[0001] This invention relates to a process for processing silver halide color photographic
materials, and more particularly to a photographic processing process giving excellent
coloring properties using an improved color developer.
[0002] Hitherto, various techniques have been proposed for increasing the color developing
speed. In these techniques, color developing agents for use in the color development
have had low hydrophilic properties, and hence the permeation of the color developing
agent into the photographic light-sensitive material has been slow. Accordingly, for
increasing the permeation thereof, various penetrating agents have been investigated,
and in particular a process for increasing the color development by adding benzyl
alcohol to the color developer shows a high coloring accelerating effect, and hence
such a process has been widely used for the processing of color photographic materials,
particularly color photographic papers.
[0003] However, when benzyl alcohol has been used in an amount of from more than 10 ml/l
to 15 ml/l, which is the amount conventionally used for processing color photographic
papers, the use of diethylene glycol, triethylene glycol, or an alkanolamine is required
as a solvent due to the low water-solubility. However, since benzyl alcohol, glycols,
and alkanolamine show high BOD (biochemical oxygen demand) or COD (chemical oxygen
demand) values, which are environmental pollution factors, it is preferred to reduce
the amount of benzyl alcohol in order to reduce environmental pollution problems.
If it is possible to reduce the amount of benzyl alcohol to less than 8 ml/l, the
use of the above-described solvent becomes unnecessary, which results in greatly reducing
the pollution problem, as described, for example, in Japanese Patent Application (OPI)
No. 50536/83 (the term "OPI" as used herein means an "unexamined published Japanese
application.").
[0004] Furthermore, when benzyl alcohol is carried into a bleach bath or a blix bath, which
is a bath after a color development bath, it causes the formation of a leuco dye of
a cyan coupler, which results in reducing the coloring density of the cyan dye. Moreover,
when benzyl alcohol is carried into a water bath which is a post path to a fix bath
or the bleach bath, the life of the color images formed is reduced. Accordingly, for
the reasons described above, it is preferred that the concentration of benzyl alcohol
in a color developer is low.
[0005] However, if the concentration of benzyl alcohol in a color developer is reduced below
about 8 ml/liter, the density of colored images is reduced, and in this case, sufficient
coloring density cannot be obtained even in the case of using various kinds of color
development accelerators as described, for example, in U.S. Patents 2,950,970, 2,515,147,
3,496,903, 2,304,925, 4,038,075, 4,119,642, British Patents 1,430,998, 1,455,413,
Japanese Patent Application (OPI) Nos. 15831/78, 62450/80, 62451/80, 62452/80, 62453/80
and Japanese Patent Publication Nos. 12422/76 and 49728/80. EP-A-0 111 919 discloses
a multicolour photographic element that is obtained by coating onto a support superimposed
emulsion layers each comprised of a dispersing medium and silver halide grains, for
example an amulsion of tabular grain silver bromide (97:3), for separately recording
blue and minus blue light.
[0006] It is the object of this invention is to provide a processing process for color photographic
materials using a color developer containing no or very little benzyl alcohol and
giving very little pollution problems.
[0007] This object is attained by processing a silver halide color photographic material
comprising a support having thereon at least one silver halide photographic emulsion
layer containing a silver bromide or silver chlorobromide emulsion in which tabular
silver halide grains having main crystal planes parallel to each other and an average
aspect ratio of at least 5 account for at least 50% of the total projected area of
the silver halide grains with a color developer containing 8 ml/l or less of benzyl
alcohol characterized in that the silver bromide or silver chlorobromide contains
no silver iodide.
[0008] Hitherto, for improving the coloring property (coloring density and/or coloring speed)
of a silver halide photographic material by a color developer, it has been considered
necessary to change the structure of couplers, increase the coating amount of couplers,
or increase the coating amount of silver halide, and hence it is an utterly unexpected
fact that the form of the crystals of the silver halide grains influences the improvement
of the coloring property even if the coating amounts of silver halide and couplers
are the same as those of other silver halide and couplers, and the halogen composition
is the same as that of other silver halide grains.
[0009] Color developers for use in this invention are described below.
[0010] The color developer for use in this invention contains from 8 ml/l or less and preferably
5 ml/l or less of benzyl alcohol, including the case in which no benzyl alcohol is
present.
[0011] The color developer for use in this invention preferably contains a known aromatic
primary amine color developing agent. Preferred aromatic primary amine color developing
agents are p-phenylenediamine derivatives, and specific examples are shown below,
although the invention is not restricted to those specifically listed.
- D - 1:
- N,N-Diethyl-p-phenylenediamine
- D - 2:
- 2-Amino-5-diethylaminotoluene
- D - 3:
- 2-Amino-5-(N-ethyl-N-laurylamino)toluene
- D - 4:
- 4-[N-Ethyl-N-(β-hydroxyethyl)amino]aniline
- D - 5:
- 2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]-aniline
- D - 6:
- N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline
- D - 7:
- N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide
- D - 8:
- N,N-Dimethyl-p-phenylenediamine
- D - 9:
- 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline
- D - 10:
- 4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline
- D - 11:
- 4-Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline
The p-phenylenediamine derivatives may be in the forms of salts such as, for example,
the sulfates, hydrochlorides, sulfites and p-toluenesulfonates.
[0012] The amount of the aromatic primary amine developing agent for the color developer
is generally from about 0.1 g to about 20 g, and preferably from 0.5 g to about 10
g per l of the developer.
[0013] The above-described color developing agent may exist in a silver halide color photographic
material for simplifying and quickening the processing.
[0014] For using the color developing agent in the color photographic material, it is preferred
to use the various precursors for the color developing agent. Examples of such precursors
are the indoaniline series compounds described in, for example, U.S. Patent 3,342,597;
the Sciff base-type compounds described in for example,, U.S. Patent 3,342,599,
Research Disclosure, RD No. 14850 (Aug., 1976)
ibid., RD No. 15159 (Nov., 1976); the aldol compounds described in
ibid., RD No. 13924 (Nov., 1975), the metal complexes described in U.S. Patent 3,719,492,
the urethane series compounds described in, for example, Japanese Patent Application
(OPI) No. 135628/78, and other various salt-type precursors described in, for example,
Japanese Patent Application (OPI) Nos. 6235/81, 16133/81, 59232/81, 67842/81, 83734/81,
83735/81, 83736/81, 89735/81, 81837/81, 54430/81, 106241/81, 107236/81, 97531/82 and
83565/82.
[0015] The silver halide color photographic material for use in this invention may, if desired,
contain various 1-phenyl-3-pyrazolidones for accelerating the color development. Examples
of these compounds are, for example, described in Japanese Patent Application (OPI)
No. 64339/81, 144547/82, 211147/82, 50532/83, 50536/83, 50533/83, 50534/83, 50535/83,
and 115438/83.
[0016] The color developer for use in this invention may further contain a hydroxylamine
of types known in the art.
[0017] Such a hydroxylamine may be used in the form of a free amine in the color developer
but is generally used in the form of a water-soluble acid salt thereof. General examples
of these salts are sulfates, oxalates, chlorides, phosphates, carbonates and acetates.
The hydroxylamines may be substituted or unsubstituted, and also the nitrogen atom
of the hydroxylamines may be substituted by an alkyl group. In particular, the hydroxylamines
substituted by a substituted or unsubstituted alkyl group are preferred.
[0018] The pH of the color developer for use in this invention is preferably from 9 to 12,
and more preferably from 9 to 11.0. The color developers for use in this invention
may further contain other components known as developer components.
[0019] Examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium
carbonate, sodium tertiary phosphate, potassium tertiary phosphate, potassium metaborate
and borax,, as an alkali agent or a pH buffer. They can be used solely or as a combination
thereof. For giving buffer function to the color developer, facilitating the preparation
of the color developer, or increasing the ionic strength of the color developer, various
salts such as, for example, disodium hydrogenphosphate, dipotassium hydrogenphosphate,
potassium dihydrogenphosphate, sodium dihydrogenphosphate, sodium hydrogencarbonate,
potassium hydrogencarbonate, borates, an alkali nitrate and an alkali sulfate can
be used.
[0020] Furthermore, various chelating agents may be used for the color developers as a precipitation
preventing agent for calcium and magnesium. Examples of such agents are polyphosphates,
aminopolycarbonates, phosphonocarbonates, aminopolyphosphonates and 1-hydroxyalkylidene-1,1-diphosphonates.
[0021] The color developer may, if desired, contain a development accelerator. Examples
of the development accelerator include various pyrimidium compounds and other cationic
compounds, a cationic dye such as phenosafranine, and neutral salts such as thallium
nitrate, potassium nitrate described in, for example, U.S. Patent 2,648,604, Japanese
Patent Publication No. 9503/69 and U.S. Patent 3,171,247; polyethylene glycol and
derivatives thereof, and nonionic compounds such as polythioethers described in, for
example, Japanese Patent Publication No. 9304/69, U.S. Patents 2,533,990, 2,531,832,
2,950,970, 2,577,127, and the thioether series compounds described in, for example,
US. Patent 3,201,242.
[0022] The color developer may further contain sodium sulfite, potassium sulfite, potassium
bisulfite, or sodium bisulfite, which are usually used as a preservative.
[0023] The color developer for use in this invention may further contain, if desired, an
antifoggant. Examples of the antifoggant are alkali metal halides such as potassium
bromide, sodium bromide and potassium iodide, and organic antifoggants. Examples of
the organic antifoggants are nitrogen-containing heterocyclic compounds such as, for
example, benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole , 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole
and hydroxyazaindrizine; mercapto-substituted heterocyclic compounds such as, for
example, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole;
and further mercapto-substituted aroamtic compounds such as, for example, thiosalicylic
acid. The nitrogen-containing heterocyclic compounds are particularly preferred. Such
an antifoggant may be used in such a manner that it is dissolved out from a color
photographic light-sensitive material and accumulates in a color developer.
[0024] The silver halide color photographic material is usually bleached after color development.
The bleach process may be performed simultaneously with a fix process (blix process)
or may be performed separately from a fix process. Suitable bleaching agent are, for
example, compounds of polyvalent metals such as, for example, iron(III), cobalt (III),
chromium(VI), copper(II); peracids, quinones and nitroso compounds. Examples of bleaching
agents are ferricyanides, dichromates, organic complex salts of iron(III) or cobalt(III),
complex salts of aminopolycarboxylic acids such as, for example, ethylenediaminetetraacetic
acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid and 1,3-diamino-2-propanoltetraacetic
acid; or organic acids such as, for example, citric acid, tartaric acid, malic acid
and; persulfates, manganates and nitrosophenol. Of these compounds, for example, potassium
ferricyanide, ethylenediaminetetraacetic acid iron(III) sodium, ethylenediaminetetraacetic
acid iron(III) ammonium, triethylenetetraaminepentaacetic acid iron(III) ammonium,
persulfates and cyclohexanediaminetetraacetic acid iron(III) salt are particularly
useful. Ethylenediaminetetraacetic acid iron(III) complex salts are useful in bleach
solutions and in blix solutions.
[0025] The bleach solution or the blix solution may further, if desired, contain various
kinds of accelerators. Examples of the bleach accelerator include thiourea series
compounds as described in U.S. Patent 3,706,561, Japanese Patent Publication Nos.
8506/70 and 26586/74, Japanese Patent Application (OPI) Nos. 32735/78, 36233/78, and
37016/78, thiol series compounds as described in Japanese Patent Application (OPI)
Nos. 124424/78, 95631/78, 57831/78, 32736/78, 65732/78, and 52534/79, and U.S. Patent
3,893,858, heterocyclic compounds as described in, for example, Japanese Patent Application
(OPI) Nos. 59644/74, 140129/75, 28426/78, 141623/78 and 104232/78, 35727/79, thioether
compounds as described in Japanese Patent Application (OPI) Nos. 20832/77, 25064/80,
and 26506/80, quaternary amines described in Japanese Patent Application (OPI) No.
84440/73, and the thiocarbamoyls as described in Japanese Patent Application (OPI)
No. 42349/74, as well as, for example, bromine ions and iodine ions.
[0026] Suitable fixing agent for use in this invention, are, for example, thiosulfates,
thiocyanates, thioether series compounds, thioureas and a large amount of iodides.
Of these compounds, thiosulfates are most generally used.
[0027] As the preservatives for the blix solution or the fix solution, sulfites, bisulfites,
or carbonylbisulfite addition products are preferably used.
[0028] After the blix process or fix process, a washing process is usually performs. In
the washing process, various known compounds may be used for the purposes of precipitation
prevention and of water saving. For example, for preventing precipitation, a water
softener such as, for example, an organic phosphoric acid, an aminopolycarboxylic
acid and an inorganic phosphoric acid can be used. Moreover, a sterilizer or an antimold
agent for preventing the generation of various bacteria, algae, and molds, a hardening
agent such as a magnesium salt or an aluminum salt, or a surface active agent for
preventing drying load (increase of energy) or uneven drying of the surface can be
used for the washing process. The compounds described in L.E. West,
Photographic Sceince and Engineering, Vol.3, No.6, p283 (1959) and Vol. 9, No. 6 (1965) may be used for the washing step.
In particular, the addition of a chelating agent or an antimold is effective. Furthermore,
it is possible to practice water saving by employing a multi-stage (e.g., 2 to 5 stages)
countercurrent system for the washing treatment step.
[0029] Moreover, after or in place of the wash treating step, multi-stage countercurrent
stabilization, as described, e.g., in Japanese Patent Application (OPI) No. 8543/82
may be applied. In this case, 2 to 9 countercurrent baths are required. In the case
of employing such stabilization step, various kinds of compounds can be used for the
stabilization baths for stabilizing the images formed. Examples of these compounds
are buffers (e.g., borates, metaborates, borax, phosphates, carbonates, potassium
hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylates, dicarboxylates and
polycarboxylates) and formalin for adjusting the pH of the layers. Furthermore, if
desired, for example, water softeners (e.g., inorganic phosphoric acids, aminopolycarboxylic
acids, organic phosphoric acids, aminopolyphosphonic acids and phosphonocarboxylic
acids, sterilizers (e.g., proxel, isothiazolone, 4-thiazolylbenzimidazole and halogenated
phenolbenzotriazoles), surface active agents, fluorescent whitening agents and hardening
agents may be added to the stabilizing bath(s).
[0030] As a film pH adjusting agent after the process, various ammonium salts such as, for
example, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate,
ammonium sulfite and ammonium thiosulfate can be also added to the stabilizing bath(s).
[0031] The tabular silver bromide or silver chlorobromide grains for use in this invention
are more excellent in coloring property as the average aspect ratio thereof becomes
higher, but the tabular grain silver bromide or silver chlorobromide emulsion wherein
the tabular silver halide grains having an average aspect ratio (defined below) of
at least 5 (i.e., 5/1), and preferably at least 8, account for at least 50% of the
total projected area of the silver halide grains can be advantageously used in this
invention with the effect of this invention as compared with ordinary silver bromide
or silver chlorobromide emulsions which are used for conventional color photographic
light-sensitive materials, and in particular for conventional color photographic papers.
[0032] The silver chloride content in the silver chlorobromide is preferably within the
range of 15 mole % to 99 mole %. For the purposes of quickening the processing and
reducing the replenishing amount, it is preferred that the amount of the silver chloride
is more increased. The silver halide grains may differ in halogen composition between
the inside and the surface layer thereof or may differ in halogen composition between
the central portion and the annular peripheral portion thereof. A mixture of silver
halide grains having a uniform halogen composition and silver halide grains having
a double layer or multilayer structure may be used.
[0033] The aspect ratio in this invention is defined as the ratio of the diameter of a circle
having the same area as the projected area formed by projecting the parallel main
crystal planes of the tabular grains onto a plane which is parallel to the crystal
planes, to the thickness of the parallel main crystal plates of the grain.
[0034] The average diameter of the tabular silver halide grains having the average aspect
ratio of at least 5 for use in this invention is preferably from 0.25 µm to 2.8 µm,
and particularly preferably from 0.45 µm to 1.9 µm. The thickness of the tabular grains
is generally at most 0.56 µm, preferably at most 0.38 µm, more preferably at most
0.2 µm.
[0035] In the silver halide emulsion containing the tabular silver halide grains for use
in this invention, the tabular silver halide grains having an average aspect ratio
of at least 5 account for at least 50%, preferably at least 70%, and particularly
preferably at least 90% of the total projected area of the silver halide grains.
[0036] The tabular grain silver halide emulsion in this invention can be used in a narrowed
distribution about the diameter or the thickness of the tabular silver halide grains.
In this invention, it is particularly preferred that the tabular silver halide grains
have a distribution of thin thickness.
[0037] The tabular silver halide grain emulsion for use in this invention is usually prepared
by mixing an aqueous solution of a water-soluble silver salt (e.g., silver nitrate)
and an aqueous solution of water-soluble halide(s), e.g., potassium bromide or sodium
chloride alone, or a mixture thereof in the presence of an aqueous solution of a water-soluble
polymer such as gelatin.
[0038] More particularly, the production of such tabular silver halide grain emulsions are
described in, for example, U.S. Patents 4,434,226, 4,439,520, 4,414,310, 4,425,425,
4,399,215, 4,435;501, 4,386,156, 4,400,463, 4,414,306, and 4,425,426, European Patent
84,637A2, Japanese Patent Application (OPI) No. 99433/84 and
Research Disclosure, RD No. 22534 (January, 1983).
[0039] The silver halide grains for use in this invention may be formed or physically ripened
in the presence of, for example, a cadmium salt, a zinc salt, a lead salt, a thallium
salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt
thereof and an iron salt or a complex salt thereof.
[0040] The silver halide emulsions for use in this invention are usually, after the formation
of the silver halide grains, subjected to physical ripening, desalting, and chemical
ripening before coating.
[0041] For the precipitation, physical ripening and chemical ripening of the silver halide
emulsions, known silver halide solvents (e.g., ammonia, potassium rhodanide, potassium
thiocyanate), and the thioethers and thione compounds described in, for example, U.S.
Patent 3,271,157, Japanese Patent Application (OPI) Nos. 12360/76, 82408/78, 144319/78,
100717/79 and 155828/79 can be used. For removing soluble salts from the silver halide
emulsions after physical ripening, a noodle washing method, flocculation-sedimentation
method, or a ultrafiltration method can be used.
[0042] The silver halide emulsions for use in this invention can be chemically sensitized
by, for example, a sulfur sensitization method using active gelatin or a sulfur-containing
compound capable of reacting silver (e.g., thiosulfates, thioureas, mercapto compounds
and rhodanine); a reduction sensitization method using a reducing material (e.g.,
stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid and silane
compounds); and a noble metal sensitizing method using a metal compound (e.g., a gold
complex salt and complex salts of metals belonging to group VIII of the periodic table,
such as, for example, platinum, iridium, palladium, rhodium and iron). These methods
may be used individually or as a combination thereof.
[0043] The silver halide photographic emulsions for use in this invention are usually spectrally
sensitized by photographic sensitizing dyes. Examples of dyes which are used for the
spectral sensitization are cyanine dyes, merocyanine dyes, complex cyanine dyes, complex
merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol
dyes.
[0044] These sensitizing dyes may be used individually or as a combination thereof. A combination
of sensitizing dyes is frequently used for the purpose of supersensitization.
[0045] The silver halide emulsion for use in this invention may contain a dye having no
spectral sensitizing action by itself or a material which does not substantially absorb
visible light, but which shows supersensitization when used together with the sensitizing
dye(s). Examples of such compounds as above, which can be incorporated in the photographic
emulsion together with the sensitizing dye(s), are, for example, an aminostilbene
compound substituted by a nitrogen-containing heterocyclic ring group (e.g., those
described in U.S. Patents 2,933,390 and 3,635,721), an aromatic organic acid-formaldehyde
condensation product (e.g., those described in U.S. Patent 3,743,510), a cadmium salt
and an azaindene compound.
[0046] The spectral sensitization can be performed at any stage of the preparation of the
silver halide emulsion, said stage being known to be a useful stage. It is most usual
to perform the spectral sensitization after completion of chemical sensitization.
However, the spectral sensitization may be performed simultaneously with chemical
sensitization, may be performed before performing chemical sensitization, or may be
performed before the end of the precipitation formation of silver halide grains as
described in U.S. Patents 3,628,960 and 4,225,666. Furthermore, a spectral sensitizing
dye is introduced into a silver halide emulsion in two split portions, i.e., a part
of the spectral sensitizing dye is introduced into a silver halide emulsion before
chemical sensitization and the remaining portion is introduced thereto after the chemical
sensitization as described in U.S. Patent 4,225,666. A spectral sensitizing dye may
be added to a silver halide emulsion after forming the 80% precipitation of the silver
halide different from the method shown in the above-described U.S. Patent. In a preferred
embodiment, a spectral sensitizing dye can be incorporated in a silver halide emulsion
after the completion of the formation of the precipitation of the silver halide and
before the chemical sensitization of the emulsion.
[0047] For satisfying the desired gradation properties with the photographic light-sensitizing
material according to this invention, two or more kinds of mono-dispersed silver halide
emulsions each composed of silver halide grains of a different size can be used for
silver halide emulsion layers having substantially the same color sensitive property
as a mixture thereof in the same emulsion layer or as separate emulsion layers. Furthermore,
two or more kinds of poly-dispersed silver halide emulsions or a mixture of a mono-dispersed
silver halide emulsion and a poly-dispersed silver halide emulsion may be used as
a mixture thereof or for separate emulsion layers.
[0048] For the photographic light-sensitive material which is processed by the process of
this invention, various color couplers can be used. The term "color coupler" in this
invention means a compound capable of forming a dye by causing coupling reaction with
the oxidation product of an aromatic primary amine developing agent. Typical examples
of useful color couplers include naphtholic and phenolic compounds, pyrazolone and
pyrazoloazole series compounds, and open chain and heterocyclic ketomethylene compounds.
Specific examples of these cyan, magenta, and yellow couplers which can be used for
the silver halide photographic materials are described in the patents cited in
Research Disclosure, RD No. 17643 (December, 1978), VII-D, and
ibid., RD No. 18717 (November, 1979).
[0049] It is preferred that the color couplers contained in the silver halide photographic
materials which are processed by the process of this invention are rendered non-diffusible
by having a ballast group or by being polymerized. In this invention, a two-equivalent
coupler having a coupling active position which is substituted by a coupling releasable
group is more preferred than a four-equivalent coupler having a hydrogen atom at the
coupling active position thereof since the coating amount of silver can be reduced
in the case of using the two-equivalent coupler. Furthermore, couplers capable of
providing coloring dyes having a proper diffusibility, non-coloring couplers, DIR
couplers, i.e., couplers releasing a development inhibitor with a coupling reaction,
or couplers releasing a development accelerator with coupling reaction can be also
used in this invention.
[0050] Typical examples of the yellow couplers for use in this invention include oil protect
type acylamide series couplers. Specific examples of these couplers are described
in U.S. Patents 2,407,210, 2,075,057, and 3,265,506. In this invention, two-equivalent
yellow couplers are preferably used. Examples of the two-equivalent yellow couplers
are the oxygen atom releasing type yellow couplers described in, for example, U.S.
Patents 3,408,194, 3,447,928, 3,933,501 and 4,022,620, and the nitrogen atom releasing
type yellow couplers described in, for example, Japanese Patent Publication No. 10739/83,
U.S. Patents 4,401,752 and 4,326,024,
Research Disclosure, RD No. 18053 (April, 1979), British Patent 1,425,020, West German Patent Application
(OLS) Nos. 2,219,917, 2,261,361, 2,329,587 and 2,433,812. Of these yellow couplers,
α-pivaloylacetanilide series couplers are excellent in fastness, in particular, light
fastness of the colored dyes formed therefrom. α-Benzoylacetanilide series couplers
are excellent in coloring density.
[0051] Magenta couplers for use in this invention include oil protect type indazolone series
couplers, cyanoacetyl series couplers, preferably 5-pyrazolone series couplers, and
pyrazoloazole series couplers such as pyrazolotriazoles. In the case of the 5-pyrazolone
series couplers, it is preferred that the 3-position of the coupler is substituted
by an arylamino group or an acylamino group from the viewpoint of the hue and the
coloring density of the colored dyes formed therefrom. Specific examples of such 5-pyrazolone
series couplers are described in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573,
3,062,653, 3,152,896, and 3,936,015. As the releasable groups for the two-equivalent
5-pyrazolone series couplers, the nitrogen atom-releasing groups described in U.S.
Patent 4,310,619 and the arylthio groups described in U.S. Patent 4,351,897 are particularly
preferred. The 5-pyrazolone series couplers having a ballast group described in European
Patent 73,636 give high coloring density.
[0052] Examples of pyrazoloazole series magenta couplers include pyrazolobenzimidazoles
described in U.S. Patent 3,061,432, preferably the pyrazolo[5,1-c][1,2,4]-triazoles
described in U.S. Patent 3,725,067, the pyrazolotetrazoles described in Research Disclosure,
RD No. 24220 (June, 1984) and Japanese Patent Application (OPI) No. 33552/85 and the
pyrazolopyrazoles described in
Research Disclosure, RD No. 24230 (June, 1984), and Japanese Patent Application (OPI) No. 43659/85. The
imidazo[1,2-b]pyrazoles described in U.S. Patent 4,500,630 are preferred from the
view point of having less yellow side adsorption of the colored dyes formed therefrom,and
light fastness. The pyrazolo[1,5-6][1,2,4]triazoles described in European Patent No.
119,860A are more preferred.
[0053] Cyan couplers for use in this invention include oil protect type naphtholic and phenolic
couplers and typical examples of these cyan couplers are the naphtholic couplers described
in U.S. Patent 2,474,293 and preferably the oxygen atom releasing type two-equivalent
naphthalic couplers described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, and
4,296,200. Also, specific examples of the phenolic cyan couplers are described in,
for example, U.S. Patents 2,369,929, 2,801,171, 2,772,162 and 2,895,826. The cyan
couplers having high fastness to humidity and temperature are preferably used in this
invention and specific examples of these cyan couplers are the phenolic cyan couplers
having an alkyl group having 2 or more carbon atoms at the meta-position of the phenol
nucleus as described in U.S. Patent 3,772,002, the 2,5-diacylamino-substituted phenolic
couplers described in, for example, 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 the phenolic couplers having a phenylureido group at the 2-position
and an acylamino group at the 5-position thereof as described in, for example, U.S.
Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767.
[0054] The silver halide photographic materials for use in this invention may contain a
compound releasing a development inhibitor with the progress of development in place
of the DIR coupler.
[0055] Two or more kinds of the above-described couplers may be used in one silver halide
emulsion layer, or the same coupler may be used for two or more different silver halide
emulsion layers for satisfying the characteristics required for the silver halide
photographic material.
[0056] Each of the couplers described above is incorporated in a silver halide emulsion
layer in an amount of generally from 2 x 10⁻³ mole to 5 x 10⁻¹ mole, and preferably
from 1 x 10⁻² mole to 5 x 10⁻¹ mole, per mole of silver in the emulsion layer.
[0057] The silver halide photographic materials which are processed by the process of this
invention may further contain, for example, hydroquinone derivatives, aminophenol
derivatives, amines, gallic acid derivatives, cathechol derivatives, ascorbic acid
derivatives, non-coloring couplers and sulfonaminophenol derivatives as a color fog
preventing agent or a color mixing preventing agent.
[0058] The photographic light-sensitive materials for use in this invention may further
contain various fading preventing agents. Examples of organic fading-preventing agents
include hindered phenols such as, for example, hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans,
spirochromans, p-alkoxyphenols and bisphenols, gallic acid derivatives, methylenedioxybenzenes,
aminophenols, hindered amines, and the ether or ester derivatives formed by silylating
or alkylating the phenolic hydroxyl groups of these compounds. Metal complexes such
as (bis-salicyclaldoxymato)nickel complex and (bis-N,N-dialkyldithiocarbamato)nickel
complex can also be used as the fading-preventing agent.
[0059] The use of a compound having a moiety structure of hindered amine and hindered phenol
in the same molecule thereof such as those described in U.S. Patent 4,268,593, gives
good results for preventing the yellow dye images from being deteriorated by heat,
humidity, and light. The use of spiroindanes as described in Japanese Patent Application
(OPI) No. 159644/81, or chromans substituted by hydroquinone diether or mono-ether
as described in Japanese Patent Application (OPI) No. 89835/80, gives good results
for preventing the magenta dye images from being deteriorated, particularly by light.
[0060] The photographic light-sensitive materials for use in this invention can contain
an ultraviolet absorbent in the hydrophilic colloid layers thereof.
[0061] The photographic light-sensitive materials for use in this invention may further
contain in the hydrophilic colloid layers thereof water-soluble dyes as filter dyes
or for irradiation prevention or halation prevention.
[0062] The photographic light-sensitive materials for use in this invention may further
contain stilbene series, triazine series, oxazole series or coumarin series whitening
agents in the photographic emulsion layers or other hydrophilic colloid layers thereof.
Such a whitening agent may be water-soluble, or a water-insoluble whitening agent
may be used in the form of a dispersion thereof.
[0063] As a binder or a protective colloid which can be used, for example, for the silver
halide emulsion layers and inter-layers of the silver halide photographic materials
for use in this invention, gelatin is advantageously used but other hydrophilic colloids
can also be used.
[0064] Useful gelatins include limed gelatin which is most generally used for that purpose,
as well as acid-treated gelatin and enzyme-treated gelatin as described in
Bull. Soc. Sci. Phot. Japan, No. 16, p. 30 (1966). Hydrolyzed or enzyme-decomposition products of gelatin can
also be used.
[0065] The photographic light-sensitive materials for use in this invention may further
contain an inorganic or organic hardening agent in the photographic silver halide
emulsion layers and other optional hydrophilic colloid layers constituting, for example,
backing layers.
[0066] The photographic light-sensitive materials for use in this invention may further
contain at least one kind of surface active agent as a coating aid or for preventing
electrification, improving the slipping property, improving emulsification-dispersibility,
preventing adhesion, and improving photographic properties (e.g., acceleration of
development, increase of contrast, and increase of sensitivity).
[0067] The photographic light-sensitive materials for use in this invention may further
contain various additives useful for photographic materials, such as, for example,
various stabilizers, stain-preventing agents, developing agents or precursors therefor,
development accelerators or precursors therefor, lubricants, mordants, matting agents,
antistatic agents and plasticizers, in addition to the above-described additives.
Specific examples of these additives are described in
Research Disclosure, RD No. 17643 (December, 1978) and
ibid., RD No. 18716 (November, 1979).
[0068] This invention can be applied to multilayer multicolor photographic materials having
at least two silver halide emulsion layers, each having a different spectral sensitivity,
on a support. A multilayer natural color photographic material usually has at least
one red-sensitive emulsion layer, at least one green-sensitive emulsion layer, and
at least one blue-sensitive emulsion layer on a support. The disposition order of
these emulsion layers can optionally be selected according to the intended purpose.
Each of the emulsion layers described above may be composed of at least two emulsion
layers, each having a different sensitivity, and a light-insensitive layer may exist
between two or more emulsion layers each having the same sensitivity.
[0069] The photographic light-sensitive material for use in this invention, for example,
has a protective layer, interlayers, a filter layer, an antihalation layer and a backing
layer in addition to the above-described silver halide emulsion layers.
[0070] The photographic light-sensitive material for use in this invention is prepared by
forming the photographic emulsion layers and other layers on a flexible support of
a type which is usually used for photographic materials, such as, for example, a plastic
film, a paper and a cloth, of a solid support such as, for example, a glass plate,
porcelain and a metal foil.
[0071] The processing process of this invention can be applied for processing general silver
halide color photographic materials such as, for example, color negative photographic
films, color photographic papers, color positive photographic films and color reversal
films, but is particularly preferably applied for processing color photographic papers.
[0072] The invention is explained in more detail by reference to the following examples.
However, the scope of the invention is not limited to these examples.
Example 1
[0073] A multilayer silver halide photographic material was prepared by forming the following
layer 1 (the lowermost layer) to layer 7 (the uppermost layer) on a paper support,
both of the surfaces of which were laminated with polyethylene.
| Layer 1: Blue-sensitive emulsion layer: |
| Silver chlorobromide emulsion shown in Table 1 below (silver coverage) (Br: 70 mol%) |
0.30 g/m² |
| Yellow coupler Y - 1 |
0.60 g/m² |
| Yellow coupler solvent (dibutyl phthalate) |
1.00 g/m² |
| Fading-preventing agent F - 3 |
0.10 g/m² |
| Layer 2: Interlayer: |
| Gelatin |
1.50 g/m² |
| Layer 3: Green-sensitive emulsion layer: |
| Silver chlorobromide emulsion shown in Table 1 (silver coverage) (Br: 70 mol%) |
0.45 g/m² |
| Magenta coupler M - 1 |
0.45 g/m² |
| Magenta coupler solvent (tri-n-octyl phosphate) |
0.44 g/m² |
| Fading-preventing agent F - 1 |
0.050 g/m² |
| Fading-preventing agent F - 2 |
0.100 g/m² |
| Layer 4: Ultraviolet absorption layer: |
| Gelatin |
2.00 g/m² |
| Ultraviolet absorbent UV - 1 |
0.015 g/m² |
| Ultraviolet absorbent UV - 2 |
0.045 g/m² |
| Ultraviolet absorbent UV - 3 |
0.090 g/m² |
| Solvent (dibutyl phthalate) |
0.060 g/m² |
| Layer 5: Red-sensitive emulsion layer: |
| Silver chlorobromide emulsion Shown in Table 1 (silver coverage) (Br: 70 mol%) |
0.300 g/m² |
| Cyan coupler C - 1 |
0.200 g/m² |
| Cyan coupler C - 2 |
0.200 g/m² |
| Cyan coupler solvent (dibutyl phthalate) |
0.240 g/m² |
| Ultraviolet absorbent UV - 1 |
0.020 g/m² |
| Ultraviolet absorbent UV - 2 |
0.050 g/m² |
| Ultraviolet absorbent UV - 3 |
0.060 g/m² |
| Layer 6: Ultraviolet absorption layer: |
| Gelatin |
1.50 g/m² |
| Ultraviolet absorbent UV - 1 |
0.050 g/m² |
| Ultraviolet absorbent UV - 2 |
0.150 g/m² |
| Ultraviolet absorbent UV - 3 |
0.300 g/m² |
| Solvent (dibutyl phthalate) |
0.200 g/m² |
| Layer 7: Protective layer: |
| Gelatin |
1.50 g/m² |
[0074] The coating composition for Layer 1 described above was prepared as follows. 100
g of the yellow coupler Y-1 having the structure shown below were dissolved in a mixture
of 166.7 ml of dibutyl phthalate (DBP) and 200 ml of ethyl acetate, the solution was
dispersed by emulsification in 800 g of a 10% aqueous gelatin solution containing
80 ml of an aqueous solution of 1% sodium dodecylbenzenesulfonate, and the emulsified
dispersion was mixed with 1450 g (containing 66.7 g of silver) of a blue-sensitive
silver chlorobromide emulsion (Br: 80 ml % of halide content) to provide the coating
composition.
[0075] The coating compositions for other layers described above were also prepared by a
manner similar to that above.
[0076] In addition, for each layer, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was used
as a hardening agent.
[0077] For each of the emulsion layers described above, the following spectral sensitizer
was used.
[0078] Spectral sensitizer for blue-sensitive emulsion layer:
3,3'-Di-(γ-sulfopropyl)-selenacyanine sodium salt (2 x 10⁻⁴ mole per 1 mole of
silver halide).
[0079] Spectral sensitizer for green-sensitive emulsion layer:
3,3'-Di-(γ-sulfopropyl)-5,5'-diphenyl-9-ethyloxacarbocyanine sodium salt (2.5 x
10⁻⁴ mole per 1 mole of silver halide).
[0080] Spectral sensitizer for red-sensitive emulsion layer:
3,3'-Di-(γ-sulfopropyl)-9-methyl-thiadicarbocyanine sodium salt (2.5 x 10⁻⁴ mole
per 1 mole of silver halide).
[0081] For the green-sensitive emulsion layer and the red-sensitive emulsion layer described
above, the following dyes were used as anti-irradiation dyes.
[0083] Each of the photographic silver halide materials thus prepared was light-exposed
through an optical wedge and then processed in the following steps.
| Processing Step |
Temperature |
Time |
| Color Development |
37°C |
3 min 30 s |
| Blix |
33°C |
1 min 30 s |
| Wash |
24-34°C |
3 min |
| Drying |
80°C |
1 min |
[0084] The compositions of the processing solutions are as follows.
| Color Developer |
| Water |
800 ml |
| Diethylenetriaminepentaacetic acid |
1.0 g |
| Benzyl alcohol |
Table 2 |
| Diethylene glycol |
Table 2 |
| Sodium sulfite |
2.0 g |
| Sodium bromide |
1.0 g |
| Sodium carbonate |
30.0 g |
| N-Ethyl-N-(p-methanesulfonamido-ethyl)-3-methyl-4-aminoaniline sulfate |
5.0 g |
| Hydroxylamine sulfate |
4.0 g |
| Fluorescent whitening agent (4,4'-diaminostilbene series) |
1.0 g |
| Water to make |
1000 ml |
| pH (25°C) |
10.10 |
| Blix Solution |
| Water |
400 ml |
| Ammonium thiosulfate (70%) |
150 ml |
| Sodium sulfite |
18 g |
| Ethylenediaminetetraacetic acid iron(III) ammonium |
55 g |
| Ethylenediaminetetraacetic acid di-sodium |
5 g |
| Water to make |
1000 ml |
| pH (25°C) |
6.70 |
[0085] After processing as above using various color developers each having changed concentrations
of benzyl alcohol and diethylene glycol, three-color reflection densities of each
sample were measured. The results obtained are shown in Table 2 below. In the table,
the relative sensitivity of each sample is shown based on the case of the benzyl alcohol
concentration of 15 ml/liter being taken as 100.

[0086] As shown in the above table, it can be seen that according to this invention, the
reductions in sensitivity and density are quite low even when the concentration of
benzyl alcohol in the color developer becomes less than 8 ml/liter, and the reduction
of the concentration of benzyl alcohol thus causes no problem in the photographic
performance. This effect is particularly large for the blue-sensitive emulsion layer.
Example 2
[0087] By following the same procedure as in Example 1 except that the yellow, magenta,
and cyan couplers shown below were used in place of the couplers in Example 1, samples
201 to 205 of photographic light-sensitive materials were prepared.
[0088] When these samples were processed as above using the five kinds of color developers,
samples 203 to 205 using the silver halide emulsions containing the tabular silver
halide grains in this invention showed less dependence on the concentration of benzyl
alcohol in the color developers, as in the case of Example 1.

Example 3
[0089] A multilayer color photographic paper was prepared by forming the layers 1 to 7 having
the following coating compsitions on paper support, both surfaces of which were laminated
with polyethylene. In the polyethylene laminated on the first layer side of the support,
white pigment (TiO₂) and bluing dye (ultramarine blue) were contained.
| Layer 1: Blue-sensitive emulsion layer: |
| Silver chlorobromide emulsion (silver coverage) (silver bromide: 1.0 mole%) |
0.30 g/m² |
| Gelatin |
1.86 g/m² |
| Yellow coupler (a) |
0.82 g/m² |
| Color image stabilizer (b) |
0.19 g/m² |
| Solvent (c) |
0.34 cc/m² |
| Layer 2: Color mixing preventing layer: |
| Gelatin |
0.99 g/m² |
| Color-mixing preventing agent (d) |
0.08 g/m² |
| Layer 3: Green-sensitive emulsion layer: |
| Silver chlorobromide emulsion (silver coverage) (silver bromide: 0.5 mole%) |
0.16 g/m² |
| Gelatin |
1.80 g/m² |
| Magenta coupler (m) |
0.34 g/m² |
| Color image stabilizer (f) |
0.20 g/m² |
| Solvent (g) |
0.68 ml/m² |
| Layer 4: Ultraviolet absorption layer: |
| Gelatin |
1.60 g/m² |
| Ultraviolet absorbent (h) |
0.62 g/m² |
| Color-mixing preventing agent (i) |
0.05 g/m² |
| Solvent (j) |
0.26 ml/m² |
| Layer 5: Red-sensitive emulsion layer: |
| Silver chlorobromide emulsion (silver coverage) (silver bromide: 1.0 mole%) |
0.26 g/m² |
| Gelatin |
0.98 g/m² |
| Cyan coupler (k) |
0.38 g/m² |
| Color image stabilizer (l) |
0.17 g/m² |
| Solvent (e) |
0.23 ml/m² |
| Layer 6: Ultraviolet absorption layer: |
| Gelatin |
0.54 g/m² |
| Ultraviolet absorbent (h) |
0.21 g/m² |
| Solvent (j) |
0.09 ml/m² |
| Layer 7: Protective layer: |
| Gelatin |
1.33 g/m² |
| Acryl-modified copolymer of polyvinyl alcohol (a modification degree: 17%) |
0.17 g/m² |
[0090] The coating composition for the first layer described above was prepared as follows.
19.1 g of the yellow coupler (a) shown below and 4.4 g of the color image stabilizer
(b) shown below were dissolved in a mixture of 27.2 mℓ of ethyl acetate and 7.9 mℓ
of the solvent (c) shown below. The resulting solution was dispersed by emulsification
in 185 mℓ of 10% aqueous gelatin solution containing 8 mℓ of 10% sodium dodecylbenzenesulfonate.
[0091] The sensitizing dye shown below for the blue-sensitive emulsion layer was added to
the silver chlorobromide emulsion (silver bromide: 1.0 mole%, containing 70 g/kg of
silver) in an amount of 5.0 × 10⁻⁴ mole per 1 mole of silver chlorobromide to provide
90 g of the blue-sensitive emulsion.
[0092] Then, the above emulsified dispersion was mixed with the above emulsion, and the
gelatin density in the mixed solution was adjusted so as to obtain the coating compositions
shown above.
[0093] The coating compositions for the other second to seventh layers were also prepared
in the same manner as in the above first layer coating composition. In addition, for
each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a hardening agent.
[0094] For each of the emulsion layer described above, the following spectral sensitizer
was used.
Spectral sensitizer for blue-sensitive emulsion layer

(7 x 10⁻⁴ mole per 1 mole of silver halide)
Spectral sensitizer for green-sensitive emulsion layer

(4 x 10⁻⁴ mole per 1 mole of silver halide)
Spectral sensitizer for red-sensitive emulsion layer

(2 x 10⁻⁴ mole per 1 mole of silver halide)
For the green-sensitive emulsion layer and the red-sensitive emulsion layer described
above, the following dyes were used as anti-irradiation dyes.
[0095] Anti-irradiation dye for green-sensitive emulsion layer:

Anti-irradiation dye for red-sensitive emulsion layer:

The chemical structures of the other compounds that were used in this example are
as follows.
(a) Yellow coupler

(b) Color image stabilizer

(c) Solvent

(d) Color-mixing preventing agent

(e) Solvent

(f) Color image stabilizer

(g) Solvent
2:1 by weight mixture of


(h) Ultraviolet absorbent
1:5:3 by mole mixture of

(i) Color-mixing preventing agent

(j) Solvent

(k) Cyan coupler

(l) Color image stabilizer
1:3:3 by mole mixture of

(m) Magenta coupler

The silver chlorobromide grains used for the above-described emulsion layers in
this example are shown in Tabel 3 below.

[0096] Each of the six color photographic papers thus prepared was light-exposed through
an optical wedge and then processed in the following steps.
| Processing Step |
Temperature |
Time |
| Color Development |
35°C |
30 s |
| Blix |
35°C |
30 s |
| Rinse 1 |
35°C |
20 s |
| Rinse 2 |
35°C |
20 s |
| Rinse 3 |
35°C |
20 s |
| Drying |
80°C |
1 min |
[0097] The compositions of the processing solutions are as follows.
| Color Developer |
| Benzyl Alcohol |
Table 4 |
| N,N-diethylhydroxylamine |
4 g |
| Triethanolamine |
10 g |
| Potassium carbonate |
30 g |
| EDTA·2Na·2H₂O |
2 g |
| Sodium chloride |
2.0 g |
| 4-Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamide)ethyl]-p-phenylenediamine sulfate |
5.0 g |
| Fluorescent whitening agent (4,4'-diaminostilbene series) |
3.0 g |
| 1,2-Dihydroxybenzene-3,4,6-triphosphonic acid |
300 mg |
| Water to make |
1000 mℓ |
| pH |
10.10 |
| Blix Solution |
| EDTA·Fe(III)·NH₄·2H₂O |
60 g |
| EDTA·2Na·2H₂O |
4 g |
| Ammonium thiosulfate (70%) |
120 mℓ |
| Sodium sulfite |
16 g |
| Glacial acetic acid |
7 g |
| Water to make |
1000 mℓ |
| pH |
5.5 |
| Rinse Solution |
| 1-Hydroxyethylidene-1,1'-diphosphonic acid (60%) |
1.6 mℓ |
| Bismuth chloride |
0.35 g |
| Polyvinyl pyrrolidone |
0.25 g |
| Aqueous ammonia (26%) |
2.5 mℓ |
| Nitrilo triacetic acid·3Na |
1.0 g |
| EDTA·4H |
0.5 g |
| Sodium sulfite |
1.0 g |
| 5-Chloro-2-methyl-4-isothiazoline-3-one |
50 mg |
| Formalin (37%) |
0.1 mℓ |
| Water to make |
1000 mℓ |
| pH(25°C) |
7.0 |
[0098] After processing as above using various color developers each having changed concentrations
of benzyl alcohol, three-color reflection densities of each sample were measured.
The results obtained are shown in Table 4 below (D
min: Minimum density, D
max: Maximum density).

[0099] As shown in the above Table 4, it can be seen that when the silver-halide color photographic
emulsion according to the present invention is used under the condition such that
the concentration of benzyl alcohol in the color developer is within the range of
not more than 8 mℓ/liter, a fog is reduced and a satisfactory coloring property can
be obtained, whereby good photographic performance can be obtained.
Example 4
[0100] The color photographic materials were prepared in the same procedure as in Example
3 except that the yellow, magenta, and cyan couplers shown below were used in place
of the couplers in Example 3. As a result, according to the present invention, good
photographic performance can be obtained.
Yellow Coupler:
[0101]

Magenta Coupler:
[0102]

Cyan Coupler:
[0103]
