Silver halide photographic sensitive material

A silver halide photographic light-sensitive material comprising a support having thereon a photographic silver halide emulsion layer is disclosed. The silver halide emulsion layer contains a magenta coupler represented by Formula I, a compound represented by Formula II and at least one compound selected from the group of compounds represented by Formula III and Formula IV; ##STR1##

FIELD OF THE INVENTION 
This invention concerns a silver halide photographic light sensitive 
material, or, in more detail, a light sensitive material in which the 
retention stability of the despersion solution is improved and has 
excellent color reproducibility and light-proof and less perspirability. 
BACKGROUND OF THE INVENTION 
Production of a color image by using a silver halide photographic light 
sensitive material is carried out through the reaction process in which 
the main developing agent is oxidized at the same time when the silver 
halide grains in the light sensitive material are reduced and then the 
obtained oxidant reacts with a coupler which has been contained in the 
light sensitive material so as to form a dye. Three kinds of couplers such 
as yellow, magenta and cyan are usually used so as to reproduce colors by 
the subtractive color process. 
Each coupler is added to a silver halide photographic emulsion by 
dissolving it in a substantially water-insoluble high-boiling point 
organic solvent and, if necessary, adding another auxiliary solvent. 
Fundamental properties demanded to each coupler are to be highly soluble to 
the high-boiling point organic solvents and auxiliary solvents, to have a 
good dispersivity and a good stability in silver halide emulsion so as not 
to be deposited in it, to have an excellent spectral characteristic which 
results a good color tone and a distinct color image in a wide range of 
color-reproducible area and the toughness of the obtained color image to 
light, heat and humidity. 
2-anilino-5-pyrazolones are widely used as the couplers to produce magenta 
dye. These couplers are inferior in solubility to high-boiling point 
organic solvent and in light proof and are not satisfactory in color tone. 
The searching for various kinds of chemical groups to obtain dispersion 
proofness has been carried out. Among them, acyl amide dispersion-proof 
group containing a terminal phenoxy group which is described in Japanese 
Patent Publication Open to Public Inspection (hereinafter referred to as 
Japanese Patent O.P.I. Publication) Nos. 40804/1976 and 126831/1976 is 
excellent in solubility and color tone. 
However, it is not sufficient in light proof and, moreover, the dispersion 
solution which uses this coupler is inferior in retention stability. 
Various kinds of organic oxidation inhibitors have been developed so as to 
improve light proof of magenta and other dyes. Examples are the compounds 
described in Japanese Patent O.P.I. Publication Nos. 72225/1977, 
20327/1978, 48538/1979 and 152225/1977. These oxidation inhibitors do, 
however, not display a sufficient effect to the above-mentioned couplers 
but represent only incomplete stability and sometimes occur perspiration 
(a phenomenon to produce oil drop on the surface of the photosensitive 
material by diffusion and condensation of oil contained in the 
photosensitive material when it is kept in a high temperature and humidity 
conditions). Light-proof property of the material can be improved in 
accordance with the increase of the amount of added oxidation inhibitor 
but the stability of dispersion solution decreases and the perspiration 
increases. 
The use of surface active agents seems to be effective for the improvement 
of the stability of dispersion solution. Examples are surface active 
agents described in Japanese Patent O.P.I. Publication Nos. 46733/1974 and 
173470/1987 and Japanese Patent Examined Publication No. 21372/1985. Their 
effects are, however, not sufficient. Almost of all other surface active 
agents are good in coating property and antistatic property but are not 
good in the stabilization of dispersion solution. These weak points can be 
improved to some extent by the increase of the amount of the added surface 
active agent; but, at the same time, it causes the increase of 
perspiration. 
Anyhow, it has been impossible to improve all of these properties - color 
tone, light proof and perspiration and retention stability of the 
dispersion solution. A method to solve all of these problems at the same 
time has long been expected. 
SUMMARY OF THE INVENTION 
The purpose of this invention is to supply an excellent silver halide 
photographic light sensitive material with which all the problems such as 
the retention stability of the dispersion solution of magenta coupler, 
perspiration, tone of the color pigment and light proof after the 
treatment are improved without failing other photographic and physical 
properties. 
DETAILED DESCRIPTION OF THE INVENTION 
The above-mentioned object of this invention can be achieved by a silver 
halide photographic light-sensitive material comprising a support having 
thereon a photographic silver halide emulsion layer, wherein said silver 
halide emulsion layer contains a magenta coupler represented by Formula I, 
a compound represented by Formula II and at least one compound selected 
from the group of compounds represented by Formula III and Formula IV; 
##STR2## 
wherein Ar represents an aryl group; Y represents a hydrogen atom or a 
group capable of releasing by reaction with an oxidation product of a 
color developing agent; X represents a halogen atom, an alkyl group or an 
alkoxy group; J represents a divalent bonding group; R represents a 
halogen atom, a hydroxy group, an alkyl group, an aralkyl group or an 
alkoxy group; m represents an integer of 0 to 5; n represents an integer 
of 0 to 4; 
##STR3## 
wherein R.sub.6 and R.sub.7 represent an alkyl group having 2 to 7 carbon 
atoms or an aralkyl group; R.sub.8, R.sub.9, R.sub.10 and R.sub.11 
represent a hydrogen atom, an alkyl group having 4 to 8 carbon atoms or an 
aralkyl group wherein three or more of R.sub.8, R.sub.9, R.sub.10 and 
R.sub.11 are not hydrogen atoms at the 
##STR4## 
wherein R.sub.12 represents an alkyl group having 1 to 16 carbon atoms or 
an aralkyl group; M represents a hydrogen atom or cation; n represents an 
integer of 1 to 7; 
##STR5## 
wherein R.sub.13 and R.sub.14 represents an alkyl group having 4 to 20 
carbon atoms; M represents a hydrogen atom or a cation. 
Description of this invention will be given in more detail. 
In the above-mentioned Formula, Y is a hydrogen atom or a releasing group; 
this group means a group which can be released by reaction with the 
oxidation product of the color developing agent. Actual examples of 
releasing group are: halogen atoms (chlorine, bromine, fluorine), alkoxy, 
aryloxy, heterocyclic-oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, 
aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, 
heterocyclicthio, alkyloxythiocarbonylthio, acylamino, sulfonamide, 
nitrogen-containing, alkyloxycarbonylamino, aryloxycarbonylamino groups; 
Ar represents an aryl group; preferably it is a phenyl group containing a 
substituent group; preferable substituent is a halogen atom (e.g. 
fluorine, chlorine, bromine) or an alkyl group (e.g. methyl, ethyl, 
butyl), an alkoxy group (e.g. methoxy, ethoxy), an aryloxy group (e.g. 
phenoxy, naphthoxy), an acylamino group (e.g. 
.alpha.-(2,4-di-t-amylphenoxy)butylamide, benzamide), a sulfonylamino 
group (e.g. hexadecane sulfonamide, benzene sulfonamide), sulfamoyl group 
(e.g. methylsulfamoyl, phenylsulfamoyl), a carbamoyl group (e.g. butyl 
carbamoyl, phenyl carbamoyl), a sulfonyl group (e.g. methylsulfonyl, 
dodecylsulfonyl, benzene sulfonyl), an acyloxy group, an ester group, a 
carboxyl group, a sulfo group, a cyano group, a nitro group, etc.; 
X represents a halogen atom (e.g. chlorine, bromine, fluorine atom) an 
alkyl group (e.g. methyl, ethyl, i-propyl, butyl, hexyl group) or an 
alkoxy group (methoxy group, ethoxy group, butoxy group); n is an integer 
from 0 to 4. When n is more than 2, two or more X's can be either same 
groups or different ones. 
J represents a divalent bonding group; it should preferably be a 
substituted or unsubstituted alkylene group. More preferably it should be 
a methylene group having either substituent or not; most preferably, it 
should be a methylene group having a substituent such as a methylene 
group, a 1,2-ethylene group, a methyl-methylene group, a ethyl-methylene 
group, a 1,3-propylene group, a propyl-methylene group and a 
octyl-methylene group. 
R represents a halogen atom, a hydroxy group, an alkyl group, an aralkyl 
group or an alkoxy group; or preferably be a halogen atom, an alkyl group 
or an aralkyl group, as a halogen atom, chlorine atom is an example; as an 
alkyl and an aralkyl group, methyl, ethyl, t-butyl, t-amyl, t-octyl, 
t-nonyl and n-dodecyl groups are examples; m is an integer from 0 to 5. 
When m is more than 2, two or more R's can be either same groups or 
different ones. 
Examples of magenta couplers used in this invention are shown in the 
following; the scope of this invention is not limited to these. 
______________________________________ 
##STR6## 
No. R 
______________________________________ 
I-1 
##STR7## 
I-2 
##STR8## 
I-3 
##STR9## 
I-4 
##STR10## 
I-5 
##STR11## 
I-6 
##STR12## 
I-7 
##STR13## 
I-8 
##STR14## 
I-9 
##STR15## 
I-10 
##STR16## 
I-11 
##STR17## 
I-12 
##STR18## 
I-13 
##STR19## 
I-14 
##STR20## 
I-15 
##STR21## 
I-16 
##STR22## 
I-17 
##STR23## 
I-18 
##STR24## 
I-19 
##STR25## 
I-20 
##STR26## 
______________________________________ 
______________________________________ 
##STR27## 
No. R 
______________________________________ 
I-21 
##STR28## 
I-22 
##STR29## 
I-23 
##STR30## 
I-24 
##STR31## 
______________________________________ 
__________________________________________________________________________ 
##STR32## 
No. 
X R 
__________________________________________________________________________ 
I-25 
H 
##STR33## 
I-26 
##STR34## 
##STR35## 
I-27 
H 
##STR36## 
I-28 
##STR37## 
##STR38## 
I-29 
H 
##STR39## 
I-30 
##STR40## 
##STR41## 
I-31 
##STR42## 
##STR43## 
I-32 
CF.sub.3 CONH 
##STR44## 
I-33 
##STR45## 
##STR46## 
I-34 
##STR47## 
##STR48## 
I-35 
##STR49## 
##STR50## 
__________________________________________________________________________ 
__________________________________________________________________________ 
##STR51## 
No. 
X R 
__________________________________________________________________________ 
I-36 
H 
##STR52## 
I-37 
##STR53## 
##STR54## 
I-38 
H 
##STR55## 
I-39 
##STR56## 
##STR57## 
I-40 
H 
##STR58## 
I-41 
CH.sub.3 CO.sub.2 
##STR59## 
I-42 
##STR60## 
I-43 
##STR61## 
I-44 
##STR62## 
I-45 
##STR63## 
I-46 
##STR64## 
__________________________________________________________________________ 
Color-producing coupler is added to the purposing hydrophilic colloid layer 
singly or mixed with other hydrophobic additives (ultraviolet-ray 
absorber, color image stabilizer and color-mixture inhibitor) usually by 
being dissolved in a high-boiling point (b.p. is 150.degree. C. or higher) 
organic solvent [with the coexistence of other low-boiling point and/or 
water soluble organic solvent(s), if necessary to be added to a 
hydrophilic binder such as an aqueous gelatin solution mixed with a 
surface active agent and emulsified or dispersed by the help of dispersing 
devices such as stirrer, homogenizer, colloid mill, flow jet mixer or 
supersonic apparatus. A process of removing a low-boiling point organic 
solvent can be performed during or at the same time of, dispersion. 
A preferable ratio of the used high-boiling point and low-boiling point 
organic solvents is in a range of 1:0.1 to 1:50; or, more preferably, 1:1 
to 1:20 in this invention. 
An organic solvent having a dielectric constant less than 6.0 is preferably 
used as the high-boiling point solvent. 
In this invention a high-boiling point solvent having a dielectric constant 
less than 6.0 should preferably be used. The lowest value of the 
dielectric constant is not specially limited but it may preferably be not 
less than 1.9. Esters such as phthalic esters, phosphate esters and 
organic acid amides, ketones and hydrocarbons having the dielectric 
constant less than 6.0 can be used. 
A high-boiling point organic solvent usable in this invention should 
preferably be a solvent having the vapor pressure at 100.degree. C. not 
more than 0.5 mmHg. Phthalic acid esters and phosphate esters having such 
vapor pressure may be usable more preferably. A mixture of two or more 
kinds of these solvents are also usable if the dielectric constant of the 
mixture is less than 6.0. In this invention, dielectric constant values 
are those measured at 30.degree. C. Usable solvents by mixing are dibutyl 
phthalate, dimethyl phthalate, tricresyl phosphate and tributyl phosphate. 
Preferably usable phthalic acid esters in this invention are those having 
the below-mentioned Formula (HA). 
##STR65## 
where, R.sub.H1 and R.sub.H2 are an alkyl and alkenyl or an aryl group, 
respectively. The sum of the carbon numbers in groups R.sub.H1 and 
R.sub.H2 should be 9 to 32, or, more preferably, be 16 to 24. In this 
invention, alkyl groups represented by R.sub.H1 and R.sub.H2 in the 
Formula (HA) are straight or branched chain alkyl groups such as butyl, 
pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, 
tetradecyl, pentadecyl hexadecyl, heptadecyl and octadecyl groups. Aryl 
groups represented by R.sub.H1 and R.sub.H2 are phenyl and naphthyl 
groups. Alkenyl groups are hexenyl, heptenyl and octadecenyl groups. These 
alkyl, and alkenyl aryl groups can either have one or more substituents. 
Examples of substituents are a halogen atom, alkoxy, aryl, aryloxy, 
alkenyl and alkoxycarbonyl groups. A substituent group in the aryl group 
is, e.g. halogen atom, alkyl, alcoxy, aryl, aryloxy, alkenyl and 
alcoxycarbonyl group. Two or more these substituents can be introduced in 
one alkyl, alkenyl or aryl group. 
In this invention, usable phosphate esters are those represented by Formula 
(HB). 
##STR66## 
in the Formula, R.sub.H3, R.sub.H4 and R.sub.H5 represent, respectively, 
alkyl, alkenyl or aryl group. The total sum of the carbon atom numbers in 
the groups, represented by R.sub.H3, R.sub.H4 and R.sub.H5 is 24 to 54. 
Where, R.sub.H3, R.sub.H4 and R.sub.H5 are aklkyl groups such as butyl, 
pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, 
tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and nonadecyl 
groups. 
These alkyl, alkenyl and aryl groups can either have one or more 
substituents. Preferably, R.sub.H3, R.sub.H4 and R.sub.H5 are alkyl groups 
such as 2-ethylhexyl, n-octyl, 3,5,5-trimethylhexyl, n-nonyl, n-decyl, 
sec-decyl, sec-dodecyl and t-octyl groups. 
Actual examples of organic solvents usable in this invention are shown 
below; of course, this invention is not limited to these. 
##STR67## 
Amount of a high-boiling point organic solvent usable in this invention is 
0.01 to 10 mols per one mol of silver halide; or, more preferably, 0.05 to 
5 mols. 
In this invention, R.sub.6 and R.sub.7 in compounds represented by the 
Formula II are either same or different from each other and are an alkyl 
group having carbon numbers 2 to 7 or an aralkyl group; or, preferably, an 
alkyl group having carbon numbers 2 to 4, alkenyl or aralkyl group. 
Actual examples are: ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, 
pentyl, i-pentyl, t-pentyl, hexyl, i-hexyl, t-hexyl, heptyl, i-heptyl, 
t-heptyl and cyclohexyl groups. 
R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are a hydrogen atom or an alkyl, 
alkenyl or aralkyl group having carbon numbers 4 to 8, respectively; three 
or more of them should not be hydrogen atoms at the same time. 
Actual examples of compounds (II) in this invention are as follows: 
______________________________________ 
##STR68## 
No. R.sub.6 R.sub.7 R.sub.8 
R.sub.9 
R.sub.10 
R.sub.11 
______________________________________ 
II-1 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
(t)C.sub.4 H.sub.9 
H H (t)C.sub.4 H.sub.9 
II-2 C.sub.2 H.sub.5 
C.sub.2 H.sub.5 
(t)C.sub.5 H.sub.11 
H H (t)C.sub.5 H.sub.11 
II-3 (i)C.sub.3 H.sub.7 
(i)C.sub.3 H.sub.7 
(t)C.sub.5 H.sub.11 
H H (t)C.sub.5 H.sub.11 
II-4 C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
(t)C.sub.5 H.sub.11 
H H (t)C.sub.5 H.sub.11 
II-5 (i)C.sub.3 H.sub.7 
(i)C.sub.3 H.sub.7 
(t)C.sub.8 H.sub.17 
H H (t)C.sub.8 H.sub.17 
II-6 C.sub.4 H.sub.9 
C.sub.4 H.sub.9 
(t)C.sub.5 H.sub.11 
H H (t)C.sub.5 H.sub.11 
II-7 C.sub.4 H.sub.9 
C.sub.4 H.sub.9 
(t)C.sub.8 H.sub.17 
H H (t)C.sub.8 H.sub.17 
II-8 C.sub. 2 H.sub.5 
C.sub.2 H.sub.5 
(t)C.sub.8 H.sub.17 
H H (t)C.sub.8 H.sub.17 
II-9 C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
(t)C.sub.4 H.sub.9 
H H (t)C.sub.4 H.sub.9 
II-10 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
(t)C.sub.8 H.sub.17 
H H (t)C.sub.8 H.sub.17 
II-11 
C.sub.4 H.sub.9 
C.sub.4 H.sub.9 
(t)C.sub.4 H.sub.9 
H H (t)C.sub.4 H.sub.9 
II-12 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
C.sub.4 H.sub.9 
H H C.sub.4 H.sub.9 
II-13 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
C.sub.4 H.sub.9 
C.sub.4 H.sub.9 
H C.sub.4 H.sub.9 
II-14 
C.sub.3 H.sub.7 
C.sub.3 H.sub.7 
C.sub.4 H.sub.9 
C.sub.4 H.sub.9 
H H 
II-15 
(i)C.sub.3 H.sub.7 
(i)C.sub.3 H.sub.7 
(t)C.sub.4 H.sub.9 
H H (t)C.sub.4 H.sub.9 
II-16 
C.sub.5 H.sub.11 
C.sub.5 H.sub.11 
(t)C.sub.4 H.sub.9 
H H (t)C.sub.4 H.sub.9 
______________________________________ 
In this invention, R.sub.12 in compounds represented by Formula III and IV 
is an alkyl or aralkyl group having carbon number 1 to 16. 
Actual examples of R.sub.12 are i-propyl, butyl, t-butyl, pentyl, t-pentyl, 
hexyl and dodecyl groups. 
R.sub.13 and R.sub.14 represent an alkyl group having carbon numbers 4 to 
20; or, preferably, alkyl groups substituted by fluorine atom. Examples of 
R.sub.13 and R.sub.14 are nonyl, octyl, dodecyl, octadecyl, 
octafluoropentyl, octafluoroheptyl and dodecafluoroheptyl groups. 
M represents a hydrogen atom or a cation. Actual examples of cation are an 
ammonium ion and an alkali-metal ion such as sodium and potassium. 
Especially preferable compounds of compounds represented by III and IV are 
those represented by IV. Actual examples of compound III and IV are as 
follows: 
##STR69## 
Silver halide photographic light sensitive material of this invention can 
be used as either the negative of color negative or positive film or 
color-print paper. And also, it can be either for monochromatic or 
polychromatic uses. In case of polychromatic silver halide photographic 
light sensitive material, its constituent layers on the support are 
composed of mutual accumulation of several layers of silver halide 
emulsion layers containing photographic couplers of magenta, yellow and 
cyan and non-light-sensitive layers. Number and order of the accumulation 
can be changeable properly. 
As the silver halide emulsion of this invention, various kinds of silver 
halides such as silver bromide, silver iodobromide, silver iodochloride 
silver chlorobromide and silver chloride can be used all of which have 
been used for conventional silver halide emulsions. A mixture of these 
silver halide grains are also usable. 
Silver halide grain used for the silver halide emulsion can be obtained by 
acid method, neutral method or ammonia method. They can be developed at 
one time or after developing the seed grain. The method for making seed 
grain may be either same as or different from that for developing. 
To make silver halide emulsion, halide ion and silver ion can be made by 
mixing at one time or made by adding one to another. It can also be made 
and developed by considering the critical developing velocity of silver 
halide crystal to add halide and silver ions by controlling the pH and pAg 
of the mixing vessel. After developing the crystals, the composition of 
halogen in grains can be modified with the conversion method after 
developing. 
During the preparation of the silver halide emulsion, various conditions 
such as the size, figure, distribution and developing velocity of silver 
halide grains, can be controlled by using a solvent for silver halide, if 
necessary. 
Silver halide grains used for silver halide emulsion can contain metal ions 
in their inside and/or on the surface by using cadmium salt, zinc salt, 
lead salt, thallium salt, iridium salt or its complex salt, rhodium salt 
or its complex salt, iron salt or its complex salt. A reduction 
sensitizing nucleus can be built up in their inside and/or on their 
surface by keeping the grains in a reductive atmosphere. 
Unnecessary soluble salts mixed in the silver halide emulsion may either be 
removed after the development of the silver halide grains or be kept in. 
For the removal, the method prescribed in Research Disclosure No. 17643 is 
applicable. 
The surface of a silver halide grains of silver halide emulsion may be 
either the same phase as or different from the inside of the grains. 
The latent image of the silver halide grains in the silver halide emulsion 
may either be built mainly on their surface or be built mainly in their 
inside. 
Crystal form of the silver halide grains in the silver halide emulsion may 
either be regular or be anomalous such as round or platy type. The ratio 
of their crystal faces (100) and (111) may be arbitrary. Complex crystal 
form or a mixture of various crystal forms can also be used. 
Two or more kinds of silver halide emulsions which have been prepared 
separately can also be used after mixing. 
The silver halide emulsion can be chemically sensitized with conventional 
methods. Various sensitizing methods such as the sulfur sensitization 
which uses a compound containing sulfur reactable with silver ion or uses 
activated gelatin, the selenium sensitization which uses a selenium 
compound, reduction sensitization which uses a reducing material or novel 
metal sensitization method which uses gold or other novel metals. These 
methods are usable singly or combined. 
The silver halide emulsion can be optically sensitized at the desirable 
wave length zone by using dyes which are known as sensitizing dyes in the 
photographic industry. Sensitizing of the emulsion can either be performed 
by using only one sensitizing dye or by mixing two or more kinds of them. 
A dye which has no optical sensitizing power or a compound which cannot 
actually absorb visible light but can intensify the sensitizing power of 
other sensitizing dye (color-intensifying sensitizer) can be mixed in the 
emulsion. 
The silver halide emulsion can contain a fog-inhibitor or a stabilizer 
known in the photographic industry added during and/or just after the 
chemical digestion process and/or before the coating of the emulsion for 
the purpose of fog prevention or stabilization of photographic performance 
during producing, storage or processing of a photographic material. 
It is convenient to use gelatin as the binder (or the protective colloid) 
for the silver halide emulsion; various other kinds of materials can also 
be used as the binder such as a gelatin derivative, a grafted polymer of 
gelatin and another polymer, a protein, a sugar derivative, a cellulose 
derivative or hydrophilic colloids such as synthetic mono- or co-polymeric 
hydrophilic highmolecular compounds. 
The photographic emulsion layer or the protective colloid of a silver 
halide photographic material of the present invention can be hardened with 
the use of a hardener or hardeners to bridging the molecules of binder (or 
protective colloid). The hardener should preferably be used with the 
amount just harden the emulsion and not necessary to add the harden any 
more to the treating solution but it is also possible to add it mixed in 
the treating solution. 
A plasticizer may be added to the silver halide emulsion layer and/or a 
hydrophilic colloid layer of a silver halide photographic material of the 
invention to improve their flexibility. 
The silver halide emulsion layer or other hydrophilic colloidal layer of 
the silver halide photo-graphic light sensitive material of this invention 
can contain water-insoluble or hardly soluble dispersion of synthetic 
polymer (latex) for the purpose to improve the dimension stability. 
A color-forming coupler to perform a coupling reaction with the oxidant of 
aromatic primary amine developer (e.g. a p-phenylene diamine derivative, 
aminophenol derivative, etc.) is used for color-developing treatment of 
emulsion layer of the silver halide photographic light sensitive material 
of this invention. 
As the color-forming coupler, a color to absorb the photosensitive spectral 
light of each emulsion layer is usually used. That is to say, a 
yellow-color forming coupler is used for the blue-light sensitive emulsion 
layer, a magenta-color forming coupler is for the green-light sensitive 
layer and a cyan-color forming layer for the red-light sensitive layer, 
respectively. A combination different from the above can, however, be used 
for some purposes. 
Acylacetamide coupler (e.g. benzoyl acetanilides, pivaloylacetanilides) is 
used as the yellow-color forming coupler. 5-pyrazolone coupler, pyrazolone 
benzimidazole coupler, pyrazolotriazole coupler and open-chain 
acylacetonitril coupler are used as the magenta-color forming coupler 
except for the coupler of this invention. Naphthol coupler and phenol 
coupler are used as the cyan-color forming coupler. These color-forming 
couplers should preferably contain a group called as ballast group in its 
molecule which can make the couplers not to diffuse and, preferably, 
include the groups containing carbon number 8 or larger. These couplers 
may be either a four-equivalent type which demands to reduce 4 silver ions 
to form one molecule of dye or a two-equivalent type which demands to 
reduce only 2 silver ions. 
A color-fog inhibitor can be used to prevent the formation of turbidness of 
color, the failure in clearness or the formation of remarkable granulation 
according to the displacement of the oxidant or the electron-transfer 
agent in the developer in between several emulsion layers (between the 
layers of the same color and/or between the layers of the different 
colors) of silver halide photographic light sensitive material of this 
invention. 
This color-fog inhibitor can be applied either to the emulsion itself or to 
the intermediate layer which is placed between the emulsion layers. 
An image-stabilizer is usable so as to prevent the failure of dye image in 
silver halide photographic light sensitive material of this invention. 
Various supplemental layers such as filter layer, halation-preventive layer 
and/or irradiation-preventive layer can be used in silver halide 
photographic light sensitive material of this invention. In these layers 
and/or in emulsion layers, a dyestuff can be contained which is washed out 
from the color photosensitive material or is bleached during the 
developing treatment can be contained. 
A matting agent can be added to reduce the glossiness of the light 
sensitive material or to increase its writability or to prevent the 
adhesion of the material in the emulsion layer and/or other hydrophilic 
colloid layer of the silver halide photographic light sensitive material 
of this invention. 
A lubricating material can be added in the silver halide photographic light 
sensitive material of this invention so as to reduce the sliding friction. 
An antistatic additive can be added to prevent the electrostatic charge in 
the silver halide photographic light sensitive material of this invention. 
It can be applied either on the support at its non-emulsion side or in the 
emulsion layer and/or on the protective colloid layer (except the emulsion 
layer itself) on the support at its emulsion side. In this invention, 
these various photographically profitable additives are finely dispersed 
in the hydrophilic colloid as water-in-oildrop type oil-protective 
dispersion. 
The photographically profitable additives described here are 
water-insoluble compounds such as ultraviolet-ray absorber, dye-image 
fading inhibitor, dye-image forming coupler, fog inhibitor, color-mixing 
inhibitor and redox compounds, etc. 
To make the water-in-oildrop dispersion, conventional methods to disperse 
hydrophobic additives such as couplers can be applicable. Usually, a high 
boiling point organic solvent (b.p. over 150.degree. C.) containing, if 
necessary, low-boiling point or water-soluble organic solvent is dispersed 
in a hydrophilic binder such as aqueous gelatin solution as emulsification 
dispersion by using a surface active agent with a stirrer, homogenizer, 
colloid mill, flow-jet mixer or ultrasonic apparatus. Then, the mixture is 
added into the purposing hydrophilic colloid. A process of removing a 
low-boiling point organic solvent can be performed during or at the same 
time of, dispersing. 
Various kinds of surface active agents can be used in the photographic 
emulsion and/or other hydrophilic colloid layer of the silver halide 
photographic light sensitive material of this invention for the purpose to 
improve the coating ability, to prevent the electrostatic charge, to 
improve smoothness, to make emulsified dispersion, to prevent adhesion and 
to improve other photographic properties (developing-acceleration, 
contrast increase and sensitizing, etc.). Various kinds of materials can 
be used as the support of the silver halide photographic light sensitive 
material of this invention as follows: flexible reflection support such as 
paper and synthetic paper laminated with baryta layer or .alpha.-olefin 
polymer; films of semi-synthetic and synthetic high polymers such as 
acetyl cellulose, nitrocellulose, polystyrene, polyvinyl chloride, 
polyethylene telephthalate, polycarbonate and polyamide; and rigid bodies 
such as glass, metals and porcelain. 
In this invention, the silver halide photographic light sensitive layer can 
be coated and formed on the surface of the support, which is, if 
necessary, subject to the treatment such as corona discharge, ultraviolet 
radiation and flaming, directly or intervened with an undercoat layer 
(one, two or more than two layers placed for the purpose to improve the 
adhesivity of support surface, prevention of electrostatic charge, 
size-stability, anti-abrasiveness, hardness, halation prevention, friction 
characteristics and/or other characteristics). 
At the coating of the silver halide photographic light sensitive layer, a 
thickener can be used to improve the coating ability. Extrusion coating 
and curtain coating are especially profitable both of which can coat two 
or more layers at the same time. 
The silver halide photographic light sensitive material of this invention 
can be exposed with electromagnetic wave having the spectral range where 
the emulsion composing the photographic material of this invention can 
react. Various kinds of light sources can be used such as natural light 
(sun beam), tungsten light, fluorescent light, mercury lamp, xenone-arc 
lamp, carbon-arc lamp, xenone flush light, cathode-ray flying spot, 
various laser-beam, light-emitting diode, the light emitted from 
fluorescent body excited with electron beam, X-ray, .gamma.-ray, 
.alpha.-ray. 
Exposure time is from one millisecond to one second which is from the 
ordinary exposure time of ordinary camera to the time shorter than one 
millisecond such as the exposure with cathode ray or xenone flush light 
(100-1 microsecond); exposure longer than one second is also possible 
which is either continuously or intermittently. 
The silver halide photographic light sensitive material of this invention 
can compose a color image by developing with color-developing methods 
conventional in the photographic world. 
Various conventional developers of aromatic primary amines used for various 
color photographic processes are usable as the developing agent. 
Aminophenol type and p-phenylenediamine type developers are included. 
These compounds are usually used as their chlorides or sulfates since they 
are more stable than free amine type. The usable concentration of these 
compounds is about 0.1 to 30 g/l of developing solution; or, preferably, 
about 1 to 15 g/l. 
Examples of aminophenol type developers are: .alpha.-aminophenol, 
p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 
2-oxy-3-amino-1,4-dimethylbenzene. 
Especially useful primary aromatic amino-type color developers are 
N,N'-dialkyl-p-phenylenediamine type compounds. Their alkyl and phenyl 
group can be substituted with some substituent groups. Especially 
profitable ones are: N,N'-diethyl-p-phenylene diamine hydrogen chloride, 
N-methyl-p-phenylene diamine hydrogen chloride, 
N,N'-dimethyl-p-phenylelnediamine hydrogen chloride, 
2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-.beta.-methane 
sulfonamideethyl-3-methyl-4-aminoaniline sulfate, 
N-ethyl-N-.beta.-hydroxyethyl amino aniline, 4-amino-3-methyl-N,N'-diethyl 
aniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methyl aniline-p-toluene 
sulfonate. 
Color developers used for the treatment of this invention can contain 
various components conventionally used as the additives for the 
above-mentioned aromatic primary amine type developer such as: alkaline 
compounds such as sodium hydroxide, sodium carbonate, potassium carbonate; 
sulfites of alkali metals, bisulfites of alkali metals, thiocyanates of 
alkali metals, alkali metal halides, benzyl alcohol, water-softening 
agents and concentrating agents. Applicable pH of the color developer 
solution is usually higher than 7; or, more usually, about 10 t0 13. After 
the color development, the photographic light sensitive material of this 
invention is treated with some solution which has fixing ability. When 
this solution is a fixing solution the bleaching treatment is carried out 
beforehand. Various kinds of metal complex salts of organic acids can be 
used as the bleacher. The metal complexes are used for the purpose to 
oxidize the metalic silver produced by developing to silver halide and 
simultaneously to develop the color in the not-developed part of the color 
developer. Preferable organic acid used in these metal complexes are 
aminopolycarboxylic acids, oxalic acid and citric acid; as the metal 
coordinate, iron, cobalt and copper are usable. Most preferable organic 
acids are polycarboxylic acid and aminopoly carboxylic acids and their 
alkali-metal salts, ammonium salts and water-soluble amine salts. Their 
actual examples are: 
[1] Ethylenediamine tetraacetic acid 
[2] Nitrotriacetic acid 
[3] Iminodiacetic acid 
[4] Disodium ethylene diaminetetraacetate 
[5] Tetra(trimethylammonium) ethylenediaminetetraacetate 
[6] Tetrasodium ethylenediamine tetraacetate 
[7] Sodium nitrotriacetate 
Used bleaching solution contains above-mentioned metal complex salts of 
organic acids as the bleachers and also can contain various additives. 
Preferable additives are: rehalogenized agents such as ammonium halides, 
for example, potassium bromide, sodium bromide, sodium chloride and 
ammonium bromide; metal salts and chelate compounds. 
It is also possible to use various compounds conventionally used as 
additives for bleachers are also usable: pH buffering salts such as 
borates, oxalates, acetates, carbonates and phosphates and alkyl amines 
and polyethylene oxides. 
Usable fixers and bleaching fixers are as follows: various bisulfites such 
as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium 
bisulfite, sodium bisulfite, ammonium metabisulfite, potassium 
metabisulfite, sodium metabisulfite; various pH buffer agents containing 
various salts such as boric acid, borax, sodium hydroxide, potassium 
hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium 
bicarbonate, potassium bicarbonate, acetic acid sodium acetate and 
ammonium hydroxide; these can be used singly or by mixing two or more. 
In case when a supplementing agent for bleach-fixer is added to the main 
bleach-fixer (or fixing bath), a thiosulfate, thiocyanate or sulfite can 
either be added to the bleach-fixer (bath) or can be contained in the 
supplementing solution and then added to the bath. 
In this invention, air or oxygen can be blowed into the bleach-fixing bath 
and in the storage tank of bleach-fixer supplementing solution so as to 
increase the activity of bleach-fixer. Or, an oxidizing agent such as 
hydrogen peroxide, a bromate or a persulfate can be added with a proper 
amount.