BACKGROUND OF THE INVENTION
[0001] This invention relates to a light-sensitive silver halide photographic material.
More particularly, it relates to a light-sensitive silver halide photographic material
having superior inscribability and erasability. Still more particularly, it is concerned
with a light-sensitive silver halide photographic material that can be effectively
used as a photographing matt film for use in the photocopying of drawings, maps, etc.
From another point of view, it is further concerned with a light-sensitive silver
halide photographic material for direct positives, and more particularly to a light-sensitive
silver halide photographic material for direct positives that has inscribability,
a high speed, and an improved whiteness.
[0002] As hitherto well known, matt films are used in the photocopying of drawings. for
machines and constructions, maps, etc.; the macro-photographying or montage-photographying
of aerial photographs dot- formed with use of a screen; and so forth. Matt films are
meant by films made opaque by adding matting agents in a large quantity in a film.
The reasons why the films are matted by adding matting agents in a large quantity
are such that matting makes it possible to inscribe something, or make correction
thereof, in pencil or ink after exposure and processing, and makes it possible to
erase with erasers something inscribed in pencil or ink, and thus it becomes possible
to make correction of drawings or writing-in. Accordingly, the matt films are used
for the purpose of making correction or writing-in something by inscribing or erasing
something as mentioned above after exposure and processing, or used for the purpose
of making diazo-printing, taking copies, or the like purposes.
[0003] The photographying matt films are used in usual cameras, and usual rapid-access processing
is employed for development. Then, what are desired for the photographying of aerial
photographs are those approximate to a continuous tone, and, for the photographying,
those having a good sharpness. However, hitherto available matt films have had the
problems that they have so a soft tone that the line photographying can not be made,
or so a high contrast that the continuous tone can not be obtained or the clearing
is inferior.
[0004] Referring to the inscribing, inks used for inscribing are mostly water-based inks,
and, in many instances, operators manually make writing-in with use of a needle pen
(Rotring pen: trade name of Rotring-Werke Riepe KG) or the like generally used in
the field of drafting. Because of the. background that the films are mainly used for
drafting, there are demands for inscription performances of a high level, as exemplified
by denseness in density of lines, uniformity in density of lines, reproducibility
of line width, constancy in line width, etc. Also important is smoothness in writing
touch, and not preferred are rugged feeling and overly strong writing resistance as
operators may suffer increasing fatigue.
[0005] In addition, also important performance is the erasability of the lines inscribed.
For erasing, erasers for exclusive use in ink are sometimes used, but it is also widely
practiced to make erasing by applying a small quantity of water to usual erasors.
When erasing is made with use of erasers applied with water like this, a problem may
arise such that the water-base ink dissolved in water spreads to leave blots in surroundings.
The blots thus left tend to conflict with the inscribability, and what has been disadvantageous
in the conventional matt films is that the blots increase with improvement in ink-fixing
performance.
[0006] Discussed below are problems arising in direct positive light-sensitive silver halide
photographic materials in which the matting agents are used.
[0007] Recent years, the direct positive light-sensitive silver halide photographic materials
applied with fog are trending achievement of higher speed. For achieving higher speed,
it is necessary to obtain sufficient development activities with fog as less as possible.
For that reason, advantageously used is a method in which fog is applied in the presence
of a reduction fogging agent and a water-soluble gold compound. Examples of such fog-applying
method are the methods described in U.S. Patents No. 3,501,305, No. 3,501,306, No.
3,501,307, etc.
[0008] On the other hand, widely used as other techniques for increasing the speed of the
direct positive light-sensitive silver halide photographic material applied with fog
is a method in which an organic desensitizer adsorbed on the surfaces of silver halide
grains is used as an electron acceptor. Examples of the above organic desensitizer
include the compounds described in U.S. Patents No. 2,930,694, No. 3,431,111, No.
3,492,123, No. 3,501,310, No. 3,501,312, No. 3,567,456, No. 3,582,343, etc.
[0009] Incidentally, when a direct positive silver halide emulsion containing the silver
halide grains fogged in the presence of the reduction fogging agent and the water-soluble
gold compound and the organic desensitizer is applied in matt films, a problem may
arise such that the organic desensitizer elutes with insufficiency to cause coloring
at non-image areas. This coloring occurs in a higher degree as compared with direct
positive light-sensitive silver halide photographic materials using the matting agent
in a less amount, and causes an extreme lowering of the commercial value.
[0010] In general, the matt films are handled under red illumination in many instances,
and therefore the matt films are usually color-sensitized so as to have color sensitivities
to the blue region and green region. Known as sensitizing dyes used for sensitization
to the green region are all sorts of cyanine dyes and merocyanine dyes, and those
capable of applying sensitivities to blue light and green light may include, for example,
cyanine dyes and merocyanine dyes described in Japanese Patent Publications No. 7828/1963,
No. 392/1965, No. 10251/1968 and No. 22884/1968, British Patents No. 815,172, No.
955,961, No. 955,912 and No. 142,228, U.S. Patents No. 1,942;854, No. 1,950,876, No.
1,957,869, No. 2,238,231, No. 2,521,705 and No. 2,647,059, Japanese Patent Publications
No. 2606/1968, No. 3644/1969, No. 18106/1971, No. 18101/1971, No. 15032/1973, No.
33782/1974, No. 34252/1979 and No. 52574/1983, U.S. Patents No. 2,839,403, No. 3,567,458
and No. 3,625,698, etc.
[0011] In general, the higher sensitizing ability the dyes have, the more strongly color
remains after development processing, and thus the dyes that can satisfy both the
high speed and the color remain are very limitedly available.
[0012] In addition, in the case of the matt films containing matting agents, an increase
in the color remain is observed which is presumed to occur because of any mutual action
between sensitizing dyes and matting agents, resulting in difficulty in selection
of sensitizing dyes.
SUMMARY OF THE INVENTION
[0013] A first object of this invention is to provide a light-sensitive silver halide photographic
material that can produce a continuous tone and make the line photographying on the
same film and show very good clearing from fixing, even when the usual rapid-access
processing is carried out.
[0014] A second object of this invention is to provide a light-sensitive silver halide photographic
material having very good inscribability and erasability.
[0015] A third object of this invention is to provide a light-sensitive silver halide photographic
material for direct positives that has inscribability, a high speed, and an improved
whiteness.
[0016] A first invention that can achieve the first and second objects is a tight-sensitive
silver halide photographic material comprising a support, at least one silver halide
emulsion layer provided on at least one side of said support, and a protective layer
provided on said silver halide emulsion layer, wherein said silver halide emulsion
layer is formed of two kinds of emulsions each having different average grain size
of the grains contained therein, the average grain size in said emulsion containing
grains of a smaller average grain size comprises from 40 to 70 % of the average grain
size in said emulsion containing grains of a larger average grain size, and said silver
halide emulsion layer has a silver amount of 4.5 g/m
2 or less, and further at least one layer of said silver halide emulsion layer and
said protective layer contains 300 mg/m
2 or more of at least one kind of matting agent.
[0017] A second invention that can achieve the second object is a light-sensitive silver
halide photographic material comprising a support and provided by coating thereon
at least one hydrophilic colloid layer containing a matting agent, wherein the center-line
average roughness of said light-sensitive material ranges from 0.15 to 0.8 u.m, and
the weight percentage of a matting agent having a particle diameter more than 6 u.m
is 5 % or less based on the whole matting agent.
[0018] A third invention that can achieve the third object is a light-sensitive silver halide
photographic material for direct positives, comprising a support and provided thereon
a direct positive silver halide emulsion layer containing silver halide grains applied
with fog in the presence of a reduction fogging agent and a water-soluble gold compound,
wherein at least 250 mg/m
2 of at least one kind of matting agent is contained and at least one of any compounds
represented by Formulas (I), (II), (III), (IV) and (V) shown below is contained, in
a photographic layer of the side on which said direct positive silver halide emulsion
layer is provided;

wherein, in Formulas (I), (II), (III), (IV) and (V), R
1, R
21 and Ra
1 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group,
an aryloxy group or a nitro group; R
2, Ra, R
4, R
22, R
2a, R
24, R
32, Raa, R
34, R
44 and R
54 each represent an alkyl group, alkenyl group, aryl group or aralkyl group which is
unsubstituted or has a substituent; Rs, R
6, Rεs, R
26, Ras, R
36, R
45, R
46Rss and R
56 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a
thienyl group, an alkoxy group, a hydroxy group, a cyano group, an alkylsulfonyl group,
an alkoxycarbonyl group, a phenylsulfonyl group, a trifluoromethyl group, a trifluoromethylsulfonyl
group or a nitro group; R
41 represents an aryl group; R
42 represents an alkyl group; R
51 an alkyl group which is unsubstituted or has a subsituent; X
9 represents an anion; and n represents 1 or 2, provided that n is 1 when the compound
forms an intramolecular salt.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] This invention will be described below in greater detail.
[0020] Described first is the emulsion layer in the first invention.
[0021] Used as the silver halide emulsion for the silver halide emulsion layer used in this
invention are emulsions comprising two kinds of emulsions. These may preferably be
monodisperse emulsions. The monodisperse emulsions herein referred to are meant by
emulsions in which the grain size of the grains comprising 90 % of the whole in the
number of silver halide grains has a distribution within ± 40 % of average grain size.
Each average grain size of the two kinds of emulsions (preferably monodisperse emulsions)
may preferably range from 0.2 to 0.6 u.m, more preferably from 0.3 to 0.5 µm, in respect
of larger grains (which is meant by grains in the emulsion containing grains having
a larger average grain size; the same applies hereinafter), and may preferably range
from 0.1 to 0.4 u.m, more preferably from 0.15 to 0.35 u.m, in respect of smaller
grains (which is meant by grains in the emulsion containing grains having a smaller
average grain size; the same applies hereinafter).
[0022] In said emulsions, the average grain size of the smaller grains ranges from 40 to
70 % based on the average grain size of the larger grains. This may be arbitrarily
selected if it is in the range of from 40 to 70 %, and this range may vary depending
on the purpose of use. The range otherwise more than 70 % may result in a high contrast
to obtain no gradation, and the same otherwise less than 40 % may result in discontinuous
gradation to be of no practical use.
[0023] The above two kinds of emulsions used in this invention may be coated to form respectively
independent layers, but may preferably be coated to form a layer using an emulsion
in which the two kinds of emulsions having different grain size are mixed. The two
kinds of emulsions may preferably be mixed in the ratio such that the mixing ratio
of the emulsion using the silver halide grains of smaller grain size ranges from 30
to 70 %, and particularly preferable results are obtained when it ranges from 40 to
60 %.
[0024] The amount of silver applied in the light-sensitive silver halide photographic material
of this invention comprising the two kinds of emulsions should be 4.5 g/m
2 or less. Though variable depending on the purpose, the amount otherwise more than
4.5 g/m
2 may result in danger of undesirably causing poor fixing in the rapid development
processing having been practiced in the present industrial field.
[0025] In this invention, the silver halide emulsion layer used for constituting the emulsion
layer can be prepared by use of the methods described in P. Glafkides, "Chimie et
Physique Photographique", published by Paul Montel Co., 1967; G.F. Duffin, "Photographic
Emulsion Chemistry", published by The Focal Press Co., 1966; V.L. Zelikman et al,
"Making and Coating Photographic Emulsion", published by The Focal Press Co., 1964.
More specifically, there may be used any methods such as an acidic method, a neutral
method and an ammoniacal method, and, as a form of reacting soluble silver salts with
soluble halogen salts, any of a one-side synthesizing method, a simultaneous mixing
method, a combination of these, etc.
[0026] It is also possible to use a method in which grains are formed in the presence of
excess silver ions (the so-called reverse-mixing method). As a form of the simultaneous
mixing method, there can be used a method in which the pAg in the liquid phase wherein
silver halides are produced is kept constant, i.e., the so-called controlled double
jet method. This method makes it possible to obtain silver halide emulsions comprising
grains having regular crystal form and substantially uniform grain size.
[0027] The light-sensitive silver halide photographic material of this invention comprises
a minimum constituent unit comprising one silver halide emulsion layer provided on
one side of support. A light-sensitive layer typified by the silver halide emulsion
layer may be provided in plural layers on at least one side of the support. In the
instance of the plural layers, it is usual to provide an intermediate layer between
the layers. There may be further provided a subbing layer, a backing layer, an intermediate
layer, an anti-halation layer, a protective layer, etc.
[0028] The light-sensitive silver halide photographic material of this invention contains
at least 300 mg,/m
2 of at least one kind of matting agent in at least one layer of the silver halide
emulsion layer and protective layer. The content of the matting agent otherwise less
than 300 mg/m
2 may make it difficult to achieve sufficient inscribability. It may also contain a
same kind or different kind of matting agent, and in such an instance the layer to
which the matting agent is added may be any of emulsion layers and protective layers,
or subbing layers, intermediate layers and so forth that are optionally provided.
The matting agent may be of any kinds, and various kinds of agents can be appropriately
used. Specifically, it is possible to use finely divided particles of water-insoluble
organic or inorganic compounds having any particle diameter. Preferably used are those
having a particle diameter of from 0.3 u.m to 5 u.m. Examples of the organic compound
are water-dispersible vinyl polymers as exemplified by polymethyl acrylate, polymethyl
methacrylate, polyacrylonitrile, an acrylonitrile/a-methylstyrene copolymer, polystyrene,
a styrene/divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene,
etc.; cellulose derivatives as exemplified by methyl cellulose, ethyl cellulose, cellulose
acetate, cellulose acetate propionate, etc.; starch derivatives as exemplified by
carboxy starch, carboxynitrophenyl starch, a urea-formaldehyde-starch reaction product,
etc.; gelatin cured with various curing agents and cured gelatin formed into microcapsule
hollow particles by coacervation curing; etc., which can be preferably used. Examples
of the inorganic compound are silicon dioxide, titanium dioxide, magnesium dioxide,
aluminum dioxide, barium sulfate, calcium carbonate, silver chloride desensitized
by various methods, silver bromide similarly desensitized, glass, diatomaceous earth,
etc., which can be preferably used. The above matting agent can be used by optionally
mixing with it materials of different kind.
[0029] The light-sensitive silver halide photographic material of this invention may preferably
be processed with use of a fixing agent containing no hardening agent.
[0030] A step for the fixing is meant by a step of effecting fixing by desilvering using
a fixing solution containing a silver halide fixing agent. The silver halide fixing
agent used in the fixing solution includes compounds capable of forming water-soluble
complex salts by reacting with silver halides as those used in usual fixing, as typically
exemplified by thiosulfates such as potassium thiosulfate, sodium thiosulfate and
ammonium thiosulfate, thiocyanates such as potassium thiocyante, sodium thiocyanate
and ammonium thiocyanate, thioureas, thioethers, etc. These fixing agents are used
generally in an amount of 5 g/lit. or more and an amount with which they can be dissolved,
but may preferably be used in an amount of from 70 g to 250 g/lit. The fixing solution
may contain solely or in combination, a variety of buffering agents such as boric
acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium
hydroxide. It may further contain all sorts of brightening agents and anti-foaming
agents or surface active agents. It may also appropriately contain preservatives such
as hydroxylamine, hydrazine and bisulfite addition products of aldehyde compounds,
organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol
and nitrates, organic solvents such as methanol, dimethylsulfonamide and dimethylsulfoxide,
etc.
[0031] The fixing solution is used generally with pH of 3.0 or more, but may desirably be
used with pH 4.0 or more and 9.5 or less. It is used with a processing temperature
desirably of 55°C or less while suppressing evaporation or the like..
[0032] Advantageously used as binders or protective colloids in photographic emulsions for
constituting the protective layers and emulsion layers used in the light-sensitive
silver halide photographic material of this invention, as well as hydrophilic colloids
in the backing layer optionally provided, is gelatin. However, there can be used hydrophilic
colloids other than it.
[0033] Used as this gelatin may be lime-treated gelatin, as well as oxygen-treated gelatin
as described in Bulletin of Society of Science of Photography of Japan (Bull. Soc.
Sci. Phot. Japn) No. 16, page 30 (1966), and hydrolysates or enzymolysates of gelatin
can be also used.
[0034] Used as gelatin derivatives are those obtained by reacting gelatin with various compounds
as exemplified by acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkanesultones,
vinylsulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds, etc..
[0035] The silver halide photographic emulsion used in this invention and the backing layer
optionally provided may contain various compounds for the purpose of preventing fogging
during preparation process, storage or photographic processing of light-sensitive
materials, or achieving stabilized photographic performances. More specifically, there
can be added a variety of compounds known as antifoggants or stabilizers including
azoles as exemplified by benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles
and benzimidazoles (particularly nitro-or halogen-substituted compounds); heterocyclic
mercapto compounds as exemplified by mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles,
mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole)
and mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble
group such as a carboxyl group and a sulfone group; thioketo compounds as exemplified
by oxazolinethione; azaindenes as exemplified by tetrazaindenes (particularly 4- .
hydroxy-substituted (1,3,3a,7)tetrazaindenes) and benzenethiosulfonic acids; benzenesulfinic
acids; etc.
[0036] The silver halide emulsion used in this invention and the backing layer optionally
provided may further contain all sorts of chemical sensitizers, torning agents, hardening
agents, surface active agents, thickening agents, plasticizers, lubricants, development
restrainers, ultraviolet absorbents, irradiation-preventive agent dyes, heavy metals,
matting agents, etc. which are incorporated according to various methods.
[0037] The silver halide emulsion used in this invention and the backing layer optionally
provided may also contain polymer latex. Used as the polymer latex are aqueous dispersions
of homo-or copolymers as exemplified by methyl acrylate, methyl methacrylate.. acrylic
acid, methacrylic acid, glycidyl acrylate, styrene, vinyl chloride, vinylidene chloride,
etc.
[0038] As the support that can be used in the light-sensitive silver halide photographic
material of this invention, transparent supports can be used, and materials for the
usable supports may include, for example, cellulose acetate, cellulose nitrate, polyesters
such as polyethylene terephthalate, polyolefin such as polyethylene and polystyrene,
glass, etc. These supports are optionally subjected to subbing processing.
[0039] The light-sensitive silver halide photographic material of this invention can be
color-sensitized with use of a variety of sensitizing dyes.
[0040] After exposure to light, the silver halide emulsion layer of this invention can be
processed for development according to various methods, for example, usually used
methods. For example, solutions for black and white development are alkaline solutions
containing developing agents such as hydroxybenzenes, aminophenols and aminobenzenes,
and may contain other sulfites, carbonates, bisulfites, bromides and iodides of alkali
metal salts.
[0041] The second invention will be described below.
[0042] As the matting agent used in the second invention, there can be used finely divided
particles of known water-insoluble organic or inorganic compounds, which are same
as those in the first invention.
[0043] The matting agent used in this invention can be added in any hydrophilic colloid
layers. Specifically, they include silver halide emulsion layers, surface-protective
layers, intermediate layers, subbing layers, backing layers, etc., preferably silver
halide emulsion layer and protective layer provided upper than the silver halide emulsion
layer.
[0044] In this invention, the kind, shape, size, amount for addition of the matting agent
used can be freely selected, but it is required to control the center-line average
roughness (Ra) of the side on which the hydrophilic colloid layers containing the
matting agent are provided, so as to be in the range of from 0.15 to 0.8 u.m. The
Ra otherwise less than 0.15 u.m may result in a poor inscribability, and Ra otherwise
more than 0.8 u.m may result in a poorness in smoothness of writing touch.
[0045] The center-line average roughness referred to in this invention is in accordance
with the method described in the Japan Industrial Standard JIS B-0601 (corresponds
to ISO/R 468).
[0046] In addition, desired as the matting agent used in this invention are matting agents
containing no matting agent particles having a particularly large particle diameter,
and the weight percentage of a matting agent having a particle diameter more than
6 u.m is required to be 5 % or less based on the whole matting agent. The above weight
percentage otherwise more than 5 % may result in loss of smoothness of writing touch
and also make it liable to give irregularities in the density of lines inscribed,
also resulting in a'poorness in the line-width constancy. The above weight percentage
may more preferably be 2 % or less, still more preferably 1 % or less. To remove the
matting agent particles having a large particle diameter, usually available centrifugal
separation type powder classifiers can be used.
[0047] In this invention, the surface tension of a coating solution for the hydrophilic
colloid layer positioned at an uppermost layer is preferably to be modified in the
range of from 28 to 38 dyne/cm. The surface tension otherwise lower than 28 dyne/cm
may cause the problems that the lines inscribed in water-base ink have a low density
and come to have non-uniformity in the density. The surface tension otherwise more
than 38 dyne/cm may bring about the problems that the lines inscribed in water-base
ink have a greater line width and also stronger blots are left when erased. More preferably,
the surface tension may desirably be in the range of from 30 to 36 dyne/cm.
[0048] The surface tension referred to in this invention is meant by static surface tension
and distinguished from dynamic surface tension.
[0049] The surface tension can be measured by use of the method described, for example,
in JIKKEN KAGAKU KOZA (Experimental Chemistry Course) Vol. 7, edited by NIPPON KAGAKUKAI
(Japan Chemical Society).
[0050] The surface tension can be modified by selecting the kind and amount of surface active
agents to be added in the coating solution. In this invention, known surface active
agents can be used alone or in combination of two or more kinds, and can be used,
for example, nonionic surface active agents such as saponin (steroid type), alkylene
oxide derivatives (as exemplified by polyethylene glycol, a polyethylene glycol/polypropylene
glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl
ethers, polyethylene glycolesters, polyethylene glycol sorbitan esters, polyethylene
glycol alkylamines or amides, and polyethylene oxide addition products of silicone),
glycidol derivatives (as exemplified by alkenylsuccinic acid polyglyceride and alkylphenol
polyglyceride), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars;
anionic surface active agents containing an acidic group such as a carboxylic group,
a sulfo group, a phospho group and a sulfuric acid ester group, including alkylcarboxilates,
alkylsulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, N-acyl-alkyltauric
acids, sulfosuccinic acid esters, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene
alkylphosphoric acid esters, etc.; surface active agents such as amino acids, aminoalkylsulfonic
acids, aminoalkylphosphoric acid or phosphoric acid esters, alkylbetaines and amine
oxides; cationic surface active agents such as alkylamines, aliphatic or aromatic
quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium
and imidazolium, and phosphonium or sulfonium salts containing an aliphatic or heterocyclic
ring, and fluorine-containing surface active agents.
[0051] Examples of these surface active agents include those described in U.S. Patents No.
2,240,472, No. 2,831,766, No. 3,158.484, No. 3,210,191, No. 3,294,540 and No. 3,507,660,
British Patents No. 1,012,495, No. 1,022,878, No. 1,179,290 and No. 1,198,450, Japanese
Unexamined Patent Publication No. 117414/1975, U.S. Patents No. 2,739,891, No. 2,823,123,
No. 3,065,101, No. 3,415,649, No. 3,666,475 and No. 3,756,828, British Patent No.
1,397,218, U.S. Patents No. 3,133,816, No. 3,441,413, No. 3,475,174, No. 3,545,974,
No. 3,726,683 and No. 3,843,368, Belgium Patent No. 731,126, British Patents No. 1,138,514,
No. 1,159,825 and No. 1,374,780, Japanese Patent Publications No. 378/1965, No. 379/1965
and No. 13822/1968, U.S. Patents No. 2,288,226, No. 2,944,900, No. 3,253,919, No.
3,671,247, No. 3,772,021, No. 3,589,906, No. 3,666,478 and No. 3,754,924, West Germany
Patent Application OLS 19 61 638, Japanese Unexamined Patent Publication No. 59025/1975,
Japanese Patent Publications No. 9303/1972 and No. 43130/1973, German Published Patents
No. 19 50 121 and No. 19 61 638, Japanese Unexamined Patent Publication No. 7781/1971,
British Patents No.1,330,356 and No. 1,524,631, U.S. Patents No. 3,666,478 and No.
3,589,906, Japanese Patent Publication No. 26687/1977, Japanese Unexamined Patent
Publications No. 46733/1974 and No. 32322/1976, etc.
[0052] The hydrophilic colloid constituting the light-sensitive material of this invention
include not only gelatin (either lime-treated or acid-treated one may be used) as
described for the first invention, but also gelatin derivatives as exemplified by
gelatin derivatives prepared by reacting gelatin with aromatic sulfonyl chloride,
acid chloride, acid anhydride, isocyanate or 1,4-diketones as described in U.S. Patent
No. 2,614,928, gelatin derivatives prepared by reacting gelatin with trimeritic acid
anhydride as described in U.S. Patent No. 3,118,766, gelatin derivatives prepared
by reacting gelatin with an organic acid having an active halogen as described in
Japanese Patent Publication No. 5514/1964, gelatin derivatives prepared by reacting
gelatin with an aromatic glycidyl ether as described in Japanese Patent Publication
No. 26845/1967, gelatin derivatives prepared by reacting gelatin with maleimide, maleamic
acid, unsaturated aliphatic diamide or the like as described in U.S. Patent No. 3,186,846,
sulfoalkylated gelatin as described in British Patent No. 1,033,189, polyoxyalkylene
derivatives of gelatin for example, U.S. Patent No. 3,312,553, etc.; polymeric grafted
products of gelatin as exemplified by those obtained by grafting on gelatin any of
acrylic acid, methacrylic acid, a monohydric or polyhydric alcohol ester of these,
similarly amide, acrylo-or methacrylonitrile, styrene, and other vinyl monomers, which
are used alone or in combination; synthetic hydrophilic polymeric substances as exemplified
by homopolymers comprised of a monomer such as vinyl alcohol, N-vinylpyrrolidone,
hydroxyalkyl acrylate or methacrylate, acryl-or methacrylamide and N-substituted acryl-or
methacrylamide, or copolymers comprised of any mutual combination of these, copolymers
of any of these with acrylate or methacrylate, vinyl acetate, styrene or the like,
copolymers of any of the above with maleic anhydride, maleamino acid or the like,
etc.; naturally occurring hydrophilic polymeric substances other than gelatin, as
exemplified by casein, agar, alginic acid polysuccharides, etc.; which can be used
alone or as a mixture.
[0053] In the light-sensitive material of this invention, the emulsion layers and other
component layers may contain plasticizers as exemplified by glycerol, diols as described
in U.S. Patent No. 2,960,404, trihydric aliphatic alcohols as described in U.S. Patent
No. 3,520,694.
[0054] In the light-sensitive material of this invention, the emulsion layers and other
component layers may contain dispersions of water-insoluble or slightly soluble synthetic
polymers for the purpose of increasing the dimension stability or the like purposes.
For example, there can be used alkyl acrylate or methacrylate, alkoxy acrylate or
methacrylate, glycidyl acrylate or methacrylate, acryl-or methacrylamide, vinyl acetate,
acrylonitrile, olefin, styrene, etc. which are used alone or in combination, or polymers
comprised of monomers comprising a combination of any of these with acrylic acid,
a,,8-unsaturated dicarboxylic acid, sulfoalkyl acrylate, styrene sulfonic acid or
the like. Specific examples thereof may include polymers described in U.S. Patents
No. 2,376,005, No. 3,607,290 and No.3,645,740, British Patents No. 1,186,699 and No.
1,307,373, U.S. Patents No. 3,062,674, No. 2,739,137, No. 3,411,911, No. 3,488,708,
No. 3,635,715 and No. 2,853,457.
[0055] In the light-sensitive material of this invention, the emulsion layers and other
component layers can be hardened by adding hardening agents usually used. The hardening
agents include, for example, aldehydes as exemplified by glyoxal described in U.S.
Patent No. 1,870,354, glutaraldehyde described in British Patent No. 825,544; N-methylol
compounds as exemplified by N,N' -dimethylol urea, dimethylolhydantoin described in
British Patent No. 676,628; dioxane derivatives as exemplified by dihydroxydioxane
described in U.S. Patent No. 3,380,829 or similar derivatives described in Japanese
Patent Publication No. 38713/1971; compounds having an epoxy group as exemplified
by the compounds described in U.S. Patents No. 3,047,394 and No. 3,091,573 and Japanese
Patent Publication No. 7133/1959; compounds having a reactive halogen, as exemplified
by 2,4-dichloro-6-hydroxy-1,3,5-triazine described in U.S. Patent No.3,325,287; mucohalogen
acids as exemplified by mucochloric acid and mucobromic acid described in U.S. Patent
No. 2,080,019 or derivatives thereof described in Japanese Patent Publication No.
1872/1971; bis-(methanesulfonic acid ester) described in U.S. Patent No. 2,726,162;
sulfonyl compounds as exemplified by bis(benzenesulfonyl chloride) described in U.S.
Patent No. 2,725,295; aziridine compounds as exemplified by the compounds described
in Japanese Patent Publications No. 4212/1958 and No. 8790/1962; divinyl sulfones
as exemplified by compounds described in U.S. Patent No. 2,579,871 or the like compounds;
compounds having a reactive olefin bond, as exemplified by divinyl ketones of the
compounds described in German Patent No. 872,153, compounds having an acryloyl group
as described in U.S. Patents No. 3,255,000 and No. 3,635,718, British Patent No. 994,869
and West German Patent No. 10 90 472; alkylene bismaleimides described in U.S. Patent
No. 2,992,109, etc.; isocyanates described in U.S. Patent No. 3,103,437, etc.; carboimides
described in U.S. Patent No. 3,100,704; isoxazole derivatives as exemplified by the
compounds described in U.S. Patents No. 3,321,313 and No. 3,543,292; carbamoyl chloride
derivatives described in Japanese Patent Publication No. 6899/1966; polymeric hardening
agents as exemplified by dialdehyde starch described in U.S. Patent No. 3,057,723
or the compounds described in Japanese Patent Publication No. 12550/1967; inorganic
hardening agents as exemplified by chrome alum, chromium acetate, zirconium sulfate,
etc.; and these many kinds of compounds can be used alone or in combination.
[0056] In this invention, the hydrophilic colloid layer containing the matting agent may
preferably be hardened with use of active halogen type hardening agents. Of course,
it is also possible to use in combination any hardening agents other than the active
halogen type hardening agents. Employment of the active halogen type hardening agents
makes it possible to decrease the blots at the time of the erasing of water-base ink
inscriptions to comtribute enhancement of removability, without damaging the inscribability.
The active halogen type hardening agent, the manner of use thereof, etc. are described,
for example, in Japanese Patent Publications No. 16928/1964, No. 2602/1968, No. 6151/1972,
No. 33380/1972, No. 13709/1973, No. 3527/1973, No. 31937/1973, No. 9434/1976, No.
78788/1976, No. 60612/1977, No. 127229/1977, No. 15958/1979, No. 27135/1981, etc.
[0057] Preferred active halogen hardening agents are dichloro-S-triazines, and may typically
include, for example, 2,4-dichloro-6-hydroxy-1,3,5-triazine (alkali metal salts),
2,4-dichloro-6-methoxy-1,3,5-triazine, 2,4-dichloro-6-ethylamino-1,3,5-triazine, 2,4-dichloro-6-hydroxyethylamino-1,3,5-triazine,
etc.
[0058] With the hardening agent of this invention, compounds capable of accelerating the
hardening of gelatin can be used in combination. Such hardening accelerators may include
non-protonic solvents described in West German Patent (Laid-Open Publication) No.
24 17 586, betaine type surface active agents described in Japanese Unexamined Patent
Publication No. 62045/1982, tertiary amines or salts thereof (as exemplified by those
described in Japanese Unexamined Patent Publications No. 1043/1981 and No. 9434/1976,
West German Patent (Laid-Open Publication) No. 21 38 305, British Patents No. 1,284,305
and No. 1,269,983, etc.), all sorts of inorganic salts or polyhydric alcohols, etc.
[0059] In the silver halide emulsion of this invention, any of silver halides can be used,
including silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
silver chloroiodobromide, silver chloride, etc. which are used in usual silver halide
emulsions.
[0060] In the light-sensitive material of this invention, various additives can be used
depending on the purpose.
[0061] These additives are more specifically described in Research Disclosure Vol. 176,
Item 17643 (December, 1978) and the ditto Vol. 187, Item 18716 (November, 1979), relevant
passages of which are summarized in the table shown below.
[0062] Also, there is no particular limitation in regard to the exposure and development
processing conditions for the light-sensitive material of this invention, and reference
can be made to the above Research Disclosure Vol. 176, pp.28-30.

[0063] The support used in the light-sensitive material of this invention may preferably
be transparent. This is because the light-sensitive material of this invention is
often used as an original for diazo print copying after development processing. Examples
of the support may include cellulose acetate, cellulose nitrate, polystyrene, polyvinyl
chloride, polyethylene terephthalate, polycarbonate, polyamide, etc.
[0064] Any known processing can be used for the development processing of the light-sensitive
material of this invention. This development processing may be either the processing
to form silver images (black and white development processing) or the development
processing to form color images, depending on the purpose.
[0065] The black and white development processing comprises a developing step, a fixing
step and a washing step. The washing step may sometimes be omitted when a stopping
step is carried out after the developing step or a stabilizing step is applied after
the fixing step. Developing agents or precursors thereof may be incorporated into
light-sensitive materials to carry out the developing step with use of an alkali solution
only. There may be also carried out a developing step using lith developers as developing
solutions.
[0066] Terms and materials used in the third invention will be described below.
[0067] In this invention, at least one of the compounds represented by Formulas (I), (II),
(III), (IV) and (V) is contained, and these are advantageously used as organic desensitizers.
These compounds are superior in that they can bring about a high speed and a low color
remain. In the light-sensitive material of this invention, at least one kind arbitrarily
selected from the group consisting of the compounds represented by Formulas (I), (II),
(III), (IV) and (V) may be contained, and there may be available either i) one, two
or more kinds of the compound represented by any one of the formulas or ii) two or
more kinds of the compounds represented by two or more formulas. When two or more
kinds of the compounds are used, they may be in any combination.
[0068] Synthesis methods for the organic desensitizer of this invention include, for example,
the methods described in U.S. Patents No. 3,567,456, No. 3,582,343, No. 3,598,596,
etc. in respect of the compounds represented by Formulas (I), (II) and (III), the
methods described in U.S. Patents No. 3,539,349, etc. in respect of the compound represented
by Formula (IV), and the methods described in U.S. Patents No. 3,431,111, No. 3,492,123,
etc. in respect of Formula (V).
[0069] Examples of the compounds represented by Formulas (I), (II), (III), (IV) and (V)
are shown below as (I-1) to (I-9), (11-1) to (11-3), (III-1) to (111-6), (IV-1), (IV-2),
(V-1) to (V-3), but needless to say this invention is by no means limited to these
specific compounds.
[0071] These organic desensitizers may desirably be dissolved in suitable solvents and added
in the silver halide having been desalted, in an amount of 10-
4 to 10-
2 mol per mole of silver halide. The above organic desensitizers may also be used alone
or as a mixture of two or more kinds.
[0072] The photographic layer referred to in this invention is a generic term for light-sensitive
layers and non-light-sensitive layers. The light-sensitive layers specifically include
direct positive silver halide emulsion layers, direct positive silver halide emulsion
layers applied with fog in the presence of a reduction fogging agent and a water-soluble
gold compound, and the like layers. The non-light-sensitive layers specifically include
subbing layers, intermediate layers, protective layers, etc.
[0073] In the light-sensitive silver halide photographic material of this invention, at
least 250 mg/m
2 of at least one kind of matting agent is contained in at least one layer of the photographic
layers. The content of the matting agent otherwise less than 250 mg/m
2 may make it difficult to achieve sufficient inscribability. A matting agent of the
same kind or different kind may be also contained in two or more layers. In such an
instance, the layer to which the matting agents are added may be any of emulsion layers,
protective layers, or subbing layers to be optionally provided, and intermediate layers.
The matting agents may be of any kind, and various ones can be used, for example.
Specifically, they include particles of water-insoluble organic and inorganic compounds,
and there can be used those having any particle diameter. Preferably, those having
a particle diameter of from 0.3 to 5 u.m should be used. Examples of the organic and
inorganic compounds are the same as those set forth in the first invention.
[0074] The reduction fogging agent used in this invention to apply fog includes, for example,
formalin, hydrazine, polyamines (as exemplified by triethylenetetramine, tetraethylenepentamine,
etc.), thiourea dioxide, tetrahydroxymethylphosphonium chloride, amine borane, boron
compound hydrides, stannous chloride, etc. which should be used generally in the range
of from 10-
7 to 10-
3 mol per mol of silver halide. These reduction fogging agents may also be used alone
or as a mixture of two or more kinds.
[0075] The water-soluble gold compound also includes, for example, potassium chloroaurate,
chloroaurate, potassium gold cyanide, potassium gold thiocyanate, sodium gold thiomaleate,
gold thioglucose, etc., which may be used generally in the range of from 10-
6 to 10-4. mol per mol of silver halide.
[0076] The silver halide emulsions used in this invention may be those having any grain
size, crystal habit, silver halide composition, etc., but useful as light-sensitive
materials are those having a grain size of approximately from about 0.1 to about 1
u.m as being preferable in view of the graininess and sharpness, and, in silver iodobromide,
those comprising preferably not more than 5 mol %, more preferably not more than 3
mol %, of silver iodide as having smaller development restraining properties and being
advantageous in practical use. These silver halide emulsions are prepared according
to a variety of methods. For example, there can be applied the method in which the
group VIII soluble gold complex salts as described in U.S. Patent No. 2,717,833, Japanese
Patent Publication No. 4125/1968, British Patent No. 1,186,717, etc., the method of
preparing ammoniacal emulsions as described in U.S. Patent No. 2,184,013, the method
of preparing monodisperse emulsions as described in U.S. Patent No. 3,501,305, the
method of preparing heterodisperse emulsions as described in Japanese Unexamined Patent
Publication. No. 43627/1974, the method of preparing regular grain emulsions as described
in U.S. Patent No. 3,501,306, the method of preparing covered-grain emulsions as described
in U.S. Patent No. 3,367,785, British Patent No. 1,229,868, No. 1,186,718, etc., and
the method of preparing internal latent image type emulsions as described in U.S.
Patent No. 2,592,250.
[0077] In the direct positive light-sensitive silver halide photographic material in this
invention, additives for other photography can be also used. There may be contained
stabilizers as exemplified by triazoles, azaindenes, quaternary benzothiazolium compounds,
mercapto compounds, or water-soluble inorganic salts of cadmium, cobalt, nickel, manganese,
gold, thallium, zinc, etc. There may be also contained hardening agents as exemplified
by formaldehydes such as formalin, glycoxal and mucochloric acid, s-triazines, epoxys,
aziridines, vinylsulfonic acid, etc; coating aids as exemplified by saponin, sodium
polyalkylenesul- fonate, lauryl or oleyl monoether of polyethylene glycol, amylated
alkyltaurines, fluorine-containing compounds, etc.; and sentizers as exemplified by
polyalkylene oxide and derivatives thereof. It is also possible for it to further
contain couplers. Besides, there can also be optionally contained antiseptic agents,
antistatic agents, developing agents, etc.
[0078] The support used in this invention includes supports made of paper, glass, cellulose
acetate, cellulose nitrate, polyester, polyamide, polystyrene, polypropylene, etc.,
or laminated materials comprising two or more kinds of substrates, as exemplified
by a laminated material comprising paper and a polyolefin (as exemplified by polyethylene,
polypropylene, etc.).
[0079] As developing solutions according to this invention, those having the composition
generally used can be used. Developing agents include hydroquinone, alklylhydroquinones
(as exemplified by methylhydroquinone, dimethylhydroquinone and t-butylhydroquinone),
catechol, pyrazole, chlorohydroquinone, dichlorohydroquinone, methoxyhydroquinone,
ethoxyhydroquinone, aminophenol developing agents (as exemplified by N-methyl-p-aminophenol
and 2,4-diaminophenol), ascorbic acid developing agents, N-methyl-p-aminophenolsulfate,
pyrazolones (as exemplified by 4-aminopyrazolone), 3-pyrazolidone developing agents
(as exemplified by 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone,
1-p-tolyl-3-pyrazolidone and 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone), etc.
which are used alone or in combination. Particularly suited for the rapid processing
of this invention is the combination of hydroquinone with 3-pyrazolidones, or hydroquinone
with aminophenols.
[0080] Besides, the developing solution of this invention may optionally contain all sorts
of additives including preservatives such as sulfites, bisulfites and hydroxylamines;
alkali agents such as hydroxides, carbonates and phosphates; pH adjusters such as
acetic acid; dissolution aids such as polyethylene glycols; sensitizers such as quaternary
ammonium salts; organic solvents such as methanol, diethylene glycol, diethanolamine,
dimethylformamide and dimethylsulfoxide; development accelerators; surface active
agents; anti-foaming agents; toning agents; viscosity-imparting agents such as carboxymethyl
cellulose and hydroxyethyl cellulose; hardening agents such as glutaraldehyde; silver
sludge preventive agents; silver halide solvents such as thioethers, thioamides, thiocyanates
and thiosulfates; antifoggants such as potassium bromide and benzotriazole; chelating
agents such as aminopolycarboxylic acids, aminopolyphosphonic acids and phosphonocarboxylic
acids; etc.
[0081] As fixing solutions used in this invention, those having the composition generally
used can be used. There can be contained fixing agents including sodium thiosulfate,
ammonium thiosulfate, sodium thiocyanate and ammonium thiocyanate, silver halide solvents
including thioureas and amine derivatives, as well as sulfites such as sodium sulfite,
ammonium sulfite, sodium bisulfite and potassium metabisulfite; borates such as borax
and sodium metaborate; organic carboxylic acids such as acetic acid, citric acid,
tartaric acid and malic acid; inorganic acids such as sulfuric acid, boric acid and
hydrochloric acid; amines such as ethylenediamine, diethanolamine and triethanolamine;
water-soluble aluminum salts such as potash alum, ammonium alum, aluminum sulfate
and aluminum chloride; organic compounds such as methanol, ethylene glycol, diethylene
glycol, triethylene glycol, polyethylene glycol, polyoxyethylene glycol and acetone;
further optionally iodides such as potassium iodide and sodium iodide; and any other
additives.
[0082] As a preferred embodiment of the above-described first to third invention, in order
to provide a light-sensitive silver halide photographic material having a better inscribability,
a higher speed and less color remain, the silver halide grains contained.in the emulsion
layers may preferably comprise silver chloride or silver chloroiodide containing 10
to 80 mol % of silver chloride, and be subjected to spectral sensitization by use
of a compound represented by Formula (VI).

[0083] In the formula, Z represents a group of atoms necessary for completing an oxazole
nucleus, a benzoxazole nucleus or a naphtoxazole nucleus, and these nuclei may have
a substituent on a carbon atom. Examples of the substituent may include halogen atoms
(as exemplified by a fluorine atom, a chlorine atom and a bromine atom), unsubstituted
alkyl groups having 1 to 6 carbon atoms (as exemplified by a methyl group, an ethyl
group, a propyl group, a butyl group, a hexyl group, etc.), alkoxy groups having 1
to 4 carbon atoms (as exemplified by a methoxy group, an ethoxy group, a propoxy group
and a butoxy group), a hydroxyl group, alkoxycarbonyl groups having 1 to 6 carbon
atoms (as exemplified by a methoxycarbonyl group, an ethoxycarbonyl group, etc.),
alkylcarbonyloxy groups having 2 to 5 carbon atoms (as exemplified by an acetyloxy
group, a propionyloxy group, etc.), a phenyl group, a hydroxyphenyl group, etc.
[0084] Examples of these nuclei may include nuclei of, as the oxazole nucleus, oxazole,
4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole, 4-phenyloxazole, etc.; as the
benzoxazole nucleus, benzoxazole, 5-chlorobenzoxazole, 5-bromobenzoxazole, 5-methylbenzoxazole,
5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole,
5-acetyloxybenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 6-methoxybenzoxazole,
5,6-dimethylbenzoxazole, 6-chloro-5-methylbenzoxazole, etc.; as the naphthoxazole
nucleus, naphtho[1,2-d]oxazole, naphtho[2,1-d]oxazole, naphtho[2,3-d]oxazole, etc.
[0085] R' represents a substituted or unsubstituted alkyl group. Examples of the substituent
may include a hydroxyl group, a sulfo group, a sulfonate group, a carboxyl group,
halogen atoms (as exemplified by a fluorine atom and a chlorine atom), substituted
or unsubstituted alkoxy groups having 1 to 4 carbon atoms (the alkoxy group may be
further substituted with a sulfo group or a hydroxyl group), alkoxycarbonyl groups
having 2 to 5 carbon atoms, alkylsulfonyl groups having 1 to 4 carbon atoms, a sulfamoyl
group, substituted or unsubstituted carbamoyl groups (including substituted carbamoyl
groups substituted with an alkyl group having 1 to 4 carbon atoms), substituted phenyl
groups (examples of the substituent are a sulfo group, a carboxyl group, a hydroxyl
group, etc.), a vinyl group, etc.
[0086] Examples of the unsubstituted alkyl group may include a methyl group, an ethyl group,
a propyl group and a butyl group. Examples of the substituted alkyl group may include
as hydroxyalkyl groups, a 2-hydroxyethyl group, a 3-hydroxypropyl group, etc., as
sulfoalkyl groups, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group,
a 4-sulfobutyl group, a 2-hydroxy-3-sulfopropyl group, a 2-chloro-3-sulfopropyl group,
etc., as carboxyalkyl groups, a carboxymethyl group, a carboxyethyl group, a carboxypropyl
group, etc., a 2,2,2-trifluoroethyl group, a 2-(3-sulfopropyloxy)ethyl group, a 2-(2-hydroxyethoxy)-ethyl
group, an ethoxycarbonylethyl group, a methylsulfonylethyl group, as sulfamoylalkyl
groups, a 2-sulfamoylethyl group, a 2-sulfamoylethylgroup, a 2-N,N-dimethylsulfamoylethyl
group, etc., a phenethyl group, a p-carboxyphenethyl group, as sulfoaralkyl groups,
a p-sulfophenethyl group, an o-sulfophenethyl group, etc., a p-hydroxyphenethyl group,
a phenoxyethyl group, etc.
[0087] R
2 represents an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl
group, a carbamoylalkyl group, a hydroxyalkylthioalkyl group, a hydroxyphenyl group,
a morpholinoalkyl group, a hydroxyalkylphenyl group, a phenyl group, an alkoxyalkyl
group, or a substituent

Herein A represents a nitrile group, an alkylsulfonyl group, a sulfonamide group,
an alkylsulfonylamino group or an alkoxy group having 1 to 8 carbon atoms, and n represents
an integer of 1 to 4.
[0088] The above groups represented by R
2 include those having a substituent. For example, those wherein the alkyl moiety in
the above groups has been substituted with a halogen atom can also be preferably used.
[0089] Examples of R
2 include alkoxycarbonylalkyl groups (as exemplified by a methoxycarbonylfluoromethyl
group, an ethoxycarbonylfluormethyl group, a fluoroethoxycarbonylethyl group, etc.),
hydroxyalkyl groups (as exemplified by a 2-hydroxyfluoroethyl group, 2-hydroxyfluoropropyl
group, 3-hydroxyfluoropropyl group, 2,3-dihydroxyfluoropropyl group, etc.), hydroxyalkoxyalkyl
groups (as exemplified by a hydroxymethox- yfluoromethyl group, a 2-(2-hydroxyfluoroethoxy)ethyl
group, a hydroxyfluoroethoxymethyl group, etc.), carbamoylalkyl groups (including
N-alkyl-substituted, N,N-dialkyl-substituted, N-hydroxyalkyl-substituted, N-alkyl-N-hydroxyalkyl-substituted
or N,N-di(hydroxylalkyl)-substituted carbamoylalkyl groups and carbamoylalkyl groups
of 5-or 6-membered cyclic amines) (as exemplified by a 2-carbamoylchloroethyl group,
a 2-N-(2-hydroxyethyl) carbamoylchloroethyl group, a N-hydroxyfluoroethylcarbamoylmethyl
group, an N,N-di(2-hydroxyfluoroethyl)carbamoylmethyl group, a 2-N,N-di(2-hydroxyethyl)carbamoylchloroethyl
group, an N,N-dimethyl)carbamoylchloromethyl group, a morpholinocarbamoylchloromethyl
group, a piperidinocar- bamoylmethyl group, etc.), a hydroxyphenyl group, hydroxyalkylphenyl
groups having 7 to 9 carbon atoms (as exemplified by a p-(2-hydroxyfluoroethyl)phenyl
group, a m-(1-hydroxyfluoroethyl)phenyl group, etc., and a substituent

Herein A represents a nitrile group, an alkylsulfonyl group, a sulfonamide group,
an alkylsulfonylamino group or a lower alkoxy group, of which the alkylsulfonyl group
may preferably include alkylsulfonyl groups having 1 to 4 carbon atoms (as exemplified
by a methylsulfonyl group, an ethylsulfonyl group, etc.), the sulfonamide group may
preferably include sulfonamide groups having 1 to 4 carbon atoms (as exemplified by
an N-methylsulfonamide group, an N,N-dimethylsulfonamide group, etc.), the alkylsulfonylamino
group may preferably include alkylsulfonylamino groups having 1 to 4 carbon atoms
(as exemplified by a methylsulfonylamino group, etc.), and the lower alkoxy group
may preferably include alkoxy groups having 1 to 4 carbon atoms (as exemplified by
a methoxy group, an ethoxy group, etc.). n represents an integer of 1 to 4.
[0090] R
3 and R
4 may be the same or different, and each represent a hydrogen atom, an alkyl group
(preferably one having 1 to 4 carbon atoms, as exemplified by a methyl group, an ethyl
group, etc.), an alkoxy group (preferably one having 1 to 4 carbon atoms, as exemplified
by a methoxy group, an ethoxy group, etc.), an alkylsulfonyl group, a sulfo group,
a chlorine atom, a fluorine atom or a carboxyl group.
[0091] In the compound represented by the above Formula (VI), particularly preferred is
an instance where R
1 represents a straight or branched alkyl group having 1 to 4 carbon atoms and substituted
with a sulfo group or a carboxyl group and/or a hydroxyl group, specifically including
a sulfoethyl group, a sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group,
a carboxymethyl group, a carboxyethyl group, a hydroxyethyl group, a 3-sulfo-2-hydroxypropyl
group, etc.
[0092] Typical examples of the compound represented by the above Formula (VI) used in this
invention are shown below, but of course the compounds used in this invention are
by no means limited to these.
[0094] The compound represented by the above Formula (VI) used in this invention can be
synthesized by the method of synthesizing dimethinemerocyanines as described in Japanese
Patent Publications No. 549/1971, No. 18105/1971, No. 18106/1971, No. 18108/1971,
No. 4085/1972 and No. 52574/1983, U.S. Patents No. 2,839,403, No. 3,384,486, No. 3,625,698,
No. 3,480,439 and No. 3,567,458, etc.
[0095] Addition and dispersion of the merocyanine dye represented by the above Formula (VI)
used in this invention in the silver halide emulsion can be carried out, for example,
by conventionally known methods. For example, the methods may include a method in
which it is added by dispersing it together with a surface active agent as described
in Japanese Patent Publication No. 44895/1974 and Japanese Unexamined Patent Publication
No. 11419/1975, a method in which it is added as a dispersion with a hydrophilic substrate
as described in Japanese Unexamined Patent Publications No. 16624/1978, No. 102732/1978
and No. 102733/1978, U.S. Patents No. 3,469,987 and No. 3,676,147, and a method in
which it is added as a solid solution as described in East German Patent No. 143,324.
Besides, the merocyanine dye may be dissolved in a water-soluble solvent as exemplified
by a solvent solely comprising water, ethanol, methanol, acetone, propanol, alcohol
fluoride, pyridine, or the like or a mixed solvent of any of these, and then added
in emulsions. It may be added at any time in the course of preparing emulsions, but
may preferably be added during chemical ripening or after chemical ripening. The dye
of the above Formula (VI) used in this invention may be added in the amount for carrying
out the spectral sensitization of silver halide emulsions, as exemplified by 10-
5 to 2 × 10
-2, preferably 10-
4 to 2
x 10-
3 mol per mol of silver halide.
[0096] The merocyanine dye used in this invention can be subjected to supersensitization,
for example, by using it in any amount in combination with other dyes as described
in Japanese Patent Publications No. 4933/1968, No. 4936/1968, No. 18107/1971, No.
1999/1971, No. 11114/1972, No. 1762/1973, No. 38408/1973, No. 38937/1981 and No. 52574/1983,
U.S. Patents No. 2,519,001 and No. 3,745,014, etc.
[0097] The silver halide grains contained in the silver halide emulsion layer of this embodiment
are required to be comprised of silver chlorobromide or silver chloroiodobromide containing
10 to 80 mol % of silver chloride. This is because the silver chloride otherwise less
than 10 mol % may result in a lowering of speed and the silver chloride otherwise
more than 80 mol % may cause an increase in fog. In the case of the silver chloroiodobromide,
the content of silver iodide may preferably be 5 mol % or less, more preferably 2
mol % or less, for the purpose of achieving a higher speed.
[0098] In the course of the formation of silver halide grains or the chemical ripening,
a compound containing a metal belonging to Group VIII can be made to coexist for improving
developability, making hardened, giving high illumination adaptability, etc.
EXAMPLES
[0099] Examples of this invention will be described in detail. As a matter of course, this
invention is by no means limited to the following examples.
Example 1
[0100] (Preparation of emulsions) Solution A: Water 9.7 lit Sodium chloride 20 g Gelatin
105 g Solution B: Water 3.8lit Gelatin 94 g Sodium chloride 58.5 g Potassium bromide
1,072 g Solution C: water 3.8 lit Silver nitate 1,700 g
[0101] In 9,800 ml of the above Solution A maintained at a temperature of 55°C, the above
Solution B and the above Solution C were simultaneously added functionally with the
time for addition as shown in Table 1 while keeping pAg 7.2. The function and the
time for addition were observed by use of an electron microscope to use a manner for
obtaining good monodispersity. The monodispersity was all found to be 10 to 12 %.

[0102] Five kinds of solutions thus obtained were respectively continued being stirred for
10 minutes, and thereafter the pH was adjusted to 6.0 with use of sodium carbonate,
to which 2 lit. of an aqueous 20 % magnesium sulfate solution and 2.55 lit. of an
aqueous 5 % polynaphthalenesulfonic acid solution were added, and then the emulsions
were flocculated at 40°C, followed by decantation, and washing with water to remove
excess salts in the solutions. Subsequently, 3.7 lit. of water was added to make dispersion,
and again 0.9 lit. of an aqueous 20 % magnesium sulfate solution was added to similarly
remove excess salts in the solutions. To the resulting solutions, 3.9 lit. of water
and 141 g of gelatin were added, and the mixtures were dispersed for 30 minutes at
50°C.
[0103] Thereafter 142 ml of a 1 % ammonium thiocyanate solution, 68 ml of a 1 % solution
of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, sodium thiosulfate in an amount optimum
for the respective grains and 227 ml of a 1 % silver nitrate solution were added,
and the mixtures were ripened at 45°C to have a maximum speed.
[0104] Five kinds of the solutions prepared in the above manner were mixed as shown in Table
2 in the proportion of 1 : 1 (respectively 5 mols calculated as silver), and thereafter
added were 80 ml of an aqueous 0.5 % solution of 1-phenyl-5-mercaptotetrazole as an
antifoggant, 350 ml of an aqueous 10 % solution of hydroquinone, 1,600 ml of an aqueous
1 % solution of 4-hydroxy-6-methyl-1,3,3a-7-tetrazaindene as a stabilizer, 1.5 g of
Compound (1) represented by the following formula as a sensitizing dye and 600 mg
of Compound (2).

[0105] Further added were 180 ml of an aqueous 20 % saponin solution as a spreading agent,
300 ml of an aqueous 4 % solution of a styrene/maleic acid copolymer as a thickening
agent, 250 g of a polymeric latex polymer of ethyl acrylate, 150 ml of 3 % formalin
as a hardening agent and 4 g of sodium 2-hydroxy-4,6-dichloro-1,3,5-triazine.
[0106] Further as a solution for protective layers, 500 mg of sodium 2-sulfonate succinic
acid bis(2-ethylhexyl) ester as a spreading agent was added in 560 g of gelatin, followed
by making up to 10 lit. with water.

(Coating)
[0107] On one side each of polyethylene terephthalate supports having been subjected to
subbing processing, the above emulsions and the above protective layer solution were
simultaneously coated to obtain 18 kinds of light-sensitive silver halide photographic
materials as shown in Table 3.
[0108] Also, the silver amount and the type of the matting agent and coating amount thereof
in the emulsion layer of each sample were as shown in Table 3, and the type of the
matting agent and coating amount thereof in the protective layer were as shown in
Table 3.
(Exposure and processing)
[0109] Part of each sample prepared in the above manner was imagewise exposed to light and
other part thereof was kept unexposed. Developing was carried out over the period
of 15 seconds at 43°C using Sakura Automatic Processor GR-26 (manufactured by Konishiroku
Photo Industry Co., Ltd.), fixing was carried out over the period of 15 seconds at
35°C, washing was carried out over the period of 15 seconds at room tremperature,
and drying was carried out for 20 seconds with warm air of 45°C.
[0110] (Developing solution recipe) Pure water about 800 ml Potassium sulfite 60 g Disodium
ethylenediaminetetraacetate 2 g Sodium sulfite 2 g . Potassium hydroxide 10.5 g 5-Methylbenzotriazole
300 mg Diethylene glycol 25 g 1-Phenyl-4,4-dimethyl-3-pyrazolidinone 300 mg 1-Phenyl-5-mercaptotetrazole
600 mg Potassium bromide 3.5 g Hydroquinone 20 g Potassium carbonate 15 g Made up
to 1,000 ml by adding pure water (ion-exchanged water).
[0111] At the time when the developing solution was used, the whole amount of the above
developing solution was dissolved in 3 lit. of pure water (ion-exchanged water) and
used.
[0112] The developing solution had the pH of about 11.4 before dilution with water, and
the developing solution had the pH of about 10.8 after dilution with water.
[0113] (Fixing solution recipe) Ammonium thiosulfate (an aqueous 72.5 % W/V solution) 240
ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate
dihydrate 2 g Acetic acid (an aqueous 90 % WN solution) 25 ml
[0114] At the time when the fixing solution was used, the above composition was dissolved
in 500 ml of water, made up to 1 lit. and used. This fixing solution had the pH of
about 4.5.
(Evaluation method)
[0115] In the table, the sharpness in line photographying was visually evaluated with use
of a 100-power magnifier, and evaluateded by a 5 rank system, indicating that 5 is
the best. Also, the gamma represents the gradation in a continuous tone, which is
a gamma value of the film density of from 0.1 to 2.5, showing that 2 to 2.6 is good
for the characteristics of the present films. The larger the value is, the higher
the contrast is, so that it becomes impossible to use the films as continuous tone
films.
[0116] The clearing performance of fixing and the inscribability and erasability with use
of a drafting pencil and a needle pen (Rotring pen) were evaluated according to the
3 rank system shown below.
(Measurement results)
[0117] Results of the measurement are shown in Table 4. Samples Nos. 1 to 5, 11, 12, 14
and 18 falling under this invention showed the sharpness of line photographying as
good as 4 to 4.5 and also the gamma value as good as 2.1 to 2.5, and also showed good
results for the inscribability and erasability with use of the pencil and the inscribability
and erasability with use of the needle pen (Rotring pen).
[0119] As described above, it is possible according to this invention to obtain a light-sensitive
silver halide photographic material that can be processed with usual rapid access,
can effect a continuous tone and line photographing on the same film, can achieve
very good fixing clearing, and can be greatly superior in the inscribability and erasability.
Example 2
Preparation of coating solutions for silver halide emulsion layers
[0120] Prepared first were the following Solutions (A), (B), (C) and (D). (A):
Water 980 ml Gelatin 10 g Sodium chloride 2 g Water 380 ml
(B): Gelatin 10 g Sodium chloride 30 g Potassium bromide 60 g
(C): Water 380 ml Silver nitrate 170 g
(D): Water 100 ml Potassium bromide 35 g
[0121] Solution (A) was maintained at 45°C, and Solutions (B) and (C) were functionally
added thereto with stirring, taking 41 minutes while keeping pH = 6.0 and pAg = 7.5.
After 2 minutes from completion of the addition, Solution (D) was added taking 4 minutes,
and subsequently the temperature was dropped to 40°C to carry out desalting and washing
according to a conventional method, followed by addition of 15 g of gelatin as a final
step to obtain Emulsion I having an average grain size of 0.25 u.m.
[0122] Prepared next were the following Solutions (E), (F), (G), (H), (I) and (J). (E):
Water 980 ml Gelatin 10 g Sodium chloride 2 g
(F): Water 120 ml Gelatin 2.5 g Sodium chloride 0.85 g Potassium bromide 1.7 g
(G): Water 370 ml Gelatin 8.8 g Sodium chloride 28 g Potassium bromide 58 g
(H): Water 120 ml Silver nitrate 4.8 g
(I): Water 370 ml Silver nitrate 165.2 g
(J): Water 100 ml Potassium bromide 35 g
[0123] Solution (E) was maintained at 45°C, and Solutions (F) and (H) were functionally
added thereto with stirring, taking 10 minutes while keeping pH = 6.0 and pAg = 7.5,
and subsequently Solutions (G) and (I) were functionally added taking 70 minutes.
Two minutes after completion of the addition, Solution (J) was added taking 4 minutes,
and subsequently the temperature was dropped to 40°C to carry out desalting and washing
according to a conventional method, followed by addition of 15 g of gelatin as a final
step to obtain Emulsion II having an average grain size of 0.40 u.m.
[0124] Next, 0.1 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 6 mg of sodium thiosulfate
were added to Emulsion I to apply sulfur sensitization with ripening for 60 minutes
at 50°C, followed by addition of 70 mg of 1-phenyl-5-mercaptotetrazole, 1 g of 4-hydroxy-6-methyf-1.3,3a,7-tetrazaindene
and 40 g of gelatin.
[0125] Also, 1.5 mg of sodium thiosulfate was added to Emulsion II to apply sulfur sensitization
with ripening for 80 minutes at 50°C, followed by addition of 70 mg of 1-phenyl-5-mercaptotetrazole,
1 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 40 g of gelatin.
[0126] Subsequently, Emulsion I and Emulsion II were mixed. Thereafter 200 mg of Compound
(a) shown below and 60 mg of Compound (b), per mol of silver halide, were added to
effect spectral sensitization, and further added were 3.7 g of saponin as a coating
aid, 2 g of hydroquinone as a stabilizer, rice starch, as a matting agent, having
the particle diameter characteristics as shown in Table 5 and in the amount as shown
in Table 5, 30 g of polybutyl acrylate as a latex polymer, 1 g of a styrene/maleic
anhydride copolymer as a thickening agent and 0.8 g of sodium 2,4-dichloro-6-hydroxy-s-triazine
as a hardening agent, followed by adjustment of the pH to 5.5 with use of citric acid
as a final step to prepare a coating solution for emulsion layers.

Preparation of coating solutions for protective layers
[0127] In 100 g of gelatin, 1,400 ml of water was added to effect dissolution, and thereafter
added were silica having the particle diameter characteristics as shown in Table 5
and in the amount as shown in Table 5, 2 g of saponin as a surface active agent, and
Compound (c) shown below so that the surface tension of the coating solutions for
protective layers comes to 42, 38, 36, 30, 28 and 24 dyne/cm, respectively, with further
addition of 3 g of formalin as a hardening agent, to prepare coating solutions for
protective layers. Here, the surface tension when no Compound (c) was added was 42
dyne/cm. The coating solutions had the pH of 6.0. The surface tension was measured
according to a vertical plate method employing a platinum plate.

[0128] The classification of rice starch and silica was carried out with use of Spedic Classifier
manufactured by Seishin Kigyo, and the average particle diameter and the weight percentage
of the matting agent having a particle diameter exceeding 6 u.m to the whole matting
agent were measured by Laser Micronsizer manufactured by Seishin Kigyo.
Preparation of coating solution for lower backing layers
[0129] In 100 g of gelatin, 1,600 ml of water was added to effect dissolution, and thereafter
added were 5 g of Compound (d), 1 g of (e) and 1.5 of (f) shown below, as dyes, 40
g of rice starch as a matting agent, having the average particle size of 3 µm and
the weight percentage of the matting agent having a particle diameter exceeding 6
u.m to the whole matting agent, of 0.5 %, 5 g of saponin as a surface active agent,
1 g of styrene-maleic anhydride as a thickening agent and 1 g of glyoxal as a hardening
agent, followed by adjustment of the pH to 5.5 with use of citric acid as a final
step to prepare a coating solution for lower backing layers.

Preparation of coating solution for upper backing layers
[0130] In 100 g of gelatin, 1,200 ml of water was added to effect dissolution, and thereafter
added were 50 g of silica as a matting agent, having the average particle size of
3 u.m and the weight percentage of the matting agent having a particle diameter exceeding
6 u.m to the whole matting agent, of 0.5 %, 3 g of saponin as a surface active agent.
0.2 g of the above Compound (c) and 1 g of glyoxal as a hardening agent, to prepare
a coating solution for lower backing layers. The coating solution had the pH of 6.0
and surface tension of 36 dyne/cm.
Preparation of samples
[0131] On polyethylene terephthalate supports having a thickness of 100 u.m and applied
with subbing processing on both sides thereof, the above lower backing layer coating
solution and upper backing layer coating solution were simultaneously coated with
lamination. Subsequently, on the side opposite to the backing layers, the above emulsion
layer coating solutions and protective layer coating solutions were simultaneously
coated with lamination to make Samples No. 1 to No. 15.
[0132] Coated silver amount was 3.5 g/m
2, and gelatin amounts were 2.5 g/m
2 for the lower backing layer, 1 g,/m
2 for the upper backing layer, 1.9 g/m
2 for the emulsion layer, and 1.4 g.lm
2 for the protective layer.
[Evaluation of inscribability and erasabilityl
[0133] The above samples were kept unexposed to light, and processed with an automatic processor
GR-26 (manufactured by Konishiroku Photo Industry Co., Ltd.) in which the developing
solution and fixing solution shown below were introduced, to obtain samples for use
in evaluation.
[0134] Processing conditions were 40°C, 20 seconds for developing, 35°C, 20 seconds for
fixing, and room temperature and 20 seconds for washing.
[0135] Next, the center-line average roughness of the surfaces were measured with use of
Perthometer manufactured by Perthen AG, West Germany. Subsequently the inscribability
was evaluated with water-base ink by use of a drafting needle pen (Rotring pen).
[0136] The evaluation was made with use of a 10-power magnifier to visually evaluate the
density of lines, the uniformity of density and the constancy of line width, and the
line width reproducibility was measured with use of a 25-power magnifier having gradations
of length. Target line width is 500 u.m. Smoothness in writing touch was evaluated
at the same time.
[0137] Lines were erased with a plastic eraser for use in pencils, applied with water in
a small quantity, to further visually evaluate the degree of blotting.
[Results of evaluation]
[0138] Results of evaluation are shown in Table 5.
[0139] Comparison of Samples No. 19 to No. 23 demonstrates that Samples No. 20 to No. 23
in which the center-line average roughness of the surfaces is in the range of from
0.15 to 0.80 have superior inscribability.
[0140] Comparison of Samples No. 22 and No. 24 to No. 28 demonstrates that Samples No. 22
and No. 24 to No. 26 in which the weight percentage of the matting agent having a
particle diameter exceeding 6 um to the whole matting agent is 5 % or less have superior
inscribability.
[0141] Comparison of Samples No. 22, and No. 29 to No. 33 demonstrates that Samples No.
22 and No. 30 to 32 in which the surface tension of the protective layers is in the
range of from 28 to 38 dyne/cm have superior inscribability and erasability.
[0142] <Developing solution recipe> Pure water (ion-exchanged water) about 800 ml Potassium
sulfite 60 g Disodium ethylenediaminetetraacetate 2 g Potassium hydroxide 10.5 g 5-Methylbenzotriazole
300 mg Diethylene glycol 25 g 1-Phenyl-4,4-dimethyl-3-pyrazolidinone 300 mg 1-Phenyl-5-mercaptotetrazole
600 mg Potassium bromide 3.5 g Hydroquinone 20 g Potassium carbonate 15 g Made up
to 1,000 ml by adding pure water (ion-exchanged water).
[0143] The developing solution had the pH of about 10.8.
[0144] <Fixing solution recipe> Ammonium thiosulfate (an aqueous 72.5 % WN solution) 240
ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate
dihydrate 2 g Acetic acid (an aqueous 90 % WN solution) 25 ml
[0146] This invention has made it possible to provide a light-sensitive silver halide photographic
material having superior inscribability and erasability.
Example 3
Preparation of emulsion coating solution
[0147] In 1 lit. of an aqueous 1 % gelatin solution of 65°C, 220 ml of an aqueous 3 % silver
nitrate solution and 220 ml of an aqueous solution containing 98 mol % of potassium
bromide and 2 mol % of potassium iodide based on said silver nitrate were added taking
30 minutes, simultaneously and while controlling the addition rate so that it increases
with time. Subsequently 280 ml of an aqueous 40 % silver nitrate solution and 280
ml of an aqueous solution containing 98 mol % of potassium bromide and 2 mol % of
potassium iodide based on said silver nitrate were added taking 100 minutes, simultaneously
and while controlling the addition rate so that it increases with time. The pH during
the above process was kept to about 2 with nitric acid, and the pAg was kept to about
7.5 with potassium bromide. After completion of the above process, the pH was adjusted
to about 5.5 with an aqueous sodium carbonate solution, and water soluble salts were
removed according to a conventional condensation method, followed by making up with
addition of 15 g of gelatin.
[0148] As a result of this, there was obtained a silver iodobromide emulsion comprising
regular cubic grains having an average grain size of 0.27 u.m, containing 2 mol %
of silver iodide and having a high monodispersity.
[0149] The above emulsion was adjusted to pH = 6.8 with an aqueous sodium carbonate solution,
to which 0.12 mg of thiourea dioxide per mol of silver halide was added under pAg
= 6.8 to carry out ripening for 60 minutes at 70°C, and then 0.50 mg of chloroaurate
per mol of silver halide was added to carry out ripening for 60 minutes at 70°C, thus
producing reduction fog and gold fog.
[0150] To the emulsion applied with fog, potassium bromide was added to make adjustment
to pAg = 9.2, followed by addition of 600 mg per mole of silver halide, of the above
compound (1-4), (11-1), (111-3), (IV-1) or (V-1) as an organic desensitizer according
to this invention, and also the following compound of Formula [A], [B], [C], [D] or
[E] as an organic desensitizer having nothing to do with this invention, and further
making adjustment to pH = 5.3 using citric acid.

[0151] Next, added were 0.2 g/m
2 of diethylene glycol as a wetting agent, 40 mg/m
2 of sodium 1-decyl-2-(3-isopentyl)succinate-2-sulfonate as a coating aid, 60 mg/m
2 of a styrene/maleic anhydride copolymer as a thickening agent and 16 mg of formalin
as a hardening agent per 1 g of gelatin, to prepare a coating solution for direct
positive silver halide emulsions.
Preparation of coating solution for protective layers
[0152] In an aqueous gelatin solution adjusted to pH = 5.3 with an aqueous citric acid solution,
1.2 g of potassium bromide per 100 g of gelatin was added, with further addition of
amorphous silica having an average particle diameter of 3.5 u.m as a matting agent
and by the amount as shown in Table 6, and then added were 30 mg/m
2 of 2-sulfonatosuccinic acid bis(2-ethylhexyl) ester sodium salt as a coating aid,
20 mg/m
2 of the compound of [A] shown below as a fluorine-containing surface active agent,
100 mg/m
2 of a styrene/maleic anhydride copolymer as a thickening agent and 16 mg of formalin
as a hardening agent per 1 g of gelatin, to prepare a coating solution for protective
layers

Preparation of coating samples
[0153] The above emulsion coating solution and protective layer coating solution were coated
with lamination on polyethylene-coated paper of 150 u.m thick having a subbing layer
to prepare samples. Coated silver amount was 1.4 g/m
2, and gelatin coating amounts were 2.0 g/m
2 for the emulsion layer and 1.5 g/m
2 for the protective layer.
Evaluation of photographic performances, color remain intensity and inscribability.
[0154] The coating samples were exposed to light through a wedge, and thereafter development
processing was carried out using Sakura Automatic Processor GR-26 (manufactured by
Konishiroku Photo Industry Co., Ltd.) as an automatic processing machine and solutions
having the following recipes as a developing solution and a fixing solution, and the
photographic performances were evaluated. The development processing conditions were
38°C, 20 seconds for developing, 35°C, 20 seconds for fixing, room temperature and
20 seconds for washing, and about 45°C for drying.
[0155] Developing solution recipe Pure water (ion-exchanged water) about 800 ml Potassium
sulfite 60 g Disodium ethylenediaminetetraacetate 2 g Potassium hydroxide 10.5 g 5-Methylbenzotriazole
300 mg Diethylene glycol 25 g 1-Phenyl-4,4-dimethyl-3-pyrazolidinone 300 mg 1-Phenyl-5-mercaptotetrazole
60 mg Potassium bromide 3.5 g Hydroquinone 20g Potassium carbonate 15 g Made up to
1,000 ml by adding pure water (ion-exchanged water). At the time when the developing
solution was used, the whole amount of the above developing solution was dissolved
in 3 lit. of pure water (ion-exchanged water) and used.
[0156] The developing solution had the pH of about 11.4 before dilution with water, and
the developing solution had the pH of about 10.8 after dilution with water.
Fixing solution recipe
[0157] (Composition A) Ammonium thiosulfate (an aqueous 72.5 % WN solution) 240 ml Sodium
sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate
2 g Acetic acid (an aqueous 90 % W/V solution) 13.6 ml
[0158] At the time when the fixing solution was used, the above Composition A was dissolved
in 500 ml of water, made up to 1 lit. and used. This fixing solution had the pH of
about 4.9.
Evaluation method
[0159] The speed is a relative value of a reciprocal of the exposure amount necessary for
giving the density of 0.5.
[0160] Regarding the color remain intensity, the reflection density of non-image areas of
the processed samples was measured under a halogen lamp light source with use of a
Type 607 color analyzer manufactured by Hitachi, Ltd., to indicate it as the absorbence
at max of the remaining organic desensitizer.
[0161] The pencil inscribability was evaluated by examining with a 10-power magnifier the
thickness and density of the lines produced when inscribed with use of a pencil having
a hardness of 2H.
[0162] The ink inscribability was evaluated by examining with a 10-power magnifier the thickness
and density of the lines produced when inscribed with use of a drafting needle pen
(Rotring pen) having an inner diameter of 0.5 mm.
Evaluation results
[0163] Results of measurement are shown in Table 6. It was found from Table 6 that Samples
No. 34 to No. 38 all have a high speed as the relative speed is as high as 80 to 120,
have less color remain as the color remain density is zero, have also superior inscribability,
and thus can be put into practical use.
[0164] In contrast with this, it was found that all of Samples No. 39 to No. 43 in Table
6, though having superior inscribability, have much color remain as the color remain
intensity is 0.03 to 0.05, have also a poorness in speed as the relative sensitivity
is 40 to 80 except for Sample No. 40 showing a speed as high as 100, and thus can
not be put into practical use.
[0165] It was also found that Samples No. 44 to 47 all have a high speed as the relative
speed is as high as 100 to 120 and have less color remain as the color remain intensity
is zero, but have so a poor inscribability that they can not be put into practical
use.
Example 4
[0167] Example 3 was repeated except that the temperature was set to 55°C, to prepare a
silver iodobromide solution.
[0168] As a result of this, there was obtained a silver iodobromide emulsion comprising
regular cubic grains having an average grain size of 0.2 u.m, containing 2 mol % of
silver iodide and having a high monodispersity.
[0169] The above emulsion was adjusted to pH = 6.8 with an aqueous sodium carbonate solution,
to which 0.3 mg of thiourea dioxide per mol of silver halide was added under pAg =
6.8 to carry out ripening for 60 minutes at 70°C, and then 1.0 mg of chloroaurate
per mol of silver halide was added to carry out ripening for 60 minutes at 70°C, thus
producing reduction fog and gold fog.
[0170] To the emulsion applied with fog, potassium bromide was added to make adjustment
to pAg = 9.2, followed by addition of 600 mg per mole of. silver halide, of the above
compound (1-7), (11-3), (III-6), (IV-2) or (V-3) as an organic desensitizer according
to this invention, and also the following compound of Formula [J], [K], [L], [M] or
[N] as an organic desensitizer having nothing to do with this invention, and further
making adjustment to pH = 5.8 using citric acid.

[0171] Next, added were rice starch having an average particle diameter of 4.0 um as a matting
agent and by the amount as shown in Table 7, 20 mg/m
2 of sodium 1-decyl-2-(3-isopentyl)succinate-2-sulfonate as a . coating aid, 0.8 mg/m
2 of polyethyl acrylate as a polymer latex and 16 mg of formalin as a hardening agent
per 1 g of gelatin, to prepare a coating solution for direct positive silver halide
emulsions.
Preparation of coating solution for protective layers
[0172] In an aqueous gelatin solution adjusted to pH = 5.3 with an aqueous citric acid solution,
1.2 g of potassium bromide per 100 g of gelatin was added, with further addition of
amorphous silica having an average particle diameter of 3.5 u.m as a matting agent
and by the amount as shown in Table 7, and then added were 20 mg/m
2 of 2-sulfonatosuccinic acid bis(2-ethylhexyl) ester sodium salt as a coating aid,
100 mg/m
2 of a styrene/maleic anhydride copolymer as a thickening agent, 50 mg/m
2 of colloidal silica for the purpose of improving the ink inscribability and 16 mg
of formalin as a hardening agent per 1 g of gelatin, to prepare a coating solution
for protective layers.
Preparation of coating samples
[0173] The above emulsion coating solution and protective layer coating solution were coated
with lamination on polyethylene terephthalate films of 100 u.m thick having a subbing
layer to prepare samples. Coated silver amount was 3.5 g/m
2, and gelatin coating amounts were 2.0 g/m
2 for the emulsion layer and 1.5 g/m
2 for the protective layer. Also, on the surfaces opposite to the emulsion layers of
the film supports, previously coated was a back coat layer containing 3.6 g/m
2 of gelatin containing 1.0 g/m
2 of rice starch and 400 mg/m
2 of amorphous silica having an average particle diameter of 3.5 u.m.
Evaluation method
[0174] Evaluation was made in the same manner as in Example 3. In measuring the color remain
intensity, measurement was made by applying to the back surfaces of the processed
samples the polyethylene-coated paper of 150 µm thick used in Example 3.
Evaluation results
[0175] Results of measurement are shown in Table 7. It was found from Table 7 that Samples
No. 54 to No. 58 all have a high speed as the relative speed is as high as 90 to 120,
have less color remain as the color remain density is 0.01 to 0.02, have also superior
inscribability, and thus can be put into practical use.
[0176] In contrast with this, it was found that all of Samples No. 59 to No. 63 in Table
7, though having superior inscribability, have much color remain as the color remain
intensity is 0.03 to 0.04, have also a poorness in speed as the relative sentivity
is 40 to 60 except for Sample No. 61 showing a speed as high as 120, and thus can
not be put into practical use.
[0177] It was also found that Samples No. 64 to No. 69 all have a high speed as the relative
speed is as high as 100 to 120 and have less color remain as the color remain intensity
is 0 to 0.01, but have so a poor inscribability that they can not be put into practical
use.
[0179] As described above, this invention can obtain a direct positive light-sensitive silver
halide photographic material having superior inscribability and high whiteness.