U.S. patent number 3,615,542 [Application Number 04/709,174] was granted by the patent office on 1971-10-26 for light-sensitive silver halide color-photographic material.
This patent grant is currently assigned to Konishiroku Photo Industry Co., Ltd.. Invention is credited to Akira Horikoshi, Masanobu Oguchi, Kensaku Tanimura.
United States Patent |
3,615,542 |
Oguchi , et al. |
October 26, 1971 |
LIGHT-SENSITIVE SILVER HALIDE COLOR-PHOTOGRAPHIC MATERIAL
Abstract
Light-sensitive silver halide color-photographic material
comprises a support and, coated thereon, a light-sensitive silver
halide emulsion layer containing a color former, and a complex
formed from (a) an alkali-soluble phenolic compound having a
hydroxyl group on its benzene nucleus and capable of reducing
silver halide and (b) a water-soluble polymeric vinyl compound
capable of forming a complex with said phenolic compound, said
complex being included in said emulsion and/or in a layer
contiguous therewith.
Inventors: |
Oguchi; Masanobu (Tokyo,
JA), Horikoshi; Akira (Tokyo, JA),
Tanimura; Kensaku (Tokyo, JA) |
Assignee: |
Konishiroku Photo Industry Co.,
Ltd. (Tokyo, JA)
|
Family
ID: |
11824025 |
Appl.
No.: |
04/709,174 |
Filed: |
February 29, 1968 |
Foreign Application Priority Data
|
|
|
|
|
Mar 3, 1967 [JA] |
|
|
42/13,111 |
|
Current U.S.
Class: |
430/545; 430/380;
430/536; 430/566; 430/510; 430/537 |
Current CPC
Class: |
G03C
7/396 (20130101); G03C 7/39208 (20130101); G03C
1/42 (20130101); G03C 1/053 (20130101) |
Current International
Class: |
G03C
1/42 (20060101); G03C 7/392 (20060101); G03C
1/053 (20060101); G03C 7/396 (20060101); G03c
001/42 () |
Field of
Search: |
;96/114,95,96,77,100 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Smith; Ronald H.
Claims
What we claim is:
1. A light-sensitive silver halide color-photographic material
which comprises a support and, coated thereon, a light-sensitive
silver halide emulsion layer containing a color coupler,
characterized in this that the combination of an alkali-soluble
phenolic compound having at least one hydroxyl group on its benzene
nucleus and capable of reducing silver halide with a water-soluble
polymeric vinyl compound containing the recurrent unit of the
general formula ##SPC7##
wherein A means an atomic grouping necessary to constitute,
together with the adjacent nitrogen and carbon atoms, a five- to
seven-membered oxygen-containing heterocyclic ring, and capable of
forming a complex with said phenolic compound through a hydrogen
bond, is present in said light-sensitive silver halide emulsion
layer and/or the layer contiguous therewith.
2. A light-sensitive silver halide color-photographic material as
claimed in claim 1, wherein said material is a monochromatic color
or tri-color photographic film.
3. A light-sensitive silver halide color-photographic material as
claimed in claim 1, wherein said combination is present in at least
one layer selected from light-sensitive emulsion layer, interlayer,
protective layer, antihalation layer, filter layer and
sublayer.
4. A light-sensitive silver halide color-photographic material as
claimed in claim 1, wherein said phenolic compound is one member
selected from black-and-white developers having at least one
phenolic hydroxyl group.
5. A light-sensitive silver halide color-photographic material as
claimed in claim 1, wherein said polymeric vinyl compound is one
member selected from polyvinyl pyrrolidone, polyvinyl oxazolidone,
polyvinyl piperidone and polyvinyl caprolactam.
Description
This invention relates to a light-sensitive silver halide
photographic material useful for color photography. This invention
particularly is directed to a light-sensitive silver halide
color-photographic material which comprises, as a developing aid,
the combination of a certain phenolic compound with a certain
polymeric compound in a light-sensitive silver halide emulsion
layer and/or the layer contiguous therewith.
In color development, as is well known in the art, a color image is
formed by the reaction of a color former with a color developer in
its oxide form. Since conversion of the color developer into its
oxide form occurs by the treatment of a latent silver image (silver
ion) with a developing solution containing said color developer,
the formation of dye is somewhat restricted to around the reduced
silver particles, thereby to cause graininess of the dye.
Various methods have been proposed heretofore to obtain improved
graininess. For example, it is a common practice to use silver
halide in the form of particles as fine as possible. However, this
usually suffer from decrease in photographic sensitivity. In some
instance, use of a color former having delayed coupling rate or a
protected oil-soluble color former having a low rate of reaction
with the oxide of a color developer is proposed thereby to have
sufficient diffusion of the oxide with the less degradation of
graininess. However, this method is disadvantageous because it
makes difficult silver development to proceed and results in
decrease in photographic speed and gradient. Use of a
black-and-white developer and a color developer in a developing
solution is also known to obtain their superadditive effect for
color development. However, this procedure makes the maintenance of
a developing bath considerably troublesome. Incorporation of a
black-and-white developer in a light-sensitive layer is not
recommendable because this causes undesired migration of said agent
into other photographic layers. Further, said agent is likely to be
dissolved out from the layer during development.
Accordingly, it is an object of the invention to provide a
light-sensitive silver halide color-photographic material with
improved graininess and free from color fog.
The above-mentioned object can be accomplished by the present
invention. In accordance with the present invention, there is
provided a light-sensitive silver halide color-photographic
material which comprises a support and, coated thereon, a
light-sensitive silver halide emulsion layer containing a color
former, characterized by that the combination of (a) an
alkali-soluble phenolic compound having a hydroxyl group on its
benzene nucleus and capable of reducing silver halide and (b) an
water-soluble polymeric vinyl compound capable of forming a complex
with said phenolic compound exists in a light-sensitive silver
halide emulsion layer and/or the layer contiguous therewith.
For the purpose of the present invention, it is essential to
incorporate the combination of both of the phenolic compound (a)
with the polymeric vinyl compound (b) into a light-sensitive silver
halide emulsion layer and/or the layer contiguous therewith. It is
presumed, without full exactness, that the above-referred
combination of the phenolic compound (a) with the polymeric vinyl
compound (b) is present in the form of a complex of the compounds
(a) and (b), as such complex is understood as the result of the
formation of a hydrogen bond between the hydroxyl group of the
phenolic compound and the oxygen atom of the heterocyclic keto
group of the polymeric vinyl compound when both of these compounds
are brought into an aqueous or alcoholic medium. As well known for
those skilled in the art, the present application is applicable to
light-sensitive silver halide color-photographic films including
monochromatic color films and tri-color films. Therefore, the
combination of the compounds (a) and (b) can be incorporated in one
or more light-sensitive silver halide emulsion layers. Similarly,
it can be incorporated in other photographic layers contiguous to
the light-sensitive emulsion layers, said other photographic layers
being inter layer, protective layer, antihalation layer, subbing
layer, and filter layer.
The essential requirements for the phenolic compound (a) outlined
before are that it is soluble in alkali; it has on its benzene
nucleus at least one hydroxyl group which serves to form a hydrogen
bond; and it is capable of reducing silver halide to silver.
Suitable phenolic compounds (a) as referred to may be obtained from
a wide variety of conventionally known black-and-white developers.
Hydroquinone, aminophenol and pyrogallol which are well known
black-and-white developers are typical phenolic compounds useful in
this invention. Nucleically substituted hydroquinones and
N-substituted aminophenols are also useful. The following are
typically suitable compounds for the purpose of this invention.
##SPC1## ##SPC2##
Almost all of the conventionally known black-and-white developers
are usable in this invention, as far as said developers have a
hydroxyl group to form a hydrogen bond. In the following
description, therefore, the term "black-and-white developer" may be
interpreted synonymous with the term "Phenolic compound (a)" as
referred to above.
Suitable water-soluble polymeric vinyl compounds (b) are those
containing the recurrent monomeric unit of the general formula
##SPC3##
wherein A means an atomic grouping necessary to constitute,
together with the adjacent nitrogen and carbon atoms, a five- to
seven-membered ring. These polymeric vinyl compounds can be
prepared by the homopolymerization or copolymerization of an
appropriate monomer corresponding to the said general formula.
Typically useable polymeric vinyl compounds (b) include, for
instance, polyvinyl pyrrolidone, polyvinyl oxazolidone, polyvinyl
piperidone, polyvinyl caprolactam, etc. If desired, these compounds
may be modified by the introduction of any suitable substituent,
e.g. a solubilizing group, so as to impart desired useful property
to said compounds. The essential requirement for the polymeric
vinyl compounds (b) is that they are soluble in water and capable
of complexing with the above-mentioned phenolic compounds (a) (or
the black-and-white developers) of the pH range of about 6.0 to
about 8.0. Preferably, these polymeric vinyl compounds should have
an average molecular weight as great as about 10,000 or more. If
these polymers have too small molecular weight, the resulting
combination products or complexes still tend to migrate in
photographic layers or induce dissolution of color formers or dyes
in developing solutions during color development. It is desirable
that the polymeric vinyl compound can produce a complex having a
sufficiently great molecular weight to prevent its migration in
photographic layers.
The ratio of these polymers with the black-and-white developer to
be combined may be defined as m:n = 2:1-100:1 , wherein m means the
polymerization degree of the polymer and n is the mole number of
the black-and-white developer. Depending on the types of the
polymer and black-and-white developer, the higher or lower ratio
(m/n) may be used. The black-and-white developer may be used singly
or in combination to form one or more complexes.
The polymer and the black-and-white developer may be added
separately to a coating liquid to form a complex in situ.
Alternatively, a complex is formed in water or alcohol by the
reaction of the polymer with the black-and-white developer and then
added to a photographic coating liquid. The amount used may be 1-30
percent based on the amount of a film-forming binder such as
gelatine, but this can be varied depending on the type of the
complex, the silver halide content of the emulsion layer, the
silver content of the filter layer, the hardness of the binder
layer, etc.
This invention is applicable to any light-sensitive silver halide
color-photographic material containing a color former which may be
alkali-soluble coupler having a nondiffuse group, oil-soluble
incorporated coupler, etc. or colorless coupler, colored coupler,
etc. Similarly, any color developer which is conventionally known
is also usable for color development of the color-photographic
material of this invention.
As explained hereinabove, the present invention can exhibit the
superadditive effect of the color developer and the black-and-white
developer in Redox system during color development, thereby to
obtain improved graininess of dyes and decrease of fogging, without
sacrificing photographic speed and gradient.
The following examples describe certain ways in which the principle
of the invention has been applied, but are not to be construed as
limiting its scope.
EXAMPLE 1
A high speed green-sensitive photographic emulsion is prepared
which contains 100 g. of gelatin and 0.35 moles of silver
bromoiodide containing 5 mole percent silver iodide. This emulsion
is divided to 12 equal portions. Six portions are added with each
one of the before-indicated phenolic compounds (II), (IV), (VI),
(VIII) and (X) and poly-N-vinyl- 2-pyrrolidone having an average
molecular weight of 350,000 (this is referred to as the compound
(P), hereinafter). Five portions are added with each one of the
compounds (II), (IV), (VI), (VIII) and (X), respectively, combined
with the compound (P) in methanolic solution. The remaining one
portion is used as a control sample by adding thereto methanol
only. Each of these emulsions are added with a magenta color
former, 1-[4-(
4-tert.butylphenoxy)-3-sulfophenyl]-3(3-palmitamidobenzamido)-5-pyrazolone
, in the proportion of 3 mole percent based on the molar content of
the silver halide and then adjusted at pH 6.8. These emulsions are
coated on cellulose triacetate film based and dried. The resulting
film strips are subjected to exposure to light in a sensitometer.
After the light exposure, these film strips are treated at
20.degree. C. for 10 minute with a developing solution of the
following formulation.
4-Amino-N-ethyl-N-[.beta.-methanesulfonamidoethyl] -m-toluidine
sesquisulfate monohydrate 5 g. Anhydrous sodium sulfite 4 g. Sodium
carbonate monohydrate 50 g. Hydroxylamine semi-sulfate 0.6 g.
Potassium bromide 2 g. Water to make up 1 l.
After development, the film strips are washed with water for 5
seconds and treated with a magnesium sulfate solution at 20.degree.
C. for 10 minutes. Then, they are rinsed, bleached, rinsed, fixed,
rinsed and dried in the manner known per se.
Complementary color density of the color-developed film strips is
measured. Fog., relative speed at the density of 0.1 above fog.,
gamma value averaging those of from the point at which the
photographic speed is obtained to the point at which an exposure
amount as much as 10 times is given are obtained. The
color-developed film negatives thus obtained are printed by
enlargement (x10) on Sakura color photographic paper. These color
prints are visually compared with the control color print by 10
persons with reference to a series of standard color image samples
which represent 10 discriminating grades of graininess. Rating of
graininess of the tested color prints is determined. For example,
+2 means that the color print in question is better in graininess
by two grades than the control color print. The results are set
forth in table 1, wherein the amount is expressed by percent weight
based on the gelatine amount. The complex is expressed as by [P] m
[II] n, wherein m and n are the molar ratio of the individual
components. ##SPC4##
As apparent from table 1, the complex compound of the polymer with
the black-and-white developer according to this invention (which
compound is expressed as by [P] 10 [II]1) can show remarkably
improved graininess of dyes without decrease in photographic speed
and gradient, in comparison with the control, the polymer alone and
the black-and-white developer alone. cEXAMPLE 2
A high speed red-sensitive photographic emulsion is prepared which
contains 80 g. of gelatine and 0.35 moles of silver bromoiodide
containing 4 mole percent silver iodide. The emulsion thus prepared
is divided to six equal portions, one of which is used as a control
emulsion and the remaining five are added with each one of the
compound (III), poly-N-vinyl-5-methyl-2-oxazolidinone having an
average molecular weight of 250,000 (this is referred to as the
compound [0] hereinafter), copolymer of poly-N-vinyl-2-pyrrolidone
having an average molecular weight of 160,000 with sodium
polymethacrylate having an average molecular weight of 32,000 (this
copolymer is referred to as the compound (PM) hereinafter), a
complex of (III) with (0) and a complex of (III) with (PM). The
thus prepared emulsions are added with a cyan color former,
1-hydroxy-2-naphthoyl-N-octadecylamido-4-sulfonic acid, in the
amount of 6 mole percent based on the silver halide content. The
emulsions are adjusted at pH 6.8. These are coated on cellulose
triacetate film bases and dried. The each samples obtained are
exposed to light in a sensitometer. The same measurement as in
example 1 is conducted. The results are set forth in table 2.
##SPC5## As apparent from table 2, use of the complexes according
to the invention is effective to improve graininess of dyes and
decrease fog, without any adverse influence on photographic speed
and gamma.
EXAMPLE 3
A colloidal silver suspension containing 100 g. of gelatine and 5.2
g. of blue colloidal silver is prepared. This suspension is for use
in the preparation of antihalation layer. This is divided to five
equal portions, one of which is used as a sample and the remaining
four are added with each of the compound (IV), the compound (XII),
poly-N-vinyl-2-pyrrolidone having an average molecular weight of
350,000 (this is referred to (P), hereinafter), the complex of (IV)
with (P) and the complex of (XII) with (P). The emulsions are
adjusted at pH 6.8 and then coated on cellulose triacetate film
bases. The high speed red-sensitive color photographic emulsion
containing a cyan color former which emulsion is used in example 2
is overcoated and dried. Each film samples thus prepared are
exposed to light in a sensitometer and then treated with a
developing solution of the following formulation:
N,N-diethyl-p-phenylenediamine monohydrochloride 2.5 g. Anhydrous
sodium sulfite 4 g. Sodium carbonate monohydrate 50 g.
Hydroxylamine semi-sulfate 0.6 g. Potassium bromide 2 g. Water to
make up 1 l.
After development, these film samples are worked up in the same
manner as in example 1. The results of measurement are set forth in
table 3. It is to be noted that the control (I) appearing in table
1 is the same as the control of example 2 and has no antihalation
layer, and the control (II) is the control sample with antihalation
layer. ##SPC6##
As apparent from table 3, the present invention is useful to
improve graininess remarkably and decrease fog., without any
adverse influence on photographic speed and gamma.
* * * * *