Color image-forming process compressing developer containing no benzyl alcohol

A color image-forming process which comprises developing, after imagewise exposure, a color photographic paper having at least one light-sensitive layer containing a core/shell surface latent image type monodispersed silver halide emulsion containing substantially no silver iodide, having a silver chloride content of up to 80 mol %, and having a silver bromide content in the shell portion lower than in the core portion with a color developer containing substantially no benzyl alcohol. When the color photographic paper described above is processed, color images having less fog can be obtained with high color density in a short time without using benzyl alcohol as a development accelerator, with the benzyl alcohol causing a pollution problem.

TECHNICAL FIELD 
This invention relates to a color image-forming process, and more 
particularly to a color image-forming process capable of saving the 
coating amount of silver and capable of performing quick processing. 
BACKGROUND ART 
For forming color photographic images, three kinds of color forming 
photographic couplers, namely yellow, magenta, and cyan color forming 
couplers are contained in light-sensitive silver halide emulsion layers, 
and the layers are exposed and then processed by a color developer 
containing a color developing agent. In this development course, the 
oxidation product of the aromatic primary amine causes coupling reactions 
with the couplers to give colored dyes and in this case, it is necessary 
to give color density as high as possible in a limited developing time. 
The purpose of obtaining high color density is usually attained by using 
couplers having a coupling speed as high as possible, by using silver 
halide emulsions which are liable to be developed and provide large amount 
of developed silver per unit coating amount, or by using a color developer 
showing a high developing speed. 
For increasing the developing speed of a silver halide emulsion, it can be 
easily considered to increase the content of silver chloride in the silver 
halide but the increase of the content of silver chloride causes a faults 
that the sensitivity is reduced and fog is liable to form. Also, it may be 
considered to increase the aforesaid content of silver chloride or 
strengthen the chemical sensitization for increasing the amount of 
developed silver but in this case also, there is a fault that fog is 
liable to form. Furthermore, it is a means for quickening the development 
to reduce the grain size in a silver halide emulsion but such an attempt 
has a fatal fault that the sensitivity is lowered. Also, a process of 
using a silver chloride emulsion is described, for example, in unexamined 
Published Japanese Patent Application Nos. 95345/83, 232342/84, and 
19140/85, but there is a problem that the control of the gradation is 
difficult. 
On the other hand, on a color developer, various attempts have hitherto 
been made for increasing the development. In these attempts, various 
additives have been investigated for increasing the permeation of a color 
developing agent into color coupler-dispersed oil drops to accelerate 
coloring, and in particular, a process of quickening the color development 
by adding benzyl alcohol to a color developer has been widely used for the 
processing of color photographic light-sensitive materials, particularly 
color photographic papers since the process has a high coloring 
accelerating effect. 
However, since benzyl alcohol has low water-solubility, in the case of 
using benzyl alcohol it is required to use a solvent such as diethylene 
glycol, triethylene glycol, alkanolamine, etc. However, since the 
aforesaid compounds including benzyl alcohol give high BOD and COD, which 
are pollution-giving values, it is preferred not to use benzyl alcohol for 
the purpose of reducing the pollution load. 
Furthermore, even in the case of using the aforesaid solvent, it takes a 
long period of time to dissolve benzyl alcohol in the solvent and hence 
for the purpose of reducing the working load for preparing the liquid, it 
is better not to use benzyl alcohol. 
Also, when benzyl alcohol is carried in a bleach bath or a blix bath, which 
is a post-bath, it causes the formation of leuco dyes of cyan dyes, which 
results in the reduction of color density. Furthermore, the entrance of 
benzyl alcohol delays the washing out speed of the developer components, 
which sometimes gives bad influences on the image storage stability of 
processed light-sensitive materials. Accordingly, it is better not to use 
benzyl alcohol in the reasons described above. 
A color development has generally been performed in from 3 minutes to 4 
minutes but it has been desired to further shorten the processing time 
with the recent desirement for shortening the time for delivery of 
finished products and the reduction of laboratory works. 
However, in the case of omitting benzyl alcohol which is a coloring 
accelerator and shortening the developing time, a severe reduction in 
color density inevitably occurs. 
For solving the problems, even when various kinds of color development 
accelerators (for example, compounds as described in U.S. Pat. Nos. 
2,950,970, 2,515,147, 2,496,903, 2,304,925, 4,038,075, and 4,119,462, 
British Patent Nos. 1,430,998, and 1,445,413, Unexamined Published 
Japanese Patent Application Nos. 15831/78, 62450/80, 62451/80, 62452/80, 
and 62453/80, Japanese Patent Publication Nos. 12422/76 and 49728/80) are 
employed together, sufficient color density has not yet been obtained. 
Also, even when techniques of incorporating 3-pyrazolidones (for example, 
techniques as described in Unexamined Published Japanese Patent 
Application Nos. 26338/85, 158444/85, and 158446/85) are used, the use of 
such a technique is accompanied by a disadvantage that the sensitivity is 
reduced and fog forms in the case of storing the color photographic 
materials in unexposed state. 
Furthermore, even when techniques of incorporating color developing agents 
(for example, techniques as described in U.S. Pat. Nos. 3,719,492, 
3,342,559, and 3,342,597, Unexamined Published Japanese Patent Application 
Nos. 6235/81, 16133/81, 97531/82, and 83565/82) are used, the use of such 
a technique is accompanied by a disadvantage that the color development is 
delayed and fog forms, and the techniques are improper. 
Still further, as a process of completely removing benzyl alcohol from a 
color developer or a process of reducing the content of benzyl alcohol in 
a color developer, it is proposed to use a silver chlorobromide core/shell 
type emulsion containing 50 to 97 mol% of silver bromide, the content of 
silver bromide in the surface portion (shell portion) thereof being higher 
than that in the inside (core portion) thereof in Unexamined Published 
Japanese Patent Application No. 48755/84 or to employ relatively small 
silver halide grains of up to 0.6 .mu.m and further to incorporate 
phenidone or a derivative thereof in light-sensitive material in 
Unexamined Published Japanese Patent Application No. 26339/85, which also 
teaches the use of a monodispersed emulsion having a variation coefficient 
of up to 0.15. However, these propositions are yet insufficient in the 
points of the color density obtained, etc., for processing light-sensitive 
materials in a short developing time of up to 2 minutes and 30 seconds 
using substantially no benzyl alcohol for the color developer. 
The first object of this invention is, therefore, to provide a color 
image-forming process giving high color density in a short period of time 
using a color developer substantially free from benzyl alcohol. 
The second object of this invention is to provide a color image-forming 
process giving less fog and with quick development 
DISCLOSURE OF THE INVENTION 
As the result of various investigations on attaining the aforesaid objects, 
the inventors have discovered that in the case of using a color 
photographic paper employing a core/shell surface latent image type 
monodispersed silver halide emulsion containing substantially no silver 
iodide, having a silver chloride content of up to 80 mol%, and having a 
silver bromide content in the shell portion lower than that in the core 
portion, high color density is obtained in a short developing time and the 
formation of fog is less even in the case of using a color developer 
containing substantially no benzyl alcohol, and they have achieved this 
invention. 
That is, according to this invention, there is provided a color 
image-forming process which comprises developing a photographic 
light-sensitive material comprising a reflective support having provided 
thereon at least one silver halide emulsion layer containing a core/shell 
surface latent image type monodispersed silver halide emulsion containing 
substantially no silver iodide, having a silver chloride content of up to 
80 mol%, and having a silver bromide content in the shell portion lower 
than that in the core portion with a color developer containing 
substantially no benzyl alcohol within 2 minutes and 30 seconds. 
Now, the term "containing substantially no benzyl alcohol or substantially 
free from benzyl alcohol" used in this invention means the concentration 
of benzyl alcohol in a color developer is less than 0.5 ml/liter, 
preferably no benzyl alcohol is present in the color developer at all. 
The core/shell surface latent image type monodispersed silver halide 
emulsion for use in this invention has an average grain size of, 
preferably, from 0.1 .mu.m to 2 .mu.m, and more preferably, from 0.2 .mu.m 
to 1.3 .mu.m in the expression by the diameter of an equivalent circle by 
projection. Also, the grain size distribution showing the extent of the 
monodispersion is, preferably, up to 0.15, and more preferably up to 0.10 
in the ratio (S/d) of the statistical standard deviation (S) to the 
average grain size (d). 
The surface latent image type monodispersed core/shell silver halide 
emulsion for use in this invention can be produced by conventionally known 
processes. Typically, the surface latent image type monodispersed 
core/shell silver halide emulsion is obtained by simultaneously adding an 
aqueous solution of an alkali halide and an aqueous solution of silver 
nitrate at definite rates with vigorously stirring at a definite 
temperature to form a silver bromide emulsion or a silver chlorobromide 
emulsion as core, and further simultaneously adding an aqueous alkali 
halide solution and an aqueous silver nitrate solution to the silver 
halide emulsion thus formed in such an amounts that a content of silver 
chloride becomes higher than that of the aforesaid silver halide to form a 
layer (shell) of silver chloride or silver chlorobromide on the surfaces 
of the aforesaid core grains. In addition, about the core/shell emulsion, 
the description of Unexamined Published Japanese Patent Application No. 
215540/86 can be referred. 
For attaining the objects of this invention, it is preferred to control the 
amount of the aqueous alkali solution added such that the content of 
silver bromide in the core portion becomes at least 10 mol% (more 
preferably at least 15 mol%, and more preferably at least 20 mol%) higher 
than the silver bromide content in the shell portion. 
A surface latent image type emulsion is an emulsion forming latent images 
mainly at the surface of the silver halide grains thereof upon exposure as 
well known in the field of the art and is distinguished from an internal 
latent image type emulsion forming latent images mainly in the inside of 
the grains. 
The core/shell surface latent image type monodispersed silver halide 
emulsion which is used for the light-sensitive material in this invention 
contains silver bromide and/or silver chlorobromide substantially free 
from silver iodide and is preferably a silver chlorobromide emulsion 
containing from 2 mol% to 80 mol%, more preferably at least 2 mol% and 
less than 50 mol% of silver chloride. 
The silver halide grains for use in this invention may have different phase 
between the inside and the surface layer thereof, may be a multiphase 
structure having a junction structure, or may be composed of a uniform 
phase through the whole grain. Also, the silver halide grains may be 
composed of a mixture of these silver halide grains. 
The silver halide grains for use in this invention may have a regular 
crystal form such as cube, octahedron, dodecahedron, tetradecahedron, 
etc., an irregular crystal form such as sphere, etc., or a composite form 
of these crystal forms but has preferably a regular crystal form such as 
cube, tetradecahedron, etc. Also, a tabular grain may be used in this 
invention and in particular, an emulsion wherein tabular grains having a 
length/thickness ratio of at least 5, and particularly at least 8, account 
for at least 50% of the total projected area of grains can be preferably 
used in this invention. The emulsion may contain these various crystal 
forms as a mixture. These various kinds of silver halide emulsions are of 
a core/shell surface latent image type forming latent images mainly on the 
surface of grain thereof. 
The photographic emulsions for use in this invention can be prepared by the 
methods described in P. Glafkides, Chimie et Physique Photographique, 
(published by Paul Montel, 1967). G.F. Duffin, Photographic Emulsion 
Chemistry, (published by Focal Press, 1966), V.L. Zelikman et al, Making 
and Coating Photographic Emulsion, (published by Focal Press, 1964), etc. 
That is, the emulsion can be prepared by any of an acid method, a neutral 
method, an ammonia method, etc., and as one system of reacting a soluble 
silver salt and a soluble halide, any of a single jet method, a double jet 
method, and a combination thereof may be employed. A method of forming 
grains in the existence of excess silver ions (so-called reverse mixing 
method) can be also used. As one system of the double jet method, a method 
of keeping pAg in a liquid phase of forming silver halide constant, that 
is, a so-called controlled double jet method, can also be used. According 
to this method, an emulsion containing silver halide grains having a 
regular crystal form and substantially uniform grain size can be obtained. 
Furthermore, an emulsion prepared by a so-called conversion method 
including a step of coverting a silver halide already formed before 
finishing the formation of the silver halide grains into a silver halide 
having small solubility product or a silver halide emulsion to which the 
similar halogenation conversion was applied after finishing the formation 
of the silver halide grains can also be used in this invention. 
During the formation or physical ripening of the silver halide grains, a 
cadmium salt, a zinc salt, a thallium salt, an iridium salt or the complex 
salt thereof, a rhodium salt or the complex salt thereof, an iron salt or 
the complex salt thereof may exist in the system for the purposes of 
preventing the reciprocity failure, increasing sensitivity, or controlling 
gradation. 
Silver halide emulsions are, after the formation of the silver halide 
grains, usually physically ripened, desalted, and chemically ripened 
before coating. 
A known silver halide solvent (e.g., ammonia, potassium rhodanate, and 
thioether and thione compounds described in U.S. Pat. No. 3,271,157, 
Unexamined Published Japanese Patent Application Nos. 12360/76, 82408/78, 
144319/78, 100717/79, 155828/79, etc.) can be used for the precipitation, 
physical ripening, and chemical ripening. 
For removing soluble salts from emulsions after physical ripening, a noodle 
washing method, a flocculation method, or an ultrafiltration method can be 
employed. 
The silver halide emulsions of the color light-sensitive materials for use 
in this invention can be sensitized by a sulfur sensitization method using 
active gelatin or a sulfur-containing compound capable of reacting with 
silver (e.g., thiosulfates, thiourea, mercapto compounds and rhodanines); 
a reduction sensitization method using a reducing substance (e.g., 
stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, 
silane compounds, etc.); a noble metal sensitization method using a metal 
compound (e.g., gold complex salts and complex salts of metals belonging 
to group VIII of the Periodic Table, such as Pt, Ir, Pd, Rh, Fe, etc.), or 
a combination thereof. 
Of the above-described chemical sensitizations, the use of the sulfur 
sensitization singly is more preferred. 
For meeting the desired gradation aimed by the color photographic 
light-sensitive material in this invention, a single layer or plural 
layers of silver halide emulsion layers having substantially same color 
sensitivity can be composed of two or more kinds of monodispersed silver 
halide emulsions (preferably having the above-described coefficient of 
deviation) each having different grain size as a mixture of the emulsions 
or with separately coating the emulsions in a form of multilayer, 
respectively. Furthermore, a combination of two or more kinds of 
monodispersed silver halide emulsions or a combination of a monodispersed 
emulsion and a polydispersed emulsion can be used in a single layer or 
plural layers. 
The blue-sensitive emulsion, green-sensitive emulsion, and red-sensitive 
emulsion of the light-sensitive material which is used in this invention 
are spectrally sensitized by methine dyes, etc., such that these emulsions 
have each color sensitivity. 
The dyes for use include cyanine dyes, merocyanine dyes, complex cyanine 
dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, 
styryl dyes, and hemioxonol dyes. Particularly useful dyes are dyes 
belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. 
For these dyes can be applied nuclei ordinarily utilized for cyanine dyes 
as basic heterocyclic nuclei. That is, pyrroline nuclei, oxazoline nuclei, 
thiazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, 
selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, 
etc.; the nuclei formed by fusing an alicyclic hydrocarbon ring to the 
aforesaid nuclei, and the nuclei formed by fusing an aromatic hydrocarbon 
ring to the aforesaid nuclei, such as indolenine nuclei, benzindolenine 
nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, 
benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, 
benzimidazole nuclei, quinoline nuclei, etc., can be applied. These nuclei 
may be substituted on carbon atoms. 
For merocyanine dyes or complex merocyanine dyes may be applied 5-membered 
or 6-membered heterocyclic nuclei such as pyrazolin-5-one nuclei, 
thiohydantoin nuclei, 2-thiooxaz-oline-2,4-dione nuclei, 
thiazolidine-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid 
nuclei, etc., as a nucleus having a ketomethylene structure. 
These sensitizing dyes may be used singly or as a combination thereof. A 
combination of sensitizing dyes is frequently used for the purpose of 
supersensitization. Typical examples of the combinations are described in 
U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 
3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 
3,769,301, 3,814,609, 3,837,862 and 4,026,70, British Patents 1,344,281 
and 1,507,803, Japanese Patent Publication Nos. 4936/68 and 12375/78, 
Unexamined Published Japanese Patent Application Nos. 110618/77, 
109925/77, etc. 
The emulsion for use in this invention may contain, together with the 
sensitizing dye (s), a dye having no spectral sensitizing activity by 
itself or a substance which does not substantially absorb visible light 
and shows supersensitizing activity. 
It is preferred that the color couplers incorporated in the light-sensitive 
materials in this invention are rendered non-diffusible by a ballast group 
or by being polymerized. Furthermore, the use of 2-equivalent color 
couplers the coupling active position of which is substituted by a 
releasing group is more effective for reducing the amount of silver coated 
than the case of using 4-equivalent color couplers having a hydrogen atom 
at the coupling active position thereof. Couplers providing colored dyes 
having a proper diffusibility, colorless compound forming couplers, DIR 
couplers releasing a development inhibitor with the coupling reaction 
thereof or couplers releasing a development accelerator with the coupling 
reaction thereof can be used. 
Typical examples of the yellow couplers for use in this invention are 
oil-protect type acylacetamide-series couplers. Specific examples of the 
couplers are described in U.S. Pat. Nos. 2,407,210, 2,875,057, 3,265,506, 
etc. 
In this invention, 2-equivalent yellow couplers are preferably used and 
typical examples thereof are oxygen atom-releasing type yellow couplers 
described in U.S. Pat. Nos. 3,408,194, 3,447,928, 3,933,501, 4,022,620, 
etc., and nitrogen atom-releasing type yellow couplers described in 
Japanese Patent Publication No. 10739/83, U.S. Pat. Nos. 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, 2,433,812, etc. .alpha.-Pivaloylacetanilide-series 
couplers are excellent in fastness, in particular, light fastness of the 
colored dyes formed, while .alpha.-benzoylacetanilide-series couplers give 
high color density. 
As the magenta couplers for use in this invention, there are oil-protect 
type indazolone-series or cyanoacetyl-series magenta couplers, preferably 
5-pyrazolone-series couplers and pyrazoloazole-series couplers such as 
pyrazolo-triazole-series couplers. 
As the 5-pyrazolone-series couplers, the couplers having an arylamino group 
or an acylamino group at the 3-position are preferred in the view points 
of the hue of the colored dyes and color density. Typical examples of the 
couplers are described in U.S. Pat. Nos. 2,311,082, 2,343,703, 2,600,788, 
2,908,573, 3,062,653, 3,152,896, 3,936,015, etc. Preferred releasing 
groups for the 2-equivalent 5-pyrazolone-series couplers include nitrogen 
atom-releasing groups described in U.S. Patent 4,310,619 and arylthio 
groups described in U.S. Pat. No. 4,351,897. Also, 5-pyrazolone-series 
couplers having a ballast group described in European Patent 73,636 give 
high color density. 
Pyrazoloazole-series couplers include pyrazolobenzimidazoles described in 
U.S. Patent 3,369,879, preferably pyrazolo[5,1-c][1,2,4]triazoles 
described in U.S. Pat. No. 3,725,067, pyrazolotetrazoles described in 
Research Disclosure, No. 24220 (June, 1984), and pyrazolotetrazoles 
described in Research Disclosure, No. 24230 (June, 1984). From the view 
point of less yellow side absorption of colored dyes and high light 
fastness of colored dyes, imidazo-[1,2-b]pyrazoles described in European 
Patent 119,741 are preferred and pyrazolo[1,5-b][1,2,4]triazoles described 
in European Patent 119,860 are particularly preferred. 
Cyan couplers for use in this invention include oil-protect type naphthoic 
and phenolic couplers. 
Typical examples of the naphtholic couplers include naphthoic couplers 
described in U.S. Pat. No. 2,474,293, and preferably oxygen atom-releasing 
type 2-equivalent naphthoic couplers described in U.S. Pat. Nos. 
4,052,212, 4,146,396, 4,228,233 and 4,296,200. Also, specific examples of 
the phenolic couplers are described in U.S. Pat. Nos. 2,369,929, 
2,801,171, 2,772,162, 2,895,826, etc. The cyan couplers having high 
fastness to moisture and heat are preferably used in this invention, and 
typical examples thereof are the phenolic cyan couplers having an ethyl 
group or higher alkyl group at the meta-position of the phenol nucleus 
described in U.S. Pat. Nos. 3,772,002, 2,5-diacylamino-substituted 
phenolic couplers described in U.S. Pat. Nos. 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, Japanese Patent Application No. 42671/83, etc., and 
phenolic couplers having a phenylureido group at the 2-position thereof 
and an acylamino group at the 5-position thereof described in U.S. Pat. 
Nos. 3,446,622, 4,333,999, 4,451,559, 4,427,767, etc. 
The graininess can be improved by using a coupler giving colored dye having 
a proper diffusibility together. In regard to such couplers giving 
diffusible dyes, specific examples of the magenta couplers are described 
in U.S. Pat. No. 4,366,237 and British Patent 2,125,570 and specific 
examples of the yellow, magenta, and cyan couplers are described in 
European Patent 96,570 and West German Patent Application (OLS) No. 
3,234,533. 
The dye-forming couplers and the specific couplers described above may form 
a dimer or higher polymer. Typical examples of the polymerized dye-forming 
couplers are described in U.S. Pat. Nos. 3,451,820 and 4,080,211. Also, 
specific examples of the polymerized magenta couplers are described in 
British Patent 2,102,173 and U.S. Pat. No. 4,367,282. 
The couplers for use in this invention can be used for one light-sensitive 
emulsion layer as a mixture of two or more for meeting the properties 
required for the light-sensitive material or the same kind of compound may 
exist in different, two or more layers. 
The couplers for use in this invention can be introduced into 
light-sensitive materials by an oil drop-in-water dispersion method. That 
is, the coupler is dissolved in a single solution of a high boiling 
organic solvent having boiling point of at least 175.degree. C. or a low 
boiling so-called auxiliary solvent, or a mixture solution of both types 
of solvents, and then finely dispersed in water or an aqueous medium such 
as an aqueous gelatin solution in the presence of a surface active agent. 
Examples of the high boiling organic solvent are described in U.S. Pat. 
No. 2,322,027, etc. In this case, the coupler may be dispersed with phase 
inversion and also, if necessary, the auxiliary solvent may be removed or 
reduced by distillation, noodle washing, ultrafiltration, etc. before 
coating the dispersion. 
Specific examples of the high boiling organic solvent are phthalic acid 
esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl 
phthalate, decyl phthalate, etc.), phosphoric acid esters or phosphonic 
acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 
2ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl 
phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl 
phosphate, di-2-ethylhexyl phenyl phosphate, etc.), benzoic acid esters 
(e.g., 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxy 
benzoate, etc.), amides (e.g., diethyldodecanamide, 
N-tetradecylpyrrolidone, etc.), alcohols or phenols (e.g., isostearyl 
alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters 
(e.g., dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl 
citrate, etc.), aniline derivatives (e.g., 
N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (e.g., 
paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), etc. 
As the auxiliary solvent, organic solvents having boiling point of at least 
about 30.degree. C., preferably from about 50.degree. C. to about 
160.degree. C. can be used, and specific examples thereof are ethyl 
acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, 
cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, etc. 
The process and effect of the latex dispersing method and specific examples 
of the latex for impregnation are described in U.S. Pat. No. 4,199,363, 
West German Patent Application (OLS) Nos. 2,541,274, 2,541,230, etc. 
A standard amount of the color coupler is in the range of from 0.001 mol to 
1 mol per mol of the light-sensitive silver halide, with from 0.01 mol to 
0.5 mol of a yellow coupler, from 0.003 mol to 0.3 mol of a magenta 
coupler, and from 0.002 mol to 0.3 mol of a cyan coupler, per mol of the 
light-sensitive silver halide being preferred. 
The light-sensitive materials for use in this invention may further contain 
hydroquinone derivatives, aminophenol derivatives, amines, gallic acid 
derivatives, catechol derivatives, ascorbic acid derivatives, colorless 
compound-forming couplers, sulfonamidophenol derivatives, etc., as color 
fog preventing agents or color stain preventing agents. 
Also, the light-sensitive materials for use in this invention can further 
contain known discoloration inhibitors. Typical examples of organic color 
stain preventing agents are hydroquinone, 6-hydroxychromans, 
5-hydroxycoumarans, spirochromans, p-alkoxyphenols, bisphenols, hindered 
phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, 
hindered amines, and the ether or ester derivatives of the aforesaid 
compounds obtained by silylating or alkylating the phenolic hydroxy groups 
of these compounds. Also, metal complexes represented by 
(bissalicylaldoxymato)nickel complexes and 
(bis-N,N-dialkyldithiocarbamato)nickel complexes can also be used. 
For preventing the deterioration of yellow dye images by heat, moisture, 
and light, the compound having both moiety structures of hindered amine 
and hindered phenol in one molecule as described in U.S. Pat. No. 
4,268,593 gives good results. Also, for preventing the deterioration of 
magenta dye images, particularly by light, spiroindans described in 
Unexamined Published Japanese Patent Application No. 159644/81 and 
chromans substituted by hydroquinone diether or monoether described in 
Unexamined Published Japanese Patent Application No. 89835/80 give 
preferred results. 
For improving the storage stability, in particular, the light fastness of 
cyan dye images, it is preferred to use a benzotriazole-series ultraviolet 
ray absorbent together. This ultraviolet ray absorbent may be 
co-emulsified with the cyan coupler(s). The coating amount of the 
ultraviolet ray absorbent is desirably sufficient for imparting light 
stability to cyan dye images, but if the amount is too much, the unexposed 
portions (background portions) of the color photographic light-sensitive 
material are sometimes yellowed, the amount thereof is usually selected in 
the range of from 1 .times. 10.sup.-4 mol/m.sup.2 to 2 .times. 10.sup.-3 
mol/m.sup.2, and particularly from 5 .times. 10.sup.-4 mol/m.sup.2 to 1.5 
.times. 10.sup.-3 mol/m.sup.2. 
In the light-sensitive layer structure of an ordinary color photographic 
paper, the ultraviolet ray absorbent(s) are incorporated in one or both 
layers adjacent to a red-sensitive emulsion layer containing cyan coupler. 
When the ultraviolet ray absorbent(s) are incorporated in the interlayer 
between a green-sensitive layer and a red-sensitive layer, the ultraviolet 
ray absorbent(s) may be emulsified together with a color stain preventing 
agent. When the ultraviolet ray absorbent(s) are incorporated in a 
protective layer, another protective layer may be formed as the outermost 
layer. The protective layer may contain a matting agent having a proper 
particle size, etc. 
In the light-sensitive materials for use in this invention, the ultraviolet 
ray absorbent(s) can be incorporated in hydrophilic colloid layers. 
The light-sensitive materials for use in this invention may further contain 
water-soluble dyes in the hydrophilic colloid layers as filter dyes or for 
the purpose of irradiation prevention, halation prevention, and the like. 
The light-sensitive materials for use in this invention may further contain 
whitening agents such as stilbene-series, triazine-series, oxazole-series, 
or coumarin-series whitening agents in the photographic emulsion layers or 
other hydrophilic colloid layers. The whitening agent may be 
water-soluble, or a water-insoluble whitening agent may be used in the 
form of a dispersion. 
The process of this invention can be applied to a multilayer multicolor 
photographic material having at least two emulsion layers each having 
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 order of these layers may 
be optionally selected as the case demands. Also, each of the aforesaid 
emulsion layers may be composed of two or more emulsion layers each having 
different sensitivity or a light-insensitive layer may exist between two 
or more emulsion layers each having the same sensitivity. 
The light-sensitive material for use in this invention preferably has 
auxiliary layers such as protective layer(s), interlayers, a filter layer, 
an antihalation layer, a back layer, etc., in addition to the silver 
halide emulsion layers. 
As a binder or protective colloid which can be used for the emulsion layers 
and auxiliary layers of the light-sensitive material for use in this 
invention, gelatin is advantageously used but other hydrophilic colloids 
can also be used. 
For example, proteins such as gelatin derivatives, graft polymers of 
gelatin and other polymers, albumin, casein, etc.; cellulose derivatives 
such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose 
sulfuric acid ester, etc.; saccharose derivatives such as sodium alginate, 
starch derivatives, etc.; and various synthetic hydrophilic polymeric 
substance such as homopolymers or copolymers, e.g., polyvinyl alcohol, 
polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic 
acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, 
polyvinylpyrazole, etc., can be used. 
As gelatin, lime-processed gelatin as well as acid-processed gelatin and 
enzyme-processed gelatin as described in Bull. Soc. Sci. Photo. Japan, No. 
16, p. 30 (1966) can be used. Furthermore, the hydrolyzed product or 
enzyme-decomposed product of gelatin can be used. 
The light-sensitive materials for use in this invention may further contain 
various stabilizers, stain preventing agents, developing agents or the 
precursors thereof, development accelerators or the precursors thereof, 
lubricants, mordants, matting agents, antistatic agents, plasticizers, or 
other various additives useful for photographic light-sensitive materials 
in addition to the above-described additives. Typical examples of such 
additives are described in Research Disclosure, No. 17643 (December, 1978) 
and ibid., No. 18716 (November, 1979). 
The "reflective support" for use in this invention is a support having high 
reflectivity for clearly viewing color images forming in silver halide 
emulsion layer(s) and includes a support coated with a hydrophilic resin 
having dispersed therein a light reflective substance such as titanium 
oxide, zinc oxide, calcium carbonate, calcium sulfate, etc., and a support 
composed of a hydrophobic resin containing the light reflective substance 
in a dispersed state. Examples of such support include baryta papers, 
polyethylene-coated papers, polypropylene-series synthetic papers, and 
transparent supports coated with the reflective layer or containing the 
reflective substance, such as glass plates, polyester films, e.g., 
polyethylene terephthalate, cellulose triacetate, cellulose nitrate, etc., 
polyamide films, polycarbonate films, polystyrene films, etc. These 
supports can be properly selected according to the using purpose thereof. 
Then, the processing steps (image-forming steps) of this invention are 
described. 
In the color image processing step in this invention, the processing time 
is as short as up to 2 min. and 30 sec., preferably from 30 sec. to 2 min. 
and 30 sec. The processing time in this case is a period from the time at 
which a light-sensitive material is brought into contact with a color 
developer to the time of the light-sensitive material coming into contact 
with the subsequent bath and includes the transporting time between both 
baths. 
A color developer which is used for the development process of this 
invention is preferably an alkaline aqueous solution containing an 
aromatic primary amine-series color developing agent as the main 
component. As the color developing agent, p-phenylenediamine-series 
compounds are preferably used and typical examples thereof are 
3-methyl-4-amino-N,N-diethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-methoxyethylaniline and the sulfates, 
hydrochlorides, phosphates, p-toluenesulfonates, tetraphenylborates, 
p-(t-octyl)benzenesulfonates, etc., thereof. In particular, the use of 
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamide and the salts thereof 
is preferred. 
Aminophenol-series derivatives include, for example, o-aminophenol, 
p-aminophenol, 4-amino-2-methylphenol, 2-amino-3-methylphenol, 
2-oxy-3-amino-1,4-dimethylbenzene, etc. 
Other color developing agents described in L.F.A. Mason, Photographic 
Processing Chemistry, pages 226-229, published by Focal Press, (1966), 
U.S. Pat. Nos. 2,193,015 and 2,592,364, Unexamined Published Japanese 
Patent Application No. 64933/73, etc., may also be used. If necessary, a 
combination of two or more kinds of color developing agents can be used. 
The processing temperature of the color developer in this invention is 
preferably from 30.degree. C. to 50.degree. C., and more preferably from 
35.degree. C. to 45.degree. C. 
As the development accelerator, various compounds may be used provided that 
benzyl alcohol is not substantially contained therein. Examples of the 
development accelerator are various pyrimidium compounds described in U.S. 
Pat. No. 2,648,604, Japanese Patent Publication No. 9503/69 and British 
Patent 3,171,247, other cationic compounds, cationic dyes such as 
phenosafranine, etc., neutral salts such as thallium nitrate, potassium 
nitrate, etc., polyethylene glycol and the derivatives thereof described 
in Japanese Patent Publication No. 9304/69, U.S. Pat. Nos. 2,533,990, 
2,531,832, 2,950,970 and 2,577,127, nonionic compounds such as 
polythioethers, etc., thioether-series compounds described in U.S. Pat. 
No. 3,201,242, etc., and other compounds described in Unexamined Published 
Japanese Patent Application Nos. 156934/83 and 220344/85. 
In short-time development processing as in this invention, not only the 
technique of accelerating the development but also the technique of 
preventing the formation of developing fog are important. As antifoggants 
for use in this invention, alkali metal halides such as potassium bromide, 
sodium bromide or potassium iodide, and organic antifoggants are 
preferred. As the organic antifoggants, there are nitrogen-containing 
heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 
5-nitroisoindazole, 5methylbenzotriazole, 5-nitrobenzotriazole, 
5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 
2-thiazolemethylbenzimidazole or hydroxyazaindolizine, mercaptosubstituted 
heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 
2-mercaptobenzimidazole or 2-mercaptobenzothiazole, and 
mercapto-substituted aromatic compounds such as thiosalicylic acid. 
Particularly preferred antifoggants are the halides. The antifoggants may 
be accumulated in a color developer dissolved out from color 
light-sensitive materials during processing. 
In addition, the color developers for use in this invention may further 
contain pH buffers such as carbonates, borates or phosphates of an alkali 
metal; preservatives such as hydroxylamine, triethanolamine, the compounds 
described in West German Patent Application (OLS) No. 2,622,950, sulfites 
or bisulfites; organic solvents such as diethylene glycol, etc.; 
dye-forming couplers; competing couplers; nucleating agents such as sodium 
borohydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; 
viscosity imparting agents; and chelating agents such as 
ethylenediaminetetraacetic acid, nitrilotriacetic acid, 
cyclohexanediaminetetraacetic acid, iminodiacetic acid, 
N-hydroxymethylethylenediaminetriacetic acid, 
diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 
aminopolycarboxylic acid represented by the compounds described in 
Unexamined Published Japanese Patent Application No. 195845/83, etc., 
1-hydroxyethylidene-1,1'-diphosphonic acid, the organic phosphonic acids 
described in Research Disclosure, No. 18170 (May, 1979), aminophosphonic 
acids, e.g., aminotris(methylenephosphonic acid), 
ethylenediamine-N,N,N'-tetramethylenephosphonic acid, etc., 
phosphonocarboxylic acids described in Unexamined Published Japanese 
Patent Application Nos. 102726/77, 42730/78, 121127/79, 4024/80, 4025/80, 
126241/80, 65955/80, 65956/80, and Research Disclosure, No. 18170 (May, 
1979), etc. 
Also, the color developing bath is composed of two or more baths and a 
replenisher for the color developer may be supplied from the foremost bath 
or the last bath to reduce the development time and the amount of the 
replenisher. 
The silver halide color light-sensitive materials are usually subjected to 
bleach processing after color development. The bleach process may be 
performed simultaneously (bleach-fix or blix) with or separately from a 
fix process. 
As the bleaching agent, compounds of polyvalent metals such as iron(III), 
cobalt(III), chromium(VI), copper(II), etc., peracids, quinones, nitroso 
compounds, etc., are used. Specific examples of the bleaching agent 
include ferricyanides; dichromates; organic complex salts of iron(III) or 
cobalt(III); organic complex salts of aminopolycarboxylic acids, e.g., 
ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 
nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, etc., or 
other organic acids, e.g., citric acid, tartaric acid, malic acid, etc.; 
persulfates; manganates; nitrosophenol; etc., can be used. Of these 
substances, potassium pherricyanide, sodium ethylenediaminetetraacetato 
ferrate, ammonium ethylenediaminetetraacetato ferrate, ammonium 
triethylenetetraminepentaacetato ferrate, and persulfates are particularly 
advantageous. Ethylenediaminetetraacetic acid iron(III) complex salts are 
advantageously used for a bleach solution or a mono bath blix solution. 
Also, the bleach solution or the blix solution may contain, if necessary, 
various kinds of accelerators. Examples of such accelerators are bromine 
ions, iodine ions as well as thiourea-series compounds described in U.S. 
Pat. No. 3,706,561, Japanese Patent Publication Nos. 8506/70 and 26586/74, 
Unexamined Published Japanese Patent Application Nos. 32735/78, 36233/78, 
and 37016/78, thiol-series compounds described in Unexamined Published 
Japanese Patent Application Nos. 124424/78, 95631/78, 57831/78, 32736/78, 
65732/78, and 52534/79, U.S. Pat. No. 3,893,858, etc., heterocyclic 
compounds described in Unexamined Published Japanese Patent Application 
Nos. 59644/74, 140129/75, 28426/78, 141623/78, 104232/78, 35727/79, etc., 
thioether-series compounds described in Unexamined Published Japanese 
Patent Application Nos. 20832/77, 25064/80, 26506/80, etc., quaternary 
amines described in Unexamined Published Japanese Patent Application No. 
84440/73, and thiocarbamoyls described in Unexamined Published Japanese 
Patent Application No. 42349/74. 
As a fixing agent, there are thiosulfates, thiocyanates, thioether-series 
compounds, thioureas, a large amount of iodide, etc., but thiosulfates are 
generally used. As preservatives for the blix solution or fix solution, 
sulfites, bisulfites, or carbonyl-bisulfite adducts are preferably used. 
After the blix or fix, water washing is usually performed. In the wash step 
various kinds of compounds may be added for the purposes of preventing 
precipitation or saving water. For example, there are water softeners such 
as inorganic phosphoric acids, aminopolycarboxylic acids, organic 
phosphoric acids, etc., for preventing precipitation, antibacterial or 
antifungal agents for preventing the growth of various bacteria, algae, 
fungi, etc., hardening agents represented by magnesium salts, aluminum 
salts, etc., and surface active agents for reducing drying load or 
preventing drying unevenness. Furthermore, the compounds described in L.E. 
West, Photographic Science and Engineering, Vol. 9, No. 6, (1965) may be 
added. The addition of chelating agents or antifungal agents is 
particularly effective. Also, by employing a multistage (e.g., 2 to 5 
stages) countercurrent system for the wash step, the amount of water can 
also be saved. 
Furthermore, after or in place of the wash step, a multistage 
countercurrent stabilization step as described in Unexamined Published 
Japanese Patent Application No. 8543/82 may be practiced. In the case of 
employing the stabilization step, 2 to 9 countercurrent baths are 
necessary. To the stabilization bath are added various compounds for 
stabilizing color images. Examples of such compounds are buffers for 
adjusting the pH of layers (e.g., borates, metaborates, borax, phosphates, 
carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, 
monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and 
formalin. Furthermore, water softeners (e.g., inorganic phosphoric acids, 
aminopolycarboxylic acids, organic phosphoric acids, aminopolyphosphonic 
acids, phosphonocarboxylic acids, etc.), biocides (e.g., Proxel, 
isothiazolone, 4-thiazolylbenzimidazole, halogenated phenolbenzotriazoles, 
etc.), surface active agents, brightening agents, hardening agents, etc., 
may be added to the stabilization bath. 
Also, as a pH controlling agent for layers after processing, various 
ammonium salts such as ammonium chloride, ammonium nitrate, ammonium 
sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc., 
can be added to the stabilization bath.

BEST MODE FOR PRACTICING THE INVENTION 
Then, the invention is explained in more detail based on the following 
examples. 
Example 1 
A multilayer color photographic paper having the layer structure shown in 
Table I below on a paper support both surfaces of which were laminated 
with polyethylene was prepared. The coating solutions were prepared as 
follows. 
Preparation of Coating Solution For Layer 1: 
27.2 ml of ethyl acetate and 7.9 ml of solvent (c) were added to 19.1 g of 
yellow coupler (a) and 4.4 g of color image stabilizer (b), the mixture 
was dissolved and the solution formed was emulsified and dispersed in 185 
ml of an aqueous 10% gelatin solution containing 8 ml of 10% sodium 
dodecylbenzenesulfonate. On the other hand, 90 g of an emulsion was 
prepared by adding the blue-sensitive sensitizing dye shown below to a 
silver chlorobromide emulsion (containing 80 mol% silver bromide and 70 
g/kg of Ag) in an amount of 7.0.times. 10.sup.-4 mol per mol of silver 
chlorobromide. The emulsified dispersion prepared above was mixed with the 
emulsion prepared above, the mixture was dissolved and the gelatin 
concentration was adjusted so as to realize the composition shown in Table 
I to provide the coating solution for layer 1. 
Coating solutions for layer 2 to layer 7 were also prepared in accordance 
with the aforesaid manner of preparing the coating solution for layer 1. 
In addition, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a 
gelatin hardening agent for each layer. 
As spectral sensitizers for each emulsion, the following sensitizers were 
used. 
For blue-sensitive emulsion layer: 
##STR1## 
(added in an amount of 7.0 .times. 10.sup.-4 mol per mol of silver halide) 
For green-sensitive emulsion layer: 
##STR2## 
(added in an amount of 4.0 .times. 10.sup.-4 mol per mol of silver halide) 
##STR3## 
(added in an amount of 7.0 .times. 10.sup.-5 mol per mol of silver halide) 
For red-sensitive emulsion layer: 
##STR4## 
(added in an amount of 1.0 .times. 10.sup.-4 mol per mol of silver halide) 
As irradiation preventing dyes for each emulsion layer, the following dyes 
were used. 
For green-sensitive emulsion layer: 
##STR5## 
For red-sensitive emulsion layer: 
##STR6## 
The structural formulae of the compounds such as couplers, etc., used in 
the example are shown below. 
(a) Yellow coupler: 
##STR7## 
(b) Color image stabilizer: 
##STR8## 
(c) Solvent: 
##STR9## 
(d) 
##STR10## 
(e) Magenta coupler: 
##STR11## 
(f) Color image stabilizer: 
##STR12## 
(g) Solvent: 
##STR13## 
(2 : 1 by weight ratio) 
(h) Ultraviolet ray absorbent: 
Mixture of 
##STR14## 
(1 : 5 : 3 by mol ratio) 
(i) Color stain preventing agent: 
##STR15## 
(i) Solvent 
##STR16## 
(k) Cyan coupler: 
##STR17## 
(1 : 1 by mol ratio) 
(l) Color image stabilizer: 
Mixture of 
##STR18## 
(1 : 3 : 3 by mol ratio) 
(m) Solvent 
##STR19## 
TABLE 1 
______________________________________ 
Amount 
Layer Main Formulation used 
______________________________________ 
Layer 7 Gelatin 1.33 g/m.sup.2 
(Protective 
layer) Acryl-modified copolymer of poly- 
vinyl alcohol (modification 
degree: 17%) 0.17 g/m.sup.2 
Layer 6 Gelatin 0.54 g/m.sup.2 
(UV ray 
absorbing 
Ultraviolet ray absorbent (h) 
0.21 g/m.sup.2 
layer) 
Solvent (i) 0.09 cc/m.sup.2 
Layer 5 Silver chlorobromide emulsion 
(Red- (AgBr: 70 mol %), Silver amount: 
0.26 g/m.sup.2 
sensitive 
layer) Gelatin 0.98 g/m.sup.2 
Cyan Coupler (k) 0.38 g/m.sup.2 
Color image stabilizer (l) 
0.17 g/m.sup.2 
Solvent (m) 0.23 cc/m.sup.2 
Layer 4 Gelatin 1.60 g/m.sup.2 
(UV ray 
absorbing 
Ultraviolet ray Absorbent (h) 
0.62 g/m.sup.2 
layer) 
Color stain preventing agent (i) 
0.05 g/m.sup.2 
Solvent (j) 0.26 cc/m.sup.2 
Layer 3 Silver chlorobromide emulsion 
(Green- (AgBr: 75 mol %), silver amount: 
0.16 g/m.sup.2 
sensitive 
layer) Gelatin 1.80 g/m.sup.2 
Magenta coupler (e) 0.34 g/m.sup.2 
Color image stabilizer (f) 
0.20 g/m.sup.2 
Solvent (g) 0.68 cc/m.sup.2 
Layer 2 Gelatin 0.99 g/m.sup.2 
(Color 
stain 
preventing 
Color stain preventing agent (d) 
0.08 g/m.sup.2 
layer) 
Layer 1 Silver chlorobromide emulsion 
(Blue- (AgBr: 80 mol %), silver amount: 
0.34 g/m.sup.2 
sensitive 
layer) Gelatin 1.86 g/m.sup.2 
Yellow Coupler (a) 0.82 g/m.sup.2 
Color image stabilizer (b) 
0.19 g/m.sup.2 
Solvent (c) 0.34 cc/m.sup.2 
Support Polyethylene-laminated paper (poly- 
ethylene at the layer 1 side contained 
a white pigment (TiO.sub.2) and a 
bluish dye (ultramarine) 
______________________________________ 
Silver halide emulsion (1) for a comparison blue-sensitive emulsion layer 
was prepared as follows. 
______________________________________ 
(Solution 1) 
##STR20## 1000 cc 5.5 g 25 g 
(Solution 2) 
Sulfuric acid (lN) 20 cc 
(Solution 3) 
Silver halide emulsion (1%) of the 
2 cc 
following structure 
##STR21## 
(Solution 4) 
##STR22## 2.80 g 0.34 g 140 cc 
(Solution 5) 
##STR23## 5 g 140 cc 
(Solution 6) 
##STR24## 67.20 g 8.26 g 0.7 cc 320 cc 
(Solution 7) 
##STR25## 120 g 320 cc 
______________________________________ 
(Solution 1) was heated to 75.degree. C. and (Solution 2) and (Solution 3) 
were added thereto. Thereafter, (Solution 4) and (Solution 5) were 
simultaneously added to the mixture over a 9 minute period. After 10 
minutes, (Solution 6) and (Solution 7) were simultaneously added thereto 
over a 45 minute period. After 5 minutes since the addition, the 
temperature of the mixture was lowered and desalting was performed. Then, 
water and dispersed gelatin were added to the mixture and the pH of the 
resultant mixture was adjusted to 6.2 to provide a monodispersed cubic 
silver chlorobromide emulsion having an average grain size of 1.01 .mu.m, 
a variation coefficient (i.e., a value obtained by dividing a standard 
deviation by average grain size: s/d) of 0.08, and containing 80 mol% of 
silver bromide. Then, sodium thiosulfate was added to the emulsion to 
apply thereto optimum chemical sensitization. 
Silver halide emulsion (2) for comparison blue-sensitive emulsion layer and 
silver halide emulsion (3) for comparison green-sensitive and 
red-sensitive emulsion layers were prepared by the same manner as above 
while changing the amounts of chemicals, the temperature, and the times. 
Silver halide emulsion (4) for comparison blue-sensitive emulsion layer was 
prepared as follows. 
______________________________________ 
(Solution 8) 
H.sub.2 O 700 cc 
NaCl 39.4 g 
Gelatin 28 g 
(Solution 9) 
Sulfuric acid (1N) 
10 cc 
(Solution 10) 
KBr 78.4 g 
K.sub.2 IrCl.sub.6 (0.001%) 
0.7 cc 
Water to make 800 cc 
(Solution 11) 
AgNO.sub.3 140 g 
Water to make 800 cc 
______________________________________ 
(Solution 8) was heated to 75.degree. C. and (Solution (b 9) was added 
thereto. Thereafter, (Solution 10) was added to the mixture over a 40 
minute period and further after one minute since the initiation of the 
addition of (Solution 10), (Solution 11) was added thereto over a 40 
minute period. After 5 minutes since the addition, the temperature of the 
mixture was lowered and desalting was performed. Then, water and dispersed 
gelatin were added to the mixture and the pH of the resultant mixture was 
adjusted to 6.2 to provide a polydispersed silver chlorobromide emulsion 
having an average grain size of 0.82 .mu.m, a deviation coefficient of 
0.27, and containing 80 mol% of silver bromide. Then, sodium thiosulfate 
was added to the emulsion to apply thereto optimum chemical sensitization. 
Silver halide emulsion (5) for comparison green-sensitive and red-sensitive 
emulsion layers was also prepared by the same manner as above while 
changing the amounts of chemicals, the temperature, and the time. 
Silver halide emulsion (6) for the blue-sensitive emulsion layer of this 
invention was prepared as follows. 
______________________________________ 
(Solution 12) 
##STR26## 1000 cc 17.5 g 25 g 
(Solution 13) 
Sulfuric acid (lN) 20 cc 
(Solution 14) 
Silver halide emulsion of the 
following structure (1%) 3 cc 
##STR27## 
(Solution 15) 
##STR28## 17.5 g 130 cc 
(Solution 16) 
##STR29## 25 g 130 cc 
(Solution 17) 
##STR30## 52.50 g 8.60 g 0.7 cc 285 cc 
(Solution 18) 
##STR31## 100 g 285 cc 
______________________________________ 
(Solution 12) was heated to 75.degree. C. and (Solution 13) and (Solution 
14) were added thereto. Thereafter, (Solution 15) and (Solution 16) were 
simultaneously added to the mixture over a 20 minute period. Furthermore, 
after 10 minutes, (Solution 17) and (Solution 18) were simultaneously 
added to the mixture over a 25 minute period. After 5 minutes since the 
addition, the temperature of the mixture was lowered and desalting was 
performed. Then, water and dispersed gelatin were added thereto and the pH 
of the resultant mixture was adjusted to 6.2 to provide a monodispersed 
cubic silver chlorobromide emulsion having an average grain size of 1.00 
.mu.m, a variation coefficient (the value obtained by dividing a standard 
deviation by average grain size) of 0.07, and containing 80 mol% of silver 
bromide. 
Then, sodium thiosulfate was added to the emulsion to apply thereto optimum 
chemical sensitization. 
Silver halide emulsion (7) for the green-sensitive and red-sensitive 
emulsion layers of this invention was also prepared by the same manner as 
above while changing the amount of chemicals, the temperature, and the 
times. 
The average grain sizes, variation coefficients, and halogen compositions 
of silver halide emulsions (1) to (7) thus obtained are shown in Table 2 
below. 
Samples (A), (B), (C), and (D) were prepared by replacing the emulsions 
shown in Table 1 with aforesaid silver halide emulsions (1) to (7). These 
structures are shown in Table 3. 
TABLE 2 
______________________________________ 
Variation Halogen 
Average Grain 
Coefficient 
Composition 
Emulsion Size (.mu.m) 
(s/-d) (%) 
______________________________________ 
(1) 
Comparison 
1.01 0.08 Br = 80, Cl = 20 
example 
(2) 
Comparison 
0.80 0.07 Br = 80, Cl = 20 
example 
(3) 
Comparison 
0.49 0.08 Br = 80, Cl = 20 
example 
(4) 
Comparison 
0.82 0.27 Br = 80, Cl = 20 
example 
(5) 
Comparison 
0.45 0.26 Br = 80, Cl = 20 
example 
(6) 
This 1.00 0.07 Br = 80, Cl = 20 
invention 
(7) 
This 0.53 0.06 Br = 80, Cl = 20 
invention 
______________________________________ 
Emulsion (1) to (3) were not core/shell emulsions but AgBr was distributed 
uniformly in the grains. Emulsions (4) and (5) were not core/shell 
emulsions and AgBr was not uniformly distributed in the grains (that is, 
AgBr was non-uniformly distributed in the grains). Emulsions (4) and (5) 
were polydisperse emulsions having variation coefficients of 0.27 and 
0.26, respectively, which were different from those of the present 
invention. Emulsions (6) and (7) were core/shell emulsions where the AgBr 
content of the core was 100 mol% (that is, the core was AgBr itself) and 
the AgBr content of the shell was 75 mol% (that is, the remainder was 25 
mol% AgCl). 
TABLE 3 
______________________________________ 
Emulsion 
Blue-Sensitive 
Green-Sensitive 
Red-Sensitive 
Sample Layer Layer Layer 
______________________________________ 
(A) (1) (3) (3) 
Comparison Comparison Comparison 
example example example 
(B) (1) + (2) (4/6*) 
(3) (3) 
Comparison Comparison Comparison 
example example example 
(C) (4) (5) (5) 
Comparison Comparison Comparison 
example example example 
(D) (6) (7) (7) 
This This This 
invention invention invention 
______________________________________ 
*4/6 is a weight ratio of (1)/(2) 
Each of Samples (A), (B), (C), and (D) described above was subjected to 
sensitometric gradation exposure through each of blue, green, and red 
filters using a sensitometer (Type FWH, color temperature of light source: 
3,200.degree. K, made by Fuji Photo Film Co., Ltd.). In this case, the 
exposure was performed in such a manner that the exposure amount became 
250 CMS for an exposure time of 0.5 second. 
Thereafter, each sample was subjected to processing A or processing B using 
color developer (A) or color developer (B), respectively, as shown below. 
Each processing was composed of a color development step, a blix step, and 
a wash step and by changing the developing time to 1 minute, 2 minutes, 
and 3 minutes, the photographic properties were evaluated. Processing A 
was different from processing B only in the composition of color developer 
A and color developer B and the processing A was the same as the 
processing B in other contents. The results obtained are shown in Table 4 
below. 
The evaluation of the photographic properties was performed on a four-point 
evaluation such as the relative sensitivity, the gradation, the maximum 
density (Dmax), and the minimum density (Dmin). 
The relative sensitivity is a relative value when the sensitivity of each 
light-sensitive layer of each light-sensitive material color developed for 
2 minutes in processing A is defined as 100. The sensitivity is shown by a 
relative value of the reciprocal of an exposure amount necessary for 
giving a density of the minimum density + 0.5. 
The gradation shows a density difference between a sensitivity point and a 
point where the sensitivity is increased by 0.5 in logarithm of exposure 
amount (logE). 
______________________________________ 
(Processing Step) 
(Temperature) (Time) 
______________________________________ 
Development 38.degree. C. 1 to 3 min. 
Blix 38.degree. C. 1.5 min. 
Wash 28 to 35.degree. C. 
3.0 min. 
______________________________________ 
______________________________________ 
(Formulation of Developer) 
Color Developer (A): 
Nitrilotriacetic Acid.3Na 
2.0 g 
Benzyl Alcohol 15 ml 
Diethylene Glycol 10 ml 
Na.sub.2 SO.sub.3 2.0 g 
KBr 0.5 g 
Hydroxylamine Sulfate 3.0 g 
4-Amino-3-methyl-N--ethyl-N--[.beta.- 
(methanesulfonamido)ethyl]-p- 
phenylenediamine.Sulfate 5.0 g 
Na.sub.2 CO.sub.3 (monohydrate) 
30.0 g 
Water to make 1,000 ml 
(pH 10.1) 
Color Developer (B): 
Nitrilotriacetic Acid.3Na 
2.0 g 
Na.sub.2 SO.sub.3 2.0 g 
KBr 0.5 g 
Hydroxylamine Sulfate 3.0 g 
4-Amino-3-methyl-N--ethyl-N--[.beta.- 
(methanesulfonamido)ethyl]-p- 
phenylenediamine.Sulfate 5.0 g 
Na.sub.2 CO.sub.3 (monohydrate) 
30.0 g 
Water to make 1,000 ml 
(pH 10.1) 
(Formulation of Blix Solution) 
Ammonium Thiosulfate (54 wt. %) 
150 ml 
Na.sub.2 SO.sub.3 15 g 
NH.sub.4 [Fe(III)(EDTA)] 55 g 
EDTA.2Na 4 g 
Water to make 1,000 ml 
(pH 6.9) 
______________________________________ 
3 TABLE 4 
Processing A Processing B Developing Time Developing Time Sam- 1 
minute 2 minutes 3 minutes 1 minute 2 minutes 3 minutes ple Layer RS Gd 
Dmax Dmin RS Gd Dmax Dmin RS Gd Dmax Dmin RS Gd Dmax Dmin RS Gd Dmax 
Dmin RS Gd Dmax Dmin 
B 59 0.99 1.99 0.10 100 1.12 2.10 0.12 119 1.14 2.11 0.12 63 1.00 
1.98 0.09 94 1.11 2.08 0.10 114 1.14 2.10 0.11 (A) G 73 1.21 2.59 0.10 
100 1.30 2.68 0.11 125 1.34 2.72 0.12 81 1.24 2.59 0.10 98 1.28 2.67 
0.11 122 1.31 2.72 0.12 R 80 1.41 2.81 0.11 100 1.43 2.83 0.12 128 1.45 
2.84 0.12 82 1.41 2.78 0.10 97 1.42 2.80 0.12 125 1.44 2.80 0.12 B 65 
1.12 2.14 0.10 100 1.13 2.23 0.12 121 1.13 2.25 0.13 70 1.11 2.13 0.10 
96 1.13 2.20 0.11 115 1.14 2.22 0.12 (B) G 75 1.26 2.57 0.12 100 1.31 
2.68 0.12 124 1.35 2.73 0.13 82 1.22 2.55 0.11 99 1.30 2.67 0.11 121 
1.34 2.71 0.12 R 81 1.40 2.81 0.11 100 1.44 2.83 0.12 129 1.45 2.83 
0.12 81 1.37 2.79 0.10 97 1.42 2.82 0.11 127 1.43 2.83 0.11 B 38 0.81 
1.91 0.12 100 1.02 2.01 0.13 116 1.13 2.04 0.21 33 0.52 1.41 0.11 74 
0.59 1.65 0.12 85 0.61 1.69 0.16 (C) G 51 1.19 2.48 0.11 100 1.24 2.52 
0.14 131 1.26 2.53 0.19 40 0.61 1.75 0.09 81 0.74 1.86 0.13 92 0.78 1.89 
0.15 R 66 1.31 2.60 0.12 100 1.37 2.70 0.14 123 1.38 2.74 0.23 53 0.77 
1.93 0.10 82 0.91 2.08 0.12 90 0.93 2.10 0.17 B 68 1.16 2.14 0.04 100 
1.30 2.24 0.10 117 1.32 2.25 0.12 65 1.15 2.13 0.08 97 1.30 2.23 0.09 
109 1.16 2.24 0.11 (D) G 77 1.24 2.70 0.10 100 1.27 3.74 0.10 129 1.30 
2.75 0.13 81 1.24 2.69 0.09 99 1.30 2.74 0.09 127 1.33 2.75 0.11 R 83 
1.53 2.86 0.11 100 1.55 2.89 0.12 130 1.56 2.89 0.12 84 1.54 2.85 0.04 
98 1.55 2.88 0.11 128 1.55 2.89 0.12 
RS: Relative Sensitivity; Gd: Gradation 
As is clear from the results shown in Table 4 above, when the silver halide 
emulsions (6) and (7) of this invention are used, good photographic 
properties of high sensitivity, high contrast and low Dmin, which are 
almost the same as those in the case of processing with processing A using 
benzyl alcohol, are shown even in the case of processing with processing B 
without containing benzyl alcohol and also sufficiently high color density 
is shown even in the processing of short period of time. Furthermore, even 
in processing B, color images having low fog and high color density with 
high sensitivity are obtained as compared with the case of using 
comparison emulsions (1), (2), and (3). 
Example 2 
Silver halide emulsion (8) for comparison blue-sensitive emulsion layer and 
silver halide emulsion (9) for comparison green-sensitive and 
red-sensitive emulsion layers were prepared by the same manner as the case 
of preparing the silver halide emulsion (6) while changing the amount of 
chemicals, the temperatures, and the times. 
The average grain sizes, the variation coefficients, and the halogen 
compositions of the silver halide emulsions (6) to (9) thus prepared are 
shown in Table 5 below. 
Also, by replacing the emulsions of the emulsion layers shown in Table 1 
with the silver halide emulsions (6) to (9) described above, samples (E), 
(F) and (G) and (I) were prepared. These structures are shown in Table 6. 
Each of the samples (E), (F) and (G) described above was exposed and 
processed in the same manner as in Example 1 and the photographic 
properties were evaluated. However, the evaluation of the photographic 
properties was made on the five points of the processing time for the 
development for 30 seconds, 45 seconds, 1 minute, 2 minutes, and 3 
minutes. 
The results obtained are shown in Table 7 and Table 8. 
TABLE 5 
______________________________________ 
5 
Average 
Grain Variation 
Size Coefficient 
Halogen Composition 
Emulsion (.mu.m) (s/-d) (%) 
______________________________________ 
(6) 
This 1.00 0.07 Br = 80, Cl = 20 
invention 
(7) 
This 0.53 0.06 Br = 80, Cl = 20 
invention 
(8) 
Comparison 
0.95 0.09 Br = 80, Cl = 18, I = 2 
(9) 
Comparison 
0.46 0.10 Br = 80, Cl = 20, I = 2 
______________________________________ 
TABLE 6 
______________________________________ 
Emulsion 
Blue-Sensitive 
Green-Sensitive 
Red Sensitive 
Sample Layer Layer Layer 
______________________________________ 
(E) (6) (7) (7) 
This This This 
invention invention invention 
(F) (8) (9) (9) 
Comparison Comparison Comparison 
example example example 
(G) (8) (7) (7) 
Comparison This This 
example invention invention 
______________________________________ 
3 TABLE 7 
Processing A Developing Time 30 seconds 45 seconds 1 minute 2 minutes 3 
minutes Sample Layer RS Gd Dmax Dmin RS Gd Dmax Dmin RS Gd Dmax Dmin RS 
Gd Dmax Dmin RS Gd Dmax Dmin 
B 22 0.23 0.82 0.08 43 0.63 1.37 0.08 68 1.16 2.14 0.09 100 1.30 2.24 0 
.10 117 1.32 2.25 0.12 (E) G 46 0.80 1.43 0.09 68 1.23 2.22 0.09 77 1.24 
2.70 0.10 100 1.27 2.74 0.10 129 1.30 2.75 0.13 R 47 1.02 1.68 0.08 67 
1.48 2.36 0.09 83 1.53 2.86 0.11 100 1.55 2.89 0.12 130 1.56 2.89 0.12 
B 7 0.12 0.71 0.09 22 0.49 1.16 0.10 47 0.92 2.11 0.10 100 1.05 2.23 
0.11 113 1.10 2.29 0.12 (F) G 21 0.52 1.33 0.09 42 0.71 1.84 0.10 69 
0.87 2.39 0.11 100 0.98 2.48 0.12 117 1.01 2.57 0.13 R 26 0.62 1.36 
0.09 45 0.89 2.14 0.10 71 1.11 2.73 0.10 100 1.25 2.82 0.11 120 1.26 
2.91 0.13 B 6 0.13 0.72 0.09 21 0.50 1.15 0.10 49 0.92 2.12 0.11 100 
1.04 2.24 0.12 115 1.10 2.30 0.12 (G) G 45 0.81 1.44 0.09 68 1.24 2.23 
0.09 78 1.24 2.71 0.10 100 1.28 2.74 0.13 128 1.31 2.74 0.13 R 46 1.03 
1.69 0.08 67 1.47 2.35 0.09 85 1.53 2.86 0.11 100 1.55 2.90 0.12 130 
1.56 2.88 0.13 
RS: Relative Sensitivity; Gd: Gradation 
3 TABLE 8 
Processing B Developing Time 30 seconds 45 seconds 1 minute 2 minutes 3 
minutes Sample Layer RS Gd Dmax Dmin RS Gd Dmax Dmin RS Gd Dmax Dmin RS 
Gd Dmax Dmin RS Gd Dmax Dmin 
B 19 0.20 0.78 0.08 38 0.63 1.30 0.08 65 1.15 2.13 0.08 97 1.30 2.23 
0.09 109 1.16 2.24 0.11 (E) G 44 0.73 1.37 0.08 66 1.17 2.20 0.09 81 
1.24 2.69 0.09 99 1.26 2.74 0.09 127 1.25 2.75 0.11 R 39 0.94 1.58 0.09 
65 1.43 2.31 0.09 84 1.54 2.85 0.09 98 1.55 2.88 0.11 128 1.55 2.89 0.12 
B *-- *-- 0.42 0.08 11 0.21 1.32 0.09 34 0.49 1.33 0.09 68 0.57 1.46 
0.11 81 0.59 1.51 0.11 (F) G 8 0.21 0.81 0.09 24 0.51 1.33 0.10 52 0.68 
1.76 0.10 79 0.76 1.84 0.12 91 0.78 1.93 0.12 R 12 0.29 0.89 0.08 32 
0.65 1.43 0.09 64 0.83 1.93 0.10 81 0.95 2.01 0.11 93 0.98 2.10 0.13 B 
*-- *-- 0.41 0.08 11 0.20 1.33 0.09 33 0.48 1.33 0.10 69 0.58 1.47 0.11 
80 0.59 1.52 0.12 (G) G 44 0.72 1.38 0.08 65 1.16 2.20 0.08 80 1.23 2.70 
0.09 98 1.24 2.74 0.11 127 1.24 2.75 0.12 R 40 0.95 1.57 0.08 64 1.42 
2.30 0.09 84 1.54 2.85 0.10 98 1.56 2.87 0.10 126 1.56 2.89 0.12 
(*): Sensitivity is not shown since Dmax does not reach for density + 0.5 
RS: Relative Sensitivity; Gd: Gradation 
As is clear from the results shown in Tables 7 and 8 above, when the silver 
halide emulsions (6) and (7) of this invention are used, good photographic 
performance, which is almost the same as the case of processing with 
processing A using benzyl alcohol, is shown even in the case of processing 
with processing B without containing benzyl alcohol and also sufficiently 
high color density is obtained even in the processing of a shortened 
processing time. On the other hand, in the case of using comparison silver 
halide emulsions (8) and (9), such disadvantages that the color density is 
insufficient even when the emulsion is a monodispersed silver halide 
emulsion and Dmin becomes high are shown. 
INDUSTRIAL UTILIZABILITY 
By the practice of this invention, by substantially containing no benzyl 
alcohol the load for pollution can be reduced, the load for working of 
preparing the developer can be reduced, and the effect of preventing the 
occurrence of reduction in density by cyan dyes which remain as leuco 
compounds can be obtained. Also, the use of the silver halide emulsions in 
this invention gives the effect of obtaining photographic properties 
having high Dmax, low Dmin, and showing less change of sensitivity and 
gradation even when benzyl alcohol is not used.