BACKGROUND OF THE INVENTION
[0001] This invention relates to a light-sensitive color photographic material suitable
for full color photographing, particularly to a negative-type light-sensitive silver
halide color photographic material of which at least one color sensitive layer is
a single layer.
[0002] Presently, color photography widely spread is the so-called negative-positive system
in which photographing is practiced with a color negative film and color print is
effected by enlarging onto a color paper.
[0003] One of the reasons is that a color negative film has very broad exposure latitude,
with very little probability of failure during photographing, and even users in general
having no special knowledge can take color photographs without any particular concern.
[0004] "Having broad exposure latitude" refers to the fact that the gradation is good over
wide exposure dose range from the shadow portion with little exposure dose to the
highlight portion with much exposure dose in the so-called characteristic curve in
which the exposure dose is taken on the axis of abscissa and the color formed density
on the axis of ordinate.
[0005] If the gradation is inferior, color reproducibility and tone reproducibility of a
dye image will be deteriorated.
[0006] Color negative film, as different from color-reversal film or color paper, is a light-sensitive
material for which gradation is demanded to be strictly controlled over wider range
of exposure dose. For that reason, color negative films for photography commercially
available at the present time are made to have an overlaid constitution comprising
a plurality of emulsion layers of higher sensitivity layer containing greater grain
sizes of silver halide grains and lower sensitivity layer containing smaller grain
sizes of silver halide grains for the respective color sensitive layers to the lights
of blue color, green color and red color. Further, the so-called DIR compound for
forming consequently a developing inhibitor through the reaction with the oxidized
product of the developing agent is employed.
[0007] Such technique is inherent in color negative film, and particularly the DIR compound
improves not only gradation but also sharpness, graininess and color reproducibility
of a dye image, and is essential in color negative film.
[0008] As the technique for improving the so-called gradation stability which strictly controls
such gradation is disclosed in, for example, Japanese Provisional Patent Publication
No. 244944/1985. Specifically, there is disclosed the method in which after chemical
sensitization of the silver. halide emulsion with equal mean grain size, sensitizing
dyes are added to the respective emulsions with various molar ratios, and the emulsions
are again mixed.
[0009] Further, color negative film is subjected to developing processing in various laboratories
as compared with color reversal film, and hence to developing processing under processing
conditions with greater fluctuation width. Accordingly, color negative film has particularly
been demanded to have higher stability to fluctuation in processing conditions.
[0010] However, as described above, color negative film has an overlaid constitution by
use of a plurality of emulsion layers containing silver halide grains with different
grain sizes, and further gradation is strictly controlled by use of a DIR compound,
whereby storability of the light-sensitive photographic material before photographing
to external conditions such as temperature, humidity, etc. is inferior, and also in
spite of the demand for high degree of stability to processing conditions, processing
stability has not been solved to be inferior in stability to processing conditions.
For such reasons, deterioration in gradation occurs, thus involving the drawbacks
of deterioration of color reproducibility and tone reproducibility, and also with
respect to sensitivity, it cannot be said to be yet satisfactory. Further, according
to the method disclosed in Japanese Provisional Patent Publication No. 244944/1985,
there is the problem that adsorption equilibrium of the dyes between grains occurs
undesirably during the standing period before coating of the remixed emulsion.
SUMMARY OF THE INVENTION
[0011] An object of the present invention is to provide a light-sensitive silver halide
color photographic material, which is excellent in sensitivity and storability before
photographing, and also excellent in stability to fluctuations in processing conditions.
[0012] The object of the present invention has been accomplished by a light-sensitive silver
halide color photographic material, comprising on a support material at least silver
halide emulsion layers which are respectively blue-sensitive, green-sensitive and
red-sensitive, wherein a compound which can react with the oxidized product of the
developing agent to scavenge said oxidized product or a compound which can release
a precursor thereof is contained, and also at least one of said blue-, green- and
red-sensitive layers has a single layer constitution.
BRIEF DESCRIPTION OF THE DRAWING
[0013] Fig. 1 is a graph showing the characteristic curve which is the standard (broken
line) and the characteristic curve which is to be evaluated (solid line) of the light-sensitive
photographic material.
[0014] Fig. 2 is a graph showing the point gamma of the light-sensitive photographic material
of the characteristic curve which is the standard (broken line) and the characteristic
curve which is to be evaluated (solid line).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0015] The compound which can react with the oxidized product of the developing agent to
scavenge said oxidized product or the compound which can release a precursor thereof
in the present invention (hereinafter called "DSR compound") may be preferably represented
by the formula (DSR-I): Coupf Time tr Sc (DSR-I)
In the above formula (DSR-I), Coup represents the coupler residue which can release
the (Time) t -Sc through the reac tion with the oxidized product of the color developing
agent, Time represents a timing group which can release Sc after Time-Sc is released
from Coup, Sc represents the scavenger of the oxidized product of the color developing
agent which can scavenge the oxidized product of the color developing agent through
redox reaction or coupling reaction after released from Coup or Time-Sc or a precursor
thereof, and

represents 0 or 1.
[0017] In the above formula (DSR-Ia), R
1 represents an alkyl group, an aryl group or an arylamino group, and R
2 represents an aryl group or an alkyl group.
[0018] In the above formula (DSR-Ib), R
3 represents an alkyl group or an aryl group, and R
4 represents an alkyl group, an acylamino group, an arylamino group, an arylureido
group or an alkylureido group.
[0019] In the above formula (DSR-Ic), R
4. has the same meaning as R
4 in the formula (DSR-Ib), and Rs represents an acylamino group, a sulfonamide group,
an alkyl group, an alkoxy group or a halogen atom.
[0020] In the above formulae (DSR-Id) and (DSR-le), R
7 represents an alkyl group, an aryl group, an acylamino group, an arylamino group,
an alkoxy group, an arylureido group, an alkylureido group, and R
6 represents an alkyl group or an aryl group.
[0021] In the above formula (DSR-If), R
9 represents an acylamino group, a carbamoyl group or an arylureido group, and R
8 represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group or
a sulfonamide group.
[0022] In the above formula (DSR-Ig), R
9 has the same meaning as R
9 in the formula (DSR-If), and R
io represents an amino group, an acid amide group, a sulfonamide group or a hydroxyl
group.
[0023] In the above formula (DSR-Ih), R
11 represents a nitro group, an acylamino group, a succinimide group, a sulfonamide
group, an alkoxy group, an alkyl group, a halogen atom or a cyano group.
[0024] In the above formulae,

in (DSR-Ic) represents an integer of 0 to 3, n in the formulae (DSR-If) and (DSR-Ih)
of 0 to 2, m in (DSR-Ig) of 0 or 1, and when

and n are 2 or more, the respective Rs, R
8 and R
11 may be either the same or different.
[0025] The above respective groups include those having substituents, and preferred substituents
may include halogen atoms, nitro group, cyano group, sulfonamide group, hydroxyl group,
carboxyl group, alkyl groups, alkoxy groups, carbonyloxy groups, acylamino group,
aryl groups, and otherwise those containing the coupler moiety constituting the so-called
bis-type coupler or polymer coupler.
[0026] The lipophilicity exhibited by R
1 to R
11 in the above respective formulae can be chosen as desired depending on the purpose.
In the case of an ordinary image forming coupler, the total carbon atoms of R
1 to R
10 should be preferably 10 to 60, more preferably 15 to 30. When a dye formed by color
developing is made migratable adequately in the light-sensitive material, the total
carbon atoms of said R
1 to R
10 are preferably 15 or less.
[0027] The coupler forming substantially no image forming chromogenic dye means, in addition
to those forming no chromogenic dye, those which give no color image remaining after
the developing processing such as the so-called flowable dye forming coupler of which
the chromogenic dye flows out into the processing solution, the so-called bleachable
dye forming coupler which is bleached through the reaction with the component in the
processing solution. In the case of the flowable dye forming coupler, the total carbon
atoms of R
1 to R
10 are preferably 15 or less, and further it is preferred that R
1 to R
10 have at least one carboxyl group, arylsulfonamide group or alkylsulfonamide group
as substituent.
[0028] In the above formula (DSR-I), the timing group represented by Time is represented
preferably by the following formula (DSR-li), (DSR-Ij) or (DSR-Ik).

wherein B represents a group of atoms necessary for completion of a benzene ring or
a naphthalene ring; Y represents -0-, -S- or

which is bonded to the active site of Coup (coupling component) of the above formula
(DSR-I); R
12, R
13 and R
14 each represent hydrogen atom, an alkyl group or an aryl group.
[0029] The above group

is substituted at the ortho- or para-relative to Y, and the other is bonded to Sc
of the above formula (DSR-I).

wherein Y, R
12 and R
13 have respectively the same meanings as in the above formula (DSR-li); R
15 represents hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl
group, an alkoxycarbonyl group or a heterocyclic residue; R
16 represents hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue,
an alkoxy group, an amino group, an acid amide group, a sulfonamide group, a carboxyl
group, an alkoxycarbonyl group, a carbamoyl group or a cyano group.
[0030] Also, the timing group represented by the above formula (DSR-Ij) has Y bonded to
the active site of Coup (coupling component) and the group

to Sc, similarly as in the above formula (DSR-li).
[0031] Next, as the Time group which releases Sc through the intramolecular nucleophilic
reaction, there is one represented by the following formula (DSR-Ik).

wherein Nu represents a nucleophilic group having oxygen, sulfur or nitrogen atom,
which is rich in electrons and bonded to the active site of Coup (coupling component)
in the above formula (DSR-I); E represents an electrophilic group having carbonyl
group, thiocarbonyl group, phosphinyl group or thiophosphinyl group, which is deficient
in electrons, which electrophilic group E is bonded to the hetero atom of Sc; D represents
a bonding group which correlates sterically Nu and E, can perform intramolecular .nucleophilic
substitution through the reaction with accompaniment of formation of a 3- to 7-membered
ring after Nu is released from Coup (coupling component), and can also release Sc
thereby.
[0032] The scavenger of the oxidized product of the color developing agent represented by
Sc (in the case when Sc is a precursor, the scavenger formed from said precursor)
is inclusive of the redox type and the coupling type.
[0033] In the formula (DSR-I), when Sc is one which scavenges the oxidized product of the
color developing agent through the redox reaction, said Sc is a group capable of reducing
the oxidized product of the color developing agent, including preferably the reducing
agents as disclosed in Angew. Chem. Int. Ed., vol. 17, pp 875 - 886 (1978), The Theory
of the Photographic Process, The 4th Ed. (Macmillan, 1977) and Japanese Provisional
Patent Publication No. 5247/1984, and Sc may be also a precursor capable of releasing
those reducing agents during developing. Specifically, aryl groups or heterocyclic
groups having at least two of -OH group, -NHS0
2R group,

group (wherein R, R represent hydrogen atom, an alkyl group, a cycloalkyl group, an
alkenyl group or an aryl group) are preferred. Among them, an aryl group is preferred,
and further a phenyl group is preferred. The lipophilicity of Sc is chosen as desired
depending on the purpose similarly as the coupler represented by the above formulae
(DSR-Ia) to (DSR-Ih), but for exhibiting the effect of the present invention to the
maximum, the total carbon atoms of Sc may be 6 to 50, preferably 6 to 30, more preferably
6 to 20.
[0034] When Sc is one which scavenges the oxidized product of the color developing agent
through the coupling reaction, said Sc can be various coupler residues, but preferably
a coupler residue which forms substantially no image forming chromogenic dye, and
the flowable dye forming couplers, bleachable dye forming couplers as described above,
and Weiss couplers having non-eliminatable substituent at the reaction active site
and forming no dye, can be utilized.
[0035] Specific examples of the compounds represented by the formula (DSR-I):

may include those disclosed in U.K. Patent No. 1546837, Japanese Provisional Patent
Publications No. 150631/1977, No. 111536/1982, No. 111537/1982, No. 138636/1982, No.
185950/1985, No. 203943/1985, No. 213944/1985, No. 214358/1985, No. 53643/1986, No.
84646/1986, No. 86751/1986, No. 102646/1986, No. 102647/1986, No. 107245/1986, No.
113060/1986, No. 231553/1986, No. 233741/1986, No. 236550/1986, No. 236551/1986, No.
238057/1986, No. 240240/1986, No. 249052/1986, No. 81638/1987, No. 205346/1987, No.
287249/1987, etc.
[0036] As Sc, the redox type scavenger can be preferably used, and in this case, the color
developing agent can be utilized again by reducing the oxidized product of the color
developing agent.
[0038] The DSR compound of the present invention can be added in the light-sensitive silver
halide photographic emulsion layer and/or the non-light-sensitive photographic constituent
layer, but preferably in the light-sensitive silver halide emulsion layer.
[0039] The DSR compound of the present invention can be contained in two or more kinds in
the same layer. Also, the same DSR compound can be contained in two or more different
layers.
[0040] These DSR compounds may be generally used in amounts preferably of 2 x 10-
4 to 5 x 10-
1 mole, more preferably of 1 x 10-
3 to 1 x 10-
1 mole, per mole of silver in the emulsion layer.
[0041] For incorporating these DSR compounds in the silver halide emulsion according to
the present invention or in other photographic constituent layer coating solutions,
when said DSR compound is alkali soluble, it may be also added as an alkaline solution,
or when it is oil soluble, the DSR compound is preferably dissolved in a high boiling
solvent optionally in combination with a low boiling solvent and added as a fine dispersion
into the silver halide emulsion, following the methods as disclosed in U.S. Patents
No. 2,322,027, No. 2,801,170, No. 2,801,171, No. 2,272,191 and No. 2,304,940.
[0042] The DSR compounds as described above can be synthesized according to the methods
as disclosed in Japanese Provisional Patent Publications No. 138638/1982, No. 155537/1982,
No. 171334/1982, No. 111941/1983, No. 53643/1986, No. 84646/1986, No. 86751/1986,
No. 102646/1986, No. 102647/1986, No. 107245/1986, No. 113060/1986, etc.
[0043] The compound which undergoes the coupling reaction or the redox reaction with the
oxidized developing agent released from the DSR compound of the present invention
corresponding to the density of the image during developing or its precursor can obtain
two kinds of image effects of inhibiting the dye forming reaction (coupling reaction)
corresponding to the image density in the light-sensitive emulsion layer, thereby
giving rise to the so-called intra-image effect such as improvement of sharpness of
image, etc., while on the other hand, in other layer to which it has been diffused,
giving rise to the so-called inter-image effect such as the masking action, etc. by
interfering with the dye forming reaction in such layers corresponding to the density
of the image in the layer of the diffusion source.
[0044] In the present invention, use of a DIR compound is further preferred with respect
to graininess.
[0045] In the present invention, the DIR compound refers to a compound which eliminates
a developing inhibitor or a compound capable of releasing a developing inhibitor through
the reaction with the oxidized product of the color developing agent.
[0046] The above-mentioned compound capable of releasing a developing inhibitor may be one
which releases the developing inhibitor either imagewise or non-imagewise.
[0047] Imagewise release may be effected by, for example, the reaction with the oxidized
product of the developing agent, while non-imagewise release by utilizing; for example,
the TIME group as described below.
[0048] In the following, representative structural formulae are shown.

wherein A represents a coupler residue, m represents 1 or 2, Y represents a group
bonded to the coupling position of the coupler residue A and eliminatable through
the reaction with the oxidized product of the color developing agent, which is a developing
inhibitor group or a group capable of releasing a developing inhibitor.
[0050] In the formulae (D-2) to (D-7), Rd
1 represents a hydrogen atom, a halogen atom or an alkyl, alkoxy, acylamino, alkoxycarbonyl,
thiazolidinylideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl,
nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N- alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino,
alkylthio, arylthio, aryl, heterocyclic, cyano, alkylsulfonyl or aryloxycarbonylamino
group. n represents 0, 1 or 2, and when n is 2, the respective Rd
1's may be either the same or different. The total carbon atoms contained in n Rd,'s
may be 0 to 10. On the other hand, the carbon atoms contained in Rd, in the formula
(D-6) may be 0 to 15.
[0051] In the above formula (D-6), X represents an oxygen atom or a sulfur atom.
[0052] In the formula (D-8), Rd
2 represents an alkyl group, an aryl group or a heterocyclic group.
[0053] In the formula (D-9), Rd
3 represents a hydrogen atom, an alkyl, cycloalkyl, aryl or heterocyclic group, Rd
4 represents a hydrogen atom, a halogen atom or an alkyl, cycloalkyl, aryl, acylamino,
alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamide, cyano, heterocyclic,
alkylthio or amino group.
[0054] When Rd
1, Rd
2, Rd
3 or Rd
4 represents an alkyl group, the alkyl group includes those having substituents, and
may be either straight or branched.
[0055] When Rdi, Rd
2, Rd
3 or Rd
4 represents an aryl group, the aryl group includes those having substituents.
[0056] When Rd
1, Rd
2, Rd
3 or Rd
4 represents a heterocyclic group, the heterocyclic group includes those having substituents,
preferably 5- or 6-membered monocyclic or fused rings containing at least one selected
from nitrogen atom, oxygen atom and sulfur atom as the hetero atom, and may be selected
from the groups of, for example, pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl,
imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imide or oxazine group.
[0057] The carbon atoms contained in Rd
2 in the formula (D-8) may be 0 to 15.
[0058] In the above formula (D-9), the total carbon atoms contained in Rd
3 and Rd
4 may be 0 to 15.

wherein the TIME group is a group bound to the coupling position of A which cleavable
through the reaction with the oxidized product of the color developing agent, which
is a group cleaved successively after cleavage from the coupler, until finally can
release the INHIBIT groups with adequate control; n is 1 to 3, and when it is 2 or
3, the respective TIME groups may be either the same or different. The INHIBIT group
is a group which becomes a developing inhibitor by the above-mentioned release (e.g.
the group represented by the above formulae (D-2) to (D-9)).
[0060] In the formulae (D-11) to (D-15) and (D-18), Rd
5 reprsents a hydrogen atom, a halogen atom or an alkyl, cycloalkyl, alkenyl, aralkyl,
alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamide, sulfamoyl,
carbamoyl, aryl, carboxy, sulfo, hydroxy or alkanesulfonyl group. In the formulae
(D-11) to (D-13), (D-15) and (D-18), Rds's may be mutually bonded together to form
a fused ring. In the formulae (D-11), (D-14), (D-15) and (D-19), Rds represents an
aralkyl, alkenyl, alkyl, cycloalkyl, heterocyclic or aryl group. In the formulae (D-16)
and (D-17), Rd
7 represents a hydrogen atom or an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic
or aryl group. Each of Rd
8 and Rd
9 in the formulae (D-19) represents a hydrogen atom or an alkyl group (preferably an
alkyl group having 1 to 4 carbon atoms), k in the formulae (D-11), (D-15) to (D-18)
represents an integer of 0, 1 or 2,

in the formulae (D-11) to (D-13), (D-15) and (D-18) represents an integer of 1 to
4, m in the formula (D-16) represents an integer of 1 or 2. When

and m are 2 or more, the respective Rd
s and Rd
7 may be either the same or different. n in the formula (D-19) represents an integer
of 2 to 4, and Rd
8 and Rd
9 in number of n may be each the same or different. B in the formulae (D-16) to (D-18)
represents an oxygen atom or

(Rds represents the same meaning as already defined), and

in the formula (D-16) may be either a single bond or a double bond, and m is 2 in
the case of the single bond or m is 1 in the case of the double bond.

wherein T, represents a component which cleaves SR(̵T
2)̵
m INHIBIT, SR represents a component which forms (T
2 )̵
m INHIBIT through the reaction with the oxidized product of the developing agent after
formation of SR(̵T
2)̵
m INHIBIT, T
2 represents a component which cleaves INHIBIT after formation of (T2)̵
m-INHIBIT, INHIBIT represents a developing inhibitor and

and m each 0 or 1.
[0061] The component represented by SR may be one which can form the component as mentioned
above through the reaction with the oxidized product of the developing agent, and
may include, for example, a coupling component which undergoes the coupling reaction
with the oxidized product of the developing agent or a redox component which undergoes
the redox reaction with the oxidized product of the developing agent.
[0062] As the coupler component, there may be included yellow couplers, magenta couplers
and cyan couplers such as acylacetanilides, 5-pyrazolones, pyrazoloazoles, phenols,
naphthols, acetophenones, indanones, carbamoylacetanilides, 2(5H)-imidazolones, 5-isoxazolones,
uracils, homophthalimides, ox- azolones, 2,5-thiadiazoiine-1,1-dioxides, triazolothiadiazines
and indoles, and otherwise those which form various dyes or form no dye. The (T,

SR(̵T
2
INHIBIT should be preferably bonded to the active site of the component A of the
formula (D-1).
[0063] When SR is a coupler component, SR is bonded to (̵T
1
and (̵T
2
INHIBIT so as to function for the first time as the coupler after cleavage from (̵T
1
.
[0064] For example, the oxygen atom of hydroxyl group when the coupler component is phenols
or naphthols, the oxygen atom at the 5-position or the nitrogen atom at the 2-position
of the enantiomer when it is 5-pyrazolones, and also the oxygen atom of hydroxyl group
of the enantiomer when it is acetophenones or indanones, are preferably bonded to-(Ti

, and (̵T
2
INHIBIT to the active site of the coupler.
[0065] In the case when SR is a redox component, its examples may include hydroquinones,
catechols, pyrogallols, aminophenols (e.g. p-aminophenols and o-aminophenols), naphthalenediols
(e.g. 1,2-naphthalenediols, 1,4-naphthalenediols and 2,6-naphthalenediols) and aminonaphthols
(e.g. 1,2-aminonaphthols, 1,4-aminonaphthols and 2,6-aminonaphthols).
[0066] In the case when SR is a redox component, SR is bonded to (̵T
1
and (̵T
2
INHIBIT so as to function for the first time as the redox component after cleavage
from (̵T
1
.
[0067] Examples of the group represented by T, and T
2 may include those represented by the formulae (D-11) to (D-19) as described above.
[0068] As the developing inhibitor represented by INHIBIT, for example, those represented
by the formulae (D-2) to (D-9) as described above may be included.
[0069] Among the DIR compounds, preferred are those wherein Y is represented by the formula
(D-2), (D-3), (D-8), (D-10) or (D-20), and among (D-10) and (D-20), those wherein
INHIBIT is represented by the formula (D-2), (D-3), (D-6) (particularly when X of
the formula (D-6) is an oxygen atom), or (D-8) are preferred.
[0070] As the coupler component represented by A in the formula (D-1), yellow color image
forming coupler residues, magenta color image forming coupler residues, cyan color
image forming coupler residues and no color exhibiting coupler residues may be included.
[0071] As preferred DIR compounds to be used in the present invention, the compounds as
shown below may be included, but these are not limitative of the invention.
Exemplary compounds:
[0073] Specific examples of the DIR compounds which can be used in the present invention,
including these are described in U.S. Patents No. 4,234,678, No. 3,227,554, No. 3,617,291,
No. 3,958,993, No. 4,149,886 and No. 3,933,500; Japanese Provisional Patent Publications
No. 56837/1982 and No. 13239/1976; U.S. Patents No. 2,072,363 and No. 2,070,266; and
Research Disclosure No. 21228, December, 1981.
[0074] The DIR compound is preferably used in an amount of 0.0001 to 0.1 mole, particularly
0.001 to 0.05 mole, per mole of silver halide.
[0075] The place in which the DIR compound to be used in the present invention is added
may be any place which can affect developing of the silver halide in the emulsion
layer which takes single layer constitution as described above, preferably a silver
halide emulsion layer, more preferably an emulsion layer which takes silgle layer
constitution.
[0076] The constitution that the color sensitive layer is a single layer is also inclusive
of the case when a plurality of emulsion layers which are the same in color sensitivity,
being the same in the kind of the couplers contained in the emulsion layers, grain
sizes of the silver halide grains, the halogen compositions and crystal habits, and
also the ratio of the coupler to the silver halide, are arranged as continuous layers.
[0077] Here, "the same in color sensitivity" or "the same color sensitivity" may be the
same in the point of, for example, blue light-sensitivity, green light-sensitivity
or red light-sensitivity, and is not required to be totally the same in spectral sensitivity
characteristics.
[0078] In the present invention, the blue light-sensitive layer is preferably a single layer,
and further preferably, both the blue light-sensitive layer and the green light-sensitive
layer are single layers. Particularly, all of the blue light-sensitive, green light-sensitive
and red light-sensitive silver halide emulsion layers are preferably single layers,
respectively.
[0079] When the same color sensitive layer has a single layer constitution, the number of
the layers coated of the light-sensitive layer can be reduced as compared with the
overlaid constitution of the prior art, whereby the film can be made thinner. Therefore,
production efficiency and sharpness are improved, and graininess is also improved.
The film thickness is preferably 20 to 3 u.m, particularly 15 to 5 µm, after drying.
[0080] The exposure latitude is the width of light received at which the exposure effect
with a significant difference can be exhibited, particularly the exposure region from
the highlight to the deep shadow in the characteristic curve, and is determined by
the method defined in "Shasin no Kagaku (Chemistry of Photography)", p. 393 (published
by Shashin Kogyo Shuppansha, Japan, 1982).
[0081] More specifically, it is the difference in log H's between the two points where the
slope of the tangential line at the leg portion and the shoulder portion of the characteristic
curve represented with log H as the axis of abscissa and the transmission density
as the axis of ordinate becomes 0.2.
[0082] The light-sensitive material of the present invention is preferably one having an
exposure latitude measured according to the method as described above of 3.0 or more,
particularly 3.0 to 8.0.
[0083] As the means for making the exposure latitude of the silver halide emulsion layer
which is a single layer 3.0 or more, it is possible to use the method in which silver
halide grains with different sensitivities are used as a mixture. Specifically, there
may be included, for example, the method in which silver halide grains with different
grain sizes are used as a mixture, and the method in which the desensitizer is contained
in at least a part of the silver halide grains.
[0084] For obtaining a broad exposure latitude, there is a method in which two kinds of
monodispersed grains having different grain sizes and each sensitized are combinedly
used. In this case, a mean grain size of the grains having larger grain size is preferably
0.2 to 2.0 u.m and that of the grains having smaller grain size is preferably 0.05
to 1.0 nm, and the latter grains have smaller mean grain size than that of the former
ones.
[0085] Also, the mean grain size of the silver halide grains with the maximum mean grain
size should be preferably 1.5 to 40 times as that of the silver halide grains with
the minimum mean grain size.
[0086] For obtaining a broad exposure latitude, silver halide grains with different mean
grain sizes can be also used as a mixture, but by using silver halide grains containing
a desensitizer in place of the low sensitivity silver halide grains with small grain
sizes, the mean grain size difference can be made smaller without changing the sensitivity
of the silver halide grains, and further it becomes possible to use silver halide
grains with equal mean grain size and different sensitivities as a mixture.
[0087] Thus, by use of silver halide grains containing a desensitizer, the exposure latitude
can be obtained even if the fluctuation coefficient of the grains as a whole may be
made smaller.
[0088] Therefore, these silver halide grains with small fluctuation coefficient exposed
to the same environment are preferably stabilized in photographic performances relative
to changes with lapse of time and fluctuations in developing processing. Further,
in aspect of production technique, it becomes also possible to chemically sensitize
a mixed system of silver halide grains with different sensitivities in the same batch.
[0089] As the desensitizer, in addition to metal ions, various ones such as antifoggants,
stabilizers and densitizing dyes can be used.
[0090] In the present invention, the metal ion doping method is preferred. As the metal
ion to be used for doping, there may be included the metal ions of the groups Ib,
lib, IIIa, IIlb, IVb, Va and VIII in the periodic table of elements. Preferred metal
ions may include Au, Zn, Cd, TI, Sc, Y, Bi, Fe, Ru, Os, Rh, Ir, Pd, Pr, Sm and Yb.
Particularly, Rh, Ru, Os and Ir are preferred. These metal ions can be used as, for
example, halogeno complexes, and the pH of the AgX suspended system during doping
is preferably 5 or lower.
[0091] The amount of these metal ions doped will differ variously depending on the kind
of the metal ion, the grain size of the silver halide grains, the doping position
of the metal ion, the desired sensitivity, etc., but may be preferably 10-
17 to 10-
2 mole, further 10-
12 to 10-
3 mole, particularly 10-
9 to 10-
4 mole, per mole of AgX.
[0092] Further, by selection of the kind of the metal ion, the doping position and the doping
amount, various different sensitivities and qualities can be given to the silver halide
grains.
[0093] With a doping amount of 10-
2 mole/AgX or less, great influence will be scarcely given to the growth of the grains,
and hence silver halide grains with small grain size distribution can be prepared
under the same grain growth conditions, even by growth in the same batch.
[0094] After the silver halide grains with different doping conditions are adjusted in conditions
to be provided for practical application, these can be also made up in the same batch
by mixing at a predetermined ratio and subjected to chemical sensitization. The respective
silver halide gains receive the sensitizing effects based on their qualities, whereby
an emulsion having a broad exposure latitude depending on the sensitivity difference
and the mixing ratio can be obtained.
[0095] As the above-mentioned antifoggants or stabilizers, there may be included azoles
(e.g. benzthiazolium salt, indazoles, triazoles, benztriazoles and benzimidazoles),
heterocyclic mercapto compounds (e.g. mercaptotetrazoles, mercaptothiazoles, mercaptothiadiazoles,
mercaptobenzthiazoles, mercaptobenzimidazoles and mercaptopyrimidines), azaindenes
(e.g. tetraazaindenes and pentaazaindenes), nucleic acid decomposed products (e.g.
adenine and guanine), benzenethiosulfonates and thioketo compounds.
[0096] As the desensitizing dyes, there may be included cyanine dyes, merocyanine dyes,
complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine
dyes, styryl dyes and hemioxonol dyes.
[0097] As the position where the desensitizer exists, it is preferably mixed internally
of the silver halide grains in the points of preservability of the light-sensitive
material and standing stability of the coating solution, and its distribution may
be either uniform, localized at the central portion of grain or the intermediate positions,
or also gradually reduced from the central portion of grain toward outside.
[0098] From the standpoint of production efficiency, the case where the desensitizer exists
as localized at the central portion of the grain is preferred, and by use of the system
in which seed grains with small fluctuation coefficient are used, the steps of grain
growth et seq can be proceeded in the same batch.
[0099] The light-sensitive material of the present invention desirably has at least one
color sensitive layer (e.g. blue light-sensitive layer) containing AgX grains which
contain a desensitizer. Preferably, it is the case when the blue light-sensitive layer
contains AgX grains which contain a desensitizer, more preferably when the blue light-sensitive
layer and the green light-sensitive layer contain them, most preferably when all of
the color light-sensitive layers contain them.
[0100] Also, the fluctuation coefficient defined by the ratio S/ r of the standard deviation
of grain size (S) as the silver halide grains contained in the respective silver halide
emulsion layers and the mean grain size ( r ) is preferably 0.4 or less, more preferably
0.33 or less, further preferably 0.25 or less, particularly preferably 0.20 or less.

[0101] The mean grain size ( r ) is defined by the following formula when the number of
grains with a grain size r (in the case of a cubic silver halide grain, its length
of one side, or in the case of a grain with other shape than cubic, the length of
one side of the cube calculated to have the same volume) is n
i:

[0102] The relationship of grain size distribution can be determined according to the method
described in the essay of Tribel and Smith in "Empirical Relationship between Sensitometry
Distribution and Grain Size Distribution in Photography", The Photographic Journal,
Vol. LXXIX (1949), pp. 330 - 338.
[0103] As the silver halide emulsion to be used in the light-sensitive material of the present
invention, any of conventional silver halide emulsions can be used, but a silver halide
containing substantially iodine in the halogen composition (e.g. silver iodobromide,
silver iodochlorobromide) may be preferred, particularly preferably silver iodobromide
with respect to sensitivity. The amount of iodine may be preferably 1 mole % to 20
mole %, particularly 3.5 mole % to 12 mole %.
[0104] A core/shell type silver halide emulsion to be used in the present invention preferably
has a grain structure comprising two or more phases different in silver iodide content
and comprises silver halide grains in which a phase containing a maximum silver iodide
content (referred to as "core") is other than the outermost surface layer (referred
to as "shell").
[0105] The content of silver iodide in an inner phase (core) having the maximum silver iodide
content is preferably 6 to 40 mole %, more preferably 8 to 40 mole %, particularly
preferably 10 to 40 mole %. The content of silver iodide in the outermost surface
layer is preferably less than 6 mole %, more preferably 0 to 4.0 mole %.
[0106] A ratio of the shell portion in the core/shell type silver halide grains is preferably
10 to 80 %, more preferably 15 to 70 %, particularly preferably 20 to 60 % in terms
of volume.
[0107] Also, a ratio of the core portion is preferably, in terms of volume, 10 to 80 %,
more preferably 20 to 50 % based on the whole grains.
[0108] Difference of silver iodide content between the core portion having higher silver
iodide content and the shell portion having less silver iodide content of the silver
halide grains may be clear with sharp boundary or may be hazy where boundary is not
clear and the content continuously changes. Also, those having an intermediate phase
with silver iodide content between those of the core portion and the shell portion,
between the core and the shell, may be preferably used.
[0109] In case of the core/shell type silver halide grains having the above intermediate
phase, a volume of the intermediate phase is preferably 5 to 60 %, more preferably
20 to 55 % based on the whole grain. Differences of the silver iodide content between
the shell and the intermediate phase, and between the intermediate phase and the core
are each preferably 3 mole % or more and the difference of the silver iodide content
between the shell and the core is preferably 6 mole % or more.
[0110] The core/shell type silver halide emulsion can be prepared according to the known
methods as disclosed in Japanese Provisional Patent Publications No. 177535/1984,
No. 138538/1985, No. 52238/1984, No. 143331/1985, No. 35726/1985 and No. 258536/1985.
[0111] For producing silver iodobromide or silver bromide, soluble silver salt and soluble
halide are generally used, but as clear from the following Examples, iodide salts
are preferably used in the form of silver iodide fine crystals in the point of preservability
and processing stability of the light-sensitive material.
[0112] Also, silver iodobromide fine crystals having high Agl content are similarly and
preferably used as the silver iodide fine crystals.
[0113] Distribution condition of the silver iodide in the above core/shell type silver halide
grains can be determined by various physical measuring method and, for example, it
can be examined by the measurement of luminescence at low temperature or X-ray diffraction
method as described in Lecture Summary of Annual Meeting, Japanese Photographic Association,
1981.
[0114] The core/shell type silver halide grain may be any shape of normal crystal such as
cubic, tetradecahedral and octahedral, or twinned crystal, or mixtures thereof, but
preferably normal crystal grains.
[0115] Said emulsion can be chemically sensitized in the conventional manner, and optically
sensitized to a desired wavelength region by use of a sensitizing dye.
[0116] In the silver halide emulsion, antifoggants and stabilizers can be added. As the
binder for said emulsion, gelatin can be advantageously used.
[0117] The emulsion layer and other hydrophilic colloid layers can be hardened, and also
a plasticizer, a dispersion (latex) of a water-insoluble or difficultly soluble synthetic
polymer can be contained therein.
[0118] In the emulsion layer of a light-sensitive material for color photography, couplers
are used.
[0119] Further, there can be used colored couplers having the effect of color correction,
competitive couplers and compounds releasing photographically useful fragments such
as developer, silver halide solvent, toning agents, hardeners, antifoggants, chemical
sensitizers, spectral sensitizers and desensitizers through the coupling reaction
with the oxidized product of the developing agent.
[0120] Furthermore, by adding a compound which can release a bleaching accelerator or precursor
thereof through the reaction with an oxidized product of a color developing agent
(hereinafter referred to as "bleaching accelerator releasing compound") in at least
one layer of the light-sensitive material of the present invention, bleachability
and processing stability can be more improved as compared with the case where it is
contained in a light-sensitive material having no single layer.
[0121] The bleaching accelerator releasing compound (BAR compound) may preferably be represented
by the following formula (BAR-I).

wherein A is a coupler residue which can be subjected to a coupling reaction with
an oxidized product of a color developing agent, or a residue of an oxidation-reduction
nucleus which can be cross-oxidized with an oxidized product of a color developing
agent; TIME is a timing group; BA is a bleaching accelerator or its precursor; m is
0 or 1; and when A is a coupler residue, 1.. is 0, and when A is a residue of an oxidation-reduction
nucleus, 1 is 0 or 1.
[0122] Of the BAR compound represented by the formula (BAR-I), preferred are those represented
by the formulae (BAR-II) and (BAR-III).

wherein Cp is a coupler residue which can be subjected to a coupling reaction with
an oxidized product of a color developing agent; is a coupling position of a coupler;
TIME is a timing group; R, is an aliphatic group, an aromatic group, a saturated heterocyclic
group or a 5- or 6-membered aromatic nitrogen-containing heterocyclic group; R
2 is a water solubilizing substituent or its precursor; R
3 is a hydrogen atom a cyano group, -COR
4, -CSR
4 ,

-SR4,

or a heterocyclic group, in which R
4 is an aliphatic group or an aromatic group, Rs, Rs and R
7 each are a hydrogen atom, an aliphatic group or an aromatic group; and m and n each
are 0 or 1.
[0123] As the coupler residue represented by Cp, there may be mentioned residues capable
of forming yellow, magenta or cyan dyes and residues forming substantially colorless
products by the coupling reaction.
[0124] The representative examples of a yellow coupler residue are described in U.S. Patents
No. 2,298,443, No. 2,407,210, No. 2,875,057, No. 3,048,194, No. 3,265,506 and No.
3,447,928, and Farbkuppler eine Literaturuverisiecht Agfa Mitteilung (Band II), pp.
112 to 126 (1961). Of these, acylacetoanilides such as benzoylacetoanilide and pyvaloylacetoanilide
are preferred.
[0125] The representative examples of a magenta coupler residue are described in U.S. Patents
No. 2,369,489, No. 2,343,703, No. 2,311,182, No. 2,600,788, No. 2,908,573, No. 3,062,653,
No. 3,152,986, No. 3,519,429, No. 3,725,067 and No. 4,540,654, Japanese Provisional
Patent Publication No. 162548/1984 and in the above-mentioned Agfa Mitteilung (Band
II), pp. 126 to 156 (1961). Of these, pyrazolone and pyrazoloazoles, e.g. pyrazoloimidazole
and pyrazolotriazole are preferred.
[0126] The representative examples of a cyan coupler residue are described in U.S. Patents
No. 2,367,531, No. 2,423,730, No. 2,474,293, No. 2,772,162, No. 2,395,826, No. 3,002,836,
No. 3,034,892, No. 3,041,236 and No. 4,666,999 and in the above-mentioned Agfa Mitteilung
(Band II), pp. 156 to 175 (1961). Of these, phenols and naphthols are preferred.
[0127] The representative examples of a coupler residue which forms substantially colorless
products are described in British Patent No. 861,138 and U.S. Patents No. 3,632,345,
No. 3,928,041, No. 3,958,993 and No. 3,961,959. Of these, a cyclic carbonyl compound
is preferred.
[0128] A timing group represented by TIME is a group which allows a bleaching accelerator
and its precursor (BA) to be split-off from Cp, while controlling time. This group
may contain a group capable of controlling the rate of a reaction between Cp and an
oxidized product of a color developing agent, the rate of diffusion of -TIME-BA split-off
from Cp, and the rate of splitting off of BA.
[0129] The representative examples of a timing group are the following known timing groups.
is a portion to be bounded to an active position of Cp; and (*)(*) is a portion to
which -S-R
1-R
2 or

is bound.
(1) A group which causes a cleavage reaction by using an electron transfer reaction
along with a conjugated system.
[0130] Examples of such a group include those described in Japanese Provisional Patent Publications
No. 114,946/1981, No. 154,234/1982, No. 188,035/1982, No. 98,728/1983, No. 160,954/1983,
No. 162,949/1983, No. 209,736/1983, No. 209,737/1983, No. 209,738/1983, No. 209,739/1983,
No. 209,740/1983, No. 86,361/1987 and No. 87,958/1987.
[0131] Of these, groups represented by the following formulae (TIME-I) and (TIME-II) are
preferred.

wherein B is a group of atoms necessary for the formation of a benzene ring or a naphthalene
ring; Y is -0-, -S- or

and R12, R
13 and R
14 each are a hydrogen atom, an alkyl group or an aryl group. The above-described

group is substituted at the ortho-or para-position relative to Y.

wherein Y, R12 and R13 are as described above; R15 is a hydrogen atom, an alkyl group,
an aryl group, an acyl group, a sulfon group, an alkoxycarbonyl group or a heterocyclic
group; and R16 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
an alkoxy group, an amino group, an acylamino group, a sulfonamido group, a carboxy
group, an alkoxycarbonyl group, a carbamoyl group or a cyano group.
(2) A group which causes a cleavage reaction by using an intramolecular nucleophilic
substitution reaction.
[0132] Examples of such a group include those described in U.S. Patent No. 4,248,962 and
Japanese Provisional Patent Publication No. 56,837/1982. Of these, preferred are those
represented by the formulae (TIME-III), (TIME-IV) and (TIME-V).

wherein Z
1 is (*)-O-, (
*)-O-CO- ,

(*)-S-,

(
*)-OCOO- , (
*)-OCO-S- or

and Z
2 is
*)-0-CH
2- , (*)-O-CO-, (*)-S- ,

or wherein R
19 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R
17 is a hydrogen atom, an alkyl group or an aryl group; and R
18 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, -0-R
20 , -S-R
20, -OCO-R
20, -OSO
2R
20,

-N-CO-R
21 , -N-S0
2-R
21 , -COOR
20 ,

a cyano group, a halogen atom or a nitro group. R
20 and R
21 may be either identical or different and each are the same group as that represented
by R
19; p is an integer of 1 to 4, q is 0, 1 or 2; r is an integer of 1 to 4; t is an integer
of 1 to 3; when r or t is 2 or more, R
18 may be either the same or different; and when r or t is 2 or more, R
18s may be combined each other to form a ring.
(3) A group which uses a cleavage reaction of hemiacetal
[0133] Examples of such a group include those described in U.S. Patent No. 4,146,396 and
Japanese Provisional Patent Publications No. 249,148/1985 and No. 249,149/1985.
[0134] Of these, groups represented by the following formula (TIME-VI) are preferred.

wherein Z3 represents (
*)-0- , (
*)-OCO-O- ,

(
*)-OCO-S- , (*)-OCH
2-O- or (
*)-OCH
2-S- ; R
17, R
18 and R
19 each have the same meaning as that mentioned in the formulae (TIME-III), (TIME-IV)
and (TIME-V).
(4) A group represented by the following formula (TIME-VII) and described in German
Patent (OLS) No. 2,626,315 and U.S. Patent No. 4,546,073.
[0135]

wherein Z
4 represents (*)-O-, (
*)-S- or

Zs represents an oxygen atom, a sulfur atom or = N-R
22; and R
22 represents a hydrogen atom or a substituent.
[0136] The aliphatic group represented by R
1 of the formula (BAR-II) and (BAR-III) may be a saturated or unsaturated, straight-chain,
branched-chain or cyclic aliphatic group having a carbon number of 1 to 8. This group
may be either substituted or unsubstituted.
[0137] The aromatic group represented by R
1 may preferably be an aromatic group having a carbon number of 6 to 10, more preferably
a substituted or unsubstituted phenylene group.
[0138] The saturated heterocyclic group represented by R
1 may be a 3- to 8-membered, preferably a 4- to 6- membered saturated heterocyclic
group having a carbon number of 1 to 7, preferably 1 to 5, and containing at least
one selected from an oxygen atom, a nitrogen atom and a sulfur atom.
[0139] The 5- or 6-membered aromatic nitrogen-containing heterocyclic group represented
by R
1 may preferably be represented by the following formulae (H-I) and (H-II).

wherein a, b, c, e, f, g, h and i each are a nitrogen atom or a methyn group; d is
an oxygen atom, a sulfur atom or an imino group; (
*) is a position to which Cp-(TIME)
m-S-

is bound; and (
*)(
*) is a position to which R
3-S- or R
2 is bound. In the above formula, at least one of e, f, g, i and h is a nitrogen atom.
R
1 may more preferably be an aliphatic group or

wherein L represents a divalent aliphatic group or a phenylene group having a carbon
number of 1 to 8.
[0140] The preferred examples of R, include -CH
2- , -CH
2CH
2- , -CH
2CH
2CH
2- ,

-CH
2CH
2CH
2CH
2- ,

-CH
2CH
20CH
2CH
2- ,

[0141] The preferred examples of an water-solubilizing substituent or its precursor represented
by R
2 include -COOH , -COONa , -COOCH
3 , -COOC
2H
5, -NHS0
2CH
3 , -NHCOOCH
3 , -NHCOOC
2H
s , -S0
3H , -S0
3K , -OH,

-SO
2NH
2, -NR
10R
11, wherein R
10 ad R
11 each are a hydrogen atom or an alkyl group having a carbon number of 1 to 4, -CONH
2 , -COCH
3 , -NHCOCH
3 , -CH
2CH
2COOH , -CH
2CH
2NH
2 , -SCH
2COOH ,

-CH
2COOH , -SCH
2CONH
2 , -SCH
2COCH
3 and -SCH
2CH
2COOH; and the particularly preferred examples of the bleaching accelerator or precursor
thereof represented by -S-R
1-R
2 include -SCH
2CH
2COOH , -SCH
2CH
2CH
2COOH ,

and

[0142] The preferred examples of R
3 include H , -CN , -COH , -COCH
3 , -COCH
20CH
3 , -COCF
3 , -CSCH
3 , -CON(CH
3)
2, -CON(C
2Hs)
2 , -CSN(CH
3)
2,

-SCH3 , -SCH2CH2N(CH3)2 , -SCH2CH20H , -SCH2CH2COOH , -NHCH
3, -NHCH
2CH
2COOH and

[0143] The particularly preferred examples of a bleaching accelerator or its precursor represented
by

include -OCOCH
2CH
2SH , -OCH
2CH
2SH ,

-OCOCH
2CH
2SCOCH
3 , -OCOCH
2CH
2SCSCH
3 , -OCOCH
2CH
2SSCH
2CH
2COOH -OCH
2CH
2SSCH
2CH
20H and -OCOCH
2CH
2SCN .
[0145] There is no restriction as to the kind of layers to which a BAR compound is added.
The BAR compound may be added to not only a silver halide light-sensitive emulsion
layer but also an anti-halation layer, an intermediate layer, a yellow colloidal silver
filter layer and a protective layer. However, the BAR compound may preferably be added
to a silver halide photosensitive emulsion layer.
[0146] The BAR compound can be added to a hydrophilic colloidal layer of a light-sensitive
material for color photography by the following method: The BAR compound is dissolved,
singly or in combination with another kinds of a BAR compound, to a mixture of a high-boiling
point solvent such as dibutyl phthalate, tricresyl phosphate and dinonyl phenol and
a low-boiling point solvent such as butyl acetate and propionic acid. The resultant
is mixed with an aqueous solution of gelatin containing a surface active agent, and
subsequently emulsified by means of a high-speed revolution mixer, a colloid mill
or an ultrasonic dispersing machine. The resultant may be directly added to a coating
liquid. Alternatively, it may be coagulated, cut into small pieces, washed with water
and then added to a coating liquid.
[0147] The amount of the BAR compound to be added may preferably be 0.0005 mole to 5.0 mole,
more preferably 0.005 mole to 1.0 mole, per mole of a silver halide.
[0148] The BAR compound may be employed either singly or in combination.
[0149] In the light-sensitive material, auxiliary layers such as filter layer, antihalation
layer and anti-irradiation layer can be provided. In these layers and/or emulsion
layers, a dye which flows out from the light-sensitive material or bleached during
developing processing may be also contained.
[0150] In the light-sensitive material, formalin scavenger, fluorescent brightener, matte
agent, lubricant, image stabilizer, surfactant, anti-color foggant, developing accelerator,
developing retarder or bleaching accelerator can be added.
[0151] For the support, papers laminated with polyethylene, etc., polyethylene terephthalate
film, baryta film, cellulose triacetate, etc. can be used.
[0152] The light-sensitive material of the present invention is particularly useful as the
negative-type light-sensitive material.
[0153] For obtaining a dye image by use of the light-sensitive material of the present invention,
after exposure, color photographic processings generally known in the art can be performed.
[0154] Also, a light-sensitive photographic material-containing package unit in which a
light-sensitive silver halide color photographic material is built-in and photographing
function is provided, which is produced by the present applicant or assignee in the
trade name of "Torezo-Kun", has spread in recent years.
[0155] These package units have been sold mainly at a sightseeing spot so that their storage
circumstance is markedly wrong whereby improvement in storage stability has been more
demanded.
[0156] The package units in which a light-sensitive silver halide color photographic material
of the present invention is built-in and photographing function is provided are excellent
in stability to long period of preservation even under bad outer conditions, and also
excellent in gradation, color reproducibility and tone reproducibility.
[0157] The above-mentioned light-sensitive photographic package unit to which photographing
function is provided comprises, for example, a first receiving room put a wound and
unphotographed light-sensitive photographic material away therein, a second receiving
room (e.g. patrone room) which receives a photographed light-sensitive photographic
material and those having a function necessary for photographing such as a lens and
a shutter.
[0158] The unphotographed light-sensitive photographic material is directly or indirectly
(for example, in the state of once received in patrone or cartridge) received in the
first receiving room.
[0159] The size of the light-sensitive photographic material may be any size such as 110
size, 135 size, 126 size, and so-called disc type size.
EXAMPLES
[0160] The present invention is described in more detail by referring to Examples, but the
present invention is not limited to these Examples at all. Prior to Examples, the
silver halide emulsions to be used in Examples were prepared.
Preparation of monodispersed emulsion
[0161] Into a reaction kettle in which an aqueous gelatin solution had been thrown, while
controlling the pAg and the pH in the reaction kettle and also controlling the addition
time, were added at the same time an aqueous silver nitrate solution, an aqueous potassium
iodide solution and an aqueous potassium bromide solution, and then precipitation
and desalting were practiced by use of a pH coagulatable gelatin, followed by addition
of gelatin to prepare a seed emulsion. The emulsion obtained is called NE-1.
[0162] Also, a seed emulsion was prepared in the same manner as described above except for
adding K
3RhCI
6 in the reaction kettle (NE-2). The emulsions and their contents are shown in Table
1.

[0163] In a reaction kettel in which the above seed emulsion and an aqueous gelatin had
been added, while controlling the pAg and the pH in the reaction kettle, were added
an aqueous ammoniacal silver nitrate solution, an aqueous potassium iodide solution
and an aqueous potassium bromide solution in proportion to the surface area during
the grain growth, followed by subsequent addition in place of the aqueous potassium
bromide solution at an adequate grain size. After precipitation and desalting were
practiced similarly as in the case of the seed emulsion, gelatin was added to effect
re-dispersion to give an emulsion having pAg 7.8 and pH 6.0. Thus, silver iodobromide
emulsions EM-1 to EM-3 with high iodine contents internally of grains were prepared.
[0164] The emulsions and their contents are shown in Table 2.

Example 1
Preparation of Sample No. 101 (Comparative)
[0165] On a cellulose acetate support applied with subbing treatment was prepared a multi-layer
color light-sensitive material with an overlayed constitution comprising the composition
shown below.
[0166] The amounts coated are indicated in the amount represented in g/m
2 unit calculated on silver for silver halide and colloidal silver, the amount represented
in g/m
2 unit for the additives and gelatin, and further in moles per mole of silver halide
within the same layer for the sensitizing dye, coupler and DIR compound. The emulsion
contained in each color sensitive emulsion layer was applied with optimum sensitization
with sodium thiosulfate and chloroauric acid.

Sensitizing dye I
[0168]

Sensitizing dye II
[0169]

Sensitizing dye III
[0170]

Sensitizing dye IV
[0171]

Sensitizing dye V
[0172]

[0173] In the following description, the respective layers with the above compositions are
referred to under the abbreviations indicated such as HC, IL-1, R-1, R-2, IL-2, G-1,
G-2, YC, B-1, B-2, Pro-1 and Pro-2.
[0174] Next, Samples No. 102 to No. 108 were prepared.
[0175] Samples No. 102 and No. 103 were prepared in the same manner as Sample No. 101 except
for changing the amount of the coupler Y-1 contained in B-2 of Sample No. 101 to 0.06
mole/mole AgX, and adding 0.02 mole/mole AgX of the DSR compound indicated in Table
3 in place of D-42.
[0176] Sample No. 104 was prepared in the same manner as Sample No. 101 except for omitting
B-2 in Sample Mo. 101, changing the emulsion contained in B-1 to a mixture of equal
moles of Em-1 and Em-2, increasing the amounts used of the emulsion, the gelatin and
TCP contained in B-1 by 15 %, and further adding 0.011 mole/mole AgX of the DIR compound
D-42 (the amounts of the sensitizing dye and the coupler of B-1 per mole of silver
halide are the same as in Sample No. 101).
[0177] Samples No. 105 and No. 106 were prepared in the same manner as Sample No. 104 except
for changing the coupler Y-1 contained in B-1 of Sample No. 104 to 0.22 mole/mole
AgX, and adding 0.07 mold/mole AgX of the DSR compound indicated in Table 3 in place
of D-42.
[0178] Samples No. 107 and No. 108 were prepared in the same manner as Sample No. 105 except
for adding 0.011 mole/mole AgX of the DIR compound indicated in Table 3 in B-1 of
Sample No. 105.
[0179] For the samples thus obtained, sensitivity and gradation stability to processing
fluctuations were evaluated. Each sample was subjected to wedge exposure in conventional
manner and processed with the following processing steps as the standard.
[0180] The results are shown in Table 3.
[0181] Sensitivity is shown in terms of the reciprocal number of the exposure dose necessary
for imparting a density of the minimum density + 0.1 as a relative value to that of
Sample No. 101 which is made 100, and the results of the green-sensitive layers are
shown in Table 3.
[0182] Gradation stability to processing fluctuations was evaluated when developed at the
color developer with a pH of 9.8 with the gradation when processed according to the
processing steps shown below as the standard.
[0183] The evaluation method of gradation stability is to be described by use of drawings.
Fig. 1 shows the character istic curve which is the standard (broken line) and the
characteristic curve (solid line) to be evaluated. Fig. 2 shows the point gamma values
of the respective exposure points from the exposure point which gives a density of
the minimum density + 1 in Fig. 1 to the exposure point of Alog H = +3.0 (Δlog H =
0.15 between the respective exposure points).
[0184] Here from Fig. 2, the absolute values Δγ of the difference of the point gamma value
at the respective exposure points of the characteristic curve which is the standard
and the characteristic curve to be evaluated are determined. Then, the gradation stability
is represented by the mean value of Δ\γ multiplied by 1000 (0.-y) and value of E of
the standard deviation a of Δγ multiplied by 1000. Thus, the difference in point gamma
between the both characteristics is greater as the value of Δγ is greater, and the
gradation change is not uniform indicating poor gradation stability as the value of
E is greater.

[0186] As is apparent from Table 3, the samples of the present invention were found to have
high sensitivity and also good gradation stability to processing fluctuations. Also,
when graininess by printing was evaluated, the samples by using in combination the
DSR compound and the DIR compound in a single layer (No. 107 and No. 108) were found
to have better graininess.
[0187] Also, in the respective samples by use of DSR-15, DSR-32 and DSR-38 in place of DSR-39
of B-1 in Sample No. 106, the effects of the present invention could be recognized.
[0188] Further, Sample No. 102 and Sample No. 105 in which a blue-sensitive emulsion layer
is a single layer constitution were cut to 35 mm size with a length which corresponds
to 24 sheets photographing. These samples were wound so as to become the color sensitivity
layers inside, contained directly in a film container of a package unit attached with
a lens as disclsed in Fig. 1 of U.S. Patent No. 4,827,298, and an outer end thereof
was provided to patrone for 35 mm size and contained in a patrone roome to obtain
a light-sensitive photographic material package unit provided to photographing function
(fixed focus F : 8, shutter speed 1/100 sec).
[0189] One unit contained each light-sensitive photographic material was stored in a refregerator
(5 ° C) (standard) and the other was stored in the conditions of 37 ° C and a relative
humidity of 80 % for each one month.
[0190] An object of continuous wedge was photographed and then processed with the processing
steps as mentioned above.
[0191] The results are shown in the following table.

[0192] As seen from the above table, Sample No. 105 of this invention shows small change
in gradation from high light portion to shadow portion of the characteristic curve
even when contained in a package unit and stored with a lapse of time and shows good
tone reproducibility. Further, exposure latitude is 3 or higher in Alog H and thus
it can be understood that it has wide exposure latitude.
Example 2
[0193] For Sample No. 201, the same one as Sample No. 104 was used.
[0194] Sample No. 202 was prepared in the same manner as Sample No. 201 except for adding
D-29 in place of the DIR compound D-42 contained in B-1 of Sample No. 201.
[0195] For Sample No. 203, the same one as Sample No. 105 was used.
[0196] Samples No. 204 and 205 were prepared in the same manner as Sample No. 203 except
for adding the DSR compound shown in Table 4 in place of DSR-2 contained in B-1 of
Sample No. 203.
[0197] Sample No. 206 was prepared in the same manner as Sample No. 201 except for omitting
D-42 from B-1 of Sample No. 201, and adding 0.07 mole/mole AgX of DSR-30.
[0198] Sample No. 207 and No. 208 were prepared in the same manner as Sample No. 204 except
for adding 0.03 mole/mole AgX of DIR compound in B-1 of Sample No. 204 as shown in
Table 4.
[0199] Sample No. 209 was prepared in the same manner as Sample No. 207 except for omitting
G-2, changing the emulsions contained in G-1 to a mixture of equal moles of EM-1 and
EM-2, further increasing the amounts used of the emulsion, gelatin and TCP contained
in G-1 by 30 %, also omitting R-2, changing the emulsion contained in R-1 to a mixture
of equal moles of EM-1 and EM-2, and further increasing the amounts used of the emulsion,
gelatin and DOP contained in R-1 by 25 % (the amounts of the sensitizing dye, coupler
and DIR compound per mole of silver halide in G-1 and R-1 are the same as in Sample
No. 207).
[0200] Sample No. 210 was prepared in the same manner as Sample No. 201 except for adding
BAR compound as shown in Table 4 in the layer of R-1 of Sample No. 201, Samples No.
211 and No. 212 were prepared in the same manner as Sample No. 203 except for adding
BAR compound as shown in Table 4 in the layer of R-1 of Sample No. 203, and Samples
No. 213 and No. 214 were prepared in the same manner as Samples No. 207 and No. 209
except for adding BAR compound as shown in Table 4 in the layer of R-1 of Samples
No. 207 and No. 209, respectively.
[0201] The samples thus prepared and their contents are shown in Table 4.
[0202] For the samples obtained as described above, sensitivity of the blue-sensitive layer,
gradation stability to external conditions, gradation stability to processing fluctuations
and bleachability were examined.
[0203] The respective samples were subjected to the same processing as in Example 1.
[0204] The results are shown in Table 4.
[0205] Sensitivity is shown in the reciprocal number of the exposure dose necessary to imparting
the density of the minimum density of the blue-sensitive layer + 0.1 as relative value
to that of Sample No. 201 which is made as 100.
[0206] For gradation stability to external conditions, stability of gradation (to be evaluated)
when stored under compulsory deterioration conditions of 40 C, relative humidity of
80 % for 7 days, relative to the gradation (the standard) when stored in a refrigerator
(5 C), was evaluated.
[0207] Bleachability was shown in the bleachability of Sample No. 201 as standard (100).
For measurement, fluorescent X ray analyzer is used and the results mean that a larger
value shows excellent in improved effect of bleachability.

[0208] As is apparent from Table 4, it can be understood that the samples of the present
invention have high sensitivity as well as good gradation stability to external conditions
and processing fluctuations.
[0209] Further, when all the color sensitive emulsion layers are made single layers, it
has been found that the improvement effect of gradation stability becomes greater,
thus providing a preferred embodiment of the present invention.
[0210] Moreover, in the samples (Samples No. 211 to No. 214) wherein the DSR compound and
the BAR compound are combinedly used in the single layer constitution, it can be understood
that gradation stability to processing fluctuations and bleachability are excellent.
[0211] Also, when graininess by print was evaluated, the samples by using in combination
the DSR compound and the DIR compound in a single layer (No. 207, No. 208 and No.
209) were found to have better graininess.
[0212] Furthermore, the samples of this invention show small change in gradation from high
light portion to shadow portion of the characteristic curve and show good tone reproducibility.
Further, exposure latitude is 3 or higher in Alog H and thus it can be understood
that they have wide exposure latitude.
[0213] In this Example, an emulsion with a fluctuation coefficient of 19 to 20 % was used,
but also the effects of the present invention could be recognized when an emulsion
with a fluctuation coefficient of 30 % was used.
Example 3
[0214] For Sample No. 301, the same one as Sample No. 101 was used.
[0215] Sample No. 302 was prepared in the same manner as Sample No. 101 except for changing
the couplers and the DIR compounds contained in the respective light-sensitive emulsion
layers to those indicated in Table 5.

[0216] For Sample No. 303, the same one as Sample No. 106 was used.
[0217] Sample No. 304 was prepared in the same manner as Sample No. 303 except for using
EM-3 in place of the emulsion contained in B-1 of Sample No. 303.
[0218] Sample No 305 was prepared in the same manner as Sample No. 302 except for omitting
B-2, changing the emulsion contained in B-1 to a mixture of equal moles of EM-1 and
EM-2, further increasing the amounts used of the emulsion, gelatin and TCP contained
in B-1 by 15 %, further changing 1/4 of mole numbers of the coupler (Y-1) contained
in B-1 to DSR-39, also omitting G-2, changing the emulsion contained in G-1 to a mixture
of equal moles of EM-1 and EM-2, further increasing the amounts used of the emulsion,
gelatin and TCP contained in G-1 by 30 %, further omitting R-2, changing the emulsion
contained in R-1 to a mixture of equal moles of EM-1 and EM-2, and further increasing
the amounts used of the emulsion, gelatin and DOP contained in R-1 by 25 % (the amounts
of the sensitizing dye, coupler and DIR compound per mole of silver halide in B-1,
G-1 and R-1 are the same as in Sample No. 302).
[0219] Sample No. 306 was prepared in the same manner as in Sample No. 305 except for using
EM-3 in place of the emulsion contained in Sample No. 305.
[0220] Sample No. 307 was prepared in the same manner as in Example No. 306 except for changing
DSR-19 contained in R-1 of Sample No. 306 to DSR-27.
[0221] Sample No. 308 was prepared in the same manner as in Example 306 except for adding
the DIR compounds indicated in Table 6 in the respective light-sensitive emulsion
layers of Sample No. 306.

[0222] The samples thus prepared and their contents are shown in Table 7.

[0223] For the samples obtained as described above, gradation stability of the blue-sensitive
layer was examined.
[0224] The respective samples were processed as described in Example 1.
[0225] The results are shown in Table 8.

[0226] As is apparent from Table 8, it can be understood that the samples of the present
have good gradation stability.
[0227] When comparison is made among the samples of the present invention, those having
all the color sensitive emulsion layers respectively of single layers (Samples No.
305 to No. 308) are preferred with greater improvement effect for gradation stability.
[0228] Also, in the respective samples by use of D-2 or D-4 in place of D-42 in B-1 of Sample
No. 308, also D-6 or D-10 in place of D-26 in G-1, and further D-17, D-19 or D-21
in place of D-42 in R-1, the effects of the present invention could be recognized.
[0229] It has also been found that the samples No. 304 and No. 306 to No. 308 are preferred
embodiments of the present invention, because gradation stability to processing fluctuation
is particularly improved due to narrow grain size distribution of the silver halide
grains of the respective light-sensitive layers because of containing emulsions having
Rh doped internally of the grains.
[0230] Also, the samples containing EM-3 are preferred with respect to production efficiency
as compared with other samples, because physical ripening and chemical ripening can
be practiced at one time in preparation of the emulsion.
[0231] Also, in the respective samples by use of seed emulsions prepared by addition of
RuC1
3, OsC1
3 or Pb-(N0
3)
2 in place of K
3RhCl
6 in place of NE-2, the effects of the present invention could be recognized.
[0232] When graininess by print was evaluated, the sample using in combination of the DSR
compound and the DIR compound in a single layer (No. 308) was found to have better
graininess.
[0233] The light-sensitive photographic material obtained by the present invention is not
only high in sensitivity, but also excellent in storability before photographing,
and also excellent in stability to fluctuations in processing conditions.