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Description  |
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FIELD OF THE INVENTION
This invention relates to a silver halide photographic material. More
particularly, this invention relates to a silver halide photographic
material having a hydrophilic colloid layer containing a dye (a colored
layer) which can be rapidly processed and to a method for processing the
photographic material.
BACKGROUND OF THE INVENTION
Conventionally-used black-and-white photographic materials (for X-rays,
plate making and microcopies) are developed in a short period of time of
from one to five minutes by using automatic processors. However,
photographic processors wish to complete processing even faster to
accommodate the increase in photographs being taken. Also, photographic
materials like those used for X-rays must be processed as soon as possible
to provide important information in a timely manner. Under these
circumstances, the time taken for the development of photographic
materials is being decreased from a period of more than one minute to a
period of one minute or less.
In addition, medical photographic materials giving X-ray photographic
images of high quality are required for improving diagnostic accuracy.
Also, photographic materials for plate making are repeatedly subjected to
processing stages. However, when the photographic materials do not have
sufficient resolving power, the image fades every time the materials are
processed. For this reason, photographic materials giving images of high
quality are being demanded.
Further, photographic materials for plate making are often being exposed to
laser beams. They must provide images of high quality even under high
illumination. In microcopies, photographed images are not directly
observed; instead, enlarged photographs are observed, and images of high
quality are demanded.
Thus, it should be understood that rapid processing in a period of time of
not longer than 60 seconds and images of high quality being required.
Attempts have been made to provide photographic materials giving images of
good quality. For example, photographic emulsion layers or other layers
have been colored to absorb light having a specific wavelength. A colored
layer has been provided between a photographic emulsion layer and a
support or on the side opposed to the emulsion layer-side of the support
for the purpose of preventing image from being faded by the fact that
incident light is reflected during the passage thereof through the
photographic emulsion layers, or transmitted light is scattered and
reflected at the interface between the emulsion layer and the support or
on the surface of the side opposed to the emulsion layer-side of the
support, and reflected light enters again the photographic emulsions, that
is, for the purpose of antihalation. The colored layer is called
antihalation layer (AH layer). In the photographic materials for X-ray
photographs, a colored layer is sometimes provided as a crossover cut
layer for reducing crossover light to improve sharpness.
These colored layers often comprise hydrophilic colloid. Hence, dyes are
generally incorporated in these layers to color them. The dyes must meet
the following requirements.
(1) The dyes must have proper spectral absorption according to the purposes
of their use.
(2) The dyes must be chemically inactive in regard to the photographic
material. Namely, they can not chemically have an adverse effects on the
performance of photographic silver halide emulsion layers. For example,
they cannot cause a lowering of sensitivity, latent image fading or
fogging.
(3) The dyes must be either decolorized, or dissolved and removed during
the course of development to prevent harmful after-color from being left
on the photographic materials after processing.
Methods for providing dye-containing layers include a method wherein
soluble dyes are dissolved in hydrophilic colloid layers as disclosed in
U.K. Patents 1,414,456, 1,477,638 and 1,477,639. This method has the
disadvantage in that when the solubility of the dyes in water is increased
to solve the problem of after-color, the fixing degree of the dyes are
reduced, the dyes are diffused in layers adjacent to the dye-containing
layer and desensitization or the re-transfer of the dyes to other
photographic materials result. Methods wherein hydrophilic polymers having
an electric charge opposite to dissociated anionic dyes are allowed to
coexist as mordants in a layer to thereby localize the dyes in a specific
layer by the interaction between dye molecules and polymers, are described
in U.S. Pat. Nos. 2,548,564, 4,124,386 and 3,625,694. However, these
methods have the disadvantages in that when anionic substances and dyes
exist in the same layer, an undesirable effect on the manufacturing
process results so that the dyes are not satisfactorily localized and the
coating solutions cause agglomeration.
To solve these problems, a method has been proposed wherein dyes dispersed
in the form of solid particle are allowed to exist between the support and
the emulsion layer as disclosed in U.S. Pat. No. 4,803,150 and WO
88/04794. This method is an excellent technique for providing an image of
high quality without causing desensitization.
However, this method has problems in the production of the photographic
materials and the rapid processing in a period of time of not longer than
60 seconds. First, the problem of rapid processing will be discussed. When
an additional layer is provided as an AH layer, the total amount of
hydrophilic colloid is increased, because the AH layer generally comprises
hydrophilic colloid. When the amount of hydrophilic colloid increases, the
amount of water absorbed by the photographic material in the processing
stage increases and drying is adversely affected. This is a serious
problem for rapid processing in a period of time of not longer than 60
seconds. Also, the amount of hypo (sodium thiosulfate) left in the
photographic materials for X-ray photographs and microcopies after
development must be small, because the photographic materials are stored
over a long period of time. When the amount of hydrophilic colloid is
large, the amount of hypo absorbed in fixing solutions increases, and the
rinsing time must be prolonged to wash the hypo off. This is a serious
problem for rapid processing. In regard to the problem in the production
of the photographic materials, the extra layer complicates the production
process and tends to cause surface troubles.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a silver halide
photographic material which experiences less after-color, gives an image
of high quality (particularly sharpness) and has improved
rapid-processability (e.g., dryness, pressure resistance).
Another object of the present invention is to provide a method for
processing the photographic material.
The above objects of the present invention have been achieved by providing:
a silver halide photographic material comprising a hydrophilic colloid
layer containing a dye dispersed in a solid particle form (which may
include microcrystalline) therein on at least one side of a support and at
least one silver halide emulsion layer, wherein the coating weight of the
hydrophilic colloid in the hydrophilic colloid layer containing a dye
dispersed in a solid particle form is from 0.05 to 0.5 g/m.sup.2 and the
total coating weight of hydrophilic colloid on each side of the support is
from 0.5 to 3 g/m.sup.2 ; and a method for rapidly processing the
photographic material in a time period of at most 60 seconds.
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, it is particularly preferred to incorporate a dye
in the hydrophilic colloid of an undercoat layer (a subbing layer) so that
an extra hydrophilic colloid layer is not needed to contain the dye, that
is, the hydrophilic colloid layer containing a dye (which is referred as
"colored layer" sometimes) is preferably an undercoat layer.
The term "undercoat layer" or "subbing layer" as used herein refers to a
layer which plays a role in imparting adhesion between the support and a
hydrophilic layer such as an emulsion layer. Undercoat layer may comprise
a first undercoat layer which contains polymers on a surface of a support
and a second undercoat layer which contains hydrophilic colloid on the
first undercoat layer, or comprise a hydrophilic colloid layer on a
surface of a support.
First, the method providing undercoat layer which comprises the first
undercoat layer and the second undercoat layer will be discussed below.
When a base coated with only a polymer is coated with hydrophilic colloid
such as an emulsion at a temperature not higher than 80.degree. C.,
adhesion between the polymer and the emulsion is poor and hence there is
the problem that the layer peels off. To solve this problem, hydrophilic
colloid for the second undercoat layer is generally coated on the of the
polymer coat (first undercoat layer) at a temperature not lower than
80.degree. C. Accordingly, the hydrophilic layer (second undercoat layer)
is considered to be an undercoat layer according to the definition of the
present invention. In a preferred embodiment of the present invention, the
dye is incorporated in this hydrophilic layer (second undercoat layer).
The thickness of the first undercoat layer is preferably not more than 0.5
.mu.m, more preferably from 0.05 to 0.4 .mu.m and the thickness of the
second undercoat layer is preferably not more than 0.5 .mu.m, more
preferably from 0.05 to 0.4 .mu.m.
Generally, the undercoat polymer layer (first undercoat layer) is
hydrophobic and does not allow water to permeate easily therethrough.
Accordingly, when the dye is incorporated in the undercoat polymer layer,
after-color is formed which cannot be discharged. Hence, it is desirable
that the dye is substantially not incorporated in the undercoat polymer
layer in the present invention.
Second, the method providing a undercoat layer which comprises a
hydrophilic colloid layer will be discussed below.
In an embodiment of the present invention, the dye is incorporated in the
hydrophilic colloid for the undercoat layer. The thickness of the
undercoat layer is preferably not more than 1.0 .mu.m, more preferably
from 0.1 to 0.8 .mu.m. Hydrophilic colloid, a polyethylene swelling agent
and organic solvents are used during coating for the undercoat layer.
Therefore, dyes which are deteriorated by the organic solvents cannot be
used, thus limiting the dyes which can be used to certain compounds.
Accordingly, undercoat layer which comprises a first undercoat layer which
contains polymers on a surface of a support and a second undercoat layer
which contains hydrophilic colloid on the first undercoat layer are
preferable in the present invention. The dye is preferably incorporated in
the second undercoat layer in the present invention.
Methods for coating the undercoat layer include a multi-layer coating
method wherein a layer having good adhesion to a support is provided as a
first layer and a hydrophilic layer provided as a second layer is coated
thereon as described in JP-A-52-49019 (the term "JP-A" as used herein
means an "unexamined published Japanese patent application"),
JP-A-52-42114 and JP-A-52-104913 and a method wherein only one layer of a
polymer layer having both a hydrophobic group and a hydrophilic group is
coated as described in JP-B-47-24270 (the term "JP-B" as used herein means
an "examined Japanese patent application") and JP-A-51-30274. The effect
of the present invention can be obtained by any of the above methods, but
the multi layer coating method is preferable.
A conventionally-used support, such as a flexible support (e.g., plastic
film, paper, cloth) or a rigid support (e.g., glass, ceramic, metal) may
be used in the present invention. Examples of useful flexible supports
include films of semisynthetic or synthetic high-molecular weight
materials such as cellulose nitrate, cellulose acetate, cellulose acetate
butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and
polycarbonate; and paper such as baryta paper and paper coated or
laminated with an .alpha.-olefin polymer (e.g., paper coated or laminated
with polyethylene, polypropylene or an ethylene/butene copolymer). These
supports may be colored by using dyes or pigments, or they may be colored
black to shield light. In any of the above-described methods, in regard to
the resulting effect, it is preferred that the surfaces of supports are
treated before the undercoat layer is coated. Examples of surface
treatments include chemical treatment, mechanical treatment, corona
discharge treatment, flame treatment, ultraviolet light treatment,
high-frequency treatment, glow discharge treatment, active plasma
treatment, laser treatment, mixed acid treatment and ozone oxidizing
treatment.
A hydrophilic layer may be provided between the polymer layer and the
colored layer. Alternatively, a hydrophilic layer may be provided between
the colored layer and the emulsion layer.
Preferably, the undercoat polymer layer (first undercoat layer) and the
hydrophilic colloid layer (second undercoat layer) adjacent thereto are
dried at a temperature of preferably from 80.degree. to 200.degree. C.,
more preferably from 80.degree. to 155.degree. C., for preferably 2
seconds to 5 minutes, more preferably 2 seconds to 60 seconds after
coating. When both layers are dried at a temperature lower than 80.degree.
C., a serious problem results in which that photographic layers (e.g.,
silver halide emulsion layers) become detached from the support and peel
off in automatic processors.
Examples of undercoat polymers which can be used for the first undercoat
layer include halogenated synthetic resins such as polyvinyl chloride,
polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, polyvinyl
acetate, chlorinated polyethylene, chlorinated polypropylene, brominated
polyethylene, chlorinated rubber, vinyl chloride-ethylene copolymer, vinyl
chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl
chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride
copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl
chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene
copolymer, vinyl chloride isoprene copolymer, vinyl chloride-chlorinated
propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate
terpolymer, vinyl chloride-acrylic ester copolymer, vinyl chloride-maleic
ester copolymer, vinyl chloride-methacrylic ester copolymer, vinyl
chloride-acrylonitrile copolymer, internally plasticized polyvinyl
chloride, vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride,
vinylidene chloride-methacrylic ester copolymer, vinylidene
chloride-acrylonitrile copolymer, vinylidene chloride-acrylic ester
copolymer, chloroethyl vinyl ether-acrylic ester copolymer and
polyvinylidene fluoride; polyolefins such as polyethylene, polypropylene
and poly-3-methylpentene; .alpha.-olefin copolymers such as
ethylene-propylene copolymer, ethylene-propylene-1,4-hexadiene copolymer,
ethylene-vinyl acetate copolymer, copolybutene-1-propylene and
butadieneacrylonitrile copolymer and blends of these copolymers with the
halogenated resins; acrylic resins such as acrylic ester-acrylonitrile
copolymer, acrylic ester-styrene copolymer, methacrylic
ester-acrylonitrile copolymer, methacrylic ester-styrene copolymer,
polyalkyl acrylate, acrylic acid-butyl acrylate copolymer, acrylic
ester-butadiene-styrene copolymer, methacrylic ester-butadiene-styrene
copolymer, methyl methacrylate/ethyl acrylate/2-hydroxyethyl
acrylate/methacrylic acid (67/23/7/3 ratio by weight) copolymer, methyl
methacrylate/ethyl acrylate/2-hydroxyethyl acrylate/methacrylic acid
(72/17/7/3 ratio by weight) copolymer, methyl methacrylate/ethyl
acrylate/2-hydroxyethyl acrylate/methacrylic acid (70/20/7/3 ratio by
weight) copolymer and methyl methacrylate/butyl acrylate/2-hydroxyethyl
acrylate/methacrylic acid (70/20/7/3 ratio by weight) copolymer;
polystyrene and copolymers of styrene with other monomers (e.g., maleic
anhydride, butadiene and acrylonitrile) such as
acrylonitrile-butadiene-styrene copolymer; polyacetal resin; polyvinyl
alcohol; blends of these resins, block copolymers and graft copolymers of
these resins; polyamide resin; polyvinyl butyral; cellulose derivatives;
polyester resins; vinyl polymers such as polyvinyl alcohol; condensed
high-molecular compounds such as polycarbonates and polyethers; rubber
such as natural rubber, butyl rubber, neoprene rubber and
styrene-butadiene copolymer rubber; natural or artificial rubber, silicone
rubber, and polyurethane; polyamide, urethane elastomer, nylon-silicone
resin, and nitrocellulose-polyamide resin; and blends of the above-listed
acrylic, methacrylic, polyolefin, polyamide, polyester, polyurethane,
polycarbonate, rubber, cellulose resin and aqueous polyester resins and
their block copolymers and graft copolymers.
Among these polymers, styrene-butadiene copolymers and vinylidene chloride
copolymers are particularly preferred.
In light-sensitive materials for printing, it is preferable to use
hydrophobic polymers as an undercoat to prevent the dimensional stability
of the support from being deteriorated by the water absorption of the
support. Vinylidene chloride polymers are preferred.
In the present invention, it is most preferable to use these polymers in
the form of latexes.
Preferably, dyes which absorb light in the sensitive region of the
photographic material are used when the colored layer is introduced into
the material to improve the quality of the image. The term "colored layer"
as used herein means a hydrophilic colloid layer containing a dye.
In the present invention, the colored layer is preferably an undercoat
layer.
The colored layer may be provided on one side or both sides of the support
in the present invention.
Dyes which can be used in the present invention can be easily synthesized
according to the methods described in WO 88/04794, European Patents
EP0274723Al, 276,566 and 299,435, JP-A-62-92716, JP-A-55-155350,
JP-A-55-155351, JP-A-61-205934, JP-A-48-68623, and U.S. Pat. Nos.
2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429 and 4,040,841.
Dyes described in WO 88/04794 (Tables I to X), dyes represented by the
following formulas (I) to (VI) and other dyes can be used in the present
invention.
##STR1##
In the above formulas, A and A' may be the same or different groups and
each represents an acid nucleus; B represents a basic nucleus; X and Y may
be the same or different groups and each represents an electron attractive
group; R represents a hydrogen atom or an alkyl group; R.sub.1 and R.sub.2
each represent an alkyl group, an aryl group, an acyl group or a sulfonyl
group, or R.sub.1 and R.sub.2 may be combined together to form a
5-membered or 6-membered ring; R.sub.3 and R.sub.6 each represent a
hydrogen atom, hydroxyl group, carboxyl group, an alkyl group, an alkoxy
group or a halogen atom; R.sub.4 and R.sub.5 each represent a hydrogen
atom or a non-metallic atomic group required for the formation of a
5-membered or 6-membered ring when R.sub.1 and R.sub.4 or R.sub.2 and
R.sub.5 are combined together; L.sub.1, L.sub.2 and L.sub.3 each represent
a methine group; m represents 0 or 1; n and q each represent 0, 1 or 2; p
represents 0 or 1 with the proviso that when p is 0, R.sub.3 is a hydroxyl
group or a carboxyl group and R.sub.4 and R.sub.5 are each hydrogen atom;
and B' represents a heterocyclic ring containing carboxyl group, a
sulfamoyl group or a sulfonamido group.
Each of the compounds represented by formulas (I) to (VI) has at least one
dissociation group exhibiting a pK of 4 to 11 in a mixed solution of water
and ethanol (1:1 by volume) per molecule.
Compounds represented by formulas (I) to (VI) will be described in more
detail below.
Preferred examples of the acid nucleus represented by A or A' include
2-pyrazoline-5-one, rhodanine, hydantoin, thiohydantoin,
2,4-oxazolidinedione, isooxazolidinone, barbituric acid, thiobarbituric
acid, indandione, pyrazolopyridine and hydroxypyridone.
Preferred examples of the basic nucleus represented by B include pyridine,
quinoline, indolenine, oxazole, benzoxazole, naphthoxazole and pyrrole.
Examples of the heterocyclinc ring represented by B' include pyrrole,
indole, thiophene, furan, imidazole, pyrazole, indolizine, quinoline,
carbazole, phenothiazine, indoline, thiazole, pyridine, pyridazine,
thiadiazine, pyran, thiopyrane, oxadiazole, benzoquinolizine, thiadiazole,
pyrrolo-thiazole, pyrrolo-pyridazine and tetrazole.
Any of groups having a dissociation proton which have a pKa (acid
dissociation constant) of 4 to 11 in a mixed solution of water and ethanol
(1:1 by volume) can be used without particular limitations with regard to
types and positions at which the groups are attached to the dye molecules,
so long as the dye molecules are substantially water-insoluble at a pH of
6 or lower and are substantially water-soluble at a pH of 8 or higher by
the presence of the groups. Preferred examples of the dissociation groups
include a carboxyl group, a sulfamoyl group, a sulfonamido group and a
hydroxyl group, with a carboxyl group being more preferred. The
dissociation group may be bonded directly to the dye molecule, or may be
attached to the dye molecule through a bivalent bonding group (e.g.,
alkylene, phenylene). Examples of the dissociation groups bonded through a
bivalent bonding group include 4-carboxyphenyl, 2-methyl-3-carboxyphenyl,
2,4-dicarboxyphenyl, 3,5-di-carboxyphenyl, 3-carboxyphenyl,
2,5-dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl,
2-carboxyphenyl, 2,4,6-trihydroxyphenyl, 3-benzenesulfonamidophenyl,
4-(p-diaminobenzenesulfonamido)phenyl, 3-hydroxyphenyl, 2-hydroxyphenyl,
4-hydroxyphenyl, 2-hydroxy-4-carboxyphenyl, 3-methoxy-4-carboxyphenyl,
2-methyl-4-phenylsulfamoylphenyl, 4-carboxybenzyl, 2-carboxybenzyl,
3-sulfamoylphenyl, 4-sulfamoylphenyl, 2,5-disulfamoylphenyl,
carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl and
8-carboxyoctyl.
Preferred examples of the alkyl group represented by R, R.sub.3 or R.sub.6
are those having from 1 to 10 carbon atoms such as methyl, ethyl,
n-propyl, isoamyl and n-octyl.
Preferably, the alkyl group represented by R.sub.1 and R.sub.4 has from 1
to 20 carbon atoms. Examples of the alkyl group include methyl, ethyl,
n-propyl, n-butyl, n-octyl, n-octadecyl, isobutyl and isopropyl. The alkyl
group may have one or more substituent groups (e.g., a halogen atom (e.g.,
chlorine, bromine), a nitro group, a cyano group, a hydroxy group, a
carboxyl group, an alkoxy group (e.g., methoxy, ethoxy), an alkoxycarbonyl
group (e.g., methoxycarbonyl, i-propoxycarbonyl), an aryloxy group .(e.g.,
phenoxy), a phenyl group, an amido group (e.g., acetylamino,
methanesulfonamido), a carbamoyl group (e.g., methylcarbamoyl,
ethylcarbamoyl) and a sulfamoyl group (e.g., methylsulfamoyl,
phenylsulfamoyl)).
Preferred examples of the aryl group represented by R.sub.1 or R.sub.2
include a phenyl group and a naphthyl group. The aryl group may have one
or more substituent groups. Examples of the substituent groups include
those already described above in the definition of the substituent groups
for R.sub.1 and R.sub.2 and an alkyl group (e.g., methyl, ethyl).
Preferably, the acyl group represented by R.sub.1 or R.sub.2 has from 2 to
10 carbon atoms. Examples of the acyl group include acetyl, propionyl,
n-octanoyl, n-decanoyl, isobutanoyl and benzoyl. Examples of the
alkylsulfonyl or arylsulfonyl group represented by R.sub.1 or R.sub.2
include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl,
n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl and
o-carboxybenzenesulfonyl.
Preferably, the alkoxy group represented by R.sub.3 or R.sub.6 has from 1
to 10 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy,
n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy and isopropoxy. Examples of
the halogen atom represented by R.sub.3 or R.sub.6 include chlorine,
bromine and fluorine.
An example of the ring formed by R.sub.1 and R.sub.4 or R.sub.2 and R.sub.5
when combined together is a durolysine ring.
Examples of 5-membered or 6-membered rings formed by R.sub.1 and R.sub.2
when combined together include a piperidine ring, a morpholine ring and a
pyrrolidine ring.
The methine group represented by L.sub.1, L.sub.2 or L.sub.3 may be
substituted. Examples of substituent groups include methyl, ethyl, cyano,
phenyl, chlorine and hydroxypropyl.
X and Y may be the same or different groups and each is an electron
attracting group. Examples of the group include a cyano group, a carboxy
group, an alkylcarbonyl group which may be substituted (e.g., acetyl,
propionyl, heptanoyl, dodecanoyl, hexadecanoyl, 1-oxo-7-chloroheptyl), an
arylcarbonyl group which may be substituted (e.g., benzoyl,
4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl), an alkoxycarbonyl group which
may be substituted (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl,
t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl,
octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl,
hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl,
2-methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl,
2-(2-chloroethoxy)ethoxycarbonyl,
2-(2-(2-chloroethoxy)ethoxy)ethoxycarbonyl), an aryloxycarbonyl group
which may be substituted (e.g., phenoxycarbonyl, 3-ethylphenoxycarbonyl,
4-ethylphenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl,
4-methoxyphenoxycarbonyl, 2,4-di-(t-amyl)phenoxycarbonyl), a carbamoyl
group which may be substituted (e.g., carbamoyl, ethylcarbamoyl,
dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl,
2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl,
4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl,
4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl,
4-hexyloxyphenylcarbamoyl, 2,4-di(t-amyl)phenylcarbamoyl,
2-chloro-3-(dodecyloxycarbamoyl)phenylcarbamoyl,
3-(hexyloxycarbonyl)phenylcarbamoyl), a sulfonyl group which may be
substituted (e.g., methylsulfonyl, phenylsulfonyl) and a sulfamoyl group
which may be substituted (e.g., sulfamoyl, methylsulfamoyl).
Examples of the dyes which can be used in the present invention include the
following compounds, although the present invention should not be
construed as being limited thereto.
##STR2##
As indicated above, dyes which can be used in the present invention are not
limited to the above compounds. Other compounds can be used, if desired.
Dyes represented by the formula (I), (III), or (IV) are preferably used in
the present invention.
The dye may be preferably used to be dispersed in a solid particle form in
a hydrophilic colloid for a colored layer.
The term "solid particle dispersion" or "dispersed in a solid particle
form" as used herein means that the solubility of dye itself is low so
that the dye cannot exist in a molecular state in hydrophilic colloid for
the colored layer, instead, it exists as a solid particle having such a
size that it cannot substantially diffuse in the layer.
The solid particle dispersion of the dye can be prepared by the methods
described in WO 88/04794, European Patent (EP) 0276566Al and
JP-A-63-197943. Preferred examples thereof include, but are not limited
to, a method wherein the dye is crushed in a ball mill and stabilized by a
surfactant and gelatin and a method wherein the dye is dissolved in an
alkaline solution and the pH of the solution is lowered to precipitate it
out. The method using a ball mill is preferable.
When the dye is incorporated in the colored layer as in the present
invention, the coating weight of hydrophilic colloid in the colored layer
is preferably from 0.05 to 0.5 g/m.sup.2. Accordingly, the particle size
which is incorporated in the colored layer is limited to a certain size.
When particles having a size not smaller than 3 .mu.m are contained in the
layer, problems results in which that dye particles come out of the
colored layer, etc. Accordingly, the particle size of the dye is generally
from 0.005 .mu.m to 3 .mu.m, preferably from 0.005 .mu.m to 1 .mu.m, more
preferably from 0.005 .mu.m to 0.5 .mu.m.
The large-size particles can be removed by filtration, centrifugation and
other conventional methods.
The dyes are used in an amount of prefrably from 5 to 400 mg/m.sup.2, more
preferably from 10 to 250 mg/m.sup.2.
Hydrophilic colloid for the preparation of the solution (coating
composition) for the colored layer may be used so that an amount ratio by
weight of a dye to a hydrophilic colloid is generally not more than 2,
preferably from 0.01 to 1.
The amount of hydrophilic colloid used in the colored layer is preferably
from 0.05 to 0.5 g/m.sup.2, more preferably from 0.05 to 0.4 g/m.sup.2.
When the total amount of hydrophilic colloid on one side of a support is
too large, the amount of water contained in the layers in developing
solutions increases, and dryness is deteriorated. Accordingly, such a
large amount of colloid is not preferred. The entire coating weight of
hydrophilic colloid on each side of a support is preferably from 0.5 to 3
g/m.sup.2, more preferably from 0.5 to 2.8 g/m.sup.2.
The pH of coating compositions comprising hydrophilic colloid for the
colored layer, overcoat layer, emulsion layer, surface protective layer,
etc. are adjusted to preferably from 5 to 7 by adding suitable amounts of
acidic solution (e.g., phosphoric acid, citric acid, and hydrochloric
acid, etc.), or alkali solution (e.g., sodium hydroxide, etc.).
A preferred example of a hydrophilic colloid for the colored layer and the
second undercoat layer is gelatin. A more preferred example is
acid-processed gelatin. However, any conventional hydrophilic colloid can
be used.
Preferred examples of silver halide emulsions which can be used in the
present invention include silver bromide, silver iodobromide, silver
iodochlorobromide, silver chlorobromide and silver chloride.
The pH of silver halide emulsion is adjusted to preferably from 5 to 7,
more preferably from 5.5 to 6.5 by adding suitable amounts of acidic
solution (e.g., phosphoric acid, citric acid, and hydrochloric acid,
etc.), or alkali solution (e.g., sodium hydroxide, etc.).
The silver halide grains of the present invention may have a regular
crystal form, such as a cube or octahedron, an irregular crystal form,
such as sphere or tube (plate form), or a composite form of these crystal
forms. A mixture of grains having various crystal forms can be used, but
grains having a regular crystal form are preferably used.
The silver halide grains of the present invention may have different phases
in the interiors of the grains and in the surface layers thereof, or may
be composed of a uniform phase. Grains where a latent image is mainly
formed on the surface thereof (e.g., negative type emulsion) as well as
grains where a latent image is mainly formed in the interior thereof
(e.g., internal latent image type emulsion, a previously fogged direct
reversal type emulsion) can be used. Grains where a latent image is mainly
formed on the surface thereof are preferred.
The silver halide emulsions of the present invention are preferably tubular
(plate form) grain emulsion wherein grains having a thickness of not
larger than 0.5 .mu.m, preferably not larger than 0.3 .mu.m, a diameter of
not smaller than 0.6 .mu.m and an aspect ratio of not lower than 5 account
for at least 50% of the entire projected area of grains, or a monodisperse
emulsion having a coefficient of variation in grain size distribution (a
value S/d obtained by dividing standard deviation S by diameter d
represented by the diameter when the projected area is considerd to be a
circle) of not more than 20%. Two or more tubular grain emulsions and
monodisperse emulsions may be mixed.
The photographic emulsions of the present invention can be prepared by the
methods described in P. Glafkides, Chimie et Physique Photographique, Paul
Montel (1967), G. F. Dufffin, Photographic Emulsion Chemistry, Focal Press
(1966) and V. L. Zelikman et al., Making and Coating Photographic
Emulsion, Focal Press (1964).
Solvents for silver halide may be used during the formation of silver
halide grains to control the growth of the grains. Examples of the
solvents include ammonia, potassium rhodanide, ammonium thiocyanate,
thioether compounds (described in U.S. Pat. Nos. 3,574,628, 3,704,130,
4,297,439 and 4,276,374), thione compounds (described in JP-A-53-144319,
JP-A-53-82408 and JP-A-55-77737) and amine compounds (described in
JP-A-54-100717).
Cadmium salts, zinc salts, thallium salts, iridium salts or | | |
