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Description  |
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to photographic sensitive materials and
particularly to photographic sensitive materials having an emulsion layer
containing a compound which releases an organic development inhibitor out
of the layer by development wherein the photographic sensitive materials
comprise a colloid layer which absorbs a part or all of the released
organic development inhibitor.
2. Description of the Prior Art
Many kinds of compounds which release an organic development inhibitor are
already known, and they are added to photographic emulsion layers for
various purposes. Such compounds are hydroquinone derivatives having a
substituted monothio group as described in U.S. Pat. Nos. 3,379,529 and
3,639,417 and U.S. patent application Ser. No. 494,955, filed on Aug. 5,
1974. These compounds are used, for example, for the purpose of improving
the graininess and sharpness of photographic images. They are also used
for the purpose of improving color reproduction of multilayer color
photographic materials as described in U.S. patent application Ser. No.
461,087, filed Apr. 15, 1974. Further, they are used for image reversal in
a dye diffusion transfer photographic process as described in U.S. Pat.
No. 3,364,022. Furthermore, they are used for the purpose of eliminating
images in adjacent layers in photographic sensitive materials for
double-image photographing as described in U.S. Pat. No. 3,620,746.
Moreover, they are used as a silver image forming material as described in
U.S. Pat. Nos. 3,705,801 and 3,737,312.
Other examples of such compounds include couplers having a triazole or
diazole group which is substituted at a coupling position as described in
U.S. patent application Ser. No. 454,525, filed on Mar. 25, 1974. These
couplers are used for color correction in multilayer color photosensitive
materials.
Additional examples of such compounds include couplers having a monothio
group or selenazole group which is substituted at a coupling position as
described in U.S. Pat. Nos. 3,701,783, 3,733,201 and 3,632,345. Such
compounds are used for the purpose of improving the graininess and
sharpness of photographic images as described in U.S. Pat. No. 3,227,554.
They are also used for the purpose of preventing fogging as described in
U.S. Pat. No. 3,703,375. Further, they are used for image reversal in a
dye diffusion transfer photographic process as described in U.S. Pat. Nos.
3,227,551 and 3,736,136. Furthermore, they are used for the purpose of
producing color photographic sensitive materials in a stable manner as
described in U.S. Pat. No. 3,632,373. Moreover, they are used for the
purpose of eliminating images of adjacent layers in photographic sensitive
materials for double-image photographing as described in U.S. Pat. No.
3,620,746. In addition, they are used for the purpose of expanding the
tolerance of exposure of photographic sensitive materials as described in
U.S. Pat. Nos. 3,620,474 and 3,615,499.
Further examples of such compounds include organic heterocyclic compounds
having an oxo or thioxo group as described in U.S. Pat. Nos. 3,713,828 and
3,723,125, and compounds having a mercapto group or a thioether bond as
described in U.S. Pat. No. 3,536,487 and U.S. Defensive Publications Nos.
T909,022 and T909,023. These compounds are used for the purpose of
strengthening the under-cut interimage effect and improving color
reproduction in multilayer color photosensitive materials.
When the above described compounds which release an organic development
inhibitor by development are used in emulsion layers of photographic
sensitive materials, serious defects result. Namely, the organic
development inhibitor released by development not only diffuses out of the
emulsion layer and causes the inhibition of the development of other
emulsion layers in the case of a multilayer photosensitive material -- the
so-called under-cut interimage effect, but also the released inhibitor
leaches into the developer to inhibit the development in an unnecessarily
wide range. The so-called under-cut interimage effect can be
advantageously utilized for image reversal or improvement of color
reproduction of multilayer color photosensitive materials. However, its
effect and range should be limited to a definite emulsion layer and it is
necessary to prevent undesired influences upon other layers. Further, in
using these compounds for the purpose of improving color reproduction, it
is sometimes necessary to obtain an optimum effect by adjusting the degree
of the under-cut interimage effect. Further, the movement of the organic
development inhibitor into the developer induces the generation of
development mottle deteriorating the finished image quality. Accordingly,
it becomes necessary to prevent movement of the organic development
inhibitor into the developer from the photosensitive materials.
SUMMARY OF THE INVENTION
One object of the present invention is to improve the above described
defects appearing in photographic sensitive materials using a compound
which releases an organic development inhibitor by development.
One method of solving this problem is a method which comprises providing an
adsorbing colloid layer containing silver halide particles. However, using
this method, the desired object has not always been attained sufficiently.
Further, if the silver halide particles are used in a large amount in
order to achieve a sufficient effect, a deterioration of sensitivity
results due to the decrease in light transmittance or a retardation of
development results due to an interruption of the diffusion of the
developing agent. Further, the surface of the photosensitive material is
damaged by the formation of silver scum by interaction with the developer.
A further object of the present invention is to provide a method for
absorbing the released organic development inhibitor while removing the
defects caused by silver halide particles used for adsorbing the released
organic inhibitor.
These and other object of the present invention will be clear from the
following descriptions and examples.
These objects of the invention have been attained with a photographic
sensitive material comprising a support having thereon at least one
photosensitive silver halide emulsion layer, at least one of the silver
halide emulsion layers containing a compound which releases an organic
development inhibitor on development, and having a colloid layer
containing a basic synthetic polymer having therein a repeating unit
represented by the following formula (I)
##STR1##
wherein R.sub.1 represents a hydrogen atom or an alkyl group having 1 to 6
carbon atoms; R.sub.2 represents a hydrogen atom, an alkyl group having 1
to 6 carbon atoms or an aryl group; m is 1 or 2; n is 1 or 2; q is 1 or 2;
A.sub.1 represents a group which contains a nitrogen atom forming a
secondary amino group, tertiary amino group or quaternary ammonium group;
and A.sub.1 and R.sub.2 can combine to form a ring; or the following
formula (II)
##STR2##
wherein A.sub.2 represents a hydrogen atom or a substituted or
unsubstituted alkyl group; A.sub.3 represents a hydrogen atom or
substituted or unsubstituted alkyl group; X represents an anion; and d is
1 or 2.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1, 2 and 3 each shows an embodiment of the layer structure of samples
used in the Examples.
FIGS. 4 and 5 each shows characteristic curves obtained in the Example.
DETAILED DESCRIPTION OF THE INVENTION
According to one preferred embodiment of the present invention, the
photographic sensitive materials comprise a support having silver halide
emulsion layer containing a compound which releases an organic inhibitor
by development and a colloid layer (ADL) containing a basic synthetic
polymer containing the repeating unit represented by the above formula (I)
or (II) on this silver halide emulsion layer or between the support and
this silver halide emulsion layer.
As described above the basic synthetic polymer which can be used includes
polymers having a recurring unit represented by the following formula (I)
##STR3##
wherein R.sub.1 represents a hydrogen atom or an alkyl group having 1 to 6
carbon atoms such as methyl, ethyl, etc.; R.sub.2 represents a hydrogen
atom, an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl,
etc. or an aryl group such as phenyl, tolyl, etc.; m represents 1 or 2;
and A.sub.1 represents a group having a nitrogen atom which forms a
secondary amino group, a tertiary amino group or a quaternary ammonium
group; and A.sub.1 and R.sub.2 can combine to form a ring; or the formula
(II)
##STR4##
wherein A.sub.2 represents a hydrogen atom or a substituted or
unsubstituted alkyl group having 1 to 6 carbon atoms) such as methyl,
ethyl, etc.); X represents a salt-forming anion; and d represents 1 or 2.
Preferred groups represented by A.sub.1 in the formula (I) are groups
represented by the following formula (Ia)
##STR5##
wherein Q.sub.1 represents a carbon atom or a nitrogen atom; and Q.sub.2
represents the non-metal atoms to form, together with Q.sub.1, a
5-membered or a 6-membered heterocyclic ring containing a nitrogen atom
which forms a secondary amino group, a tertiary amino group or a
quaternary ammonium group; or the formula (Ib)
-- (Q.sub.3).sub.l.sub.-1 --Q.sub.4 (Ib)
wherein Q.sub.3 represents --O--R.sub.3 --, --OCO--R.sub.3 --,
--COO--R.sub.3 --, --CO--R.sub.3 --,
##STR6##
or an arylene group (such as phenylene, etc.); Q.sub.4 represents
##STR7##
l represents 1 or 2; R.sub.3 represents an alkylene group (e.g., having 1
to 6 carbon atoms) or an arylene group (such as phenylene, etc.); R.sub.4
represents a hydrogen atom, an alkyl group (e.g., having 1 to 6 carbon
atoms, such as methyl, ethyl, etc.), an aryl group (such as phenyl, etc.),
or an alkylene group (e.g., having 1 to 6 carbon atoms) connected to
Q.sub.4 ; R.sub.4 represents an alkyl group (e.g., having 1 to 6 carbon
atoms such as methyl, ethyl, butyl, etc.), an aryl group (e.g., such as
phenyl) or an aralkyl group (e.g., such as benzyl), R.sub.6 represents a
hydrogen atom, an alkyl group (e.g., having 1 to 6 carbon atoms such as
methyl, ethyl, butyl, etc.), an aryl group (e.g., such as phenyl) or an
aralkyl group (e.g., such as benzyl); and R.sub.6 and R.sub.4 can combine
to form a ring; R.sub.7 represents a hydrogen atom, an alkyl group (e.g.,
having 1 to 6 carbon atoms such as methyl, ethyl, butyl, etc.), an aryl
group (e.g., such as phenyl) or an aralkyl group (e.g., such as benzyl);
R.sub.8 represents a hydrogen atom, an alkyl group, (e.g., having 1 to 6
carbon atoms such as methyl, ethyl, butyl, etc.), an aryl group (e.g.,
such as phenyl), an aralkyl group (e.g., such as benzyl), a carboxyalkyl
group (e.g., having 1 to 6 carbon atoms) or a sulfoalkyl group (e.g.,
having 1 to 6 carbon atoms); R.sub.9 represents an alkyl group (e.g.,
having 1 to 6 carbon atoms); R.sub.9 represents an alkyl group (e.g.,
having 1 to 6 carbon atoms such as methyl, ethyl, butyl, etc.); X
represents a salt-forming anion; and p represents 1 or 2.
When A.sub.1 and R.sub.2 combine with Q.sub.3 or Q.sub.4 in the formula
(Ib) or when R.sub.4 and R.sub.6 combine in the formula (Ib), such group
can be a group represented by the following general formulas
##STR8##
wherein R.sub.3, R.sub.5, R.sub.7, Q.sub.4 and X each has the same meaning
as defined above.
The non-metal atoms represented by Q.sub.2 in the formula (Ia) can be
selected from a carbon atom, an oxygen atom, a sulfur atom, a selenium
atom and a nitrogen atom. Further, the moiety represented by Q.sub.2 can
be substituted with a substituted or unsubstituted alkyl group (e.g.,
having 1 to 6 carbon atoms), a substituted or unsubstituted aryl group
(e.g., phenyl) or a fused ring. Preferred examples of heterocyclic rings
are pyridine, imidazole, pyrozine, pyrrole and the like.
A polymer containing a recurring unit represented by the following formula
(III)
##STR9##
wherein A.sub.4, A.sub.5, A.sub.6 and A.sub.7 each represents a lower
alkyl group (e.g., having 1 to 6 carbon atoms) or A.sub.4 and A.sub.5
and/or A.sub.6 and A.sub.7 can combine to form a nitrogen containing
heterocyclic ring (s); Y.sub.1 and Y.sub.2 each represents an alkylene
group, a phenylene group, a xylylene group or a cyclohexylene group, and
the alkylene group can contain a double bond, a triple bond, --SO.sub.2 --
or --O-- in the chain thereof; Y.sub.3 and Y.sub.4 each represents --COO--
or
##STR10##
Y.sub.5 represents a hydrogen atom or an alkyl group (e.g., having 1 to 6
carbon atoms); X represents a salt-forming anion; and f, h and k each
represents 1 or 2.
The anion represented by X in the above-described formulas (I), (II) and
(III) includes a mono-valent anion which can form a conventional
quaternary salt, such as a halogen ion such as a chlorine ion, a
perchlorate ion, an acetate ion, a sulfonate ion such as a p-toluene
sulfonate ion, a monoalkylsulfate ion, dialkylphosphate ion and the like.
A basic polymer of particular use is the polymer represented by the formula
(I) wherein R.sub.1 represents a hydrogen atom or a methyl group; R.sub.2
represents a hydrogen atom; m, n and q each represents 1; A.sub.1
represents a pyridine or imidazole structure or --COO--R.sub.3 --Q.sub.4,
--CO--R.sub.3 --Q.sub.4 or --CONH--R.sub.3 --Q.sub.4 ; wherein R.sub.3 and
Q.sub.4 each has the same meaning as defined above.
Examples of basic polymers used in the present invention and processes for
their synthesis are described in, for example, British Pat. Nos. 786,592,
906,083, 1,034,044, 1,151,877, 1,161,131, 1,162,214 and 1,261,925, U.S.
Pat. Nos. 3,282,699, 3,408,193 and 3,445,231, German Patent Publications
(OLS) Nos. 1,803,634, 1,914,361 and 1,914,362, and Japanese Patent
Publication No. 10254/1968.
Typical examples of the repeating unit which comprises the basic synthetic
polymers used in the present invention are described in the following
##STR11##
It is preferred that about 20 mol% or more of the repeating units in the
basic polymers used in the present invention be composed of the above
described repeating unit containing a nitrogen atom which forms a
secondary amino, tertiary amino or quaternary ammonium group.
Particularly, those compounds containing above 50 mol% of such repeating
unit are preferred. Examples of monomer units which can form polymers
together with these basic monomer units include methyl acrylate, ethyl
acrylate, hydroxyethyl acrylate, butyl acrylate, methyl methacrylate,
ethyl methacrylate, hydroxyethyl methacrylate, acrylamide, methacrylamide,
N-methyl acrylamide, methylol acrylamide, N,N-diethyl acrylamide,
N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylcaprolactam,
N-vinyl-N-methylacetamide, acrylonitrile, vinyl acetate, vinyl propionate,
styrene, methylstyrene, methyl vinyl ketone, maleic acid anhydride, methyl
vinyl ether, butadiene, isoprene and chlorprene, etc.
In the ADL of the present invention, two or more basic synthetic polymers
represented by the formula (I) or (II) can be used together in an amount
of about 0.001 to about 10 g/m.sup.2, preferably 0.01 to 1 g/m.sup.2 of
the support. Further, it is possible to further improve the function of
adsorbing the organic development inhibitor by using the silver halide
particles as described in U.S. patent application Ser. No. 484,742, filed
July 1, 1974, colloidal silver, colloidal gold or colloidal silica
together with the polymers. Such a colloidal material can be used in an
amount of about 0.001 to about 20 g/m.sup.2, preferably 0.01 to 5
g/m.sup.2 of the support. A suitable particle size of the colloidal
material ranges from about 0.01 to 1 .mu., preferably 0.01 to 0.5 .mu.. It
is also possible to provide the functions of antiirradition, antihalation
and a light filter, to improve safe-light stabilization, or to control
printing conditions for positive sensitive materials by using the acid
dyes described in U.S. patent application Ser. No. 501,107, filed on Aug.
27, 1974.*
*(Japanese Japanese Patent Application No. 96965/73 )
An acid dye which can be used in the present invention is a water soluble
dye containing an anionic water-solubilizing group such as a sulfo group,
a carboxylic acid group, a phosphoric acid group, a sulfuric acid group,
particularly a sulfo group. As such a dye, an oxonol dye, a
triphenylmethane dye, an anthraquinone dye, a benzoquinone dye, an azo dye
and an organometal complex dye, particularly a dye in which an anionic
water-solubilizing group is introduced into the dye skeleton which is
known as a sensitizing dye such as those described in F. M. Hamer, The
Cyanine Dyes and Related Compounds, Interscience Publishers (1964), are
useful. For example, a cyanine dye, a merocyanine dye, a complex
merocyanine dye, a hemicyanine dye and the like are illustrated. In
greater detail, the dyes described in U.S. Pat. Nos. 3,260,601; 3,282,699;
3,294,539; 3,316,091; 3,352,680; 3,379,533; 3,382,074; 3,384,487;
3,389,994; 3,406,069; 3,409,433; 3,417,084; 3,423,207; 2,440,051;
3,468,883; 3,471,293; 3,480,436; 3,485,632; 3,481,927; 3,486,897;
3,493,375; 3,497,502; 3,531,287; 3,540,887; 3,540,888; 3,563,748;
3,560,214; 3,547,640; 3,573,289; 3,576,640; 3,615,546 and 3,615,432;
Japanese Patent Pulications Nos. 18459/66; 35041/68; 13168/68; 13498/68
and 21766/68; and British Patent Nos. 1,025,567; 1,027,747; 1,030,392;
1,034,044; 1,091,366; 1,112,035; 1,167,026; 1,177,429 and 1,241,692, etc.
are useful.
Specific examples of dyes are shown below.
##STR12##
The ADL of the present invention can be advantageously used for all
photosensitive materials containing a compound which releases an organic
development inhibitor. Particularly preferred results can be obtained if
the ADL is used for multilayer color photosensitive materials containing
an interlayer color correction coupler, an interlayer color correction
hydroquinone or an organic accelertor having an under-cut interimage
effect.
The interlayer color correction couplers (ICC-coupler) used in the present
invention designate those couplers as defined in U.S. patent application
Ser. No. 467,539, filed May 6, 1974, that is, couplers which provide an
interlayer effect and, consequently, have the function of color
correction. Preferred couplers are those described in U.S. patent
application Ser. No. 454,525, filed Mar. 25, 1974, which include the
so-called DIR-couplers as a portion thereof. Particularly, they are
couplers represented by the formula (IV):
cp -- Z (IV)
where, Cp represents a coupler residue which reacts with the oxidation
products of primary aromatic amine color developing agents by a coupling
reaction, and Z represents an organic residue which can be released by the
coupling reaction with the oxidation products of primary aromatic amine
color developing agents and has a property of inhibiting the development
by diffusion after its release. Cp can be chosen from, for example, the
residues of 4-equivalent couplers used for color photosensitive materials.
Examples of such couplers include 5-pyrazolone couplers,
cyanoacetylcoumarone couplers, imidazolone couplers, acylacetanilide
couplers, pivaloylacetanilide couplers, aroylacetamide couplers, naphthol
couplers and phenol couplers, etc. Z represents a heterocyclic residue
having a 1-triazole ring or 1-diazole ring as described in U.S. patent
application Ser. No. 454,525, filed on Mar. 25, 1974, a 2-benzotriazole
residue as described in U.S. Pat. No. 3,617,291, an aryl monothio group,
or a heterocyclic thio group wherein the heterocyclic rirng represents a
tetrazole, triazinyl, triazolyl, oxazolyl, imidazolyl, oxadiazolyl,
thiadiazolyl, benzothiazolyl, pyrimidyl or pyridinyl group, as described
in, for example, U.S. Pat. Nos. 3,617,291, 3,622,328, 3,632,373,
3,620,745, 3,620,747 and 3,615,506, and British Patent No. 1,201,110 and
U.S. Pat. No. 3,703,375. Particularly, residues represented by the formula
(IVa) are preferred:
##SPC1##
wherein, V represents a benzene bype aromatic ring or a heterocyclic
aromatic ring containing at least one nitrogen atom, and L represents a
methine group. V can be a substituted with one or more of an amino group,
an acylamino group, a halogen atom such as chlorine, bromine, iodine and
fluorine, and alkyl group, nitro group, an alkoxy group, an alkylthio
group or aryl group, etc. wherein the acyl and alkyl moieties thereof
contain 1 to 15 carbon atoms. ZH is described in, for example, U.S. Pat.
Nos. 3,185,570, 3,244,521, 3,499,761, 3,473,924, 3,575,699 and 3,554,757,
British Patent Nos. 919,061 and 1,031,262, French Patent Nos. 1,346,227
and 1,594,983 and German Patent No. 1,294,188.
The interlayer color correction (I.C.C.) hydroquinone derivatives used in
the present invention designate compounds which release a diffusible
development inhibitor with an image wise distribution on development
during a color development step and inhibit selectively color development
in the adjacent emulsion layer to, consequently exhibit an interlayer
color correcting effect. Preferably, they are hydroquinone derivatives
substituted with a heterocyclic monothio group which becomes a development
inhibitor and an aliphatic thio or aliphatic oxy group having 8 or more
carbon atoms which serves as an antidiffusion ballasting group or
precursors of such hydroquinone derivatives. Preferred compounds are
represented by the following formula (V)
##SPC2##
wherein, A.sub.8 and A.sub.9 each represents a hydrogen atom or a group
which can be released by alkali (e.g., an alkoxycarbonyl group or an acyl
group, etc.), wherein A.sub.9 may form a ring by combining with R.sub.8 or
Q.sub.5 (e.g., an oxathiazole ring, an oxazole ring, an oxadiazole ring, a
furyl ring etc.). P, Q.sub.5 and R.sub.8 each represents a hydrogen atom,
an alkyl group (e.g., having 1 to 18 carbon atoms such as methyl, ethyl,
octyl, tridecyl and the like), an alkenyl group (e.g., having 2 to 18
carbon atoms such as allyl, octadecenyl and the like), a hydroxyl group,
an alkoxy group (e.g., having 1 to 18 carbon atoms such as methoxy, ethoxy
and the like), an amino group (e.g., an amino group or a substituted amino
group having 1 to 30 total carbon atoms such as diethylamino, phenylamino,
octadecylamino and the like), an alkylthio group (e.g., nonylthio,
tridecylthio and the like), an aryl group (e.g., phenyl, tolyl, and the
like), an arylthio group (e.g., phenylthio, tolylthio and the like), a
halogen atom, a heterocyclic group (e.g., tetrazolyl, thiazolyl, quinonyl
and the like) or a --SZ group (e.g., tetrazolylthio, thiadiazolylthio and
the like), and P and Q can combine to form a carbocyclic ring group (e.g.,
a benzene ring group or a tetrahydrobenzene ring group). A.sub.8 and
A.sub.9 each represents a hydrogen atom or alkaline splitable group
selected from acyl groups and alkoxycarbonyl groups (e.g., having 1 to 8
carbon atoms such as acetyl, phenoxycarbonyl, methoxycarbonyl, etc.). Z
represents a heterocyclic residue which is photographically inactive in a
combined state and which can be released at development, and particularly
a heterocyclic aromatic group such as a tetrazolyl group (e.g.,
1-phenyltetrazolyl, 1-alkoxyphenyltetrazolyl and the like), a triazolyl
group (e.g., 1-phenyl, 3-n-amyl, 1,2,4-triazolyl and the like), a
thiadiazolyl group (e.g., 5-methylthio-thiadiazolyl, 5 propylthiadiazolyl
and the like), an oxazolyl group (e.g., 4-methyloxazolyl, benzoxazolyl,
.beta.-naphthoxazolyl and the like), an oxadiazolyl group, a thiazolyl
group or a pyrimidyl group.
It is possible to render these ICC-hydroquinone derivatives diffusion
resistant by combining them with polymers by a ballasting group through P,
Q.sub.5 or R.sub.8 or by a residue of P, Q.sub.5 or R.sub.8. For example,
these ICC-hydroquinone derivatives (I) can be rendered diffusion resistant
by P, Q.sub.5 or R.sub.8 containing a ballasting group, e.g., a
hydrophobic group having 8 to 32 carbon atoms. It is also possible to
render the hydroquinone derivatives (I) diffusion resistant by combining
them with polymer residues through the P, Q.sub.5 or R.sub.8 group.
Suitable examples of such ballasting groups are described in detail
hereinafter.
The organic accelerator having an interlayer under-cut interimage effect
used in the present invention designates an organic compound which is
incorporated optionally in an certain photosensitive emulsion layer to
enhance the uner-cut interimage effect to other adjacent photosenitive
emulsion layers at development, which has been described in, for example,
U.S. Defensive Publications Nos. T909,022 and T909,023 and U.S. Pat. Nos.
3,713,828 and 3,723,125. For example, such compounds are represented by
the formula (VI)
##STR13##
wherein, X.sub.1 represents a sulfur atom, an oxygen atom, a selenium atom
or a =N--R.sub.11 group wherein R.sub.11 represents a hydrogen atom, an
aliphatic group, an aryl group or a heterocyclic ring, and R.sub.9 and
R.sub.10 each represents a hydrogen atom, an aliphatic group or an aryl
group. Q.sub.6 represents the non-metal atoms required to form a
heterocyclic ring used generally as a nucleus of cyanine dyes; and the
formula (VII)
##STR14##
In the formula Q.sub.6 is as defined above and R.sub.12 has the same
meanings as R.sub.9 of formula (VI).
Where the development inhibiting releasable group (Z in formula (IV)) of
the interlayer color correction coupler is a mercapto residue, the
interlayer color correction effect arises to a comparatively low degree
while the development inhibiting effect in the layer occurs to a
comparatively high degree, because the mercapto group is firmly adsorbed
on the photosensitive silver halide by a chemical bond. On the contrary,
where the development inhibiting releasable group is the group represented
by the formula (IVa), the interlayer color correction effect arises to a
comparatively high degree. In this case, the effect caused by providing
the adsorbing colloid layer for the organic development inhibitor
according to the present invention appears markedly.
The adsorbing colloid layer for the organic development inhibitor (ADL) of
the present invention designates a colloid layer which has the function
whereby the organic development inhibitor released from compounds such as
an I.C.C. coupler or an I.C.C. hydroquinone or from an organic accelerator
providing an under-cut interimage effect adsorbed previously on the silver
halide particles by development of the particles is fixed by adsorption to
prevent introduction thereof into the developer, a colloid layer having
the function of removing the once released inhibitor in the developer by
adsorption, or a colloid layer having the function of controlling the
diffusion of the development inhibitor into each emulsion layer of the
photosensitive material. This colloid layer contains a basic synthetic
polymer having a repeating unit represented by the formula (I) or (II). It
has been found that such synthetic polymers have the function of adsorbing
effectively the organic development inhibitor. This is a surprising fact
which was not known at all. The ADL of the present invention can contain
silver halide particles, colloidal silver, colloidal gold or colloidal
silica etc. in addition to the synthetic polymer so as to further enhance
the adsorbability for the development inhibitor.
It is particularly advantageous for the ADL of the present invention to be
used for multilayer color photographic materials containing color forming
couplers. Namely, enhancing the under-cut interimage effect between
emulsion layers is an important technique in order to improve color
reproduction in the multilayer color photosensitive materials. Thus,
I.C.C. couplers, I.C.C. hydrroquinones or organic accelerators having an
under-cut interimage effect are used for such a purpose. In such
multilayer color photosensitive materials, it is necessary to maintain a
balance between each under-cut interimage effect and to prevent generation
of "development mottle" caused by the development inhibitor over a too
wide range in the planar direction of the photosensitive material, and
thus the ADL is advantageously used. In this case, it is preferable that
the ADL be provided between each emulsion layers. Futhermore, in this
case, if acid dyes as described in U.S. patent application Ser. No.
501,107, filed Aug. 27, 1974* are added to the ADL to mordant a part of
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