FIELD OF THE INVENTION
[0001] The present invention relates to a silver halide photographic light-sensitive material
spectrally sensitized to the infrared region. More particularly, it relates to a silver
halide photographic light-sensitive material obtained using an emulsion layer coating
solution inhibited in the deterioration of performance during its standing, and also
promising a good storage stability of the light-sensitive material thus obtained.
BACKGROUND OF THE INVENTION
[0002] Use of an infrared light-emitting source as a light source for exposure enables use
of a bright safelight, and is advantageous from the view point of readiness in handling.
For this reason, proposals have been made on silver halide photographic papers spectrally
sensitized to the infrared region.
[0003] Such photographic papers can be exposed to light to form an image by utilizing an
image forming process of, for example, the so-called scanner system.
[0004] In the image forming process according to the scanner system, an original is scanned,
an image signal resulting therefrom is converted to light, to which a silver halide
photographic light-sensitive material is exposed, and thus a negative image or positive
image corresponding to the image on the original is formed. There are various types
of recording apparatus in which the image forming process according to the scanner
system is practically employed. As light sources for the recording in such scanning
recording apparatus, a glow lamp, a xenon lamp, a mercury lamp, a tungsten lamp, a
light-emitting diode and so forth have been hither to used. All of these light sources,
however, involves practical problems that they give a weak output and have a short
lifetime. As a means for solving such problems, there are scanners in which a coherent
laser light source such as a helium-neon laser, an argon laser or a helium-cadmium
laser is used as a light source in the scanner system. These can give a high output,
but have the problems that the apparatus must be large, they are expensive, they require
a modulator, and also they have inferior handling characteristics because the safelight
for a light-sensitive material must be limited on account of use of visible light.
[0005] In contrast, semiconductor lasers are small in size, inexpensive, and yet can be
readily modulated, having a longer lifetime than the above lasers. Moreover, since
they emit light in the infrared region, the photographic papers spectrally sensitized
to the infrared region is suitably used. Such photographic paper can be handled under
a bright safelight and has the advantage of more readiness in handling.
[0006] On the other hand, it is a well known technique to use a fluorescent brightening
agent in order to increase the whiteness of silver halide photographic papers that
have been processed.
[0007] It is more advantageous to use an oil-soluble fluorescent brightening agent as the
fluorescent brightening agent than to use a water-soluble fluorescent brightening
agent, in view of the fact that the former fluorescent brightening agent may be flowed
out with difficulty in the course of processing.
[0008] Incidentally, a silver halide emulsion spectrally sensitized to the infrared region
may undergo a serious decrease in sensitivity when an emulsion layer coating solution
is prepared and thereafter left to stand. Thus the emulsion has been strongly desired
to be stable from the viewpoint of the manufacture of light-sensitive materials.
[0009] Light-sensitive materials obtained using such an emulsion also have a poor storage
stability after manufacture, thus having the disadvantage that they are greatly susceptible
to desensitization during storage.
[0010] Studies made by the present inventors have revealed that such a negative phenomenon
is further double strengthened when the fluorescent brightening agent is used for
the purpose of increasing the whiteness of photographic papers.
SUMMARY OF THE INVENTION
[0011] Accordingly, a first object of the present invention is to provide an infrared-sensitive
silver halide photographic material obtained using an emulsion layer coating solution
free from the decrease in sensitivity during its standing, and also having good storage
stability after the manufacture.
[0012] A second object of the present invention is to provide an infrared-sensitive silver
halide photographic paper that may cause no deterioration of sensitivity even with
use of an oil-soluble fluorescent brightening agent, and also having superior storage
stability.
[0013] The above objects can be achieved by the following:
[0014] A silver halide photographic light-sensitive material comprising a support and a
silver halide photographic emulsion layer provided on the support. The silver halide
photographic emulsion layer has been spectrally sensitized with at least one selected
from a cationic dicarbocyanine dye and a cationic tricarbocyanine dye, and at least
one of the silver halide photographic emulsion layer and other hydrophilic colloid
layer contains at least one of the compounds represented by the following Formulas
I, II and III.
wherein R₄, R₅ and R₆ each represent a hydrogen atom, an alkyl group, alkenyl group,
alkoxy group or alkoxycarbonyl group having 1 to 12 carbon atoms, an amino groupl
an aryl group, a hydroxyl group, a mercapto group, a carboxyl group, or a salt thereof;
and all the alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, amino
group and aryl group may each have a substituent.
wherein R₇, R₈ and R₉ each represent a hydrogen atom, a halogen atom, a hydroxyl
group, or an amino group which may have a substitutent; R₁₀ represents a phosphoric
acid group, or an alkyl group having 1 to 8 carbon atoms which may be substituted
with a hydroxyl group, as exemplified by a methyl, ethyl or hydroxyethyl group.
wherein R₁₁ and R₁₂ each represent a hydrogen atom, a hydroxy group, a methyl group,
or an amino group which may have a substituent; R₁₃ represents a phosphoric acid group
or an alkyl group having 1 to 8 carbon atoms which may be substituted with a hydroxyl
group, as exemplified by a methyl, ethyl or hydroxyethyl group.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The present invention will now be described below in detail.
[0017] Typical examples of the compound represented by the above Formula II or III are the
following:
(II-1) 6-Amino-purine ribocide
(II-2) 6-Chloro-purine ribocide
(II-3) 6-Methylamino-purine ribocide
(II-4) 5′-Phosphoric acid-6-amino-purine ribocide
(II-5) 5′-Phosphoric acid-6-chloro-purine ribocide
(II-6) 5′-Phosphoric acid-6-amino-purine ribocide
(II-7) 5′-Hydroxymethyl-6-methylamino-purine ribocide
(II-8) 5′-Methyl-6-amino-purine ribocide
(III-1) 6-Oxy-purine ribocide
(III-2) 2-Amino-6-oxy-purine ribocide
(III-3) 5′-Phosphoric acid-6-oxy-purine ribocide
[0018] The amount of the compound represented by the above Formula I, II or III may vary
depends on the type of a silver halide emulsion and the kind of the compound. In usual
instances, it may preferably be used in an amount ranging from 5 mg to 5 g, and more
preferably from 10 mg to 1 g, per mol of silver halide. The compound may be added
in a layer other than a silver halide emulsion layer, for example, a layer such as
a protective layer, an intermediate layer or an under coat layer, adjacent to the
silver halide emulsion layer. In such an instance, the amount of the compound added
may be determined according the amount of an emulsion added.
[0019] The compounds represented by the above Formula I, II or III are known compounds,
and can be synthesized making reference to the methods disclosed in, for example,
J.A.C.S. 74, 411 (1952), U.S. Patents No. 2,721,866 and No. 2,724,711, Merck Index
10.4452, Beil. 31.27, and Beil. 26.449, or they are commercially readily available.
[0020] Next, as the cationic di- or tricarbocyanine infrared sensitizing dye used in the
present invention may preferably include the compound represented by the following
Formula I-a or I-b.
[0021] In the formulas, Y₁₁, Y₁₂, Y₂₁ and Y₂₂ each represent a group of non-metallic atoms
necessary to complete a nitrogen-containing heterocyclic ring of 5 or 6 members, including,
for example, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring,
a naphthoselenazole ring, a benzoxyazole ring, a naphthoxazole, a quinoline ring,
a 3,3-dialkylindolenine ring, a benzimidazole ring and a pyridine ring.
[0022] The heterocyclic rings may each be substituted with a lower alkyl group, an alkoxy
group, a hydroxyl group, an aryl group, an alkoxycarbonyl group or a hydrogen atom.
[0023] R₁₁, R₁₂, R₂₁ and R₂₂ each represent a substituted or unsubstituted alkyl group,
aryl group or aralkyl group.
[0024] R₁₃, R₁₄, R₁₅, R₂₃, R₂₄, R₂₅ and R₂₆ each represent a hydrogen atom, a substituted
or unsubstituted alkyl group, alkoxy group, phenyl group or benzyl group, or
where W₁ and W₂ each represent a substituted or unsubstituted alkyl group, the alkyl
moiety has 1 to 18, and preferably 1 to 4, carbon atoms, or a substituted or unsubstituted
aryl group, and W₁ and W₂ may each combine each other to form a nitrogen-containing
heterocyclic ring of 5 or 6 members.
[0025] R₁₃ and R₁₅, and R₂₃ and R₂₅ may also combine each other to form a 5-membered ring
or 6-membered ring. X₁₁ and X₂₁ each represent an anion. n₁₁, n₁₂, and n₂₁ and n₂₂
each represent 0 or 1.
[0027] The sensitizing dye of the present invention may be contained in a silver halide
photographic emulsion preferably in an amount ranging from 1 mg to 2 g, and more preferably
from 5 mg to 1 g, per mol of silver halide.
[0028] The sensitizing dye of the present invention may be directly dispersed in the emulsion.
It may also be first dissolved in a suitable solvent as exemplified by methyl alcohol,
ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent of any
of these, and then added in the emulsion in the form of a solution.
[0029] The sensitizing dye of the present invention may be used alone or in combination
of two or more kinds. A sensitizing dye other than that of the present invention may
also be used in combination. When sensitizing dyes are used in combination, they may
preferably be used so as to be in the above amount in total.
[0030] The sensitizing dye of the present invention can be readily synthesized making reference
to U.S. Patent No. 2,503,776, British Patent No. 742,112, French Patent No. 2,065,662
and Japanese Examined Patent Publication No. 2346/1965.
[0031] The phenol resin further includes a resol, a resltol a resite, which are different
from each other in the degree of its condensation, prepared by condensation using
an alkali.
[0032] The phenol resin used in the present invention is a phenol resin obtained by condensation
of at least one of phenols with at least one of aldehydes. It may also be a phenol
resin obtained by mixture of two or more kinds of phenol resins, or by further condensation
of at least two different kinds of phenol resins.
[0033] The phenol resins are described in "Phenol Resins", Nikkan Kogyo Shinbun-sha, Course
of Plastic Materials, as well as Japanese Patent Publication Open to Public Inspection
(hereinafter referred to as Japanese Patent O.P.I. Publication) No. 123035/1979, No.
105254/1980, No. 105380/1980, No. 153948/1980 and No. 161250/1980, and Japanese Examined
Patent Publication No. 20543/1981.
[0035] Degree of polymerization of these phenol resins may range from 2 to 10,000, and preferably
from 3 to 1,000.
[0036] The above phenol resin may be contained in a sensitizing dye solution preferably
in an amount of from 1 x 10⁻⁴ g to 100 g, and more preferably from 1 x 10⁻³ g to 10
g, per mol of silver halide.
[0037] The fluorescent brightening agent relating to the present invention will be described
below. It is conventionally well known to use a fluorescent brightening agent for
the purpose of increasing the whiteness of a silver halide photographic paper that
has been processed.
[0038] As the fluorescent brightening agent, it is more advantageous to use an oil-soluble
fluorescent brightening agent than to use a water-soluble fluorescent brightening
agent, in view of the fact that the former fluorescent brightening agent may be flowed
out with difficulty in the course of processing.
[0039] A technique by which the oil-soluble fluorescent brightening agent is added in a
light-sensitive material is known to include a method in which an oil-soluble fluorescent
brightening agent is dissolved in an organic solvent, and added in a light-sensitive
material as an emulsified dispersion, as disclosed, for example, in British Patent
No. 1,072,915, Japanese Examined Patent Publication No 37376/1970 and Japanese Patent
O.P.I. Publication No. 134232/1985. In particular, Japanese Patent O.P.I. Publication
No. 134232/1985 questions about a decrease in fluorescent brightening effect that
may occur when an oil-soluble fluorescent brightening agent and a developing agent
are present together in a light-sensitive material, and provides a means for solving
this problem.
[0040] However, as previously discussed, a silver halide photographic infrared-sensitive
material in which the oil-soluble fluorescent brightening agent is used has the negative
effect that the sensitivity and storage stability of the light-sensitive material
is deteriorated.
[0041] As a method in which the oil-soluble fluorescent brightening agent is dissolved in
a high-boiling organic solvent to make an emulsified dispersion, advantageously used
is the same method as used for dispersing an oil-soluble coupler or an oil-soluble
ultraviolet absorbent, i.e., a method in which the agent is dissolved in a high-boiling
organic solvent optionally together with a low- boiling organic solvent, and the
resulting dispersion is mixed with an aqueous gelatin solution containing a surface
active agent, followed by emulsifying dispersion using an emulsifying machine such
as a colloid mill, a homogenizer or an ultrasonic dispersion machine. Here, the high-boiling
organic solvent used includes carboxylic acid esters, phosphoric acid esters, carboxylic
amides, and hydrocarbons. For the sake of reference, examples of the high-boiling
organic solvent advantageously used in the present invention are shown below.
[0042] Oil-soluble fluorescent brightening agents that can be advantageously used include
those represented by the following Formulas II-a, II-b, II-c and II-d.
[0043] In the above Formulas II-a to II-d, Y₁ and Y₂ each represent an alkyl group, Z₁ and
Z₂ each represent a hydrogen atom or an alkyl group, n is 1 or 2, R₁, R₂, R₄ and R₅
each represent an aryl, alkyl, alkoxy, aryloxy, hydroxyl, amino, cyano, carboxyl,
amido, ester, alkylcarbonyl, alkylsulfonyl or dialkylsulfonyl group or a hydrogen
atom. R₆ and R₇ each represent a hydrogen atom, an alkyl group such as a methyl group
or an ethyl group, or a cyano group. R₁₆ represents a phenyl group, a halogen atom
or an alkyl-substituted phenyl group. R₁₅ represents an amino group or an organic
primary or secondary amino group.
[0045] The above exemplary compounds may be used alone or in combination of two or more
kinds.
[0046] The fluorescent brightening agent may preferably be so added that it is present in
a photographic paper in an amount of from 1 to 200 mg/m², and may most preferably
be used in an amount of from 5 to 50 mg/m².
[0047] The layer to which the emulsified dispersion of the fluorescent brightening agent
used in the present invention is added may be any layers as long as they are photographic
component layers on a support. From the viewpoint of the prevention of so-called blooming,
it should be added to a silver halide emulsion layer or a layer as near as possible
to the support (a hydrophilic colloid layer such as an intermediate layer).
[0048] The above fluorescent brightening agents are known compounds. The exemplary compound
II-13, for example, is sold in the market from Ciba-Geigy Corp. under a trade name
of Ubitex-OB, and is readily available.
[0049] In the silver halide photographic light-sensitive material of the present invention,
it is preferred to use a compound of Formula VI shown below.
[0050] In the formula, Y represents a hydrogen atom, an alkali metal atom, an ammonium group
or an organic amine residual group. Z represents a heterocyclic ring of 5 or 6 members,
in which the heterocyclic nucleus may preferably be a heterocyclic nucleus selected
from nuclei including imidazole, thiazole, oxazole, benzimidazole, benzothiazole,
benzoxazole, oxadiazole, thiadiazole, triazole, tetrazole, pyrimidine, triazine, and
tetrazaindene.
[0052] These compounds of the present invention represented by Formula VI, usable in the
present invention, can be readily synthesized by the methods as disclosed in, for
example, U.S. Patents No.3,615,501, No. 2,324,123, No 2,384,593, No. 2,496,940, No.
3,137,578, No. 2,496,940, No. 3,082,088, No. 3,473,924, No. 3,575,699, No. 3,687,660,
No. 2,271,229 and No. 2,496,940, and British Patents No. 1,141,773 and No. 1,376,600,
or by methods corresponding thereto. These compounds can also be readily synthesized
by the method disclosed in DAI-YUUKI-KAGAGU (Grand Organic Chemistry), edited by
Munio Kotake, Askura Shoten, 1971 Edition, or A. Weissberger, The Chemistry of Heterocyclic
Compounds, N.Y. Interscience, the years 1950 to 1964, or methods corresponding thereto.
[0053] The amount of the compound represented by the above Formula VI may vary depending
on the type of silver halide emulsions and the type of the compounds. In usual instances,
the compound may be added in an amount of from 5 mg to 500 mg per mol of silver halide.
[0054] In the silver halide emulsion used in the present invention, it is possible to use
any of silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
silver chloroiodobromide and silver chloride, which are used in ordinary silver halide
emulsions.
[0055] Silver halide grains used in the silver halide emulsions may be obtained by any of
an acidic method, a neutral method and an ammoniacal method. The grains may be made
to grow at one time, or grow after seed grains have been formed. The manner of preparing
the seed grains and the manner of growing them may be the same or different.
[0056] The silver halide emulsion may be obtained by simultaneously mixing halide ions and
silver ions, or by preparing an aqueous solution in which either one of them is present
and then mixing in it the other of them. Alternatively, taking into account the critical
growth rate of silver halide crystals, it may be formed by successively simultaneously
adding halide ions and silver ions while controlling pH and/or pAg in a mixing vessel.
Silver halide grains having regular crystal forms and substantially uniform grain
size can thereby be obtained. Halogen composition in a grain may be changed after
growth by employing a conversion method.
[0057] In preparing the silver halide emulsion, a silver halide solvent can be optionally
used for controlling the grain size, grain shape, grain size distribution and grain
growth rate of the silver halide grains.
[0058] In the course of formation and/or growth of the silver halide grains, metal ions
may be added to the grains by the use of at least one of a cadmium salt, a zinc salt,
a lead salt, a thallium salt, an iridium salt including a complex salt thereof, a
rhodium salt including a complex salt thereof, and an iron salt including a complex
salt thereof, to incorporate any of these metal elements into the inner parts of grains
and/or the surfaces of the grains, and also reduction sensitizing nuclei can be imparted
to the inner parts of the grains and/or the surfaces of the grains by placing the
grains in a suitable reducing atmosphere.
[0059] The silver halide emulsion may be either the one from which unnecessary soluble salts
have been removed after completion of the growth of silver halide grains, or the one
from which they remain unremoved. When the salts are removed, they can be removed
according to the method disclosed in Research Disclosure No. 17643 (hereinafter "RD"),
Paragraph II.
[0060] The silver halide grains may have a uniform compositional distribution of silver
halide in a grain, or may be comprised of a core/shell grain having different silver
halide composition between the inner part and surface layer of a grain.
[0061] The silver halide grains may be grains such that a latent image is formed chiefly
on the surface, or grains such that a latent image is formed chiefly in the inner
part of a grain.
[0062] The silver halide grains may be any of those having a regular crystal form such as
a cube, an octahedron or a tetradecahedron, or those having an irregular crystal form
such as a sphere and a plate. In these grains, those having any ratio of {100} face
to {111} face can be used. They may also have a composite form of these crystal forms,
or comprise a mix of grains having various crystal forms.
[0063] Average grain size (grain size is expressed as a diameter of a circle having an area
equal to a projection area) of the silver halide grains may preferably be not more
than 2 µm, and particularly preferably not more than 0.7 µm.
[0064] The silver halide emulsion used may have any grain size distribution. An emulsion
having a broad grain size distribution, which is called a polydisperse emulsion, may
be used, or an emulsion having a narrow grain size distribution, which is called a
monodisperse emulsion, may also be used alone or by combination of several kinds.
The monodisperse emulsion herein referred to is an emulsion having a value of not
more than 0.20 obtained when the standard deviation of grain size distribution is
divided by an average grain size. The polydisperse emulsion and the monodisperse emulsion
may be used in the form of a mixture.
[0065] The silver halide emulsion may be used in the form of a mixture of two or more emulsions
separately formed.
[0066] Various additives can be used in the light-sensitive material of the present invention.
[0067] Such additives are described in detail in RD No. 17643 (December, 1978) and RD. No.
18716 (November, 1976). Corresponding passages thereof are summarized in the following
table.
[0068] There are not particular limitations on the conditions for exposure and development
processing, and reference may be made to, for example, the descriptions at 28 to 30
pages of the above RD 17643.
Type of additives |
RD 17643 |
RD 18716 |
1. Chemical sensitizer |
p.23 |
p.648, right col. |
2. Speed-increasing agent Supersensitizer |
|
ditto p.649, right col. |
3. Brightening agent |
p.24 |
|
4. Antifoggant and stabilizer |
pp.24-25 |
p.649, right col. |
5. Light-absorbent, filter dye, and ultraviolet absorbent |
pp.25-26 |
p.649, right col. to p.650, left col. |
6. Anti-stain agent |
p.25, right col. |
p.650, left to right col. |
7. Hardening agent |
p.26 |
p.651, left col. |
8. Binder |
p.26 |
ditto |
9. Plasticizer Wetting agent |
p.27 |
p.650, right col. |
10. Coating aid Surfactant |
pp.26-27 |
ditto |
11. Antistatic agent |
p.27 |
ditto |
[0069] For the purpose of improving dimensional stability of the light-sensitive material,
a dispersion of a water-soluble or sparingly water-soluble synthetic polymer (i.e.
latex) may be contained in photographic emulsion layers in which the silver halide
emulsions of the present invention are used, and other hydrophilic colloid layers.
[0070] The support used in the light-sensitive material of the present invention includes,
for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper,
glass plates, cellulose acetate films, cellulose nitrate films, polyester films of,
e.g., polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate
films, and polystyrene films, which can be used depending on the purpose.
[0071] In the support for the photographic paper of the present invention, it is possible
to add various inorganic white pigments, inorganic color pigments, dispersants, fluorescent
brightening agents, antistatic agents, antioxidants, and stabilizers. The surface
of the support may be subjected to surface-activation treatment such as corona discharge
treatment or flame treatment, and may optionally provided with an under-coat layer.
EXAMPLES
Example 1
[0072]
Preparation of emulsion layer coating solution: |
Solution A: |
|
Water |
980 mℓ |
Sodium chloride |
2.0 g |
Gelatin |
20 g |
Aqueous 0.10 % solution of potassium hexachloroiridate |
0.28 mℓ |
Aqueous 0.001 % solution of potassium hexabromoiridate |
8.5 mℓ |
Solution B: |
|
Water |
380 mℓ |
Sodium chloride |
38 g |
Potassium bromide |
42 g |
Solution C: |
|
Water |
380 mℓ |
Silver nitrate |
170 g |
[0073] To the above Solution A kept at 40°C, the above Solutions B and C were simultaneously
added with speed controlled in accordance with growing silver halide grains over a
period of 80 minutes while keeping the pH to 3 and the pAg to 7.7. After continuous
stirring for 5 minutes, the pH was adjusted to 5.6 with an aqueous sodium carbonate
solution, followed by usual desalting and washing. Thereafter, 500 mℓ of water and
30 g of gelatin were added, followed by dispersion at 50°C for 30 minutes. An emulsion
comprising cubic grains with 35 mol % of silver bromide, 65 mol % of silver chloride
and an average grain size of 0.27 µm was thus obtained.
[0074] To the emulsion adjusted to pH 5.5 and pAg 7 by adding 10 mℓ of an aqueous 1 % citric
acid solution and 10 mℓ of an aqueous 5 % sodium chloride solution, 10 mℓ of an aqueous
0.1 % sodium thiosulfate solution and 7 mℓ of an aqueous 0.2 % chloroauric acid solution
were added, and the emulsion was ripened at 57°C to have a maximum sensitivity.
[0075] The emulsion thus obtained was divided, and 25 mℓ of an aqueous 0.5 % solution of
1-phenyl-5-mercaptotetrazole as an antifoggant was added to each portion, and 180
mℓ of an aqueous 1 % solution of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer
and gelatin were further added thereto to terminate the ripening.
[0076] To each emulsion, an aqueous 0.1 % solution of the exemplary sensitizing dye according
to the present invention was added in the amount as shown in Table 1, and well adsorbed.
Thereafter, 15 mℓ of an aqueous 10 % solution of sodium tri-isopropylnaphthalenesulfonate
as a spreading agent, 50 mℓ of an aqueous 4 % solution of a styrene/maleic acid copolymer
as a thickening agent, 30 g of a polymer latex of butyl acrylate, 20 mℓ of an aqueous
20 % solution of hydroquinone as a stabilizer and 20 mℓ of an aqueous 10 % solution
of potassium bromide were added, followed by stirring.
[0077] Next, as shown in Table 1, an emulsified dispersion of the fluorescent brightening
agent (as described later) was added so as to give a coating weight of 10 mg/m².
[0078] To each emulsion thus obtained, 50 mg/g gelatin of a hardening agent comprising a
1:0.25 mol reaction product of tetrakis(vinylsulfonylmethyl)methane and taurine potassium
salt was added, and the pH was adjusted to 5.6 with citric acid. Emulsion layer coating
solutions were thus obtained.
Preparation of anti-halation layer coating solution:
[0079] To an aqueous 40 g gelatin solution, the following dye (m) was added so as to give
a coating weight of 60 mg/m², and 15 mℓ of an aqueous 4 % solution of a styrene/maleic
anhydride copolymer as a thickening agent was further added. A coating solution for
an anti-halation layer was thus prepared.
[0080] In preparing the coating solution, a fluorescent brightening agent was added to the
anti-halation layer coating solution used in the sample as shown in Table 1, in which
the fluorescent brightening agent had been contained, in the same manner as in the
above emulsion coating solution so as to give a coating weight of 10 mg/m².
Preparation of protective layer coating solution:
[0081] Next, to an aqueous gelatin solution, 30 mg/m² of sodium salt of 2-sulfo-bis(2-ethylhexyl)succinate
as a coating aid, 40 mg/m² of polymethyl methacrylate particles with an average diameter
of 4 µm as a matting agent, 30 mg/m² of the following compound (n) as a fluorine-containing
surface active agent, and 10 mg/g gelatin of formalin as a hardening agent were added
to prepare a coating solution for a protective layer.
Preparation of samples and evaluation thereon:
[0082] The anti-halation layer coating solution, emulsion layer coating solution, and protective
layer coating solution prepared in this way were simultaneously coated in three layers
on a 110 µm thick polyethylene-coated paper having a hydrophilic colloid backing layer
and an under-coat layer and containing 15 wt.% of TiO₂. In order to examine coating
solution stability of the emulsion layer coating solution, samples were prepared for
both instances in which emulsion layer coating solutions were left to stand for 1
hour and 10 hours after their preparation. The resulting samples had a coating weight
of silver of 1.4 g/m², and a coating weight of gelatin of 1.4 g/m² for the anti-halation
layer, 1.4 g/m² for the emulsion layer and 0.9 g/m² for the protective layer.
[0083] Samples thus obtained were each subjected to flash exposure for 10⁻⁵ second using
a xenon flash lamp through an optical wedge and Kodak Wratten Filter No. 88A, and
then processed using Konica Automatic Processor GR-14 (manufactured by Konica Corporation)
by the use of the developing solution and fixing solution as described below. Evaluation
was made on the items shown in Table 1. The processing was carried out under conditions
of 30°C, 20 seconds, for developing; about 38°C, 20 seconds, for fixing; room temperature,
20 seconds, for washing; and about 40°C for drying.
[0084] Results obtained are shown in Table 1. Sensitivity is expressed as a reciprocal of
the amount of exposure necessary for giving a density of 1.0, and a relative value
assuming that of Sample No. 1 as 100.
[0085] The whiteness shown in Table 1 expresses the whiteness of a sample having been processed,
and is visually evaluated according to a five-rank system. The best is evaluated as
5, and the poorest as 1.
Preparation of emulsified dispersion of oil-soluble fluorescent brightening agent:
[0086] In a mixed solvent of 200 mℓ of cresyldiphenyl phosphate and 100 mℓ of n-butanol,
5.0 g of an oil-soluble fluorescent brightening agent was dissolved. The resulting
solvent was mixed in its total amount with 1,500 mℓ of an aqueous 12 % gelatin solution
containing 3 g of sodium tripropylnaphthalenesulfonate, and thereafter a butyl acrylate
polymer latex was added in an amount of 200 g as a solid. An emulsified dispersion
of an oil-soluble fluorescent brightening agent was thus prepared.
Formulation of developing solution: |
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 |
20 g |
Potassium carbonate |
15 g |
Made up to 1,000 mℓ by adding pure water (ion-exchange water). The pH value of the
developing solution was about 10.8. |
Formulation of fixing solution: |
(Composition A) |
|
Ammonium thiosulfate (an aqueous 72.5% w/w 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/w solution) |
13.6 mℓ |
(Composition B) |
|
Pure water (ion-exchanged water) |
17 mℓ |
Acetic acid (an aqueous 50% w/w solution) |
4.7 g |
|
Aluminum sulfate (a aqueous solution with a content of 8.1% w/w in terms of Al₂O₃ |
26.5 g |
[0087] When the fixing solution was used, the above compositions were dissolved in 500 mℓ
of water in the order of Composition A and Composition B so as to be made up to 1
ℓ. The pH of the resulting fixing solution was about 4.3.
Table 1
|
Sensitizing dye |
Formula I, II, III |
Fluorescent brightening agent No. |
Coated after 1 hour* |
Coated after 10 hours |
*Sample left at 50°C,50%RH for 3 days |
|
Sample No. |
No. |
(mg/mol AgX) |
No. |
(mg/mol AgX) |
|
Sensitivity |
Whiteness |
Sensitivity |
Whiteness |
Sensitivity |
Whiteness |
Remarks |
1-1 |
I-4 |
40 |
- |
- |
- |
100 |
3 |
82 |
3 |
59 |
2 |
X |
1-2 |
I-16 |
50 |
- |
- |
- |
95 |
3 |
80 |
3 |
53 |
2 |
X |
1-3 |
I-4 |
40 |
- |
- |
II-13 |
80 |
5 |
40 |
5 |
38 |
5 |
X |
1-4 |
I-16 |
50 |
- |
- |
II-13 |
82 |
5 |
45 |
5 |
41 |
5 |
X |
1-5 |
I-4 |
40 |
- |
- |
II-4 |
75 |
5 |
35 |
4 |
40 |
4 |
X |
1-6 |
I-4 |
40 |
- |
- |
II-8 |
82 |
5 |
38 |
4 |
42 |
4 |
X |
1-7 |
I-4 |
40 |
- |
- |
II-19 |
88 |
4 |
42 |
4 |
39 |
4 |
X |
1-8 |
I-4 |
40 |
- |
- |
II-25 |
72 |
4 |
36 |
3 |
35 |
3 |
X |
1-9 |
I-4 |
40 |
I-1 |
300 |
- |
135 |
3 |
135 |
3 |
130 |
3 |
Y |
1-10 |
I-16 |
50 |
I-1 |
300 |
- |
120 |
3 |
120 |
3 |
125 |
3 |
Y |
1-11 |
I-4 |
40 |
I-3 |
200 |
- |
125 |
3 |
125 |
3 |
122 |
3 |
Y |
1-12 |
I-4 |
40 |
I-7 |
150 |
- |
122 |
3 |
123 |
3 |
118 |
3 |
Y |
1-13 |
I-4 |
40 |
I-18 |
200 |
- |
130 |
3 |
130 |
3 |
129 |
3 |
Y |
1-14 |
I-4 |
40 |
II-3 |
270 |
- |
115 |
3 |
114 |
3 |
110 |
3 |
Y |
1-15 |
I-4 |
40 |
III-2 |
200 |
- |
110 |
3 |
112 |
3 |
115 |
3 |
Y |
1-16 |
I-4 |
40 |
I-3 |
200 |
II-4 |
125 |
5 |
121 |
5 |
120 |
5 |
Y |
1-17 |
I-4 |
40 |
I-3 |
200 |
II-13 |
120 |
5 |
114 |
5 |
109 |
5 |
Y |
1-18 |
I-4 |
40 |
I-3 |
200 |
II-19 |
132 |
5 |
130 |
5 |
121 |
5 |
Y |
1-19 |
I-4 |
40 |
I-3 |
200 |
II-25 |
113 |
5 |
103 |
5 |
110 |
5 |
Y |
1-20 |
I-4 |
40 |
II-3 |
270 |
II-4 |
120 |
5 |
118 |
5 |
110 |
5 |
Y |
1-21 |
I-3 |
20 |
- |
- |
- |
110 |
3 |
90 |
3 |
70 |
2 |
X |
|
I-4 |
20 |
|
|
|
|
|
|
|
|
|
|
1-22 |
I-4 |
20 |
- |
- |
II-13 |
90 |
5 |
40 |
5 |
35 |
5 |
X |
1-23 |
I-4 |
20 |
I-3 |
200 |
- |
130 |
3 |
130 |
3 |
125 |
5 |
Y |
1-24 |
I-4 |
20 |
I-3 |
200 |
II-13 |
130 |
5 |
128 |
5 |
122 |
5 |
Y |
X: Comparative Example, Y: Present Invention |
[0088] As will be evident from Table 1, the samples according to the present invention have
caused no deterioration of sensitivity even after standing of the emulsion layer coating
solutions for a long period of time, and also showed a stable storage stability as
a light-sensitive material.
[0089] No deterioration of photographic performance was also seen even when the fluorescent
brightening agent was incorporated in the samples according to the present invention.
Example 2
[0090]
(Preparation of emulsion layer coating solution) |
Solution A: |
|
Water |
9.7 ℓ |
Sodium chloride |
20 g |
Gelatin |
105 g |
Solution B: |
|
Water |
3.8 ℓ |
Sodium chloride |
365 g |
Gelatin |
94 g |
Potassium bromide |
450 g |
Aqueous 0.10 % solution of potassium hexachloroiridate |
28 mℓ |
Aqueous 0.01 % solution of potassium hexabromoiridate |
1.0 mℓ |
Solution C: |
|
Water |
3.8 ℓ |
Silver nitrate |
1,700 g |
[0091] To the above Solution A kept at 40°C, the above Solutions B and C were simultaneously
added over a period of 60 minutes while keeping the pH to 3.0 and the pAg to 7.7.
The rate of addition of the solutions was controlled corresponding to the growing
of the silver halide grains. After continuous stirring for 10 minutes, the pH was
adjusted to 6.0 with an aqueous sodium carbonate solution, to which 2 ℓ of an aqueous
20 % magnesium sulfate solution and 2.55 ℓ of an aqueous 5 % polynaphthalenesulfonic
acid solution were added. The emulsion was flocculated at 40°C, followed by decantation
and washing to remove excess salts from the emulsion. Next, 3.7 ℓ of water was added
to the resulting emulsion to carry out dispersion, to which 0.9 ℓ of an aqueous 20
% magnesium sulfate solution was again added, and excess salts were removed from the
emulsion in the same manner. To the resulting emulsion, 3.7 ℓ of water and 141 g of
gelatin were added to carry out dispersion at 55°C for 30 minutes. An emulsion comprising
grains with 35 mol % of silver bromide, 65 mol % of silver chloride, an average grain
size of 0.25 µm and a degree of monodispersion of 9 % was thus obtained. Next, 120
mℓ of an aqueous 1 % citric acid solution and 220 mℓ of an aqueous 5 % sodium chloride
solution were added. Thereafter, 80 mℓ of an aqueous 1 % sodium thiosulfate solution
and further 70 mℓ of an aqueous 0.2 % chloroauric acid solution were added, and the
emulsion was ripened at 55°C for 80 minutes.
[0092] To the above emulsion, 15 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer
and 1,600 mℓ of an aqueous 20 % gelatin solution were added to terminate the ripening.
[0093] Subsequently, the compounds represented by Formulas I, II and III were each added
in the amount as shown in Table 2, and the red-sensitive sensitizing dyes I-8, I-19,
I-4, I-3 and I-16 according to the present invention and the phenol resins V-1 and
V-17 were each further used in combination in the amount as shown in Table 2.
[0094] Thereafter, after adjustment of the pH and pAg, 30 g of hydroquinone as an antifoggant
and 10 g of sodium p-dodecylbenzenesulfonate as a spreading agent were further added.
Subsequently, 20 g of a styrene/maleic anhydride copolymer as a thickening agent and
120 g of a polymer latex of ethyl acrylate were added, and 1-hydroxy-3,5-dichloro-s-triazine
sodium salt and formalin were added as hardening agents immediately before coating.
The above emulsion was coated on a polyethylene terephthalate support having a backing
layer and also having been subbed, so as to give a silver weight of 3.5 g/m². As a
protective layer coating solution, 15 g of the following compound (a) as a spreading
agent was added in an aqueous solution containing 500 g of gelatin and 20 g of amorphous
silica with an average particle diameter of 3.5 µ was further added, which were then
dispersed. These were simultaneously coated to provide an emulsion layer and a protective
layer so as to give a gelatin weight of 1.1 g/m²
[0095] In order to evaluate the storage stability of the emulsion layer coating solution,
an emulsion layer coating solution to which no hardening agent had been added was
stored for 12 hours with stirring at 40°C, and changes in sensitivity and gamma with
respect to a coating solution similarly stored for 1 hour was examined.
[0096] Samples thus obtained were each exposed to light for 10⁻⁵ second using a xenon light
source through an optical wedge and Kodak Wratten Filter No. 88A. Thereafter, the
samples were processed under the same conditions as in Example 1.
[0097] Transmission density of the samples having been processed was measured using a digital
densitometer PDA-65 Type (manufactured by Konica Corporation), and photographic performance
was evaluated based on the characteristic curve.
[0098] First, the photographic sensitivity was determined from a reciprocal of the amount
of exposure necessary for giving a density of 2.5, and is expressed as a relative
value assuming that of Sample No. 2-1 as 100. The gamma is expressed as a gradient
at the straight-line portion of the characteristic curve. Results obtained are shown
in Table 2.
[0099] As will be evident from Tables 1 and 2, the present invention has achieved a high
sensitivity, a high gamma, and has caused only very small deterioration of performance
in the storage stability test.
Table 2
|
Sensitizing dye |
Compound of Formula I, II, III |
Phenol resin |
(1) |
(2) |
(3) |
(4) |
|
Sample No. |
Type |
Amount (mg/mol AgX) |
Spectral sensitivity, maximum (nm) |
Type |
Amount (mg/mol AgX) |
Type |
Amount (mg/mol AgX) |
|
(%) |
|
|
Remarks |
2-1 |
I-8 |
60 |
780 |
- |
- |
- |
- |
100 |
+25 |
5.7 |
5.0 |
X |
2-1 |
I-8 |
60 |
780 |
I-1 |
400 |
- |
- |
92 |
+8 |
6.9 |
6.0 |
Y |
2-3 |
I-8 |
60 |
780 |
I-1 |
400 |
V-1 |
20 |
132 |
-4 |
7.7 |
7.5 |
Y |
2-4 |
I-8 |
60 |
780 |
I-1 |
400 |
V-17 |
20 |
124 |
-4 |
7.3 |
7.1 |
Y |
2-5 |
I-8 |
60 |
780 |
I-3 |
400 |
V-17 |
20 |
119 |
-3 |
7.6 |
7.5 |
Y |
2-6 |
I-8 |
60 |
780 |
I-9 |
400 |
V-17 |
20 |
122 |
-4 |
7.6 |
7.5 |
Y |
2-7 |
I-8 |
60 |
780 |
II-1 |
400 |
V-17 |
20 |
110 |
-5 |
7.8 |
7.7 |
Y |
2-8 |
I-8 |
60 |
780 |
III-2 |
400 |
V-17 |
20 |
115 |
-5 |
7.9 |
7.7 |
Y |
2-9 |
I-8 |
60 |
780 |
- |
- |
V-17 |
20 |
125 |
-25 |
6.5 |
5.4 |
X |
2-10 |
I-19 |
60 |
785 |
- |
- |
- |
- |
108 |
+18 |
6.1 |
6.1 |
X |
2-11 |
I-19 |
60 |
785 |
I-3 |
400 |
- |
- |
90 |
+7 |
6.7 |
6.2 |
Y |
2-12 |
I-19 |
60 |
785 |
- |
- |
V-1 |
20 |
120 |
-16 |
7.3 |
5.9 |
X |
2-13 |
I-19 |
60 |
785 |
I-3 |
400 |
V-1 |
20 |
128 |
+3 |
7.8 |
7.7 |
Y |
2-14 |
I-4 |
50 |
780 |
I-3 |
400 |
V-1 |
20 |
120 |
-5 |
7.9 |
7.7 |
Y |
2-15 |
I-16 |
50 |
800 |
II-1 |
400 |
V-1 |
20 |
125 |
-3 |
7.8 |
7.7 |
Y |
2-16 |
I-3/I-4 |
20/20 |
786 |
II-1 |
400 |
V-1 |
20 |
135 |
-6 |
7.8 |
7.7 |
Y |
X: Comparative Example, Y: Present Invention |
(1): Sensitivity before storage of coating solution |
(2): Rate of change in sensitivity after storage of coating solution |
(3): Gamma before storage of coating solution |
(4): Gamma after storage of coating solution |
1. A silver halide photographic light-sensitive material comprising a support having
thereon a silver halide emulsion layer being spectrally sensitized with at least one
selected from a ctionic di-carbocyanine and a cationic tri-carbocyanine sensitizing
dye, and at least one of said silver halide emulsion layer and an hydrophilic colloid
layer other than said silver halide emulsion layer, which is provided on the side
of said support on which said silver halide emulsion layer is provided, contains a
compound represented by the following formular I, II or III:
wherein R₄, R₅ and R₆ each represent a hydrogen atom, an alkyl group, alkenyl group,
alkoxy group or alkoxycarbonyl group each having 1 to 12 carbon atoms, an amino group,
an aryl group, a hydroxyl group, a mercapto group or a carboxyl group or a salt thereof,
and said alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, amino group
and aryl group may have a substituent;
wherein R₇, R₈ and R₉ each represent a hydrogen atom, a halogen atom, a hydroxyl
group, an amino group which may have a substituent; R₁₀ represents a phosphoric acid
group or an alkyl group having 1 to 8 carbon atoms which may have a substituent;
wherein R₁₁ and R₁₂ each represent a hydrogen atom, a hydroxyl group or a substituted
or unsubstituted methyl group; R₁₃ represents a phosphoric acid group or an alkyl
group having 1 to 8 carbon atoms.
2. The material of claim 1, wherein said di- and tri-carbocyanine dye are represented
by the following formulas Ia and Ib, respectively;
wherein Y₁₁, Y₁₂, Y₂₁ and Y₂₂ each represent a group of non-metal atoms necessary
to complete a nitrogen-containing heterocyclic ring of 5 or 6 members; R₁₁, R₁₂, R₂₁
and R₂₂ each represent an alkyl group, aryl group or aralkyl group which may have
a substituent; and R₁₃, R₁₄, R₁₅, R₂₃, R₂₄, R₂₅ and R₂₆ each represent a hydrogen
atom, an alkyl group, alkoxy group, phenyl group, benzyl group, which may have a substituent,
or a
group, in which W₁ and W₂ each represent an alkyl group or aryl group, which may
have a substituent and may combine each other to form a nitrogen-containing heterocyclic
ring, and R₁₃ and R₁₅, and R₂₃ and R₂₅ may combine each other to form a 5-membered
or 6-membered ring; X₁₁ and X₂₁ each represent an anion; and n₁₁, n₁₂, n₂₁ and n₂₂
each represent 0 or 1.
3. The material of claim 1, wherein said compound represented by formula I, II or
III is contained said light-sensitive material in an amount of from 5 mg to 5 g per
mol of silver halide contained said silver halide emulsion layer.
4. The material of claim 3, wherein said compound represented by formula I, II or
III is contained said light-sensitive material in an amount of from 10 mg to 1 g
per mol of silver halide contained said silver halide emulsion layer.
5. The material of claim 1, wherein said silver halide emulsion layer contains a phenol
resin formed by condensation of a kind of phenols and a kind of aldehydes.
6. The material of claim 5, the polymerization degree of said phenol resin is within
the range of rom 2 to 10,000.
7. The material of claim 6, the polymerization degree of said phenol resin is within
the range of rom 3 to 1,000.
8. The material of claim 5, wherein said phenol resin is contained in said silver
halide emulsion layer in an amount of from 1× 10⁻⁴ g to 100 g per mol of silver halide
contained in said silver halide emulsion layer.
9. The material of claim 8, wherein said phenol resin is contained in said silver
halide emulsion layer in an amount of from 1× 10⁻³ g to 10 g per mol of silver halide
contained in said silver halide emulsion layer.
10. The material of claim 1, wherein at least one of said silver halide emulsion layer
or said hydrophilic colloid layer contains an oil-soluble fluorescent brightning agent.
11. The material of claim 10, wherein said oil-soluble fluorescent brightning agent
is represented by the following formula II-a, II-b, II-c or II-d;
wherein Y₁ and Y₂ each represent an alkyl group; Z₁ and Z₂ each represent a hydrogen
atom or an alkyl group; n represents 1 or 2; R₁, R₂, R₃, R₄ and R₅ each represent
an aryl group, an alkyl group, an aryloxy group, a hydroxyl group, an amino group,
a cyano group, a carboxyl group, an amido group, an ester group, an alkylcarbonyl
group, an alkylsulfo group, a dialkylsulfonyl group or a hydrogen atom; R₆ and R₇
each represent a hydrogen atom, an alkyl group or a cyano group; R₁₆ represents a
phenyl group, a phenyl group substituted by an alkyl group or a halogen atom; R₁₅
represents an amino group or a primary or secondary organic amino group.