF THE INVENTION
The present invention relates to the method for processing silver halide
color photographic materials and particularly to the method for processing
silver halide color photographic materials capable of improving remarkably
the processing variation in the color development and of realizing the low
environmental pollution.
Generally, color photographic materials produce thereon photographic images
after they pass through the processing steps including a color developing
step wherein color photographic materials, after they are exposed to
light, are processed in the developer containing paraphenylene type color
developing agent, a bleaching step and a fixing step or a bleach-fix step
in place of previous two steps and a washing step.
In aforesaid color developing step, color images are formed by the coupling
reaction between an oxidation product of color developing agent and a
color coupler and metallic silver are concurrently produced in the
photographic step. The metallic silver are oxidized by bleaching agents in
the succeeding desilverizing step and then form, through the aid of fixing
agents, the soluble silver complexes which are dissolved away.
Researches for low environmental pollution have been made recently from the
viewpoints of an environmental protection and a cost and have been put to
practical use in a partial processing steps. Especially in the color
developing step, various technologies for low environmental pollution have
been proposed in the past due to the level of an influence of the color
developing step upon environmental pollution. For example, regenerating
methods through an electrolysis described in Japanese Patent Publication
Open to Public Inspection Nos. 37731/1979, 1048/1981, 1049/1981,
27142/1981, 33644/1981 and 149036/1981 (hereinafter referred to as
Japanese Patent O.P.I. Publication), generating methods by means of
activated carbon described in Japanese Patent Examined Publication No.
1571/1980 and Japanese Patent O.P.I. Publication No. 14831/1983, an ion
exchange membrane method described in Japanese Patent O.P.I. Publication
No. 105820/1977 and methods by means of an ion exchange resin described in
Japanese Patent O.P.I Publication Nos. 132343/1978, 144240/1980,
146249/1982 and U.S. Pat. No. 4,348,475 and disclosed. However, aforesaid
methods require a large and expensive regenerating apparatus and a skilled
person who can analyze regenerating liquid for keeping the development
level constant and therefore the methods are not utilized except an
occasion where the methods are used by only a few photofinishing
laboratories. Recently, on the other hand, a method for reducing waste
liquid not by using a regenerating method but by reducing replenisher for
the color developer has become popular. This method does not require a
large and expensive apparatus and a skilled analyzer and therefore it is a
desirable method for achieving low environmental pollution, which is
different from aforesaid methods. Through this method, it is possible to
attain a low replenishment to a certain extent but this method has serious
disadvantages such as the condensation of color developer caused by
evaporation, mixing of iron salt and thiosulfate caused by the belt
contamination and back contamination and a large process variation and a
large process stain both caused by the substances eluted from the emulsion
such as, for example, an outflow of activator and inhibitor. This tendency
is remarkable especially when the low replenishment is accelerated under
the conditions of high temperature processing and low volume processing.
As a technology for preventing the process variation caused by iron salt
and thiosulfate both mixed into color developer during the low
replenishment, various types of chelating agents are disclosed and further
polyvinyl pirrolidone type compounds and polyethylene glycol type
compounds are disclosed in Japanese Patent O.P.I. Publication Nos.
150847/1982, 120250/1983 and 121036/1983, but all of them only prevent
iron salt and thiosulfate both in a small amount to be mixed and they are
not so effective when the low replenishment is accelerated and the amount
level of iron salt and thiosulfate mixed into color developer is high.
Further, when aforesaid chelating agents and polyvinyl pirrolidone type
and polyethylene glycol type high molecular compounds are added in
abundance, the photographic characteristics of photosensitive materials
are adversely affected, which is not desirable.
SUMMARY OF THE INVENTION
An object of the invention is to improve greatly the process variation for
silver halide photographic materials caused by the low replenishment and
another object is to attain a remarkable low environmental pollution
through a simple and inexpensive method. Further object of the invention
is to provide a processing method capable of forming a color photographic
image that is high sensitive and is excellent in its image quality.
After an enthusiastic study, the inventors of the present invention found
that the processing of silver halide color photographic material having at
least one layer of core/shell emulsion containing 3 mol% or more of silver
iodide and containing magenta coupler represented by following general
formula [I] is attained by replenishing 9 ml and less of the replenisher
for color development containing 3.0.times.10.sup.-3 mol and less of
bromides per 100 cm.sup.2 of silver halide color photographic material.
##STR1##
In the formula, Z represents a nonmetallic atom group necessary for forming
a nitrogen-containing heterocyclic ring and a ring formed by said Z may
have a substituent. X represents a hydrogen atom or a substituent capable
of splitting off through the reaction with an oxidized substance of color
developing agent.
R, on the other hand, represents a hydrogen atom or a substituent.
Further, the embodiments of the invention wherein chelating agents
represented by following general formulas [XI]-[XIII] are contained and
further 2.0.times.10.sup.-3 mol and less of bromides are contained in the
replenisher for color development and aforesaid replenisher for color
development in the amount of 7.5 ml and less is replenished per 100
cm.sup.2 of silver halide color photographic material, show remarkable
effects of the invention.
General formula [XI] A-COOM
General formula [XII] B-PO.sub.3 M.sub.2
##STR2##
In the formulas, A and B represent respectively a monovalent group or an
atom and they may be either an inorganic substance or an organic one. D
represents a group of non-metal atoms necessary for forming an aromatic
cyclic ring or a heterocyclic ring which may have a substituent and M
represents a hydrogen atom or an alkali metal atom.
DETAILED DESCRIPTION OF THE INVENTION
Following is a detailed description of the invention. The inventors of the
invention found that the process variation and process stain for color
photographic materials grow large when the low replenishment is made for
realizing a low environmental pollution and a low cost and especially when
9 ml and less of the replenisher for color development is replenished for
processng per 100 cm.sup.2 of silver halide color photographic material,
the process variation grows large remarkably. Generally, color
photographic materials containing silver iodide such as, for example,
color negative films like color photographic materials for use in
photographing require the replenishment of about 15 ml of the replenisher
for color development per 100 cm.sup.2 of the color photographic material.
In this case, there is no big problem except mixing of ingredients from a
previous bath such as iron salt and thiosulfate because the amount of
replenishment is large. However, when the amount of replenishment is
lowered down to 9 ml and below, the problems including the condensation of
color developer caused by the evaporation and the accumulation of the
substances eluted from the emulsion take place and especially, the density
variation of a green-sensitive layer and stain tend to be caused, which
was found by the inventors of the invention. Therefore, it is necessary to
prevent the condensation of color developer caused by evaporation or to
prevent the influence on color photographic material to some extent
despite the condensation and further it is necessary to prevent or to
control constant the accumulation of the substances eluted from emulsion,
especially of alkali salt halide.
A lower replenishment has hitherto been impossible because no solutions for
the aforesaid problems have been found out. However, with silver halide
color photographic material having at least one emulsion layer containing
core/shell type silver halide grains holding 3 mol% or more of silver
iodide and containing magenta coupler represented by general formula [I],
the low replenishment of 9 ml/100 cm.sup.2 and less has been realized by
keeping bromides in the replenisher for color development at
3.0.times.10.sup.-3 mol per liter and less and by maintaining at bromide
concentration which causes no problem in the color development.
Further detailed description of the invention will be made as follows. The
replenishing amount of replenisher for color development of the invention
is 9 ml and less but when the evaporating amount is taken into
consideration, the range from 1 ml to 9 ml in replenishment is preferable
and the range from 3 ml to 8 ml is especially preferable.
With regard to the replenishing method, the replenisher for color
development is replenished through a known method but it is recommendable
to use a metering pump such as a bellows pump. The replenisher for color
development of the invention contains 3.0.times.10.sup.-3 mol per liter
and less of bromides and it is necessary to adjust the concentration of
bromide depending on the level of low replenishment. In general, it is
necessary to reduce the concentration of bromide contained in the
replenisher for color development as a replenishing amount is reduced.
The concentration of bromide in the replenisher for color development is
adjusted so that the concentration of bromide (mainly determined by
elution from emulsion and evaporation) is kept constant, and when the
concentration of bromide is 3.0.times.10.sup.-3 mol per liter and less and
the amount of the replenisher for color development is within the range of
from 0.5 to 9 ml/100 cm.sup.2 a stable processing can be achieved without
so affecting any photographic characteristics.
As an actual compound of bromide, there may be given an alkali metal salt
such as sodium bromide, potassium bromide and ammonium bromide as well as
hydrobromic acid.
A concrete description of the invention will be made as follows.
In magenta coupler of the invention represented by aforesaid general
formula [I],
##STR3##
Z represents a nonmetallic atom group necessary for forming a
nitrogen-containing heterocyclic ring and a ring formed by aforesaid Z may
have a substituent.
X represents a hydrogen atom or a substituent capable of splitting off
through the reaction with an oxidation product of color developing agent.
R, on the other hand, represents a hydrogen atom or a substituent.
As a substituent represented by aforesaid R, there may be given, for
example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl
group, a cycloalkenyl group, an alkinyl group, an aryl group, a
heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a
phosphonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, a
spiro-compound residue, a bridge-type hydrocarbon compound residue, an
alkoxy group, an aryloxy group, a heterocyclicoxy group, a cyloxy group,
an acyloxy group, a carbamoyloxy group, an amino group, an acylamino
group, a sulfonamide group, an imido group, an ureido group, a
sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonyl
group, an alkylthio group, an arylthio group and a heterocyclicthio group.
As a halogen atom, a chlorine atom and a bromine atom, for example, are
given and a chlorine atom is particularly preferable.
As an alkyl group represented by R, the alkyl group having the number of
carbons of 1-32 and an alkenyl group, the one having the number of carbons
of 2-32 and a cycloalkyl group and the one having the number of carbons of
3-12, especially of 5-7 as a cycloalkenyl group are preferable and an
alkyl group, an alkenyl group and an alkinyl group may be of the type of
either straight chain or branching.
Further, these alkyl group, alkenyl group, alkinyl group, cycloalkyl group
and cycloalkenyl group may have a substituent [for example, in addition to
an aryl group, a cyano group, a halogen atom, a heterocyclic group, a
cycloalkyl group, a cycloalkenyl group, a spiro-compound residue and a
bridge-type hydrocarbon compound residue, the substituent that substitutes
through a carbonyl group such as an acyl group, a carboxy group, a
carbamoyl group, an alkoxycarbonyl group and an aryloxycarbonyl group, the
substituent that substitutes through a hetero-atom {concretely, the
substituent that substitutes through an oxygen atom such as a hydroxy
group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, a
cyloxy group, an acyloxy group and a carbamoyloxy group, the substituent
that substitutes through a nitrogen atom such as a nitro group, an amino
(including dialkylamino and others) group, a sulfamoylamino group, an
alkoxycarbonylamino group, an alkoxycarbonylamino group, an
aryloxycarbonylamino group, an acylamino group, a sulfonamide group, an
imido group and a ureido group, the substituent that substitutes through a
sulfur atom such as an alkylthio group, an arylthio group, a
heterocyclicthio group, a sulfonyl group, a sulfinyl group and a sulfamoyl
group and the substituent that substitutes through a phosphorus atom such
as a phosphonyl group}].
Concretely, there are given a methyl group, an ethyl group, an isopropyl
group, a t-butyl group, a pentadecyl group, a heptadecyl group, a
1-hexylnonyl group, a 1,1'-dipentylnonyl group, a 2-chloro-t-butyl group,
a trifluoromethyl group, a 1-ethoxytridecyl group, a 1-methoxyisopropyl
group, a methanesulfonylethyl group, a 2,4-di-t-amylphenoxymethyl group,
an anilino group, a 1-phenylisopropyl group, a
3-m-butanesulfonaminophenoxypropyl group, a
3-4'-{.alpha.-[4"(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylp
ropyl group,
3-{4'-[.alpha.-(2",4"-di-t-amylphenoxy)butaneamide]phenyl}-propyl group,
4-[.alpha.-(o-chlorophenoxy)tetradecaneamidephenoxy]propyl group, an aryl
group, a cyclopentyl group and a cyclohexyl group.
As an aryl group represented by R, a phenyl group is preferable and it may
have a substituent (for example, an alkyl group, an alkoxy group or an
acylamino group).
Concretely, there are given phenyl group, a 4-t-butylphenyl group, a
2,4-di-t-amylphenyl group, a 4-tetradecaneamidephenyl group, a
hexadecyloxyphenyl group and a
4'-[.alpha.-(4"-t-butylphenoxy)tetradecaneamide]phenyl group.
As a heterocyclic group represented by R, the heterocyclic group having 5-7
members is preferable and it can either be substituted or condensed.
Concrete examples are a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl
group, a benzothiazolyl group and others.
As an acyl group represented by R, an alkylcarbonyl group such as, for
example, an acetyl group, an phenylacetyl group, a dodecanoyl group and an
.alpha.-2,4-di-t-amylphenoxybutanoyl group and an arylcarbonyl group such
as a benzoyl group, a 3-pentadecyloxybenzoyl group and a p-chlorobenzoyl
group are given.
As a sulfonyl group represented by R, an alkylsulfonyl group such as a
methylsulfonyl group and a dodecylsulfonyl group as well as an
arylsulfonyl group such as a benzenesulfonyl group and a p-toluenesulfonyl
group are given.
As a sulfinyl group represented by R, an alkylsulfinyl group such as an
ethylsulfinyl group, an octylsulfinyl group and a 3-phenoxybutylsulfinyl
group as well as an arylsulfinyl group such as a phenylsulfinyl group and
a m-pentadecylphenylsulfinyl group are cited.
As a phosphonyl group represented by R, there may be cited an
alkylphosphonyl group such as a butyloctylphosphonyl group, an
alkoxyphosphonyl group such as an octyloxyphosphonyl group, an
aryloxyphosphonyl group such as phenoxyphosphonyl group and an
arylphosphonyl group such as a phenylphosphonyl group.
A carbamoyl group represented by R may be substituted with an alkyl group
or with an aryl group (preferably, phenyl group) and there may be cited,
for example, an N-methylcarbamoyl group, an N,N-dibutylcarbamoyl group, an
N-(2-pentadecyloctylethyl)carbamoyl group, an N-ethyl-N-dodecylcarbamoyl
group and an N-{3-(2,4-di-t-amylphenoxy)propyl}carbamoyl group.
A sulfamoyl group represented by R may be substituted with an alkyl group
or with an aryl group (preferably, a phenyl group) and there may be cited
as an example, an N-propylsulfamoyl group, an N,N-diethylsulfamoyl group,
an N-(2-pentadecyloxyethyl)sulfamoyl group, an N-ethyl-N-dodecylsulfamoyl
group and an N-phenylsulfamoyl group.
As a spiro-compound residue represented by R, spiro[3.3]heptane-1-yl may be
cited as an example.
As a bridge-type carbonized compound residue represented by R,
bicyclo[2.2.1]heptane-1-yl, tricyclo[3.3.1.1.sup.3,7 ]decane-1-yl and
7,7-dimethyl-bicyclo[2.2.1]heptane-1-yl are cited as an example.
An alkoxy group represented by R may further be substituted with a
substituent cited for aforesaid alkyl group and a methoxy group, a propoxy
group, a 2-ethoxyethoxy group, a pentadecyloxy group, a 2-dodecyloxynitoxy
group and a phenethyloxyethoxy group are cited as an example.
As an aryloxy group represented by R, a phenyloxy group is preferable and
an aryl nucleus may further be substituted with a substituent or an atom
cited for aforesaid aryl group and a phenoxy group, a p-t-butylphenoxy
group and an m-pentadecylphenoxy group may be cited as an example.
As a heterocyclicoxy group represented by R, a group having a heterocyclic
ring of 5-7 members is preferable and the heterocyclic ring may further
have a substituent and a 3,4,5,6-tetrahydropyranyl-2-oxy group and a
1-phenyltetrazole-5-oxy group are given as an example.
A cyloxy group represented by R may further be substituted with an alkyl
group and others and a trimethylcyloxy group, a triethylcyloxy group and a
dimethylbutylcyloxy group are given as an example.
As an acyloxy group represented by R, an alkylcarbonyloxy group and an
arylcarbonyloxy group are cited as an example and they may further have a
substituent and concrete examples thereof include an acetyloxy group, an
.alpha.-chloroacetyloxy group and a benzoyloxy group.
A carbamoyloxy group represented by R may be substituted with an alkyl
group or with an aryl group and an N-ethylcarbamoyloxy group, an
N,N-diethylcarbamoyloxy group and an N-phenylcarbamoyloxy group may be
cited as an example.
An amino group represented by R may be substituted with an alkyl group or
with an aryl group (preferably, a phenyl group) and examples thereof are
an ethylamino group, an anilino group, an m-chloroanilino group, a
3-pentadecyloxycarbonylanilino group and a
2-chloro-5-hexadecaneamidoanilino group.
As an acylamino group represented by R, an alkylcarbonylamino group, an
arylcarbonylamino group (preferably, a phenylcarbonylamino group) and
others are given and they may further have a substituent and there are
concretely cited an acetamido group, an .alpha.-ethylpropaneamido group,
an N-phenylacetamido group, a dodecaneamido group, a
2,4-di-t-amylphenoxyacetamido group, .alpha.-3-t-butyl
4-hydroxyphenoxybutaneamido group and others.
As a sulfonamide group represented by R, an alkylsulfonylamino group, an
arylsulfonylamino group and others are given and they may further have a
substituent. A methylsulfonylamino group, a pentadecylsulfonylamino group,
a benzenesulfonamido group, a p-toluenesulfonamido group, a
2-methoxy-5-t-amylbenzenesulfonamido group and others are concretely
cited.
An imido group represented by R may be either of an open-chain type or of a
cyclic type and it may have a substituent. A succinic acid amide group and
a 3-heptadecyl succinic acid amide group, a phthalimido group, a
glutarimide group and others are given as an example.
An ureido group represented by R may be substituted with an alkyl group or
with an aryl group (preferably, a phenyl group) and an N-ethylureido
group, an N-methyl-N-decylureido group, an N-phenylureido group, an
N-p-tolylureido group and others are given as an example.
A sulfamoylamino group represented by R may be substituted with an alkyl
group or with an aryl group (preferably, a phenyl group) and an
N,N-dibutylsulfamoylamino group, an N-methylsulfamoylamino group, an
N-phenylsulfamoylamino group and others are given as an example.
An alkoxycarbonylamino group represented by R may further have a
substituent and a methoxycarbonylamino group, a methoxyethoxycarbonylamino
group, an octadecyloxycarbonylamino group and others are given as an
example.
An aryloxycarbonylamino group represented by R may have a substituent and a
phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group are
given as an example.
An alkoxycarbonyl group represented by R may further have a substituent and
a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl
group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a
benzyloxycarbonyl group and others are given as an example.
An aryloxycarbonyl group represented by R may further have a substituent
and a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, an
m-pentadecyloxyphenoxycarbonyl group and others are given as an example.
An alkylthio group represented by R may further have a substituent and an
ethylthio group, a dodecylthio group, an octadecylthio group, a
phenetilthio group and a 3-phenoxypropylthio group are given as an
example.
As an arylthio group represented by R, a phenylthio group is preferable and
it may further have a substituent and a phenylthio group, a
p-methoxyphenylthio group, a 2-t-octylphenylthio group, a
3-octadecylphenylthio group, a 2-carboxyphenylthio group, a
p-acetaminophenylthio group and others are given as an example.
As a heterocyclicthio group represented by R, a heterocyclicthio group with
5-7 members is preferable and it may further have a condensed ring and
even a substituent. For example, a 2-pyridylthio group, a
2-benzthiazolylthio group and a 2,4-diphenoxy-1,3,5-triazole-6-thio group
are given.
As a substituent represented by X capable of splitting off through the
reaction with an oxidation product of color developing agent, the groups
substituted through carbon atoms, oxygen atoms, sulfur atoms or nitrogen
atoms are given as an example in addition to the group substituted through
halogen atoms (chlorine atom, bromine atom, fluorine atom or the like).
As a group substituted through carbon atoms, a group represented by the
following general formula, a hydroxymethyl group and a triphenylmethyl
group are given in addition to carboxyl group.
##STR4##
(R.sub.1 ' is synonymous with aforesaid R, Z' is synonymous with aforesaid
Z and R.sub.2 ' and R.sub.3 ' represent a hydrogen atom, an aryl group, an
alkyl group or a heterocyclic group.)
As a group substituted through oxygen atoms, an alkoxy group, an aryloxy
group, a heterocyclicoxy group, an acyloxy group, a sulfonyloxy group, an
alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxyalyloxy
group and an alkoxyoxalyloxy group are given as an example.
Aforesaid alkoxy group may further have a substituent and an ethoxy group,
a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a phenethyloxy group, a
p-chlorobenzyloxy group and others are given as an example.
As an aryloxy group, a phenoxy group is preferable and aforesaid aryl group
may further have a substituent. Concrete examples thereof are a phenoxy
group, a 3-methylphenoxy group, a 3-dodecylphenoxy group, a
4-methanesulfonamidephenoxy group, a
4-[.alpha.-(3'-pentadecylphenoxy)butaneamide]phenoxy group, a
hexydecylcarbamoylmethoxy group, a 4-cyanophenoxy group, a
4-methanesulfonylphenoxy group, a 1-naphthyloxy group, a p-methoxyphenoxy
group and others.
As a heterocyclicoxy group, a heterocyclicoxy group with 5-7 members is
preferable and it may be a condensed ring and it may have a substituent.
Concretely, a 1-phenyltetrazolyloxy group, a 2-benzthiazolyloxy group and
others are given.
As aforesaid acyloxy group, an alkylcarbonyloxy group such as acetoxy group
and a butanoloxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy
group and an arylcarbonyloxy group such | | |
