FIELD OF THE INVENTION
The present invention relates to a silver halide color
photographic light sensitive material (hereinafter referred to
also as a light sensitive material) and particularly to a
silver halide color photographic light sensitive material,
which can provide reduced aging deterioration of glossiness
and image sharpness, reduced aging coloration of white
background and an image with excellent fastness.
BACKGROUND OF THE INVENTION
As silver halide color photographic light sensitive
materials become more popular, high quality images have been
demanded. Under such circumstances, studies on improvement of
color reproduction, image storage stability and image
sharpness have been made in color print light sensitive
materials.
Irradiation or halation is generally known as a factor
influencing image sharpness. The former is caused by
scattering of incident light due to silver halide grains or
coupler oil drops dispersed in a gelatin layer. The degree of
the scattering depends mainly on the amount of the gelatin,
silver halide grains and oil drops. The degree of the latter
depends on the degree of light reflected from a support and on
reflectance or refractive index of the support.
Dyes have been improved for anti-irradiation. This is
disclosed in Japanese Patent O.P.I. Publication Nos. 50-145125/1975.
52-20830/1977, 50-111641/1975, 61-148448/1986,
61-151650/1986, 62-275562/1987 and 62-283336/1987.
A method of providing an anti-halation layer is known as
an anti-halation method. The improvement is disclosed in, for
example, Japanese Patent O.P.I. Publication Nos. 55-33172/1980.
59-193447/1984, 59-151650/1984 and 62-33448/1987.
These methods improve image sharpness but cause marked
lowering of sensitivity, and it is difficult to improve image
sharpness, while maintaining practically sufficient
sensitivity.
The improvement of a support has been studied. Recently,
a waterproofing support, in which a polyolefin is laminated on
a base paper, is used as a support of a color print light
sensitive material for rapid processing. White pigment such
as titanium oxide is dispersed in a polyolefin layer on the
silver halide emulsion layer side to secure image sharpness
and white background. As disclosed in Japanese Patent O.P.I.
Publication Nos. 54-46035/1979, 64-18144/1989 and 2-71256/1990,
the use of a support in which the polyolefin layer on the
silver halide emulsion side contains more white pigment is
effective but not satisfactory. The support further has
disadvantages in that smoothness of the polyethylene layer
deteriorates and adhesion between the polyethylene layer and
the emulsion layer also deteriorates.
The color print using the above described support
exhibits a problem in that discoloration of the white
background (after-yellowing) during long term storage occurs.
Improvement of the defect has been demanded.
The color reproduction method based on the so-called
subtractive color system, which employs a yellow, magenta and
cyan dye, is used in widespread color print. The degree that
a color image obtained from a light sensitive material for
color print reproduces an original image depends on
photographic properties of the light sensitive material. The
light sensitive material for color print giving excellent
color image reproduction has been studied from various points
of view. How wide a range of color can be reproduced in color
print depends on color tone of the above described dye used as
a primary color dye, and therefore, development of dyes having
an excellent light absorption property has been an important
problem to be solved in the art. The dye having a light
absorption profile which is broad or has undesirable side
absorption can not provide excellent color reproduction of the
original color image.
In a silver halide photographic light sensitive material
for color print, a compound having active methylene or another
active point in the molecule is usually used as so-called a
dye-forming coupler forming yellow, magenta and cyan dyes.
The example of the yellow dye-forming coupler includes
pivaloylacetoanilides, the example of the magenta dye-forming
coupler includes 5-pyrazolones, and the example of the cyan
dye-forming coupler includes phenols and naphthols.
Of these, phenols and naphthols used as a cyan dye-forming
coupler have undesirable side absorption in the region
of a blue or green light wavelength, and also have a problem
in that color reproduction markedly deteriorates and image
fastness is relatively poor under high temperature and high
humidity.
As a method for overcoming this problem is proposed a
cyan coupler having an alkyl group in a 5-position of the
phenols, a pyrazoloazole cyan coupler as disclosed in Japanese
Patent O.P.I. Publication Nos. 64-552/1989, 64-553/1989, 64-554/1989,
64-555/1989, 64-556/1989, 64-557/1989 and 1-144052/1989,
a pyrroloazole cyan coupler as disclosed in
Japanese Patent O.P.I. Publication Nos. 4-174429/1992, 4-230746/1992,
5-165172/1993, 5-204107/1993, 5-313324/1993 and
5-313325/1993 and a cyan coupler as disclosed in Japanese
Patent O.P.I. Publication Nos. 4-133055/1992 and 5-232648/1993.
A cyan dye image obtained from these couplers is excellent in
color reproduction, but is not satisfactory in image fastness
under high temperature and high humidity. Further, a color
print image obtained from a light sensitive material employing
these couplers shows aging deterioration of glossiness and
image sharpness, and the improvement is desired.
[PROBLEMS TO BE SOLVED BY THE INVENTION]
Accordingly, a first object of the invention is to
provide a silver halide color photographic light sensitive
material which can provide reduced aging deterioration of
glossiness.
A second object of the invention is to provide a silver
halide color photographic light sensitive material which can
provide reduced aging deterioration of image sharpness.
A third object of the invention is to provide a silver
halide color photographic light sensitive material which can
provide an image with excellent fastness.
A fourth object of the invention is to provide a silver
halide color photographic light sensitive material which can
provide reduced aging coloration of white background.
[MEANS FOR SOLVING THE PROBLEMS]
The above object of the invention could be attained by
the following constitution:
1. A silver halide color photographic material comprising
a paper support, and provided thereon, a light sensitive
silver halide emulsion layer and a non-light sensitive layer,
said support comprising a paper base and a resin layer coated
on each side of the paper base, the resin layer on the silver
halide emulsion layer side comprising two or more resin layers
containing white pigment and having a different white pigment
content, at least one of the resin layers being composed of a
polyolefin or polyester resin, and at least another one layers
being composed of a resin other than the polyolefin resin,
wherein the silver halide emulsion layer comprises a silver
halide emulsion having a silver chloride content of 95 to 99.9
mol% and contains at least one cyan coupler selected from a
compound represented by Formula [C-1] or, Formula [I], [II],
[III] or [IV]:
wherein R21 represents an alkyl group having 2 to 6 carbon
atoms; R22 represents a ballast group; and Z1 represents a
hydrogen atom or an atom or group capable of being released on
reaction with an oxidation product of a color developing agent,
wherein R1 represents a hydrogen atom or a substituent; R2 is
a substituent; m is the number of substituent R2, provided
when m is zero, R1 represents an electron attractive group
having a Hammett's substituent constant σp of not less than
0.20, while when m is 1, 2 or more, at least one of R1 and R2
represents an electron attractive group having a Hammett's
substituent constant σp of not less than 0.20; Z1 represents a
group of non-metallic atoms necessary to form a nitrogen-containing
5-membered heterocyclic ring which may be condensed
with a benzenering; R3 represents a hydrogen atom or a
substituent; Z2 represents a group of non-metallic atoms
necessary to form a nitrogen-containing 6-membered
heterocyclic ring together with -NH-, which may have a
substituent and may be condensed with a benzene ring; R4 and
R5 each represent an electron attractive group having a
Hammett's substituent constant σp of not less than 0.20,
provided the sum of σp values of R4 and R5 is not less than
0.65; Z3 represents a group of non-metallic atoms necessary to
form a nitrogen-containing 5-membered heterocyclic ring, which
may have a substituent; R6 and R7 each represent a hydrogen
atom or a substituent; Z4 represents a group of non-metallic
atoms necessary to form a nitrogen-containing 6-membered
heterocyclic ring, which may have a substituent; and X1, X2, X3
and X4 each represent a hydrogen atom or a group capable of
being released upon a coupling reaction with an oxidation
product of color developing agent.
Next, the invention will be explained in detail.
The support in the invention comprises a base paper, and
a resin layer provided on each side of the paper, and the
resin layer on a silver halide emulsion layer side
(hereinafter an obverse resin layer) comprising two or more
layers containing white pigment.
The base paper used in the invention is selected from a
conventional material generally used in a photographic print,
but paper is usually used. For example, the base paper
includes natural pulp, synthetic pulp, a mixture thereof and
material for various combination paper. Generally, natural
pulp containing mainly a coniferous tree pulp, a broadleaf
tree and a mixture thereof are widely used. Neutral paper,
acidic paper or various other papers can be used, but paper
for photographic use is preferably used and neutral paper for
photographic use is especially preferable. The thickness of
paper is preferably 40 to 250 µm.
The support described above may contain additives such as
a sizing agent, a fixing agent, a reinforcing agent, a filling
agent, an anti-static agent, a dye or an anti-foggant and
which are used in paper manufacture. A surface sizing agent,
a surface reinforcing agent and an antistatic agent may be
coated on the surface of the support.
In the support in the invention, a method providing a
resin layer (hereinafter referred to as a reverse resin layer)
on the side opposite the silver halide emulsion layer includes
lamination of a polyolefin or a polyester resin such as a
polyethylene terephthalate resin on the base paper.
The olefin resin used in the lamination can be selected
from polyethylene, poly-α-olefins and a mixture containing at
least the two. The polyolefin resin widely used is low
density polyethylene, high density polyethylene or a mixture
thereof.
Generally, the lamination of a resin is carried out by
extrusion coating a resin composition on a support. In order
to carry out this coating, the resin composition is melt-extruded
in a single layer or plural layers from a slit die of
an extrusion apparatus.
Usually, melt-extrusion temperature is preferably 200 to
350°C.
The thickness of the resin layer is not specifically
limited, but usually 15 to 60 µm.
The paper support used in the invention has two or more
surface resin layers containing white pigment in which at
least one resin layer is composed of a polyolefin or polyester
resin and at least another one resin layer is composed of a
resin, other than a polyolefin resin, preferably a electron
beam hardenable resin.
The resin layer composed of a polyolefin or polyester
resin is preferably a resin layer composed of a polyolefin
resin.
The polyolefin resin in the invention is selected from
polyethylene, poly-α-olefins and a mixture containing at least
the two. The widely used polyolefin resin is a low density
polyethylene, a high density polyethylene or a mixture thereof.
The polyester useful for the invention includes
polyethylene terephthalate and a modified polyester comprising
a polyethylene terephthalate unit as a main component
(hereinafter referred to as simply a modified polyester). The
modified polyester is composed of a polyethylene terephthalate
unit portion as a most part and a modified portion in the main
chain. The dicarboxylic acid capable of constituting the
ester part of the modified portion includes terephthalic acid,
isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene
dicarboxylic acid, 1,4-naphthalene dicarboxylic
acid, 2,7-naphthalene dicarboxylic acid, p-xylidene
dicarboxylic acid, 1,4-dicyclohexane dicarboxylic acid, adipic
acid, sebatic acid, 5-alkalimetalsulfo isophthalic acid or 4-alkalimetalsulfo-2,6-naphthalene
dicarboxylic acid.
The glycol (diol) capable of constituting the ester part
of the modified portion includes ethylene glycol, propylene
glycol, 1,4-butane diol, 1,4-hexylene diol, diethylene glycol,
triethylene glycol, tetraethylene glycol, polyethylene glycol
(number average molecular weight 300 to 30,000) and
polypropylene glycol (number average molecular weight 300 to
30,000).
The dibasic acid preferably includes terephthalic acid,
isophthalic acid, 4-metalsulfo-2,6-naphthalene dicarboxylic
acid, and 4-metalsulfo-isophthalic acid. The glycol
preferably includes ethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol
and polyethylene glycol (having a number
average molecular weight of 300 to 30,000).
The alkalimetal ion of the alkalimetalsulfo group
includes a sodium, potassium, lithium, and cesium ion, and
preferably a sodium ion.
The modified portion content of the modified polyester
useful for the invention is not more than 50 mol% based on the
total ester bond. When the modified portion exceeds 50 mol%,
for example, mechanical strength, glass transition temperature
and water proof is deteriorated, and therefore, it is
difficult to use it as a support. The content is preferably
not more than 40 mol%, and more preferably not more than 30
mol%.
The content of a compound having an alkalimetalsulfo
group in the modified portion of the modified polyester is
preferably 2 to 10 mol% based on the total ester bond, wherein
its adhesion to an emulsion layer, another resin layer or
paper is excellent. When the content of the compound having
an alkalimetalsulfo group, for example, 5-sodiumsulfo
isophthalic acid is not more than 2 mol%, the modified polymer
is not substantially different from polyethylene terephthalate
and is almost the same as an unmodified polyester. When the
content is not less than 10 mol%, the modified polymer
increases water absorption, and adhesion between the resin
layer and the paper support is decreased. As a result, there
occur problems as a photographic support that the separation
of the resin layer from the paper support occurs in a
photographic process or water proofing of the support
deteriorates. The content of the compound is preferably 2 to
7 mol%, and more preferably 3 to 6 mol%.
As the ester part of the modified portion, besides the
above sulfo compound, polyethylene glycol and/or an aliphatic
dicarboxylic acid, for example, adipic acid, are preferably
used.
The modified polyester useful for the invention can be
synthesized according to a conventional synthetic method of
polyesters. For example, esterification is carried out by
direct reaction of a dicarboxylic acid and a glycol or ester
exchange reaction of a diester and a glycol. Polyesters can
be synthesized by optionally using an ester exchange catalyst
in the ester exchange reaction or using a polymerization
catalyst such as antimony oxide in the polymerization. The
component constituting the polyester or the synthetic method
of the polyester can be referred to for example, Kobunshi
Jikken Kagaku, Vol. 5 (Kyoritsu Shuppan), "Polycondensation
and Addition polymerization" page 103-136 (1980) or "Gosei
Kobunshi" (Asakura Shoten), page 187-286 (1971).
The typical synthetic methods of the modified polyester
are disclosed in US Patent No. 4,217,441 and Japanese Patent
O.P.I. Publication No. 5-210119/1993, and the modified
polyester useful for the invention can be synthesized
according to these methods.
The molecular weight of the polyester (including a
modified polyester) useful for the invention needs to be
sufficiently high. Generally, the molecular weight of a
polymeric compound such as polyester is expressed in terms of
intrinsic viscosity (see, for example, Nihon Kagakukai
edition, "Hyoujun Kagakuyogo Jiten", p. 24, 1991, Maruzen).
The intrinsic viscosity of the polyester used in the invention
needs to be not less than 0.50, is preferably not less than
0.53, and more preferably not less than 0.55. When the
intrinsic viscosity is not more than the described above, the
resin whitens and be brittle after the melt-extrusion. The
melt-extrusion of the polyester containing moisture greatly
reduces the intrinsic viscosity, since hydrolysis occurs
during the extrusion. Even if the intrinsic viscosity is
sufficiently high, much attention must be paid to drying
before the extrusion of the polyester. The resin chips are
usually dried at about 150°C and at a pressure of 10-3 Torr.
The polyolefin or polyester resin layer is formed by
melt-extrusion coating the polyolefin or polyester resin on a
paper support. The resin composition is melted at a specific
temperature in a melt-extrusion machine, and melt-coated from
a die-slit on a moving paper support (a coating position is
supported by a roller provided on the side of the paper
opposite the coated side). The melt-coated resin layer may be
a single layer extruded from a single slit or plural layers
extruded from plural slits.
Usually, melt-extrusion temperature is preferably 200 to
350°C.
The resin other than the polyolefin resin in the
invention includes the polyester resin described above, a
polyether resin such as polyethylene glycol, polyoxymethylene
or polyoxypropylene, a urethane resin such as polyester
urethane or polyether urethane, a polycarbonate resin, a
polystyrene resin, an electron beam hardened resin, a
cellulose derivative such as cellulose nitrate or cellulose
triacetate, and they are used singly or in admixture. The
preferable resin is a polyethylene terephthalate resin, a
modified polyester resin or an electron beam hardenable resin,
and these resins may be used singly and in admixture with
another resin as described above.
Any electron beam hardenable compound for the electron
beam hardened resin useful for the invention may be used, as
long as it can be hardened by electron beam irradiation. The
electron beam hardenable compound in the invention includes an
electron beam hardenable compound disclosed in Japanese Patent
Publication No. 60-17104/1985 and Japanese Patent O.P.I.
Publication Nos. 60-126649/1985 and 2-157747/1990, that is, an
electron beam hardenable monomer or oligomer. The monomer or
oligomer useful for the invention capable of being hardened by
electronic beam irradiation includes an unsaturated compound
containing two or more double bonds in its molecule, for
example, an acryl or methacryl oligomer, a multifunctional
acryl or methacryl monomer. In addition, the monomer by which
the above described hardenable monomer is diluted includes an
unsaturated compound containing at least one double bond in
one molecule such as an acryl, methacryl or vinyl monomer.
The acryl or methacryl oligomer includes an acryl or
methacryl ester of polyurethane, an acryl or methacryl ester
of polyetheralcohol, an acryl or methacryl ester of bisphenol
A, and a maleic or fumalic ester of polyester. The
multifunctional acryl or methacryl monomer includes 1,6-hexanedioldiacrylate,
neopentyldiacrylate, diethyleneglycol
diacrylate, butadieneacrylate, diethyleneglycol dimethacrylate,
tetraethyleneglycol diacrylate, grycerolmethacrylate,
stearylacrylate, polyethyleneglycol diacrylate,
butoxyethylacrylate, 1,3-butanedioldiacrylate, ethyleneglycol
dimethacrylate, glycidylmethacrylate, methylacrylate,
ethylacrylate, butylacrylate, 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate,
2-hydroxypropylacrylate,
phenoxyethylacrylate, cyclohexylacrylate, benzylacrylate, N,N-dimethylaminoethyl-acrylate,
N,N-diethylaminoethylacrylate,
ethyleneoxide modified phenoxyphosphoricacrylate,
neopentylglycoldiacrylate, isocyanuric diacrylate, isocyanuric
triacrylate, trimethylol-propanetriacrylate, propyleneoxide
modified trimethylol-propanetriacrylate, glycidylmrthacrylate,
1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, trimethylol-propanetriacrylate,
pentaerythritolacrylate, and
pentaerythritolpentaacrylate.
The unifunctional acryl, methacryl or vinyl monomer
includes styrene, N-vinylpyrrolidone,
polyoxyethylenephenylalcohol acrylate, and
2-ethylhexylacrylate.
The coating method includes a roller coating method and a
conventional method used for sheet coating such as a bar coat
method, a air-doctor coat method, a blade coat method, a
squeeze coat method, a air-knife coat method, a reverse-roll
coat method, a fountain coat method or a silt orifice coat
method.
The electron beam irradiation machine is not specifically
limited, and generally a curtain beam method, which is
relatively cheap and gives large output, is used as an
electron beam accelerator. On electron beam irradiation, the
accelerating voltage is preferably 100-300 kv, and the
absorbed dose is preferably 0.5-10 Mrad.
The thickness of each of the polyolefin resin layer and
the resin layer other than the polyolefin, which constitute a
laminated layer, is not limited but usually 5 to 60 µm.
In the invention the obverse resin layer is a laminated
layer composed of two or more resin layers, at least one
comprising a polyolefin or polyester resin, at least another
one comprising a resin other than the polyolefin resin and
each layer having a different white pigment content. The
white pigment content of the polyolefin or polyester resin
layer is different from that of the resin layer other than the
polyolefin resin layer. The average white pigment content of
the two or more resin layers is preferably 16 weight % or more,
and the white pigment content of the layer closest to the
silver halide emulsion layer is preferably 1 to 25 weight %.
The white pigment content of one layer of the two or more
resin layers may be 0 weight %.
The average white pigment content herein referred to is
an average content a value obtained by dividing the total
white pigment content of the two or more layers with the total
weight of the two or more layers. The average content is
preferably 16 weight % or more, and more preferably 18 to 60
weight %.
The white pigment content of the resin layer closest to
the silver halide emulsion layer is preferably 1 to 25
weight %, and more preferably 5 to 20 weight %.
The white pigment includes rutile type titanium dioxide,
anatase type titanium dioxide, barium sulfate, barium stearate,
silica, alumina, zirconium oxide and caorin. calcium
carbonate, aluminium oxide, and magnesium oxide. Titanium
dioxide is preferable for various reasons.
Titanium dioxide may be anatase or rutile type, but
anatase type is preferable in view of whiteness and rutile
type is preferable in view of sharpness. The mixture of
rutile type and anatase type titanium dioxide is preferable in
view of both whiteness and sharpness. Some layers of the
multi-layers may contain anatase type titanium dioxide and the
others the rutile type titanium dioxide.
In order to restrain activity of titanium dioxide or to
prevent after yellowing, the titanium dioxide may be surface
treated with an inorganic substance such as hydrated aluminum
or hydrated silicon oxide, an organic substance such as
polyhydric alcohol, polyamine, metal soap, alkyl titanate or
polysiloxane or a mixture thereof. In the surface treated
titanium dioxide, the content of the inorganic substance is
preferably 0.2 to 2.0 weight %, and the content of the organic
substance is preferably 0.1 to 1.0 weight %, based on the
titanium dioxide. The particle diameter of the titanium
dioxide is preferably 0.1 to 0.4 µm.
In order to disperse white pigment in the resin, a three
roll mill, a two roll mill, a colloid mill, a homogenizer, a
sand grinder and an ultrasonic dispensing machine can be used.
Optionally, the surface of the resin layer after coating
or hardening is smoothened by a mirror roller or is matted by
a matting roller.
The cyan coupler represented by Formula [C-I] will be
explained below.
In the cyan coupler represented by Formula [C-I], R21
represents an alkyl group having 2 to 6 carbon atoms, which
may be straight chained or branched or may have a substituent.
R21 preferably represents an ethyl group.
R22 represents a ballast group which is an organic group
giving size or shape enough to give bulkiness to a coupler
molecule such that the coupler is not diffused from the
coupler containing layer to another layer. The balast group
preferably represents -CH(R23)-O-Ar.
R23 represents an alkyl group having 1 to 12 carbon atoms,
Ar represents an aryl group such as a phenyl group, which may
have a substituent.
In Formula [C-1], the atom or group represented by Z1,
which is capable of being released on reaction with an
oxidation product of a color developing agent, includes a
halogen atom, an alkoxy group, an aryloxy group, an acyloxy
group, a sulfonyloxy group, an acylamino group, a
sulfonylamino group, an alkoxycarbonyl group, an
aryloxycarbonyloxy group or an imido group, each of which may
have a substituent, and is preferably a halogen atom, an
alkoxy group or an aryloxy group.
The exemplified coupler represented by Formula [C-1] will
be shown below, but the coupler is not limited thereto.
The examples of the cyan coupler in the invention are
described in Japanese Patent Publication No. 49-11572/1974,
Japanese Patent O.P.I. Publication Nos. 61-3142/1986, 61-9652/1986,
61-9653/1986, 61-39045/1986, 61-50136/1986, 61-99141/1986,
and 61-105545/1986.
The coupler in the invention represented by Formula [C-1]
can be used in an amount of 1x10-3 mol to 1 mol, and
preferably 1x10-2 to 8x10-1 mol per mol of silver halide.
The coupler in the invention may be used in combination
with other cyan couplers different from the coupler in the
invention. The other couplers include a phenol type cyan
coupler having a methyl group at a 5-position and a 2,5-diacylaminophenol
type cyan coupler.
The cyan coupler represented by Formula [C-1] will be
explained below.
Examples of the substituent according to the invention
having a Hammett's substituent constant σp of +0.20 or more
are sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl,
carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyano, nitro,
halogenated alkyl, halogenated alkoxy, halogenated aryloxy,
pyrrolyl and tetrazolyl groups and a halogen atom.
The sulfonyl group includes alkylsulfonyl, arylsulfonyl,
halogen-substituted alkylsulfonyl and halogen-substituted
arylsulfonyl groups; the sulfinyl group includes alkylsulfinyl
and arylsulfinyl groups; the sulfonyloxy group includes
alkylsulfonyloxy and arylsulfonyloxy groups; the sulfamoyl
group includes N,N-dialkylsulfamoyl, N,N-diarylsulfamoyl and
N-alkyl-N-arylsulfamoyl groups; the phosphoryl group includes
alkoxyphosphoryl, aryloxyphosphoryl, alkylphosphoryl and
arylphosphoryl groups; the carbamoyl group includes N,N-dialkylcarbamoyl,
N,Ndiarylcarbamoyl and N-alkyl-N
arylcarbamoyl groups; the acyl group includes alkylcarbonyl
and arylcarbonyl groups; the acyloxy group includes
alkylcarbonyloxy groups; the oxycarbonyl group includes
alkoxycarbonyl and aryloxycarbonyl groups; the halogen-substituted
alkoxy group includes a-halogen-substituted alkoxy
groups; the halogen-substituted aryloxy group includes
tetrafluoroaryloxy and pentafluoroaryloxy groups; the pyrrolyl
group includes 1-pyrrolyl group; and the tetrazolyl group
includes 1-tetrazolyl group.
Besides the above substituents there may also be suitably
used a trifluoromethyl, heptafluoroisopropyl, nonylfluoro-t-butyl,
tetrafluoroaryl or pentafluoroaryl group.
In Formula [I], among the substituents represented by R1
or R2, the substituents having a σp of less than 0.20 include
alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio,
arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl,
heterocyclic, alkoxy, aryloxy, heterocylic oxy, siloxy, amino,
alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino,
aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl,
heterocyclic thio, thioureido, hydroxy and mercapto groups,
spiro compound residues, and closslinked hydrocarbon compound
residues.
The above alkyl group includes a straight-chained or
brancheded alkyl group having preferably 1 to 32 carbon atoms.
The above aryl group is preferably a phenyl group.
The above acylamino group includes alkylcarbonylamino and
arylcarbonylamino groups: the sulfonamido group includes
alkylsulfonylamino and arylsulfonylamino groups. The alkyl
component and the aryl component of the above alkylthio group
and arylthio group correspond to the above alkyl groups and
the aryl groups, respectively.
The alkenyl group may be either straight-chained or
branched and includes those having 2 to 32 carbon atoms. The
cycloalkyl group incudes those having preferably 3 to 12
carbon atoms, more preferably 5 to 7 carbon atoms. The
cycloalkenyl group includes those having preferably 3 to 12
carbon atoms, more preferably 5 to 7 carbon atoms.
The ureido group includes alkylureido and arylureido
groups; the sulfamoylamino group includes alkylsulfamoylamino
and arylsulfamoylamino groups; the heterocyclic group is
preferably a 5- to 7-membered cyclic group such as 2-furyl, 2-thienyl,
2-pyrimidinyl and 2-benzothiazolyl groups; the
heterocyclic oxy group is preferably one having a 5- to 7-member
heterocyclic ring such as 3,4,5,6-tetrahydropyranyl-2-oxy
and 1-phenyltetrazole-5-oxy groups; the heterocyclic thio
group is preferably a 5- to 7-membered heterocyclic thio group
such as 2-pyridylthio, 2 benzothiazolylthio and 2,4-diphenoxy-1,3,5-triazole-6-thio
groups; the siloxy group includes
trimethylsiloxy, triethylsiloxy and dimethylbutylsiloxy
groups; the imido group includes succinic acid imido, 3-heptadecylsuccinic
acid imido, phthalimido and glutarimido
groups; the spiro compound residue includes spiro[3.3]heptane-1-yl
group; the closslinked hydrocarbon compound residue
includes bicyclo[2.2.1]heptane-1-yl, tricyclo[3.3.1.13
7]decane-1-yl and 7,7-dimethyl-bicyclo[2.2.1]heptane-1-yl
groups.
The above groups each may have further a substituent, a
non-diffusible group such as a long-chain hydrocarbon group, a
polymer residue, etc.
In Formula [I], the group represented by X1 capable of be
released upon reaction with an oxidation product of a color
developing agent includes a halogen atom such as chlorine,
bromine or fluorine, and alkoxy, aryloxy, heterocyclic oxy,
acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio,
heterocyclicthio, alkoxycarbonylthio, acylamino, sulfonamido,
N atom-bonded nitrogen-containing heterocyclic,
alkoxycarbonylamino, aryloxycarbonylamino and carboxyl groups.
The preferred among these are a hydrogen atom and the alkoxy,
aryloxy, alkylthio, arylthio, and N atom-bonded nitrogen-containing
heterocyclic groups.
In Formula [I], the nitrogen-containing 5-membered
heterocyclic ring formed with Z1 includes pyrazole, imidazole,
benzimidazole, triazole and tetrazole rings. The nitrogen-containing
5-membered heterocyclic ring may form a condensate
with a benzene ring.
To be concrete, the compounds represented by Formula [I]
comprise those represented by the following Formulas [I]-1 to
[I]-7.
In the above Formulas, at least one of R1 and R11 of
Formula [I]-1, at least one of R1 and R12 of Fomula [I]-2, at
least one of R1, R13 and R14 of Formula [I]-3, at least one of
R1, R15 and R16 Formula [I]-4, at least one of R1 and R17 of
Formula [I]-5, R1 of Formula [I]-6 and at least one of R1, R18
of Formula [I]-7 independently represent an electron
attractive group having a σp of not less than 0.20.
X1 is the same as defined in X1 of Formula [I]; and p is
an integer of 0 to 4.
In Formulas [I]-1 to [I]-7, of the groups represented by
R1 and R11 to R18 those other than the non-electron-attractive
group having a σp of not less than 0.20 represent a hydrogen
atom or a substituent having a σp of less than 0.20; of the
groups represented by R18 those having a σp of less than 0.20
can be any substituents without limit which, where the R1 or
R2 in Formula [I] is one of those other than the electron-attractive
group having a σp of not less than 0.20, include
those described as the substituent represented by the R1 or R2
of Formula [I].
The cyan coupler having the electron attractive group
according to the invention can be easily synthesized according
to appropriate one of the methods described in Japanese Patent
O.P.I. Publication Nos. 64-554/1989, 64-555/1989, 64-557/1989,
and 1-105251/1989.
The cyan coupler represented by Formula [II] will be
explained.
The cyan coupler of Formula [II] is of a structure of a
6-membered heterocyclic ring condensate with a pyrazole ring,
wherein the substituent represented by R3 can be any group
with no restriction; examples of it include alkyl, aryl,
anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl
and cycloalkyl groups, and further a halogen atom, and
cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl,
phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy,
sulfonyloxy, aryloxy, heterocyclic oxy, siloxy, acyloxy,
carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino,
alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl,
aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl,
hydroxyl, mercapto, nitro and sulfo groups, and spiro compound
residues and closslinked hydrocarbon conspound residues.
The alkyl group represented by R3 may be a straight-chained
or branched alkyl group having preferably 1 to 32
carbon atoms. The aryl group is preferably a phenyl group.
The acylamino group represented by R3 includes
alkylcarbonylamino and arylcarbonylamino groups; the
sulfonamido group includes alkylsulfonylamino and
arylsulfonylamino groups. The alkyl and aryl components of
the alkylthio group and the arylthio group are the same as
those defined for the alkyl group and the aryl group,
respectively, represented by the above R3.
The alkenyl group represented by R3 may be a straight-chained
or branched alkenyl group having preferably 2 to 32
carbon atoms. The cycloalkyl group is preferably one having 3
to 12 carbon atoms, more preferably 5 to 7 carbon atoms. The
cycloalkenyl group is preferably one having 3 to 12 carbon
atoms, more preferably 5 to 7 carbon atoms.
The sulfonyl group represented by R3 includes
alkylsulfonyl and arylsulfonyl groups; the sulfinyl group
includes alkylsulfinyl and arylsulfinyl groups; the phosphonyl
group includes alkylphosphonyl, alkoxyphosphonyl,
aryloxyphosphonyl and arylphosphonyl groups; the acyl group
includes alkylcarbonyl and arylcarbonyl groups; the carbamoyl
group includes alkylcarbamoyl and arylcarbamoyl groups; the
sulfamoyl group includes alkyl sulfamoyl and arylsulfamoyl
groups; the acyloxy group includes alkylcarbonyloxy and
arylcarbonyloxy groups; the carbamoyloxy group includes
alkylcarbamoyloxy and arylcarbamoyloxy groups; the ureido
group includes alkyl ureido and arylureido groups; the
sulfamoylamino group includes alkylsulfamoylamino and
arylsulfamoylamino groups; the heterocyclic group is
preferably 5 to 7-membered one including 2-furyl, 2-thienyl,
2-pyrimidinyl, 2-benzothiazolyl, 1-pyrrolyl and 1-tetrazolyl
groups; the heterocyclic oxy group is preferably one having a
5- to 7-member heterocyclic ring, such as 3,4,5,6-tetrahydropyranyl-2-oxy
and 1-phenyltetrazole-5-oxy groups;
the heterocyclic thio group is preferably a 5- to 7-membered
heterocyclic thio group such as 2-pyridylthio, 2-benzothiazolylthio
and 2,4-diphenoxy-1,3,5-triazolo-6-thio
groups; the siloxy group includes trimethylsiloxy,
triethylsiloxy and dimethylbutylsiloxy groups; the imido group
includes succinic acid imido, 3-heptadecylsuccinic acid imido,
phthalimido and clutarinido groups; the spiro compound residue
includes a spiro[3.3]heptane-1-yl group; the crosslinked
hydrocarbon compound residue includes bicyclo-[2.2.1]heptane-1-yl,
tricyclo[3.3.1.13 7]decane-1-yl and 7,7-dimethylbicyclo[2.2.1]heptane-1-yl
groups.
The above groups each may further have a substituent, a
non-diffusible group such as a long-chain hydrocarbon group or
a polymer residue.
The group represented by X2 capable of splitting upon
reaction with an oxidation product of a color developing agent
is the same group as defined for the X1 of Formula [I].
In Formula [II], the 6-membered nitrogen-containing
heterocyclic ring formed with Z2, is preferably of the 6π
electron or 8π electron system. The ring contains at least
one -NH-, and preferably further contains >C=0, >C=S, -SO2-.
The examples the 6-membered rings include diazines, triazines
and tetrazines.
The preferable examples of the cyan coupler of the
invention include those represented by the following Formulas
[II]-1 to [II]-6:
wherein R3, R21, R22, R23, R24, R25, R26, R27 and R28 are as
defined for the R1 of Formula [I]; X2 is as defined for the X1
of Formula [I]. In Formula [II]-1 or [II]-5, n is an integer
of 0 to 4, provided that when n is an integer of 2 to 4, the
plural number of R21s and R26s may be either the same or
different, respectively.
In Formulas [II]-4 and [II]-6, R24, R25, R27 and R28 are
as defined for the R1 of Formula [I], but R24 and R27 each can
not be a hydroxyl group.
In Formula [III], R4 and R5 each represent an electron
attractive group having a Hammett's substituent constant σp of
not less than 0.20, and the electron attractive group includes
the same groups as those represented by the R1 and R2 of
Formula [I], provided that the sum of the σp values of R4 and
R5 is not less than 0.65. X3 represents the same group as X1 of
Formula [I].
The nitrogen-containing 5-membered heterocyclic ring
formed with Z3 is a pyrazole ring, imidazole ring or tetrazole
ring, which may have a substituent.
The compounds represented by Formula [III] are classified
into those having the following Formulas [III]-1 to [III]-8:
wherein R4, R5 and X3 are as defined in Formula [III]; R31
represents a hydrogen atom or a substituent; R32 represents an
electron attractive group having a Hammett's substituent
constant σp of not less than 0.20.
The substituent represented by R31 is as defined for the
R3 of Formula [II]; and the electron attractive group
represented by R32 is the same as those represented by the R1
and R2 of Formula [I].
The preferred as the cyan coupler represented by Formula
[III] are those represented by Formulas [III]-1, [III]-2 and
[III]-3, and the most preferred is one having Formula [III]-2.
In Formula [IV], R6 and R7 each represent a hydrogen atom
or a substituent which is as defined for the R3 of Formula
[II]. X4 represents the same group as X1 of Formula [I].
In Formula [IV], Z4 represents a group of non-metallic
atoms necessary to form a 6-membered nitrogen-containing
heterocyclic ring, provided the heterocyclic ring has at least
one dissociation group. As the four divalent linkage groups
for constituting the nitrogen-containing 6-membered
heterocyclic ring there are, e.g., -NH-, -N(R)-, -N=, -CH(R)-,
-CH=, -C(R)=, -CO-, -SO- and -SO2∼, wherein R represents a
substituent, whose examples include those represented by R31.
The dissociation group is one having an acidic proton such as
-NH- or -CH(R)-, and is preferably one having a pKa value of 3
to 12 in water. The above nitrogen-containing 6-membered
heterocyclic ring may have a substituent. The example of Z4
includes a group capable of forming a diazine, triazine or
tetrazine ring.
Preferable examples of the coupler represented by Formula
[IV] include those having the following Formulas [IV]-1 to
[IV]-6.
wherein R6, R7 and X4 are as defined in Formula [IV]; R41 and
R42 each represent a hydrogen atom or a substituent; and R43
represents an electron attractive group having a Hammett's
substituent constant op of not less than 0.20;
The examples of the substituent represented by R41 or R42
are the same as those of the R3 of Formula [II], while the
examples of the electron attractive group represented by R43
are the same as those of the R1 and R2 of Formula [I].
The examples of the group represented by X4 capable of
being released upon reaction with an oxidation product of a
color developing agent are the same as those of the X1 of
Formula [I].
The following are examples of the cyan coupler
(hereinafter referred to as the cyan coupler of the invention)
represented by Formulas [I] through, but the invention is not
limited thereto.
The cyan coupler of the invention can be used in an
amount of 1x10-3 mol to 1 mol, and preferably 1x10-2 to 8x10-1
mol per mol of silver halide. The coupler of the invention
may be used in combination with different other cyan couplers.
Those methods and techniques for ordinary cyan dye
forming couplers may apply to the cyan coupler of the
invention as well. Typically, the cyan coupler of the
invention is incorporated into a silver halide emulsion, and
the emulsion is coated on a support to form the color
photographic light sensitive material of the invention.
The coupler used in the silver halide photographic light
sensitive material of the invention may be any compound which
can produce a coupling product having a spectral absorption
maximum of 340 nm or longer on coupling reaction with an
oxidation product of a color developing agent. As the typical
coupler are known a coupler for forming a yellow dye having a
spectral absorption maximum in a wavelength of 350 to 500 nm,
a coupler for forming a magenta dye having a spectral
absorption maximum in a wavelength of 500 to 600 nm and a
coupler (in the invention at least one cyan coupler of the
invention is used) for forming a cyan dye having a spectral
absorption maximum in a wavelength of 600 to 750 nm.
The yellow coupler used in the invention is a yellow
coupler represented by the following Formula (Y-I), (Y-II) or
(Y-III):
wherein R1 represents an alkyl group or a cycloalkyl group; R2
represents an alkyl group, a cycloalkyl group or an aryl
group; R3 represents a substituent; and Z1 represents a
hydrogen atom or a group capable of being released upon
reaction with an oxidation product of a color developing agent,
wherein R11 represents a monovalent group other than a hydrogen
atom; Q represents a 3- to 5-membered hydrocarbon ring with
the C or a non-metallic atomic group necessary to form a 3- to
5-membered heterocyclic ring with at least one atom selected
from the group consisting of N, S, O and P; R12 represents a
hydrogen atom, a halogen atom, an alkyl group, an alkoxy group,
an aryloxy group or an amino group; a cycloalkyl group or an
aryl group; R13 represents a substituent; and Z2 represents a
hydrogen atom or a group capable of being released upon
reaction with an oxidation product of a color developing agent,
wherein R21 and R22 independently represent an alkyl group, an
aryl group or a heterocyclic group, provided that R21 and R23
may combine with each other to form a nitrogen-containing
heterocyclic ring together with the N; R23 represents an alkyl
group, a cycloalkyl group or an aryl group; and Z3 represents a
hydrogen atom or a group capable of being released upon
reaction with an oxidation product of a color developing agent.
The yellow coupler represented by Formula (Y-I) will be
explained below.
In Formula (Y-I), the alkyl group represented by R1
includes a straight-chained or branched alkyl group such
methyl, ethyl, i-propyl, t-butyl, dodecyl or 1-hexylnonyl.
The cycloalkyl group represented by R1 includes cyclopropyl,
cyclohexyl and adamantyl.
The alkyl or cycloalkyl group represented by R1 may have a
substituent. The substituent includes a halogen atom (for
example, chlorine or bromine), cyano, nitro, an aryl group
(for example, phenyl, p-t-octylphenyl, 2,4-di-t-amylhexyl),
hydroxyl, an alkoxy group (for example, methoxy or ethoxy), an
aryloxy group (for example, phenoxy, 2,4-di-t-amylphenoxy or
4-(hydroxyphenylsulfonyl)phenoxy), a heterocyclicoxy group
(for example, 4-pyridyloxy or 2-hexahydropyranyl), a
carbonyloxy group (for example, alkylcarbonyloxy such as
acetyloxy or pivaloyloxy, arylcarbonyloxy such as benzoyloxy),
a sulfonyloxy group (for example, alkylsulfonyloxy such as
methanesulfonyloxy, trifluoro methanesulfonyloxy or
dodecanesulfonyloxy or arylsulfonyloxy such as
benzenesulfonyloxy or p-toluenesulfonyloxy), a carbonyl group
(for example, alkylcarbonyl such as acetyl or pyvaloyl,
arylcarbonyl such as benzoyl or 3,5-di-t-butyl-4-hydroxybenzoyl),
an oxycarbonyl group (for example,
alkoxycarbonyl such as methoxycarbonyl, cyclohexyloxycarbonyl
or dodecyloxycarbonyl, aryloxycarbonyl such as 2,4-di-t-amylphenoxycarbonyl,
heterocyclicoxycarbonyl such as 2-pyridyloxycarbonyl
or 1-phenylpyrazolyl-5- oxycarbonyl), a
carbamoyl group (for example, alkylcarbamoyl such as
dimethylcarbamoyl, 4-(2,4-di-t-amylphenoxybutyl)aminocarbonyl
or arylcarbamoyl such as phenylcarbamoyl or 1-naphthylcarbamoyl),
a sulfonyl group (for example,
alkylsulfonyl such as methanesulfonyl or trifluoro
methanesulfonyl or arylsulfonyl such as p-toluenesulfonyl), a
sulfamoyl group (for example, alkylsulfamoyl dimethylsulfamoyl
or 4-(2,4-di-t-amylphenoxybutyl)aminosulfonyl, arylsulfamoyl
such as phenylsulfamoyl, or acylsulfamoyl such as
acetylsulfamoyl or ethylcarbonylaminosulfamoyl), an amino
group (for example, alkylamino such as dimethylamino,
cyclohexylamino, or dodecylamino), a sulfonamido group (for
example, alkylsulfonamido such as methanesulfonamido,
heptafluoroprapanesulfonamido or hexanedecylsulfonamido or
arylsulfonamido such as p-toluenesulfonamido or
pentafluorobenzenesulfonamido), an acylamino group (for
example, alkylamino such as dimethylamino, cyclohexylamino or
dodecylamino, arylamino such as anilino, p-t-octylanilino), an
alkylthio group (for example, methylthio or octylthio), an
arylthio group (for example, phenylthio), a heterocyclicthio
group (for example, 1-phenyltetrazole-5-thio or 5-methyl-1,3,4-oxadiazole-2-thio).
R1 represents preferably an alkyl group, more preferably
a branched alkyl group, and especially preferably a t-butyl
group.
The alkyl or cycloalkyl group represented by R2 includes
the same as the alkyl or cycloalkyl group represented by R1.
The aryl group represented by R2 includes a phenyl or naphthyl
group. The alkyl, cycloalkyl or aryl group represented by R2
may have a substituent. The substituent includes the same as
the alkyl or cycloalkyl group represented by R1 or the
substituent denoted above in the alkyl or cycloalkyl group
represented by R1.
R2 represents preferably an alkyl group, more preferably
an unsubstituted alkyl group, and especially preferably a
methyl group.
The group represented by Z1, which is capable of being
released upon reaction with an oxidation product of a color
developing agent, includes a nitrogen-containing heterocyclic
group capable of coupling at the coupling position through its
nitrogen atom, an aryloxy group, an arylthio group, a
heterocyclicoxy group, an acyloxy group, a carbamoyloxy group,
an alkylthio group and a halogen atom.
The nitrogen-containing heterocyclic group represented by
Z1, which is capable of coupling at the coupling position
through its nitrogen atom, has 1-15, preferably 1-10 carbon
atoms. The nitrogen-containing heterocyclic group preferably
represents a 5-6 membered, substituted or unsubstituted,
saturated or unsaturated heterocyclic group or a single or
condensed heterocyclic group. The heterocyclic group may
contain, as a hetero atom, an oxygen or sulfur atom, in
addition to a nitrogen atom. The preferable example of the
heterocyclic group includes a 1-pyrazolyl, 1-imidazolyl,
pyrrolyno, 1,2,3-triazole-2-yl, 1,2,3-triazole-1-yl,
benzotriazolyl, benzimidazolyl, imidazolidine-2,4-dione-3-yl,
1, oxazolidine-2,4-dione-3-yl, 1,2,3-triazolidine-3,5-dione-4-yl,
imidazolidine-2,4,5-trione-3-yl, 2-imidazolinone-1-yl,
3,5-dioxomorpholino and 1-indazolyl. When the heterocyclic
group has a substituent, the substituent is not limited but
preferably represents an alkyl group, an alkoxy group, a
halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl
group, an alkylthio group, an acylamino group, a sulfonamido
group, an aryl group, a nitro group, a carbamoyl group, a
cyano group or a sulfonyl group.
The aryloxy group represented by Z1 represents a
substituted or unsubstituted aryloxy group having preferably
6-10 carbon atoms, and more preferably a substituted or
unsubstituted phenoxy group. When the aryloxy group has a
substituent, at least one substituent preferably represents an
electron attractive group such as a sulfonyl group, an
alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a
carbamoyl group, a nitro group, a cyano group or an acyl group.
The arylthio group represented by Z1 represents a
substituted or unsubstituted arylthio group having preferably
6-10 carbon atoms, and more preferably a substituted or
unsubstituted phenylthio group. When the arylthio group has a
substituent, at least one substituent preferably represents an
alkyl group, an alkoxy group, a sulfonyl group, an
alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a
carbamoyl group, or a nitro group.
The heterocyclicoxy group represented by Z1 represents a
heterocyclicoxy group having 1-20 carbon atoms, and 1-10
carbon atoms, which includes a 3-12, preferably 5-6 membered,
substituted or unsubstituted, saturated or unsaturated
heterocyclic group or a single or condensed heterocyclic group,
each containing at least one of a nitrogen atom, an oxygen
atom and a sulfur atom as a hetero atom. The heterocyclicoxy
group includes pyridyloxy, pyrazolyloxy and furyloxy. When
the heterocyclicoxy group has a substituent, at least one
substituent preferably represents an alkyl group, an aryl
group, a carboxy group, an alkoxy group, a halogen atom, an
alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio
group, an acylamino group, a sulfonamide group, a nitro group,
a carbamoyl group or a sulfonyl group.
The heterocyclic group of the heterocyclicthio group
represented by Z1 represents a 3- to 12-, preferably 5- or 6-membered,
substituted or unsubstituted, saturated or
unsaturated, single or condensed heterocyclic group having 1-20
carbon atoms, and preferably 1-10 carbon atoms and
containing, as a hetero atom, at least one selected from the
group consisting of a nitrogen, oxygen and sulfur atom. The
heterocyclicthio group includes tetrazolylthio, 1,3,4-thiadiazolylthio,
1,3,4-oxadiazolylthio, 1,3,4-triazolylthio,
benzimidazolylthio, benzothiazolylthio and 2-pyridylthio.
When the heterocyclicthio group has a substituent, at least
one substituent preferably represents an alkyl group, an aryl
group, a carboxy group, an alkoxy group, a halogen atom, an
alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio
group, an acylamino group, a sulfonamide group, a nitro group,
a carbamoyl group, a heterocyclic group or a sulfonyl group.
The acyloxy group represented by Z1 represents a single or
condensed ring having preferably 6-10 carbon atoms. The
acyloxy group represents a substituted or unsubstituted
aromatic acyloxy group or a substituted or unsubstituted
aliphatic acyloxy group having 2-30, preferably 2-20 carbon
atoms. The acyloxy group may further have a substituent.
The carbamoyloxy group represented by Z1 represents a
carbamoyloxy group containing an aliphatic group of 1-30,
preferably 1-20 carbon atoms, an aryl group or a heterocyclic
group or a substituted or unsubstituted carbamoyloxy group.
The carbamoyloxy group includes N,N-diethylcarbamoyloxy, N-phenylcarbamoyloxy,
l-imidazolylcarbonyloxy and 1-pyrrolocarbonyloxy.
The alkylthio group represented by Z1 represents a
straight-chained or branched, saturated or unsaturated,
substituted or unsubstituted alkylthio group having 1-30,
preferably 1-20 carbon atoms. The alkylthio group may further
have a substituent.
The preferred Z1 is a group represented by the following
Formula (I), (II), (III) :
Formula (I) -OR4
Formula (II) -OCOR4
In Formula (I) or (II), R4 represents an alkyl group, a
cycloalkyl group, an aryl group or a heterocyclic group. The
alkyl group, a cycloalkyl group or an aryl group represented
by R4 is the same as the alkyl, cycloalkyl or aryl group
denoted in R2 of Formula (Y-I). The heterocyclic group
represented by R4 includes 4-pyridyl and 2-hexahydropyranyl.
The alkyl group, a cycloalkyl group or an aryl group
represented by R4 may have a substituent. The substituent
includes the same as the substituent of the alkyl, cycloalkyl
or aryl group represented by R2 of Formula (Y-I) denoted above.
Of the alkyl, cycloalkyl aryl or heterocyclic group
represented by R4, the aryl group is preferable. The
substituent of R4 preferably represents an electron attractive
group, for example, oxycarbonyl such as carboxyl,
methoxycarbonyl or i-propyloxycarbonyl, acyl such as acetyl or
benzoyl, sulfonyl group such as trifluoromethanesulfonyl or 4-hydroxyphenyosulfonyl,
nitro, cyano, halogen, sulfamoyl such
as dimethylsulfamoyl, acylamino such as acetylamino or
pentafluorobenzoyl or sulfonamido such as methanesulfonamido.
In Formula (III), X1 represents a non-metallic atomic
group necessary to form a 5- or 6-membered ring together with
a nitrogen atom. An atomic group necessary to form the non-metallic
atomic group includes methylene, methine, substituted
methine-CO-, -N(R5)- in which R5 represents a hydrogen atom, an
alkyl group, an aryl group or a heterocyclic group, -N=, -O-or
-S(O)u- in which u represents an integer of 0 to 2.
The especially preferred Z1 is a group represented by the
following Formula (IV):
In Formula (IV), Y1 represents -N(R6)- in which R6
represents the same as the group represented by R5 of Formula
(III), -O-, -S(O)r- in which r represents an integer of 0 to 2,
-C(O)-, -C(R7)(R8)- in which R7 and R8 independently represent a
hydrogen atom or the same group as the substituent of the
alkyl, cycloalkyl or aryl group represented by R2 of Formula
(Y-I), or -C(R9)- in which R9 represents a hydrogen atom or the
same group as the substituent of the alkyl, cycloalkyl or aryl
group represented by R2 of Formula (Y-I).
X2 represents a non-metallic atomic group necessary to
form a 5- or 6-membered ring together with -Y1-N-CO-. An
atomic group necessary to form the non-metallic atomic group
includes the same as the atomic group represented by X1 of
Formula (III).
R3 represents a substituent, preferably an unsubstituted
alkyl group having 11 to 21 carbon atoms, and more preferably
a straight-chained alkyl group.
The two-equivalent yellow coupler represented by Formula
(Y-I) can form a dimer, trimer or tetramer or polymer in which
two or more of the coupler combine with each other through the
substituent of the coupler.
The yellow coupler represented by Formula (Y-I) can be
easily synthesized from starting materials commercially
available according to a conventional method disclosed in
Japanese Patent O.P.I. Publication Nos. 63-123047/1988, 4-9051/1992
and 4-124661/1992.
The example of the yellow coupler represented by Formula
(Y-I) will be shown below, but is not limited thereto.
The yellow coupler represented by Formula (Y-II) will be
explained below.
In Formula (Y-II), R11 preferably represents a halogen
atom, a cyano group, or an aliphatic group of 1 to 30 carbon
atoms (for example, alkyl, alkoxy) or an aromatic group of 6
to 30 carbon atoms (for example, aryl or aryloxy), each of
which may have a substituent. The substituent includes
halogen, alkyl, alkoxy, nitro, amino, acylamino, sulfonamido
and acyl.
In Formula (Y-II), Q preferably represents a non-metallic
atomic group necessary to form a substituted or unsubstituted,
3- to 5-membered hydrocarbon ring of 3-30 carbon atoms with
the C or a substituted or unsubstituted, 3- to 5-membered
heterocyclic ring of 3-30 carbon atoms containing a hetero
atom selected from the group consisting of N, S, O and P. The
ring which Q forms with the C may have an unsaturated bond.
The ring which Q forms with the C includes a cyclopropane,
cyclobutane, cyclopentane, cyclopropene, cyclobutene,
cyclopentene, oxetane, oxolane, 1,3-dioxolane, thiethane,
thielane and pyrrolidine ring. The substituent includes
halogen, hydroxyl, alkyl, aryl, acyl, alkoxy, aryloxy, cyano,
alkoxycarbonyl, alkylthio and arylthio group.
R12 preferably represents a halogen atom or an alkoxy
group of 1 to 30 carbon atoms, an aryloxy group of 6 to 30
carbon atoms, an alkyl group of 1 to 30 carbon atoms or an
amino group of 0 to 30 carbon atoms, each of which may have a
substituent. The substituent includes halogen, alkyl, alkoxy,
and aryloxy.
R13 preferably represents a halogen atom or an alkyl group
of 1 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms,
an alkoxy group of 1 to 30 carbon atoms, an alkoxycarbonyl
group of 2 to 30 carbon atoms, an aryloxycarbonyl group of 7
to 30 carbon atoms, an acylamino group of 1 to 30 carbon atoms,
a sulfonamido group of 1 to 30 carbon atoms, a carbamoyl group
of 1 to 30 carbon atoms, a sulfamoyl group of 0 to 30 carbon
atoms, an alkylsulfonyl group of 1 to 30 carbon atoms, an
arylsulfonyl group of 6 to 30 carbon atoms, a ureido group of
1 to 30 carbon atoms, a sulfamoylamino group of 0 to 30 carbon
atoms, an alkoxycarbonylamino group of 2 to 30 carbon atoms, a
heterocyclic group of 1 to 30 carbon atoms, an acyl group of 1
to 30 carbon atoms, an alkylsulfonyloxy group of 1 to 30
carbon atoms or an arylsulfonyloxy group of 6 to 30 carbon
atoms, each of which may have a substituent. The substituent
includes halogen, alkyl, aryl, heterocyclic, alkoxy, aryloxy.
heterocyclicoxy, alkylthio, arylthio, heterocyclicthio,
alkylsulfonyl, arylsulfonyl, acyl, acylamino, sulfonamide,
carbamoyl, sulfamoyl, alkoxycarbonylamino, sulfamoylamino,
ureido, cyano, nitro, acyloxy, alkoxycarbonyl, aryloxycarbonyl,
alkylsulfonyloxy, arylsulfonyloxy and aryloxy.
The position of R13 is preferably at a meta or para
position, on the benzene ring of the anilide, to the group,
Z2 represents the same as Z1 in Formula (Y-I).
In formula (Y-II), an especially preferable substituent
will be explained below.
R11 especially preferably represents a halogen atom or an
alkyl group, and most preferably a methyl group. Q especially
preferably represents a non-metallic atomic group necessary to
form a 3- to 5-membered hydrocarbon ring with the C, for
example,
wherein R represents a hydrogen atom, a halogen atom or an
alkyl group, provided that plural Rs may be the same or
different. Q most preferably represents
which forms a 3-membered ring with the C.
R12 especially preferably represents a chlorine atom, a
fluorine atom, an alkyl group of 1-6 carbon atoms (for example,
methyl, trifluoromethyl, ethyl, i-propyl, t-butyl), an alkoxy
group of 1-8 carbon atoms (for example, methoxy, ethoxy,
methoxyethoxy, butoxy), or an aryloxy group of 6-24 carbon
atoms (for example, phenoxy, p-tolyloxy, p-methoxyphenoxy),
and most preferably a chlorine atom, a methoxy group or a
trifluoromethyl group.
R13 especially preferably represents a halogen atom, an
alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl
group, an acylamino group, a sulfonamido group, a carbamoyl
group or a sulfamoyl group, and most preferably an alkoxy
group, an alkoxycarbonyl group, an acylamino group, or a
sulfonamido group.
Z2 especially represents a group represented by Formula
(IV) denoted in Formula (Y-I).
The yellow coupler represented by Formula (Y-II) can be
easily synthesized from starting materials commercially
available according to a conventional method disclosed in
Japanese Patent O.P.I. Publication No. 4-218042/1992.
The example of the yellow coupler represented by Formula
(Y-II) will be shown below, but is not limited thereto.
The coupler represented by Formula (Y-III) will be
explained below.
The alkyl group represented by R21 or R22 represents a
straight-chained, branched or cyclic, saturated or unsaturated,
substituted or unsubstituted alkyl group having 1 to 30,
preferably 1 to 20 carbon atoms. The example includes methyl,
ethyl, propyl, butyl, cyclopropyl, allyl, t-octyl, i-butyl,
dodecyl and 2-hexyldecyl.
The heterocyclic group represented by R21 or R22 represents
a 3 to 12-, preferably 5 to 6-membered, substituted or
unsubstituted, saturated or unsaturated, single or condensed
heterocyclic group having 1-20 carbon atoms, and preferably 1-10
carbon atoms and containing, as a hetero atom, at least one
selected from the group consisting of a nitrogen, oxygen and
sulfur atom. The example of the heterocyclicthio group
includes 3-pyrrolidinyl, 1,2,4-triazole-3-yl, 2-pyridyl, 4-pyrimidinyl,
3-pyrazolyl, 2-pyrrolyl, 2,4-dioxo-1,3-imidazolidine-5-yl
and pyranyl.
The aryl group represented by R21 or R22 represents an aryl
group having 6-20, preferably 6-10 carbon atoms. The example
of the aryl group includes phenyl and naphthyl.
The nitrogen-containing heterocyclic group in which R21
and R22 combine with each other represents a 3- through 12-,
preferably 5- or 6-membered, substituted or unsubstituted,
saturated or unsaturated, single or condensed heterocyclic
group having 1 to 20, preferably 1 to 15 carbon atoms, which
may contain an oxygen or sulfur atom in addition to a nitrogen
atom. The example of the heterocyclic group includes
pyrrolidino, piperidino, morpholino, 1-pyperadinyl, 1-indolinyl,
1,2,3,4-tetrahydroquinoline-1-yl, 1-imidazolidinyl,
1-pyrazolyl, 1-pyrrolinyl, 1-pyrazolinyl, 2,3-dihydro-1-indazolyl,
2-isoindolinyl, 1-indolyl, 1-pyrrolyl, 4-thiazine-S,S-dioxo-4-yl
and benzoxazine-4-yl.
The alkyl, aryl or heterocyclic group represented by R21
or R22 or the nitrogen-containing heterocyclic group in which
R21 and R22 combine with each other may have a substituent. The
substituent includes halogen (for example, fluorine, chlorine),
alkoxycarbonyl of 2-30, preferably 2-20 carbon atoms (for
example, methoxycarbonyl, dodecyloxycarbonyl,
hexadecyloxycarbonyl), acylamino of 2-30, preferably 2-20
carbon atoms (for example, acetoamido, tetradecanamido, 2-(2,4-di-t-amylphenoxy)butanamido,
benzamido), sulfonamido of
1-30, preferably 1-20 carbon atoms (for example,
methanesulfonamido, dodecanesulfonamido, hexadecanesulfonamido,
benzenesulfonamido), carbamoyl of 1-30, preferably 1-20 carbon
atoms (for example, N-butylcarbamoyl, N,N-diethylcarbamoyl),
N-sulfonylcarbamoyl of 1-30, preferably 1-20 carbon atoms (for
example, N-mesylcarbamoyl, N-dodecylsulfonylcarbamoyl),
sulfamoyl of 1-30, preferably 1-20 carbon atoms (for example,
N-butylsulfamoyl, N-dodecylsulfamoyl, N-hexadecylsulfamoyl, N-3-(2,4-di-t-amylphenoxy)butylsulfamoyl,
N,N-diethylsulfamoyl),
alkoxy of 1-30, preferably 1-20 carbon atoms (for example,
methoxy, hexadecyloxy, i-propoxy), aryloxy of 6-20, preferably
6-10 carbon atoms (for example, phenoxy, 4-methoxyphenoxy, 3-t-butyl-4-hydroxyphenoxy,
naphthoxy), aryloxycarbonyl of 7-21,
preferably 7-11 carbon atoms (for example, phenoxycarbonyl),
N-acylsulfamoyl of 2-30, preferably 2-20 carbon atoms (for
example, N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl),
sulfonyl of 1-30, preferably 1-20 carbon atoms (for example,
methanesulfonyl, octanesulfonyl, 4-hydroxyphenylsulfonyl,
dodecanesulfonyl), alkoxycarbonylamino of 1-30, preferably 1-20
carbon atoms (for example, ethoxycarbonylamino), cyano,
nitro, carboxy, sulfo, alkylthio of 1-30, preferably 1-20
carbon atoms (for example, methylthio, dodecylthio,
dodecylcarbamoylmethylthio), ureido of 1-30, preferably 1-20
carbon atoms (for example, N-phenylureido, N-hexylureido),
aryl of 6-20, preferably 6-10 carbon atoms (for example,
phenyl, naphthyl, 4-methoxyphenyl), heterocyclic of 1-20,
preferably 1-10 carbon atoms (for example, a 3- through 12-,
preferably 5- or 6-membered, substituted or unsubstituted,
saturated or unsaturated, single or condensed heterocyclic
group such as 2-pyridyl, 3-pyrazolyl, 1-pyrrolyl, 2,4-dioxo-1,3-imidazolidine-1-yl,
2-benzoxazolyl, morpholino, indolyl),
a straight-chained, branched or cyclic, saturated or
unsaturated, alkyl of 1 to 30, preferably 1 to 20 carbon atoms
(for example, methyl, ethyl, i-propyl, cyclopropyl, t-pentyl,
t-octyl, cyclopentyl, t-butyl, sec-butyl, dodecyl, 2-hexyldecyl),
acyl of 1 to 30, preferably 2 to 20 carbon atoms
(for example, acetyl, benzoyl), acyloxy of 2 to 30, preferably
2 to 20 carbon atoms (for example, propanoyloxy,
tetradecanoyloxy), arylthio of 6 to 20, preferably 6 to 10
carbon atoms (for example, phenylthio, naphthylthio),
sulfamoylamino of 0 to 30, preferably 0 to 20 carbon atoms
(for example, N-butylsulfamoylamino, N-dodecylsulfamoylamino,
N-phenylsulfamoylamino), and N-sulfonylsulfamoylamino of 1 to
30, preferably 1 to 20 carbon atoms (for example, N-mesylsulfamoylamino,
N-ethanesulfonylsulfamoylamino, N-dodecanesulfonylsulfamoylamino,
N-hexanesulfonylsulfamoylamino).
The above substituent may further have a substituent,
which includes the above described group.
The preferable substituent is alkoxy, halogen,
alkoxycarbonyl, acyloxy, acylamino, sulfonyl, carbamoyl,
sulfamoyl, sulfonamido, nitro, alkyl or aryl.
The aryl group represented by R23 in Formula (Y-III)
represents a substituted or unsubstituted aryl group having 6-20,
preferably 6-10 carbon atoms. The example includes phenyl
or naphthyl.
The heterocyclic group represented by R23 in Formula (Y-III)
represents the same as the heterocyclic group represented
by R21 or R22 described above.
The aryl or heterocyclic group represented by R23 may have
a substituent. The substituent includes that denoted above in
R21. The substituent of R23 preferably represents halogen,
alkoxycarbonyl, sulfamoyl, carbamoyl, sulfonyl, N-sulfonylsulfamoyl,
sulfonylsulfamoyl, N-acylsulfamoyl, alkoxy, acylamino,
sulfonamido, and alkyl.
The especially preferable R23 is a phenyl group having at
least one substituent in an ortho position.
The group represented by Z3 in Formula (Y-III) represents
the same as the group denoted above in Z1 of Formula (Y-I), and
preferably the group represented by Formula (IV).
The especially preferable coupler represented by Formula
(Y-III) will be explained below.
The group represented by R21 in Formula (Y-III) represents
preferably an alkyl group, and especially preferably an alkyl
group having 1 to 10 carbon atoms.
The group represented by R23 in Formula (Y-III) represents
preferably an aromatic group, and especially preferably a
phenyl group having at least one substituent in an ortho
position. The substituent or preferable substituent R23 may
have is the same as the substituent denoted above in the aryl
group of R23.
The group represented by Z3 in Formula (Y-III) represents
preferably a 5 or 6-membered nitrogen-containing heterocyclic
group combining with a coupling position through a nitrogen
atom, an aryloxy group, a 5 or 6-membered heterocyclicoxy
group or a 5 or 6-membered heterocyclicthio group.
Of the couplers represented by Formula (Y-III), the
especially preferable is a coupler represented by the
following Formula (Y-IIIa), (Y-IIIb) or (Y-IIIc):
In Formula above, Z3 represents the same as the group
denoted above in Formula (Y-III), R24 represents an alkyl group,
R25 represents an alkyl group or an aromatic group, Ar
represents a phenyl group having at least one substituent in
an ortho position, X3 represents an organic residue necessary
to form a nitrogen-containing single or condensed heterocyclic
ring together with -C(R26)(R27) and -N=, X4 represents an
organic residue necessary to form a nitrogen-containing single
or condensed heterocyclic ring together with -C(R28)=C(R29) and
-N=, and R26, R27, R28 and R29 independently represent a hydrogen
atom or a substituent.
In Formula (Y-IIIa), (Y-IIIb) or (Y-IIIc), R24 through R29,
X3, X4, and Ar independently represents the same as the
corresponding group denoted above in Formula (Y-III). The
substituent of R26, R27, R28 and R29 includes the same as the
substituent that the nitrogen-containing heterocyclic group,
in which R21 and R22 described above combine with each other,
may have.
Of Formulas (Y-IIIa), (Y-IIIb) and (Y-IIIc), especially
preferable is a coupler represented by Formula (Y-IIIb) or (Y-IIIc).
The coupler represented by Formula (Y-III) may be a dimer
or a polymeride (for example, telomer or polymer) in which two
or more of the coupler combine with each other through a
divalent or polyvalent linkage in the group represented by R21,
R22, R23 or Z3.
The coupler represented by Formula (Y-III) is preferably
a non-diffusible coupler. The non-diffusible coupler herein
referred to means a coupler having a high molecular weight
group (a non-diffusible group) in its molecule to make the
coupler immobile in the layer containing the coupler. As the
non-diffusible group is used an alkyl group having 8-30,
preferably 10-20 carbon atoms or an aryl group having a
substituent of 4-20 carbon atoms. The non-diffusible coupler
may have the non-diffusible group in any position in the
coupler molecule and may have plural non-diffusible groups.
The yellow coupler represented by Formula (Y-III) can be
easily synthesized from starting materials commercially
available according to a conventional method disclosed in
Japanese Patent O.P.I. Publication Nos. 4-174428/1992, 4-184434/1992,
and 5-11416/1993.
The example of the yellow coupler represented by Formula
(Y-III) will be shown below, but is not limited thereto.
The yellow coupler used in the invention can be used in
an amount of 1.0 to 1.0 × 10-3 preferably 5.0 × 10-1 to 5.0
× 10-2, and more preferably 4.0 × 10-1 to 2.0 × 10-2 mol per mol
of silver halide.
The magenta coupler used in the invention is a magenta
coupler represented by the following Formula [M-I] or [M-II]:
wherein Ra, Rb, Rc and Rd independently represent a hydrogen
atom or a substitent, provided that two or more of Ra, Rb, Rc
and Rd are not simultaneously hydrogen atoms or two or more of
Ra, Rb and Rc combine with each other to form a ring; and X
represents a hydrogen atom or a group capable of being
released upon reaction with an oxidation product of a color
developing agent.
The magenta coupler represented by Formula [M-1] or [M-II]
will be explained below.
In Formula [M-1] or [M-II], Ra, Rb, Rc and Rd independently
represent a hydrogen atom or a substitent, provided that two
or more of Ra, Rb, Rc and Rd are not simultaneously hydrogen
atoms. Two or more of Ra, Rb and Rc may combine with each other
to form a ring. The substituent represented by Ra, Rb and Rc is
not specifically limited but the typical group includes alkyl,
aryl, cycloalkyl, heterocylic, halogen, hydroxy, alkoxy,
anilino, acylamino and sulfonamido, and represents preferably
alkyl. The substituent represented by Rd is not specifically
limited but the typical group includes alkyl, aryl, cycloalkyl,
heterocylic, halogen, anilino, acylamino, alkoxy, aryloxy,
heterocylic oxy, alkylthio, arylthio, sulfonyl, ureido,
carbamoyl and sulfamoyl.
X represents a hydrogen atom or a group capable of being
released upon reaction with an oxidation product of a color
developing agent, and the group includes a halogen atom, an
alkoxy group, an aryloxy group, an acyloxy group, an
sulfonyloxy group, an alkylthio group or an arylthio group,
represents preferably a halogen atom and more preferably a
chlorine atom.
The magenta coupler represented by Formula [M-1] is more
preferable of the above two.
The examples of the magenta coupler represented by
Formula [M-I] or [M-II] will be shown below, but are not
limited thereto.
The magenta coupler used in the invention is used in an
amount of preferably 1 × 10-3 to 5 mol per mol of silver halide,
and more preferably 1 × 10-2 to 1 mol per mol of silver halide.
The silver halide composition used in the invention is
preferably silver bromochloride containing 95 mol % of silver
chloride and containing substantially no silver iodide. The
silver bromochloride more preferably contains 97 mol % of
silver chloride, and still more preferably contain 98 to 99.9
mol % of silver chloride.
In order to obtain the silver halide emulsion in the
invention, a silver halide emulsion comprising a high
concentration of silver bromide is preferably used.
The above silver halide emulsion may be a silver halide
emulsion layer comprising epitaxial depositions, so-called a
core/shell emulsion, or a silver halide emulsion comprising in
admixture silver halide grains different in halide composition.
The silver halide grain composition may be varied continuously
or discontinuously. The portions in which silver bromide
comprises in a high concentration are especially preferable
corners of the surface of silver halide crystals.
The silver halide grains advantageously contain a heavy
metal ion. The heavy metal ion includes an ion of the eighth
to tenth group metal in the periodic table such as iron,
iridium, platinum, palladium, nickel, rhodium, osmium,
ruthenium or cobalt, the twelfth group metal in the periodic
table such as cadmium, zinc or mercury, lead, rhenium,
molybdenum, tungsten, gallium or chromium. Of these, an
iridium, platinum, ruthenium, gallium and osmium ion are
preferable. These metal ions are preferably added to a silver
halide emulsion in the form of their salts or complexes.
When the heavy metal ions form complexes, a ligand or
ligand ion includes a cyanide ion, a thiocyanate ion, a
cyanate ion, a chloride ion, a bromide ion, an iodide ion, a
nitrate ion, carbonyl and ammonia. Of these, a cyanide ion, a
thiocyanate ion, an isothiocyanate ion, a chloride ion and a
bromide ion are preferable.
In order to incorporate the heavy metal ion into a silver
halide emulsion, the heavy metal compound may be added before
or during silver halide grain formation or during physical
ripening after the silver halide grain formation. In order to
obtain a silver halide emulsion meeting the above described, a
solution containing the heavy metal compound and a halide in
admixture may be added continuously during silver halide grain
formation.
The addition amount of the heavy metal compound is
preferably 1 × 10-9 mol or more, more preferably 1 × 10-2 mol or
less, and especially preferably 1 × 10-8 to 1 × 10-5 mol based
on 1 mol of silver halide.
The silver halide grains may be of any shape. The
preferable example is a cube having (100) face as a crystal
surface. The silver halide grains having octahedron,
tetradecahedron or dodecahedron prepared according to the
descriptions described in U S Patent Nos. 4,183,756 and
4,225,666, Japanese Patent O.P.I. Publication Nos. 55-26589/1980
and Japanese Patent No. 55-42737/1980 may be used.
Further, the silver halide grains having twin plains may be
used.
The silver halide grains used in the invention is
preferably of single shape, but two or more kinds of
monodispersed silver halide emulsions are preferably contained
in the same silver halide emulsion layer.
The grain size of the silver halide emulsion is not
specifically limited, but is preferably 0.1 to 1.2 µm, and
more preferably 0.2 to 1.0.
This grain size can be measured using a projected area of
the grains or an approximate diameter. When the grains are
uniform, the grain size distribution can be considerably
correctly expressed in terms of a diameter or a projected area.
The silver halide grains are monodispersed grains having
a grain size distribution of a variation coefficient of
preferably 0.05 to 0.22, and more preferably 0.05 to 0.15.
Especially preferably, two or more kinds of the monodispersed
grains having a grain size distribution of a variation
coefficient of 0.15 to 0.22 are incorporated in the same
silver halide emulsion layer. Herein, a variation coefficient
shows the broadness of the grain size distribution, and is
defined as the following expression:
Variation coefficient = S/R,
wherein S represent a standard deviation of grain size
distribution; and R represent an average grain size.
Herein, when the grains are spherical, grain size
represents a diameter, and when the grains are cubic or not
spherical, grain size represents a diameter of a circle
corresponding to a projected area of the grains.
As an apparatus and a method for preparing silver halide
emulsions, various conventional ones known in the field can be
used.
The silver halide emulsions of the present invention may
be prepared through any of those including an acid process, a
neutral process and an ammonia process. Aforesaid grains may
be grown directly, or may be grown after producing seed grains.
A method for producing seed grains and a method for growing
them may be the same or different.
In addition, as a method to cause soluble silver salt and
a soluble halogenated salt to react, any of a normal
precipitation method, a reverse precipitation method, a
double-jet method and combination thereof are allowed. Of
them, those obtained through a double-jet method is desirable.
In addition, as one type of a double-jet method, pAg-controlled
double jet method described in Japanese Patent
O.P.I. Publication No. 48521/1979 can also be used.
In addition, an apparatus disclosed in Japanese Patent
O.P.I. Publication Nos. 92523/1982 and 92524/1982 wherein
water-soluble silver salt and water-soluble halogenated
compound salt aqueous solution is fed from an addition device
placed in an initial solution for reaction, an apparatus
disclosed in German Patent No. 2921164 wherein the
concentration of water-soluble silver salt and water-soluble
halogenated compound salt aqueous solution is continuously
changed for adding, or an apparatus disclosed in Japanese
Patent Publication No. 501776/1981 wherein grains are formed
while the distance between each silver halide grain is kept
constant by taking an initial solution outside of a reactor
and concentrating it by the use of a ultra filtration method
may be used.
In addition, if necessary, silver halide solvents such as
thioether may be used. In addition, compounds having a
mercapto group and compounds such as nitrogen-containing
heterocycles or sensitizing dyes may be used by adding during
formation of silver halide grains or after completion of
forming grains.
The silver halide emulsion may be sensitized by the use
of sensitizing methods using gold compounds and sensitizing
methods using chalcogen sensitizers in combination.
As chalcogen sensitizers applicable, sulfur sensitizers,
selenium sensitizers and tellurium sensitizers can be used.
Among them, sulfur sensitizers are desirable. As sulfur
sensitizers, thiosulfate, allylthiocarbamidothiourea,
allylisothiacyanate, cystine, p-toluenethiosulfonate salt,
rhodanine and an inorganic sulfur are cited.
The added amount of sulfur sensitizers is different
depending upon the kind of silver halide emulsion and intended
effects, preferably 5 × 10-10 to 5 × 10-5 mol per mol of silver
halide, and more preferably 5 × 10-8 to 3 × 10-5 mol per mol of
silver halide.
The gold sensitizers applicable can be added in the form
of gold chloride, silver chloride, gold sulfide, gold
thiosulfate and various gold complex. As compounds to be used
therein, dimethylrhodanine, thiocyanate, mercaptotetrazole and
mercaptotriazole are cited. The added amount of gold
compounds is different depending upon the kind of silver
halide emulsion, kind of compounds used and ripening
conditions, preferably 1 × 10-4 to 1 × 10-8 mol per mol of
silver halide, and more preferably 1 × 10-5 to 1 × 10-8 mol per
mol of silver halide.
As chemical sensitizing of the silver halide emulsion
reduction sensitizing may be carried out.
In the silver halide emulsion, conventional anti-foggants
and stabilizers can be used for preventing fog which occurs
during preparation step of a silver halide photographic light-sensitive
material, for reducing fluctuation in properties
during storage and preventing fog which occurs when being
developed. As an example of compounds used for such purposes,
compounds represented by formula (II) described in the lower
column on page 7 of Japanese Patent O.P.I.. Publication No.
146036/1990 are cited. Practical examples thereof are
compounds (IIa-1) through (IIa-8) and (IIb-1) through (IIb-7);
1-(3-methoxyphenyl)-5-mercaptotetrazole and 1-(4-ethoxyphenyl)-5-mercaptotetrazole
are cited.
These compounds are added, depending upon their purposes,
in a preparation step, in a chemical sensitization step, at
the end of chemical sensitization step and in a preparation
step for a coating solution. When chemical sensitization is
carried out in the presence of these compounds, the addition
amount of these compounds are preferably 1 × 10-5 to 5 × 10-4
per 1 mol of silver halide. When these compounds are added
after completion of chemical sensitization, the addition
amount of these compounds are preferably 1 × 10-6 to 1 × 10-2,
and more preferably 1 × 10-5 to 5 × 10-3 per 1 mol of silver
halide. When these compounds are added to the silver halide
emulsion during preparation of the coating solution, the
addition amount of these compounds are preferably 1 × 10-6 to 1
× 10-1, and more preferably 1 × 10-5 to 1 × 10-2 per 1 mol of
silver halide. When these compounds are added to coating
layers other than silver halide emulsion layers, the content
in the coating layer of these compounds are preferably 1 × 10-9
to 1 × 10-3 per m2 of the coating layer.
To the silver halide photographic light-sensitive
materials of the present invention, dyes having absorption
ability for various wavelength can be used for preventing
irradiation and halation. The conventional dyes can be used,
and, dyes AI-1 to AI-11 described in Japanese Patent O.P.I.
Publication No. 3-251840/1991, page 308 or dyes described in
Japanese Patent O.P.I. Publication No. 6-3770/1994 are
preferably used, as dyes having an absorption in the visible
light wavelength region. The dyes represented by the general
formula (I), (II) or (III) described in Japanese Patent O.P.I.
Publication No. 1-280750/1989, page 2, lower left side are
preferably used as infrared absorption dyes which have
preferable spectral characteristic, in view of no adverse
affect on photographic properties of photographic emulsions or
staining due to remaining color. The preferable examples
includes exemplified compounds (1) through (45) described in
Japanese Patent O.P.I. Publication No. 1-280750/1989, page 3,
lower left side through page 5, lower left side.
The addition amount of these dyes is preferably an amount
necessary to give a spectral reflective density at 680 nm of
preferably 0.7 to 3.0, and more preferably 0.8 to 3.0 in non-processed
light sensitive material, in view of sharpness
improvement.
The light sensitive material preferably contains a
brightening agent in view of white background improvement.
The brightening agent preferably includes the compound
represented by formula II described in Japanese Patent O.P.I.
Publication No. 2-2326520/1990.
The light sensitive material of the invention includes a
silver halide emulsion layer containing a yellow coupler, a
magenta coupler and a cyan coupler in combination, which is
sensitized in the specific range of 400 to 900 nm. The silver
halide emulsion layer comprises one or more sensitizing dyes.
The conventional spectral sensitizing dye can be used in
the silver halide emulsion in the invention. As a blue
sensitive sensitizing dye, dyes BS-1 through BS-8 described in
Japanese Patent O.P.I. Publication No. 3-251840/1991, page 28
are preferably used singly or in combination. As a green
sensitive sensitizing dye, dyes GS-1 through GS-5 described in
the same Japanese Patent O.P.I. Publication, page 28 are
preferably used, and as a red sensitive sensitizing dye, dyes
RS-1 through RS-8 described in the same Japanese Patent O.P.I.
Publication, page 29 are preferably used. When imagewise
exposure is carried out using an infrared light such as a
semi-conductor laser, an infrared sensitizing dye needs to be
used. In such case, as an infrared sensitive sensitizing dye,
dyes IRS-1 through IRS-11 described in Japanese Patent O.P.I.
Publication No. 4-285950/1992, pages 6 to 8 are preferably
used. In addition to these infrared, red, green and blue
sensitizing dyes, super sensitizers SS-1 through SS-9
described in Japanese Patent O.P.I. Publication No. 4-285950/1992,
pages 8 to 9 or compounds S-1 through S-17
described in Japanese Patent O.P.I. Publication No. 5-66515/1993,
pages 15 to 17 are preferably used in combination.
These sensitizing dyes are added in any step from silver
halide grain formation to completion of chemical sensitization.
The sensitizing dyes are added to the silver halide
emulsion in the form of solution, in which the dyes are
dissolved in water or a water-miscible organic solvent such as
methanol, ethanol, fluorinated alcohol, acetone or
dimethylformamide or their solid dispersion.
When a coupler or another organic compound is added to
the silver halide photographic light sensitive material in the
invention using an oil in water type emulsifying method, the
coupler is usually dissolved in a water-insoluble, high
boiling point organic solvent having a boiling point of 150°C
or more, a low boiling point and/or water soluble organic
solvent being optionally added, the solution is added to a
hydrophilic binder solution such as a gelatin solution, and
then emulsified using a surfactant. The emulsifying means
includes a stirrer, a homogenizer, a colloid mill, a flow-jet
mixer and a ultrasonic emulsifier. The process removing a low
boiling point organic solvent may be added during or after the
emulsification. As a high boiling point organic solvent used
for dissolving and emulsifying a coupler, phthalates such as
dioctyl phthalate, diisodecyl phthalate and dibutyl phthalate
or phosphates such as tricresyl phosphate and trioctyl
phosphate are preferable. The dielectric constant of the high
boiling point solvent is preferably 3.5 to 7.0. Two or more
high boiling point solvents can be used in combination.
Beside the method employing a high boiling point organic
solvent, a method is used in which a water insoluble, organic
solvent soluble polymer are dissolved in a high boiling point
organic solvent and optionally in a low boiling point and/or
water soluble organic solvent and emulsified in a hydrophilic
binder solution such as a gelatin solution, using a surfactant.
The water insoluble and organic solvent soluble polymer
includes poly(N-t-butylacrylamide).
The preferable surfactant used in dispersing photographic
additives or adjusting surface tension includes compounds
which have a hydrophobic group with 8 to 30 carbon atoms and a
sulfonic acid group or its salt group in a molecule. The
examples include compounds A-1 to A-11 described in Japanese
Patent O.P.I. Publication No. 62-26854/1987. The surfactant
having a fluorinated alkyl group is preferably used. The
dispersion solution of the compounds is usually added to a
coating solution containing a silver halide emulsion. The
time between their dispersion and their addition to the
coating solution or the time between their addition and the
coating is preferably shorter, each being preferably 10 hours
or less, more preferably 3 hours or less and still more
preferably 20 minutes or less.
The anti-fading additive is preferably added to each
coupler layer in the invention in order to prevent
discoloration of a formed dye image due to light, heat or
humidity. The especially preferable compounds include
phenylether compounds represented by formulas I to II
described in Japanese Patent O.P.I. Publication No. 2-66541/1990,
3 page, phenol compounds A-1 to A-11 represented
by formula IIIB described in Japanese Patent O.P.I.
Publication No. 3-174150/1987, amine compounds represented by
formula A described in Japanese Patent O.P.I. Publication No.
64-90445/1989, and metal complexes represented by formula XII,
XIII, XIV or XV described in Japanese Patent O.P.I.
Publication No. 62-182741/1987, which are preferable
especially for a magenta dye. The compounds represented by
formula I' described in Japanese Patent O.P.I. Publication No.
1-196049/1989 or compounds represented by formula II described
in Japanese Patent O.P.I. Publication No. 5-11417/1993 are
preferable for a yellow or cyan dye.
For the purpose of shifting an absorption wavelength of a
color dye compound (d-11) described on pages 33 and compound
(A'-1) described on pages 35 of Japanese Patent O.P.I.
Publication No. 4-114152/1992 can be used. Besides the
compounds, a fluorescent dye releasing compound disclosed in
US Patent No. 4,774,187 are used.
In the silver halide light sensitive material in the
invention, the compound capable of reacting with an oxidation
product of a color developing agent is preferably added to the
layers between the two silver halide emulsion layers to
prevent color mixture or to the silver halide emulsion layers
to restrain fog. The compounds include preferably
hydroquinone derivatives, more preferably dialkylhydroquinone
such as 2,5-di-t-octylhydroquinone. The especially preferable
compounds includes a compound represented by formula II
described in Japanese Patent O.P.I. Publication No. 4-133056/1992,
and compounds II-1 through II-14 on pages 13 and
14 and compound 1 described on page 17, of the same Japanese
Patent.
The UV absorber is preferably added to light sensitive
material in the invention to restrain static fog or to improve
light fastness of a formed dye image. The preferable UV
absorber includes benzotriazoles, and more preferably a
compound represented by formula III-3 described in Japanese
Patent O.P.I. Publication No. 1-250944/1989, a compound
represented by formula III described in Japanese Patent O.P.I.
Publication No. 64-66646/1989, UV-1L through UV-27L described
in Japanese Patent O.P.I. Publication No. 63-187240/1988, a
compound represented by formula I described in Japanese Patent
O.P.I. Publication No. 4-1633/1992, and a compound represented
by formula (I) or (II) described in Japanese Patent O.P.I.
Publication No. 5-165144/1993.
For the silver halide photographic light-sensitive
materials, it is advantageous to use gelatin as a binder. In
addition, other gelatins, gelatin derivatives, graft polymers
between gelatin and other polymers, proteins other than
gelatin, sugar derivatives, cellulose derivatives and
hydrophilic colloid such as synthetic hydrophilic polymers
including homopolymers or copolymers can also be used if
necessary.
The hardeners for a binder may be used. As hardeners,
vinylsulfone type hardeners and chlorotriazine type hardeners
are preferably used singly or in combination. The compounds
described in Japanese Patent O.P.I. Publication Nos. 61-249054/1986
and 61-245153/1986 are preferably used. The
antiseptic agent or anti-fungal described in Japanese Patent
O.P.I. Publication No. 3-157646/1991 are preferably added to
the colloid layer in order to prevent breed of bacilli or
fungi which adversely affects photographic properties or image
storage stability. The lubricant or matting agent described
in Japanese Patent O.P.I. Publication Nos. 6-118543/1994 and
2-73250/1990 is preferably added to a protective layer in
order to improve surface property of the non-processed or
processed light sensitive material.
After the surface of the support is provided with corona
discharge, UV ray irradiation and firing treatment if
necessary, a light-sensitive materials may be coated directly
or through subbing layers (one or two or more subbing layer in
order to improve adhesiveness, anti-static property stability
in sizing, anti-abrasion property, stiffness, anti-halation
property, abrasion property and/or other properties of the
surface of the support.)
When a light-sensitive materials using silver halide
emulsions is coated, a thickener may be used. As coating
methods, an extrusion coating method and a curtain coating
method is especially advantageous because they can coat 2 or
more layers concurrently.
An image forming method employing the color light
sensitive material of the invention includes a method
comprising printing on a photographic paper an image formed on
a negative, a method comprising converting an image to digital
information, displaying the image from the information on a
CRT (cathode ray tube), and then printing the displayed image
on a photographic paper, and a method comprising printing an
image on a photographic paper by scanning a laser light which
strength is varied based on digital information.
The invention is applied to preferably a light sensitive
material containing no color developing agent, and more
preferably a light sensitive material capable of forming an
image for direct appreciation. The example includes color
paper, color reversal paper, a light sensitive material
capable of forming a positive image, a light sensitive
material for display and a light sensitive material for color
proof. The invention is applied to especially preferably a
light sensitive material having a reflective support.
The aromatic primary amine color developing agents used
in the present invention include a conventional compound. The
examples will be shown below.
- CD-1) :
- N,N-Diethyl-p-phenylenediamine
- CD-2) :
- 2-Amino-5-diethylaminotoluene
- CD-3) :
- 2-Amino-5-(N-ethyl-N-laurylamino)toluene
- CD-4) :
- 4-(N-ethyl-N-β-hydroxyethyl)aminoaniline
- CD-5) :
- 2-Methyl-4-(N-ethyl-N-β-hydroxyethyl)aminoaniline
- CD-6) :
- 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline
- CD-7) :
- 4-amino-3-(β-methanesulfonamidoethyl)-N,N-diethylaniline
- CD-8) :
- N,N-Dimethyl-p-phenylenediamine
- CD-9) :
- 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline
- CD-10) :
- 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline
- CD-11) :
- 4-Amino-3-methyl-N-ethyl-N-(γ-hydroxypropyl)aniline
In the invention the pH of color developer may be any,
but preferably within the range of 9.5 to 13.0, and more
preferably within the range of 9.8 to 12.0 in view of rapid
processing.
The color developing temperature is preferably 35 to 70°C.
The temperature is preferably higher in view of shorter
processing time, but is preferably not so high in view of
processing stability. The developing is carried out at
preferably 37 to 60°C.
The color developing is carried out ordinarily in about
3.5 minutes. The color developing is carried out preferably
in not more than 40 seconds, and more preferably in not more
than 25 seconds, in view of rapid processing.
The color developer may contain conventional developing
components in addition to the above color developer. The
developing components include an alkaline agent having a
buffer effect, a chloride ion or a developing inhibitor such
as benzotriazole, a preservative and a chelating agent.
The light sensitive material is color developed, bleached
and then fixed. The bleaching may be carried out at the same
time as fixing. After the fixing, washing is usually carried
out. Stabilizing may be carried out instead of washing. The
developing apparatus using development of light sensitive
material may be a roller transport type which transports the
light sensitive material sandwiched between the rollers or an
endless belt type which transports the light sensitive
material fixed on the belt. As a processing method is used a
method of feeding light sensitive material and a processing
solution into a slit-shaped processing tank, a method of
processing light sensitive material jetting a processing
solution, a web method of contacting light sensitive material
with a carrier impregnated with a processing solution or a
method of processing light sensitive material with a viscous
processing solution. A large amount of light sensitive
materials are usually running processed using an automatic
processor. The replenishing amount of replenisher is
preferably small, and the replenishing is most preferably
carried out using replenisher tablets in view of environmental
property. The replenishing method is most preferably a method
described in Journal of Technical Disclosure 94-16935.
EXAMPLE
The invention will be explained according to the
following examples, but is not limited thereto.
The supports A through L were prepared according to the
following procedures, including the inventive supports.
[Preparation of supports]
Polyethylene (density of 0.95 g/cc, melt index (MI) of
8.0g/10 minutes) was extrusion coated on one side of white
paper base (basis weight of 175 g/m2, thickness of 180 µm) for
photographic print to form a back laminate layer. Thus, a
sheet substrate was prepared.
The following resin layer composition was coated on the
surface of the substrate opposite the back laminate layer.
Thus, supports A through L were prepared.
Support A:
Polyethylene (density of 0.92 g/cc, melt index (MI) of
5.0g/10 minutes) of 90 weight % and 10 weight % of titanium
oxide (anatase type) white pigment were kneaded and extrusion
coated on the surface of the substrate opposite the back
laminate layer to obtain a water proofing resin layer of 30
g/m2.
Support B:
The composition containing the following electron beam
hardenable organic compound and white pigment was prepared.
Polyester acrylate | 25 weight % |
Hexanediol diacrylate | 25 weight % |
Trimethylolpropane triacrylate | 15 weight % |
Titanium oxide (anatase type) | 40 weight % |
The above mixture was kneaded for 20 hours in a ball mill.
The above mixture was coated on the surface of the
substrate to obtain a coating amount after hardening of 30 g/m2.
The coated was irradiated with an electron beam from the back
laminate layer side at an accelerating voltage of 200 KV and
at an absorbed dose of 2 Mrad to obtain a hardened resin layer.
Support C:
Polyethylene (density of 0.95 g/cc, melt index (MI) of
8.0g/10 minutes) of 80 weight % and 20 weight % of titanium
oxide (anatase type) white pigment were kneaded and extrusion
coated on the surface of the substrate to obtain a water
proofing resin layer of 10 g/m2 for a resin layer (hereinafter
referred to as an inner resin layer) adjacent to the paper
base.
Next, polyethylene (density of 0.92 g/cc, melt index (MI)
of 5.0g/10 minutes) of 90 weight % and 10 weight % of titanium
oxide (anatase type) white pigment were kneaded and extrusion
coated on the inner resin layer to obtain a water proofing
resin layer of 20 g/m2 for a resin layer (hereinafter referred
to as an outer resin layer) closest to the silver halide
emulsion layer.
Support D:
Polyethylene terephthalate (intrinsic viscosity of 0.72
cc/g) of 75 weight % and 25 weight % of titanium oxide
(anatase type) white pigment were kneaded and extrusion coated
at 300°C on the surface of the substrate to obtain a water
proofing resin layer of 15 g/m2 for an inner resin layer.
Support D:
Next, polyethylene terephthalate (intrinsic viscosity of
0.72 cc/g) of 85 weight % and 15 weight % of titanium oxide
(anatase type) white pigment were kneaded and extrusion coated
at 300°C on the inner resin layer to obtain a water proofing
resin layer of 15 g/m2 for an outer resin layer.
Support E:
The following modified polyester was prepared.
The ester exchange reaction was carried out according to
a conventional method in a mixture of 100 weight % dimethyl
terephthalate, 14 weight % dimethyl naphthalene-2,6-dicarboxylate
and 80 weight % ethylene glycol. The resulting
mixture was mixed with 0.05 weight % antimony trioxide and
gradually heated and evacuated. Polymerization was carried
out at 280°C and 0.5 mmHg. Thus, modified polyester
containing a terephthalic acid and naphthalene-2,6-dicarboxylic
acid unit (90/10, mol ratio) was obtained. The
intrinsic viscosity of the resulting modified polyester was
0.7 cc/g.
The modified polyester of 78 weight % and 22 weight % of
titanium oxide (rutile type) white pigment were kneaded and
extrusion coated at 300°C on the surface of the substrate to
obtain a water proofing resin layer of 20 g/m2 for an inner
resin layer.
Next, polyethylene (density of 0.92 g/cc, melt index (MI)
of 5.0g/10 minutes) of 85 weight % and 10 weight % of titanium
oxide (anatase type) white pigment were kneaded and extrusion
coated on the inner resin layer to obtain a water proofing
resin layer of 10 g/m2 for an outer resin layer.
Support F:
The composition containing the following electron beam
hardenable organic compound and white pigment was prepared.
Urethane acrylate oligomer | 25 weight % |
Diethylene glycol diacrylate | 25 weight % |
Titanium oxide (anatase type) | 50 weight % |
The above mixture was kneaded for 20 hours in a ball mill.
The above mixture was coated on the surface of the
substrate to obtain a coating amount after hardening of 20 g/m2.
The coated was irradiated with an electron beam from the back
laminate layer side at an accelerating voltage of 200 KV and
at an absorbed dose of 2 Mrad to obtain a hardened resin layer
for an inner resin layer.
Next, polyethylene (density of 0.92 g/cc, melt index (MI)
of 5.0g/10 minutes) of 99.5 weight % and 10 weight % of
titanium oxide (anatase type) white pigment were kneaded and
extrusion coated on the inner resin layer to obtain a water
proofing resin layer of 10 g/m2 for an outer resin layer.
Support G:
The composition containing the following electron beam
hardenable organic compound and white pigment was prepared.
Urethane acrylate oligomer | 25 weight % |
Diethylene glycol diacrylate | 25 weight % |
Titanium oxide (anatase type) | 50 weight % |
The above mixture was kneaded for 20 hours in a ball mill.
The above mixture was coated on the surface of the
substrate to obtain a coating amount after hardening of 20 g/m2.
The coated was irradiated with an electron beam from the back
laminate layer side at an accelerating voltage of 200 KV and
at an absorbed dose of 2 Mrad to obtain a hardened resin layer
for an inner resin layer.
Next, polyethylene terephthalate (intrinsic viscosity of
0.72 cc/g) of 80 weight % and 20 weight % of titanium oxide
(anatase type) white pigment were kneaded and extrusion coated
at 300°C on the inner resin layer to obtain a water proofing
resin layer of 10 g/m2 for an outer resin layer.
Support H:
Polyethylene (density of 0.92 g/cc, melt index (MI) of
5.0g/10 minutes) of 85 weight % and 15 weight % of titanium
oxide (anatase type) white pigment were kneaded and extrusion
coated on the surface of the substrate to obtain a water
proofing resin layer of 20 g/m2 for an inner resin layer.
The composition containing the following electron beam
hardenable organic compound and white pigment was prepared.
Polyester acrylate | 35 weight % |
Hexanediol diacrylate | 35 weight % |
Trimethylolpropane triacrylate | 15 weight % |
Titanium oxide (anatase type) | 15 weight % |
The above mixture was kneaded for 20 hours in a ball mill.
The above mixture was coated on the surface of the
substrate to obtain a coating amount after hardening of 10 g/m2.
The coated was irradiated with an electron beam from the back
laminate layer side at an accelerating voltage of 200 KV and
at an absorbed dose of 2 Mrad to obtain a hardened resin layer
for an outer layer.
Support I:
Polyethylene terephthalate (intrinsic viscosity of 0.72
cc/g) of 70 weight % and 30 weight % of titanium oxide
(anatase type) white pigment were kneaded and extrusion coated
at 300°C on the surface of the substrate to obtain a water
proofing resin layer of 15 g/m2.
The composition containing the following electron beam
hardenable organic compound and white pigment was prepared.
Polyester acrylate | 30 weight % |
Hexanediol diacrylate | 30 weight %
|
Trimethylolpropane triacrylate | 25 weight % |
Titanium oxide (anatase type) | 15 weight % |
The above mixture was kneaded for 20 hours in a ball mill.
The above mixture was coated on the inner layer to obtain
a coating amount after hardening of 15 g/m2. The coated was
irradiated with an electron beam from the back laminate layer
side at an accelerating voltage of 200 KV and at an absorbed
dose of 2 Mrad to obtain a hardened resin layer for an outer
layer.
Support J:
Polyethylene (density of 0.92 g/cc, melt index (MI) of
5.0g/10 minutes) of 90 weight % and 10 weight % of titanium
oxide (anatase type) white pigment were kneaded and extrusion
coated on the surface of the substrate to obtain a water
proofing resin layer of 10 g/m2 for an inner resin layer.
The composition containing the following electron beam
hardenable organic compound and white pigment was prepared.
Urethane acrylate oligomer | 25 weight % |
Acrylate monomer | 25 weight % |
Titanium oxide (anatase type) | 50 weight % |
The above mixture was kneaded for 20 hours in a ball mill.
The above mixture was coated on the inner layer to obtain
a coating amount after hardening of 15 g/m2. The coated was
irradiated with an electron beam from the back laminate layer
side at an accelerating voltage of 200 KV and at an absorbed
dose of 2 Mrad to obtain a hardened resin layer for an
intermediate resin layer.
The composition containing the following electron beam
hardenable organic compound and white pigment was prepared.
Polyester acrylate | 35 weight % |
Hexanediol diacrylate | 35 weight % |
Trimethylolpropane triacrylate | 30 weight % |
The above mixture was coated on the intermediate resin
layer to obtain a coating amount after hardening of 5 g/m2.
The coated was irradiated with an electron beam from the back
laminate layer side at an accelerating voltage of 200 KV and
at an absorbed dose of 2 Mrad to obtain a hardened resin layer
for an outer layer.
Support K:
Polyethylene (density of 0.92 g/cc, melt index (MI) of
5.0g/10 minutes) of 85 weight % and 10 weight % of titanium
oxide (anatase type) white pigment were kneaded and extrusion
coated on the surface of the substrate to obtain a water
proofing resin layer of 10 g/m2 for an inner resin layer.
The composition containing the following electron beam
hardenable organic compound and white pigment was prepared.
Polyester acrylate | 25 weight %
|
Hexanediol diacrylate | 25 weight % |
Trimethylolpropane triacrylate | 10 weight % |
Titanium oxide (anatase type) | 40 weight % |
The above mixture was kneaded for 20 hours in a ball mill.
The above mixture was kneaded for 20 hours in a ball mill.
The above mixture was coated on the inner layer to obtain
a coating amount after hardening of 15 g/m2. The coated was
irradiated with an electron beam from the back laminate layer
side at an accelerating voltage of 150 KV and at an absorbed
dose of 2 Mrad to obtain a hardened resin layer for an
intermediate resin layer.
The composition containing the following electron beam
hardenable organic compound and white pigment was prepared.
Dipentaerythritol hexacrylate | 80 weight % |
Titanium oxide (anatase type) | 20 weight % |
The above mixture was kneaded for 20 hours in a ball mill.
The above mixture was coated on the intermediate layer to
obtain a coating amount after hardening of 5 g/m2. The coated
was irradiated with an electron beam from the back laminate
layer side at an accelerating voltage of 200 KV and at an
absorbed dose of 2 Mrad to obtain a hardened resin layer for
an outer resin layer.
The composition containing the following electron beam
hardenable organic compound and white pigment was prepared.
Polyester acrylate | 35 weight % |
Hexanediol diacrylate | 35 weight % |
Trimethylolpropane triacrylate | 30 weight % |
The above mixture was coated on the intermediate resin
layer to obtain a coating amount after hardening of 5 g/m2.
The coated was irradiated with an electron beam from the back
laminate layer side at an accelerating voltage of 200 KV and
at an absorbed dose of 2 Mrad to obtain a hardened resin layer
for an outer layer.
Support L:
Polyethylene terephthalate (intrinsic viscosity of 0.72
cc/g) of 75 weight % and 25 weight % of titanium oxide
(anatase type) white pigment were kneaded and extrusion coated
at 300°C on the surface of the substrate to obtain a water
proofing resin layer of 15 g/m2.
The obverse surface of the above obtained supports A
through L were corona discharged at an output electric current
of 2 A and coated with a gelatin subbing layer to obtain a
gelatin content of 40 mg/m2.
Example 1
Each layer having a composition as shown below was coated
on Support A to prepare a silver halide photographic light-sensitive
material. The coating solution was prepared as
follows:
First layer coating solution
To 23.4 g of yellow coupler (Y-1), 3.34 g of each of dye
image stabilizers (ST-1), (ST-2) and (ST-5), 0.34 g of anti-stain
agent (HQ-1), 5.0 g of image stabilizing agent A, 3.33 g
of high boiling organic solvent (DBP) and 1.67 g of high
boiling organic solvent (DNP), 60 cc of ethyl acetate were
added and dissolved. The solution was emulsified and
dispersed into 220 ml of a 10% aqueous gelatin solution
containing 7 ml of 20% surfactant (SU-1) by the use of a
supersonic homogenizer to prepare yellow coupler dispersion
solution. This dispersion solution was mixed with the blue
sensitive silver halide emulsion prepared according to the
following to prepare the first layer coating solution.
The 2nd layer through the 7th layer were prepared to have
a coating amount as shown in Tables 1 and 2 in the same manner
as in the above-mentioned coating solution for the 1st layer.
In addition, as a hardener, (H-1) and (H-2) were added.
As a coating aid, surfactants SU-2 and SU-3 were added to
adjust a surface tension. Further, F-1 was added in a total
amount of 0.04 g/m
2.
Layer | Structure | Added amount (g/m2) |
7th layer | Gelatin | 1.00 |
(Protective layer) | DIDP | 0.002 |
DBP | 0.002 |
Silicone dioxide | 0.003 |
6th layer | Gelatin | 0.40 |
(UV absorbing layer) | UV absorber (UV-1) | 0.12 |
UV absorber (UV-2) | 0.04 |
UV absorber (UV-3) | 0.16 |
Anti-stain Agent (HQ-5) | 0.04 |
PVP | 0.03 |
Anti-irradiation agent (AI-1) | 0.01 |
5th layer | Gelatin | 1.30 |
(Red sensitive layer) | Red sensitive silver bromochloride emulsion (Em-R) | 0.21 |
Cyan coupler (C-I-4) | 0.25 |
Cyan coupler (C-2') | 0.08 |
Dye image stabilizer (ST-1) | 0.10 |
Anti-stain agent (HQ-1) | 0.004 |
DBP | 0.10 |
DOP | 0.20 |
4th layer | Gelatin | 0.94 |
(UV absorbing layer) | UV absorber (UV-1) | 0.28 |
UV absorber (UV-2) | 0.09 |
UV absorber (UV-3) | 0.38 |
Anti-stain agent (HQ-5) | 0.10 |
Anti-irradiation agent (AI-1) | 0.02 |
3rd layer | Gelatin | 1.30 |
(Green sensitive layer) | Green sensitive silver halide emulsion (Em-G) | 0.14 |
Magenta coupler (M-1) | 0.20 |
Dye image stabilizer (ST-3) | 0.20 |
Dye image stabilizer (ST-4) | 0.17 |
DIDP | 0.13 |
DBP | 0.13 |
Anti-irradiation agent (AI-2) | 0.01 |
Layer | Structure | Added amount (g/m2) |
2nd layer | Gelatin | 1.20 |
(Intermediate layer) | Anti-stain agent (HQ-2) | 0.03 |
Anti-stain agent (HQ-3) | 0.03 |
Anti-stain agent (HQ-4) | 0.05 |
Anti-stain agent (HQ-5) | 0.23 |
DIDP | 0.04 |
DBP | 0.02 |
Fluorescent brightening agent (W-1) | 0.10 |
Anti-irradiation agent (AI-3) | 0.01 |
1st layer | Gelatin | 1.20 |
(Blue sensitive layer) | Blue sensitive silver halide emulsion (Em-B) | 0.26 |
Yellow coupler (Y-1) | 0.70 |
Dye image stabilizer (ST-1) | 0.10 |
Dye image stabilizer (ST-2) | 0.10 |
Dye image stabilizer (ST-5) | 0.10 |
Image stabilizer A | 0.15 |
Anti-stain agent (HQ-1) | 0.01 |
DBP | 0.10 |
DNP | 0.05 |
Support | Paper laminated with polyethylene (containing minute colorant) |
The added amount of the silver halide emulsion is
illustrated in terms of silver.
- SU-1 :
- Sodium tri-i-propylnaphthalene sulfonate
- SU-2 :
- Sodiumsulfo di(2-ethylhexyl)succinate
- SU-3 :
- Sodiumsulfo di(2,2,3,3,4,4,5,5-octafluoropentyl)succinate
- DBP :
- Dibutylphthalate
- DNP :
- Dinonylphthalate
- DOP :
- Dioctylphthalate
- DIDP :
- Diisodecylphthalate
- PVP :
- Polyvinylpyrrolidone
- H-1 :
- Tetrakis (vinylsulfonylmethyl)methane
- H-2 :
- Sodium 2,4-dichloro-6-hydroxy-s-triazine
- HQ-1 :
- 2,5-Di-t-octylhydroquinone
- HQ-2 :
- 2,5-Di-sec-dodecylhydroquinone
- HQ-3 :
- 2,5-Di-sec-tetradecylhydroquinone
- HQ-4 :
- 2-Sec-dodecyl-5-sec-tetradecylhydroquinone
- HQ-5 :
- 2,5-Di-(1,1-dimethyl-4-hexyloxycarbonyl)butyl-hydroquinone
- Image stabilizer A :
- p-Octylphenol
(Preparation of blue sensitive silver halide emulsion)
To 1 liter of a 2% aqueous gelatin solution kept at 40°C,
the following Solutions A and B were concurrently added
spending 30 minutes while pAg was controlled to 7.3 and pH was
controlled to 3.0, and then, the following Solution C and D
were concurrently added spending 180 minutes while pAg as
controlled to 8.0 and pH was controlled to 5.5. The pAg was
adjusted according to descriptions of Japanese Patent O.P.I.
Publication No. 59-45437/1984, and the pAg was controlled with
an aqueous sulfuric acid or sodium hydroxide solution.
(Solution A) |
Sodium chloride | 3.42 g |
Potassium bromide | 0.03 g |
Water was added to make a 200 ml solution.
(Solution B) |
Sodium nitrate | 10 g |
Water was added to make a 200 ml solution.
(Solution C) |
Sodium chloride | 102.7 g |
K2IrCl6 | 4 × 10-8 molAg |
K4Fe(CN)6 | 2 × 10-5 molAg |
Potassium bromide | 1.0 g |
Water was added to make a 600 ml solution.
(Solution D) |
Sodium nitrate | 300 g |
Water was added to make a 600 ml solution.
After the addition was completed, the solution was
subjected to desalting by the use of a 5% aqueous solution of
Demol N produced by Kao Atlas Co., Ltd. and a 20% aqueous
solution of magnesium sulfate. Then, the resulting solution
was mixed with an aqueous gelatin solution to prepare a mono-dispersed
cubic emulsion EMP-1 having an average grain size of
0.71 µm, a variation coefficient of grain size distribution of
0.07 and a silver chloride content of 99.5 mol%. The mono-dispersed
cubic emulsion EMP-1B was prepared in the same
manner as in EMP-1, except that the addition time of Solutions
A And B, and the addition time of Solutions C And D were
varied. The emulsion EMP-1B had an average grain size of 0.64
µm, a variation coefficient of grain size distribution of 0.07
and a silver chloride content of 99.5 mol%.
The above-mentioned emulsions EMP-1 and EMP-1B were
subjected to the most suitable sensitization employing the
following compounds. Then, the sensitized EMP-1 and EMP-1B
were mixed in a ratio (in terms of silver) of 1:1 to obtain a
blue sensitive silver halide emulsion (Em-B).
Sodium thiosulfate | 0.8 mg/mol Ag |
Chloroauric acid | 0.5 mg/mol Ag |
Stabilizer STAB-1 | 3 × 10-4 mol/mol Ag |
Stabilizer STAB-2 | 3 × 10-4 mol/mol Ag |
Stabilizer STAB-3 | 3 × 10-4 mol/mol Ag
|
Sensitizer BS-1 | 4 × 10-4 mol/mol Ag |
Sensitizer BS-2 | 1 × 10-4 mol/mol Ag |
(Preparation of green sensitive silver halide emulsion)
The mono-dispersed cubic emulsion EMP-2 was prepared in
the same manner as in EMP-1, except that the addition time of
Solutions A And B, and the addition time of Solutions C And D
were varied. The emulsion EMP-2 had an average grain size of
0.40 µm, a variation coefficient of 0.08 and a silver chloride
content of 99.5 mol%. The mono-dispersed cubic emulsion EMP-2B,
which had an average grain size of 0.38 µm, a variation
coefficient of 0.08 and a silver chloride content of 99.5 mol%,
was prepared in the same manner as in EMP-2.
The above-mentioned emulsions EMP-2 and EMP-2B were
subjected to the most suitable sensitization employing the
following compounds. Then, the sensitized EMP-2 and EMP-2B
were mixed in a ratio (in terms of silver) of 1:1 to obtain a
green sensitive silver halide emulsion (Em-G).
Sodium thiosulfate | 1.5 mg/mol Ag |
Chloroauric acid | 1.0 mg/mol Ag |
Stabilizer STAB-1 | 3 × 10-4 mol/mol Ag |
Stabilizer STAB-2 | 3 × 10-4 mol/mol Ag |
Stabilizer STAB-3 | 3 × 10-4 mol/mol Ag
|
Sensitizer GS-1 | 4 × 10-4 mol/mol Ag |
(Preparation of red sensitive silver halide emulsion)
The mono-dispersed cubic emulsion EMP-3 was prepared in
the same manner as in EMP-1, except that the addition time of
Solutions A And B, and the addition time of Solutions C And D
were varied. The emulsion EMP-3 had an average grain size of
0.40 µm, a variation coefficient of 0.08 and a silver chloride
content of 99.5 mol%. The mono-dispersed cubic emulsion EMP-3B,
which had an average grain size of 0.38 µm, a variation
coefficient of 0.08 and a silver chloride content of 99.5 mol%,
was prepared in the same manner as in EMP-3.
The above-mentioned emulsions EMP-3 and EMP-3B were
subjected to the most suitable sensitization employing the
following compounds. Then, the sensitized EMP-3 and EMP-3B
were mixed in a ratio (in terms of silver) of 1:1 to obtain a
red sensitive silver halide emulsion (Em-R).
Sodium thiosulfate | 1.8 mg/mol Ag |
Chloroauric acid | 2.0 mg/mol Ag |
Stabilizer STAB-1 | 3 × 10-4 mol/mol Ag |
Stabilizer STAB-2 | 3 × 10-4 mol/mol Ag |
Stabilizer STAB-3 | 3 × 10-4 mol/mol Ag
|
Sensitizer RS-1 | 1 × 10-4 mol/mol Ag |
Sensitizer RS-2 | 1 × 10-4 mol/mol Ag |
- STAB-1 :
- 1-(3-acetoamidophenyl)-5-mercaptotetrazole
- STAB-2 :
- 1-phenyl-5-mercaptotetrazole
- STAB-3 :
- 1-(4-ethoxyphenyl)-5-mercaptotetrazole
SS-1 was added to the red sensitive emulsion in an amount
of 2 × 10-3 mol/mol Ag.
Thus obtained sample was designated as sample 101.
Further, samples 301 through 317 were prepared in the same
manner as in sample 101, except that the support as shown in
Table 3 was used and cyan couplers as shown in Table 3 was
used instead of C-I-4. The resulting samples were evaluated
as follows:
<Evaluation of aging deterioration of image sharpness>
The samples were exposed to a red light through a
resolving power test chart, and processed according to the
following process. The density of the cyan image was measured
by means of a microdensitometer PDM-5D (produced by Konica
Corporation), and the value obtained by the following equation
was designated as sharpness of fresh samples.
Sharpness of fresh sample
=(Dmax - Dmin) at 3 lines/mm image/(Dmax - Dmin) at an image
of large area
wherein Dmax represents a maximum density, and Dmin represents
a minimum density.
The above evaluated fresh samples were stored for 14 days
at 75°C and at 60%RH, and then evaluated for sharpness in the
same manner as above.
The sharpness deterioration degree after the storage was
obtained by the following equation.
Sharpness deterioration degree = Sharpness after the 14
day storage (%) / Sharpness of fresh sample (%)
The closer to 1 this value, the less the sharpness
deterioration degree.
<Evaluation of aging deterioration of glossiness>
The samples were exposed to a white light and processed
according to the following process A. The surface glossiness
of the resulting black image was measured at an incident light
angle of 60° and at a light receiving angle 60° by means of a
glossmeter type VG-ID (produced by Nihon Denshoku Corporation),
and the value above obtained was designated as glossiness of
fresh samples.
The above glossiness evaluated fresh samples were stored
for 14 days at 75°C and at 60%RH, and then evaluated for
glossiness in the same manner as above.
The glossiness deterioration degree after the storage was
obtained by the following equation.
Glossiness deterioration degree = Glossiness after the 14 day storage (%)/Glossiness of fresh sample (%)
The closer to 1 this value, the less the Glossiness
deterioration degree.
<Evaluation of aging coloration of white background>
The unexposed samples were processed according to the
following process A, and were stored for one month at 40°C and
at 80%RH. The coloration (after-yellowing) of white
background of the resulting samples was visually evaluated.
The evaluation criteria are as follows:
A : Little coloration, extremely excellent
B : Slight coloration, excellent C :
Coloration is observed but no problem D : Much coloration, problematic.
<Color fading in the dark (cyan image)>
The samples were wedge exposed to a red light, and
processed according to the following process A. The density
of the above obtained cyan image was measured at portions
having a red light reflection density of 1.0, using a
densitometer PDA-65 (produced by Konica Corporation). The
processed samples were stored for 20 days at 85°C and at 60%RH,
and the blue density after the storage was measured in the
same manner as above. Thus, remaining rate (%) at initial
density 1.0 of the dye image was obtained and evaluated.
The above obtained samples were wedge exposed according
to a conventional method, and processed according to the
following developing processes.
Processing step | Processing temperature | Time | Amount of replenishing |
Color developing | 38.0 ± 0.3°C | 45 seconds | 80 cc/m2 |
Bleach-fixing | 35.0 ± 0.5°C | 45 seconds | 120 cc/m2 |
Stabilizing | 30 - 34°C | 60 seconds | 150 cc/m2 |
Drying | 60 - 80°C | 30 seconds |
The following shows a composition of a color developing
solution.
Color developer and color developer replenisher |
| Color developer | Color developer replenisher |
Pure water | 800 cc | 800 cc |
Triethylenediamine | 2 g | 3 g |
Diethylene glycol | 10 g | 10 g |
Potassium bromide | 0.01 g |
Potassium chloride | 3.5 g |
Potassium sulfite | 0.25 g | 0.5 g |
N-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate | 6.0 g | 10.0 g |
N,N-diethylhydroxylamine | 6.8 g | 6.0 g |
Triethanolamine | 10.0 g | 10.0 g |
Sodium diethylenetriamine pentaacetate | 2.0 g | 2.0 g |
Fluorescent brightening agent |
(4,4'-diaminostylbenzsulfonate derivative) | 2.0 g | 2.5 g |
Potassium carbonate | 30 g | 30 g |
Water was added to make 1 ℓ in total. The pH's of color
developer and color developer replenisher were regulated to
10.10 and 10.60, respectively.
Bleach fixer and bleach fixer replenisher |
Diethylenetriamine pentaacetate ferric ammonium dihydrate | 65 g |
Diethylenetriamine pentaacetate | 3 g |
Ammonium thiosulfate (70% aqueous solution) | 100 ml |
2-Amino-1,3,4-thiadiazole-2-thiol | 2.0 g |
Ammonium thiosulfate (40% aqueous solution) | 27.5 ml |
Water was added to make 1 liter in total, and pH was
regulated to 5.0 with potassium carbonate or glacial acetic
acid.
Stabilizer and stabilizer replenisher |
Orthophenylphenol | 1.0 g |
5-chloro-2-methyl-4-isothiazoline-3-on | 0.02 g |
2-methyl-4-isothiazoline-3-on | 0.02 g |
Diethyleneglycol | 1.0 g |
Fluorescent brightening agent (Thinopal SFP) | 2.0 g |
1-Hydroxyethylidene-1,1-diphosphonic acid | 1.8 g |
Bismuth chloride (45% aqueous solution) | 0.65 g |
Magnesium sulfate·heptahydrate | 0.2 g |
PVP | 1.0 g
|
Aqueous ammonia (25% aqueous solution of ammonium hydroxide) | 2.5 g |
Trisodium nitrilotriacetate | 1.5 g |
Water was added to make 1 liter in total, and pH was
regulated to 7.5 with sulfuric acid or aqueous ammonia.
The results are shown in Table 3.
As is apparent from the above, inventive samples are
superior to comparative samples.
Example 2
The processing was carried out in the same manner as in
Example 1, except that the processing was varied as follows:
Processing step | Processing temperature | Time | Amount of replenishing |
Color developing | 38.0 ± 0.3°C | 22 seconds | 81 ml |
Bleach-fixing | 35.0 ± 0.5°C | 22 seconds | 54 ml |
Stabilizing | 30 - 34°C | 25 seconds | 150 ml |
Drying | 60 - 80°C | 30 seconds |
The following shows a composition of a color developing
solution.
Color developer and color developer replenisher |
| Color developer | Color developer replenisher |
Pure water | 800 ml | 800 ml |
Diethylene glycol | 10 g | 10 g |
Potassium bromide | 0.01 g |
Potassium chloride | 3.5 g |
Potassium sulfite | 0.25 g | 0.5 g |
N-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate | 6.5 g | 10.5 g
|
N,N-diethylhydroxylamine | 3.5 g | 6.0 g |
N,N-bis(2-sulfoethyl)hydroxylamine | 3.5 g | 6.0 g |
Triethanolamine | 10.0 g | 10.0 g |
Sodium diethylenetriamine pentaacetate | 2.0 g | 2.0 g |
Fluorescent brightening agent (4,4'-diaminostylbenzsulfonate derivative) | 2.0 g | 2.5 g |
Potassium carbonate | 30 g | 30 g |
Water was added to make 1 ℓ in total. The pH's of color
developer and color developer replenisher were regulated to
10.10 and 10.60, respectively.
Bleach fixer and Bleach fixer replenisher |
| Bleach fixer | Bleach fixer replenisher |
Diethylenetriamine pentaacetate ferric ammonium dihydrate | 100 g | 50 g |
Diethylenetriamine pentaacetate | 3 g | 3 g |
Ammonium thiosulfate (70% aqueous solution) | 200 ml | 100 ml |
2-Amino-5-mercapto-1,3,4 -thiadiazole | 2.0 g | 1.0 g |
Ammonium sulfite (40% aqueous solution) | 50 ml | 25 ml |
Water was added to make 1 liter in total, and the pH's of
bleach fixer and bleach fixer replenisher was regulated to 7.0
and 6.5, respectively, with potassium carbonate or glacial
acetic acid.
Stabilizer and stabilizer replenisher |
Orthophenylphenol | 1.0 g |
5-chloro-2-methyl-4-isothiazoline-3-on | 0.02 g |
2-methyl-4-isothiazoline-3-on | 0.02 g |
Diethyleneglycol | 1.0 g |
Fluorescent brightening agent (Thinopal SFP) | 2.0 g |
1-hydroxyethylidene-1,1-diphosphonic acid | 1.8 g |
PVP | 1.0 g |
Aqueous ammonia (25% aqueous solution of ammonium hydroxide) | 2.5 g |
Ethylenediamine tetraacetic acid | 1.0 g |
Ammonium sulfite (40% aqueous solution) | 10 ml |
Water was added to make 1 liter in total, and pH was
regulated to 7.5 with sulfuric acid or aqueous ammonia.
The processing was conducted in the same manner as in
Example 1, and the effects of the invention were obtained.
Example 3
The running processing was conducted in the same manner
as in Example 2, except that an automatic processor NPS-868J
produced by Konica Corporation, a processing agent ECOJET-P
and processing name CPK-2-J1 were used. The same evaluation
as Example 1 was conducted, and it has proved that the effects
of the invention was obtained.