[0001] The present invention relates to a silver halide color photographic material and
a color photographic print, and more particularly to a color photographic print suitable
for use as, for example, an ID card, a cashing card or a telephone card.
[0002] Conventional silver halide color photographic materials comprise a silver halide
emulsion layer containing a cyan color forming coupler, a silver halide emulsion layer
containing a magenta color forming coupler and a silver halide emulsion layer containing
a yellow color forming coupler coated on various kinds of supports.
[0003] For example, EP-A-0 162 328 discloses a silver halide color photographic light-sensitive
material having a good color formability, color reproducibility, image preservability
and color balance, said material comprising a support and red-sensitive, green-sensitive
and blue-sensitive light-sensitive layers formed on the support.
[0004] It is known that as a light transmissive photographic support, a transparent plastic
film, for example, a cellulose triacetate film, a polyethylene terephthalate film
or a vinyl resin film may be employed, and as a reflective support, for example, baryta
coated paper, synthetic paper, polyethylene laminated paper, a plastic sheet containing
a white pigment, a glass plate or a metal plate (for example, an aluminium plate having
an anodized surface) may be employed.
[0005] With respect to reflective supports, it has been proposed that a white pigment be
incorporated into a plastic material or that a white pigment containing layer is provided
on a surface of a plastic material in order to particularly improve the whiteness
of the supports.
[0006] When the whiteness of a support is increased, the reproducibility of a white object
is improved, however, the sharpness of images usually decreases due to, for example,
reflection during exposure and halation. Therefore, attempts have been made to incorporate
an irradiation preventing dye into a light-sensitive silver halide emulsion layer
provided on the support or to apply an antihalation layer to the support. EP-A-0 065
329 discloses a surface-treated polyvinyl chloride material which may contain pigments
including an adhering hydrophilic layer containing a mixture of a hydrophilic colloid
binder, gelatin in particular, and dispersed colloidal silica. The surface-treated
polyvinyl chloride material is particularly suitable for use in identification document
production.
[0007] Further, when baryta coated paper or polyethylene laminated paper is employed as
a support, the smoothness of the support is poor due to the unevenness of the paper
fiber and thus an uneven thickness of the silver halide emulsion layer occurs, resulting
in a severe problem with the regularity of the image density obtained after development
processing.
[0008] Such a problem is particularly noticeable when a sky scene is photographed and especially
when it is photographed in color.
[0009] It is the object of the present invention to provide a reflective color photographic
light-sensitive material having a reflective support with a good smoothness and which
forms color images having an improved sharpness as well as a color photographic print
having a reflective support with a good smoothness and color images of improved sharpness
which, when used as various kinds of cards, can be subjected to embossment with heat
processing. According to the present invention this object is attained with a silver
halide color photographic material comprising a reflective support composed of a vinyl
chloride resin containing a white pigment and having thereon in an appropriate order
at least one red-sensitive silver halide emulsion layer containing a cyan color forming
coupler represented by the general formula (1) or (2) shown below, at least one green-sensitive
silver halide emulsion layer containing a magenta color forming coupler represented
by the general formula (3) or (4) shown below, and at least one blue-sensitive silver
halide emulsion layer containing a yellow color forming coupler represented by the
general formula (5) shown below
wherein R₁, R₄ and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic
groups an aromatic amino group or a heterocyclic amino group; R₂ represents an aliphatic
group; R₃ and R₆ each represents a hydrogen atom, a halogen atom, an aliphatic groups
an aliphatic oxy group or an acylamino group; R₇ and R₈ each represents a substituted
or unsubstituted phenyl group; R₉ represents a hydrogen atom or a substituent; R₂
and R₃ or R₅ and R₆ may be connected with each other to form a 5-membered to 7-membered
ring; Q represents a substituted or unsubstituted N-phenylcarbamoyl group; Za and
Zb, which may be the same or different, each represents a group of -CH=, a group of
or a group of -N=; R₁₀ represents the same substituent as that represented by R₉;
and X₁, X₂, X₃, X₄ and X₅ each represents a hydrogen atom or a group capable of being
released upon a reaction with an oxidation product of an aromatic primary amine developing
agent.
[0010] Further, in accordance with the present invention the aforementioned object is attained
with a color photographic print comprising a reflective support composed of a vinyl
chloride resin containing a white pigment and having thereon in an appropriate order
at least one emulsion layer containing a cyan dye obtained by a reaction of a cyan
color forming coupler represented by the general formula (1) or (2) shown below with
an oxidation product of an aromatic primary amine developing agent, at least one emulsion
layer containing a magenta dye obtained by a reaction of a magenta color forming coupler
represented by the general formula (3) or (4) shown below with an oxidation product
of an aromatic primary amine developing agent, and at least one emulsion layer containing
a yellow dye obtained by a reaction of a yellow color forming coupler represented
by the general formula (5) shown below with an oxidation product of an aromatic primary
amine developing agent
wherein R₁, R₄ and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic
group, an aromatic amino group or a heterocyclic amino group; R₂ represents an aliphatic
group; R₃ and R₆ each represents a hydrogen atom, a halogen atom, an aliphatic group,
an aliphatic oxy group or an acylamino group; R₇ and R₈ each represents a substituted
or unsubstituted phenyl group; R₉ represents a hydrogen atom or a substituent; R₂
and R₃ or R₅ and R₆ may be connected with each other to form a 5-membered to 7-membered
ring; Q represents a substituted or unsubstituted N-phenylcarbamoyl group; Za and
Zb, which may be the same or different, each represents a group of -CH=, a group of
or a group of -N=; R₁₀ represents the same substituent as that represented by R₉;
and X₁, X₂, X₃, X₄ and X₅ each represents a hydrogen atom or a group capable of being
released upon a reaction with an oxidation product of an aromatic primary amine developing
agent.
[0011] Hereinafter, the oxidation product of an aromatic primary amine developing agent
will be referred to as "CD".
[0012] The color photographic print according to the present invention includes a color
photographic print obtained by conducting at least the step or processing the silver
halide color photographic material of the present invention, after imagewise exposure,
with a color developing solution containing an aromatic primary amine color developing
agent, and a color photographic print obtained by adhering the above-described color
photographic print (but employing a transparent support) on a reflective support composed
of a vinyl chloride resin containing a white pigment.
[0013] In the general formula (1), (2), (3), (4) or (5), the groups capable of being released
represented by X₁, X₂, X₃, X₄ or X₅ include those described in U.S. Patent 4,540,654,
column 4, line 30 to column 5, line 24. Among them, a chlorine atom for X₁ or X₂,
a hydrogen atom or a group capable of being released containing a sulfur atom as a
releasing atom for X₃ or X₄ and a group capable of being released containing an oxygen
atom or a nitrogen atom as a releasing atom for X₅ are preferred.
[0014] The reflective support which can be employed in the present invention will now be
explained in detail below.
[0015] The vinyl chloride resin which constitutes the reflective support used in the present
invention is a homopolymer or copolymer containing a vinyl chloride monomer as at
least one kind of monomer. It is preferred that the vinyl chloride monomer occupies
at least 50% by weight of the total monomer component. Suitable examples of comonomer
component include, for example, methyl methacrylate, vinyl acetate, acrylonitrile,
a fluorinated olefin, a vinyl ether, vinyl bromide, maleic acid, dichlorobutadiene,
vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene,
vinylidene chloride, styrene, butadiene and chloroprene. Two or more of these comonomer
components may be employed.
[0016] To the vinyl chloride resin may be added various fillers, plasticizers and stabilizers.
Suitable examples of fillers include starch, wood flour, clay, calcium carbonate and
bentonite. Suitable examples of plasticimers include a phthalic ester (e.g., dibutyl
phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, butyllauryl
phthalate, dilauryl phthalate, butylbenzyl phthalate), a phosphoric ester (e.g., tricresyl
phosphate, trixylenyl phosphate, trioctyl phosphate), a straight chain dibasic acid
ester (e.g., dioctyl adipate, dioctyl azelate, dioctyl sebacate) and butylphthalyl
butylglycolate. Suitable examples of stabilizers include tribasic lead sulfate, dibasic
lead stearate and lead orthostearate.
[0017] A filler may be added in an amount of from about 20 parts to 100 parts by weight
per 100 parts by weight of the resin material.
[0018] The white pigments which can be added to the vinyl chloride resin include, for example,
titanium white, zinc white, calcium carbonate, barium sulfate, white lead, white organic
pigments or dyes and brightening agents.
[0020] The vinyl chloride resin as used in the present invention exhibits resistance to
heat deformation, preferably to at least 50°C, more preferably to at least 70°C thereby
preventing a dimensional change during the drying step after preparation and development
steps of light-sensitive materials or during their use.
[0021] It is preferred that the average reflectivity of the reflective support used in the
present invention in a visible range is from 80 to 98%.
[0022] The thickness of the reflective support is preferably from 50 µm to 500 µm and more
preferably from 100 µm to 300 µm.
[0023] When a hydrophilic colloid layer such as a silver halide emulsion layer is coated
on the reflective support, a subbing treatment may be conducted in order to improve
adhesion of both materials. With respect to the subbing treatment, various kinds of
methods are known and a suitable method can be appropriately selected therefrom.
[0024] For instance, there may be employed a method wherein the surface of the support is
etched with acetone to make a rough surface, wood flour (cellulose component) is coated
to fill in a concave portion of the surface and to cover a convex portion of the surface
and thereby an affinity with gelatin is provided (because of a good affinity between
cellulose and protein) and then a subbing solution containing pearl essence is coated
thereon as described in Japanese Patent Publication No. 3583/60, a method wherein
at least one layer composed of a mixture of cellulose nitrate and a vinyl acetate-vinyl
chloride copolymer is coated as a subbing agent as described in Japanese Patent Publication
No. 25742/64, a method wherein a support is subjected to corona discharge treatment
to a specified degree and then a layer containing a hydrophilic colloidal binder (such
as gelatin) and dispersible colloidal silica at a weight ratio of 5/1 to 1/2 is coated
thereon as described in European Patent Application (OPI) No. EP 0065329A1 (the term
"OPI" as used herein refers to a "published unexamined application"), a method wherein
a straight chain polyphosphoric acid ester resin is coated on a support as described
in British Patent 742,370, a method wherein a hardened gelatin subbing layer is subjected
to corona discharge treatment and then a light-sensitive silver halide emulsion layer
is coated as described in British Patent 1,472,854, a method wherein an epoxidated
rubbery polymer and a film-forming unsaturated polyester are coated as subbing agents
as described in British Patent 1,179,563, a method wherein first a solution of an
isobutyl methacrylate polymer dissolved in a solvent which does not affect the vinyl
chloride polymer and then a usual subbing layer composed of gelatin and cellulose
nitrate is coated thereon as described in U.S. Patent 2,388,817, and a method wherein
a subbing solution having the composition shown below is coated on a support as described
in U.S. Patent 2,483,966.
Composition of Subbing Solution |
Parts by Weight |
Cellulose Nitrate (nitrogen content 11%) |
5.0 to 7.0 |
Acetone |
40.0 to 50.0 |
Methyl Ethyl Ketone |
9.0 to 10.0 |
Methanol |
25.0 to 35.0 |
Dioctyl Phosphate |
2.5 to 4.2 |
Ethanol |
0.0 to 3.5 |
[0025] It is preferred that a development inhibitor releasing compound (DIR compound) is
added to the color photographic light-sensitive material according to the present
invention for the purpose of further improving the sharpness.
[0026] Suitable DIR compounds include DIR couplers as described in U.S. Patents 3,933,500,
4,187,100 and 4,477,563, British Patent 1,504,094 and Japanese Patent Application
(OPI) Nos. 206834/84, 210440/84 and 92556/85.
[0027] The dye which is formed upon the coupling reaction of the color image forming coupler
represented by the above-described general formula (1), (2), (3), (4) or (5) which
is used in the present invention with an oxidation product of an aromatic primary
amine color developing agent (CD) will be explained in greater detail below.
[0028] As yellow dyes, those dyes formed from pivaloyl acetanilide type couplers are preferred.
These dyes have the excellent features that the long wavelength side of their spectral
absorptions is sharply cut and that their fastness is excellent. Further, they are
easily dispersed in a hydrophilic colloid using a small amount of an organic solvent
or using a water-insoluble and organic solvent soluble polymer, in comparison with
benzoyl acetanilide type couplers, and thus they enable the provision of a color-forming
layer which is thin and has strong physical properties.
[0029] The yellow dyes which are preferably employed in the present invention are those
represented by the following general formula (5-1):
wherein R₁₄ and R₁₅, which may be the same or different, each represents a hydrogen
atom or a substituent which is ordinarily used for a yellow coupler, provided that
both R₁₄ and R₁₅ are not hydrogen atoms at the same time; and
represents a coupling residue of an aromatic primary amine developing agent.
[0030] Suitable examples of the substituents represented by R₁₄ and R₁₅ include an alkyl
group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom,
an alkoxycarbamoyl group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido
group, an alkylureido group, an alkyl-substituted succinimido group, an aryloxy group,
an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl
group, an arylsulfonamido group, an arylureido group, a carboxy group, a sulfo group,
a nitro group, a cyano group and a thiocyano group. The coupler used may be, for instance,
a polymer coupler including a bis coupler.
[0031] In the general formula (5-1),
preferably represents a coupling residue of a phenylenediamine derivative represented
by the following general formula (6):
wherein R₁₁ and R₁₂ each represents a substituted or unsubstituted alkyl group; and
R₁₃ represents one to four hydrogen atoms or one to four substituents.
[0032] In the general formula (6), the alkyl group represented by R₁₁ or R₁₂ is preferably
an alkyl group having from 1 to 4 carbon atoms. Suitable examples of the substituents
for the alkyl group include a hydroxy group, an alkylsulfonamido group and an alkoxy
groups. Specific examples of R₁₁ or R₁₂ include an ethyl group, a β-hydroxyethyl group,
a β-methanesulfonamidoethyl group and a β-methoxyethyl group. Further, a representative
example of the substituent represented by R₁₃ is an alkyl group (for example, a methyl
group).
[0033] As the magenta dyes used in the present invention, those represented by the following
general formula (4-1) or (4-2) are preferred.
wherein
represents a coupling residue of an aromatic primary amine developing agent and R₁₆
and R₁₇, which may be the same or different, each represents a hydrogen atom, a halogen
atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy
group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy
group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group,
a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an
alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino
group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl
group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group
or an aryloxycarbonyl group. Of these groups, an alkyl group, an alkoxy group, an
alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acylamino
group and an anilino group are particularly preferred. R₁₆ or R₁₇ may also be a divalent
group to form a bis compound. Further, the magenta dye represented by the general
formula (4-1) or (4-2) may be in the form of a polymer dye in which the dye moiety
represented by the general formula (4-1) or (4-2) exists at the main chain or the
side chain of the polymer and particularly a polymer derived from a vinyl monomer
having the moiety represented by the general formula (4-1) or (4-2) is preferred.
In this case, R₁₆ or R₁₇ represents a linking group connected to a vinyl group.
[0034] The linking group represented by R₁₆ or R₁₇ in the cases wherein the part represented
by the general formula (4-1) or (4-2) is included in a vinyl monomer includes an alkylene
group (including a substituted or unsubstituted alkylene group, e.g., a methylene
group, an ethylene group, a 1,10-decylene group or -CH₂CH₂OCH₂CH₂-), a phenylene group
(including a substituted or unsubstituted phenylene group, e.g., a 1,4-phenylene group,
a 1,3-phenylene group,
or
-NHCO-, -CONH-, -O-, -OCO-, and an aralkylene group (e.g.,
or
or a combination thereof.
[0035] Specific examples of preferred linking groups include -NHCO-, -CH₂CH₂-,
-CH₂CH₂NHCO-,
-CONHCH₂CH₂NHCO-, -CH₂CH₂OCH₂CH₂NHCO-, and
[0036] Further, the vinyl group in the vinyl monomer may further have a substituent in addition
to the moiety represented by the general formula (4-1) or (4-2). Preferred examples
of these substituents include a chlorine atom or a lower alkyl group having from 1
to 4 carbon atoms (e.g., a methyl group, an ethyl group or a butyl group).
[0037] The polymer derived from the vinyl monomer having the dye moiety may be a copolymer
with a non-color forming ethylenic monomer.
[0038] Suitable examples of the non-color forming ethylenic monomers include an acrylic
acid such as acrylic acid, α-chloroacrylic acid, α-alacrylic acid (e.g., methacrylic
acid), an ester or an amide derived from an acrylic acid (e.g., acrylamide, n-butylacrylamide,
tert-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl
acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate,
2-ethylhexyl acrylate, n-octyl acrylate, vinyl propionate, vinyl laurate), acrylonitrile,
methacrylonitrile, an aromatic vinyl compound (e.g., styrene and a derivative thereof,
vinyltoluene, divinylbenzene, vinylacetophenone, sulfostyrene), itaconic acid, citraconic
acid, crotonic acid, vinylidene chloride, a vinyl alkyl ether (e.g., vinyl ethyl ether),
maleic acid, maleic anhydride, a maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine
and 2- or 4-vinylpyridine. Particularly, an acrylic acid ester, a methacrylic acid
ester and a maleic acid ester are preferred.
[0039] Two or more non-color forming ethylenically unsaturated monomers can be used together.
For example, a combination of n-butyl acrylate and methyl acrylate, styrene and methacrylic
acid, methyl acrylate and diacetoneacrylamide can be used.
[0040] As is well known in the field of polymer color couplers, the non-color forming ethylenically
unsaturated monomer which is used to copolymerize with a solid water-insoluble monomer
coupler can be selected in such a manner that the copolymer to be formed has good
physical properties and/or chemical properties, for example, solubility, compatibility
with a binder in a photographic colloid composition such as gelatin, flexibility and
heat stability.
[0041] The magenta dyes according to the present invention are characterized by good spectral
absorption characteristics wherein the characteristic second absorption on the short
wavelength side is not present or, if present, is small and the absorption on the
long wavelength side is sharply cut, and by an excellent fastness to high humidity
and heat. Further, when polymer magenta dyes are used, they can be dispersed as a
latex and thus an organic solvent having a high boiling point is not necessary, or
is used only in a reduced amount. As a result, it is possible to decrease the thickness
of the color forming layer and to increase the physical strength thereof.
[0042] The cyan dyes used in the present invention are most typically dyes which are obtained
upon an oxidation coupling reaction of phenol type couplers with paraphenylenediamine
color developing agents. These phenol type cyan couplers may be used together with
naphthol type cyan couplers. Specific examples of naphthol type couplers include those
as described, for example, in U.S. Patent 2,474,293 and preferably those as described,
for example, in U.S. Patents 4,052,212, 4,146,396, 4,228,233 and 4,296,200. Specific
examples of phenol couplers include those as described, for example, in U.S. Patents
2,396,929, 2,801,171, 2,772,162 and 2,895,826.
[0043] Cyan couplers which are stable against humidity and temperature are advantageously
used in the present invention. Typical examples of those couplers include phenol cyan
couplers having an alkyl group more than a methyl group at the meta-position of the
phenol nucleus as described in, for example, U.S. Patent 3,772,002, cyan couplers
as described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173,
West German Patent Application (OLS) No. 3,329,729 and European Patent 121,365 and
cyan couplers as described in, for example, U.S. Patents 3,446,622, 4,333,999, 4,451,559
and 4,427,767.
[0044] The cyan dyes according to the present invention can cover a wavelength range of
600 µm to 700 µm by using two or more dyes represented by the general formula (1)
or (2) in combination. The cyan dyes can provide cyan color images having a small
absorption on the short wavelength side and they are excellent in fastness to high
humidity and heat.
[0046] The dyes which form images according to the present invention are preferably used
in combination with one or more kinds of organic solvents having a high boiling point
of at least 160°C represented by the general formula (7), (8), (9), (10) or (11) as
shown below. Details of these organic solvents are described in Japanese Patent Application
(OPI) No. 215272/87, pages 138 to 144. Further, it is particularly preferred that
the dyes are used in combination with water-insoluble, organic solvent-soluble polymers
as described in, for example, Japanese Patent Publication No. 30474/73, U.S. Patent
3,619,195 and International Application No. PCT/JP 87/00492 filed July 9, 1987. Moreover,
the dyes may be used in combination with loaded polymeric latexes as described in
U.S. Patent 4,203,716.
W₁ - COO - W₂ (8)
W₁ - O - W₂ (11)
wherein W₁, W₂ and W₃ each represents a substituted or unsubstituted alkyl group,
a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl
group, a substituted or unsubstituted aryl group or a substituted or unsubstituted
heterocyclic group; W₄ represents W₁, -O-W₁ or -S-W₁; n represents an integer from
1 to 5, when n is two or more, two or more W₄'s may be the same or different; and
W₁ and W₂ in the general formula (11) may be connected with each other to form a condensed
ring.
[0047] Preferred specific examples of water-insoluble, organic solvent-soluble polymers
include polyvinyl acetate, polyvinyl propionate, and polymethyl methacrylate.
[0048] Further, the specific examples of polymers (P-4) to (P-158) as described in International
Application No. PCT/JP 87/00492, pages 22 to 30, and the specific examples of polymers
1 to 35 as described in Japanese Patent Publication No. 30494/73, pages 4 to 5 are
also preferred.
[0049] These polymers may be employed together with the above described organic solvent
having a high boiling point of at least 160°C.
[0050] Furthermore, it is preferred that the dyes according to the present invention are
used in combination with color fading preventing agents or antioxidizing agents represented
by the general formula (12) or (13) shown below. Of these compounds, those which are
soluble in organic solvents are preferred.
wherein R₂₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic
group or a hydrolyzable protective group; R₂₁, R₂₂, R₂₃, R₂₄ and R₂₅, which may be
the same or different, each represents a hydrogen atom or a substituent; R₃₀ represents
a hydrogen atom, an aliphatic group, an acyl group, a sulfonyl group, a sulfinyl group,
an oxy radical group or a hydroxy group; A represents a non-metallic atomic group
necessary to form a 5-membered, 6-membered or 7-membered ring; and R₂₆, R₂₇, R₂₈ and
R₂₉, which may be the same or different, each represents a hydrogen atom or an alkyl
group.
[0051] Specific examples of substituents represented by R₂₁ or R₂₅ include a hydrogen atom
and an alkyl group, and preferred examples of the alkyl group include a straight chain
or branched chain alkyl group having from 1 to 8 carbon atoms, particularly a methyl
group, an n-butyl group, a t-butyl group, a t-pentyl group and an n-octyl group. Specific
examples of substituents represented by R₂₂, R₂₃ or R₂₄ include a hydrogen atom, an
alkyl group, -NHR₃₁, an alkoxy group and -COO-R₃₂, R₃₁ represents a nitrogen-containing
heterocyclic group and R₃₂ represents an alkyl group or an aryl group. The above-mentioned
alkyl, alkoxy or aryl group means a substituted or unsubstituted alkyl, alkoxy or
aryl group.
[0052] Of the substituents represented in the general formula (12), R₂₀ and R₂₁ or two of
R₂₁, R₂₂, R₂₃, R₂₄ and R₂₅ which are present in ortho-positions of each other may
be connected with each other to form a 5-membered, 6-membered or 7-membered ring.
[0053] Of the substituents represented in the general formula (13), R₂₆ and R₂₇, R₂₈ and
R₂₉ or R₃₀ and R₂₆ may be connected with each other to form a 5-membered, 6-membered
or 7-membered ring.
[0054] Specific examples of the compounds represented by the general formula (12) or (13)
are set forth below.
The color print according to a preferred embodiment of the present invention can
be obtained by subjecting to color development processing, after imagewise exposure,
a color printing paper which comprises a thin reflective support having thereon a
yellow color forming layer containing a blue-sensitive silver halide emulsion and
a yellow color forming coupler, a magenta color forming layer containing a green-sensitive
silver halide emulsion and a magenta color forming coupler, and a cyan color forming
layer containing a red-sensitive silver halide emulsion and a cyan color forming coupler,
and optionally further, e.g., an antihalation layer, an intermediate layer, a yellow
filter layer and a protective layer, if appropriate for the desired photographic material.
[0055] The silver halide emulsion which is used in the present invention is usually prepared
by mixing an aqueous solution of a water-soluble silver salt (for example, silver
nitrate) with an aqueous solution of a water-soluble halide (for example, potassium
bromide, sodium chloride, potassium iodide or a mixture thereof) in the presence of
an aqueous solution of a water-soluble polymer (for example, gelatin). As the silver
halide thus-prepared, in addition to silver chloride and silver bromide, a mixed silver
halide, for example, silver chlorobromide, silver chloroiodobromide and silver iodobromide
are representative examples. The silver halide which is preferably employed in the
present invention is silver chloroiodobromide, silver iodochloride or silver iodobromide,
each containing 3 mol% or less silver iodide.
[0056] The silver halide grains may have different layers in the inner portion and the surface
portion, multi-phase structures containing junctions, or may be uniform throughout
the grains. Further, a mixture of these silver halide grains having different structures
may be employed. For instance, with respect to silver chlorobromide grains having
different phases, those having nuclei or a single layer or plural layers which are
rich in silver bromide as compared with the mean halogen composition in their inner
portion, or those having nuclei or a single layer or plural layers which are rich
in silver chloride as compared with the mean halogen composition in their inner portion
may be employed. Therefore, surface layers of the grains are rich in silver bromide
as compared with the mean halogen composition or contrary to this, surface layers
are rich in silver chloride.
[0057] The average grain size of the silver halide grains (the grain size being defined
as the grain diameter if the grain has a spherical or a nearly spherical form and
as the length of the edge if the grain has a cubic form, and being averaged based
on projected areas of the grains) is preferably from 0.1 µm to 2 µm, and particularly
from 0.15 µm to 1 µm. The grain size distribution may be either narrow or broad.
[0058] A so-called monodispersed silver halide emulsion having a narrow grain size distribution
which comprises at least 90%, particularly at least 95% by number or by weight of
the total silver halide grains having a size within the range of the average grain
size ±40% is preferably employed in the present invention. Further, in order to achieve
the desired gradation of the light-sensitive material, two or more monodispersed silver
halide emulsions which have different grain sizes from each other can be mixed in
one emulsion layer or can be coated in the form of superimposed layers which have
substantially the same spectral sensitivity. Moreover, two or more polydispersed silver
halide emulsions or combinations of a monodispersed emulsion and a polydispersed emulsion
may be employed in a mixture or in the form of superimposed layers.
[0059] The silver halide grains which can be used in the present invention may have a regular
crystal structure, for example, a cubic, octahedral, dodecahedral or tetradecahedral
structure, an irregular crystal structure, for example, a spherical structure, or
a composite structure thereof. Further, tabular silver halide grains can be used.
Particularly, a silver halide emulsion wherein tabular silver halide grains having
a ratio of diameter/thickness of not less than 5, preferably not less than 8 account
for at least 50% of the total silver halide grains present, calculated based on the
projected area of the silver halide grains, can be employed. In addition, mixtures
of silver halide grains having different crystal structures may be used. These silver
halide emulsions may be those of the surface latent image type in which the latent
images are formed mainly on the surface thereof, or those of the internal latent image
type in which the latent images are formed mainly in the interior thereof.
[0060] Dyes are employed in the present invention for various purposes, for example, as
filter dyes, for irradiation prevention or for antihalation. Examples of such dyes
which are preferably used are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine
dyes, anthraquinone dyes and azo dyes. Further, cyanine dyes, azomethine dyes, triarylmethane
dyes and phthalocyanine dyes are also useful. Oil-soluble dyes may be added to the
hydrophilic colloid layer by emulsification using an oil droplet-in-water dispersing
method.
[0061] In the color photographic light-sensitive material of the present invention, inorganic
or organic hardening agents may be employed in order to harden the hydrophilic colloid
layers applied on the support. For example, active halogen compounds (for example,
2,4-dichloro-6-hydroxy-1,3,5-triazine) and active vinyl compounds (for example, 1,3-bisvinylsulfonyl-2-propanol,
1,2-bisvinylsulfonylacetamidoethane or a vinyl type polymer having a vinylsulfonyl
group in its side chain) are preferred since they rapidly act on hydrophilic colloid
such as gelatin to harden and provide stable photographic properties. Also N-carbamoylpyridinium
salts and haloamidinium salts are excellent in view of their high hardening speed.
[0062] The color developing solution used for development processing of the color photographic
light-sensitive material of the present invention to obtain a color print is preferably
an alkaline aqueous solution containing an aromatic primary amine color developing
agent as the main component. As a color developing agent, while an aminophenol type
compound is useful, a p-phenylenediamine type compound is preferably used. Typical
examples of the p-phenylenediamine type compounds include 3-methyl-4-amino-N,N-diethylaniline,
3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, or a sulfate, hydrochloride or p-toluenesulfonate
thereof. These diamines are preferably employed in the form of salts since the salts
are generally more stable than their free forms.
[0063] The color developing solution generally contains pH buffering agents such as carbonates,
borates or phosphates of alkali metals, and development inhibitors or antifogging
agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
In addition, if desired, the color developing solution may also contain, for example,
preservatives such as, for example, hydroxylamines, derivatives thereof (for example,
N,N-dialkyl substituted derivatives) or sulfites; organic solvents such as, for example,
triethanolamine, derivatives thereof or diethylene glycol; development accelerators
such as, for example, benzylalcohol, polyethyleneglycol, quaternary ammonium salts
or amines; competing couplers; nucleating agents such as, for example, sodium borohydride;
auxiliary developing agents such as, for example, 1-phenyl-3-pyrazolidone; viscosity
imparting agents; various chelating agents as represented, for example, by aminopolycarboxylic
acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids;
and antioxidants as described in West German Patent Application (OLS) No. 2,622,950.
[0064] In the case of development processing for reversal color photographic light-sensitive
materials, the color development is usually conducted after the black-and-white development.
[0065] After color development, the photographic emulsion layer is usually subjected to
bleach processing. The bleach processing can be carried out simultaneously with or
separately from fix processing. Further, in order to perform rapid processing, a processing
method in which bleach-fix processing is conducted after bleach processing can be
employed. As bleaching agents, iron (III) salts of ethylenediaminetetraacetic acid,
iron (III) salts of diethylenetriaminepentaacetic acid and persulfates are preferred
in view of rapid processing and less environmental pollution. Further, ethylenediaminetetraacetic
acid iron (III) complex salts are particularly useful both in an independent bleaching
solution and in a mono-bath bleach-fixing solution. Further, thiosulfates are ordinarily
employed as fixing agents. In the bleach-fixing solution or the fixing solution, sulfites,
bisulfites, carbonylbisulfite adducts, for instance, are preferably employed as preservatives.
[0066] After the bleach-fix processing or fix processing, water wash processing and/or stabilization
processing are usually conducted. In the water washing step or stabilizing step, various
known compounds may be employed, for instance, for the purpose of preventing precipitation
or saving water. For example, a water softener such as, for example, an inorganic
phosphoric acid, an aminopolycarboxylic acid, an organic aminopolyphosphonic acid,
or an organic phosphoric acid for the purpose of preventing the formation of precipitation;
a sterilizer or antimold for the purpose of preventing the propagation of various
bacteria, algae and molds; a metal salt such as, for example, a magnesium salt, an
aluminum salt or bismuth salt; or a surface active agent for the purpose of reducing
the drying load or preventing drying marks; and various hardening agents; may be added,
if desired. Further, the compounds as described in L.E. West,
Photo. Sci. Eng., Vol. 6, pages 344 to 359 (1965) may be added. Particularly, the addition of chelating
agents and antimolds is effective.
[0067] Further, the color photographic light-sensitive material according to the present
invention may contain, if appropriate, various 1-phenyl-3-pyrazolidones for the purpose
of accelerating the color development. Typical examples of the compounds include those
as described in Japanese Patent Application (OPI) Nos. 64339/81, 144547/82, 211147/82,
50532/83, 50536/83, 50533/83, 50534/83, 50535/83 and 115438/83.
[0068] In the present invention, the various kinds of processings described above can be
conducted in a temperature range of from 10°C to 50°C. Although the standard temperature
is from 33°C to 38°C, it is possible to carry out the processing at higher temperatures
in order to accelerate the processing whereby the processing time is shortened, or
on the other hand, at lower temperatures in order to achieve an improvement in image
quality and to maintain the stability of the processing solutions.
[0069] Further, for the purpose of reducing the amount of silver employed in the color photographic
light-sensitive material, the photographic processing may be conducted utilizing color
intensification using cobalt or hydrogen peroxide as described in West German Patent
Application (OLS) No. 2,226,770 or U.S. Patent 3,674,499.
[0070] Moreover, in the case of continuous processing, the variation of the composition
in each processing solution can be prevented by using a replenisher for each processing
solution, whereby a constant finish can be achieved. The amount of replenisher can
be reduced to one half or less of the standard amount of replenishment for the purpose
of reducing the costs.
[0071] Direct positive color prints can be obtained with respect to the color photographic
light-sensitive materials by using an internal latent image type emulsion which was
not previously fogged as a silver halide emulsion, and performing a fogging treatment
after the imagewise exposure but before or during the color development step.
[0072] As the fogging treatment, a method conducting fogging exposure or a method using
a nucleating agent (a chemical fogging method) are effective. More specifically, a
light fogging method and a chemical fogging method (a method using a nucleating agent
together with a nucleating accelerator) as described, for example, in U.S. Application
Serial No. 60,790 filed June 12, 1987, pages 55 to 88, or European Patent Application
No. 87 108489.3 filed June 12, 1987, pages 55 to 88 (corresponding to Japanese Patent
Application No. 136949/86) can be utilized.
[0073] The color photographic print obtained by development processing of the color photographic
light-sensitive material according to the present invention advantageously not only
has a good fastness to light, humidity and heat but also has an excellent sharpness
of color images.
[0074] Further, since it has a good smoothness of the emulsion layer, the irregularity of
the color image density is remarkably reduced.
[0075] Moreover, the support composed of a vinyl chloride resin used in the present invention
is excellent in flexibility and strength and its variation in the degree of elasticity
on change in humidity is small and can be ignored in comparison with other photographic
supports.
[0076] Furthermore, it is easy to emboss a card after printing and thus the color photographic
light-sensitive material and the color photographic print according to the present
invention can be suitably employed as, for instance, ID cards, cashing cards and telephone
cards.
[0077] The present invention is explained in greater detail with reference to the following
examples.
EXAMPLE 1
[0078] On a support composed of a hard vinyl chloride resin (a copolymer containing at least
50 mol% of vinyl chloride monomer component, with the remainder thereof being vinylidene
chloride and methyl methacrylate, and further containing 12 parts by weight of TiO₂
per 100 parts of total weight of the copolymer) and having a thickness of 150 µm and
an average reflectance in the visible range of 85% or more, provided with subbing
treatment, the first layer to the seventh layer described below were coated to prepare
a color photographic light-sensitive material which was designated Sample 101. The
support used was in conformity with a standard of JIS-K-6734-Class C, No. 1, as described
in JIS published by Japanese Standards Association.
[0080] The following dyes were used as spectral sensitizing dyes in the emulsion layers,
respectively.
Blue-sensitive Emulsion Layer:
[0081] 4-{5-chloro-2-[5-chloro-3-(4-sulfonatobutyl)benzothiazolin-2-ylidenemethyl]-3-benzothiazolino}-butanesulfonatotriethylammonium
salt (2x10⁻⁴ mol per mol of silver halide)
Green-Sensitive Emulsion Layer:
[0082] 3,3ʹ-Di-(γ-sulfopropyl)-5,5ʹ-diphenyl-9-ethoxacarbocyanine sodium salt (2.5x10⁻⁴
mol per mol of silver halide)
Red-Sensitive Emulsion Layer:
[0083] 3,3ʹ-Di-(γ-sulfopropyl)-9-methylthiacarbocyanine sodium salt (2.5x10⁻⁴ mol per
mol of silver halide)
The following dyes were employed as irradiation preventing dyes in the emulsion
layers, respectively.
Red-sensitive Emulsion Layer:
[0085] These samples were stepwise exposed and then subjected to development processing
according to the processing steps as shown below.
Processing Step |
Temperature |
Time |
Development |
33°C |
3 min 30 s |
Bleach-fixing |
33°C |
1 min 30 s |
Washing with Water |
28 to 35°C |
3 min |
[0086] The composition of each processing solution used in the above-described processing
steps is as follows:
Developing Solution |
Trisodium nitrilotriacetate |
2.0 g |
Benzyl alcohol |
15 ml |
Diethylene glycol |
10 ml |
Sodium sulfite |
2.0 g |
Potassium bromide |
0.5 g |
Hydroxylamine sulfate |
3.0 g |
4-Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate |
5.0 g |
Sodium carbonate (monohydrate) |
30 g |
Water to make |
1 l |
(pH: 10.1) |
Bleach-Fixing Solution |
Ammonium thiosulfate (54 wt%) |
150 ml |
Sodium sulfite |
15 g |
Ammonium iron (III) ethylenediaminetetraacetate |
55 g |
Disodium ethylenediaminetetraacetate |
4 g |
Water to make |
1 l |
(pH: 6.9) |
[0087] The sharpness of Samples 101, 102 and A' thus-processed was determined. The sharpness
is a value indicating clearness of the outlines of images and the ability to duplicate
fine images. The value known as CTF was used herein. CTF means the degree of decrease
in amplitude against a spatial frequency as a rectangular wave. The sharpness at 15
lines/mm of spatial frequency thus-measured is shown in Table 2 below. The larger
value indicates the better sharpness.
TABLE 2
Sharpness |
Sample 101 |
Sample 102 |
Sample A'* |
B |
25.4 |
27.2 |
22.4 |
G |
33.0 |
35.6 |
29.3 |
R |
34.9 |
37.1 |
30.7 |
[0088] An irregularity of the image density was not observed in both Samples 101 and 102.
EXAMPLE 2
[0089] Silver Halide Emulsion (7) for a blue-sensitive silver halide emulsion layer was
prepared in the following manner.
Solution 8 |
H₂O |
1,000 ml |
NaCl |
5.8 g |
Gelatin |
25 g |
Solution 9 |
Sulfuric acid (1N) |
20 ml |
Solution 11 |
KBr |
0.18 g |
NaCl |
8.51 g |
H₂O to make |
130 ml |
Solution 12 |
AgNO₃ |
25 g |
H₂O to make |
130 ml |
Solution 13 |
Pb(CH₃COO)₂·3H₂O (0.1%) |
28 ml |
Solution 14 |
KBr |
0.70 g |
NaCl |
34.05 g |
H₂O to make |
285 ml |
Solution 15 |
AgNO₃ |
100 g |
H₂O to make |
285 ml |
[0090] Solution 8 was heated at 60°C, Solution 9 and Solution 10 were added thereto and
then Solution 11 and Solution 12 were added thereto simultaneously over a period of
60 min. One minute after the completion of the addition of Solution 11 and Solution
12, Solution 13 was added and then after 9 min Solution 14 and Solution 15 were added
simultaneously over a period of 25 min. After 5 min, the temperature was dropped and
the mixture was desalted. Water and gelatin were added thereto for dispersion and
the pH was adjusted to 6.0 whereby a mono-dispersed cubic silver chlorobromide emulsion
(having an average grain size of 1.00 µm, a coefficient of variation of 0.11 and a
silver bromide content of 1 mol%) was obtained. The emulsion was subjected to optimum
chemical sensitization using triethyl thiourea and chloroauric acid. Thereafter, the
Spectral Sensitizer (S-1) shown below was added in an amount of 5 x 10⁻⁴ mol per mol
of silver halide.
[0091] Silver Halide Emulsion (8) for a green-sensitive silver halide emulsion layer and
Silver Halide Emulsion (9) for a red-sensitive silver halide emulsion layer were prepared
in the same manner as described above except for changing the amounts of chemicals
used in Solution 8 and Solution 10, the kinds and amounts of spectral sensitizers,
and the temperatures and times for addition. Spectral Sensitizer (S-2) shown below
was used for Silver Halide Emulsion (8) and Spectral Sensitizer (S-3) shown below
was used for Silver Halide Emulsion (9).
Spectral Sensitizer (S-1):
[0092]
(5 x 10⁻⁴ mol per mol of silver halide)
Spectral Sensitizer (S-2):
[0093]
(4 x 10⁻⁴ mol per mol of silver halide)
(7.0 x 10⁻⁵ mol per mol of silver halide)
Spectral Sensitizer (S-3):
[0094]
(0.9 x 10⁻⁴ mol per mol of silver halide)
Further, to the red-sensitive silver halide emulsion layer, the compound described
below was added in an amount of 2.6 x 10⁻³ mol per mol of silver halide.
Moreover, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive
emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer in
the amounts of 8.5 x 10⁻⁵ mol, 7.7 x 10⁻⁴ mol and 2.5 x 10⁻⁴ mol per mol of silver
halide present in the layer, respectively.
[0095] The average grain sizes, coefficients of variation and halide compositions of Silver
Halide Emulsions (7) to (9) are shown in Table 3 below.
[0096] Samples 103 and 104 were prepared in the same manner as described for Samples 101
and 102, respectively, except that the silver halide emulsions used in the first layer,
the third layer and the fifth layer were changed to Silver Halide Emulsions (7), (8)
and (9), respectively. These samples were stepwise exposed in the same manner as described
in Example 1 and then subjected to development processing consisting or color development,
bleach-fixing and rinse steps as shown below.
Processing Step |
Temperature |
Time |
Color Development |
35°C |
45 s |
Bleach-Fixing |
35°C |
45 s |
Rinse |
28 to 35°C |
1 min 30 s |
[0097] The compositions of each processing solution used in the above-described processing
steps are as follows:
Color Developing Solution: |
Water |
800 ml |
Pentasodium diethylenetriaminepentaacetate |
1.0 g |
Sodium sulfite |
0.2 g |
N,N-Diethylhydroxylamine |
4.2 g |
Potassium bromide |
0.01 g |
Sodium chloride |
1.5 g |
Triethanolamine |
8.0 g |
N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate |
4.5 g |
Potassium carbonate |
30.0 g |
4,4'-Diaminostilbene type brightening agent (Whitex 4 manufactured by Sumitomo Chemical
Co., Ltd.) |
2.0 g |
Water to make |
1,000 ml |
pH 10.1 |
Bleach-Fixing Solution: |
Water |
700 ml |
Ammonium thiosulfate (54% by weight aq. soln.) |
150 ml |
Sodium sulfite |
15 g |
NH₄[Fe(III)(EDTA)] |
55 g |
EDTA·2Na·2H₂O |
4 g |
Glacial acetic acid |
8.61 g |
Water to make |
1,000 ml |
pH 5.4 |
Rinse Solution: |
EDTA·2Na·2H₂O |
0.4 g |
Water to make |
1,000 ml |
pH 7.0 |
[0098] The sharpness of the samples thus-processed was measured and it was determined that
a further improvement in sharpness was obtained.
EXAMPLE 3
1) Preparation of Emulsions
[0099] Emulsions A to H were prepared as follows.
Emulsion A
[0100] An aqueous solution of potassium bromide and an aqueous solution of silver nitrate
were simultaneously added to a gelatin aqueous solution under vigorous stirring at
75°C over a period of 40 min to obtain a monodispersed silver bromide emulsion containing
octahedral grains of 0.4 µm in average grain size. Four mg of sodium thiosulfate and
4 mg of chloroauric acid (4 hydrate) were added to the emulsion per mol of silver,
followed by heating at 75°C for 80 min to effect chemical sensitization. The thus
obtained silver bromide grains were used as cores, and were allowed to further grow
in the same precipitating environment as the first step for 40 min to finally obtain
an octahedral monodispersed core/shell silver bromide emulsion of 0.6 µm in average
grain size (coefficient of variation : 14%). After washing with water and desalting
of the emulsion, 0.9 mg of sodium thiosulfate were added thereto per mol of silver,
followed by heating at 65°C for 60 min to effect chemical sensitization. Thus, internal
latent image type silver halide emulsion A was obtained.
Emulsion B
[0101] 30 g of gelatin were added to 1 l of a solution containing 0.5 mol of KBr, 0.2 mol
of NaCl and 0.0015 mol of KI and dissolved. To the solution 700 ml of a 1 mol/ℓ silver
nitrate aqueous solution were added at 60°C over a period of 20 min, followed by effecting
physical ripening for 20 min. The emulsion was washed with water to remove water-soluble
halides, then 20 g of gelatin were added thereto, and thereafter water was added thereto
to make the total volume 1,200 ml. Thus, an emulsion of 0.4 µm in average grain size
was obtained. The emulsion was washed with water and desalted to obtain internal latent
image type silver halide emulsion B.
Emulsion C
[0102] 30 g of gelatin were added to 1 l of a solution containing 0.5 mol of KBr, 0.2 mol
of NaCl and 0.0015 mol of KI and dissolved. To the solution 700 ml of a 1 mol/ℓ silver
nitrate aqueous solution were added at 60°C over a period of 20 min, followed by effecting
physical ripening for 20 min. The emulsion was washed with water to remove water-soluble
halides, then 20 g of gelatin were added thereto, and thereafter water was added thereto
to make the total volume 1,200 ml. Thus, an emulsion of 0.4 µm in average grain size
was obtained. To 300 ml of the emulsion were added simultaneously 500 ml of a 1 mol/ℓ
silver nitrate aqueous solution and 500 ml of a 2 mol/ℓ sodium chloride aqueous solution
at 60°C to precipitate silver chloride shells, followed by washing with water. Thus,
silver halide emulsion C of 0.7 µm in average grain size was obtained.
Emulsion D
[0103] An aqueous solution of potassium bromide and an aqueous solution of silver nitrate
were simultaneously added to a gelatin aqueous solution under vigorous stirring at
75°C over a period of 40 min to obtain a monodispersed silver bromide emulsion containing
octahedral grains of 0.4 µm in average grain size. Four mg of sodium thiosulfate and
4 mg of chloroauric acid (4 hydrate) were added to this emulsion per mol of silver,
followed by heating at 75°C for 80 min to effect chemical sensitization. The thus
obtained silver bromide grains were used as cores, and were allowed to further grow
by adding a 2 mol/ℓ sodium chloride aqueous solution and a 1 mol/ℓ silver nitrate
aqueous solution at 75°C for 40 min to obtain a cubic core/shell silver chlorobromide
emulsion of 0.6 µm in average grain size (coefficient of variation: 15%). After washing
with water and desalting of the emulsion, 0.5 mg of sodium thiosulfate were added
thereto per mol of silver, then heated at 55°C for 60 min to effect chemical sensitization,
whereby silver halide emulsion D was obtained.
Emulsion E
[0104] An aqueous solution of potassium bromide and an aqueous solution of silver nitrate
were simultaneously added to a gelatin aqueous solution under vigorous stirring at
75°C over a period of 90 min to obtain a silver bromide emulsion containing octahedral
grains of 0.8 µm in average grain size (core grains). In the above procedure, before
the precipitation of the silver halide grains of the emulsion 0.65 g of 3,4-dimethyl-1,3-thiazoline-2-thione
were added to the aqueous gelatin solution and the pH and the pAg were maintained
at 6 and 8.7, respectively, during the precipitation step. To the silver bromide emulsion
3.4 mg of sodium thiosulfate and 3.4 mg of potassium chloroaurate per mol of silver
were added to effect chemical sensitization. The thus obtained chemically sensitized
grains were allowed to further grow in the same precipitating environment as the core
grain formation to finally obtain an octahedral core/shell silver bromide emulsion
of 1.2 µm in average grain size. Then, 9.6 x 10⁻⁴ mol of potassium iodide and 4.2
x 10⁻² g of an N-vinylpyrrolidone polymer (weight-average molecular weight : 38,000)
were added to the emulsion per mol of silver to obtain silver halide emulsion E.
Emulsion F
[0105] An aqueous solution of potassium bromide and an aqueous solution of silver nitrate
were simultaneously added to a gelatin aqueous solution under vigorous stirring at
75°C over a period of 60 min to obtain a silver bromide emulsion. Before precipitation,
100 mg of 3,4-dimethyl-1,3-thiazoline-2-thione and 15 g of benzimidazole per mol of
silver were added to a precipitation tank. After the completion of precipitation,
crystals of 1.1 µm in average grain size were obtained. Then, 5.4 mg of sodium thiosulfate
and 3.9 mg of potassium chloroaurate were added to the emulsion per mol of silver,
followed by heating at 75°C for 80 min to effect chemical sensitization. To the thus
chemically sensitized core emulsion an aqueous solution of potassium bromide and an
aqueous solution of silver nitrate were added simultaneously over a period of 40 min
in the same manner as the first step to finally prepare a core/shell silver halide
emulsion of 1.5 µm in average grain size. Then, 0.32 mg of sodium thiosulfate and
57 mg of poly(N-vinylpyrrolidone) (weight-average molecular weight : 38,000) were
added to the core/shell emulsion per mol of silver, followed by heating at 60°C for
60 min to effect chemical sensitization on the surfaces of grains, whereby silver
halide emulsion F was obtained.
Emulsion G
[0106] An aqueous solution of potassium bromide and an aqueous solution of silver nitrate
were simultaneously added to a gelatin aqueous solution containing potassium bromide
under vigorous stirring at 75°C over a period of about 60 min to obtain a silver bromide
emulsion. Before precipitation (before the simultaneous addition), 150 mg of 3,4-dimethyl-1,3-thiazoline-2-thione
as a silver halide solvent and 15 g of benzimidazole per mol of silver were added
to the aqueous gelatin solution. After the completion of precipitation, uniform grain
size octahedral silver bromide crystals of 0.8 µm in average grain size were obtained.
Then, 4.8 mg of sodium thiosulfate and 2.4 mg of potassium chloroaurate were added
to the silver bromide emulsion per mol of silver, followed by heating at 75°C for
80 min to effect chemical sensitization. To the thus chemically sensitized inner nucleus
(core) silver bromide emulsion an aqueous solution of potassium bromide and an aqueous
solution of silver nitrate were added simultaneously over a period of 45 min in the
same manner as the first step to precipitate an internal latent image type core/shell
emulsion. To the emulsion 2.5 g of hydrogen peroxide per mol of silver were added
as an oxidizing agent, the emulsion was heated at 75°C for 8 min and then washed with
water to obtain an emulsion of 1.0 µm in average grain size (coefficient of variation
: 12%). Then, 0.75 mg of sodium thiosulfate and 20 mg of poly(N-vinylpyrrolidone)
per mol of silver were added to the internal latent image type core/shell silver bromide
emulsion, followed by heating at 60°C for 60 min to effect chemical sensitization
(ripening) on the surfaces of the grains, whereby silver halide emulsion G was obtained.
Emulsion H
[0107] An aqueous solution of potassium bromide and an aqueous solution of silver nitrate
were simultaneously added to a gelatin aqueous solution containing 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione
per mol of silver under vigorous stirring at 75°C over a period of 20 min to obtain
a monodispersed silver bromide emulsion containing octahedral grains of 0.4 µm in
average grain size. 6 mg of sodium thiosulfate and 6 mg of chloroauric acid (4 hydrate)
were added to the emulsion per mol of silver, followed by heating at 75°C for 80 min
to effect chemical sensitization. The thus obtained silver bromide grains were used
as cores, and were allowed to further grow in the same precipitating environment as
the first step for 40 min to finally obtain an octahedral monodispersed core/shell
silver bromide emulsion of 0.7 µm in average grain size. After washing with water
and desalting of the emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric
acid (4 hydrate) were added thereto per mol of silver, followed by heating at 60°C
for 60 min to effect chemical sensitization. Thus, internal latent image type silver
halide emulsion H was obtained.
II) Preparation of Direct Positive Color Photographic Printing Paper
[0108] Using core/shell type direct positive emulsions A to H as described above, layers
were coated on a reflective support composed of a vinyl chloride resin containing
white pigments provided with subbing treatment as used in Example 1 to prepare a multilayer
direct positive color photographic printing paper having the layer structure shown
in Table 4 below. Coating solutions were prepared in the following manner.
Preparation of Coating Solution for First Layer
[0109] 10 ml of ethyl acetate and 4 ml of solvent (c) were added to 6.4 g of Cyan Coupler
(a) and 2.3 g of Color image stabilizer (b) to dissolve them, and the resulting solution
was emulsified and dispersed in 90 ml of a 10% gelatin aqueous solution containing
5 ml of a 10% aqueous sodium dodecylbenzenesulfonate solution. On the other hand,
2.0 x 10⁻⁴ mol of a red-sensitizing dye shown below were added per mol of silver halide
to the aforesaid silver halide emulsion (containing 70 g of silver/kg) to prepare
90 g of a red-sensitive emulsion. The emulsified dispersion and the emulsion were
mixed and dissolved, followed by adjusting the concentration of the dissolved mixture
by the addition of gelatin so as to obtain the composition as shown in Table 4 below.
Further, 30 mg of Nucleating agent (n) and 5 x 10⁻⁴ mol of Nucleation accelerating
agent (o) were added thereto per mol of silver to prepare a coating solution for the
first layer.
Blue-Sensitive Emulsion Layer:
[0111]
Green-Sensitive Emulsion Layer:
[0112]
Red-Sensitive Emulsion Layer:
[0113]
The following dyes were employed as irradiation preventing dyes in the emulsion
layers, respectively.
Green-Sensitive Emulsion Layer:
[0114]
Red-Sensitive Emulsion Layer:
[0115]
The chemical structures of the compounds such as couplers employed in this example
are shown below.
Yellow couper (k)
[0116]
Color image stabilizer (ℓ)
[0117]
Solvent (m)
[0118]
Development controlling agent (x)
[0119]
Nucleating gent (n)
[0120]
Nucleation accelerating agent (o)
[0121]
Color mixing preventing agent (d)
[0122]
Magenta coupler (e)
[0123]
Color image stabilizer (f)
[0124]
Solvent (g)
[0125] a mixture (2:1 by weight ratio) of
UV ray absorbent (h)
[0126] a mixture (1:5:3 by molar ratio) of
Color mixing preventing agent (i)
[0127]
Solvent (j)
[0128]
Cyan coupler (a)
[0129] a mixture (1:1 by molar ratio) of
Color image stabilizer (b)
[0130] a mixture (1:3:3 by molar ratio) of
and
Solvent (c)
[0131]
After adjusting the balance of surface tension and viscosity thereof simultaneously
the coating solutions for the first layer to the seventh layer were coated on the
support to prepare the multilayer silver halide direct positive color photographic
printing papers A to H.
III) Development Processing
[0132] The direct positive color photographic printing papers A to H thus prepared were
imagewise exposed at color temperature of 4,800°K in an amount of 100 CMS at 1/10
second and then subjected to Processing Step A (pH of the color developing solution:
10.2) shown below and Processing Step B (same a Processing Step A except adjusting
the pH of the color developing solution to 11.0), respectively. Direct positive color
photographic prints having excellent sharpness and no irregularity of image density
were obtained.
Processing Step A:
[0133]
Step |
Time |
Temperature |
Color Development |
2 min 30 s |
38°C |
Bleach-fixing |
40 s |
38°C |
Stabilizing (1) |
20 s |
38°C |
Stabilizing (2) |
20 s |
38°C |
Stabilizing (3) |
20 s |
38°C |
[0134] The stabilizing baths were replenished according to a so-called countercurrent replenishing
system of adding the replenisher to the stabilizing bath (3), introducing the overflow
from the stabilizing bath (3) into the stabilizing bath (2), and the overflow from
the stabilizing bath (2) into the stabilizing bath (1).
[0135] The composition of each processing solution used in the above described processing
steps is as follows:
Color Developing Solution: |
Mother Solution |
Diethylenetriaminepentaacetic acid |
2.0 g |
Benzyl alcohol |
12.8 g |
Diethylene glycol |
3.4 g |
Sodium sulfite |
2.0 g |
Sodium bromide |
0.26 g |
Hydroxylamine sulfate |
2.60 g |
Sodium chloride |
3.20 g |
3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline |
4.25 g |
Potassium carbonate |
30.0 g |
Brightening agent (stilbene type) |
1.0 g |
Water to make |
1,000 ml |
pH |
10.20 |
[0136] The pH was adjusted with potassium hydroxide or hydrochloric acid.
Bleach-Fixing Solution: |
Mother Solution |
Ammonium thiosulfate |
110 g |
Sodium hydrogensulfite |
10 g |
Ammonium iron (III) diethylenetriaminepentaacetate monohydrate |
56 g |
Disodium ethylenediaminetetraacetate dihydrate |
5 g |
2-Mercapto-1,3,4-triazole |
0.4 g |
Water to make |
1,000 ml |
pH |
6.5 |
[0137] The pH was adjusted with aqueous ammonia or hydrochloric acid.
Stabilizing solution: |
Mother Solution |
1-Hydroxyethylidene-1,1'-di phosphonic acid (60%) |
1.6 ml |
Bismuth chloride |
0.35 g |
Polyvinylpyrrolidone |
0.25 g |
Aqueous ammonia |
2.5 ml |
Trisodium nitrilotriacetate |
1.0 g |
5-Chloro-2-methyl-4-isothiazolin3-one |
50 mg |
2-Octyl-4-isothiazolin-3-one |
50 mg |
Brightening agent (4,4'-diamino-stilbene type) |
1.0 g |
Water to make |
1,000 ml |
pH |
7.5 |
[0138] The pH was adjusted with potassium hydroxide or hydrochloric acid.
EXAMPLE 4
[0139] The first layer to the eleventh layer as described in Example 1 of Japanese Patent
Application (OPI) No. 174760/87, pages 18, upper half portion in the right-hand column
to page 21, lower half portion in the right-hand column were coated on a reflective
support composed of a vinyl chloride resin containing white pigments provided with
subbing treatment in place of the first layer to the seventh layer to prepare a reversal
color photographic light-sensitive material. The color photographic material was processed
according to the prescribed development processing steps. A reversal color photographic
print having excellent sharpness and no irregularity of image density was obtained.
1. A silver halide color photographic material comprising a reflective support composed
of a vinyl chloride resin containing a white pigment and having thereon in an appropriate
order at least one red-sensitive silver halide emulsion layer containing a cyan color
forming coupler represented by the general formula (1) or (2) shown below, at least
one green-sensitive silver halide emulsion layer containing a magenta color forming
coupler represented by the general formula (3) or (4) shown below, and at least one
blue-sensitive silver halide emulsion layer containing a yellow color forming coupler
represented by the general formula (5) shown below
wherein R₁, R₄ and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic
group, an aromatic amino group or a heterocyclic amino group; R₂ represents an aliphatic
group; R₃ and R₆ each represents a hydrogen atom, a halogen atom, an aliphatic group,
an aliphatic oxy group or an acylamino group; R₇ and R₈ each represents a substituted
or unsubstituted phenyl group; R₉ represents a hydrogen atom or a substituent; R₂
and R₃ or R₅ and R₆ may be connected with each other to form a 5-membered to 7-membered
ring; Q represents a substituted or unsubstituted N-phenylcarbamoyl group; Za and
Zb, which may be the same or different, each represents a group of -CH=, a group of
or a group of -N=; R₁₀ represents the same substituent as that represented by R₉;
and X₁, X₂, X₃, X₄ and X₅ each represents a hydrogen atom or a group capable of being
released upon a reaction with an oxidation product of an aromatic primary amine developing
agent.
2. A silver halide color photographic material as claimed in Claim 1, wherein X₁ and
X₂ each represents a chlorine atom, X₃ and X₄ each represents a hydrogen atom or a
group capable of being released containing a sulfur atom as a releasing atom; and
X₅ represents a group capable of being released containing an oxygen atom or a nitrogen
atom as a releasing atom.
3. A silver halide color photographic material as claimed in Claim 1, wherein the vinyl
chloride resin is a copolymer containing a vinyl chloride monomer.
4. A silver halide color photographic material as claimed in Claim 3, wherein the vinyl
chloride monomer occupies at least 50% by weight of the total monomer component.
5. A silver halide color photographic material as claimed in Claim 3, wherein a comonomer
component is selected from methyl methacrylate, fluorinated olefin, a vinyl ether,
vinyl bromide, vinyl acetate, maleic acid, dichlorobutadiene, vinyl fluoride, vinylidene
fluoride, trifluorochloroethylene, tetrafluoroethylene, vinylidene chloride, acrylonitrile,
styrene, butadiene, and chloroprene.
6. A sliver halide color photographic material as claimed in Claim 1, wherein the white
pigment is selected from titanium white, zinc white, calcium carbonate, barium sulfate,
white lead, white organic pigments and dyes, and brightening agents.
7. A silver halide color photographic material as claimed in Claim 1, wherein the total
amount of the white pigment added is from 1 part by weight to 30 parts by weight per
100 parts by weight of the vinyl chloride resin material.
8. A silver halide color photographic material as claimed in Claim 1, wherein an average
reflectivity of the reflective support in a visible range is from 80 to 98%.
9. A silver halide color photographic material as claimed in Claim 1, wherein the thickness
of the reflective support is from 50 µm to 500 µm.
10. A silver halide color photographic material as claimed in Claim 1, wherein a surface
of the reflective support to which a hydrophilic colloid layer is applied is subjected
to subbing treatment.
11. A silver halide color photographic material as claimed in Claim 1, wherein the color
photographic material further comprises a development inhibitor releasing compound.
12. A silver halide color photographic material as claimed in Claim 1, wherein a silver
halide emulsion used in the silver halide emulsion layers is a mono-dispersed silver
halide emulsion.
13. A color photographic print comprising a reflective support composed of a vinyl chloride
resin containing a white pigment and having thereon in an appropriate order at least
one emulsion layer containing a cyan dye obtained by a reaction of a cyan color forming
coupler represented by the general formula (1) or (2) shown below with an oxidation
product of an aromatic primary amine developing agent, at least one emulsion layer
containing a magenta dye obtained by a reaction of a magenta color forming coupler
represented by the general formula (3) or (4) shown below with an oxidation product
of an aromatic primary amine developing agent, and at least one emulsion layer containing
a yellow dye obtained by a reaction of a yellow color forming coupler represented
by the general formula (5) shown below with an oxidation product of an aromatic primary
amine developing agent
wherein R₁, R₄ and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic
group, an aromatic amino group or a heterocyclic amino group; R₂ represents an aliphatic
group; R₃ and R₆ each represents a hydrogen atom, a halogen atom, an aliphatic group,
an aliphatic oxy group or an acylamino group; R₇ and R₈ each represents a substituted
or unsubstituted phenyl group; R₉ represents a hydrogen atom or a substituent; R₂
and R₃ or R₅ and R₆ may be connected with each other to form a 5-membered to 7-membered
ring; Q represents a substituted or unsubstituted N-phenylcarbamoyl group; Za and
Zb, which may be the same or different, each represents a group of -CH=, a group of
or a group of -N=; R₁₀ represents the same substituent as that represented by R₉;
and X₁, X₂, X₃, X₄ and X₅ each represents a hydrogen atom or a group capable of being
released upon a reaction with an oxidation product of an aromatic primary amine developing
agent.
14. A color photographic print as claimed in Claim 13, wherein the yellow dye is a dye
represented by the following general formula (5-1):
wherein R₁₄ and R₁₅, which may be the same or different, each represents a hydrogen
atom or a substituent which is ordinarily used for a yellow coupler, provided that
both R₁₄ and R₁₅ are not hydrogen atoms at the same time; and
represents a coupling residue of an aromatic primary amine developing agent.
15. A color photographic print as claimed in Claim 14, wherein the substituent represented
by R₁₄ or R₁₅ is selected from an alkyl group, an alkenyl group, an alkoxy group,
an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group, an aliphatic amido
group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an
alkyl-substituted succinimido group, an aryloxy group, an aryloxycarbonyl group, an
arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide
group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano
group and a thiocyano group.
16. A color photographic print as claimed in Claim 14, weherein
represents a coupling residue of a phenylenediamine derivative represented by the
following general formula (6):
wherein R₁₁ and R₁₂ each represents a substituted or unsubstituted alkyl group; and
R₁₃ represents one to four hydrogen atoms or one to four substituents.
17. A color photographic print as claimed in Claim 16, wherein a substituent for the substituted
alkyl group represented by R₁₁ or R₁₂ is selected from a hydroxy group, an alkylsulfonamido
group and an alkoxy group, and the substituent represented by R₁₃ is an alkyl group.
18. A color photographic print as claimed in Claim 13, wherein the magenta dye is a dye
represented by the following general formula (4-1) or (4-2):
wherein R₁₆ and R₁₇, which may be the same or different, each represents a hydrogen
atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano
group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group,
a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an
anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino
group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino
group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl
group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group
or an aryloxycarbonyl group, or R₁₆ or R₁₇ may be a divalent group to form a bis compound
or a linking group to form a polymer dye, and
represents a coupling residue of an aromatic primary amine developing agent.
19. A color photographic print as claimed in Claim 18, wherein the linking group is connected
to a vinyl group from which the polymer is formed.
20. A color photographic print as claimed in Claim 13, wherein the cyan dye is composed
of two or more dyes formed from two or more cyan color forming couplers represented
by the general formula (1) or (2).
21. A color photographic print as claimed in Claim 13, wherein the dyes are used in combination
with one or more kinds of organic solvents having a high boiling point of at least
160°C represented by the following general formula (7), (8), (9), (10) or (11):
W₁ - COO - W₂ (8)
W₁ - O - W₂ (11)
wherein W₁, W₂ and W₃ each represents a substituted or unsubstituted alkyl group,
a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl
group, a substituted or unsubstituted aryl group or a substituted or unsubstituted
heterocyclic group; W₄ represents W₁, -O-W₁ or -S-W₁; n represents an integer from
1 to 5, when n is two or more, two or more W₄'s may be the same or different; and
W₁ and W₂ in the general formula (11) may be connected with each other to form a condensed
ring.
22. A color photographic print as claimed in Claim 13, wherein the dyes are used in combination
with one or more kinds of water-insoluble, organic solvent-soluble polymers.
23. A color photographic print as claimed in Claim 13, wherein the dyes are used in combination
with one or more kinds of color fading preventing agents or antioxidants represented
by the following general formula (12) or (13):
wherein R₂₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a
heterocyclic group or a hydrolyzable protective group; R₂₁, R₂₂, R₂₃, R₂₄ and R₂₅,
which may be the same or different, each represents a hydrogen atom or a substituent;
R₃₀ represents a hydrogen atom, an aliphatic group, an acyl group, a sulfonyl group,
a sulfinyl group, an oxy radical group or a hydroxy group; A represents a non-metallic
atomic group necessary to form a 5-membered, 6-membered or 7-membered ring; and R₂₆,
R₂₇, R₂₈ and R₂₉, which may be the same or different, each represents a hydrogen atom
or an alkyl group, or R₂₀ and R₂₁ or two of R₂₁, R₂₂, R₂₃, R₂₄ and R₂₅ which are present
in ortho-positions with respect to each other may be connected with each other to
form a 5-membered, 6-membered or 7-membered ring, or R₂₆ and R₂₇, R₂₈ and R₂₉ or R₃₀
and R₂₆ may be connected with each other to form a 5-membered, 6-membered or 7-membered
ring.
24. A color photographic print prepared by conducting at least a step of processing the
silver halide color photographic material as claimed in Claim 1, after imagewise exposure,
with a color developing solution containing an aromatic primary amine color developing
agent.
25. A color photographic print prepared by adhering a color photographic print obtained
by conducting at least a step of processing the silver halide color photographic material
as claimed in Claim 1 except using a transparent support instead of the reflective
support, after imagewise exposure, with a color developing solution containing an
aromatic primary amine color developing agent, on a reflective support composed of
a vinyl chloride resin containing a white pigment.
1. Farbphotographisches Silberhalogenidmaterial, umfassend einen reflektiven Träger,
zusammengesetzt aus einem Vinylchloridharz, das ein weißes Pigment enhält, und darauf
in geeigneter Reihenfolge mindestens eine rotempfindliche Silberhalogenidemulsionsschicht,
enthaltend einen einen Cyanfarbstoff bildenden Kuppler, dargestellt durch die nachstehend
gezeigte allgemeine Formel (1) oder (2), mindestens eine grünempfindliche Silberhalogenidemulsionsschicht,
enthaltend einen einen Magentafarbstoff bildenden Kuppler, dargestellt durch die nachstehend
gezeigte allgemeine Formel (3) oder (4), und mindestens eine blauempfindliche Silberhalogenidemulsionsschicht,
enthaltend einen einen gelben Farbstoff bildenden Kuppler, dargestellt durch die nachstehend
gezeigte allgemeine Formel (5), aufweist:
worin R₁, R₄ und R₅ jeweils eine aliphatische Gruppe, eine aromatische Gruppe, eine
heterocyclische Gruppe, eine aromatische Aminogruppe oder eine heterocyclische Aminogruppe
darstellen; R₂ eine aliphatische Gruppe darstellt; R₃ und R₆ jeweils ein Wasserstoffatom,
ein Halogenatom, eine aliphatische Gruppe, eine aliphatische Oxygruppe oder eine Acylaminogruppe
darstellen; R₇ und R₈ jeweils eine substituierte oder unsubstituierte Phenylgruppe
darstellen; R₉ ein Wasserstoffatom oder einen Substituenten darstellt; R₂ und R₃ oder
R₅ und R₆ miteinander verbunden sein können, um einen fünfgliedrigen bis siebengliedrigen
Ring zu bilden; Q eine substituierte oder unsubstituierte N-Phenylcarbamoylgruppe
darstellt; Za und Zb, die gleich oder verschieden sein können, jeweils eine Gruppe
aus -CH=, eine Gruppe aus
oder eine Gruppe aus -N= darstellen; R₁₀ den gleichen Substituenten, wie durch R₉
dargestellt, darstellt; und X₁, X₂, X₃, X₄ und X₅ jeweils ein Wasserstoffatom oder
eine Gruppe darstellen, die fähig ist, durch eine Reaktion mit einem Oxidationsprodukt
eines aromatischen primären Aminentwicklungsmittels freigesetzt zu werden.
2. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei X₁ und X₂ jeweils
ein Chloratom darstellen, X₃ und X₄ jeweils ein Wasserstoffatom oder eine Gruppe darstellen,
die fähig ist, freigesetzt zu werden, enthaltend ein Schwefelatom als freisetzendes
Atom; und X₅ eine Gruppe darstellt, die fähig ist, freigesetzt zu werden, enthaltend
ein Wasserstoffatom oder ein Stickstoffatom als ein freisetzendes Atom.
3. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei das Vinylchloridharz
ein Copolymer, enthaltend ein Vinylchloridmonomer, ist.
4. Farbphotographisches Silberhalogenidmaterial nach Anspruch 3, wobei das Vinylchloridmonomer
mindestens 50 Gew.-% des gesamten Monomerbestandteils einnimmt.
5. Farbphotographisches Silberhalogenidmaterial nach Anspruch 3, wobei ein Comonomerbestandteil
ausgewählt ist aus Methylmethacrylat, fluoriertem Olefin, einem Vinylether, Vinylbromid,
Vinylacetat, Maleinsäure, Dichlorbutadien, Vinylfluorid, Vinylidenfluorid, Trifluorchlorethylen,
Tetrafluorethylen, Vinylidenchlorid, Acrylonitril, Styrol, Butadien und Chloropren.
6. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei das weiße Pigment
ausgewählt ist aus Titanweiß, Zinkweiß, Calciumcarbonat, Bariumsulfat, Bleiweiß, weißen
organischen Pigmenten und Farbstoffen und Aufhellern.
7. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei die Gesamtmenge
des weißen Pigments, die zugefügt wird, 1 Gewichtsteil bis 30 Gewichtsteile pro 100
Gewichtsteile des Vinylchloridharz-Materials ist.
8. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei ein durchschnittlicher
Reflexionsgrad des reflektiven Trägers in einem sichtbaren Bereich von 80 bis 98%
beträgt.
9. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei die Dicke des
reflektiven Trägers von 50 µm bis 500 µm beträgt.
10. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei eine Oberfläche
des reflektiven Trägers, auf die eine hydrophile Kolloidschicht aufgetragen wird,
einer Vorbehandlung ausgesetzt wird.
11. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei das farbphotographische
Material weiterhin eine einen Entwicklungsinhibitor freisetzende Verbindung umfaßt.
12. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, wobei eine Silberhalogenidemulsion,
die in den Silberhalogenidemulsionsschichten verwendet wird, eine monodisperse Silberhalogenidemulsion
ist.
13. Farbphotographischer Abzug, umfassend einen reflektiven Träger, zusammengesetzt aus
einem Vinylchloridharz, enthaltend ein weißes Pigment, mit darauf in einer geeigneten
Reihenfolge mindestens einer Emulsionsschicht, enthaltend einen Cyanfarbstoff, erhalten
durch eine Reaktion eines einen Cyanfarbstoff bildenden Kupplers, dargestellt durch
die nachstehend gezeigte allgemeine Formel (1) oder (2), mit einem Oxidationsprodukt
eines aromatischen primären Aminentwicklungsmittels, mindestens einer Emulsionsschicht,
enthaltend einen Magentafarbstoff, erhalten durch eine Reaktion eines einen Magentafarbstoff
bildenden Kupplers, dargestellt durch die nachstehend gezeigte allgemeine Formel (3)
oder (4), mit einem Oxidationsprodukt eines aromatischen, primären Aminentwicklungsmittels,
und mindestens einer Emulsionsschicht, enthaltend einen gelben Farbstoff, erhalten
durch eine Reaktion eines einen gelben Farbstoff bildenden Kupplers, dargestellt durch
die nachstehend gezeigte allgemeine Formel (5), mit einem Oxidationsprodukt eines
aromatischen, primären Aminentwicklungsmittels:
worin R₁, R₄ und R₅ jeweils eine aliphatische Gruppe, eine aromatische Gruppe, eine
heterocyclische Gruppe, eine aromatische Aminogruppe oder eine heterocyclische Aminogruppe
darstellen; R₂ eine aliphatische Gruppe darstellt; R₃ und R₆ jeweils ein Wasserstoffatom,
ein Halogenatom, eine aliphatische Gruppe eine aliphatische Oxygruppe oder eine Acylaminogruppe
darstellen; R₇ und R₈ jeweils eine substituierte oder unsubstituierte Phenylgruppe
darstellen; R₉ ein Wasserstoffatom oder einen Substituenten darstellt; R₂ und R₃ oder
R₅ und R₆ miteinander verbunden sein können, um einen fünfgliedrigen bis siebengliedrigen
Ring zu bilden; Q eine substituierte oder unsubstituierte N-Phenylcarbamoylgruppe
darstellt; Za und Zb, die gleich oder verschieden sein können, jeweils eine Gruppe
aus -CH=, eine Gruppe aus
oder eine Gruppe aus -N= darstellen; R₁₀ den gleichen Substituenten, wie durch R₉
dargestellt, darstellt; und X₁, X₂, X₃, X₄ und X₅ jeweils ein Wasserstoffatom oder
eine Gruppe darstellen, die fähig ist, durch eine Reaktion mit einem Oxidationsprodukt
eines aromatischen primären Aminentwicklungsmittels freigesetzt zu werden.
14. Farbphotographischer Abzug nach Anspruch 13, wobei der gelbe Farbstoff ein Farbstoff,
dargestellt durch die folgende allgemeine Formel (5-1):
ist, worin R₁₄ und R₁₅, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom
oder einen Substituenten darstellen, der normalerweise für einen Gelbkuppler verwendet
wird, mit der Maßgabe, daß R₁₄ und R₁₅ nicht beide gleichzeitig Wasserstoffatome sind;
und
einen Kupplungsrest eines aromatischen primären Aminentwicklungsmittels darstellt.
15. Farbphotographischer Abzug nach Anspruch 14, wobei der durch R₁₄ oder R₁₅ dargestellte
Substituent ausgewählt ist aus einer Alkylgruppe, einer Alkenylgruppe, einer Alkoxygruppe,
einer Alkoxycarbonylgruppe, einem Halogenatom, einer Alkoxycarbamoylgruppe, einer
aliphatischen Amidogruppe, einer Alkylsulfamoylgruppe, einer Alkylsulfonamidgruppe,
einer Alkylureidogruppe, einer alkylsubstituierten Succinimidogruppe, einer Aryloxygruppe,
einer Aryloxycarbonylgruppe, einer Arylcarbamoylgruppe, einer Arylamidogruppe, einer
Arylsulfamoylgruppe, einer Arylsulfonamidgruppe, einer Arylureidogruppe, einer Carboxylgruppe,
einer Sulfogruppe, einer Nitrogruppe, einer Cyanogruppe und einer Thiocyanogruppe.
16. Farbphotographischer Abzug nach Anspruch 14, worin
einen Kupplungsrest eines Phenylendiaminderivates, dargestellt durch die folgende
allgemeine Formel (6):
darstellt, worin R₁₁ und R₁₂ jeweils eine substituierte oder unsubstituierte Alkylgruppe
darstellen; und R₁₃ 1 bis 4 Wasserstoffatome oder 1 bis 4 Substituenten darstellt.
17. Farbphotographischer Abzug nach Anspruch 16, wobei ein Substituent für die substituierte
Alkylgruppe, dargestellt durch R₁₁ oder R₁₂, ausgewählt ist aus einer Hydroxylgruppe,
einer Alkylsulfonamidogruppe und einer Alkoxygruppe, und der Substituent, dargestellt
durch R₁₃, eine Alkylgruppe ist.
18. Farbphotographischer Abzug nach Anspruch 13, wobei der Magentafarbstoff ein Farbstoff,
dargestellt durch die folgende allgemeine Formel (4-1) oder (4-2):
ist, worin R₁₆ und R₁₇, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom,
ein Halogenatom, eine Alkylgruppe, eine Arylgruppe, eine heterocyclische Gruppe, eine
Cyanogruppe, eine Alkoxygruppe, eine Aryloxygruppe, eine heterocyclische Oxygruppe,
eine Acyloxygruppe, eine Carbamoyloxygruppe, eine Silyloxygruppe, eine Sulfonyloxygruppe,
eine Acylaminogruppe, eine Anilinogruppe, eine Ureidogruppe, eine Imidogruppe, eine
Sulfamoylaminogruppe, eine Carbamoylaminogruppe, eine Alkylthiogruppe, eine Arylthiogruppe,
eine heterocyclische Thiogruppe, eine Alkoxycarbonylaminogruppe, eine Aryloxycarbonylaminogruppe,
eine Sulfonamidogruppe, eine Carbamoylgruppe, eine Acylgruppe, eine Sulfamoylgruppe,
eine Sulfonylgruppe, eine Sulfinylgruppe, eine Alkoxycarbonylgruppe oder eine Aryloxycarbonylgruppe
darstellen, oder R₁₆ und R₁₇ eine zweiwertige Gruppe sein können, um eine Bisverbindung
oder eine verbindende Gruppe zu bilden, um einen Polymerfarbstoff zu bilden, und
einen Kupplungsrest eines aromatischen, primären Aminentwicklungsmittels darstellt.
19. Farbphotographischer Abzug nach Anspruch 18, wobei die verbindende Gruppe mit einer
Vinylgruppe verbunden ist, woraus das Polymer gebildet wird.
20. Farbphotographischer Abzug nach Anspruch 13, wobei der Cyanfarbstoff aus zwei oder
mehreren Farbstoffen, gebildet aus zwei oder mehreren Cyanfarbstoff bildenden Kupplern,
dargestellt durch die allgemeine Formel (1) oder (2), zusammengesetzt ist.
21. Farbphotographischer Abzug nach Anspruch 13, wobei die Farbstoffe in Kombination mit
einem oder mehreren Arten organischer Lösungsmittel mit einem hohen Siedepunkt von
mindestens 160°C, dargestellt durch die folgende allgemeine Formel (7), (8), (9),
(10) oder (11):
W₁ - COO - W₂ (8)
W₁ - O - W₂ (11)
verwendet werden, worin W₁, W₂ und W₃ jeweils eine substituierte oder unsubstituierte
Alkylgruppe, eine substituierte oder unsubstituierte Cycloalkylgruppe, eine substituierte
oder unsubstituierte Alkenylgruppe, eine substituierte oder Arylgruppe oder eine substituierte
oder unsubstituierte heterocyclische Gruppe darstellen; W₄ W₁, -O-W₁ oder -S-W₁ darstellt;
n eine ganze Zahl von 1 bis 5 darstellt, wenn n zwei oder mehr ist, zwei oder mehr
W₄ gleich oder verschieden sein können; und W₁ und W₂ in der allgemeinen Formel (11)
miteinander verbunden sein können, um einen kondensierten Ring zu bilden.
22. Farbphotographischer Abzug nach Anspruch 13, wobei die Farbstoffe in Kombination mit
einem oder mehreren Arten wasserunlöslicher, in organischem Lösungsmittel löslicher
Polymere verwendet werden.
23. Farbphotographischer Abzug nach Anspruch 13, wobei die Farbstoffe in Kombination mit
einem oder mehreren Arten von Farbverblassung verhindernden Mittel(n) oder Antioxidanzien,
dargestellt durch die folgende allgemeine Formel (12) oder (13):
verwendet werden, worin R₂₀ ein Wasserstoffatom, eine aliphatische Gruppe, eine aromatische
Gruppe, eine heterocyclische Gruppe oder eine hydrolysierbare Schutzgruppe darstellt;
R₂₁, R₂₂, R₂₃, R₂₄ und R₂₅, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom
oder einen Substituenten darstellen; R₃₀ ein Wasserstoffatom, eine aliphatische Gruppe,
eine Acylgruppe, eine Sulfonylgruppe, eine Sulfinylgruppe, eine Oxyradikalgruppe oder
eine Hydroxylgruppe darstellen; A eine nichtmetallische Atomgruppe darstellt, die
für einen fünfgliedrigen, sechsgliedrigen oder siebengliedrigen Ring notwendig ist,
und R₂₆, R₂₇, R₂₈ und R₂₉, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom
oder eine Alkylgruppe darstellen, oder R₂₀ und R₂₁ oder zwei von R₂₁, R₂₂, R₂₃, R₂₄
und R₂₅, die in ortho-Position zueinander anwesend sind, miteinander verbunden sein
können, um einen fünfgliedrigen, sechsgliedrigen oder siebengliedrigen Ring zu bilden,
oder R₂₆ und R₂₇, R₂₈ und R₂₉ oder R₃₀ und R₂₆ miteinander verbunden sein können,
um einen fünfgliedrigen, sechsgliedrigen oder siebengliedrigen Ring zu bilden.
24. Farbphotographischer Abzug, hergestellt durch Durchführen von mindestens einer Behandlungsstufe
des farbphotographischen Silberhalogenidmaterials nach Anspruch 1 mit einer Farbentwicklungslösung,
enthaltend ein aromatisches, primäres Aminfarbentwicklungsmittel, nach bildweiser
Belichtung.
25. Farbphotographischer Abzug, hergestellt durch Festmachen eines farbphotographischen
Abzugs, erhalten durch Durchführen von mindestens einer Behandlungsstufe des farbphotographischen
Silberhalogenidmaterials nach Anspruch 1, ausgenommen das Verwenden eines transparenten
Trägers anstelle eines reflektiven Trägers, mit einer Farbentwicklungslösung, enthaltend
ein aromatisches, primäres Aminfarbentwicklungsmittel, auf einem reflektiven Träger,
zusammengesetzt aus einem Vinylchloridharz, enthaltend ein weißes Pigment.
1. Matériau photographique couleur à l'halogénure d'argent comprenant un support réfléchissant
constitué d'une résine de chlorure de vinyle contenant un pigment blanc et sur lequel
sont disposées dans un ordre approprié au moins une couche d'émulsion d'halogénure
d'argent sensible au rouge contenant un coupleur chromogène cyan représenté par la
formule générale (1) ou (2) représentées ci-dessous, au moins une couche d'émulsion
d'halogénure d'argent sensible au vert contenant un coupleur chromogène magenta représenté
par la formule générale (3) ou (4) représentées ci-dessous, et au moins une couche
d'émulsion d'halogénure d'argent sensible au bleu contenant un coupleur chromogène
jaune représenté par la formule générale (5) représentée ci-dessous :
dans lesquelles R₁, R₄ et R₅ représentent chacun un groupement aliphatique, un groupement
aromatique, un groupement hétérocyclique, un groupement amino aromatique ou un groupement
amino hétérocyclique ; R₂ représente un groupement aliphatique ; R₃ et R₆ représentent
chacun un atome d'hydrogène, un atome d'halogène, un groupement aliphatique, un groupement
oxy aliphatique ou un groupement acylamino ; R₇ et R₈ représentent chacun un groupement
phényle substitué ou non substitué ; R₉ représente un atome d'hydrogène ou un substituant;
R₂ et R₃ ou R₅ et R₆ peuvent être reliés les uns aux autres de façon à former un cycle
comportant 5 à 7 chaînons ; Q représente un groupement N-phénylcarbamoyle substitué
ou non substitué ; Za et Zb, qui peuvent être identiques ou différents représentent
chacun un groupement -CH=, un groupement
ou un groupement -N= ; R₁₀ représente le même substituant que R₉ ; et X₁, X₂, X₃,
X₄ et X₅ représentent chacun un atome d'hydrogène ou un groupement capable d'être
libéré par réaction avec un produit d'oxydation d'un développateur de type amine aromatique
primaire.
2. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1,
dans lequel X₁ et X₂ représentent chacun un atome de chlore, X₃ et X₄ représentent
chacun un atome d'hydrogène ou un groupement capable d'être libéré contenant un atome
de soufre en tant qu'atome partant; et X₅ représente un groupement capable d'être
libéré contenant un atome d'oxygène ou un atome d'azote en tant qu'atome partant.
3. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1,
dans lequel la résine de chlorure de vinyle est un copolymère contenant un monomère
chlorure de vinyle.
4. Matériau photographique couleur à l'halogénure d'argent selon la revendication 3,
dans lequel le monomère chlorure de vinyle représente au moins 50 % en poids du composant
monomérique total.
5. Matériau photographique couleur à l'halogénure d'argent selon la revendication 3,
dans lequel le composant comonomère est choisi parmi les suivants : méthacrylate de
méthyle, oléfine fluorée, éther vinylique, bromure de vinyle, acétate de vinyle, acide
maléique, dichlorobutadiène, fluorure de vinyle, fluorure de vinylidène, trifluorochloroéthylène,
tétrafluoroéthylène, chlorure de vinylidène, acrylonitrile, styrène, butadiène et
chloroprène.
6. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1,
dans lequel le pigment blanc est choisi parmi les suivants : blanc de titane, blanc
de zinc, carbonate de calcium, sulfate de baryum, blanc de plomb, pigments et colorants
organiques blancs et agents de luminosité.
7. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1,
dans lequel la quantité totale du pigment blanc ajouté est comprise entre 1 partie
en poids et 30 parties en poids pour 100 parties en poids du produit constitué de
résine de chlorure de vinyle.
8. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1,
dans lequel le pouvoir réfléchissant moyen du support réfléchissant dans une gamme
visible est compris entre 80 et 98 %.
9. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1,
dans lequel l'épaisseur du support réfléchissant est comprise entre 50 µm et 500 µm.
10. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1,
dans lequel la surface du support réfléchissant sur laquelle est déposée une couche
de colloïde hydrophile est soumise à un traitement substratant.
11. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1,
dans lequel le matériau photographique couleur comprend de plus un composé libérant
un inhibiteur de développement.
12. Matériau photographique couleur à l'halogénure d'argent selon la revendication 1,
dans lequel l'émulsion d'halogénure d'argent utilisée dans les couches d'émulsion
d'halogénure d'argent est une émulsion d'halogénure d'argent monodispersée.
13. Epreuve photographique en couleur comprenant un support réfléchissant constitué d'une
résine de chlorure de vinyle contenant un pigment blanc et comportant, disposées sur
celui-ci dans un ordre approprié au moins une couche d'émulsion contenant un colorant
cyan obtenu par réaction d'un coupleur chromogène cyan représenté par la formule générale
(1) ou (2) représentées ci-dessous, avec un produit d'oxydation d'un développateur
de type amine aromatique primaire, au moins une couche d'émulsion contenant un colorant
magenta obtenu par réaction d'un coupleur chromogène magenta représenté par la formule
générale (3) ou (4) représentées ci-dessous, avec un produit d'oxydation d'un développateur
de type amine aromatique primaire, et au moins une couche d'émulsion contenant un
colorant jaune obtenu par réaction d'un coupleur chromogène jaune représenté par la
formule générale (5) représentée ci-dessus, avec un produit d'oxydation d'un développateur
de type amine aromatique primaire
dans lesquelles R₁, R₄ et R₅ représentent chacun un groupement aliphatique, un groupement
aromatique, un groupement hétérocyclique, un groupement amino aromatique ou un groupement
amino hétérocyclique ; R₂ représente un groupement aliphatique, R₃ et R₆ représentent
chacun un atome d'hydrogène, un atome d'halogène, un groupement aliphatique, un groupement
oxy aliphatique ou un groupement acylamino ; R₇ et R₈ représentent chacun un groupement
phényle substitué ou non substitué ; R₉ représente un atome d'hydrogène ou un substituant
; R₂ et R₃ ou R₅ et R₆ peuvent être liés les uns avec les autres pour former un cycle
comportant 5 à 7 chaînons ; Q représente un groupement N-phénylcarbamoyle substitué
ou non substitué ; Za et Zb, qui peuvent être identiques ou différents, représentent
chacun un groupement -CH=, un groupement
ou un groupement -N= ; R₁₀ représente le même substituant que R₉ ; et X₁, X₂, X₃,
X₄ et X₅ représentent chacun un atome d'hydrogène ou un groupement capable d'être
libéré par réaction avec un produit d'oxydation d'un développateur de type amine aromatique
primaire.
14. Epreuve photographique couleur selon la revendication 13, dans laquelle le colorant
jaune est un colorant représenté par la formule générale suivante (5-1):
dans laquelle R₁₄ et R₁₅, qui peuvent être identiques ou différents, représentent
chacun un atome d'hydrogène ou un substituant qui est utilisé de façon usuelle pour
un coupleur jaune, à condition que R₁₄ et R₁₅ ne représentent pas en même temps des
atomes d'hydrogène ; et
représente un résidu d'une réaction de couplage d'un développateur de type amine
aromatique primaire.
15. Epreuve photographique couleur selon la revendication 14, dans laquelle le substituant
représenté par R₁₄ ou R₁₅ est choisi parmi les suivants : groupements alkyle, alcényle,
alcoxy, alcoxycarbonyle, atome d'halogène, groupements alcoxycarbamoyle, amido aliphatique,
alkylsulfamoyle, alkylsulfonamido, alkyluréido, succinimido alkyle-substitué, aryloxy,
aryloxycarbonyle, arylcarbamoyle, arylamido, arylsulfamoyle, arylsulfonamide, aryluréido,
carboxyle, sulfo, nitro, cyano et thiocyano.
16. Epreuve photographique couleur selon la revendication 14, dans laquelle
représente un résidu d'une réaction de couplage d'un dérivé de phénylènediamine représenté
par la formule générale (6) :
dans laquelle R₁₁ et R₁₂ représentent chacun un groupement alkyle substitué ou non
substitué ; et R₁₃ représente 1 à 4 atomes d'hydrogène ou 1 à 4 substituants.
17. Epreuve photographique couleur selon la revendication 16, dans laquelle un substituant
du groupement alkyle substitué représenté par R₁₁ ou R₁₂ est choisi parmi les suivants
: groupements hydroxyle, alkylsulfonamido et alcoxy et le substituant représenté par
R₁₃ est un groupement alkyle.
18. Epreuve photographique couleur selon la revendication 13, dans laquelle le colorant
magenta est un colorant représenté par les formules générales suivantes (4-1) ou (4-2)
:
dans lesquelles R₁₆ et R₁₇, qui peuvent être identiques ou différents, représentent
chacun un atome d'hydrogène, un atome d'halogène, un groupement alkyle, aryle, hétérocyclique,
cyano, alcoxy, aryloxy, oxy hétérocyclique, acyloxy, carbamoyloxy, silyloxy, sulfonyloxy,
acylamino, anilino, uréido, imido, sulfamoylamino, carbamoylamino, alkylthio, arylthio,
thio hétérocyclique, alcoxycarbonylamino, aryloxycarbonylamino, sulfonamido, carbamoyle,
acyle, sulfamoyle, sulfonyle, sulfinyle, alcoxycarbonyle ou aryloxycarbonyle, ou R₁₆
et R₁₇ peuvent être un groupement divalent pour former un composé dimère ou un groupement
de liaison destiné à former un colorant polymérique, et
représente un résidu d'une réaction de couplage d'un développateur de type amine
aromatique primaire.
19. Epreuve photographique couleur selon la revendication 18, dans laquelle le groupement
de liaison est lié à un groupement vinylique à partir duquel le polymère est constitué.
20. Epreuve photographique couleur selon la revendication 13, dans laquelle le colorant
cyan est constitué de deux colorants ou plus formés à partir de deux coupleurs chromogènes
cyan ou plus représentés par la formule générale (1) ou (2).
21. Epreuve photographique couleur selon la revendication 13, dans laquelle les colorants
sont utilisés en combinaison avec un ou plusieurs types de solvants organiques ayant
un point de fusion élevé d'au moins 160°C, qui sont représentés par la formule générale
suivante (7), (8), (9), (10) ou (11) :
W₁ - COO - W₂ (8)
W₁ - O - W₂ (11)
dans lesquelles W₁, W₂ et W₃ représentent chacun un groupement alkyle substitué ou
non substitué, un groupement cycloalkyle substitué ou non substitué, un groupement
alcényle substitué ou non substitué, un groupement aryle substitué ou non substitué
ou un groupement hétérocyclique substitué ou non substitué ; W₄ représente W₁, -O-W₁
ou -S-W₁ ; n représente un nombre entier compris entre 1 et 5, quand n vaut deux ou
plus, deux W₄ ou plus peuvent être identiques ou différents ; et dans la formule générale
(11) W₁ et W₂ peuvent être liés l'un avec l'autre de façon à former un cycle condensé.
22. Epreuve photographique couleur selon la revendication 13, dans laquelle les colorants
sont utilisés en combinaison avec un ou plusieurs polymères solubles dans des solvants
organiques, insolubles dans l'eau.
23. Epreuve photographique couleur selon la revendication 13, dans laquelle les colorants
sont utilisés en combinaison avec un ou plusieurs types d'agents de prévention de
l'affaiblissement des couleurs ou d'agents anti-oxydants représentés par la formule
générale (12) ou (13) :
dans lesquelles R₂₀ représente un atome d'hydrogène, un groupement aliphatique, un
groupement aromatique, un groupement hétérocyclique ou un groupement protecteur hydrolysable
; R₂₁, R₂₂, R₂₃, R₂₄ et R₂₅, qui peuvent être identiques ou différents, représentent
chacun un atome d'hydrogène ou un substituant ; R₃₀ représente un atome d'hydrogène,
un groupement aliphatique, acyle, sulfonyle, sulfinyle, radical oxy ou un groupement
hydroxyle ; A représente un groupement atomique non métallique nécessaire pour constituer
un cycle à 5, 6 ou 7 chaînons ; et R₂₆, R₂₇, R₂₈ et R₂₉, qui peuvent être identiques
ou différents, représentent chacun un atome d'hydrogène ou un groupement alkyle, ou
R₂₀ et R₂₁ ou deux parmi R₂₁, R₂₂, R₂₃, R₂₄ et R₂₅ qui sont présents en position ortho
l'un par rapport à l'autre peuvent être liés l'un avec l'autre de façon à former un
cycle à 5, 6 ou 7 chaînons, ou R₂₆ et R₂₇, R₂₈ et R₂₉ ou R₃₀ et R₂₆ peuvent être liés
l'un avec l'autre pour former un noyau à 5, 6 ou 7 chaînons.
24. Epreuve photographique couleur préparée en mettant en oeuvre au moins une étape de
traitement du matériau photographique couleur à l'halogénure d'argent selon la revendication
1, après exposition selon une image, avec un révélateur chromogène contenant un développateur
chromogène de type amine aromatique primaire.
25. Epreuve photographique couleur préparée en collant une épreuve photographique couleur
obtenue en mettant en oeuvre au moins une étape de traitement du matériau photographique
couleur à l'halogénure d'argent selon la revendication 1 mais en utilisant un support
transparent à la place du support réfléchissant, après exposition selon une image,
avec un révélateur chromogène contenant un développateur chromogène de type amine
aromatique primaire, sur un support réfléchissant constitué d'une résine de chlorure
de vinyle contenant un pigment blanc.