Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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1 320657
SILVER HALIDE COLOR PHOTOGRAPHIC
MATERIAL AND MET~OD FOR
PRODUCT~ON OF COLOR IMAGE USING THE SAM~
FIELD OF THE INVENTION
This invention relates to a color photographic
material, and more specifically to a color pho~ographic
material having high saturation and excellent color
reproducibility and gradation reproducibilityl and a
method for production of a color image using the same.
BACKGROUND ~OF THE INVENTION
It has been known to utilize an interlayer
inhibiting effect as means for improving color reproduc-
ibility in color photographic materials. For- example,
in the case of a color negative photographic material,
by imparting a development inhibiting effect to a red-
sensitive layer from a green-sensitlve layer, coloration
of the red~sensitive layer in white light exposure can
be inhibited as compared with that in the case of red
light exposure. Since a color negative paper system is
balanced in gradation so that when it is exposed by
white light, the color is reproduced in gray on a color
print, the aforesaid effect gives a cyan color of a
higher density in red exposure than in the case of gray
exposure. Consequently, a red color of a higher degree
of saturation with inhibited cyan coloration can be
reproduced on the print. Likewise, the development
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inhibiting effect from a red-sensitive layer to a green-
sensitive layer gives a reproduction of green having a
high degree of saturation.
One known method of enhancing the interlayer
effect involves using an iodine ion released from the
silver halide emulsion during development. According to
this method, the silver iodide content of a layer which
imparts the interlayer effect is increased and that of a
layer which receives this effect is decreased. Another
method of enhancing the interlayer effect is to add a
coupler which reacts with the oxidation product of a
developing agent in a p-phenylenediamine-type color
developer to release a development inhibitor, as dis-
closed in JP-A-50-2537. ("JP-~" as used herein means
an "unexamined published Japanese patent application",
Foreign patents corresponding to Japanese patent publi-
cations are shown hereinfater.) Still another method of
enhancing the interlayer effect is called "automatic
masking" whereby a colored coupler is added to a
colorless coupler to mask the unwanted absorption of a
formed dye from the colorless coupler. The method using
the colored coupler gives masking to a greater extent
than the unwanted absorption of the colorless coupler
are masked by increasing the amount of the colored
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coupler added, and can impart the same effect as the
interlayer effect.
These methods have the defect that when the
saturations of the primary colors, red, green and blue
are increased, a yellowish to cyan-like green color is
not faithful. As a measure to remedy this defect, the
technique disclosed in JP-A-61-34541 was proposed. This
technique contemplates the achievement of clear and
faithful color reproduction by a silver halide color
photographic material comprising a support and formed
thereon, at least one blue-sensitive silve:r halide
emulsion layer containing a color coupler which forms
yellow, at least one green-sensitive silver halide
emulsion layer containing a color co~pler which forms
magenta and at least one red-sensitive silver halide
emulsion layer containing a color coupler which forms
cyan; wherein : ;
the center of the sensitivity wavelength (~G) of
the spectral sensitivity distribution of the green-
sensitive layer is 520 nm~G~580 nm,
the center of the wavelength (~-R) of the dis-
tribution of the magnitude of the interlayer effect
which at least one said red-sensitive silver halide
emulsion layer receives from another layer in a range of
500 nm to 600 nm is 500 nm~_R5560 nm, and
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~G ~ ~-R < 5 nm.
The center of the wavelength ~-R of the wave-
length distribution of the magnitude of the interlayer
effect which the red-sensitive silver halide emulsion
layer receives from another layer in a range of 500 nm
to 600 nm is determined by the following procedure.
~ 1) A uniform exposure is given to the photo-
graphlc material to fog it using a red filter which
permits passage of wavelengths above specific wavelength
to which the red-sensitive layer which forms cyan at
wavelengths above 600 nm is sensitive but the other
layers are not sensitive, or~ using an interference
filter which~ permits passage of only the specific
wavelength, thereby uniformly fogging the red-sensitive
layer which forms a cyan color to a suitable value.
(2) When spectral exposure is then imparted, the
interlayer effect of development inhibition acts on the
fogged emulsion from the blue-sensitive layer and the
green-sensit1ve layer to give a reversal image (see Fig.
lA)-
(3) The spectral sensltivity distribution S_R(~) of the reversal photographic material is determined
from the reversal ima~e. [S_R(~) for a given
(wavelengthj can be determined relatively from point a
in Fig. lA]
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(4) The center of the wavelength (~-R) of the
interlayer effect is calculated from the following
equation.
J500 nm A-S R(~)d~
~-R 15 nm~ S (~)d~
The center of the sensitivity wavelength AG iS
given by the following equation.
600 nm
r500 m SG(~d~
SG(~) is 'che spectral sensitivity distribution
curve, and SG(~) at a given ~ can be determined from
point b of Fig. lB as a relative value.
When all objects existing in nature were
photographed using the above-described photographic
material and the images were printed on commercial coior
prints, it was found that the photographic material was
sufficient for reproduction of conspicuous colors as in
a color chart, but this improvement is still insuffi-
cient for subtle reproduction of skin colors which are
most important colors. A further development in tech-
nique is necessary in order to depict accurately the
continuity of the highlights and shadows of colors of a
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human face and skin colors of white, black and yellow
human species. Furthermore, reproduction of hair colors
like skin colors is also important. Reproduction of
fair or red hairs in black at a shadow portion is most
disliked because the black shadow portion is mistaken
for dyed hair. The technique of the above-discussed
invention is not sufficient, and a new technique is
required.
SUMMARY OF THE INVENTION
An object of the present invention is to provide
a color photographic material having high saturation and
excellent color reproducibility and gradation reproduci~
bility.
The present inventors worked extensively and
have found that when the gradations of the blue-, green,
and red-sensitive silver halide emulsion layers of a
photographic material meet certain conditions in a white
light source and a spectrum light source, respectively,
the object of the present invention can be achieved.
Specifically, according to this invention, the
foregoing problem is solved by a silver halide color
1~1 t ~
photographic material comprising a support -~n~~ formed
thereon at least one red-sensitive silver halide emul-
sion layer, at least one green-sensitive silver halide
emulsion layer and at least one blue-sensitive silver
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halide emulsion layer, wherein yradients yP, yP and YB in
monochroma~ic exposure o~ wavelengths giving peak
sensitivities are
0.80 < y~
0.80 < YG
0.6$ < yP ,
and maximum gradients Y~, YG and y~ in standard white
light source exposure are
y~ < 0.65
~G < 0.65
y~ < ~.75.
BRIEF DESCRIPTION or THE DRAWINGS
Fig. 1~ is the characteristic curve of a revers-
al image obtained as a result of the red-sensitive layer
receiving the interlayer e~ect from the green-sensitive
layer at a wavelength ~.
Fig. lB is the characteristic curve of the
green-sensitive layer at a wavelength ~.
Fig. lC shows a method of determining the
magnitude of the interlayer effect. Fig. lC shows the
interlayer effect of color sensitivity Y on color
sensitivity X. When exposure increases by 1.0 of log E
from sensitivity point C (C is defined as the logarithm of
the amount of exposure which gives a density of fog + 0.2
for color sensikivity Y), the corresponding density
A
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decrease of color sensitivity X is defined a~ IE(X/Y).
~ ig. 2 ~hows the equivalent energy spectra of
~ypical samples. The ordinate shows the logarithm of
the reciprocal of the relative sensitivity. ~he curves
arranged in the order from that having smaller values,
i.e. higher sensitivities show sensitivities a~ a
density of fog+0.4, fog+0.6, fog+0.8, and fog+l.0,
respectively. The cixcular marks show points which give
peaks. The averages of these are calculated as 413 nm,
543 nm an.d 621 nm, respectively.
Fig. 3 shows absorpticn spectra o blue, green
and red optical filters using in density measurement.
DETAILE~ DESCRIPTION OF THE INVENTION
The present inventors also found that by
providing some restrictions on the 4 directions of the
interlayer eff2ct in addition to the above conditions,
more favorable eolor reproduction can be obtained.
Specifically, with regard to the magnitude
IE(X/Y) of the interlayer effect defined in ~ig. lC, the
f ollowing conditions are set down.
0.15 < IE (R/G)
0.15 ~ IE (G/R)
0.15 < IE (G/B)
IE(R/B)/IE(G/B) < 1Ø
A
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IE(X/Y) above represents the magnitude of the
interlayer effect of Y on X.
This effect is most favorable in the structure
shown in JP-A 61-34541 which has a donar layer for
giving the effect. It has been ascertained however that
with an ordinary layer structure, the same effect
exists.
A preferred range of YR , YG , and YB is as
follows:
o.90 < yP < 1.15
0 90 ~ YG ~ 1.10
0.70 < yP < 1.2,
A preferred range of YR' YG and YB is as followsO
. 4 < YR < 0 . 60
0 4 < YG < 0~60
. 4 ~ YB < . 65 .
A silver halide color negative film is required
to have a broad exposure latitude, and variations in
color reproducibility according to the amount of
exposure are undesirable. It is generally desirable
therefore that the spectral sensitivity distributions of
the same color developing layers coincide with each
other. But subtle differences in spectral sensitivity
distribution may arise depending upon the halogen
composition of the emulsion, the state of adsorption of
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sensitizing dyes, and the absorptions of diffusion-
resistant dyes and a colored coupler in the coating
composition. Accordingly, gradations may vary according
to wavelengths. There is also the case where the
spectral sensitivity distribution is intentionally
changed. For example, if a high-sensitivity emulsion
layer of a red-sensitive layer is set at a longer
wavelength than the spectral sensitivity distribution of
its low-sensitivity emulsion layer, the red-sensitive
layer as a whole becomes a soft gradation on the long
wavelength side and a hard gradation on the short
wavelength side. If at this time, the low-sensitivity
layer is a layer contributing greatly to the color
density, the gradation at the peak wavelength of the
low-sensitivity emulsion contributes greatly to color
reproducibility.
The wavelength which gives a peak sensitivity is
defined as folIows:
The wavelength which gives the peak sensitivity
of a red-sensitive silver halide emulsion layer is
obtained by determining the wavelength at which the
spectral sensitivity distribution of the silver halide
emulsion layer becomes highest at varying densitiesl the
fog~O.4, 0.6, 0.8 and 1.0, and calculating an arithmetic
mean of these wavelengths. The spectral sensitivity
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distribution is given by the reciprocal of the amount of
exposure which gives the density of (fog + a given
density) of the silver halide emulsion layer having
sensitivity in the range of from 550 nm to 700 nm and
containing a color coupler which couples with the
oxidation product of the developing agent to develop
cyan.
Likewise, the wavelength which gives the peak
sensitivity of a green-sensitive silver halide emulsion
layer is obtained by determining the wavelength at which
the spectral sensitivity distribution of the silver
~halide emulsion layer becomes highest at varying densi-
ties, the fog+0.4, 0.6, O.B and 1.0, and calculating an
arithmetic mean o~ these wavelengths. The spectral
sensitivity distribution is given by the reciprocal of
the amount of exposure which gives the density of (fog
a given density) of the silver halide emulsion layer
having sensitivity in the range of from 480 nm to 620 nm
and containing a color coupler which couples with the
oxidation product of the developing agent to develop
magenta.
hikewise, the wavelength which gives the peak
sensitivity of a blue-sensitive silver halide emulsion
layer is obtained by determining the wavelength at which
the spectral sensitivity distribution of the silver
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halide emulsion layer becomes highest at varying densi-
ties, the fog+0.4, 0.6, 0.8 and 1.0, and calculating an
arithmetic mean of these wavelengths. The spectral
sensitivity distribution is given by the reciprocal of
the amount of exposure which gives the density of (fog +
a-given density) of the silver halide emulsion layer
having sensitivity in the range of from 400 nm to 520 nm
and containing a color coupler which couples with the
oxidation product of the developing agent to develop
yellow.
Examples of wavelengths obtained by the above
methods are shown in Fig. 2.
In the present invention, the gradient at a
wavelength which gives the peak sensitivity is determin-
ed b,y the following procedure.
A test photographic material is exposed through
a wedge using a metal vapor-deposited interference
filter (e.g., Model MIF-W, made by Japan Vacuum Optical
Co., Ltd.) having the peak wavelengths obtained by the
above method, and subjected to a designated development.
The density of the developed photographic material is
measured through a red, a green and a blue filter having
the absorption characteristics shown below and in Figure
3.
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Filter Maximum Wavelenqth Half ~7idth
(nm) (nm)
Blue 434 9
Green 550 8
Red 690 52
On a graph having the logarithm of the amount of
exposure on the abscissas and the density on the
ordinates, values giving densities, the fog+0.4, 0.6,
0.8 and 1.0, are plotted. These points are approximated
to a straight line by the method of least square. Then
tan ~ values with respect to the angle ~ from the
abscissa are defined as yP , YG , and yP of this
photographic material.
Likewise, the gradients in a standard white
light source are determined by the following procedure.
A photographic material is exposed through a
wedge to a standard white light source, for example, a
light source having an energy distribution of 5,500K of
black body radiation if the photographic material is of
the daylight type. The exposed photographic material is
subjected to a designated development, and the density
of the developed photQgraphic material is measured
through a red, a green and blue filter having the
absorption characteristics shown in Fig. 3. On a graph
having the logarithm of the amount of exposure on the
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abscissa and the density on the ordinates, values giving
densities, fog+0.4, 0.6, 0.8 and 1.0, are plotted.
These points are approximated to a straight line by the
method of least square. The tan 0 values with respect
to the angle 0 from the abscissa are defined as YR~ YG
and y~ of this photographic material~
When the silver halide color photographic
material of th.is invention is a color nagative ~ilm,
those commercially available as color papers giving
prints can all be used.
The preferred gradient of color paper is about
2~7+0.1 in terms of colorimetric density (for the
colorimetric density, see, for example, Fundamentals of
Photoqraphic Enq---eerinq, Silver Halide Photography,
edited by Japan Society of Photography, page 387).
Should the average gradient of color papers be
A ~h ~
increased by ~ times in~ future for some reason, the
gradients in this invention may be set as follows:-
Namely, the gradients of the wavelengths givingthe peak sensitivities in monochromatic exposure are set
at
0.80 < p
0~ YR
0.80 < p
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0.65 < p
and the gradients in a standard white light source
exposure are set:
0.65
YR ~ ~
0.65
YG < Cl
< 0 7 5
The preferred ranges of yP, yP, and yP are set:
R G B
0.90 p 1.15
~ YR
0.90 < yp < 1~10
0-70 < yp< 1.2
and the preferred ranges of yR, yG and yB are set:
0.4 < < 0.60
0~ Y R C~
0.4 0.60
C~ YG Cl
0.4 0.65
C~< YB ~ C~
The present invention has succeeded in enhancing
color reproducibility and contrast reproducibility by
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setting certain restrictions on the gradients of red-,
green- and blue-sensitive silver halide emulsion layers
to certain spectral lights and to white light, and quite
differs from technique of obtaining an effect in color
reproduction by specifying the spectral sensitivity and
the magnitude of the interlayer effect which is
disclosed in JP-A-62-160447.
This means that by employing whatever combina-
tions of the spectral sensitivity and the interlayer
effect, good results cannot be obtained if the grada-
tions of red-, green- and blue-sensitive silver halide
emulsion layers to specific spectral lights and to white
light in this invention are not satisfied. This will be
clarified in working examples to be given later on.
The present invention pertains to a photographic
material which has a high gradient when no interlayer
inhibiting effect is received from another layer and a
low gradient when this effect is received. Desirably~
the silver halide to be coated should have excellent
granularity irrespective of the presence of the
interlayer inhibiting effect. Thus, it is preferred to
use double-structure grains or multi-structure grains
having high quantum sensitivity. For the same reasons,
it is preferred to use flat tabular grains having a high
color sensitization ratio.
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Use of an emulsion having a hiyh gradation in
the same amount of coating is preferred in view of the
cost, the increase of the rate of desilvering in
processing and the incr~ase of the sharpness of the
image as a result of reduced optical scattering.
Accordingly, the silver halide grains used in this
invention preferably contain from O to 15 mol%l more
preferably not more than 10 mol~, most preferably not
more than 8 mol~, on an average of silver iodide.
When silver halide containing at least 8 mol% of
silver iodide is used in any one layer of the
photographic material of this inven~ion, the content of
silver iodide on the surface of silver halide grains is
from O to 6 mol~, preferably not more than 4 mol%~ for
the same reason.
Now, means for controlling the interlayer effect
used in this invention will be described.
Usually, development of a given layer is
inhibited or the dye formed is masked when another
color-sensitive layer(s) exposed is developed. In the
present inventionl this effect is referred to as a plus
interlayer effect. Conversely, when the other color-
sensitive layer(s) exposed is developed, the development
of the given layer is promoted or the color density of
the given layer looks as it is increased because of the
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turbidity of the color formed of the other layer, this
effect is referred to as a minus interlayer effect.
The following methods, for example, are avail-
able for imparting the plus interlayer effect.
A masking technique using colored couplers as
described in U.S. Patents 2,983,808 and 3,034,8g2.
A method involving the use of DIR compounds
having a great interlayer effect as described in JP-A-
57-151944, JP-A-56-114946 and JP-A-54-145135.
A method involving including a DIR compound into
a non-photosensitive layer as described in JP-A-61-
43745.
A method involving skillfully sel;ecting the
properties of a DIR compound as described in JP-A-62-
54244.
A method in which an emulsion is monodispersed
to reduce adsorption of an inhibiting substance by a
fine particulate emulsion as described in JP-A-58-
100847.
When the pyrazolotriazole magenta couplerdescribed in JP-A-61-0222342 iS used in a green sensi-
tive silver halide emulsion layer, the interlayer effect
on a substantially blue-sensitive layer can be increased
because there is no subsidiary absorption of yellow.
Furthermore, when the S-amide naphthol-type cyan coupler
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described in JP-~-61-153460 is used in a blue-sensitive
layer, the interlayer effect on a green-sensitive efect
can be increased because there is little subsidiary
absorption of magenta.
Means for increasing the gradient yP at a
wavelength which ~ives a peak sensitivity will be
specifically described without any limitation thereby.
The simplest method is to increase the amount of
the silver halide or the coupler coated. Increasing the
developability of the silver halide, for example,
decreasing of the content of silver iodide whose
development inhibition is large, and including silver
chloride having a high rate of development are also
availabIe. Likewise, there is a method in which the
amount of a development inhibitor releasing compound
(DIR compound) is decreased.
The above-cited methods increase not only yP but
also y in white light exposure. Accordingly, means for
confining y within the range specified by this invention
become necessary. Examples of such means are listed
below.
1. The amount of a coupler which forms a dye
having an absorption at the same wavelength as the color
developed of an emulsion layer desired to be inhibited
is reduced. For example, in a working example of this
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invention, YR is decreased by reducing the amounts of
the cyan couplers ExC-l and ExC-~ in the 12th layer
(blue-sensitive layer). Furthermore, YB can be
decreased by replacing the 5-pyrazolone-type magenta
coupler used in a green-sensitive layer by a pyrazole-
type magenta coupler having a little subsidiary
absorption of yellow.
2. Automasking by colored couplers is
strengthened.
For example, in the working example of this
invention, YB can be decreased by increasing the amount
of the yellow colored magenta coupler ExM-7 in the 7th
layer.
Likewise, YG can be decreased by increasing the
amount of the magenta colored cyan coupler ExC-3 in the
third layer.
3. The interlayer development inhibiting effect
iS increased.
For example, YR and YB can be decreased by
increasing the amount of the DIR coupler ExM-lO in the
10th layer in the example of this invention. Likewise,
YG and YB can be decreased by increasing the amount of
the coupler ExC-2 in the third layer.
The inclusion of at least one nondiffusible
coupler which releases a diffusible development inhibi-
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tor or its precursor onl~ in one of the blue-sensitive,
green-sensitive and blue-sensitive layers is effective.
But to obtain better color reproducibility, it is
preferred to include them in two or more layersO It is
also possible to include the diffusible DIR compound
into a layer containing no silver halide or having no
color sensitivity so long as it substantially couples
with the oxidaticn product of the color developing agent
diffused from another layer to release a releasing group
during color development.
Alternatively, it is possible to divide a color-
sensitive layer into two or more layers and include the
diffusible DIR compound into one or more layers without
including it in the remained layers. The sensitivities
of the layers may differ from each other, for example,
one being a more-sensitive layer and another, a less-
sensitive layer. Or they may not be completely the same
color sensitivity.
To change the degree of the interlayer inhibit-
ing effect, it is possible to properly change the iodine
content of the emulsion, or to add a colored coupler to
the emulsion, thereby masking an unwanted absorption of
a colored dye. There can also be used a method in which
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the interlayer inhibiting effect is set off by inten-
tionally mixing a colored dye having different color
from the color to which the layer ls sensitive and thus
increasing color tubidity.
Nondiffisuble couplers which release a diffusi-
ble development inhibitor or its precursor during
coupling with a color developing agent in this invention
are represented by the following formula.
J~)h (I)
wherein J represents a coupler component, h represents 1
or 2, and Y is a group which is bonded to the coupling
site of the coupler component J and split off upon
reaction with an oxidation product of a color developing
agent, to produce a development inhibitor having high
diffusibility or a compound which can release a develop-
ment inhibitor having high diffusibility (preferably
having a diffusibility, measured by the method to be
described hereinbelow, of at least 0.4).
Y in general formula (I) above preferably
includes the following groups of general formulae (II)
to (V).
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/N ~N
(II)
( Rl ~ i
~N~ ( F~l ) i ( I I I )
_S~ (IV)
N--N
R2
N--N
-S~w~R4 (v,
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1 320657
In the formulae, W represents -S-, -O-, or
-N(R3)-, Rl, R2, R3 and R4 each represents a substituent
selected so that they each has a diffusibility of at
least 0.4, and i represents an integer of from 1 to 4.
Rl group(s) may be substituted at any position(s) on the
ring.
Examples of Rl include a lower alkyl group
having from 1 to 4 carbon atoms (preferably, the total
number of carbon atoms in Rl group~s) is 2, for example,
Rl is CH3 and i=2), and a halogen atom, for example, Cl
and Br an~ i=l or 2, preferably R1 is Br and i=l.
Furthermomre, examples of Rl include -NHCOR' (R' has 3
to 7 carbon atoms), -NHSO2R' (R' has 4 to 8 carbon
atoms), -OR' (R' has 2 to 5 carbon atoms),
-R' (1-3 carbon atoms), -CO2 ~ , and -CO2R' ~R' has 2
to 6 carbon atoms); R' herein represents a substituted
or unsubstituted chain, cyclic or branched aliphatic
hydrocarbon group, i is preferably 1. When i is 2 or
more, groups represented by Rl may be the same or
different from each other.
R2 represents a substituted or unsubstituted
alkyl group having from 1 to 4 carbon atoms in the alkyl
moiety. Examples of the substituent include a sulfo
group, a carboxyl group, a hydroxyl group, an alkoxy
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group, a halogen atom, an alkyl, aryl or heterocyclic
ring, sulfonyl group, a nitro group, an amino group, or
an aryl group. Examples of an alkyl group include an
ethyl group and propyl group.
R2 further represents a substituted or unsubsti-
tuted phenyl group. Examples of substituents include a
sulfo group, an alkoxycarbonyl group, a carboxyl group,
a hydroxyl group, an alkoxy group, a halogen atom, a
cyano group, a ni~ro group, an amino group, an alkyl
group, a carbamoyl group and a ureido groupO These
substituents preferably substituted at m- or p-position
of the phenyl group.
Examples of the substituted phenyI group include
a hydroxyp~enyl group, an aminophenyl group, a sulfa-
moylphenyl group, a carboxyphenyl group, a methoxy-
carbonylphenyl group, a 3-methoxyphenyl group, a 3-
carbamoylphenyl group and a 3-ureidophenyl group.
R2 also represents -(CH2)2_3COOR' (R' has 2 to 3
R'
caFbon atoms), -(CH2)2-3N (the two Rf' groups may be
identical or different and have 2 to 3 carbon atoms),
and -(CH2)20CH3. R' is as defined above with regard to
Rl .
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Examples of R3 are a hydrogen atom and alkyl
groups as defined the alkyl group represented by R2-
Examples of R4 are an amino group, -NHCOR' (R'
represents an alkyl group having from 1 to 6 carbon
R'
atoms), -NHC~2CH2N (the two R's are identical or
R'
different and each represents a methyl or ethyl group),
a methyl group, an ethyl group, a propyl group,
-(CH2~2_3COOH and -(CH2)2-4SO3H.
The diffusibility of the development inhibitor
is evaluated by the following method.
A photographic materlal (sample B) WdS prepared
by forming the following two layers on a transparent
support.
First layer: red-sensitive silver halide emulsion layer
- An emulsion obtained by rendering a sllver
iodobromide emulsion (silver iodide 5 mol%, average size
0.4 ~) red-sensitive using 6x10-5, per mole of silver, of
sensitizing dye I in Example 1, and a gelatin coating
solution containing 0.0015 mole, per mole of silver, of
coupler X were coated so that the amount of silver
coated was 1.8 gjm2 (coating thickness 2 ~).
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Coupler X
OH
CONHC16H33
OcH2cH2 S02CH3
Second layer:
A gelatin layer (the amount of silver coated 2
g/m2, coating thickness 1.5 ~ containing the same
silver iodobromide emulsion as used in the first layer
(having no red-sensitivityj and polymethyl methacrylate
particles (diameter about 1.5 ~).
Another gelatin hardener or a surface-active
agent is incorporated in each of these layers.
A photographic material having the same
structure as the sample B except that the silver
iodobromide was not contained in the second layer was
prepared as sample A.
The samples A and B were each exposed to red
light through a wedge, and processed in accordance with
the processing recipe in Example 1 except that the
developing time was changed to 2 minutes and 10 seconds.
As development inhibitor was added to the developing
solution so that the density of sample A decreased to
1/2. The decrease of the density of sample B at this
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time was used as a measure of the diffusibility of the
silver halide emulsion coating. The results are shown
below.
- 28 -
1 320657
Degree of
decrease
Amount of of densitY Diffusi-
added to the Sample Sample bility
Development inhibitor developer A 8 (=B/A)
HS~
--N o . 75x10-4M so10 0 . 2
'
Cl H3
N ~ S ~ 0.5x10-4 50 150.3
(A mixture of 5- or
6-substituted compounds)
~,N ~ COO ~ 2x10-4 52 370.74
H
(A mixture of 5- or
6-substituted compounds)
H
N\~ ~}Br 2 . 5x10-4 51 45 0 . 9
-- 29 --
1 320657
In general formula (I), Y further represents the
following general formula (VI):
-TIME-INHIBIT (VI)
In the formula, the TIME group is a group which
is bonded to the coupling site of the coupler and can be
cleaved by reaction with a color developing agent, and
which after being cleaved from the coupler, can release
the INHIBIT group under moderate control; and the
INHIBIT group forms a development inhibitor.
In general formula (VI), the TIME-INHIBIT group
is preferably one of those represented by the following
general formulae (VII) to (XIII).
- 30 -
1 320657
~/ (R2O)K
( VI I )
(CH2)Q-N-CO-INHIBIT
R2l
(R20)K
( VI I I )
(CH2)Q-INHIBIT
--O ~ CH2-INHIBIT ( IX )
(R2O)K
Rl 2 2
-o ~ N ( X )
r~
R20
CEI2--INHIE~IT
-- 31 --
1 320657
o ( CH2 ) Q--NOC--INHIBIT ( XI )
--N~ R2 1
(R20)X
/1~
-N~N-R2 3 ( X I I )
o ( CH2 ) Q-L-CO-INHIE~IT
0~
--N~(R20)k ~XIII)
(CH2)Q-L-CO-INHIBIT
1 320657
In general formulae (VII) to (XIII), R20
represents a hydrogen or halogen atom, or an alkyl,
alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acyl-
amino, ureido, cyano, nitro, sulfonamide, sulfamoyl,
carbamoyl, aryl, carboxyl, sulfo, hydroxyl or alkane-
sulfonyl group. These groups preferably have from 1 to
20 carbon atoms.
In general formulae (VII), (VIII), ~IX), (XI)
and (XIII), k represents 1 or 2.
In general formulae (VII), (XI), (XII) and
(XIII), Q represents an integer from 0 to 2.
In general formulae (VII), (X) and (XI), R23
represents an alkyl, alkenyl, aralkyl, cycloalkyl or
aryl group. These groups preferably have from 1 to 20
carbon atoms.
In general formulae (XII) and (XIII), L repre-
sents an oxygen atom, or a group of the formula -N-
R24
in which R24 represents a hydrogen atom or a lower alkylgroup, preferably having from 1 to 5 carbon atoms.
Preferably, the INHIBIT group is represented by
general formulae (II)', (III)', (IV)' and (V)'.
- 33 -
1 320657
/N~N
( R
/N~
: \N ~ (Rl~)i~ (III)'
:
/,N - N
-S ~ (IV)~
7 ::
R2
N-N
-S ~W~R4 ~ ~
In the formulae,~ W represents -5-, ~-0-, or
-N~R3)-, Rl', R2',~R3' and R4' each represents a substi-
tuent selected so that they each has:a diffusibility:of
at Ieast 0.4, and 1l represents~an 1nteger of from l to
4. Rl' group(s) may ~be substituted at any position(s)
on the ring.
Rl' represents a halogen atom or an alkyl,
alkoxy, acylami~no, alkoxycarbonyl, thiazolydenamino,
aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl,
N,N-dlalkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy,
- 34 -
1 320657
sulfamoyl, N-alkylcarbamoyloxy, hydroxyl, alkoxy-
carbonylamino/ alkylthio, arylthio, aryl, heterocyclic,
cyano, alkylsulfonyl or aryloxycarbonylamino group.
In general formulae (II)' and (III)', i'
represents 1 or 2, and when i' is 2, two or more Rl'
groups may be identical or different, and i' Rl' groups
may contain O to 32 carbon atoms in total.
In general formula (IV), R2' represents an
alkyl, aryl or heterocyclic group.
In general formula (V), R3' represents a
hydrogen or halogen atom, or an alkyl, aryl or hetero-
cyclic group; and R4' represents a hydrogen or halogen
atom or an alkyl, aryl, acylamino, alkoxycarbonylamino,
aryloxycarbonylamino, alkanesulfonamide, cyano, hetero-
cyclic, alkylthio or amino group.
When Rl', R2', R3' or R4' represents an alkyl
group, it may be substituted or unsubstituted and linear
or cyclic. Examples of substituents on such alkyl
groups include halogen atoms, and nitro, cyano, aryl,
alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl,
sulfamoyl, carbamoyl, hydroxyl, alkanesulfonyl, aryl-
sulfonyl, alkylthio and arylthio groups.
When Rl', R2', R3' or R4' represents an aryl
group, the aryl group may be substituted. Examples of
- 35 -
1 320657
substituents on the aryl group include halogen atoms
and alkyl, alkenyl, alkoxy, alkoxycarbonyll nitro,
amino, sulfamoyl, hydroxyl, carbamoyl, aryloxycarbonyl-
amino, alkoxycarbonylamino, acylamino, cyano and ureido
groups.
~ hen Rl', R2', R3' or R4' represents a
heterocyclic group, it represents a 5- or 6-membered
monocyclic or fused ring group containing at least one
of a nitrogen, oxygen and sulfur atoms as a hetero atom.
It may be substituted by a substituent selected, for
example, from pyridyl, quinolyl, furyl, benzothiazolyl,
oxazolyl, imidazolyl, thiazolyl, triazolyl, benzotri-
azolyl, imido and oxazine group and these groups may be
substituted with at least one of the substituents listed
above with regard to the aryl group.
In general formula (IV), the number of carbon
atoms contained in R2' is 1 to 32.
In general formula (V), the total number of
carbon atoms contained in R3' and R4' is 1 to 32.
When R20 and R23 represent an alkyl group, it is
substituted or unsubstituted and linear or cyclic. The
same substituents as listed above with regard tc the
alkyl groups Rl' to R4' above may be cited as examples of
substituents in this case.
- 36 -
1 320657
R2l, R22 and R23 each represent a hydrogen atom
or a lower alkyl group.
Examples of the yellow image-forming coupler
residue represented by J in general formula (I) include
coupler residues of the pivaloyl acetanilide, benzoyl
acetanilide, malonic diester, malondiamide, dibenzoyl
methane, benzothiazolyl acetamide, malonic ester mono-
amide, benzothiazolyl acetate, benzoxazolyl acetamide,
benzoxazolyl acetate, benzimidazolyl acetamide and
benzimidazolyl acetate types; coupler residues derived
from hetero ring-substituted acetamides or hetero ring-
substituted acetates disclosed in U.S. Patent 3,841,880;
coupler residues derived from acylacetamides described
in U.S. Patent 3,770,446, British Patent 1,459,171, West
German Patent (OLS) 2,503,009, JP-A-50-139738 or
Research Disclosure No. 15737; and heterocyclic type
coupler residues described in U.S. Patent 4,046,574.
Coupler residues having a 5-oxo-2-pyrazoline
ring, a pyrazolo[l,5-a]benzimidazole ring or a cyano-
acetophènone-type coupler residue are preferred as the
magenta image-forming coupler residue represented by J.
Couplers having a phenol ring or an ~-naphthol
ring are preferred as the cyan image-forming coupler
residue represented by J.
1 320657
Even if the coupler does not substantially forms
a dye after it has coupled with the oxidation product of
a developing agent and released a development inhibitor,
its effect as a DIR coupler remains the same. Examples
of coupler residues of this type represented by J are
the couplers described in U.S. Patents 4,052,213,
4,088,491, 3,632,345, 3,958,993 and 3,961,959.
In general formula (I), J preferably represents
general formulae (XIV), (XV), (XVI), (XVII), (XVIII),
(XIX), (XX), (XXI) and (XXII).
, O O
11
R5 C-CH-C-Rs (XIV)
O O
Il 11
R5-C-CH-C-N~-R (XV)
O O
Il 11
R7-NH-C-CH-C-NH-R7 (XVI)
- 38 -
1 320657
R8
N~o (XVII)
Rg
R8h~
N/~N( XVI I I )
RlO~
OH
( Rll ) m ~( XIX )
:
OH
~,N 'R12 (XX)
( Rl l ) m ~¦ R1 3
- 39 -
1 320657
OH
CON~ 12 ~XXI)
(XXII)
(Rll)p~ ~
In the formulae, R5 represents an aliphatic
hydrocarbon group, an aromatic hydrocarbon group, an
alkoxy group, or a heterocyclic group, and R6 and R7
represent an aromatic hydrocarbon groupi an aliphatic
hydrocarbon group or a heterocyclic group.
The aliphatic hydrocarbon group represented by
R5 has 1 to 22 carbon atoms and is substituted or
unsubstituted and linear or cyclic. Preferred: substi-
tuents on the~ alkyl groups are alkoxy, aryloxy, amino,
and acylamino groups and halogen atoms which themselves
may be further substituented with these groups.
Specific examples of useful aliphatic hydrocarbon groups
Rs, R6 and R7 are isopropyl, isobutyl, tert-butyl,
isoamyl, tert-amyl, l,l-dimethylbutyl, l,l-dimethyl-
hexyl, l,l-diethylhexyl, dodecyl, hexadecyl, octadecyl,
- 40 -
.
.
.
1 320657
cyclohexyl, 2-methoxyisopropyl, 2-phenoxyisopropyl, 2-p-
tert-butylphenoxyisopropyl, ~-aminoisopropyl, ~-~di-
ethylamino)isopropyl, ~-(succinimido) isopropyl, ~-
(phthalimido)isopropyl, and ~-(benzenesulfonamido)iso-
propyl groups.
When Rs, R6 or R7 represents an aromatic
hydrocarbon group (particularly, a phenyl group), the
aromatic hydrocarbon group may be substituted. The
aromatic hydrocarbon group (e.g., phenyl) may be
substituted by, for example, an alkyl, alkenyl, alkoxy,
alkoxycarbonyl, alkoxycarbonylamino, aliphatic amido,
alkylsulfamoyl, alkylsulfonamido, alkylureido or alkyl-
substituted succinimido group having not more than 32
carbon atoms. The phenyl group may also be substituted
by, for example, an aralkyl, aryloxy, aryloxycarbonyl,
arylcarbamoyl, arylamido, arylsulfamoyl, arylsulfonamido
or arylureido group. The aryl moiety of these
substituents may further be substituted by at least one
alkyl group having 1 to 22 carbon atoms in total.
The phenyl group represented by R5, R6 and R7
may further be substituted by an amino (which may be
substituted by an alkyl group having 1 to 6 carbon
atoms), hydroxyl, carboxyl, sulfo, nitro, cyano or
thiocyano group or a halogen atom.
1 320~51
Furthermore, R5, R6 and R7 may represent a
substituent resulting from fusion of the phenyl group
with another ring, such as a naphthyl, quinolyl, iso
~uinolyl, chromanyl, coumaranyl or tetrahydronaphthyl
group. These substituents may further be substituted
with a substituent disclosed above as examples of
substituents for the phenyl group~
When Rs represents an alkoxy group, its alkyl
moiety represents a Cl to C40, preferably Cl to C22~
linear -or hranched alkyl group, an alkenyl group, a
cycloalkyl group or a cycloalkenyl group, which may be
substituted by, for example, a halogen atom, an aryl
group or an alkoxy group.
When Rs, R6 or R7 represents a heterocyclic
group, the heterocyclic group is bonded to the nitrogen
atom of the amido group or the carbon atom of the
carbonyl group of the acyl group in the ~-acylacetamido
via one of the carbon atoms forming the ring. Examples
of such heterocyclic rings are thiophene, furaner
pyrane, pyrrole, pyrrazole, pyridine, pyrazine,
pyrimidine, pyridazine, indolidine, imidazole, thiazole,
oxazole, triazine, thiadiazine and oxazine rings. They
may further be substituted with a substituent disclosed
above as examples of the substituted aromatic hydro-
carbon group.
~ ~2 -
1 320657
In general formula (XVII), Rg represents a
linear or branched alkyl group having 1 to 40 carbon
atoms, preferably 1 to 22 carbon atoms, (such as a
methyl, isopropyl, tert-butyl, hexyl or dodecyl group),
an alkenyl group (such as an allyl group), a cycloalkyl
group (such as a cyclopentyl, cyclohexyl or norbornyl
group), an aralkyl group (such as a benzyl or ~-
phenylethyl group), or a cycloalkenyl group (such as a
cyclopentenyl or cyclohexenyl group), which may
substituted by, for example, a halogen atom, or a nitro,
cyano, aryl, alkoxy, aryloxy, carboxyl, al~ylthio-
carbonyl, arylthiocarbonyl, alkoxycarbonyl, aryloxy-
carbonyl, sulfo, sulfamoyl, carbamoyl, acylamino, di-
acylamino, ureido, urethane, thiourethane, sulfonamido,
heterocyclic, arylsulfonyl, alkylsulfonyl, arylthlo,
alkylthio alkylamino, dialkylamino, anilino, N-aryl-
anilino, N-alkylanilino, N-acylanilino, hydroxyl or
mercapto group.
Furthermore, Rg may represent an aryl group such
as a phenyl or ~- or ~-naphthyl group. The aryl group
may contain at least one substituent. Examples of the
substituent include halogen atoms, and alkyl, alkenyl,
cycloalkyl, aralkyl, cycloalkenyl, nitro, cyano, aryl,
alkoxy, aryloxy, carboxyl, alkoxycarbonyl, aryloxy-
carbonyl, sulfOr sulfamoyl, carbamoyl, acylamino, di-
- ~3 -
1 320657
acylamino, ureido, urethane, sulfonamido, heterocyclic,
arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkyl-
amino, dialkylamino, anilino, N-alkylanilino, N-aryl-
anilino, N-acylanilino, hydroxyl and mercapto groups.
More preferred as Rg is a phenyl group in which at least
one ortho position is substituted by, for example, an
alkyl group, an alkoxy group, or a halogen atom because
it reduces coloration of the coupler remaining in the
film under the action of light or heat.
Rg may also represent a heterocyclic group, for
example, a 5- or 6-membered heterocyclic or fused
heterocyclic group containing at least one of nitrogen,
oxygen and sulfur atoms as hetero atoms, such as a
pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl,
imidazolyl or naphthoxazolyl group. A heterocyclic
group substituted by the substituents listed above for
the aryl group, or an aliphatic or aromatic acyl group,
an alkylsulfonyl group, an arylsulfonyl group, an
alkylcarbamoyl group, an arylcarbamoyl group, an alkyl-
thiocarbamoyl group or an arylthiocarbamoyl group.
In the formulae, R8 represents a hydrogen atom,
a Cl to C40, preferably Cl to C22~ linear or branched
alkyl or alkenyl, cycloalkyl, aralkyl or cycloalkenyl
group (which may be substituted by the substituents
listed above with regard to Rg), an aryl or heterocyclic
- 44 -
1 320657
group (which may have the substituents listed above with
regard to Rg), an alkoxycarbonyl group (such as a
methoxycarbonyl, ethoxycarbonyl or stearyloxycarbonyl
group), an aryloxycarbonyl group (such as a phenoxy-
carbonyl or naphthoxycarbonyl group), an aralkyloxy-
carbonyl group (such as a benzyloxycarbonyl group~, an
alkoxy group (such as a methoxy, ethoxy or heptadecyloxy
group), an aryloxy group (such as a phenoxy or tolyloxy
group), an alkylthio group (such as an ethylthio or
dodecylthio group), an arylthio group ~such as a
phenylthio or ~-naphthyl group), a carboxyl group, an
acylamino group (such as an acetylamino or 3-[(2,4-di-
tert-amylphenoxy)acetamido]benzamido group), a diacyl-
amino group, an N-alkylacylamino group (such as an N-
methylpropionamido group), an N-aryIacylamino group
(such as an N-phenylacetamido group), a ureido group
(such as a ureido, N-arylureido or N-alkylureido group),
a urethane group, a thiourethane group, an arylamino
group (such as a phenylamino, N-methylanilino, diphenyl-
amino, N-acetylanilino or 2-chloro-5-tetradecaneanilino
group), a dialkylamlno group (such as a dibenzylamino
group), an alkylamino group (such as an n-butylamino,
methylamino or cyclohexylamino group), a cycloamino
group (such as a piperidino or pyrrolidino group), a
heterocyclic amino group (such as a 4-pyridylamino or 2-
- 45 -
1 320657
benzoxazolylamino group), an alkylcarbonyl group (such
as a methylcarbonyl group), an arylcarbonyl group (such
as a phenylcarbonyl group), a sulfonamido group (such as
an alkylsulfonamido or arylsulfonamido group), a
carbamoyl group (such as an ethylcarbamoyl, dimethyl-
carbamoyl, N-methylphenylcarbamoyl or N-phenylcarbamoyl
group), a sulfamoyl group (such as an N-alkylsulfamoyl,
N,N-dialkylsulfamoyl, N-arylsulfamoyl, N alkyl-N-aryl-
sulfamoyl or N,N-diarylsulfamoyl group), a cyano group,
a hydroxyl group, a mercapto group, a halogen atom, or a
sulfo group.
In the formulae, Rlo represents a hydrogen atom,
or a Cl to C32, preferably Ci to C22, linear or branched
alkyl or alkenyl, cycloalkyl, aralkyl or cycloalkenyl
group which may have the substituents listed above with
regard to Rg.
Rlo may also represent an aryl or heterocyclic
group which may have the substituents listed above with
regard to R~.
Furthermore, Rlo may represent a halogen atom,
or a cyano, alkoxy, aryloxy, carboxyl, alkoxycarbonyl,
aryloxycarbonyl, acyloxy, sulfo, sulfamoyl, carbamoyl,
acylamino, diacylamino, ureido, urethane, sulfonamido,
arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkyl-
- 46 -
1 320657
amino, dialkylamino, anilino, N-arylanilino, N-alkyl-
anilino, N-acylanilino, hydroxyl or mercapto group.
Each of Rll, R12 and R13 represents groups which
are used in ordinary 4-equivalent phenol or a-naphthol
couplers. Specifically, Rll represents a halogen atom,
an aliphatic hydrocarbon group, an acylamino group, -O-
R14 or -S-R14 (in which R14 represents an aliphatic
hydrocarbon group). When two or more Rll groups exist in
the same molecule, they may be different, and the
aliphatic hydrocarbon group may be substituted. Rl2 and
R13 may represent groups selected from aliphatic
hydrocarbon groups, aryl groups and heterocyclic groups.
Alternatively, one of them may be a hydrogen atom.
These groups may have a substituent. Furthermore, taken
together, R12 and R13 may form a nitrogen-containing
heterocyclic ring. _ is an integer of O to 4; n is an
integer of 0 to 3; and ~ is an integer of O to 5. The
aliphatic hydrocarbon groups may be saturated or
unsaturated, and linear, branched or cyclic. Prefer-
ably, they are alkyl groups (such as methyl, ethyl,
propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl,
octadecyl, cyclobutyl and cyclohexyl groups) or alkenyl
groups (such as allyl and octenyl groups). The aryl
groups are phenyl and naphthyl groups. Typical examples
of the heterocyclic group are pyridinyl, quinolyl,
- 47 -
1 320657
thienyl, piperidyl and imidazolyl groups. Substituents
which may be introduced into the aliphatic hydrocarbon
groups, aryl groups and heterocyclic groups include, for
example, halogen atoms, and nitro, hydroxyl, carboxyl,
amino, substituted amino sulfo, alkyl, alkenyl, aryl,
heterocyclic (as listed above with regard to R12 and
R13), alkoxy, aryloxy, arylthio, arylazo, acylamino,
carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl,
alkyl or aryl sulfonyl and morpholino groups.
The substituents Rs, R6, R7, Rg, Rg, Rlo~ Rl1, R12
and R13 of the couplers represented by general formulae
(XIV) to (XXII) may be bonded to each other, or any of
them becomes a divalent group to form symmetric or
asymmetric compound couplers.
Examples of preferred diffusible DIR compounds
used in this invention are shown below.
- ~8 -
1 320657
D - 1
NHCO(CH2)30 ~ ~ - C;Hl,(tj
(CH3)3CCOCHCONH ~ C.H " (t)
C~
~ ~ ~ CH3
N CH3
D - ~
~iHCO(C~Iz)30~ C;l{" (t)
(CH3)3CCOCHC0.9H ~ ~ C.Hl,(t)
\
C~
~COO ~
N 7
(a compound substituted at
4-, 5-, 6- or 7- ~osition
or a mixture thereof:
the same hereinafter)
- 49 -
1 3206~7
D--3
C,zH2;005800CNHCOCHCONH COOCIICOOC,2H7;
Cl~
CQ
N/ )~5 \~ J ~ COO
D--4
Cl zHz;OOCNHCOCHCONH COOC, LH2;
CQ
N ~J
~, Br
-- 50 -- -
1 320657
D--.J
~ ~S ~.
N N
N ~ C z H;
C H ~--C s H I I ( t)
2 5
C;H~ I (t3
D--6
(t)CsHIl ~
(t)~sHI I ~ ~\\
~ ~ N ~' "`b \~
CQ ~ ce
CQ
-- 51 ~
1 320657
D
COzCI2H
COCHCONH
N`~G~O C ~
N - N
CH2NCOS
I \N - N
CzHs
D -
Cl2H2sOOCCHCOOCI2H2;
1 CO~
- 52 -
1 320657
D--9
CQ
N H ~< ~ N l!
C 2 1~;
Cl 3H 2 ~CONH N O
c ~ T ,~ c ~
CQ
D--1 O
(t)CsH
//~ '
(t)CsH~ OCHzCONH
s ~ \--I'p
o C4H~
-- 53 ~
1 3206S7
D - 1 1
0~1
1~ ~1
N N
N ~
H NH2
D - 1 2
NHCO(CHz) 30 4~ CsHIl(t)
(CHs)3CCOCHCONH ~ C,HIl(t)
o~N~o c~
~ - ~CHI N--N
CH2 ~COS - ~ ~, N
C3H7
- 5~ -
- 1 320657
D - 1 3 ,~
NHCO(CHz)30 ~ ~ CsHll(t)
~` s ~--~
(CH3)3CCOCHCO!iH ~ / \~ C~HIl(t)
~=/
~ CQ
O ~' ~rO
NCOS ~ / 9
I N - N
C3H7
~1
D - 1 4
OH
r ~-~ ~J / Cos!~lc~s~l37
/ N~
CH3 CH3
1 320657
D - 1
NH50(CH2) 30~ C~H " lt~
(CH 3 ) 3 CCOCHCO`iH ~ C a Hll(~)
C~
CH2NCOS / I!
. ~ C2H5
NO2
D - 1 6
QH
CO~ (C~ O - ~ - C,~,(t)
.CH2S
CH3 ¦
- 56 -
1 320657
D - 1 7
OH
,~G ~ "CO~lH~ )
CH2NCOS
I ~ CsH~
D - 1 8
OH
- ~ NHCOCHO ~ - CsHI~(t)
~ ~ ~ C2~1s
Clls ~ ~ C Q CiHll(t)
N; N - CzH;
N ~ N
1 320657
D--1 9
CO~
N ~1--C 2 H s
\~ I
D--2 0
I ~/ ( '
:
- 58 -
1 320657
D - 2 1
C,5H3, OCHCONH ~ '
C ~ ~r ~ C ~ OC411q
.-'' ~
D - 2 2
C~zH2sococNcoaclzHz~ ~
Y~ ~ ~ b~HCOC.~Hq
- 59 -
,
1 320657
D - 2 3
Cl2H7aOOC NHCOCHCONH COOC~zH2;
\[~`C~ ~
C~
R ~HCOC;H,
D - 2 4
COYII ~
"CHz~CO~
CzH ~ ~
~02 CO2CHzCHzCN
- 60 -
1 320657
D--2 5
OH
f C O N H C, ~ H 3 3
~J ~ N--~1
I~To, ~'lOH
D--2 6
~ ~C~h~
O N_N
CHzNCO5 ~ \~--~1112
NO2
-- 61 --
- 1 320657
D - 2 7
CO2CI4H2s
~CH 3) 3CCOCHCONH ~
>==/
C Q
NOz
N
CH2S ~ N--11
I ,CzH;
CH2CHzN ~
\ CzHs
D - 2 8
OH
CONH(CH 2) 30C~zHzs
O N _ N
HzS ~ ~ ~ - C~Hs
(~;==.~)
- 62 -
1 320657
D--2 9 ~ ~
~0~ !102
~3 ~oCH 2~jCOS ~' . N
C2Hs
~3 C2H;
IHCOCHO ~--C~H" (t~
CzHs
D--3 0 C sH I I ( t)
C ~ sH3 ~0 ~ r COCHCO~III
. r zli~s
D--3 1 ~ ~N CzHs
C 1 sH 3 1 ~ ~ COCHCO!3H
N ~ 3
N NHCOCsH1 3
-- 63 --
1 320657
3 - 3 ~
O
O~ ,C~
C2H3
C2H~C
NHCOCHO
C2H; ~--~(
ClsH
D - 3 3
r Q ~ C ~i 2 ) 3 C--`. / `' ' " ~ ~
~CHa)CCOCHCQNH $ . CsHIl(t)
~ ~ C'Q
\ l H ~NHCOC~H~ 3
~J CHz~'COS
-CH2 1 ~CH3 ~N ~i
CH2CH~
`CHa
- 64 -
1 320657
D--3 4
C, 3H27CONH
O ~
~ .
COOCH2CON I
3 5
CH 30COCHCONH ~'~\~
: I `>=/
S oc~ l2Y
,`'3 N ~\'~--N P 2
N =N
-- 65 --
1 320657
~ = ~ ~.,
2 2
~ O
2 ~
O __
2~ 0
~J ~/~
~;3 r ~'
o
C~
.,
o
-
-
-- 66 --
1 320657
D - 3 7
OH
/CO~N(CNz)30 ~/ ~ C.N" (cj
,N - N
CH3
D - 3 8
COzCH502C~2H2
(CH3)3CCOCHCONN ~ CH3
d >='
I C ~ : N - N
CHzCHzCO2
NO2
- 67 -
1 320651
~Z~ ~ ~
g ~
~,~,,,
.
.,. o
~,
=
o
[~"'
~,
- 68 -
1 320657
D--4 O
N _ N
S ~5~ NHCOC~H,
Cl 7H3,~< ~S~
N /~O
' ~
D--4 1
CQ
~ S
C,~H3,~'`1 ~` /``i` /~
~1 C~ ~C~
CO.~12
CQ
-- 69 --
1 320657
D-- ' 2
C : Z li ~ ;
Hd ~3--OCHCO`~ H ;~ ~C
C 4 H 9 ( t) \ / S--<~
N .~
C Q `~,~ C ~ H
C~
D--ds 3
0 H ~iN ~",
C ~ ,,C ~
c e
-- 70 --
1 320657
D--4 4
C l zH 2 ;OOG ~'HCOCHCONH C00C I 7H 2;
\~3``c.e c~ '~
/N, ~
h Br
D--4 5
OH
CONNC,"N"
O N_N
~CH S // \~
1~ H
.
1 320~57
Examples of preferred timing DIR compounds used
in this invention are shown below.
D - ~ 6
~ ~
N--N
N--N
~,J'
D--ds 7
OH
CONHCH zCH zGOO~l
I ~ (M: an alkali
~',1~ ~ ' metal ~tom such
f as Na ~nd K or
I NH4)
0 2 N ~ ~ C N 7 S
Cl ~H23 [~,¦
- 72 ~
1 320657
D--~ 8
OH
f o 1 -- CONHCH zCH zCOOCH 3
o ~ CH2S ~/
C, IHz3
D--4 9
3 ~, ~ CO:I N ~ OC ~ .~11 Z 9
S--CH ,~ ¦
CH3
-- 73 --
1 320~57
D--5 0
0~
CONH (CHz) .10 ~C;H I I ~t)
CsHI t (t)
C2~s 0
Il />--S--CH 2~
C~3
D-S 1
~,CO~ r~ oc,~llz~
CzH; O
S--CH 2 $ j
CH3
-- 74 --
1 320657
D--5 2
OH
,~/ CONHCH zCH zCOOH
CæHs
N--N ~LN ~NOz
S CHz~ I ~/
N--N ~ )= N
Cl ~H~3
D--5 3
OH
~ CO~ ~ OC ~ ~ z ~
~1--N ~N
J~. "LS--CHz~--\CH3
CH3 O
1 320657
D - 5 4
OH
Co~i HcH 2ch 2cooc~ 3
O N - N
02N ~ N ~ O
CIlH23
The above-disclosed compounds can be easily
synthesized by the methods described in U.S. Patents
4,234,678, 3,227,554, 3,617,291, 3,958,993, 4,149,886
and 3,933,500, JP-A-57-56837 and JP-A-51-13239 and
British Patents 2,072,363 and 2,070,266, and Research
Disclosure, No.21228, December, 1981.
The coupler may be introduced into a silver
halide emulsion layer by a known method, for example,
the method described in U.S. Patent 2,322,027. The
coupler is dissolved in, for example, an alkyl phthalate
(e.g., dibutyl or dioctyl phthalate), a phosphate (e.g.,
diphenyl, triphenyl, tricresyl or dioctylbutyl
phosphate), a citrate (e.g., tributyl acetylcitrate), a
benæoate (e.g., octyl benzoate), an alkylamide (e.g.,
diethyllaurylamide), a fatty acid ester (e.g., dibutoxy-
ethyl succinate or dioctyl azelate), a trimesate (e.g.,
tributyl trimesate), or an organic solvent having a
- 76 -
1 320657
boiling point of about 30 to 150C such as a lower alkyl
acetate (e.g., ethyl or butyl acetate), ethyl
propionate, sec-butyl alcohol, methyl isobutyl ketone,
~-ethoxyethyl acetate or methyl cellosolve acetate; and
then dispersed in a hydrophilic colloid. A mixture of
the above-described high-boiling solven~ and low-boiling
organic solvent may also be used. There can also be
used the dispersing methods using polymers as described
in JP-B-51-39853 ("JP-B" herein means an "examined
Japanese patent publication") and JP-A-51-59g43.
When the coupler has an acid group such as a
carboxylic acid group or a sulfonic acid group, it may
be introduced as an aqueous alkaline solution into a
hydrophilic colloid.
The high-boiling organic solvent is described,
for example, in U.S. Patents 2,322,027, 2,533,514 and
2,835,579, JP-B-46-23233, U.S. Patent 3,287,134, British
Patent 958,414, JP-A-47-1031, British Patent 1,222,753,
U.S. Patent 3 r 936,303, JP-A-51-26037 and JP-50-82078,
U.S. Patents 2,353,262, 2,852,383, 3,554,755, 3,676,137,
3,676,142, 3,700,454, 3,748,141 and 3,837,863, German
OLS 2,538,889, JP-A-51-27921, JP-A-51-27922, JP-A-51-
26035, JP-A-26036 and JP-A-50-62632, JP-B-49-29461, U.S~
Patents 3,936,303 and 3,748,141, and JP-A-53-1521.
- 77 -
1 320657
In the photographic emulsion layers of photo-
graphic materials used in this invention, any of silver
bromide, silver iodobromide, silver iodochlorobromide,
silver chlorobromide and silver chloride may be used.
As stated hereinabove, preferred silver halides contain
not more than 15 mol%, more preferably not more than lO
mol~, especially pre~erably not more than 8 mol%~ on an
average of silver iodide.
The silvex halide grains in the photographic
emulsions may be so-called regular grains having regular
crystals such as cubic, octahedral and tetradecahedral
crystals, or have irregular crystal shapes~ such as a
spherical shape or crystal defects such as a twinning
plane, or may be combinations of these various types.
As stated hereinabove, they preferably have excellent
granularity. It is preferred to use grains of a double
or a multiple structure having high quantum sensitivity,
or tabular grains having a high color sensitization
ratio.
The silver halide grains may be fine grains
having a size of less than about 0.1 micron or large
grains with a projected area diameter of up to about lO
microns. They may be monodisperse emulsions having a
narrow distribution, or polydisperse emulsions having a
broad distribution.
~ 78 -
1 320657
The silver halide photographic emulsions that
can be used in this invention can be produced by known
methods, for example, the methods disclosed in Research
Disclosure (RD), No. 17~43 (December 1978), pages 22-23~
"I. Emulsion Preparation and Types", and ibid. No. 18716
(November 1979), page 648.
The photographic emulsions used in this
invention can be prepared by using the methods described
in P. Glafkides, Chimie et Physique PhotoqraPhique, Paul
Montel, 1967, G.F. Duffin, PhotoqraPhic Emulsion
Chemistry (Focal Press, 1966), and V.L. Zelikman et al.,
Makinq and_Co t_nq Photoqraphic Emulsion, Focal Press,
1964. Namely, any of the acid method, neutral method
and ammonia method may be used. The mode of reacting a
soluble silver salt with a soluble halogen salt may be a
single jet method, a double jet method, or a combination
of these. There can also be used a method in which
grains are formed in the presence of an excess of a
silver ion (the so-called reverse mixing method). As
one example of the double jet method, a controlled
double jet method may be used in which pAg in the liquid
phase where silver halide is formed is maintained
constant. This method gives a silver halide emulsion
having a regular crystal shape and a nearly uniform
grain size.
1 320657
Two or more silver halide emulsions separately
formed may be used as a mixture.
The silver halide emulsion composed of regular
grains may be obtained by controlling pAg and pH during
grain formation. Details of this method ar~ described,
for example, in Photoqraphic Science and En~ineerinq,
vol. 6, page 159 to 165 (1962), Journal of Photoqraphic
Science, vol. 12, pages 242 to 251 (1964), U.S. Patent
3,655,394, and British Patent 1,413,748.
A typical monodisperse emulsion contains silver
halide grains having an average grain diameter of more
than about 0.1 micron, and at least about 95% by weight
of which have a size within +40% of the avèrage grain
diameter. In the present invention, an emulsion in
which the silver halide grains have an average grain
diameter of about 0. 25 to 2 micronsj and at least 95% by
weight, or at least 95% by number, of the silver halide
grains have a grain size within ~20% of the average
grain diameter may be used. The methods of preparing
such an emulsion are described in U.S. Patents 3,574,628
and 3,655,394 and Rritish Patent 1,413,748. The
monodisperse emulsions described in JP-A-48-8600, JP-A-
51-39027, JP-A-51-83097, JP-A-53-137133, JP-A-54-48521,
JP-A-54-99419, JP-A-58-37635 and JP-A-58-49938 can be
used preferably in the present invention.
- 80 -
1 320657
Tabular grains having an aspect ratio of at
least about 5 may also be used in this invention. The
tabular grains can be easily prepared by the methods
described in Gutoff, Photoqraphic Science and
Enqineerinq, vol. 14, pages 248 to 257 (1970), U S.
Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520l
and British Patent 2,112,157. U.S. Patent 4,434,226
cited above states in detail that the use of tabular
particles has the advantage of increasing the efficiency
of color sensitization with sensitizing dyes and
enhancing the granularity of the grains and the
sharpness of images.
Emulsion grains having a uniform crystal
struture but different halogen compositions between the
interior and the exterior may aIso be used. Or
emulsions having a layered structure may also be used.
These emulsion grains are disclosed, for example, in
British Patent 1,027,146, U.S. Patents 3,505,068 and
4,444,877 and JP-A-60-143331. Silver halide grains in
which silver halides of different compositions are
conjugated by epitaxial conjugation may also be used.
Or they may be conjugated with compounds other than
silver halide, such as silver rhodanate and lead oxide.
These emulsion grains are disclosed, for example, in
U.S. Patents 4,094,634, 4,142,900 and 4,459,353, British
- 81 - ~
1 320657
Patent 2,038,7g2r U.S. Patents 4,349,6~2, 4,395,478,
4,433,501, 4,463,087, 3,656,962 and 3,852,067, and JP-A-
58-162540.
A mixture of grains having various crystal
shapes may be used.
The emulsions to be used in this invention
usually undergo physical ripening, chelllical ripening and
spectral sensitization. Additives used in these steps
are described in Research Disclosure, Nos. 17643 and
18716, and the pertinent portions are tabulated below.
Known photographic additives that can be used in
this invention are also described in the above-cited two
Research Disclosure publications and the pertinent
portions are tabulated below.
Additive RD17643 RD18716
-
1. chemical sensitizer p. 23 p. 63B, right
column
2. sensitivity enhancer ditto
3. spectral sensitizer pp. 23-24 p. 648, right
column to
supersensitizer p. 649, right
column
4. bleaching agent p. 24
5. antifoggant and pp. 24-25 p. 649, right
stabilizer column
- 82
1 320657
6. light absorber, pp. 25-26 p. 649, right
~ilter dye, and column to
ultraviolet p. 650, left
absorber ~olumn
7. stain preventing p. 25, right p. 650, left to
agent column right column
8. dye image p. 25
stabilizer
9. hardener p. 26 p. 651, left
column
lO. binder p. 26 ditto
ll. plasticizer and p.27 p. 650, right
lubricant column
12. coating aid and pp. 26-27 ditto
surface active
agent
13. antistatic agent p. 27 ditto
Various color couplers can be used in this
invention. Specific examples are described in the
patents described in the above-cited Research Disclo-
sure, No. 17643, VII-C to G. Important dye-forming
couplers give three primary colors of the subtractive
process (i.e., yellow, magenta and cyan). Specific
examples of nondiffusion 4-equivalent or 2-equivalent
couplers are those described in the patents described in
the above-cited RD 17643, VII-C and D and the following
couplers can also be preferably used in this invention.
Typical examples of the yellow coupler that can
be used in this invention are hydrophobic acylacetamide-
- 83 -
1 320657
type couplers having a ballast group, specific examples
of which are given, for example, in U.S. Patents
2,407,210, 2,875,057 and 3,265,506. The use of 2-
equivalent yellow couplers is preferred in this
invention. Typical examples are the oxygen atom
releasing type yellow couplers described in U.S. Patents
3,408,194, 3~447,928, 3,933,501 and 4,022,620, and the
nitrogen atom-releasing type yellow couplers described
in JP-B-58-10739, and U.S. Patents 4,401,752 and
4,326,024, RD 18053 (April 1979), British Patent
1,425,020, and West German OLS Nos. 2,219,917,
2,261,361, 2,329,587 and 2,433,812. ~-Pivaloyl
acetanilide-type couplers give dyes having excellent
fastness characteristics, particularly light fastness.
a-Benzoyl a~etanilide type couplers can give a high
color density.
Examples of the magenta couplers that can be
used in this invention are hydrophobic and ballast
group-having couplers of the indazolone and cyanoacetyl
types, preferably of the 5-pyrazolone and pyrazoloazole
types. 5-pyrazolone-type couplers are those in which
the 3-position is substituted by an arylamino group or
an acylamino group are preferred from the viewpoint of
the color hue of the developed dye and its density.
Typical examples are described, for example, in U.S.
~ 84 ~
1 320657
Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573,
3,062,653, 3,152,896 and 3,936,015. The nitrogen atom
releasing groups described in U.S. Patent 4,310,619 and
the arylthio groups described in U.S. Patent 4,351,897
are especially preferred as the releasing groups of 2-
equivalent 5-pyrazolone-type couplers. The 5-
pyrazolone~type couplers having a ballast group which
are described in European Patent 73,636 can give high
color development densities. Examples of pyrazoloazole-
type couplers include the pyrazolobenzimidazoles
described in U.S. Patent 3,061,432, preferably the
pyrazolo[5,1-c][1,2,4]triazoles described in U.S. patent
3,725,087, pyrazolotetrazoles déscribed in Research
Disclosure, 24220 (June 1984) and JP A-60-33552, and the
pyrazolopyrazoles described in Research Disclosure,
24230 (June 1984) and JP-A-60-43659. In view of the
less yellow subsidiary absorptions of formed dyes and
lightfastness, the imidazo~1,2-b]pyrazoles described in
U.S. Patent 4,500,630 are preferred, and the pyrazolo-
[1,5-b][1,2,4]triazole described in U.S. Patent
4,540,654 is especially preferred.
Hydrophobic nondiffusible naphthol type and
phenol type couplers may be used as the cyan couplers in
this invention. Typical examples of the naphthol-type
cyan couplers are the naphthol-type couplers described
- 85 -
1 320657
in u.S. Patent 2/474,293, preferably the oxygen atom
releasing type 2-equivalent naphthol-type couplers
described in U.S. Patents 4,052,212, 4,146,396,
4,228,233 and 4,296,200. Specific examples of the
phenolic couplers are described, for example, in U.S.
Patents 2,369,9~9, 2,801,171, 2,772,162 and 2,895,826.
Couplers capable of forming cyan dye which is fast to
humidity and temperature can be preferably used in this
invention. Typical examples include the phenolic cyan
couplers having an alkyl group with at least 2 carbon
atoms at the meta-position of the phenol ring, the 2,5-
diacylamino-substituted phenolic couplers described in
U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011
and 4,327,173, West German OLS 3,329,729, and European
Patent7 121,365, and the phenolic couplers having a
phenylureido group at the 2-positlon and an acylamino
group at the 5-position described in U.S. Patents
3,446,622, 4,333,999, 4,451,559 and 4,427,767. Cyan
couplers having a sulfonamide group, an amide group,
etc. substituted at the 5-position of naphthol, which
are described in European Patent 161,626A gives a
colored image of excellent fastness, and can be
preferably used in this invention.
In order to correct unwanted absorptions of the
formed dye, it is preferred to mask the coupler in the
- 86 -
1 320657
color light-sensitive material for photographing by
using a colored coupler in combination. The yellow-
colored magenta couplers described in U.S. Patent
4,163,S70 and JP-B-57-39413 and the magenta-colored cyan
couplers described in U.S. Patents 4,00~,929 and
4,138,258 and British Patent 1,146,368 may be cited as
typical examples of such couplers. Other colored
couplers are described in the above-cited RD 17643, VII
to G. There can also be cited compounds having a group
capable of being coordinated with a metal and f~rming a
color, as a releasing group described in U.S. Patents
4,555,477 and 4,555,478. Unlike the colored couplers,
these couplers are colorless before coupling with the
oxidation product of a developing agent. But after
development, the exposed area assumes the color of the
dye formed by coupling as the released metal ligand is
washed out. In the uhexposed area, the metal ligand
fixed to the coupler is coordinated with a metal ion
such as Fe (II) in the processing liquor to form a
color. As a result, the decrease of sensitivity due to
the filter effect of the colored coupler is reduced, and
the above couplers can be favorably used in this
invention. A photographic material containing the above
coupler may be processed in an ordinary development
processings, or in a separate processing step in a
- 87 -
1 320657
specific ba~h containing a metal ion. Examples of the
metal ion are Fe (II), Co (II), Cu (I), Cu (II) and Ru
(II). Fe (II) is preferably used.
Granularity may be improved by using a coupler
which sives a dye having moderate diffusibility in
combination with the above-described couplers. Specific
examples of such a coupler are described in U.S. Patent
4,366,237 and British Patent 2,125,570 (magenta
couplers), and European Patent 96,570 and West German
OLS 3,234,533 (yellow, magenta and cyan couplers).
The dye-forming couplers and the special
couplers described above may form dimers or higher
polymers. Typlcal examples of polymerized dye-forming
couplers are described in U.S. Patents 3,451,820 and
4,080,211. Typical examples of polymerized magenta
couplers are described in British Patent 2,102,173 and
U.S. Patent 4,367,282. Couplers which release photo-
graphically useful residues during couplinq may
favorably be used in this invention. Useful DIR
couplers which release development inhibitors are
described in the patents disclosed in the above-cited RD
17643, VII to F~
Examples of preferred couplers used in combina-
tion with this invention are the developer solution
deactivating type couplers typically described in JP-A-
- 88 -
1 320~57
57-151944, the timing-type couplers typically described
in U.S. Patent 4,248,962 and JP-A-57-154234, and the
reactive type couplers typically described in JP-A-59-
39653. Especially preferred are the developer solution
deactivating type DIR couplers described in JP-A-57-
151944 and JP-A-58-217932, and JP-A-60-218644, JP-A-60-
225156, and JP-A-60-233550, and the reactive-type DIR
couplers described in JP-A-60-184248.
In the photographic material, a coupler which
releases a nucleating agent or a development accelerator
or a precursor thereof imagewise during development may
be used. Specific examples of such a compound are
described in British Patents 2, 097,140 and 2,131,188.
Couplers which releases a nucleating agent, etc. having
adsorptive action on silver hallde are especially
preferred, and specific examples thereof are described,
for example, in JP-A-59-157638 and JP-A-59-170840.
In the present invention, red-sensitive layer, a
green-sensitive layer and a blue~sensitive layer may be
provided on a support in any order, however, it is
preferably provided in this order (i.e., B/G/R//
support). When a color sensitive layer is divided in
two layers, the slow speed layer is provided prior to
providing the fast speed layer (e.g., B/Gf/Rf/Gs/Rs//
- 89 -
1 320657
support: wherein f means fast speed and s means slow
speed).
In the present invention the combination of each
coupler and color sensitivity of the emulsion layer
containing the coupler is also optional, however, from
the view point of proper printing characteristics to
color paper, it is preferable that a cyan coupler is
incorporated into a red-sensitive layer, a magenta
coupler is incorporated into a green-sensitive layer and
a yellow coupler is incorporated into a blue-sensitive
layer.
Supports which can be suitably used in this
invention are described, for example, in the above-cited
RD No. 17643, page ~8, and ibid. No. 18716, page 647,
right column to page 648, left column.
The color photographic material in accordance
with this invention can be developed by ordinary methods
described, for example, in the above-cited RD No. 17643,
pages 28 to 29 and No. 18716, page 651, left column to
right column.
The color photographic material of this
invention is subjected to an ordinary rinsing treatment
or stabilizing treatment after development, bleach-
fixing or fixing.
-- 90
1 320657
Generally, the rinsing step is carried out by
providing two or more tanks in a countercurrent manner,
and thus saving rinsing water. A typical example of the
stabilization treatment is a multistage countercurrent
stabilization treatment as described in JP-A-57-8543 to
be carried out in place of the rinsing step. This step
requires 2 to 9 countercurrent baths. Various compounds
are added to the stabilizing bath in order to stabilize
the image. Typical examples of the additives include
various buffers for adjusting the film pH (for example,
pH 3 to 8) (e.g., boratesj metaborates, borax,
phosphates, carbonates, potassium hydroxide, sodium
hydroxide, aqueous ammonia, monocarboxylic acids,
dlcarboxylic acids and polycarboxylic acids used in
combination), and formalinO As required, hard water
softening agents (e.g., inorganic phosphoric acid,
aminopolycarboxylic acids, organic phosphoric acid,
aminopolyphosphonic acid and phosphonocarboxylic acid),
fungicides ~e.q., benzointhiazolinone, isothiazolone, 4-
thiazolinebenzimidazole and a halogenated phenol),
surface active agents, fluorescent bleaching ayents, and
hardeners may also be used. Two or more of such
additives having the same or different purposes may~ be
used in combination~
-- 91 --
l 32~651
It is also preferred to add various ammonium
salts such as ammonium chloride, ammonium nitrate,
ammonium sulfate, ammonium phosphate, ammonium sulfite
and ammonium thiosulfate as a film p~ adjusting agent
after processing.
The present invention can be applied to various
color light-sensitive materials for photographing,
typically general or motion-picture color negative
films, and slide or television color reversal films~
The following examples clarify the effects of
this invention. It should be understood, however, that
the scope of the invention are not limited to these
examples. It is particularly noted that the same effect
can be obtained even in a photographic material of an
ordinary layer construction corresponding to the
photographic material in the examples which does not
have the 11th layer (a toner layer to a red-sensitive
layer) and contains large amounts of the DIR compounds
in the 6th, 7th and 8th yreen-sensitive layers.
EXAMPLE
A multilayer color photographic material
composed of layers of the following compositions on an
undercoated cellulose triacetate film support was
prepared as Sample 101.
-- g2 --
1 320657
Composition of the photoqraphic layers
The amounts of silver halide and colloid silver
are expressed by g/m2 as silver. The amounts of the
couplers, additives and gelatin are expressed by g/m2.
The amount of each sensitizing dye is expressed by moles
per mole of silver halide in the same layer. The
symbols showing the additives have the following
meanings. Where an additive has two more utilities,
only one of them is indicated as a representative.
UV: ultraviolet absorber
Solv: high-boiling organic solvent
ExF: dye
ExS: sensitizing dye
ExC: cyan coupler
ExM: magenta coupler
ExY: yellow coupler
Cpd: additive
First layer (antihalation layer)
Black colloidal silver 0.15
Gelatin 2.9
UV-l 0.03
UV-2 0.06
UV-3 0.07
Solv-2 0.08
ExF-l 0.01
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1 320657
ExF-2 0.01
Second_l yer(low-sensitivity red-sensitive emulsion
layer3
Silver iodobromide emulsion 0.4
(AgI 4 mol~; uniform type;
sphere equivalent diameter 0.4 ~;
variation coefficient of the sphere
equivalent diameter 37%; tabular
grains; diameter/thickness ratio 3.0)
Gelatin 0.3
ExS-l 2.3x10-4
ExS-2 1.4x10-4
ExS-5 2.3x10-4
ExS-7 8.0x10-6
ExC-l 0.17
ExC-2 0.03
ExC-3 0.13
hird layer (medium-sensitivity red-sensitive emulsion
laYer ?
Silver iodobromide emulsion 0.65
(AgI 6 mol%; high internal AgI type
with a core-shell ratio of 2:1
(molar ratio of AgX: the sane
hereinafter); sphere equivalent
diameter 0.65 ~; variation
coefficient of the sphere
equivalent diameter 25%; tabular
grains; diameter/thickness ratio 2.0)
Silver iodobromide emulsion 0.1
(AgI 4 mol%; uniform AgI type;
sphere equivalent diameter 0.4 ~;
variation coefficient of the sphere
equivalent diameter 37%; tabular
grains; diameter/thickness ratio 3.0)
- 94 -
- 1 320657
Gelatin 1.0
ExS-l 2x10-4
ExS-2 1.2x10-4
ExS-5 2x10-4
Ex5-7 7x10-6
ExC-l 0.31
ExC-2 0.01
ExC-3 0.06
Fourth laYer (hiqh-sensitivity red-sensitive emulsion
layer)
Silver iodobromide emulsion 0.9
(AgI 6 mol%, high internal AgI type
with a core-shell ratio of 2:1;
sphere equivalent diameter 0.7 ~
variation coefficient of the sphere
equivalent diameter 25%; tabular
grains; diameter/thickness ratio 2.5)
Gelatin ~ 0.8
ExS-l 1.6x10-4
ExS-2 1.6x10-4
ExS-5 1.6x10-4
ExS-7 6x10-4
ExC-l 0.07
ExC-4 0.05
Solv-l 0.07
Solv-2 0.20
Cpd-7 4.6x10-4
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1 320657
Fifth laYer (interlayer)
Gelatin 0.6
UV-4 0.03
UV-5
Cpd-1 0.1
Polyethylacrylate latex 0.08
(solid content3
Solv-1 0.05
ixth layer (low-sensitivity qreen-sensitive emulsion
layer)
Silver iodobromide emulsion 0.18
(AgI 4 mol%; uniform type;
sphere equivalent diameter 0.4 ~;
the variation coefficient of the sphere
equivalent diameter 37g6; tabular
grains; diameter/thickness ratio 2.0)
Gelatin 0,4
ExS-3 2x10-4
ExS-4 7x10-4
ExS-5 lx10-4
ExM-5 0.11
ExM-7 0'03
ExY-8 0.01
Solv-l 0.09
Solv-4 0.01
- 96 -
1 320657
eventh layer (medium-sensitivity qreen-sensitive
emulsion layer)
Silver iodobromide emulsion 0.27
(AgI 4 mol~; high surface AgI type
with a core-shell ratio of 1:1;
sphere equivalent diameter 0~5 ~,
variation coefficient of the sphere
equivalent diameter 25~; tabular
grains; diameter/thickness ratio 4.0)
Gelatin 0.6
ExS-3 2x10-4
ExS-4 7x10-4
ExS-5 lx10-4
ExM-5 0.17
ExM-7 '
ExY-8 0.02
Solv-l 0.14
Solv-4 0.02
iqhth layer (hiqh-sensitivity qreen-sensitive emulsion
layer)
Silver iodobromide emulsion 0.7
(AgI 8.7 mol%; grains of a multi-
layerstructure with a silver amount
ratio of 3:4:2 (from the center);
AgI content 24, 0 and 3 mol% from
the interior; sphere equivalent
diameter 0.7 ~; variation coefficient
of the sphere equivalent diameter 25%;
tabular grains; diameter/thickness ratio 1.6)
Gelatin 0.8
ExS-4 5.2x10-4
ExS-5 lx10-4
- 97 -
1 320657
ExS-8 0.3x10-4
ExM-5 0.1
ExM-6 0 03
ExY-8 0.02
~xC-l 0.02
ExC-4 0.01
Solv-l 0.25
Solv-2 0.06
Solv-4 0.01
Cpd-7 lx10-4
Ninth layer (interla~er)
Gelatin 0.6
Cpd-l 0.04
Polyethylacrylate latex 0.12
(solid content)
Solv-l 0.02
Tenth laYer (interlayer effect donor laYer for the red-
sensitive laYer)
Silver iodobromide emulsion 0.68
tAgI 6 mol%; high internal AgI type
with a core-shell ratio of 2:1;
sphere equivalent diameter 0.7 ~;
variation coefficient of the sphere
equivaIent diameter 18%; monodisperse
tabular grains; diameter/thickness
ratio 2.0)
Silver iodobromide emulsion 0.19
(AgI 4 mol%; uniform type; sphere
equivalent diameter 0.3 ~; variation
coefficient of the sphere equivalent
diameter 37%; tabular grains;
diameter/thickness ratio 3.0)
- 98 -
1 320657
Gelatin 1.0
ExS-3 6x10-4
ExM-10 0.19
Solv-1 0.20
Eleventh layer (yellow filter layer)
Yellow colloidal silver 0.06
Gelatin 0.8
Cpd-2 0.13
Solv-l 0.13
Cpd-1 0.07
Cpd-6 0.002
H-l 0.13
Twelvth layer (low-sensitivity blue-sensitive layer~
Silver iodobromide emulsion 0.3
(AgI 4.5 mol%; uniform AgI type;
sphere equivalent diameter 0.7 ~;
variation coefficient of the sphere
equivalent diameter 25%; tabular
grains; diameter/thickness ratio 7.0)
Silver iodobromide emulsion 0.15
(AgI 3 mol%; uniform AgI type;
sphere equivalent diameter 0.3 ~;
variation coefficient of the sphere
equivalent diameter 30%; tabular
grains; diameter/thickness ratio 7.0)
Gelatin 1.8
ExS-6 9xl0-4
ExC-l 0.06
ExC-4 0 03
ExY-9 0.14
_ 99 _
1 320657
ExY-ll 0.89
Solv-l 0,42
Thirteenth laYer (interlayer)
Gelatin 0.7
ExY-12 0.20
Solv-l 0.34
ourteenth layer (hiqh-sensitivity blue-sensitive
emulsion layer)
Silver iodobromide emulsion 0.5
(AgI 10 mol%; high internal AgI
type; sphere equivalent diameter
1.0 ~; variation coefficient of
the sphere equivalent diameter 25%;
multiple twinning tabular crystals;
diameter/thickness ratio 2.0)
Gelatin 0.5
ExS-6 lxlO-4
ExY-9 0.01
ExY-ll 0.20
ExC-l 0.02
Solv~l 0.10
Fifteenth la~er (first protective layer)
Fine grain silver iodobromide emulsion 0.12
(AgI 2 mol%; uniform AgI type;
sphere equivalent diameter 0.07 ~)
Gelatin 0.9
UV-~ O.11
UV-5 0.16
Solv-5 0.02
-- 100 --
1 320657
H-l 0.13
Cpd-5 0.10
Polyethylacrylate latex 0.09
(solid content)
Sixteenth layer (second protective layer)
Fine grain silver iodobromide emulsion 0.36
(AgI 2 mol~; uniform AgI typei
sphere equivalent diameter 0.7 ~)
Gelatin: 0.55
Polymethylmethacrylate par~icles 0.2
(diameter 1.5 ~)
H-l 0.17
In addition to the above components, a stabi-
lizer for the emulsion, Cpd`-3 ~0.07 g/m2), and a surface
active agent, Cpd-4 (0.03 g/m2), were added to each of
the layers as coating aids.
-- 101 --
1 320657
UV- 1
OH
~ ~ 3
H 3C--C--CH 3
CH3
U V - 2
OH
N ~
p~r--C--CH~
CH3
UV- 3
OH
~N~r ¦ll CH~CH,--CH3
H 3C--C--CH 3
CH 3
- 102
1 320657
~ V - 4
CH3 CH3
-~-CH2C )~ - ~ CH2c )Y (x/y=7/3 hy weight)
C0 C0 -0 -CH3
CH2
CH20 - C0 - C =CH ~ - CH3
C~l
U V - 5
HsCz C0 -0 -C3H I 7
N -CH =CH -CH =C
- 103 -
1 320~57
So 1 v-l
CH3
0-~
CH3
O=P/ O -~
CH3
\-`~ .
So l v--2 .
O :
C--0--CH 2--CH z--CH z--CH 3
~\/ ~
C--0 ~CH 2--CH 2--CH 2--CH 3
o
-- 104 --
1 320657
S G 1 v - 4
H3CHzC - C ~ j ~ O
H 3C -C -CH3 C -OH
H2
lHs
S o 1 v - 5
11/ -CH2-CH2-CH2-CH2-CH2-CH3
CH3-CH2-CH2-CH2-CH2-CH2-O -P
\0 -CHz-CH2-CH2-CH2-CH2-CH3
E x F - 1
~, ~C0--I~'N CN2t~0 ~ C.ll"~
i\i
CH3
HsC3 ~ \ C~H~
- 105 -
~ 3~0657
E x F--2
C6H ~ 3 ~ ~3 ~ NH CO ~)
tert-H"cS ~r--CH--C0--~ . ~ C Q
C~ I
HsCz/ ~CzH;
E~c S--1
~CH-C--CH--~
t C112t~S0~ ( CH2~SOsNa
-- 106 -
1 320657
E x S--2
C ~ )~ `\ C 2 H s ~S,~C Q
( CH2t rS0~ ( CHz ) 3 -S03H
E x S--3
~CII= I--CH
(CHz) 4 (CH2) z
SO3Na SO~)
E x S--4
J~ \~CH--C=C~
CH2-CH2-S0~) ¦ /CzHs
CH~CHz ) z S03H ~ C2Hs
C2~1s
-- 107 ~
1 ~20657
E X S - ~
CHz-CH3
~/ \F C N--C = C U ~
CHz CHz
CHz CHz
so 3Q c~l z
CN2
S0 sK
ExS--6
CQ~ CU~ CQ
(CH2) 4 (CHz) 4
soQ S0 3 H N--C z H s
\CzH;
-- 108 --
1 320657
E x S--7
CzHs
(CHz) 3 (CHz) 3
C2Hs
SO~) SO3H N--CzHs
CzHs
E~ S--8
~r ~ C~=c C~
( GHz~S(~) ¦
CzHs
-- 109 --
1 320657
Ex C-- 1
OH
f~ CO--NH~CNzt~0-CIzH2s
~IH--CO--O--C4Hg (iso)
E x C--2
OH F
~,l ~NH--CO ~ CH 2 ~C--F
ter~~HI ,C,~----CHz-CO--~H ~ F
CsH, l-~tert
HO ~
H0'~' CO~ C3117
S
\5,~
S--OH--CO--C--CH 3
C~1 3
-- 110 --
1 320657
E x C - 3
OH
" ` ~" i~ " CO -NH-- ~
O -CH2-CH
J _ CH2-CH2- l \C6Hl 3
f~3
CH NH - CO -CH 2
N =N
110~5 ~`~503:`~a
E x C - 4
OH
f~ ~,co NH--~-CI~ t~ O~C 12H 7~
Hqc4-o-co-~H O -CHzCHz-S-CHzCOOH
1 320657
x~
CH3
--~CHzC )~ ( CHz-CH )y ( CH CH )z
/ ==\ CO--O--C ~ H q 2
CO--N H~N \~
N / 0 x = 50
CQ~CQ y= 25
z= 25
nlol.wt. about 20,000
E x M--6
C~13
H 3 C--C--CH 3 //~--C~--N H N = IN ~ --0 - C 133
CH3 ~ 0 \~
CH3-CH2-C~ O--CH--e NN N~ 0
CH3 ' CNz CQ~ --~ "C~
- 112 -
1 320657
E x ~- 7
H~7CI 3--CO--NH ~--C Q CH3
~H ~ N=N~ OH
N .~.o
C ~ C ~
C~
E x M - 1 0
H 2 ,C I 3 - GO - ~H ~ ~ ' O (A mixture of 5- or 6-
I substituted compounds:
CQ ~,~ ~ C~ the same hereinafter)
C~
- 113 -
1 320657
ExY--8
ce
CH3
H 3C--1--CO--CH--CO--NH ~ \) t e r t - H " C ~
IH--CO~Hz~O (=~ C.N"-'e"
~N
ExY--9
.
cl2E~25 ~G~ C.~- / CO-O-CH-CO-O
l~i'H- CO- CH - CO- NH
.
-- 114 -
1 320657
E ~ Y- 1 1
CO--O--C, 2HZ;
CH 3 - O ~ ~r CO CO--NH
C~
~CH2 0--C2Hs
ExY--1 2
NH- CO ~ CU2~ 0 ~ C H - t e r t
CH3-c-cO-CN-CO-NN~ tert-H~ lCs
CH3 ~ ¦ CQ
~/ =co-o~3
- 115 -
1 320657
CP d 7
Il \~.s~l
N_ 1
SG 3~a
CP d
\~ .
H CO~NH
}l ~ 5C 6 \--~ OH
H 7C8 ~\~CO--NH
~H CO NH
Hl 3C6 ~ IH
116
1 3~0657
C p d - 2
,YC CHz-CO-O-C4Hq
\C=C1 ~ CHz-CO-O-C4Hq
C p d - 6
o
SH ~'H -C -NH -CH3
7 1~
N ~ N
H - 1
O O O O
CH2=CH - S -CH2-C- N'H - CHz-CH2-NH - C - CH2-S - CH = CHz
il Il
O O
- 117 -
1 320657
C~ d--5
C~13
O ~H N O
f
NH ~'H
Cp d--3
CH3
N ~
~R ---N
OH
C p d--4
: ~ :
H, 7C" ~/>--~ O--CH2--CH~ ~SO3~la
.
;
-- 118 --
1 320657
In the above Example, the following material,
emulsion, etc. are used. They are, however, not
essential for obtaining the effects of the invention,
i.e. excellent color reproduction and tone reproduction,
and may be replaced by other materials and emulsions to
obtain similar color reproduction and tone reproduction
so long as the photographic material falls within the
scope of the invention.
For example, the fine grain silver iodobromide
emulsions in the 15th and 16th layers may be omitted,
and Cpd-5 in the 15th layer may be omitted.
Preparation of a SamPle 102 (comparison)
Sample 102 was prepared by making the following
changes to Sample 101.
The iodine content in the silver iodobromide
emulsions in the third layer was changed from 6 mol% to
3 mol%~ and from 4 mol% to 2 mol%, respectively.
The iodine content of the silver iodobromide
emulsion in the seventh layer was changed from 4 mol% to
2 mol%.
The iodine content of the silver iodobromide
emulsion in the twelfth layer was changed from 4.5 mol%
to 2.5 mol%~ and from 3 mol% to 1.5 mol%~ respectively.
-- 119 --
1 320657
Preparation of a Sample_103 (comparison)
Sample 103 was prepared by making the following
changes to Sample 101.
The amounts of silver iodobromide emulsions in
the third layer coated were decreased from 0.65 to 0.46
and from 0.1 to 0.07, respectively.
The amounts of cyan couplers ExC-l and ExC-4 in
the twelfth layer were increased from 0.06 to 0.12 and
from 0.03 to 0.06, respectively. The amount of yellow
coupler ExY-ll was increased from 0.89 to 0.93.
Preparation of a SamPle 104 (comparison)
Sample 104 was prepared by making the following
changes to Sample 101.
The amounts of cyan couplers ExC-l and ExC-4 in
the twelfth layer were increased from 0.06 to 0.12 and
from 0.03 to 0.06, respectively.
The amount of yellow coupler ExY-ll was
increased from 0~89 to 0.93.
Preparation of a Sample 105 (comparisonl
Sample 105 was prepared by making the following
changes to Sample 101.
The amounts of silver iodobromide emulsions
coated in the third layer were decreased from 0.65 to
0.46 and from 0.1 to 0.07, respectively.
- 120 -
1 320657
The amount of magenta coupler ExM~5 in the
seventh layer was increased from 0.17 to 0.25.
The amount of DIR coupler ExM-10 in the tenth
layer was decreased from 0.19 to 0.095.
The amount of yellow coupler ExY-ll in the
twelfth layer was decreased from 0.89 to 0.80.
Preparation of a Sample 106 (comparison)
Sample 106 was prepared by making the following
changes to Sample 101.
The amount of DIR coupler ExM-10 was decreased
from 0.19 to 0.095.
The amount of yellow coupler ExYU-ll in the
twelfth layer was decreased from 0.89 to 0.80~
The amount of magenta coupler ExM-5 in the
seventh layer was increased from 0.17 to 0.25.
PreParation of a Sample 107 (comparison)
Sample 107 was prepared by making the following
changes to Sample 101.
Coupler ExC-2 in the third layer was excluded,
and the amounts of the silver iodobromide emulsions were
decreased from 0.65 to 0.52 and from 0.1 to 0.08,
respectively.
The amount of silver iodobromide coated in the
seventh layer was decreased from 0.27 to 0.22.
- 121 -
l 320651
Yellow coupler ExY 11 in the twelfth layer was
decreased from 0.89 to 0.85.
Preparation of a Sample 108 (comparison)
Sample 108 was prepared by making the following
changes to 5ample 101.
Coupler ExC-2 in the third layer was excluded,
and the amounts of silver iodobromide emulsions were
decreased from 0.65 to 0.52 and from 0.1 to 0.08,
respectively.
The amount of yellow coupler ExY-ll in the
twelfth layer was decreased from 0.89 to 0.85.
Preparation of a Sample 109 (comPariSon~
Sample 109 was prepared by making the following
changes to Sample 101.
The amount of the silver iodobromide emulsion
coated in the seventh layer was decreased from 0.27 to
0.22.
DIR coupler ExY-9 in the twelfth layer was
excluded. Cyan couplers ExC-l and ExC-4 were also
excludedO The amount of yellow coupler ExY-ll was
decreased from 0.~9 to 0.62.
Preparation of a Sample 110 (comparison)
Sample 110 was prepared by making the following
changes to Sample 101.
- 122 -
1 320657
DIR coupler ExY-9 in the twelfth layer was
excluded. Cyan couplers ExC-l and ExC-4 were also
excluded. The amount of yellow coupler ExY-ll was
decreased from 0.89 to 0.62.
Preparation of a Sample 111 (comparison)
Sample 111 was prepared by making the following
changes to Sample 101.
Colored coupler ExM-7 in the seventh layer was
excluded.
The amounts of silver iodobromide emulsions in
the twelfth layer were decreased from 0.3 to 0.24 and
from 0.15 to 0.12, respectively.
Preparation of a Sample 112 (comParlson)
Sample 112 was prepared by making the following
changes to Sample 101.
Colored coupler ExM-7 in the seventh layer was
excluded.
Preparation of a Sample 113 (comparison)
Sample 113 was prepared by making the following
changes to Sample 101.
Yellow coupler ExY-ll was added to the third
layer in an amount of 0.10.
The amounts of the silver iodobromide emulsions
in the twelfth layer were decreased from 0.3 to 0.24 and
from 0.15 to 0.12, respectively.
- 123 -
1 320657
Preparation of a Sample 114 ~inven i~
Sample 114 was prepared by making the following
changes to Sample 101.
Yellow coupler ExY-ll was added to the third
layer in an amount of 0.10.
Preparation of a SamPle 115 (invention~
Sample 115 was prepared by making the following
changes to Sample 101.
The amounts of the silver iodobromide emulsions
coated in the third layer were increased from 0.65 to
0.78 and from 0.1 to 0.12, respectively.
Cyan couplers ExC-l and ExC-4 were removed from
the twelfth layer. The amount of yellow coupler ExY-ll
was decreased from 0.89 to 0.85.
Preparation oE a SamPle 116 (invention)
Sample 116 was prepared by making the following
changes to Sample 101.
The amounts of the silver iodobromide emulsions
coated in the third layer were increased from 0.65 to
0.78 and from Ool to 0.12, respectively.
The amount of magenta coupler ExM-5 in the
seventh layer was decreased from 0.17 to 0.01.
The amount of DIR coupler ExM-10 in the tenth
layer was increased from 0.19 to 0.27, and the amounts
of the silver iodobromide emulsions coated were
- 12~ -
1 320657
decreased from 0.68 to 0.54 and from Ool9 to 0.15,
respectively.
Preparation of a Sample 117 (inventionl
Sample 117 was prepared by making the following
changes to Sample 101.
The amount of coupler ExC-2 in the third layer
was increased from 0.01 to 0.15. The amounts of the
silver iodobromide emulsions coated were increased from
0.65 to 0.78 and from 0.10 to 0.12, respectively.
The amount of the silver iodobromide emulsion
coated in the seventh layer was increased from 0.27 to
0,32.
Preparation of a SamPle 118 (inventionl
Sample 118 was prepared by making the following
changes to Sample 101.
The amount of the silver iodobromide emulsion
coated in the seventh layer was increased from 0.27 to
0.32.
The amounts of the silver iodobromide emulsions
coated in the twelfth layer were increased from 0.3 to
0.36 and from 0.15 to 0.18, respectively. The amount of
DIR coupler ExY-9 was increased from 0.14 to 0.20. The
amounts of cyan couplers ExC-l and ExC-4 were increased
from 0.06 to 0.07 and from 0.03 to 0.04.
- 125 -
1 320657
Preparation of a Sam~le ll9 (invention)
Sample ll9 was prepared by making the following
changes to Sample lOl.
The amount of magenta coupler ExM-5 in the
seventh layer was increased from 0.17 to 0.25.
The amount of DIR coupler ExM-10 in the 10th
layer was decreased from 0.19 to 0.095.
Cyan couplers ExC-l and ExC-4 in the twelfth
layer were excluded, and the amount of yellow coupler
ExY-ll was decreased from 0.89 to 0.80.
Preparation of a Sample 120 (invention)
Sample 120 was prepared by making the following
changes to Sample lOl.
Coupler ExC-2 in the third layer was excluded.
The amounts of the silver iodobromide emulsions were
decreased from 0.65 to 0.52 and from 0.1 to 0.08,
respectively.
The amounts of the silver iodobromide emulsions
coated in the twelfth layer were increased from 0.3 to
0.36 and from 0.15 to 0.18, respectively. The amount of
DIR coupler ExY-9 was in~reased from 0.14 to 0.20. The
amounts of cyan couplers ExC-l and ExC-4 were increased
from 0.06 to 0.07 and from 0.03 to 0.04, respectively.
- 126 -
1 320657
Preparation of a SamPle 121 (invention)
Sample 121 was prepared by making the following
changes to Sample 101.
The amount of coupler ExC-2 in the third layer
was increased from 0.01 to 0.015. The amounts of the
silver iodobromide emulsions coated were increased from
0.65 to 0.78 and from 0.10 to 0.12, respectively.
DIR coupler ExY-9 in the twelfth layer was
excluded. Cyan couplers ExC-l and ExC-4 were also
excluded. The amount of yellow coupler ExY-ll was
decreased from 0.89 to 0.62.
Test
Samples 101 to 121 were processed into formats
and skins and hairs of black, white and y~llow human
species and the color rendition chart of MacBeth Company
were photographed on these formats under various
illuminations. The photographic materials were then
subjected to the color processing shown below, and
printed properly on Fuji color papers. The photographs
were evaluated by a panel of 20 persons. Significant
results obtained by the organoleptic evaluation of the
panelists were gathered, and are summarized in Table 1.
The results show that Samples 115 to 118 which
satisfy the conditions of the invention, YP~ YG ' YB ' YR'
YG and YB' showed generally good color reproduction,
- 127 -
1 320657
Samples 119-121 which satisfy the preferred conditions
of the above-described yP to YB showed more preferred
results, and above all, ideal color reproduction was
obtained with Sample 101 which also satisfied the
IE(X/Y) conditions. These results clearly substantiate
the effects of the present invention.
- 128 -
1 320657
c o ul ~ ~a a
11 ~ .r~ al V U~
U rl 3 a u u a .rl U t ~ LJ rl .C O O rl ~ ~ 07
~ v a~ ~ a Q rl 1~ 1 0 a ~
o 11 11~ U r--l ~ 'nr~ ~1 ,r 0 0 5 ~rl .C 3 11~ 3
111 r~ CJ r-l O ,Q _I ~1 ~ ID r~l U) Ll .rl .~C U~ a o ~ ~ o
U ~ l rl O ~ V Ll U ~ CI r-i Ul U r~l
al x IZJ w ~1 o h O O rl 1: .C O li r~l IIJ Id '1 51 Id :~ CJ
4 0 0 ~.) .0 Pl ~ .C 11) ~1 a.4 1.~1 V V r;l ~ 3
~0 r~ .r h
.rl ~ ,11 U ~ 01
U~ Q 4_~ o O U .C ~ l Q ~1 Q
a 3 I s O ~ Id rl = ~ .rl = )'I
~rl V ~ ~ O
dl r ,0 V O IU r-l ~,~ 15 O 4'~ 0 t) V
O ni I r V nl V ~ V >1 r V a P-
m ~ u~
.c~ ~ ~0
IJ IH
I
r l 'U~ H ~ ¦ . O
r ¦ 1 H ~ ¦ ~ O
~7 N
W ~? o O
O ~ O I r l O
?- ~`O co X l`o ~Do l`o r~O
O O O O O O
r-l O Ir~ 1~1 O O
~0 ~ X ~0 ~0 ~0 ~0
O O O O O O
va ~KI ~0 r`x lODo l`X IDo r~x
rl O O O O O O
~m O N O 1~ 111 U~
;>_ ~0 ~0 'O '`O I`o r'O
O O O O O O
~ ¦ . O ~ O ~ O ~ O ~ O ~ O
O rl O O O O
1~
~; ~ O 1` X a~O 1` X ~0
t_ O r l O O O O
v ~ a
D. ~
a u
rl
~ 1~1 N 1~1 ~r IO ID
d r-l r l r l r l r l r-l
Ul
- 129 -
1 320657
C ~ C ~ V C ~ L ~
,~ U.. ~ O O ~ 6 -~ C a~~ 0~ "' V O
." ~ ~ ~ JJ a~ w ~ ~ a~: v C a~
o ~ W C r-l h .~ 0 aJ L~ .0 C ~J
.. ~ ''~ J ~ aa~~ C C: O ~a~ c
U ~ h '~) ~ W OJ .1 ~ )~ d W ~ ~ a~
~ w o ~cl .a i~l u o ~1 ~ O .C O .a ~: Ll 6
3 .C: ~ .t ~ .-1 ~ .. 1
. 3 3 W W 3 U ~ J ~ W
~, a~ a~ O o
C S I g-1 C
v g ~
¦ C .C W ~ o .C ~
.. ~
~a w~
_ H ~ ¦
U ,~ ~ I
a~ c~ r~
E-~ H ~ ¦
~ ¦ O .0 . O Ø0~ X ~0 ~ X
?-- ¦ . O 1` X~D O. X . O . O . O O
O O O O O O O O
C ;~ Do U~o ~Do ~Do ~Do o ~Do Ulo
~1 ~ ~ ~ ~o x O 0 00
~1~) co ~ '1 N N ~ ~
~X O o oO oO oO ~o o
0 ~o a~O ~0 ~J)o ~0 0~0 ~nO
O O O O O O
~C
6 W
O O cn o ~-~ N
- 130 -
1 320657
~, o ." ~ r~
~ U .r~ b`l ~ Id V rcl ID ~
o ~ ~ O ~ ~ D7 'U V r~ .C r rd w V o.~ V ,~
S E~ 3 ~ ~ u~ V,a) C tr),C O
c~ -~ u,~ o-~ V
~ tD ~ .C ~ r~ U~
C~ U~ Ll E'_I U~ u~ o .~ o o 3~ O v~-,
3 J 3
O '~ ~ ~ ~.C
., :~ r ,s:: S ~ "J ~o ,C ~ V
o ~ 'I U
0 n~ 0 ~0 Ll
~_
_ U~ O
~ X ~0 r~x
.C C' W W ~1 0 r~
JJ ~1 H
_O H ~ ¦ N 11~
~r W ~ ¦ (~) O
r~~ H _ O O O
E lW ~ ¦ , X O O
O !` O r( O O O
o ~Do ~o ~0 ~0 ~0 ~0
O O O O O O O
O rl N O O N O
~D o ~o ~0 ~Do ~Do ~o ~Do
O O O O O O O
1~ 0 0 a I N O r l
Va ~ ~D O ~D o ~o O U~ o ~ O ~ O ~D o
.Q~ O ~ O O o o o
~ ~ m O O O co co tn N
~!1 ;_ a~ O ~0 ~0 1~0 r~O r~O ~oO
O O O O O O O
~1 ~1 Il'~ O N t'l ~ 1-'1 It'l
o~ o a~O '~G ~o a o ~o ~0
o o ,~ ,~ o o o
~1 P~ 110 O) O ~JI O 0~ 0 Cil O
~ I r; r; O O O O O
o
rl .
H
r~l
a. u ~u~ I~ co a~ o r1
EI r1 ~1 ~ l N N
U~
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Notes; O: The value is within the scope of the
present invention
x: The value is outside the scope of the
present invention
~: The value is within the scope of the
present invention but is not within the
preferred range of the present invention
Effects of the Invention
~ 1~ When YR ~ 0.80, various defects occur~
Specifically, the skin of ~he black is reproduced in a
darker color than the actual model. Reproduction of the
root of fair hair is excessively dark. ~he saturation
of the skin of the whitP is low, and the face looks that
of a sick person. Yellow green is reproduced as yellow.
(2) When YG < 0.80, various deects occur. For
example, the skin of the black is reproduced in a color
with a tint of cyan~ The skins of the white and the
yellow are reproduced in a yellowish color. Or -the
skins of the white and the yellow are reproduced in a
reddish color.
(3) When YB < 0.65, yellow color is excessively
removed from the skin color of the yellow or the skin of
the white is reproduced in an excessively reddish color.
(4) When YR/ YG > . 65 and y~> 0.75, the skin of
the black is excessively dark, and the skin of the white
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is excessively bright. Furthermore, the ability to
depict the highlight and shadow portions of various
objects is inferior. Furthermore, if an~ of ~Rr YG and
YB falls outside the scope of this invention, the image
of a gray object forms color shift in addition to the
defects in color reproduction shown in Table 1 above.
The samples of this invention show excellent
reproduction of the color of the skin which is most
important, and can perform reproduction with a
sufficient three-dimensional feel without a color change
in the highlight to shadow portions of various objects.
Foreign patents corresponding to Japanese Patent
Publications cited in this application are shown below.
JP-A-50-2537: U.S. Patent 3,990,899,
West German OLS 2,421,544,
British Patent 1,460,991
JP-A-61-34541 U.S. Patent 4,705,744,
EP 167,173
JP-A-57-151944: U.S. Patent 4,477,563,
DE 3,209,486,
British Patent 2,099,167
JP-~-54-145135: U.S. Patent 4,248,962,
DE 2,855,697,
British Patent 2,010,818
JP-A-62-54255: EP 2,00,502,
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1 320657
WO 83/234
JP-58-100847: U.S. Patent 4,511,648,
EP 70,182
JP - A-61 - 153460: EP 161,626
While the invention has been described in detail
and with reference to specific embodiments thereof, it
will be apparent to one skilled in the art that various
changes and modifications can be made therein without
departing from the spirit and scope thereof.
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