FIELD OF THE INVENTION
[0001] This invention relates to a color photographic material, and more specifically to
a color photographic material having high saturation and excellent color reproducibility
and gradation reproducibility, and a method for production of a color image using
the same.
BACKGROUND OF THE INVENTION
[0002] It has been known to utilize an interlayer inhibiting effect as means for improving
color reproducibility 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-sensitive 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 inhibiting effect from a red-sensitive layer to a green-sensitive
layer gives a reproduction of green having a high degree of saturation.
[0003] 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 disclosed in JP-A-50-2537. ("JP-A" as used herein means an "unexamined
published Japanese patent application". Foreign patents corresponding to Japanese
patent publications 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 coupler added, and can impart the same effect as the interlayer effect.
[0004] 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 silver halide emulsion layer containing a color coupler
which forms yellow, at least one green-sensitive silver halide emulsion layer containing
a color coupler 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 (λ
G) of the spectral sensitivity distribution of the green-sensitive layer is 520 nm≦λ
G≦580 nm,
the center of the wavelength (λ
-R) of the distribution 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≦λ
-R≦560 nm, and
λ
G - λ
-R≦ 5 nm.
[0005] The center of the wavelength λ
-R of the wavelength 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 photographic 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-sensitive
layer to give a reversal image (see Fig. 1A).
(3) The spectral sensitivity distribution S-R (λ) of the reversal photographic material is determined from the reversal image.
[S-R(λ) for a given λ (wavelength) can be determined relatively from point a in Fig. 1A]
(4) The center of the wavelength (λ-R) of the interlayer effect is calculated from the following equation.

[0006] The center of the sensitivity wavelength λ
G is given by the following equation.

[0007] S
G(λ) is the spectral sensitivity distribution curve, and S
G(λ) at a given λ can be determined from point
b of Fig. 1B as a relative value.
[0008] When all objects existing in nature were photographed using the above-described photographic
material and the images were printed on commercial color 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 insufficient for subtle reproduction
of skin colors which are most important colors. A further development in technique
is necessary in order to depict accurately the continuity of the highlights and shadows
of colors of a 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
[0009] An object of the present invention is to provide a color photographic material having
high saturation and excellent color reproducibility and gradation reproducibility.
[0010] 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.
[0011] Specifically, according to this invention, the foregoing problem is solved by a silver
halide color photographic material comprising a support and formed thereon at least
one red-sensitive silver halide emulsion layer, at least one green-sensitive silver
halide emulsion layer and at least one blue-sensitive silver halide emulsion layer,
wherein gradients γ

, γ

and γ

in monochromatic exposure of wavelengths giving peak sensitivities are
0.80 < γ

0.80 < γ

0.65 < γ

,
and maximum gradients γ
R, γ
G and γ
B in standard white light source exposure are
γ
R < 0.65
γ
G < 0.65
γ
B < 0.75.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012]
Fig. 1A is the characteristic curve of a reversal image obtained as a result of the
red-sensitive layer receiving the interlayer effect from the green-sensitive layer
at a wavelength λ.
Fig. 1B is the characteristic curve of the green-sensitive layer at a wavelength λ.
Fig. 1C shows a method of determining the magnitude of the interlayer effect. Fig.
1C shows the interlayer effect of color sensitivity Y on color sensitivity X. The
density decrease of color sensitivity X which decreases during movement toward a
higher exposure by 1.0 of log E from the sensitivity point (the logarithm of the amount
of exposure which gives a density of fog +0.2) of color sensitivity Y is defined as
IE(X/Y).
Fig. 2 shows the equivalent energy spectra of typical samples. The ordinate shows
the logarithm of the reciprocal of the relative sensitivity. The curves arranged in
the order from that having smaller values, i.e. higher sensitivities show sensitivities
at a density of fog+0.4, fog+0.6, fog+0.8, and fog+1.0, respectively. The circular
marks show points which give peaks. The averages of these are calculated as 413 nm,
543 nm and 621 nm, respectively.
Fig. 3 shows absorption spectra of blue, green and red optical filters using in density
measurement.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The present inventors also found that by providing some restrictions on the 4 directions
of the interlayer effect in addition to the above conditions, more favorable color
reproduction can be obtained.
[0014] Specifically, with regard to the magnitude IE(X/Y) of the interlayer effect defined
in Fig. 1C, the following 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) < 1.0.
[0015] IE(X/Y) above represents the magnitude of the interlayer effect of Y on X.
[0016] 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.
[0017] A preferred range of γ

, γ

, and γ

is as follows:
0.90 < γ

< 1.15
0.90 < γ

< 1.10
0.70 < γ

< 1.2,
[0018] A preferred range of γ
R, γ
G and γ
B is as follows:
0.4 < γ
R < 0.60
0.4 < γ
G < 0.60
0.4 < γ
B < 0.65.
[0019] 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 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.
[0020] The wavelength which gives a peak sensitivity is defined as follows:
[0021] 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 densities,
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 550 nm to 700 nm and containing a color
coupler which couples with the oxidation product of the developing agent to develop
cyan.
[0022] 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
densities, 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 480 nm to 620 nm and
containing a color coupler which couples with the oxidation product of the developing
agent to develop magenta.
[0023] Likewise, 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 halide emulsion layer becomes highest at varying
densities, 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.
[0024] Examples of wavelengths obtained by the above methods are shown in Fig. 2.
[0025] In the present invention, the gradient at a wavelength which gives the peak sensitivity
is determined by the following procedure.
[0026] 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.

[0027] 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 ϑ values with respect to the angle ϑ from the abscissa are defined
as γ

, γ

, and γ

of this photographic material.
[0028] Likewise, the gradients in a standard white light source are determined by the following
procedure.
[0029] A photographic material is exposed through a wedge to a standard white light source,
for example, a light source having an energy distribution of 5,500°K 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
photographic 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 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 ϑ values with respect to the
angle ϑ from the abscissa are defined as γ
R, γ
G and γ
B of this photographic material.
[0030] When the silver halide color photographic material of this invention is a color nagative
film, those commercially available as color papers giving prints can all be used.
[0031] 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 Photographic Engineering, Silver Halide Photography, edited by Japan Society of Photography, page 387).
[0032] Should the average gradient of color papers be increased by α times in future for
some reason, the gradients in this invention may be set as follows:-
[0033] Namely, the gradients of the wavelengths giving the peak sensitivities in monochromatic
exposure are set at


and the gradients in a standard white light source exposure are set:

[0034] The preferred ranges of γ

, γ

, and γ

are set:

and the preferred ranges of γR, γG and γB are set:

[0035] The present invention has succeeded in enhancing color reproducibility and contrast
reproducibility by 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.
[0036] This means that by employing whatever combinations of the spectral sensitivity and
the interlayer effect, good results cannot be obtained if the gradations 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.
[0037] 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.
[0038] Use of an emulsion having a high 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
increase 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
0 to 15 mol%, more preferably not more than 10 mol%, most preferably not more than
8 mol%, on an average of silver iodide.
[0039] When silver halide containing at least 8 mol% of silver iodide is used in any one
layer of the photographic material of this invention, the content of silver iodide
on the surface of silver halide grains is from 0 to 6 mol%, preferably not more than
4 mol%, for the same reason.
[0040] Now, means for controlling the interlayer effect used in this invention will be described.
[0041] 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 invention, 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 turbidity
of the color formed of the other layer, this effect is referred to as a minus interlayer
effect.
[0042] The following methods, for example, are available for imparting the plus interlayer
effect.
[0043] A masking technique using colored couplers as described in U.S. Patents 2,983,808
and 3,034,892.
[0044] 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.
[0045] A method involving including a DIR compound into a non-photosensitive layer as described
in JP-A-61-43745.
[0046] A method involving skillfully selecting the properties of a DIR compound as described
in JP-A-62-54244.
[0047] 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.
[0048] When the pyrazolotriazole magenta coupler described in JP-A-61-0222342 is used in
a green sensitive 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 5-amide naphthol-type cyan coupler described in JP-A-61-153460
is used in a blue-sensitive layer, the interlayer effect on a green-sensitive effect
can be increased because there is little subsidiary absorption of magenta.
[0049] Means for increasing the gradient γ
P at a wavelength which gives a peak sensitivity will be specifically described without
any limitation thereby.
[0050] 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 available. Likewise, there
is a method in which the amount of a development inhibitor releasing compound (DIR
compound) is decreased.
[0051] The above-cited methods increase not only γ
P but also γ in white light exposure. Accordingly, means for confining γ within the
range specified by this invention become necessary. Examples of such means are listed
below.
[0052] 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 invention, γ
R is decreased by reducing the amounts of the cyan couplers ExC-1 and ExC-4 in the
12th layer (blue-sensitive layer). Furthermore, γ
B 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.
[0053] 2. Automasking by colored couplers is strengthened.
[0054] For example, in the working example of this invention, γ
B can be decreased by increasing the amount of the yellow colored magenta coupler EXM-7
in the 7th layer.
[0055] Likewise, γ
G can be decreased by increasing the amount of the magenta colored cyan coupler ExC-3
in the third layer.
[0056] 3. The interlayer development inhibiting effect is increased.
[0057] For example, γ
R and γ
B can be decreased by increasing the amount of the DIR coupler EXM-10 in the 10th layer
in the example of this invention. Likewise, γ
G and γ
B can be decreased by increasing the amount of the coupler ExC-2 in the third layer.
[0058] The inclusion of at least one nondiffusible coupler which releases a diffusible development
inhibi tor or its precursor only 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 layers. 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 oxidation product of
the color developing agent diffused from another layer to release a releasing group
during color development.
[0059] 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.
[0060] To change the degree of the interlayer inhibiting 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 the interlayer inhibiting effect is set off by intentionally mixing
a colored dye having different color from the color to which the layer is sensitive
and thus increasing color tubidity.
[0061] Nondiffisuble couplers which release a diffusible development inhibitor or its precursor
during coupling with a color developing agent in this invention are represented by
the following formula.
JY)
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 development inhibitor
having high diffusibility (preferably having a diffusibility, measured by the method
to be described hereinbelow, of at least 0.4).
[0062] Y in general formula (I) above preferably includes the following groups of general
formulae (II) to (V).

[0063] In the formulae, W represents -S-, -O-, or -N(R₃)-, R₁, 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. R₁ group(s) may be substituted at any position(s)
on the ring.
[0064] Examples of R₁ include a lower alkyl group having from 1 to 4 carbon atoms (preferably,
the total number of carbon atoms in R₁ group(s) is 2, for example, R₁ is CH₃ and i=2),
and a halogen atom, for example, Cl and Br and i=1 or 2, preferably R₁ is Br and i=1.
Furthermomre, examples of R₁ 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),

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 R₁ may be the same or different from each other.
[0065] 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 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.
[0066] R₂ further represents a substituted or unsubstituted 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 nitro group, an amino group, an
alkyl group, a carbamoyl group and a ureido group. These substituents preferably substituted
at m- or p-position of the phenyl group.
[0067] Examples of the substituted phenyl group include a hydroxyphenyl group, an aminophenyl
group, a sulfamoylphenyl group, a carboxyphenyl, group, a methoxycarbonylphenyl
group, a 3-methoxyphenyl group, a 3-carbamoylphenyl group and a 3-ureidophenyl group.
[0068] R₂ also represents (CH₂)₂₋₃COOR′ (R′ has 2 to 3 carbon atoms),

(the two Rf′ groups may be identical or different and have 2 to 3 carbon atoms),
and -(CH₂)₂OCH₃. R′ is as defined above with regard to R₁.
[0069] Examples of R₃ are a hydrogen atom and alkyl groups as defined the alkyl group represented
by R₂.
[0070] Examples of R₄ are an amino group, -NHCOR′ (R′ represents an alkyl group having from
1 to 6 carbon atoms),

(the two R′s are identical or 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.
[0071] The diffusibility of the development inhibitor is evaluated by the following method.
[0072] A photographic material (sample B) was prepared by forming the following two layers
on a transparent support.
First layer: red-sensitive silver halide emulsion layer
[0073] An emulsion obtained by rendering a silver iodobromide emulsion (silver iodide 5
mol%, average size 0.4 µ) red-sensitive using 6×10⁻⁵, 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 g/m²
(coating thickness 2 µ).
Coupler X
[0074]

Second layer:
[0075] A gelatin layer (the amount of silver coated 2 g/m², coating thickness 1.5 µ) containing
the same silver iodobromide emulsion as used in the first layer (having no red-sensitivity)
and polymethyl methacrylate particles (diameter about 1.5 µ).
[0076] Another gelatin hardener or a surface-active agent is incorporated in each of these
layers.
[0077] 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.
[0078] 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 time was used as a measure of the diffusibility
of the silver halide emulsion coating. The results are shown below.

[0079] In general formula (I), Y further represents the following general formula (VI):
-TIME-INHIBIT (VI)
[0080] 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.
[0081] In general formula (VI), the TIME-INHIBIT group is preferably one of those represented
by the following general formulae (VII) to (XIII).

[0082] In general formulae (VII) to (XIII), R₂₀ represents a hydrogen or halogen atom, or
an alkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano,
nitro, sulfonamide, sulfamoyl, carbamoyl, aryl, carboxyl, sulfo, hydroxyl or alkanesulfonyl
group. These groups preferably have from 1 to 20 carbon atoms.
[0083] In general formulae (VII), (VIII), (IX), (XI) and (XIII), k represents 1 or 2.
[0084] In general formulae (VII), (XI), (XII) and (XIII), ℓ represents an integer from 0
to 2.
[0085] 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.
[0086] In general formulae (XII) and (XIII), L represents an oxygen atom, or a group of
the formula

in which R₂₄ represents a hydrogen atom or a lower alkyl group, preferably having
from 1 to 5 carbon atoms.
[0087] Preferably, the INHIBIT group is represented by general formulae (II)′, (III)′, (IV)′
and (V)′.

[0088] In the formulae, W represents -S-, -O-, or -N(R₃)-, R₁′, 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. R₁′ group(s) may be substituted at any position(s)
on the ring.
[0089] R₁′ represents a halogen atom or an alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolydenamino,
aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro,
amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxyl, alkoxycarbonylamino,
alkylthio, arylthio, aryl, heterocyclic, cyano, alkylsulfonyl or aryloxycarbonylamino
group.
[0090] In general formulae (II)′ and (III)′, i′ represents 1 or 2, and when i′ is 2, two
or more R₁′ groups may be identical or different, and
i′ R₁′ groups may contain 0 to 32 carbon atoms in total.
[0091] In general formula (IV), R₂′ represents an alkyl, aryl or heterocyclic group.
[0092] In general formula (V), R₃′ represents a hydrogen or halogen atom, or an alkyl, aryl
or heterocyclic group; and R₄′ represents a hydrogen or halogen atom or an alkyl,
aryl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamide, cyano,
heterocyclic, alkylthio or amino group.
[0093] When R₁′, 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, arylsulfonyl, alkylthio and arylthio groups.
[0094] When R₁′, R₂′, R₃′ or R₄′ represents an aryl group, the aryl group may be substituted.
Examples of substituents on the aryl group include halogen atoms and alkyl, alkenyl,
alkoxy, alkoxycarbonyl, nitro, amino, sulfamoyl, hydroxyl, carbamoyl, aryloxycarbonylamino,
alkoxycarbonylamino, acylamino, cyano and ureido groups.
[0095] When R₁′, 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, benzotriazolyl, 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.
[0096] In general formula (IV), the number of carbon atoms contained in R₂′ is 1 to 32.
[0097] In general formula (V), the total number of carbon atoms contained in R₃′ and R₄′
is 1 to 32.
[0098] 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 to the alkyl groups
R₁′ to R₄′ above may be cited as examples of substituents in this case.
[0099] R₂₁, R₂₂ and R₂₃ each represent a hydrogen atom or a lower alkyl group.
[0100] 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 monoamide, 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.
[0101] Coupler residues having a 5-oxo-2-pyrazoline ring, a pyrazolo[1,5-a]benzimidazole
ring or a cyanoacetophenone-type coupler residue are preferred as the magenta image-forming
coupler residue represented by J.
[0102] Couplers having a phenol ring or an α-naphthol ring are preferred as the cyan image-forming
coupler residue represented by J.
[0103] 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.
[0104] In general formula (I), J preferably represents general formulae (XIV), (XV), (XVI),
(XVII), (XVIII), (XIX), (XX), (XXI) and (XXII).

[0105] 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 group, an aliphatic hydrocarbon group or a heterocyclic group.
[0106] The aliphatic hydrocarbon group represented by R₅ has 1 to 22 carbon atoms and is
substituted or unsubstituted and linear or cyclic. Preferred substituents 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 R₅, R₆ and R₇ are isopropyl, isobutyl, tert-butyl, isoamyl,
tert-amyl, 1,1-dimethylbutyl, 1,1-dimethylhexyl, 1,1-diethylhexyl, dodecyl, hexadecyl,
octadecyl, cyclohexyl, 2-methoxyisopropyl, 2-phenoxyisopropyl, 2-p-tert-butylphenoxyisopropyl,
α-aminoisopropyl, α-(diethylamino)isopropyl, α-(succinimido) isopropyl, α-(phthalimido)isopropyl,
and α-(benzenesulfonamido)isopropyl groups.
[0107] When R₅, 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.
[0108] 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.
[0109] Furthermore, R₅, R₆ and R₇ may represent a substituent resulting from fusion of the
phenyl group with another ring, such as a naphthyl, quinolyl, isoquinolyl, chromanyl,
coumaranyl or tetrahydronaphthyl group. These substituents may further be substituted
with a substituent disclosed above as examples of substituents for the phenyl group.
[0110] When R₅ represents an alkoxy group, its alkyl moiety represents a C₁ to C₄₀, preferably
C₁ to C₂₂, linear or branched 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.
[0111] When R₅, 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 α-acylacetamido via one of the carbon atoms forming the ring.
Examples of such heterocyclic rings are thiophene, furane, 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 hydrocarbon group.
[0112] In general formula (XVII), R₉ 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 β-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, alkylthiocarbonyl, arylthiocarbonyl,
alkoxycarbonyl, aryloxycarbonyl, sulfo, sulfamoyl, carbamoyl, acylamino, diacylamino,
ureido, urethane, thiourethane, sulfonamido, heterocyclic, arylsulfonyl, alkylsulfonyl,
arylthio, alkylthio alkylamino, dialkylamino, anilino, N-arylanilino, N-alkylanilino,
N-acylanilino, hydroxyl or mercapto group.
[0113] Furthermore, R₉ may represent an aryl group such as a phenyl or α- or β-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, aryloxycarbonyl, sulfo, sulfamoyl,
carbamoyl, acylamino, di acylamino, ureido, urethane, sulfonamido, heterocyclic,
arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, dialkylamino, anilino,
N-alkylanilino, N-arylanilino, N-acylanilino, hydroxyl and mercapto groups. More
preferred as R₉ 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.
[0114] R₉ 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
alkylthiocarbamoyl group or an arylthiocarbamoyl group.
[0115] In the formulae, R₈ represents a hydrogen atom, a C₁ to C₄₀, preferably C₁ 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 R₉), an aryl or
heterocyclic group (which may have the substituents listed above with regard to R₉),
an alkoxycarbonyl group (such as a methoxycarbonyl, ethoxycarbonyl or stearyloxycarbonyl
group), an aryloxycarbonyl group (such as a phenoxycarbonyl or naphthoxycarbonyl
group), an aralkyloxycarbonyl 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 α-naphthyl group), a carboxyl group,
an acylamino group (such as an acetylamino or 3-[(2,4-di-tert-amylphenoxy)acetamido]benzamido
group), a diacylamino group, an N-alkylacylamino group (such as an N-methylpropionamido
group), an N-arylacylamino 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, diphenylamino,
N-acetylanilino or 2-chloro-5-tetradecaneanilino group), a dialkylamino 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- 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, dimethylcarbamoyl,
N-methylphenylcarbamoyl or N-phenylcarbamoyl group), a sulfamoyl group (such as an
N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N-alkyl-N-arylsulfamoyl
or N,N-diarylsulfamoyl group), a cyano group, a hydroxyl group, a mercapto group,
a halogen atom, or a sulfo group.
[0116] In the formulae, R₁₀ represents a hydrogen atom, or a C₁ to C₃₂, preferably C₁ to
C₂₂, linear or branched alkyl or alkenyl, cycloalkyl, aralkyl or cycloalkenyl group
which may have the substituents listed above with regard to R₉.
[0117] R₁₀ may also represent an aryl or heterocyclic group which may have the substituents
listed above with regard to R₉.
[0118] Furthermore, R₁₀ 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 amino, dialkylamino, anilino, N-arylanilino, N-alkylanilino, N-acylanilino,
hydroxyl or mercapto group.
[0119] Each of R₁₁, R₁₂ and R₁₃ represents groups which are used in ordinary 4-equivalent
phenol or α-naphthol couplers. Specifically, R₁₁ 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 R₁₁ groups exist in the same molecule,
they may be different, and the aliphatic hydrocarbon group may be substituted. R₁₂
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.
m is an integer of 0 to 4;
n is an integer of 0 to 3; and
p is an integer of 0 to 5. The aliphatic hydrocarbon groups may be saturated or unsaturated,
and linear, branched or cyclic. Preferably, 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, 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.
[0120] The substituents R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, 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.
[0123] 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.
[0124] 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 benzoate (e.g., octyl benzoate), an alkylamide (e.g., diethyllaurylamide),
a fatty acid ester (e.g., dibutoxyethyl succinate or dioctyl azelate), a trimesate
(e.g., tributyl trimesate), or an organic solvent having a boiling point of about
30 to 150°C such as a lower alkyl acetate (e.g., ethyl or butyl acetate), ethyl propionate,
sec-butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate or methyl cellosolve
acetate; and then dispersed in a hydrophilic colloid. A mixture of the above-described
high-boiling solvent 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-51-59943.
[0125] 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.
[0126] 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 3,936,303, 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.
[0127] In the photographic emulsion layers of photographic 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 10 mol%, especially preferably
not more than 8 mol%, on an average of silver iodide.
[0128] The silver 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.
[0129] 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 10 microns. They
may be monodisperse emulsions having a narrow distribution, or polydisperse emulsions
having a broad distribution.
[0130] 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. 17643 (December 1978), pages 22-23, "I. Emulsion Preparation and Types",
and
ibid. No. 18716 (November 1979), page 648.
[0131] The photographic emulsions used in this invention can be prepared by using the methods
described in P. Glafkides,
Chimie et Physique Photographique, Paul Montel, 1967, G.F. Duffin,
Photographic Emulsion Chemistry (Focal Press, 1966), and V.L. Zelikman et al.,
Making and Coating Photographic 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.
[0132] Two or more silver halide emulsions separately formed may be used as a mixture.
[0133] The silver halide emulsion composed of regular grains may be obtained by controlling
pAg and pH during grain formation. Details of this method are described, for example,
in
Photographic Science and Engineering, vol. 6, page 159 to 165 (1962),
Journal of Photographic Science, vol. 12, pages 242 to 251 (1964), U.S. Patent 3,655,394, and British Patent 1,413,748.
[0134] 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 average 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 microns, 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 British 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.
[0135] 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,
Photographic Science and Engineering, vol. 14, pages 248 to 257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and
4,439,520, 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.
[0136] Emulsion grains having a uniform crystal struture but different halogen compositions
between the interior and the exterior may also 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
Patent 2,038,792, U.S. Patents 4,349,622, 4,395,478, 4,433,501, 4,463,087, 3,656,962
and 3,852,067, and JP-A-58-162540.
[0137] A mixture of grains having various crystal shapes may be used.
[0138] The emulsions to be used in this invention usually undergo physical ripening, chemical
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.
[0139] 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. 638, 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 stabilizer |
pp. 24-25 |
p. 649, right column |
6. light absorber, filter dye, and ultraviolet absorber |
pp. 25-26 |
p. 649, right column to p. 650, left column |
7. stain preventing agent |
p. 25, right column |
p. 650, left to right column |
8. dye image stabilizer |
p. 25 |
|
9. hardener |
p. 26 |
p. 651, left column |
10. binder |
p. 26 |
ditto |
11. plasticizer and lubricant |
p.27 |
p. 650, right column |
12. coating aid and surface active agent |
pp. 26-27 |
ditto |
13. antistatic agent |
p. 27 |
ditto |
[0140] Various color couplers can be used in this invention. Specific examples are described
in the patents described in the above-cited
Research Disclosure, 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.
[0141] Typical examples of the yellow coupler that can be used in this invention are hydrophobic
acylacetamide- 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. α-Pivaloyl acetanilide-type couplers give dyes having excellent fastness
characteristics, particularly light fastness. α-Benzoyl acetanilide type couplers
can give a high color density.
[0142] 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. 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 described 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.
[0143] 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 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 2,369,929, 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 Patent 121,365, and the phenolic couplers having a phenylureido group
at the 2-position 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.
[0144] In order to correct unwanted absorptions of the formed dye, it is preferred to mask
the coupler in the color light-sensitive material for photographing by using a colored
coupler in combination. The yellow-colored magenta couplers described in U.S. Patent
4,163,670 and JP-B-57-39413 and the magenta-colored cyan couplers described in U.S.
Patents 4,004,929 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 forming 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 unexposed 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 specific bath 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.
[0145] Granularity may be improved by using a coupler which gives 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).
[0146] The dye-forming couplers and the special couplers described above may form dimers
or higher polymers. Typical 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 photographically useful residues during coupling 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.
[0147] Examples of preferred couplers used in combination with this invention are the developer
solution deactivating type couplers typically described in JP-A- 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-60-233650, and the
reactive-type DIR couplers described in JP-A-60-184248.
[0148] 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
halide are especially preferred, and specific examples thereof are described, for
example, in JP-A-59-157638 and JP-A-59-170840.
[0149] 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/G
f/R
f/G
s/R
s// support: wherein f means fast speed and s means slow speed).
[0150] 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.
[0151] Supports which can be suitably used in this invention are described, for example,
in the above-cited RD No. 17643, page 28, and
ibid. No. 18716, page 647, right column to page 648, left column.
[0152] 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.
[0153] The color photographic material of this invention is subjected to an ordinary rinsing
treatment or stabilizing treatment after development, bleach-fixing or fixing.
[0154] 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., borates, metaborates, borax, phosphates, carbonates,
potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic
acids and polycarboxylic acids used in combination), and formalin. As required, hard
water softening agents (e.g., inorganic phosphoric acid, aminopolycarboxylic acids,
organic phosphoric acid, aminopolyphosphonic acid and phosphonocarboxylic acid), fungicides
(e.g., benzointhiazolinone, isothiazolone, 4-thiazolinebenzimidazole and a halogenated
phenol), surface active agents, fluorescent bleaching agents, and hardeners may also
be used. Two or more of such additives having the same or different purposes may be
used in combination.
[0155] 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 pH adjusting agent after processing.
[0156] 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.
[0157] 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 green-sensitive
layers.
EXAMPLE
[0158] A multilayer color photographic material composed of layers of the following compositions
on an undercoated cellulose triacetate film support was prepared as Sample 101.
Composition of the photographic layers
[0159] 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

[0161] 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.
[0162] 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)
[0163] Sample 102 was prepared by making the following changes to Sample 101.
[0164] 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.
[0165] The iodine content of the silver iodobromide emulsion in the seventh layer was changed
from 4 mol% to 2 mol%.
[0166] 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.
Preparation of a Sample 103 (comparison)
[0167] Sample 103 was prepared by making the following changes to Sample 101.
[0168] 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.
[0169] The amounts of cyan couplers ExC-1 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-11 was increased from 0.89 to 0.93.
Preparation of a Sample 104 (comparison)
[0170] Sample 104 was prepared by making the following changes to Sample 101.
[0171] The amounts of cyan couplers ExC-1 and ExC-4 in the twelfth layer were increased
from 0.06 to 0.12 and from 0.03 to 0.06, respectively.
[0172] The amount of yellow coupler ExY-11 was increased from 0.89 to 0.93.
Preparation of a Sample 105 (comparison)
[0173] Sample 105 was prepared by making the following changes to Sample 101.
[0174] 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.
[0175] The amount of magenta coupler ExM-5 in the seventh layer was increased from 0.17
to 0.25.
[0176] The amount of DIR coupler ExM-10 in the tenth layer was decreased from 0.19 to 0.095.
[0177] The amount of yellow coupler ExY-11 in the twelfth layer was decreased from 0.89
to 0.80.
Preparation of a Sample 106 (comparison)
[0178] Sample 106 was prepared by making the following changes to Sample 101.
[0179] The amount of DIR coupler ExM-10 was decreased from 0.19 to 0.095.
[0180] The amount of yellow coupler ExYU-11 in the twelfth layer was decreased from 0.89
to 0.80.
[0181] 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)
[0182] Sample 107 was prepared by making the following changes to Sample 101.
[0183] 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.
[0184] The amount of silver iodobromide coated in the seventh layer was decreased from 0.27
to 0.22.
[0185] Yellow coupler ExY-11 in the twelfth layer was decreased from 0.89 to 0.85.
Preparation of a Sample 108 (comparison)
[0186] Sample 108 was prepared by making the following changes to Sample 101.
[0187] 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.
[0188] The amount of yellow coupler ExY-11 in the twelfth layer was decreased from 0.89
to 0.85.
Preparation of a Sample 109 (comparison)
[0189] Sample 109 was prepared by making the following changes to Sample 101.
[0190] The amount of the silver iodobromide emulsion coated in the seventh layer was decreased
from 0.27 to 0.22.
[0191] DIR coupler ExY-9 in the twelfth layer was excluded. Cyan couplers ExC-1 and ExC-4
were also excluded. The amount of yellow coupler ExY-11 was decreased from 0.89 to
0.62.
Preparation of a Sample 110 (comparison)
[0192] Sample 110 was prepared by making the following changes to Sample 101.
[0193] DIR coupler ExY-9 in the twelfth layer was excluded. Cyan couplers ExC-1 and ExC-4
were also excluded. The amount of yellow coupler ExY-11 was decreased from 0.89 to
0.62.
Preparation of a Sample 111 (comparison)
[0194] Sample 111 was prepared by making the following changes to Sample 101.
[0195] Colored coupler ExM-7 in the seventh layer was excluded.
[0196] 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 (comparison)
[0197] Sample 112 was prepared by making the following changes to Sample 101.
[0198] Colored coupler ExM-7 in the seventh layer was excluded.
Preparation of a Sample 113 (comparison)
[0199] Sample 113 was prepared by making the following changes to Sample 101.
[0200] Yellow coupler ExY-11 was added to the third layer in an amount of 0.10.
[0201] 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.
Preparation of a Sample 114 (invention)
[0202] Sample 114 was prepared by making the following changes to Sample 101.
[0203] Yellow coupler ExY-11 was added to the third layer in an amount of 0.10.
Preparation of a Sample 115 (invention)
[0204] Sample 115 was prepared by making the following changes to Sample 101.
[0205] 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.
[0206] Cyan couplers ExC-1 and ExC-4 were removed from the twelfth layer. The amount of
yellow coupler ExY-11 was decreased from 0.89 to 0.85.
Preparation of a Sample 116 (invention)
[0207] Sample 116 was prepared by making the following changes to Sample 101.
[0208] 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.
[0209] The amount of magenta coupler ExM-5 in the seventh layer was decreased from 0.17
to 0.01.
[0210] 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 decreased from 0.68
to 0.54 and from 0.19 to 0.15, respectively.
Preparation of a Sample 117 (invention)
[0211] Sample 117 was prepared by making the following changes to Sample 101.
[0212] 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.
[0213] 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 (invention)
[0214] Sample 118 was prepared by making the following changes to Sample 101.
[0215] The amount of the silver iodobromide emulsion coated in the seventh layer was increased
from 0.27 to 0.32.
[0216] 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-1
and ExC-4 were increased from 0.06 to 0.07 and from 0.03 to 0.04.
Preparation of a Sample 119 (invention)
[0217] Sample 119 was prepared by making the following changes to Sample 101.
[0218] The amount of magenta coupler ExM-5 in the seventh layer was increased from 0.17
to 0.25.
[0219] The amount of DIR coupler ExM-10 in the 10th layer was decreased from 0.19 to 0.095.
[0220] Cyan couplers ExC-1 and ExC-4 in the twelfth layer were excluded, and the amount
of yellow coupler ExY-11 was decreased from 0.89 to 0.80.
Preparation of a Sample 120 (invention)
[0221] Sample 120 was prepared by making the following changes to Sample 101.
[0222] 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.
[0223] 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-1
and ExC-4 were increased from 0.06 to 0.07 and from 0.03 to 0.04, respectively.
Preparation of a Sample 121 (invention)
[0224] Sample 121 was prepared by making the following changes to Sample 101.
[0225] 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.
[0226] DIR coupler ExY-9 in the twelfth layer was excluded. Cyan couplers ExC-1 and ExC-4
were also excluded. The amount of yellow coupler ExY-11 was decreased from 0.89 to
0.62.
Test
[0227] Samples 101 to 121 were processed into formats and skins and hairs of black, white
and yellow 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.
[0228] The results show that Samples 115 to 118 which satisfy the conditions of the invention,
γ

, γ

, γ

, γ
R, γ
G and γ
B, showed generally good color reproduction. Samples 119-121 which satisfy the preferred
conditions of the above-described γ

to γ
B 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.

Effects of the Invention
[0229]
(1) When γ

< 0.80, various defects occur. Specifically, the skin of the black is reproduced
in a darker color than the actual model. Reproduction of the root of fair hair is
excessively dark. The saturation of the skin of the white is low, and the face looks
that of a sick person. Yellow green is reproduced as yellow.
(2) When γ

< 0.80, various defects 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 γ

< 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 γR, γG >0.65 and γB> 0.75, the skin of the black is excessively dark, and the skin of the white is excessively
bright. Furthermore, the ability to depict the highlight and shadow portions of various
objects is inferior. Furthermore, if any of γR, γG and γB 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.
[0230] 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.
[0231] Foreign patents corresponding to Japanese Patent Publications cited in this application
are shown below.

[0232] 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.