FIELD OF THE INVENTION
[0001] This invention relates to a silver halide photographic material and, more particularly,
to a silver halide photographic material which provides a negative image having high
contrast, high sensitivity, and satisfactory dot image quality.
BACKGROUND OF THE INVENTION
[0002] In the field of photomechanical systems, there is a demand for satisfactory image
reproducibility, stable processing solutions, and simplification of replenishment,
in order to cope with the recent diversity and complexity of printed materials.
[0003] In particular, originals in line work comprise photo-composed letters, hand-written
letters, illustrations, dot prints, etc. and thus contain images having different
densities and line widths. There has therefore been a demand to develop a process
camera, a photographic light-sensitive material and an image formation system which
would enable one to reproduce an original with high fidelity. In the photomechanical
reproduction of catalogues or large posters, enlargement or reduction of a dot print
is often required. When a dot print is enlarged in plate making, the line number per
inch is reduced and the dots are blurred. When a dot print is reduced, the line number
per inch increases, and the dots become finer. Accordingly, there has been a demand
for an image formation system having a broader latitude to maintain reproducibility
of halftone gradation.
[0004] A halogen lamp or a xenon lamp is employed as a light source for a process camera.
In order to obtain photographic sensitivity to these light sources, photographic materials
are usually subjected to orthochromatic sensitization. However, orthochromatic materials
are susceptible to influences of chromatic aberration of a lens and thus likely to
suffer from deterioration of image quality. The deterioration is conspicuous when
a xenon lamp is the light source.
[0005] Known systems to meet the demand for a broad latitude include one in which a lith
silver halide light-sensitive material comprising silver chlorobromide (containing
at least 50% of silver chloride) is processed with a hydroquinone developer having
an extremely low sulfite ion effective concentration (usually 0.1 mol/ℓ or less).
A line or dot image is thereby obtained having high contrast and high density in which
image areas and non-image areas are clearly distinguishable. With this method, however,
development is extremely unstable because of air oxidation due to the low sulfite
concentration of the developer. Hence, various efforts and devices are required to
stabilize the developing activity and, also, the processing speed is quite low, reducing
work efficiency.
[0006] There is therefore a demand for an image formation system which eliminates the image
formation instability associated with the above-described lith development system
and provides an ultrahigh contrast image by using a processing solution having a satisfactory
preservation stability. In this connection, a surface latent image type silver halide
photographic material has been proposed containing a specific acylhydrazine compound,
which is developed with a developing solution having a pH between 11.0 and 12.3 and
containing at least 0.15 mol/ℓ of a sulfite preservative. This material exhibits satisfactory
preservation stability to form an ultrahigh contrast negative image having a gamma
exceeding 10 as disclosed in U.S. Patents 4,166,742, 4,168,977, 4,221,857, 4,224,401,
4,243,739, 4,272,606, and 4,311,781. This new image formation system is characterized
in that silver iodobromide and silver chloroiodobromide as well as silver chlorobromide
are applicable thereto, whereas the conventional ultrahigh contrast image formation
systems are applicable only to photographic materials comprising silver chlorobromide
of a high silver chloride content.
[0007] While the above-described image formation system is excellent in sharpness of halftone
dots, processing stability, speed, and reproducibility of originals, the recent diversity
of prints has required further improvement in the reproduction of originals.
[0008] In an attempt to improve image quality, a method of using a redox compound having
a carbonyl group which is capable of imagewise releasing a developing inhibitor has
been suggested as disclosed, e.g., in JP-A-61-213847 (the term "JP-A" as used herein
means an "unexamined published Japanese patent application"). However, extension of
halftone gradation is insufficient, even with these compounds.
[0009] A light-sensitive material is therefore needed which, when developed with a stable
developer, provides a high contrast dot image whose tone is broadly controllable.
[0010] On the other hand, improvement in working efficiency in a lay-out process and dot-to-dot
work (a so-called contact work) has been attempted by performing the work in a brighter
environment. Accordingly, light-sensitive materials for plate making which can be
handled in an environment that may be called a bright room and exposure printers for
these materials have been developed.
[0011] The term "light-sensitive material for a bright room" as used herein means a light-sensitive
material which can be safely handled for a long time with a safe light which includes
no ultraviolet light component and has a wavelength of substantially 400 nm or more.
[0012] A light-sensitive material for a bright room which can be used in a lay-out process
and dot-do-dot work may be exposed to light while in intimate contact with a developed
film having a letter or dot image (original) to effect negative-positive conversion
or positive-positive conversion. The material must achieve negative-positive conversion
of a dot image or a line or letter image according to the dot area or the line or
letter image width of the original. Further, dot image tone or line or letter width
must be controllable. Light-sensitive materials for bright room contact work which
meet these requirements have been supplied.
[0013] However, when a conventional light-sensitive material for a bright room is used in
bright room dot-to-dot work in the highly technical image conversion technique called
super-imposed letter image formation by contact work, the resulting white letter
image has poor quality as compared to that obtained by the technique comprising dark
room dot-to-dot work using a conventional light-sensitive material for dark room contact
work.
[0014] The super-imposed letter image formation by contact work is illustrated in detail
by reference to the sole Figure of this specification. A film (2) having a letter
or line image shown in black (line original) and a film (4) having a dot image shown
in black (dot original ) are adhered to transparent or semi-transparent bases (1)
and (3), respectively. Bases (3) and (4) usually are polyethylene terephthalate films
having a thickness of about 100 µm. The line original and the dot original are superposed
on each other to make an original. The emulsion layer (shaded part) of a light-sensitive
material (5) for dot-to-dot work is brought into contact with the dot original (4)
and exposed to light. The exposed light-sensitive material is then subjected to development
to form a white line image within a dot image.
[0015] What is important in the above-described super-imposed letter image formation is
that the negative-positive conversion should be conducted precisely according to the
dot area of the dot original and the line width of the line original. As is apparent
from the Figure, the dot original (4) is in intimate contact with the emulsion layer
of the light-sensitive material (5). On the other hand, line original (2) is not directly
superposed on light-sensitive material (5), but base (3) and dot original (4) are
interposed therebetween. Therefore, when material (5) is exposed to light at an exposure
amount sufficient to effect negative-positive conversion faithfully to the dot original,
the exposure through the line original is through base (3) and dot original (4), causing
a reduction of the line width of the transparent line image. This causes deterioration
of the super-imposed letter image quality.
[0016] In order to solve the above-described problem, systems using a hydrazine derivative
have been proposed as disclosed in JP-A-62-80640, JP-A-62-235938, JP-A-235939, JP-A-63-104046,
JP-A-103235, JP-A-63-296031, JP-A-63-314541, and JP-A-64-13545, but sufficient effects
have not yet been obtained, leaving a need for further improvements.
SUMMARY OF THE INVENTION
[0017] One object of the present invention is to provide a photographic light-sensitive
material having a broad exposure latitude in line image formation, an ultrahigh contrast
(particularly having a gamma of 10 or more), and a high resolving power.
[0018] Another object of the present invention is to provide an ultrahigh contrast photographic
light-sensitive material which satisfactorily reproduces a line image with a high
background density (D
max).
[0019] A further object of the present invention is to provide an ultrahigh contrast photographic
light-sensitive material having a broad exposure latitude in dot image formation and
providing excellent dots having a high density, a sharp outline, and a uniform shape.
[0020] These and other objects of the present invention are accomplished by a silver halide
photographic material containing a compound represented by formula (I):

wherein R represents an aliphatic group, an aromatic group, or a heterocyclic group;
and Z represents an atom group necessary to form a nitrogen-containing heterocyclic
aromatic group.
BRIEF DESCRIPTION OF THE DRAWING
[0021]
The figure illustrates a structure at the time of exposure during the formation of
a super-imposed letter image by the contact work.
DETAILED DESCRIPTION OF THE INVENTION
[0022] In formula (I), the aliphatic group represented by R includes a straight chain, a
branched or cyclic alkyl, an alkenyl or an alkynyl group.
[0023] The aromatic group represented by R includes a monocyclic or a bicyclic aryl group,
e.g., phenyl and naphthyl groups.
[0024] The heterocyclic group (heterocyclic ring) represented by R includes a saturated
or unsaturated 3- to 10-membered hetero ring containing at least one nitrogen, oxygen
or sulfur atom. The hetero ring may be monocyclic or may form a condensed ring with
other aromatic or heterocyclic rings. The hetero ring preferably includes a 5- or
6-membered aromatic heterocyclic group, e.g., those containing a pyridyl group, an
imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a
pyrazolyl group, an isoquinolinyl group, a thiazolyl group, or a benzthiazolyl group.
[0025] Preferred as R is an aromatic group.
[0026] R may have a substituent. Examples of suitable substituents for R include an alkyl
group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an
aryl group, a substituted amino, an aryloxy group, a sulfamoyl group, a carbamoyl
group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group,
a hydroxyl group, a halogen atom, a cyano group, a sulfo group, a carboxyl group,
an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl
group, an acyloxy group, a carbonamido group, a sulfonamido group, a nitro group,
and a group represented by formula (II):

wherein R₃ represents an alkoxy group or an aryloxy group; L represents a single
bond, -O-, -S-, or

wherein R₄ represents a hydrogen atom, an aliphatic group, or an aromatic group;
and R₁ and R₂, which may be the same or different, each represents a hydrogen atom,
an aromatic group, an aliphatic group, or a heterocyclic group, or R₁ and R₂ are connected
to each other to form a ring.
[0027] R may comprise one or more of the groups represented by formula (II).
[0028] In formula (II), the aliphatic group represented by R₁ includes a straight chain,
branched or cyclic alkyl, alkenyl or alkynyl group.
[0029] The aromatic group represented by R₁ includes a monocyclic or bicyclic aryl group,
e.g., phenyl and naphthyl groups.
[0030] The heterocyclic group represented by R₁ includes a saturated or unsaturated 3- to
10-membered hetero ring containing at least one nitrogen, oxygen or sulfur atom. The
hetero ring may be monocyclic or may form a condensed ring with other aromatic or
heterocyclic rings. The hetero ring preferably includes a 5- or 6-membered aromatic
heterocyclic group, e.g., those containing a pyridyl group, an imidazolyl group, a
quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an
isoquinolinyl group, a thiazolyl group, or a benzthiazolyl group.
[0031] R₁ may have a substituent. Examples of suitable substituents for R₁ include an alkyl
group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, an
aryl group, a substituted amino, an acylamino group, a sulfonylamino group, a ureido
group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an
alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxyl
group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, an alkyloxycarbonyl
group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy
group, a carbonamido group, a sulfonamido group, and a nitro group. These substituents
may further be substituted and may be taken together, if possible, to form a ring.
[0032] The aliphatic group represented by R₂ includes a straight chain, branched or cyclic
alkyl, alkenyl or alkynyl group.
[0033] The aromatic group represented by R₂ includes a monocyclic or bicyclic aryl group,
e.g., a phenyl group.
[0034] R₂ may have a substituent, such as those mentioned as the substituent of R₁.
[0035] R₁ and R₂ may be taken together, if possible, to form a ring.
[0036] R₂ preferably represents a hydrogen atom.
[0037] Y preferably represents -

- or -SO₂-.
[0038] L preferably represents a single bond or

[0039] The aliphatic group represented by R₄ includes a straight chain, branched or cyclic
alkyl, alkenyl or alkynyl group.
[0040] The aromatic group represented by R₄ includes a monocyclic or bicyclic aryl group,
e.g., a phenyl group.
[0041] R₄ may have a substituent, such as those mentioned as the substituent of R₁.
[0042] R₄ preferably represents a hydrogen atom.
[0043] R in formula (I) may have a substituent containing a group which accelerates adsorption
onto silver halide (hereinafter referred to as an adsorption accelerating group).
[0044] The adsorption accelerating group with which R may be substituted is represented
by formula X(̵L′)̵
t, wherein X represents an adsorption accelerating group; L′ represents a divalent
linking group; and t represents 0 or 1.
[0045] Examples of suitable adsorption accelerating groups represented by X include a thioamido
group, a mercapto group, a group having a disulfide linkage, and a 5- or 6-membered
nitrogen-containing heterocyclic group.
[0046] The thioamido adsorption accelerating group represented by X is a divalent group
represented by
-

-amino- which may be a part of a cyclic structure or may be an acyclic thioamido group.
Useful thioamido adsorption accelerating groups can be selected from those disclosed
in U.S. Patents 4,030,925, 4,031,127, 4,080,207, 4,245,037, 4,255,511, 4,266,013,
and 4,276,364, and
Research Disclosure, Vol. 151, No. 15162 (Nov., 1976) and
ibid, Vol. 176, No. 17626 (Dec., 1978).
[0047] Specific examples of acyclic thioamido groups are thioureido, thiourethane and dithiocarbamic
ester groups. Specific examples of cyclic thioamido groups are 4-thiazoline-2-thione,
4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione,
1,2,4-triazoline-3-thione, 1,3,4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione,
benzimidazoline-2-thione, benzoxazoline-2-thione, and benzothiazoline-2-thione. These
groups may further be substituted.
[0048] The mercapto group represented by X includes an aliphatic mercapto group, an aromatic
mercapto group, and a heterocyclic mercapto group. A heterocyclic mercapto group wherein
the carbon atom to which -SH is bonded is adjacent to a nitrogen atom is the same
as a cyclic thioamido group, being a tautomeric isomer of such a heterocyclic mercapto
group. Specific examples of such a group are the same as those mentioned above with
respect to the cyclic thioamido group.
[0049] The 5- or 6-membered nitrogen-containing heterocyclic group represented by X includes
those composed of at least one carbon atom and at least one atom selected from nitrogen,
oxygen, sulfur atoms. Examples of preferred groups are benzotriazole, triazole, tetrazole,
indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole,
thiadiazole, oxadiazole, and triazine. These groups may further be substituted with
an appropriate substituent. Substituents include those mentioned with respect to the
substituents of R.
[0050] Preferred among the groups represented by X are a cyclic thioamido group (i.e., a
mercapto-substituted nitrogen-containing heterocyclic group, e.g., 2-mercaptothiadiazole,
3-mercapto-1,2,4-triazole, 5-mercaptotetrazole, 2-mercapto-1,3,4-oxadiazole, and
2-mercaptobenzoxazole groups) and a nitrogen-containing heterocyclic group (e.g.,
benzotriazole, benzimidazole, and indazole groups).
[0051] X(̵L′)̵
t may have two or more substituents which may be the same or different.
[0052] The divalent linking group as represented by L′ is an atom or atom group containing
at least one of carbon, nitrogen, sulfur, and oxygen atoms. Examples of L′ include
an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-,
-S-, -NH-, -N=, -CO-, -SO₂-, etc., either alone or in combination thereof. These groups
may have a substituent.
[0053] Specific examples of the linking group L, are -CONH-, -NHCONH-, -SO₂NH-, -COO-, -NHCOO-,

[0054] These divalent groups may further have a substituent selected from those mentioned
with respect to the substituents of R.
[0055] R may further contain a ballast group commonly employed in immobile photographic
additives, such as couplers.
[0056] A ballast group is an organic group which has a molecular weight sufficient to substantially
prevent the compound represented by formula (I) from diffusing into other layers or
processing solutions. It comprises at least one of an alkyl group, an aryl group,
a heterocyclic group, an ether group, a thioether group, an amido group, a ureido
group, a urethane group, a sulfonamido group, etc. Preferred ballast groups are those
having a substituted benzene ring, and more preferably those having a benzene ring
substituted with a branched alkyl group.
[0057] In formula (I), the heterocyclic aromatic group represented by

is preferably a substituted or unsubstituted 5- or 6-membered ring, either monocyclic
or fused to other rings.
[0058] Typical examples of preferred heterocyclic aromatic rings include, for example, pyrrole,
imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, 2-thioxathiazoline,
2-oxathiazoline, 2-thioxaoxazoline, 2-oxaoxazoline, 2-thioxamidazoline, 2-oxaimidazoline,
1,2-oxazoline-5-thione, 1,2-thiazoline-5-thione, 1,2-oxazoline-5-one, 1,2-thiozoline-
5-one, 5-thioxatetrazoline, 2-thioxa-1,3,4-thiadiazoline, 2-oxa-1,3,4-thiadiazoline,
2-thioxa-1,3,4-oxadiazoline, 2-oxa-1,3,4-oxadiazoline, 3-thioxa-1,2,4-triazoline,
2-thioxadihydropyridine, 2-oxadihydropyridine, 4-thioxadihydropyridine, 4-oxadihydropyridine,
isoindole, indole, indazole, benzimidazole, 2-thioxabenzimidazole, 2-oxabenzimidazole,
benzoxazoline-2-thione, azaindenes, benzooxazoline-2-one, benzothiazoline-2-thione,
benzothiazoline-2-one, carbamole, purine, carboline, phenoxazine, phenothiazine,
and condensed rings at various condensing positions such as pyrazolopyridines, pyrazolopyrimidines,
pyrazolopyrroles, pyrazolooxazoles, pyrazolothiazoles, pyrazolotriazoles, imidazolopyridines,
imidazolopyrimidines, imidazolopyrroles, imidazoloimidazoles, imidazolooxazoles, imidazolothiazoles,
imidazolotriazoles, etc.
[0059] More preferred examples of the heterocyclic aromatic rings include, pyrrole, imidazole,
pyrazole, triazole, tetrazole, 2-thioxathiazoline, 2-thioxaoxazoline, indole, indazole,
benzimidazole, 2-thioxa-1,3,4-thiadiazoline, azaindene, 5-thioxa-tetrazoline, 2-thioxa-1,3,4-oxadiazoline,
3-thioxa-1,2,4-triazoline, and condensed rings at various condensing positions such
as pyrazolopyridines, pyrazoloimidazoles, etc. Most preferred examples of the heterocyclic
aromatic rings include a ring containing pyrazole nucleus such as pyrazole, indazole,
pyrazolopyridine, etc.
[0060] These heterocyclic groups may have a substituent. Suitable substituents include a
mercapto group, a nitro group, a carboxyl group, a sulfo group, a phosphono group,
a hydroxyl group, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group,
an aryl group, an alkoxyl group, an aryloxy group, an amino group, an acylamino group,
a sulfonylamino group, a ureido group, a urethane group, a sulfamoyl group, a carbamoyl
group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group,
a halogen atom, a cyano group, an aryl oxycarbonyl group, an acyl group, an alkoxycarbonyl
group, an acyloxy group, a carbonamido group, a sulfonamido group, and a phosphonamido
group. The heterocyclic group is preferably substituted with one or more nitro groups.
[0062] The compounds of formula (I) according to the present invention can be synthesized
by reacting a compound of formula (IV) and a corresponding bydrazine compound of formula
(V), generally, in an aprotic solvent (e.g., tetrahydrofuran, dimethylformamide, dimethyl
sulfoxide, acetonitrile) according to the reaction scheme shown below:

wherein Z and R are as defined above.
[0063] The compound of formula (IV) can be prepared by reacting a compound of formula

with trichloromethyl chloroformate in the presence of a base. Alternatively, in the
above reaction scheme, a compound of formula

(wherein Z is as defined above) can be used instead of the compound of formula (IV).
[0064] The hydrazine compounds of formula (V) are commercially available or can be generally
prepared by acid hydrolysis of a corresponding known formylhydrazine compound. Also,
the compounds of formula (V) can be effectively prepared by forming a protected hydrazine
using a carbobenzoxy group (CBZ group) or a t-butoxycarbonyl group (Boc group) as
a protective group for hydrazine and removing the protective group according to a
conventional method well known in the field of peptide chemistry.
[0065] Typical synthesis examples of the compounds of formula (I) are described below.
SYNTHESIS EXAMPLE 1
Synthesis of Compound 4
[0066] To a mixture of 32.6 g of 5-nitroindazole and 500 mℓ of tetrahydrofuran was added
dropwise 6.0 mℓ of trichloromethyl chloroformate over 30 minutes under ice-cooling.
Then, 28 mℓ of triethylamine was added dropwise thereto over 30 minutes. The mixture
was warmed to room temperature and stirred for 2 hours at that temperature. After
ice-cooling, 15.9 g of p-tolylhydrazine hydrochloride was added to the mixture, and
14 mℓ of triethylamine was then slowly added thereto. The temperature of the mixture
was returned to room temperature, and the mixture was stirred for a whole day. Any
insoluble matter was separated by filtration, and the volatile component was removed
by distillation under reduced pressure. The residue was purified by silica gel column
chromatography to obtain 18.7 g of Compound 4. The chemical structure of the product
was confirmed by NMR spectrum, IR spectrum, and elemental analysis.
SYNTHESIS EXAMPLE 2
Synthesis of Compound 17
[0067] Four milliliters of concentrated hydrochloric acid was added to a mixture of 11.7
g of a compound of formula:

and 100 mℓ of methanol, followed by stirring at room temperature for 3 hours. The
volatile component was removed by distillation under reduced pressure. The resulting
product was reacted with carbonyl-di-(6-nitroindazole) which was synthesized in the
same manner as in Synthesis Example 1 in tetrahydrofuran in the presence of triethylamine,
and the reaction mixture was purified by column chromatography to obtain 6.2 g of
Compound 17. The chemical structure of the product was confirmed by NMR spectrum,
IR spectrum, and elemental analysis.
SYNTHESIS EXAMPLE 3
Synthesis of Compound 8
[0068] Four milliliters of concentrated hydrochloric acid was added to a mixture of 10 g
of a compound of formula:

and 80 ml of ethanol, followed by stirring at room temperature for 24 hours. The
volatile component was distilled off under reduced pressure. Then, 100 ml of dimethylformamide,
7.9 g of a compound having the formula

(prepared by reacting p-nitrophenyl (chlorocarbonate with 6-nitroindazole in the
presence of DBU) and 3.4 ml of triethylamine were added to the residue, and the resulting
mixture was stirred for 24 hours in a nitrogen atmosphere. The reaction mixture was
poured into 1N hydrochloric acid, and the resulting mixture was extracted with ethyl
acetate. The extract was dried, concentrated, purified by silica gel column chromatography
to obtain 8.4 g of the desired compound. The chemical structure of the product was
confirmed by NMR spectrum, IR absorption spectrum and elementary analysis.
[0069] The compound of formula (I) is incorporated into a photographic emulsion layer or
a hydrophilic colloidal layer by dissolving the compound in water or a water-miscible
organic solvent (if desired, an alkali hydroxide or a tertiary amine may be added
to form a salt) and adding the solution to a hydrophilic colloid solution (e.g., a
silver halide emulsion, a gelatin aqueous solution, etc.). If desired, the pH of the
resulting mixture may be adjusted by addition of an acid or an alkali.
[0070] The compounds of the present invention can be used either individually or in a combination
of two or more thereof. The amount to be added is selected appropriately depending
on the properties of a silver halide emulsion with which it is to be combined, preferably
ranging from 1 × 10⁻⁵ to 5 × 10⁻² mol, more preferably from 2 × 10⁻⁵ to 1 × 10⁻² mol,
per mol of silver halide.
[0071] It is preferable that the compound of formula (I) according to the present invention
be used in combination with a hydrazine compound represented by formula (III):

wherein R₃₁ represents an aliphatic group or an aromatic group; R₃₂ represents a
hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an
amino group, a carbamoyl group, or an oxycarbonyl group; G₁ represents a carbonyl
group, a sulfonyl group, a sulfoxy group, a

group, or an iminomethylene group; A₁ and A₂ each represents a hydrogen atom, or
one of A₁ and A₂ represents a hydrogen atom and the other represent a substituted
or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl
group, or a substituted or unsubstituted acyl group.
[0072] In formula (III), the aliphatic group represented by R₃₁ preferably includes those
containing from 1 to 30 carbon atoms, and more preferably a straight chain, branched
or cyclic alkyl group having from 1 to 20 carbon atoms. The branched alkyl group may
be cyclized to form a saturated heterocyclic ring containing at least one hetero atom.
Further, the alkyl group may be substituted with an aryl group, an alkoxy group, a
sulfoxy group, a sulfonamido group, a carbonamido group, etc.
[0073] The aromatic group represented by R₃₁ is a monocyclic or bicyclic aryl group or an
unsaturated heterocyclic group. The unsaturated heterocyclic group may be condensed
with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples of the
aromatic group include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine
ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring,
a benzimidazole ring, a thiazole ring, and a benzothiazole ring, with those containing
a benzene ring being particularly preferred.
[0074] R₃₁ preferably represents an aryl group.
[0075] The aryl group or unsaturated heterocyclic group represented by R₃₁ may have a substituent
typically including an alkyl group, an aralkyl group, an alkenyl group, an alkynyl
group, an alkoxyl group, an aryl group, a substituted amino group, an acylamino group,
a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl
group, a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group,
a sulfinyl group, a hydroxyl group, a halogen atom, a cyano group, a sulfo group,
an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl
group, an acyloxy group, a carbonamido group, a sulfonamido group, a carboxyl group,
a phosphoric acid amide group, a diacylamino group, and an imido group. Preferred
among these substituents are a straight chain, branched or cyclic alkyl group (more
preferably, having from 1 to 20 carbon atoms , an aralkyl group (more preferably a
monocyclic or bicyclic group having from 1 to 3 carbon atoms in the alkyl moiety thereof),
an alkoxyl group (more preferably, having from 1 to 20 carbon atoms), a substituted
amino group (more preferably, an amino group substituted with an alkyl group having
from 1 to 20 carbon atoms), an acylamino group (more preferably, having from 2 to
30 carbon atoms), a sulfonamido group (more preferably, having from 1 to 30 carbon
atoms), a ureido group (more preferably, having from 1 to 30 carbon atoms), and a
phosphoric acid amide group (more preferably having from 1 to 30 carbon atoms).
[0076] The alkyl group represented by R₃₂ in formula (III) preferably contains from 1 to
4 carbon atoms and may have a substituent, e.g., a halogen atom, a cyano group, a
carboxyl group, a sulfo group, an alkoxyl group, a phenyl group, or a sulfonyl group.
[0077] The aryl group represented by R₃₂ preferably includes a monocyclic or bicyclic aryl
group, such as those containing a benzene ring. The aryl group may have a substituent,
e.g., a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group,
or a sulfonyl group.
[0078] The alkoxy group represented by R₃₂ preferably contains from 1 to 8 carbon atoms
and may be substituted with a halogen atom, an aryl group, etc.
[0079] The aryloxy group represented by R₃₂ is preferably monocyclic and may be substituted
with a halogen atom, etc.
[0080] The amino group represented by R₃₂ may be substituted with an alkyl group, a halogen
atom, a cyano group, a nitro group, a carboxyl group, etc. Preferred among the amino
groups are an unsubstituted amino group, an alkylamino group having from 1 to 10 carbon
atoms, and an arylamino group.
[0081] The carbamoyl group represented by R₃₂ may be substituted with an alkyl group, a
halogen atom, a cyano group, a carboxyl group, etc. Preferred among the carbamoyl
groups are an unsubstituted carbamoyl group, an alkylcarbamoyl group having from 1
to 10 carbon atoms, and an arylcarbamoyl group.
[0082] The oxycarbonyl group represented by R₃₂ preferably includes an alkoxycarbonyl group
having from 1 to 10 carbon atoms and an aryloxycarbonyl group. The hydroxycarbonyl
group may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro
group, etc.
[0083] Where G₁ is a carbonyl group, R₃₂ preferably represents a hydrogen atom, an alkyl
group (e.g., methyl, trifluoromethyl, 3-hydroxypropyl, 3-methanesulfonamidopropyl,
and phenylsulfonylmethyl), an aralkyl group (e.g., o-hydroxybenzyl), or an aryl group
(e.g., phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, and 4-methanesulfonylphenyl),
and more preferably a hydrogen atom.
[0084] Where G₁ is a sulfonyl group, R₃₂ preferably represents an alkyl group (e.g., methyl),
an aralkyl group (e.g., o-hydroxyphenylmethyl), an aryl group (e.g., phenyl), or a
substituted amino group (e.g., dimethylamino).
[0085] Where G₁ is a sulfoxy group, R₃₂ preferably represents a cyanobenzyl group or a methylthiobenzyl
group.
[0086] Where G₁ is

R₃₂ preferably represents a methoxy group, an ethoxy group, a butoxy group, a phenoxy
group, or a phenyl group, and more preferably a phenoxy group.
[0087] Where G₁ is an N-substituted or unsubstituted iminomethylene group, R₃₂ preferably
represents a methyl group, an ethyl group, or a substituted or unsubstituted phenyl
group.
[0088] Groups mentioned above as the substituents of R₃₁ are also appropriate substituents
for the R₃₂ groups.
[0089] G₁ preferably represents a carbonyl group.
[0090] R₃₂ may be a group which makes the G₁-R₃₂ moiety split off from the remainder of
formula (III) to induce cyclization producing a cyclic structure containing the -G₁-R₃₂
moiety. More specifically, this separation is effected by a cleaving agent represented
by formula (a):
-R₃₃ - Z₃₁ (a)
wherein Z₃₁ represents a group which nucleophilically attacks G₁ to split the G₁-R₃₃-Z₃₁
moiety from the remainder of formula (a); R₃₃ represents a group obtained by removing
one hydrogen atom from R₃₂; and R₃₃ and Z₃₁ form a cyclic structure together with
G₁ upon nucleophilic attack of Z₃₁ on G₁.
[0091] More specifically, when the hydrazine compound of formula (III) undergoes a reaction
such as oxidation to produce an intermediate represented by formula R₃₁-N=N-G₁-R₃₃-Z₃₁,
Z₃₁ easily reacts nucleophilically with G₁ to separate R₃₁-N=N from G₁. The Z₃₁ group
includes a functional group capable of directly reacting with G₁, e.g., OH, SH, NHR₃₄
(wherein R₃₄ represents a hydrogen atom, an alkyl group, an aryl group, -COR₃₅, or
-SO₂R₃₅, wherein R₃₅ represents a hydrogen atom, an alkyl group, an aryl group, a
heterocyclic group, etc.), -COOH (these functional groups may be temporarily protected
so as to release the functional group upon hydrolysis with an alkali, etc.), or a
functional group which becomes capable of reacting with G₁ on reacting with a nucleophilic
agent (e.g., a hydroxide ion and a sulfite ion), such as

(wherein R₃₆ and R₃₇ each represents a hydrogen atom, an alkyl group, an alkenyl
group, an aryl group, or a heterocyclic group).
[0092] The ring formed by G₁, R₃₃, and Z₃₁ is preferably a 5- or 6-membered ring.
[0093] Preferred among the groups represented by formula (a) are those represented by either
formula (b) or (c):

wherein Z₃₁ is as defined above; R
b¹, R
b², R
b³, and R
b⁴, which may be the same or different, each represents a hydrogen atom, an alkyl group
(preferably having from 1 to 12 carbon atoms , an alkenyl group (preferably having
from 2 to 12 carbon atoms), an aryl group (preferably having from 6 to 12 carbon atoms),
etc.; B represents an atom group necessary to form a substituted or unsubstituted
5- or 6-membered ring; m and n each represents 0 or 1; and (n+m) is 1 or 2.
[0094] In formula (b), the 5- or 6-membered ring formed by B includes a cyclohexene, cycloheptene,
benzene, naphthalene, pyridine, or quinoline ring.
[0095] Formula (c) is shown below:

wherein Z₃₁ is as defined above; R
c¹ and R
c², which may be the same or different, each represents a hydrogen atom, an alkyl group,
an alkenyl group, an aryl group, a halogen atom, etc.; R
c³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group;
p represents 0 or 1; q represents an integer of from 1 to 4; R
c¹, R
c², and R
c³ may be taken together to form a ring provided that Z₃₁ is capable of intramolecular
nucleophilic attack on G₁.
[0096] R
c¹ and R
c² each preferably represents a hydrogen atom, a halogen atom, or an alkyl group, and
R
c³ preferably represents an alkyl group or an aryl group.
[0097] q preferably represents an integer of from 1 to 3. When q is 1, p represents 1; when
q is 2, p represents 0 or 1; when q is 3, p represents 0 or 1; and when q is 2 or
3, the CR
c¹R
c² moieties may be the same or different.
[0098] In formula (III), A₁ and A₂ each represents a hydrogen atom, an alkylsulfonyl or
arylsulfonyl group having not more than 20 carbon atoms (preferably a phenylsulfonyl
group or a phenylsulfonyl group which is substituted so that the sum of the Hammett's
σ values is -0.5 or more), an acyl group having not more than 20 carbon atoms (preferably
a benzoyl group, which is substituted so that the sum of the Hammett substituent group
constants (σ values) is -0.5 or more), or a straight chain, branched or cyclic substituted
or unsubstituted aliphatic acyl group (the substituent includes a halogen atom, an
ether group, a sulfonamido group, a carbonamido group, a hydroxyl group, a carboxyl
group, and a sulfo group)).
[0099] A₁ and A₂ each preferably represents a hydrogen atom.
[0100] R₃₁ or R₃₂ in formula (III) may contain a ballast group commonly employed in immobile
photographic additives such as couplers. A ballast group is a group which contains
at least 8 carbon atoms and is relatively inert to photographic characteristics. Suitable
ballast groups are selected from an alkyl group, an alkoxyl group, a phenyl group,
an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc.
[0101] R₃₁ or R₃₂ may further contain a group which accelerates adsorption to silver halide
grain. Examples of such an adsorption accelerating group are described in U.S. Patents
4,385,108 and 4,459,347, JP-A-59-195233, JP-A-59-200231, JP-A-59-201045, JP-A-59-201046,
JP-A-59-201047, JP-A-59-201048, JP-A-59-201049, JP-A-61-170733, JP-A-61-270744, JP-A-62-948,
and Japanese Patent Application Nos. 62-67508, 62-67501 and 62-67510, including a
thiourea group, a heterocyclic thioamido group, a mercapto heterocyclic group, and
a triazole group.
[0103] The compound of formula (I) and the hydrazine compound of formula (III) can be incorporated
into the same layer or different layers.
[0104] In the present invention, the hydrazine compound represented by formula (III) is
preferably incorporated into silver halide emulsion layer(s), but can be incorporated
into other non-light sensitive hydrophilic colloid layers (e.g., a protecting layer,
an intermediate layer, a filter layer, an anti-halation layer, etc.). More specifically,
when the hydrazine compound is water-soluble, an aqueous solution of the hydrazine
compound or, when the hydrazine compound is difficultly soluble in water, a solution
of the hydrazine compound in a water-miscible organic solvent such as alcohols, esters,
ketones, etc. can be added to hydrophilic colloid layers. When the solution of hydrazine
compound is added to a silver halide emulsion layer, it may be added at any time between
the initial stage of chemical ripening and the coating of the emulsion, but it is
preferably added to the emulsion after completion of the chemical ripening and prior
to the coating. In particular, it is most preferable to add the compound to a coating
composition prepared for coating.
[0105] It is desirable that the optimum amount of the compound represented by formula (III)
to be used is selected depending upon the grain size of the silver halide emulsion,
the halogen composition, the method and the degree of chemical sensitization, the
relationship between the layer in which the compound is incorporated and the silver
halide emulsin layers, the type of antifoggant used. Test methods for selecting the
optimum amount of the compound are well known in the art. Generally, the compound
of formula (III) can be preferably used in an amount ranging from 1×10⁻⁶ to 1×10⁻⁴
mol, more preferably from 1×10⁻⁵ to 4×10⁻² mol, per mol of the silver halide.
[0106] In addition to the above-described hydrazine compound of formula (III), the compound
of formula (I) of the present invention can also be combined with other known hydrazine
compounds. Examples of usable hydrazine compounds are described in
Research Disclosure, Item 23516, p. 346 (Nov., 1983) and references cited therein, U. S. Patents 4,080,207,
4,269,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347, 4,560,638, and 4,478,928, British
Patent 2,011,391B, JP-A-60-179734, JP-A-62-270948, JP-A-63-29751, JP-A-61-170733,
JP-A-61-270744, JP-A-62-948, EP 217,310, JP-A-63-32538, JP-A-63-104047, JP-A-63-121838,
JP-A-63-129337, JP-A-63-223744, and JP-A-64-10233, U.S. Patent 4,686,167, JP-A-62-178246,
JP-A-63-234244, JP-A-63-234245, JP-A-63-234246, JP-A-63-294552, JP-A-63-306438,
JP-A-64-90439, JP-A-01-276128, JP-A-01-283548, JP-A-01-280747, JP-A-01-283549, JP-A-01-285940,
and Japanese Patent Application Nos. 63-147339, 63-179760, 63-229163, 1-18377, 1-18378,
1-18379, 1-15755, 1-16814, 1-40792, 1-42615, and 1-42626.
[0107] When combined with the hydrazine compound of formula (III) and a negatively working
emulsion, the compound of formula (I) provides a negative image of high contrast.
On the other hand, the compound of formula (I) of the present invention may be used
in combination with an internal latent image type silver halide emulsion. It is preferable
to take advantage of a combination of the compound of formula (I) with the hydrazine
compound of formula (III) and a negatively working emulsion in obtaining a negative
image of high contrast.
[0108] When the photographic material of the present invention is used in the formation
of a high contrast negative image, fine silver halide grains having a mean grain size
of 0.7 µm or less and particularly 0.5 µm or less are preferably employed. Grain size
distribution is not essentially limited, but a mono-dispersion is preferred. The terminology
"mono-dispersion" means a dispersion in which at least 95% by weight or number of
grains fall within a size range of ±40% of a mean grain size.
[0109] The silver halide grains which can be used in the practice of the present invention
to provide a photographic emulsion may have a regular crystal form, such as an octahedral
form, a rhombic dodecahedral form, and a tetradecahedral form; or an irregular crystal
form, such as a spherical form and a plate-like form; or a composite form of these
crystal forms.
[0110] Individual silver halide grains may have a uniform phase therethrough or different
phases between the inside and the surface layer thereof.
[0111] During silver halide grain formation or physical ripening of the grains, a cadmium
salt, a sulfite salt, a lead salt, a thallium salt, a rhodium salt or a complex thereof,
an iridium salt or a complex thereof, etc. may be present in the system.
[0112] The silver halide emulsion used in the present invention can be any of silver chloride,
silver bromide, silver iodobromide and silver iodochlorobromide emulsions.
[0113] The silver halide emulsion which can be used in the present invention may or may
not be chemically sensitized. Chemical sensitization of silver halide emulsions can
be carried out by any of the known techniques, such as sulfur sensitization, reduction
sensitization, and noble metal sensitization, either alone or in combination thereof.
[0114] Among the noble metal sensitization techniques, typical is gold sensitization using
a gold compound, usually a gold complex. Complexes of noble metals other than gold,
e.g., platinum, palladium and rhodium, may also be employed. Specific examples of
these noble metal compounds are described in U.S. Patent 2,448,060 and British Patent
618,016.
[0115] Sulfur sensitization is effected by using a sulfur compound contained in gelatin
as well as various sulfur compounds, e.g., thiosulfates, thioureas, thiazoles, and
rhodanines.
[0116] In the above-described silver halide emulsion preparation, it is preferable to add
an iridium salt or a rhodium salt before completion of physical ripening, particularly
during grain formation.
[0117] To obtain an increased maximum density (D
max), a silver halide emulsion layer of the light-sensitive material according to the
present invention preferably contains two mono-dispersed emulsions differing in mean
grain size as taught in JP-A-61-223734 and JP-A-62-90646. In this case, the mono-dispersed
grains of smaller size is preferably chemically sensitized, more preferably sulfur
sensitized. The mono-dispersed grains of larger size may or may not be chemically
sensitized. In general, since the latter grains (larger grains) tend to cause black
pepper when chemically sensitized, no chemical sensitization is conducted on the larger
grains. In cases where chemical sensitization of the larger grains is carried out,
it is preferable to conduct a light chemical sensitization so as not to cause black
pepper. Light chemical sensitization can be performed by reducing the time or temperature
of chemical sensitization or the amount of chemical sensitizer which is added, as
compared with the chemical sensitization of the smaller grains. The difference in
sensitivity between the larger size mono-dispersed emulsion and the smaller size mono-dispersed
emulsion is not particularly limited, but the difference as expressed in terms of
ΔlogE is usually from 0.1 to 1.0, preferably from 0.2 to 0.7. The larger size mono-dispersed
emulsion preferably has a higher logE. The terminology "sensitivity" as herein referred
to means sensitivity of a sample prepared by coating each emulsion containing the
hydrazine compound on a support and processing the coated material with a developer
having a pH of from 10.5 to 12.3 and containing at least 0.15 mol/ℓ of a sulfite ion.
The grain size of the smaller size mono-dispersed grains is not more than 90%, preferably
not more than 80%, of the mean grain size of the larger size mono-dispersed grains.
The mean grain size of the silver halide emulsion grains preferably is from 0.02 to
1.0 µm, and more preferably from 0.1 to 0.5 µm, and the mean grain size of each of
the larger size grains and the smaller size grains is preferably within this range.
[0118] Where two or more emulsions differing in grain size are employed, the smaller size
mono-dispersed emulsion is preferably coated to a silver coverage of from 40 to 90%
by weight, more preferably from 50 to 80% by weight, based on the total silver coverage.
[0119] The mono-dispersed emulsions having different grain sizes may be incorporated into
the same layer or separate layers. In the latter case, it is preferable to incorporate
the larger size emulsion into an upper layer, and the smaller size emulsion into a
lower layer, respectively.
[0120] The total silver coverage preferably is from 1 to 8 g per m².
[0121] For the purpose of increasing sensitivity, the light-sensitive material according
to the present invention can contain sensitizing dyes, such as cyanine dyes and merocyanine
dyes, as described in JP-A-55-52050, pp. 45-53. The sensitizing dyes may be used either
individually or in combination of two or more thereof. A combination of sensitizing
dyes is frequently used for supersensitization. The emulsion may also contain, in
addition to the sensitizing dye, a dye which has no spectral sensitization activity
per se but exhibits supersensitization activity or a substance which does not substantially
absorb visible light but exhibits supersensitization activity. Examples of useful
sensitizing dyes, dyes exhibiting supersensitization, and substances exhibiting supersensitization
are described in
Research Disclosure, Vol. 176, No. 17643, p. 23, IV-J (Dec., 1978).
[0122] To prevent fog during preparation, preservation or photographic processing of the
light-sensitive material or to stabilize photographic properties, various compounds
can be introduced into the light-sensitive material of the present invention. Such
compounds include: azoles, such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles,
bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles,
aminotriazoles, benzothiazoles, and nitrobenzotriazoles; mercaptopyrimidines; mercaptotriazines;
thioketo compounds, such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes
(especially 4-hydroxy-substituted (1,3,3a,7)-tetraazaindenes), and pentaazaindenes;
benzenethiosulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides, and
many other compounds known as antifoggants or stabilizers. Preferred among them are
benzotriazoles (e.g., 5-methylbenzotriazole) and nitroindazoles (e.g., 5-nitroindazole).
If desired, these compounds may be introduced into processing solutions.
[0123] Examples of a development accelerator or a nucleation infectious development accelerator
which can be suitably used in the present invention include the compounds disclosed
in JP-A-53-77616, JP-A-54-37732, JP-A-53-137133, JP-A-60-140340, and JP-A-60-14959
as well as various compounds containing a nitrogen or sulfur atom.
[0124] These accelerators are used usually in an amount of from 1.0 × 10⁻³ to 0.5 g/mz,
and preferably from 5.0 × 10⁻³ to 0.1 g/m², although the optimum amount varies depending
on the kind of accelerator.
[0125] The photographic emulsion layers or other hydrophilic colloidal layers may contain
a desensitizer.
[0126] An organic desensitizer which can be used in the present invention is specified by
its polarographic half wave potential, i.e., an oxidation-reduction potential determined
by polarography. That is, it is specified to have a positive sum of a polarographic
anode potential and a cathode potential. Determination of the oxidation-reduction
potential by polarography is described, e.g., in U.S. Patent 3,501,307. Organic desensitizers
containing at least one water-soluble group, e.g., a sulfo group and a carboxyl group,
are preferred. The water-soluble group may be in the form of a salt with an organic
base, e.g., ammonia, pyridine, triethylamine, piperidine, and morpholine, or an alkali
metal, e.g., sodium and potassium.
[0127] Preferred as organic desensitizers are those described in JP-A-63-133145, pp. 55-72
(especially the compounds represented by formulae (III) to (V)).
[0128] The organic desensitizer is added to silver halide emulsions in an amount usually
of from 1.0 × 10⁻⁸ to 1.0 × 10⁻⁴ mol/m², and preferably of from 1.0 × 10⁻⁷ to 1.0
× 10⁻⁵ mol/m².
[0129] The emulsion layers or other hydrophilic colloidal layers may contain a water-soluble
dye as a filter dye or for the purpose of preventing irradiation or for other purposes.
Filter dyes to be used are dyes for reducing photographic sensitivity, preferably
ultraviolet absorbents having a spectral absorption maximum in the intrinsic sensitivity
region of silver halide and dyes showing substantial light absorption in the region
mainly in the range of from 380 to 600 nm which are used for improving safety against
safelight in handling light-sensitive materials for bright room.
[0130] These dyes are preferably fixed by a mordant to an emulsion layer or a light-insensitive
hydrophilic colloidal layer farther from the support than the silver halide emulsion
layer, depending on the purpose.
[0131] The ultraviolet absorbent is usually used in an amount of from 1 × 10⁻² to 1 g/m²,
and preferably from 50 to 500 mg/m², though the amount varies somewhat depending on
the absorbent's molar extinction coefficient.
[0132] The ultraviolet absorbent can be incorporated into a coating composition in the form
of a solution in an appropriate solvent, e.g., water, an alcohol (e.g., methanol,
ethanol and propanol), acetone, methyl cellosolve, or a mixture thereof.
[0133] Suitable ultraviolet absorbents which can be used include aryl-substituted benzotriazole
compounds, 4-thiazolidone compounds, benzophenone compounds, cinnamic ester compounds,
butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers. Specific
examples of these ultraviolet absorbents are described in U.S. Patents 3,533,794,
3,314,794, and 3,352,681, JP-A-46-2784, U.S. Patents 3,705,805, 3,707,375, 4,045,229,
3,700,455, and 3,499,762, and West German Patent Publication 1,547,863.
[0134] Filter dyes which can be used include oxonol dyes, hemioxonol dyes, styryl dyes,
merocyanine dyes, cyanine dyes, and azo dyes. To minimize color remaining after development
processing, water-soluble dyes or dyes which are discolored with an alkali or a sulfite
ion are preferred.
[0135] Specific examples of suitable filter dyes include pyrazolone oxonol dyes described
in U.S. Patent 2,274,782, diarylazo dyes described in U.S. Patent 2,956,879, styryl
dyes and butadienyl dyes described in U.S. Patents 3,423,207 and 3,384,487, merocyanine
dyes described in U.S. Patent 2,527,583, merocyanine dyes and oxonol dyes described
in U.S. Patents 3,486,897, 3,652,284, and 3,718,472, enaminohemioxonol dyes described
in U.S. Patent 3,976,661, and dyes described in British Patents 584,609 and 1,177,429,
JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, and U.S. Patents 2,533,472, 3,148,187,
3,177,078, 3,247,127, 3,540,887, 3,575,704, and 3,653,905.
[0136] The dyes are added to a coating composition for a light-insensitive hydrophilic colloidal
layer in the form of a solution in an appropriate solvent, e.g., water, an alcohol
(e.g., methanol, ethanol, and propanol), acetone, methyl cellosolve, or a mixture
thereof.
[0137] A suitable amount of the dye to be added is usually from 1 × 10⁻³ to 1 g/m², and
particularly from 1 × 10⁻³ to 0.5 g/m².
[0138] The photographic emulsion layers or other hydrophilic colloidal layers may contain
an organic or inorganic hardening agent, such as chromates, aldehydes (e.g., formaldehyde
and glutaraldehyde), N-methylol compounds (e.g., dimethylolurea), active vinyl compounds
(e.g., 1,3,5-triacryloyl-hexahydro-s-triazine and 1,3-vinylsulfonyl-2-propanol),
active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), and mucohalogenic
acids, either individually or in combination thereof.
[0139] The photographic emulsion layers or other hydrophilic colloidal layers may further
contain various surface active agents for the purpose of a coating aid, static charge
prevention, improvement of slip properties, emulsification and dispersion aid, prevention
of blocking, and improvement of photographic characteristics (e.g., acceleration of
development, increase of contrast, and increase of sensitivity). Surface active agents
which are particularly useful in the present invention are polyalkylene oxides having
a molecular weight of 600 or more as disclosed in JP-B-58-9412 (the term "JP-B" as
used herein means an "examined published Japanese patent application"). For particular
use as an antistatic agent, fluorine-containing surface active agents are preferred.
For the details of fluorine-containing surface active agents, reference can be made
to U.S. Patent 4,201,586, JP-A-60-80849, and JP-A-59-74554.
[0140] For the purpose of preventing blocking, the photographic emulsion layers or other
hydrophilic colloidal layers may furthermore contain a matting agent, such as silica,
magnesium oxide, and polymethyl methacrylate.
[0141] For the purpose of improving dimensional stability and the like, the photographic
emulsions can contain a dispersion of a water-insoluble or sparingly water-soluble
synthetic polymer. Examples of such a polymer include homopolymers or copolymers of
an alkyl (meth)acrylate, an alkoxyalkyl (meth)acrylate, and glycidyl (meth)acrylate
and copolymers comprising these monomers and acrylic acid, methacrylic acid, etc.
[0142] The silver halide emulsion layers and other layers preferably contain a compound
having an acid radical. Examples of suitable acid radical-containing compounds are
organic acids, e.g., salicylic acid, acetic acid, and ascorbic acid; and homopolymers
or copolymers comprising an acid monomer, e.g., acrylic acid, maleic acid, and phthalic
acid. With respect to these compounds, reference can be made to JP-A-61-223834, JP-A-61-228437,
JP-A-62-25745, and JP-A-62-55642. Preferred among them are ascorbic acid as a low-molecular
compound and an aqueous latex of a copolymer comprising an acid monomer (e.g., acrylic
acid) and a crosslinking monomer having at least two unsaturated groups (e.g., divinylbenzene)
as a high-molecular compound.
[0143] The silver halide light-sensitive material of the present invention can be processed
with a stable developing solution to obtain ultrahigh contrast and high sensitivity.
There is no need to use conventional infectious developers or highly alkaline developers
having a pH of nearly 13 as described in U.S. Patent 2,419,975.
[0144] More specifically, a negative image having sufficiently high contrast can be obtained
by processing the silver halide light-sensitive material of the present invention
with a developer containing 0.15 mol/ℓ or more of a sulfite ion as a preservative
and having a pH between 10.5 and 12.3, particularly between 11.0 and 12.0.
[0145] The developing agent which can be used in the developer is not particularly restricted.
In view of the ease of obtaining satisfactory dot quality, the developer preferably
contains dihydroxybenzenes. A combination of a dihydroxybenzene and a 1-phenyl-3-pyrazolidone
or a combination of a dihydroxybenzene and a p-aminophenol is sometimes employed.
The developing agent is preferably used in an amount of from 0.05 to 0.8 mol/ℓ. When
using a combination of a dihydroxybenzene and a 1-phenyl-3-pyrazolidone or a p-aminophenol,
the former is preferably used in an amount of from 0.05 to 0.5 mol/ℓ, and the latter
is preferably used in an amount of not more than 0.06 mol/ℓ.
[0146] Sulfites which can be used in the developer as a preservative include sodium sulfite,
potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium
metabisulfite, and formaldehyde sodium bisulfite. The sulfite is preferably used in
a concentration of 0.4 mol/ℓ or higher, and particularly 0.5 mol/ℓ or higher.
[0147] The developer may contain the compound disclosed in JP-A-56-24347 as a silver stain
inhibitor; the compound disclosed in JP-A-61-267759 as a dissolving aid; and the compound
disclosed in JP-A-60-93433 or the compound disclosed in JP-A-62-186259 as a pH buffer.
[0148] As stated above, the compound represented by formula (I) can be used in combination
with an internal latent image type silver halide emulsion as well as with a negatively
working emulsion. When combined with an internal latent image type silver halide emulsion,
the compound of formula (I) is preferably introduced into an internal latent image
type silver halide emulsion layer. It may also be introduced into a hydrophilic colloidal
layer adjacent to the internal latent image type silver halide emulsion layer. Hydrophilic
colloidal layers in which the compound of formula (I) can be introduced are not limited
in function, provided that the nucleating agent is not inhibited from diffusing to
silver halide grains. Possible layers include color material layers, intermediate
layers, filter layers, protective layers, and antihalation layers.
[0149] The amount of the compound of formula (I) to be used varies depending on characteristics
of silver halide emulsions used, the chemical structure of the nucleating agent, and
conditions of development and is therefore subject to wide variation. From a practical
standpoint, a useful amount is from about 0.005 mg to 500 mg, and preferably from
about 0.01 to 100 mg, per mol of silver in an internal latent image type silver halide
emulsion. When the compound is incorporated into a hydrophilic colloidal layer adjacent
to the emulsion layer, it is used in the same amount as recited above per mol of silver
contained in the same area of the internal latent image type emulsion layer. The terminology
"internal latent image type silver halide emulsion" as used herein is defined in JP-A-61-170733,
p. 10, upper column and British Patent 2,089,057, pp. 18-20.
[0150] Reference can be made to European Patent No. 267482, p. 10, line 57 to p. 11, line
36 with respect to preferred internal latent image type emulsions for use in the present
invention and in
ibid, p. 11, line 37 to p. 11, line 56 with respect to preferred silver halide grains
therefor.
[0151] The internal latent image type emulsion may be spectrally sensitized to blue light
of a relatively longer wavelength, green light, red light or infrared light by using
sensitizing dyes. Sensitizing dyes to be used include cyanine dyes, merocyanine dyes,
complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes,
hemicyanine dyes, oxonol dyes, and hemioxonol dyes. These sensitizing dyes include,
for example, cyanine dyes or merocyanine dyes described in JP-A-59-40638, JP-A-59-40636,
and JP-A-59-38739.
[0152] The light-sensitive material according to the present invention can contain dye image-forming
couplers (i.e., cyan, magenta, and yellow couplers as color materials. It is also
possible to develop the light-sensitive material with a developer containing the dye
image-forming couplers.
[0153] Specific examples of the cyan, magenta and yellow couplers which can be used in this
invention are described in
Research Disclosure, 17643, Item VII-D (Dec., 1978) and
ibid, 18717 (Nov., 1979).
[0154] In addition, couplers producing dyes having moderate diffusibility, colorless couplers,
DIR couplers capable of releasing a developing inhibitor on a coupling reaction, or
couplers capable of releasing a developing accelerator on coupling reaction can also
be employed.
[0155] Yellow couplers which can be used in this invention typically include oil-protected
acylacetamide couplers.
[0156] It is advantageous to use two-equivalent yellow couplers typically including oxygen-release
yellow couplers and nitrogen-release yellow couplers. α-Pivaloylacetanilide couplers
are excellent in dye stability, particularly stability to light. On the other hand,
α-benzoylacetanilide couplers provide high color densities.
[0157] Magenta couplers which can be used in the present invention include oil-protected
type indazolone or cyanoacetyl couplers, and preferably 5-pyrazolone couplers and
pyrazoloazole couplers, such as pyrazolotriazoles. 5-Pyrazolone couplers having an
arylamino group or an acylamino group at the 3-position are preferred in view of hue
and density of developed dyes.
[0158] Releasable groups of 2-equivalent 5-pyrazolone couplers preferably include nitrogen-release
groups described in U.S. Patent 4,310,619 and arylthio groups described in U.S. Patent
4,351,897. 5-Pyrazolone couplers having a ballast group as described in EP 73,636
provide high color densities.
[0159] Pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Patent 3,379,899,
and preferably pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Patent 3,725,067,
pyrazolotetrazoles described in
Research Disclosure, 24220 (Jun., 1984), and pyrazolopyrazoles described in
Research Disclosure, 24230 (Jun., 1984). From the standpoint of reduced yellow side absorption and light
stability of produced dyes, imidazolo[1,2-b]pyrazoles described in EP 119,741 are
preferred. Pyrazolo[1,5-b][1,2,4]triazole described in EP 119,860 is particularly
preferred.
[0160] Cyan couplers which can be used in the present invention include oil-protected naphthol
and phenol couplers. Typical examples of cyan couplers are naphthol couplers described
in U.S. Patent 2,474,293, preferably oxygen-release 2-equivalent naphthol couplers
described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, and 4,296,200. Examples
of phenol couplers are described in U.S. Patents 2,369,929, 2,801,171, 2,772,162,
and 2,895,826. Cyan couplers exhibiting stability to moisture and heat are preferably
used in the present invention. Typical examples of such cyan couplers are phenol couplers
having an alkyl group of 2 or more carbon atoms at the m-position of the phenolic
nucleus as described in U.S. Patent 3,772,002, 2,5-diacylamino-substituted phenol
couplers, and phenol couplers having a phenylureido group at the 2-position and an
acylamino group at the 5-position.
[0161] In order to correct undesired absorption in the shorter wavelength region as possessed
by the dyes formed from the magenta and cyan couplers, it is preferable to use colored
couplers in color light-sensitive materials for shooting.
[0162] Graininess can be improved by using couplers producing dyes having moderate diffusibility.
Examples of such couplers are described in U.S. Patent 4,366,237 and British Patent
2,125,570 (magenta couplers); EP 96,570 and West German Patent Publication 3,234,533
(yellow, magenta or cyan couplers).
[0163] Dye-forming couplers and the above-described special couplers may have the form of
a polymer, including that of a dimer. Typical examples of polymerized dye-forming
couplers are described in U.S. Patents 3,451,820 and 4,080,211. Specific examples
of polymerized magenta coupler are described in British Patent 2,102,173 and U.S.
Patent 4,367,282.
[0164] In order to satisfy the characteristics required for light-sensitive materials, two
or more of the above-described couplers can be incorporated into the same light-sensitive
layer, or the same coupler can be introduced into two or more layers.
[0165] The standard amount of color couplers to be used is in the range of from 0.001 to
1 mol per mole of light-sensitive silver halide. More preferably, 0.01 to 0.5 mol
of a yellow coupler, 0.003 to 0.3 mol of a magenta coupler, and 0.002 to 0.3 mol of
a cyan coupler are used per mol of silver halide.
[0166] Developing agents, such as hydroxybenzenes (e.g., hydroquinone), aminophenols, and
3-pyrazolidones, may be incorporated into the emulsions or light-sensitive materials.
[0167] The photographic emulsion which can be used in the present invention can also be
combined with a dye image providing compound (color material) in a color diffusion
transfer process which releases a diffusive dye in accordance with development of
silver halide to provide a desired transferred image on an image-receiving layer.
Several color materials for color diffusion transfer process have been proposed. Preferred
among them are color materials which are non-diffusive as they are, but become capable
of releasing a diffusive dye when split off during an oxidation-reduction reaction
with an oxidation product of a developing agent (or an electron transfer agent) (hereinafter
referred to as DRR compound), with those having an N-substituted sulfamoyl group being
particularly preferred. Among others, DRR compounds having an o-hydroxyarylsulfamoyl
group as described in U.S. Patents 4,055,428, 4,053,312, and 4,336,322 and DRR compounds
having a redox nucleus as described in JP-A-53-149328 are suitable for combination
with a nucleating agent. The combined use of such DRR compounds markedly reduces temperature
dependence of processing performance.
[0168] After imagewise exposure, processing of the light-sensitive material is preferably
carried out by color development with a surface developer having a pH of 11.5 or lower
and containing an aromatic primary amine color developing agent, either after or during
light fogging or chemical fogging using a nucleating agent, followed by bleaching
and fixing thereby to directly form a positive color image. The developer to be used
more preferably has a pH between 10.0 and 11.0.
[0169] Fogging can be effected by either a light fog method in which the entire area of
a light-sensitive layer is subjected to a second exposure or a chemical fog method
in which development processing is carried out in the presence of a nucleating agent.
Development processing may be conducted in the presence of a nucleating agent and
fogging light. Also, a light-sensitive material containing a nucleating agent may
be subjected to fogging exposure.
[0170] The light fog method is described in European Patent No. 267482, p. 17, line 15 to
p. 17, line 46. Useful nucleating agents are described in
ibid., p. 17, line 47 to p. 21, line 31. In particular, compounds represented by formulas
(N-1) and (N-2) are preferred. Specific examples of these compounds are (N-I-1) to
(N-I-10) shown on p. 19 and (N-II-1) to (N-II-12) shown on p. 21 of the above European
Patent.
[0171] Nucleation accelerators which can be used in this invention are described in
ibid., p. 21, ℓ. 48 to p. 22, ℓ. 17. In particular, (A-1) to (A-13) on pp. 21-22 are preferred.
[0172] Color developers which can be used for development processing of the light-sensitive
material of the invention are described in
ibid., p. 22, ℓ. 18 to p. 22, ℓ. 29. Preferred examples of the aromatic primary amine color
developing agents are p-phenylenediamine compounds, typically including 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline,
3-methyl-4-amino-N-ethyl-N-(β-hydroxyethyl)aniline,3-methyl-4-amino-N- ethyl-N-methoxyethylaniline
and salts thereof (e.g., sulfate and hydrochloride).
[0173] To form a direct positive color image by color diffusion transfer using the light-sensitive
material of the invention, black-and-white developers, such as phenidone compounds,
are also employable.
[0174] Photographic emulsion layers, after color development, are usually subjected to bleaching.
Bleaching may be carried out simultaneously with fixing (combined bleaching and fixing),
or these two steps may be conducted separately. To speed up processing, bleaching
may be followed by bleach-fix, or fixing may be followed by bleach-fix.
[0175] A bleaching solution or a bleach-fix solution usually contains an aminopolycarboxylic
acid iron complex salt as the bleaching agent. Additives which can be used in the
bleaching or bleach-fix solution are described in JP-A-62-215272, pp. 20-30.
[0176] Desilvering (bleach-fix or fixing) is followed by washing and/or stabilizing. Water
which has been rendered soft is preferably used as washing water or a stabilizing
solution. Treatments for rendering water soft can be performed by means of an ion-exchange
resin as described in JP-A-62-288838 or by a method using an apparatus for back osmosis.
The method described in JP-A-62-288838
supra is particularly preferred.
[0177] Additives which can be used in the washing and stabilizing steps include those described
in JP-A-62-215272, pp. 30-36.
[0178] The rate of replenishment in each processing step is preferably low. It is preferably
0.1 to 50 times, more preferably 3 to 30 times, the amount of the prebath which has
been carried over per unit area of a light-sensitive material.
[0179] The compounds of the present invention can be used in heat-developable light-sensitive
materials which are described in, for example, U.S. Patents 4,463,079, 4,474,867,
4,478,927, 4,507,380, 4,500,626, 4,483,914, JP-A-58-149048, JP-A-58-149047, JP-A-59-152440,
JP-A-59-154445, JP-A-59-165054, JP-A-59-180548, JP-A-59-168439, JP-A-59-168439 JP-A-59-174832,
JP-A-59-174833, JP-A-59-174834, JP-A-59-174835, JP-A-61-232451, JP-A-62-65038, JP-A-62-253159,
JP-A-63-316848, JP-A-64-13546, European Patent Publication Nos. 210,660A2 and 220,746A2.
[0180] The heat-developable light-sensitive material basically comprises a support having
provided thereon a light-sensitive silver halide, a binder, a dye-providing compound,
and a reducing agent (the reducing agent may also function as a dye-providing material),
and, if necessary, an organic silver salt and other additives may be incorporated
therein.
[0181] The heat-developable light-sensitive material may be either a negative image forming
material or a positive image forming material. For the positive image forming material,
a direct-positive emulsion which includes a system using a nucleating agent and a
system using a fogging agent is used as a silver halide emulsion, or a dye-providing
compound which releases a positively diffusible dye-image is used.
[0182] The transfer of a diffusible dye can be effected by various methods. For example,
methods of transfer to a dye-fixing layer using an image-forming solvent, transfer
to a dye-fixing layer using a high boiling-point organic solvent, transfer to a dye-fixing
layer using a hydrophilic hot solvent, and transfer to a dye-fixing layer containing
a dye-receiving polymer by utilizing heat-diffusible or sublimable property of the
diffusible dye have been proposed, and any of these methods can be used in the present
invention.
[0183] The above-described image-forming solvent includes, for example, water which can
be pure water as well as water usually used. The solvent may be a mixture of pure
water and a low boiling point solvent such as methanol, dimethylformamide, acetone,
diisobutyl ketone. Further, the solvent may be a solution containing an image-formation
accelerator, an antifoggant, a development-stopping agent, a hydrophilic hot solvent,
etc.
[0184] The present invention is now illustrated in greater detail by way of Examples, but
it should be understood that the present invention is not limited thereto.
EXAMPLE 1
Preparation of Light-Sensitive Emulsion:
[0185] A silver nitrate aqueous solution and a mixed aqueous solution of potassium iodide
and potassium bromide were simultaneously added to a gelatin aqueous solution kept
at 50°C in the presencdye and e of 4 × 10⁻⁷ mol per mol of silver of iridium (III)
chloride and ammonia while maintaining a pAg at 7.8 to prepare a cubic mono-dispersed
emulsion having a mean grain size of 0.28 µm and an average silver iodide content
of 0.3 mol%. After the emulsion was desalted by a flocculation method, 40 g of inert
gelatin per mol of silver was added thereto. 5,5′-Dichloro-9-ethyl-3,3′-bis(3-sulfopropyl)-oxacarbocyanine
as a sensitizing dye and a solution containing 10⁻³ mol of potassium iodide per mol
of silver were added to the emulsion while it was maintained at 50°C. After allowing
the emulsion to stand for 15 minutes, the temperature was decreased.
Coating of Light-Sensitive Emulsion Layer:
[0186] The above prepared emulsion was re-melted, and the hydrazine compounds shown below
were added thereto at 40°C in the amounts shown.

[0187] Further, each of the compounds shown in Table 1 below was added to the emulsion.
Moreover, 5-methylbenzotriazole, 4-hydroxy-1,3,3a,7-tetraazaindene, Compounds (i)
and (ii) shown below, 30% by weight (based on gelatin) of polyethyl acrylate, and
Compound (iii) shown below as a gelatin hardening agent were added thereto. The resulting
coating composition was coated on a 150 µm thick polyethylene terephthalate film having
a subbing layer comprising a vinylidene chloride copolymer to a silver coverage of
3.8 g/m² and dried to form an emulsion layer.

Coating of Protective Layer:
[0188] A composition comprising 1.5 g/m² of gelatin, 0.3 g/m² of polymethyl methacrylate
particles (mean particle size: 2.5 µm), and the surface active agents shown below
was coated on the emulsion layer and dried to form a protective layer.

Evaluation of Performance:
[0189] Each of the resulting samples was exposed to tungsten light of 3200°K through an
optical wedge and a contact screen ("150L Chain Dot Type", produced by Fuji Photo
Film Co., Ltd.), developed with a developer having the following formulation at 34°C
for 30 seconds, fixed, washed, and dried.
[0190] Dot quality and dot gradation of the processed samples were evaluated, and the results
obtained are shown in Table 1.
1) Dot gradation was determined by the equation:
Dot Gradation = Exposure amount providing dot area ratio of 95% ΔlogE (logE95%) -
Exposure amount providing dot area ratio of 5% (logE5%)
2) Dot quality was rated according to the following system by visual observation:
5 ... Best quality
4 ... Acceptable for practical use
3 ... Lower limit for practical use
2 ... Unacceptable for practical use
1 ... Worst quality
Developer Formulation: |
Hydroquinone |
50.0 g |
N-Methyl-p-aminophenol |
0.3 g |
Sodium hydroxide |
18.0 g |
5-Sulfosalicylic acid |
55.0 g |
Potassium sulfite |
110.0 g |
Disodium ethylenediaminetetraacetate |
1.0 g |
Potassium bromide |
10.0 g |
5-Methylbenzotriazole |
0.4 g |
2-Mercaptobenzimidazole-5-sulfonic acid |
0.3 g |
Sodium 3-(5-mercaptotetrazole)benzenesulfonate |
0.2 g |
N-n-Butyldiethanolamine |
15.0 g |
Sodium toluenesulfonate |
8.0 g |
Water to make |
1 ℓ |
pH (adjusted with potassium hydroxide) |
pH 11.6 |
[0191] As is apparent from the results shown in Table 1 below, the samples containing the
compound of formula (I) according to the present invention exhibit considerably broadened
dot gradation and improved dot quality as compared with the samples containing the
comparative compound.
TABLE 1
Sample No. |
Compound |
Dot Gradation |
Dot Quality |
Remark |
|
Kind |
Amount |
ΔlogE |
|
|
|
|
(mol/m²) |
|
|
|
1 |
- |
- |
1.19 |
3 |
Comparison |
2 |
Compound a |
2.0×10⁻⁵ |
1.32 |
4 |
" |
3 |
Compound b |
" |
1.23 |
3 |
" |
4 |
Compound c |
" |
1.20 |
3 |
" |
5 |
Compound d |
" |
1.19 |
3 |
" |
6 |
Compound 6 |
" |
1.42 |
4 |
Invention |
7 |
Compound 8 |
" |
1.41 |
4 |
" |
8 |
Compound I-11 |
" |
1.42 |
4 |
" |
9 |
Compound I-14 |
" |
1.48 |
5 |
" |
10 |
Compound I-15 |
" |
1.46 |
4 |
" |
11 |
Compound I-17 |
" |
1.46 |
4 |
" |
12 |
Compound I-20 |
" |
1.48 |
5 |
" |
13 |
Compound I-24 |
3.0×10⁻⁶ |
1.46 |
5 |
" |
14 |
Compound I-34 |
2×10⁻⁵ |
1.47 |
5 |
" |
15 |
Compound I-45 |
" |
1.46 |
4 |
" |

EXAMPLE 2
[0192] Each of the samples prepared in Example 1 was exposed to light in the same manner
as in Example 1 and developed at 34°C for 30 seconds under the following condition
(A), (B) or (C) by using an automatic developing machine for plate making ("Model
FG 660F" produced by Fuji Photo Film Co., Ltd.) filled with the same developer as
used in Example 1, followed by fixing, washing, and drying.
Development Condition:
[0193]
(A) Development processing was conducted immediately after the temperature of the
developer in the automatic developing machine reached 34°C (development with a fresh
developer).
(B) Development processing was conducted after the developer filled in the automatic
developing machine was allowed to stand for 4 days (development with an air-fatigued
developer).
(C) Commercially available films ("GRADEX GA-100" produced by Fuji Photo Film Co.,
Ltd.; 50.8 cm × 61.0 cm) were exposed to light in such a manner that 50% of the area
would be developed and developed by means of the automatic developing machine filled
with the developer at a processing rate of 200 films per day for consecutive 5 days.
The development of the sample was conducted with the thus fatigued developer (development
with a large volume processing-fatigued developer). The developer was supplied at
a replenishment rate of 100 cc per film.
[0194] Photographic sensitivity of each processed sample was determined to evaluate processing
running stability, and the results obtained are shown in Table 2 below. From the standpoint
of running stability, it is desirable that the difference in sensitivity between processing
conditions (A) and (B) or (C) be minimized. As can be seen from the results of Table
2, use of the compound according to the present invention unexpectedly improves processing
running stability.
TABLE 2
Sample No. |
Air-Fatigued Developer (ΔSB-A*) |
Large Volume Processing-Fatigued Developer (ΔSC-A**) |
Remark |
1 |
+0.07 |
-0.14 |
Comparison |
2 |
+0.04 |
-0.08 |
" |
3 |
+0.07 |
-0.14 |
" |
4 |
+0.08 |
-0.15 |
" |
5 |
+0.07 |
-0.15 |
" |
6 |
+0.02 |
-0.07 |
Invention |
7 |
+0.03 |
-0.06 |
" |
8 |
+0.02 |
-0.07 |
" |
9 |
+0.02 |
-0.05 |
" |
10 |
+0.02 |
-0.06 |
" |
11 |
+0.03 |
-0.07 |
" |
12 |
+0.02 |
-0.07 |
" |
13 |
+0.03 |
-0.07 |
" |
14 |
+0.02 |
-0.07 |
" |
15 |
+0.02 |
-0.07 |
" |
* ΔSB-A: Difference between sensitivity (SA) when in using a fresh developer and sensitivity (SB) when in using an air-fatigued developer. |
**ΔSC-A: Difference between sensitivity (SA) when in using a fresh developer and sensitivity (SC) when in using a large volume processing-fatigued developer. |
EXAMPLE 3
[0195] A silver nitrate aqueous solution and a sodium chloride aqueous solution were simultaneously
added to a gelatin aqueous solution kept at 50°C in the presence of 5.0 × 10⁻⁶ mol
per mol of Ag of (NH₄)₃RhCℓ₆. After soluble salts were removed in the usual manner,
gelatin was added to the emulsion. Since no chemical ripening was conducted, 2-methyl-4-hydroxy-1,3,3a,7-tetraazaindene
was added thereto as a stabilizer. The resulting emulsion was a cubic mono-dispersed
emulsion having a mean grain size of 0.15 µm.
[0196] To the emulsion was added 49 mg/m² of a hydrazine compound of formula:

[0197] To the emulsion was added each of the compounds shown in Table 3 below. A polyethyl
acrylate latex was added in an amount of 30% by weight (on solid basis) based on gelatin,
and 1,3-vinylsulfonyl-2-propanol was added as a hardening agent. The resulting coating
composition was coated on a polyester support to a silver coverage of 3.8 g/m². The
gelatin coverage was 1.8 g/m².
[0198] On the thus formed emulsion layer was coated and dried a protective layer having
the following composition.

[0199] Each of the resulting samples was imagewise exposed to light through an original
as illustrated in Figure, developed at 38°C for 20 seconds, fixed, washed, and dried
by means of a bright room printer ("P-607" manufactured by Dai- Nippon Screen K.K.).
Image quality of the thus formed white line image was evaluated and rated as follows.
[0200] The light-sensitive material for dot-to-dot work was exposed to light at a proper
exposure so that a dot area of 50% of the original might form a dot area of 50% on
the light-sensitive material. As a result, when a 30 µm wide letter could be reproduced,
the image quality was rated 5 (best quality). On the other hand, with the exposure
condition being equal, only a 150 µm wide letter could be reproduced, and the image
quality was rated 1 (worst quality). Image quality between 5 and 1 was rated 2 to
4 according to visual observation. Quality rated 3 or higher is a level acceptable
for practical use.
[0201] The results obtained are shown in Table 3. It can be seen that the samples according
to the present invention exhibit excellent super-imposed letter quality.
TABLE 3
Sample No. |
Kind |
Amount |
Super-imposed Letter Quality |
Remark |
|
|
(mol/m²) |
|
|
1 |
- |
- |
3.0 |
Comparison |
2 |
Compound a |
5.0×10⁻⁵ |
3.5 |
" |
3 |
Compound b |
" |
3.0 |
" |
4 |
Compound c |
" |
3.0 |
" |
5 |
Compound d |
" |
3.0 |
" |
6 |
Compound I-7 |
" |
4.5 |
Invention |
7 |
Compound I-8 |
" |
4.0 |
" |
8 |
Compound I-11 |
" |
4.0 |
" |
9 |
Compound I-15 |
" |
4.5 |
" |
10 |
Compound I-19 |
" |
4.5 |
" |
11 |
Compound I-20 |
" |
5.0 |
" |
12 |
Compound I-24 |
7.0×10⁻⁶ |
4.0 |
" |
13 |
Compound I-29 |
" |
4.0 |
" |
14 |
Compound I-34 |
5×10⁻⁵ |
5.0 |
" |
15 |
Compound I-36 |
" |
5.0 |
" |
16 |
Compound I-41 |
" |
4.5 |
" |
17 |
Compound I-45 |
" |
4.5 |
" |
EXAMPLE 4
[0202] Emulsions for photographic layers, a dispersion of zinc hydroxide, a dispersion of
active charcoal, a dispersion of an electron-transmitting agent, dispersions of yellow,
magenta and cyan couplers and a dispersion for an interlayer were prepared as described
below. Then, a photographic material (Sample No. 401) was prepared using these materials
as described below. Additionally, an image-receiving material was prepared, also as
described below.
Emulsion for Blue-sensitive layer:
[0203] The following solution (1) and solution (2) were simultaneously added to a well-stirred
aqueous gelatin solution (which was prepared by adding 20 g of gelatin, 3 g of potassium
bromide, 0.03 g of the following compound (1) and 0.25 g of HO(CH₂)₂S(CH₂)₂(CH₂)₂OH
to 800 cc of water and heated at 50°C), over a period of 30 minutes. Thereafter, the
following solution (3) and solution (4) were further added thereto at the same time
over a period of 20 minutes. 5 minutes after the initiation of adding the solution
(3), a dye solution described below was added over a period of 18 minutes.
[0204] After washing with water and desalting, 20 g of lime-processed ossein gelatin was
added to the mixture, the pH was adjusted to 6.2, and the pAg to 8.5. Then, sodium
thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and chloroauric acid were
added for optimum chemical sensitization to obtain 600 g of a monodispersed cubic
silver chlorobromide emulsion having a mean grain size of 0.40 microns.
Solution (1): |
AgNO₃ (g) |
30 g |
Water to make |
180 cc |
Solution (2): |
KBr (g) |
17.8 g |
NaCl (g) |
1.6 g |
Water to make |
180 cc |
Solution (3): |
AgNO₃ (g) |
70 g |
Water to make |
350 cc |
Solution (4): |
KBr (g) |
49 g |
Water to make |
350 cc |
Dye Solution:
[0205] The following dyes were dissolved in 160 cc of methanol.

Emulsion for Green-sensitive Layer:
[0206] The following solutions (I) and (II) were added over a period of 30 minutes to the
aqueous gelatin solution shown below which was well stirred and heated at 50°C. Then,
the solutions (III) and (IV) were added thereto over a period of 30 minutes, and,
thereafter, the dye solution described below was added one minute after the completion
of the addition of the solutions (III) and (IV).

[0207] After washing with water and desalting, 20 g of gelatin was added thereto, the pH
and pAg were adjusted, and triethylthiourea, chloroauric acid and 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene
were added for optimum chemical sensitization.
Emulsion for Red-sensitive Layer:
[0208] The following solutions (I) and (II) were added to a well-stirred aqueous gelatin
solution (as prepared by adding 20 g of gelatin, 0.3 g of potassium bromide, 6 g of
sodium chloride and 30 mg of the following compound (A) to 800 ml of water and heated
at 50°C) at the same time and at the same flow rate over a period of 30 minutes. Thereafter,
the following solutions (III) and (IV) were also added at the same time over a period
of 30 minutes. 3 minutes after the initiation of adding the solutions (III) and (IV),
the dye solution described below was added over a period of 20 minutes.
[0209] After washing with water and desalting, 22 g of lime-processed ossein gelatin was
added thereto, the pH was adjusted to 6.2, and the pAg to 7.7. Then, sodium thiosulfate,
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and chloroauric acid were added for optimum
chemical sensitization at 60°C to obtain a monodispersed cubic silver chlorobromide
emulsion having a mean grain size of 0.38 microns. The yield of the emulsion was 635
g.
Solution (I): |
AgNO₃ (g) |
50.0 g |
Water to make |
200 ml |
Solution (II): |
KBr |
28.4 g |
NaCl |
3.4 g |
Water to make |
200 ml |
Solution (III): |
AgNO₃ (g) |
50.0 g |
Water to make |
200 ml |
Solution (IV): |
KBr |
35.0 g |
Water to make |
200 ml |

Dye Solution:
[0210] 67 mg of the following dye (a) and 133 mg of the following dye (b) were dissolved
in 100 ml of methanol.

[0211] Then, a dispersion of zinc hydroxide was prepared as described below.
[0212] 12.5 g of zinc hydroxide having a mean grain size of 0.2 microns, 1 g of carboxymethyl
cellulose as a dispersing agent, and 0.1 g of sodium polyacrylate were added to 100
cc of 4% aqueous gelatin solution and milled for 30 minutes with glass beads having
a mean grain size of 0.75 mm. The glass beads were then removed to obtain a dispersion
of zinc hydroxide.
[0213] A dispersion of active charcoal was prepared by adding 2.5 g of active charcoal powder
(special grade, product by Wako Pure Chemical), 1 g of Demole N (product by Kao Soap
Co.) as a dispersing agent, and 0.25 g of polyethylene glycol nonylphenylether to
100 cc of 5% aqueous gelatin solution, and then milling for 120 minutes with glass
beads having a mean grain size of 0.75 mm. After removal of the glass beads, a dispersion
of active charcoal having a mean grain size of 0.5 microns was obtained.
[0214] A dispersion of an electron-transmitting agent was prepared by adding 10 g of an
electron-transmitting agent described below, 0.5 g of polyethylene glycol as a dispersing
agent, and 0.5 g of an anionic surfactant described below to a 5% aqueous gelatin
solution, and then milling for 60 minutes with glass beads having a mean grain size
of 0.75 mm. After removal of the glass beads, a dispersion of an electron-transmitting
agent having a mean grain size of 0.3 micron was obtained.

[0215] Gelatin dispersions each containing a dye-providing compound were prepared as described
below.
[0216] An yellow, magenta or cyan dye-providing composition as indicated below was added
to 50 cc of ethyl acetate and dissolved while heating at about 60°C to form a uniform
solution. The resulting solution was blended with 100 g of 10% lime-processed gelatin-containing
aqueous solution, 0.6 g of sodium dodecylbenzenesulfonate and 50 cc of water by stirring
and then dispersed for 10 minutes with a homogenizer at 10000 rpm. The dispersion
thus prepared was designated as a gelatin dispersion of a dye-providing compound.
|
Yellow |
Magenta |
Cyan |
Dye-providing Compound (1) |
13 g |
- |
- |
Dye-providing Compound (2) |
- |
15.5 g |
- |
Dye-providing Compound (3) |
- |
- |
16.6 g |
Electron-donating Compound |
10.2 g |
8.6 g |
8.1 g |
High Boiling Point Solvent |
6.5 g |
7.8 g |
8.3 g |
Electron-transmitting Agent Precursor |
0.4 g |
0.7 g |
0.7 g |
Compound (A) |
3.9 g |
- |
- |

[0217] A gelatin dispersion of electron-donating compound (4) for an interlayer was prepared
as described below.
[0218] 23.6 g of the following electron-donating compound (4) and 8.5 g of the above-described
high boiling point solvent (2) were added to 30 cc of ethyl acetate to form a uniform
solution. The solution was blended with 100 g of 10% aqueous solution of lime-processed
gelatin, 0.25 g of sodium hydrogen sulfite, 0.5 g of sodium dodecylbenzenesulfonate
and 30 cc of water with stirring, and then dispersed for 10 minutes with a homogenizer
at 10000 rpm. The resulting dispersion was designated as a gelatin dispersion of electron-donating
compound (4).

[0219] Constitution of Sample No. 401 was as follows:
Sixth Layer: Protective Layer |
Coated Amount (mg/m²) |
Gelatin |
900 |
Silica (size, 4 microns) |
40 |
Zinc Hydroxide |
900 |
Surfactant (5)*¹ |
130 |
Surfactant (6)*² |
26 |
Polyvinyl Alcohol |
63 |
Lactose |
153 |
Water-soluble Polymer*³ |
8 |
Fifth Layer: Blue-sensitive Emulsion Layer |
Light-sensitive Silver Halide Emulsion |
380 as Ag |
Antifoggant (7)*⁴ |
0.9 |
Gelatin |
560 |
Yellow Dye-providing Compound (1) |
400 |
Electron-donating Compound (1) |
320 |
Electron-transmitting Agent Precursor (3) |
25 |
Compound (A) |
120 |
High Boiling Point Solvent (2) |
200 |
Surfactant (8)*⁵ |
45 |
Water-soluble Polymer*³ |
13 |
Fourth Layer: Interlayer |
Gelatin |
355 |
Electron-donating Compound (4) |
130 |
High Boiling Point Solvent (2) |
48 |
Electron-transmitting Agent (10)*⁷ |
85 |
Surfactant (6)*² |
15 |
Surfactant (8)*⁵ |
4 |
Surfactant (9)*⁶ |
30 |
Polyvinyl Alcohol |
30 |
Lactose |
155 |
Water-soluble Polymer*³ |
19 |
Hardening Agent (11)*⁸ |
37 |
Third Layer: Green-sensitive Emulsion Layer |
Light-sensitive Silver Halide Emulsion |
220 as Ag |
Antifoggant (12)*⁹ |
0.7 |
Gelatin |
370 |
Magenta Dye-providing Compound (2) |
350 |
Electron-donating Compound (1) |
195 |
Electron-transmitting Agent Precursor (3) |
33 |
High Boiling Point Solvent (2) |
175 |
Surfactant (8)*⁵ |
47 |
Water-soluble Polymer*³ |
11 |
Second Layer: Interlayer |
Gelatin |
650 |
Zinc Hydroxide |
300 |
Electron-donating Compound (4) |
130 |
High Boiling Point Solvent (2) |
50 |
Surfactant (6)*² |
11 |
Surfactant (8)*⁵ |
4 |
Surfactant (9)*⁶ |
50 |
Polyvinyl Alcohol |
50 |
Lactose |
155 |
Water-soluble Polymer*³ |
12 |
Active Charcoal |
25 |
First layer: Red-sensitive Emulsion Layer |
Light-sensitive Silver Halide Emulsion |
230 as Ag |
Antifoggant (12)*⁹ |
0.7 |
Gelatin |
330 |
Cyan Dye-providing Compound (3) |
340 |
Electron-donating Compound (1) |
133 |
Electron-transmitting Agent Precursor (3) |
30 |
High Boiling Point Solvent (2) |
170 |
Surfactant (8)*⁵ |
40 |
Water-soluble Polymer*³ |
5 |
Support:
[0221] Composition of image-receiving material used herein was as follows:
Third Layer: |
Coated Amount (g/m²) |
Gelatin |
0.05 |
Silicone Oil (1) |
0.04 |
Surfactant (1) |
0.001 |
Surfactant (2) |
0.02 |
Surfactant (3) |
0.10 |
Matting Agent (1) (silica) |
0.02 |
Guanidine Picolinate |
0.45 |
Water-soluble Polymer (1) |
0.24 |
Second Layer: |
Mordant Agent (1) |
2.35 |
Water-soluble Polymer (1) |
0.20 |
Gelatin |
1.40 |
Water-soluble Polymer (2) |
0.60 |
High Boiling Point Solvent (1) |
1.40 |
Guanidine Picolinate |
2.25 |
Brightening Agent (1) |
0.05 |
Surfactant (5) |
0.15 |
First Layer: |
Gelatin |
0.45 |
Surfactant (3) |
0.01 |
Water-soluble Polymer (1) |
0.04 |
Hardening Agent (1) |
0.30 |
Support
[0222] The constitution of the support is described below.
First Backing Layer: |
Gelatin |
3.25 |
Hardening Agent (1) |
0.25 |
Second Backing Layer: |
Gelatin |
0.44 |
Silicone Oil (1) |
0.08 |
Surfactant (4) |
0.04 |
Surfactant (5) |
0.01 |
|
Matting Agent (2) (Benzoguanamine Resin having a mean grain size of 15 microns) |
0.02 |
[0223] The constitution of Support was as follows:
Surface Subbing layer: |
0.1 micron (thickness) |
Gelatin |
|
Surface PE Layer (glossy): |
45.0 microns (thickness) |
Low-density Polyethylene (density: 0.923) |
89.2 parts |
Surface-treated Titanium Oxide |
10.0 parts |
Ultramarine |
0.8 part |
Pulp Layer: |
92.6 microns (thickness) |
High-quality Paper (LBKP/NBKP=1/1, density: 1.080) |
|
Back Surface PE Layer (mat): |
36.0 microns (thickness) |
High-density Polyethylene (density: 0.960) |
|
Back Surface Subbing Layer: |
|
Gelatin |
0.05 micron (thickness) |
Colloidal Silica |
0.05 micron (thickness) |
|
Total |
173.8 microns (thickness) |
[0224] Compounds used above are as follows:
Water-soluble Polymer (1):
Sumicagel L 5-H (product of Sumitomo Chemical Co., Ltd.)
Water-soluble Polymer (2):
Dextran (molecular weight: 70,000)

[0225] In the same manner as the preparation of Sample No. 401, other Sample Nos. 402 to
406 were prepared, as indicated in Table 4 below. Sample Nos. 402 to 406 each contained
a compound of the present invention, which had been dispersed in gelatin by an oil
dispersion method, in the second and fourth layers each in an amount of 3x10⁻³ mol/m².
[0226] The sample Nos. 401 to 406 thus prepared were exposed by using a spectrophotometric
camera through an optical wedge where the optical density continuously varied in the
direction vertical to the wavelength.
[0227] The exposed samples were then wetted with water by applying a hot water (35°C) to
the emulsion surface of each sample in an amount of 15 ml/m² for 3 seconds. The thus
wetted sample was attached to the previously prepared image-receiving material so
that the coated surfaces of the two faced to each other.
[0228] The combined sample was then heated with a heat roller for 15 seconds whereupon the
temperature of the wetted layer was adjusted to be 78°C. Then, the image receiving
material was peeled off from the photographic material and, as a result, a blue-green-red
spectrographic image was formed on the image-receiving layer in accordance with the
wavelength of the light as exposed.
[0229] The density of each of the yellow, magenta and cyan colors was measured with 310
Type Densitometer (manufactured by X-rite Co.). The results obtained are shown in
Table 4 below.
Table 4
|
Sample No. |
|
401 |
402 |
403 |
404 |
405 |
406 |
|
(Comparison) |
(Invention) |
(Invention) |
(Invention) |
(Invention) |
(Invention) |
Compound Added to 2nd and 4th Layers |
- |
I-8 |
I-9 |
I-12 |
I-41 |
I-44 |
Blue-exposed Region |
Yellow |
0.80 |
0.60 |
0.60 |
0.65 |
0.65 |
0.70 |
Magenta |
2.00 |
2.10 |
2.15 |
2.10 |
2.15 |
2.10 |
Cyan |
2.05 |
2.10 |
2.05 |
2.10 |
2.10 |
2.05 |
Green-exposed Region |
Yellow |
1.95 |
2.10 |
2.05 |
2.05 |
2.10 |
2.05 |
Magenta |
0.75 |
0.60 |
0.65 |
0.60 |
0.65 |
0.65 |
Cyan |
2.00 |
2.15 |
2.15 |
2.10 |
2.15 |
2.10 |
Red-exposed Region |
Yellow |
1.95 |
2.05 |
2.00 |
2.00 |
1.95 |
2.05 |
Magenta |
1.95 |
2.05 |
2.00 |
2.05 |
1.95 |
1.95 |
Cyan |
0.40 |
0.35 |
0.30 |
0.30 |
0.35 |
0.35 |
[0230] From the results above, it is noted that the density of all the blue, green and red
colors increased by adding the compound of the present invention. Additionally, the
color purity also increased by adding the compound of the present invention due to
the decrease in complementary components. Accordingly, it was proved that the compounds
of the present invention had an excellent ability to improve the color reproducibility.
[0231] Then, the above-described photographic material samples were stored for one month
under the condition of 30°C and 70% RH and thereafter subjected to the same treatment.
After the treatment, the same results as those in Table 4 were obtained. accordingly,
it was confirmed that the compounds of the present invention did not adversely affect
the storability of the photographic materials containing the compound.
EXAMPLE 5
[0232] Each of Compounds I-9, I-11, I-17 and I-21 of the present invention was added to
the timing layer of the cover sheet as described in Example 1 of JP-A-63-289551 in
an amount of 0.825 mmol/m² to prepare Cover Sheet Samples (5-1), (5-2), (5-3) and
(5-4). Each of these cover sheets was attached to Light-sensitive Sheet (102) of the
same Example and then processed in the same manner as in the same Example. The liquid-spreading
temperature was 10°C, 25°C and 35°C.
[0233] As a result, it was found that all the samples had little processing temperature-dependence
and had excellent photographic properties with a high Dmax value and a low Dmin value.
EXAMPLE 6
[0234] Each of Compounds I-12, I-36 and I-1 of the present invention was added to each of
the 3rd, 4th, 6th, 7th, 9th and 10th layers of Sample 102 described in Example 1 of
JP-A-01-112241 in an amount of 3 mg/m² to prepare Sample Nos. 6-1, 6-2 and 6-3.
Each of these samples was then treated and evaluated in the same manner as described
in the same example as above and found to be excellent in color reproducibility.
EXAMPLE 7
[0235] 15 mg of Compound I-9 of the present invention was added to each of the 3rd, 4th,
5th, 7th, 8th, 9th, 11th, 12th and 13th layers of Sample 101 as described in Example
1 of JP-A-01-267638 to prepare Sample 7-1. The resulting sample was then treated
and evaluated in the same manner as described in the same example as above and found
to be excellent in sharpness and color reproducibility.
EXAMPLE 8
[0236] 20 mg of Compound I-28 of the present invention was added to each of the 4th, 5th,
6th, 9th, 10th, 11th, 14th, 15th and 16th layers of Sample No. 208 as described in
Example 2 of JP-A-01-291250 to prepare Sample No. 8-1. The resulting sample was developed
in the same manner as described in the same example as above and found to be excellent
in sharpness, graininess and color reproducibility.
EXAMPLE 9
[0237] Compound I-14 of the present invention was added to each of the 3rd, 4th, 6th, 7th,
11th and 12th layers of Sample No. 502 as described in Example 4 of European Patent
No. 327066A in an amount of 3 mg/m² per layer to prepare Sample No. 9-1. The resulting
sample was developed in the same manner as described in the same example as above
and found to be excellent in color reproducibility.
EXAMPLE 10
[0238] Compound I-12 of the present invention was added to the emulsion layer of Sample
No. 1 as described in Example 1 of JP-A-01-234840 in an amount of 560 mg per 1 mol
of silver halide to prepare Sample No. 10-1. The resulting sample was developed in
the same manner as described in the same example as above and found to be excellent
in blackened density and image quality.
[0239] While the invention has been described in detail and with reference to specific embodiments
thereof, it will be apparent to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope thereof.