Silver halide photographic light-sensitive material

A silver halide photographic light-sensitive material having a support with at least one silver halide emulsion layer is provided. The silver halide emulsion layer containing in combination at least one yellow dye image-forming coupler of Formula I and at least one high-boiling organic solvent of Formula II to reduce the light discoloration of a yellow dye image.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a silver halide photographic 
light-sensitive material, and more particularly to a silver halide 
photographic light-sensitive material capable of forming a dye image whose 
yellow dye is remarkably improved on the resistance to light. 
2. Description of the Prior Art 
Of silver halide photographic light-sensitive materials (hereinafter 
referred to as photographic light-sensitive materials), in the 
black-and-white photographic light-sensitive material, the image formed 
therefrom is generally of matallic silver. In recent years, however, a 
silver-saving promotion has been taking place in an effort to cope with 
the shortage of silver resources and to reduce the cost of photographic 
light-sensitive materials. One of measures for solving this problem is the 
application of the color photographic technique that reproduces a neutral 
tone by mixing yellow, magenta and cyan dyes instead of using metallic 
silver. 
In the field of color photographic techniques, it is already known that, 
for example, a coupler-containing photographic light-sensitive material, 
after being exposed to light, is processed in a color developer bath 
containing an aromatic primary amine-type color developing agent, thereby 
forming a dye image. Of the couplers used in the technique, the yellow dye 
image-forming coupler (hereinafter referred to as yellow coupler) has an 
active methylene radical useful for the formation of an yellow dye by the 
coupling reaction thereof with the oxidized product of an aromatic primary 
amine-type color developing agent. If the active methylene is 
unsubstituted (i.e., active site-unsubstituted-type yellow coupler), the 
coupler, because it requires 4 molecules of silver halide for the 
formation of its dye in a color developing reaction, is called a 
4-equivalent coupler. On the other hand, it is also known that the same 
dye as in the unsubstituted-type coupler can also be formed from a coupler 
wherein one of the hydrogen atoms of the active methylene radical thereof 
is substituted by such a substituent component as a halogen atom, i.e., 
the so-called active site-substituted-type yellow coupler. In this 
instance, such the substituent component as a halogen atom splits off 
during a color developing reaction, and the coupler can form one molecule 
of its dye by two molecules of the developed silver halide, so that this 
coupler is called a two-equivalent coupler. 
As the framework of yellow couplers, benzoylacetanilides were formerly 
widely used, but in recent years, particularly for color paper 
light-sensitive materials, pivaloylacetanilides have become mostly used. 
The transit into pivaloylacetanilides is considered mainly due to the fact 
that they are superior in the resistance to light of the image formed 
therefrom to benzoylacetanilides. However, even the yellow dye image 
derived from thus improved pivaloylacetanilides still not have any 
sufficient resistance to light for satisfying the social demand for the 
image preservability (the image lasting properties). 
As the technique of improving the resistance to light of such the yellow 
dye image there are widely used such a method that, because the yellow dye 
image is inferior in the resistance particularly to the rays in the 
ultraviolet region, for the purpose of removing the ultraviolet rays, an 
ultraviolet absorbing agent is incorporated into the interlayer or the 
like of a photographic light-sensitive material. As the ultraviolet 
absorbing agent for this purpose there are known those 
2-(2'-hydroxyphenyl)benzotriazole-type compounds as described in U.S. Pat. 
No. 3,253,921, Japanese Patent Examined Publication Nos. 10466/1961, 
5496/1973 and 4157/1973, and Japanese Patent Publication Open to Public 
Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) 
No. 87326/1975. However, when any of these ultraviolet absorbing agents is 
used by being dispersed into a color photographic light-sensitive 
material, the agent not only has the disadvantage that because of its low 
solubility in organic solvents it is deposited into crystals to adversely 
affect the manufacturing process and photographic characteristics of the 
light-sensitive material, but, although useful for the protection from 
ultraviolet rays, is ineffective at all on the prevention of possible 
discoloration (same meaning of fading) by the light in the visible ray 
region, so that the addition of the agent exceeding a certain amount is 
practically meaningless. 
On the other hand, there are also known the method for improving the 
resistance to light of the foregoing dye by rendering an antidiscoloration 
agent present under the environment of the formed dye, and as the 
antidiscoloration agent there are proposed the uses of bisphenols as 
disclosed in Japanese Patent Examined Publication Nos. 31256/1973 and 
31625/1973; of 6-hydroxychromans as in U.S. Pat. Nos. 3,432,300 and 
2,574,627; of 6,6'-dihydroxy-2,2'-disspirochromans as in Japanese Patent 
Examined Publication No. 20977/1974; of hydroquinone derivatives as in 
Japanese Patent Examined Publication No. 24257/1981; and of 
4-hydroxybenzoate compounds as in Japanese Patent O.P.I. Publication No. 
48535/1979. However, these compounds certainly have good effects on the 
improvement of the light resistance of magenta dyes, but has no effect at 
all on the yellow dye image, and on the contrary accelerate the light 
discoloration of the yellow dye. Japanese Patent O.P.I. Publication No. 
65954/1980 proposes the presence of hindered amine-type compounds in the 
environment of the formed dye, but these compounds are so less soluble in 
organic solvents as to be deposited to adversely affect the manufacturing 
process of as well as the photographic characteristics of the 
light-sensitive material. Japanese Patent O.P.I. Publication No. 
103551/1980 proposes a method for improving the resistance to light of an 
yellow dye image by the use in combination of a slightly-water-soluble 
hight-boiling organic solvent and a pivaloyl-type yellow coupler, but the 
method has the disadvantage that the gamma, as one of the sensitometric 
characteristics, becomes lowered. 
Further, it is also well-known that the image preservability of a formed 
yellow dye image differs depending on the kind of generally used 
high-boiling organic solvents (having a boiling point of not less than 
175.degree. C.). Japanese Patent O.P.I. Publication No. 119922/1979 
proposes the use in combination of an yellow coupler and a branched-chain 
alkyl phosphate-type high-boiling solvent, but the proposal is 
disadvantageous in respect that the light-resistance effect is extremely 
small. 
It is therefore the status quo that any satisfactory method for improving 
the resistance to light of the yellow dye image of a color photographic 
light-sensitive material is still not found. 
SUMMARY OF THE INVENTION 
Objects of the Invention 
It is therefore a first object of the present invention to provide a method 
which can be carried out conveniently for and which has a large effect 
upon improving the resistance to light of an yellow dye image. 
It is a second object of the present invention to provide a photographic 
light-sensitive material which is remarkably improved on the 
anti-light-discoloration characteristic of the yellow dye image thereof. 
It is a third object of the present invention to provide a method for 
improving the resistance to light of the yellow dye image without 
adversely affecting the manufacturing process of as well as the 
photographic characteristics of the photographic light-sensitive material. 
It is a fourth object of the present invention to provide a method which 
can be carried out economically for improving the resistance to light of 
the yellow dye image and the stability of the yellow coupler dispersion. 
Construction of the Invention 
It has now been found that the above objects can be accomplished by the 
following silver halide photographic light-sensitive material: In a silver 
halide photographic light-sensitive material comprising a support having 
thereon at least one silver halide emulsion layer, the silver halide 
photographic light-sensitive material wherein the foregoing silver halide 
emulsion layer contains in combination at least one of those yellow dye 
image-formable couplers having the following Formula (I) and at least one 
of those high-boiling organic solvents having the following Formula (II): 
##STR1## 
wherein R.sub.1 represents an alkyl radical or an aryl radical; R.sub.2 
represents an aryl radical; and X is a hydrogen atom or a radical that can 
be split off by the reaction of the coupler with the oxidized product of 
an aromatic primary amine-type color developing agent, 
##STR2## 
wherein R.sub.3 and R.sub.4 each is a nonyl radical, a decyl radical or an 
undecyl radical, the R.sub.3 and R.sub.4 being allowed to be either the 
same of different. 
DETAILED DESCRIPTION OF THE INVENTION 
In the present invention, the R.sub.1, R.sub.2 and X of the coupler having 
the foregoing Formula (I) (hereinafter referred to as the yellow coupler 
of the invention) are as defined in above, and the radicals represented by 
the R.sub.1 include alkyl radicals such as, e.g., pivalyl and aryl 
radicals such as, e.g., phenyl, and preferably alkyl radicals, 
particularly pivalyl; the radicals represented by the R.sub.2 are aryl 
radicals, preferably phenyl; and the radicals represented by the X which 
can be split off by the coupling reaction are preferably those having the 
following Formula (III) or (IV), and further, of those radicals having 
Formula (III), the particularly preferred are those having the following 
Formula (V) or (VI): 
##STR3## 
wherein Z.sub.1 represents a group of nonmetallic atoms capable of forming 
a 4- to 7-member cyclic ring, 
EQU --O--R.sub.5 Formula (IV) 
wherein R.sub.5 is an aryl radical such as, e.g., phenyl, a heterocyclic 
radical or an acyl radical such as, e.g., acetyl, and the most preferred 
one is an aryl radical, 
##STR4## 
wherein Z.sub.2 is a group of nonmetallic atoms capable of forming a 4- to 
6-member ring together with 
##STR5## 
wherein R.sub.7 and R.sub.8 each is a hydrogen atom, a halogen atom (such 
as, e.g., chlorine), an alkyl radical (such as, e.g., methyl, ethyl, 
propyl), an alkenyl radical (such as, e.g, butenyl), an alkoxy radical 
(such as, e.g., methoxy), an aryl radical (such as, e.g., phenyl), a 
carboxy radical, an alkoxycarbonyl radical (such as, e.g., 
methoxycarbonyl), a carbamyl radical, a sulfone radical, a sulfamyl 
radical, a sulfonamido radical (such as, e.g., methanesulfonamido), an 
acylamido radical (such as, e.g., acetylamido), an ureido radical or an 
amino radical. 
In Formula (I), the preferred yellow couplers of the present invention have 
the following Formula (VII): 
##STR6## 
wherein R.sub.9 is a hydrogen atom, a halogen atom (such as, e.g., 
chlorine) or an alkoxy radical (such as, e.g., methoxy, dodecyloxy), and 
preferably a halogen atom; R.sub.10, R.sub.11 and R.sub.12 each is a 
hydrogen atom, a halogen atom (such as, e.g., chlorine), an alkyl radical 
(such as, e.g., methyl, ethyl, nonyl), an alkenyl radical, an alkoxy 
radical (such as, e.g., methoxy, dodecyloxy), an aryl radical (such as, 
e.g., phenyl), carboxyl radical, an alkoxycarbonyl radical (such as, e.g., 
methoxyhexadecenyl), a carbamyl radical, a sulfone radical, a sulfamyl 
radical, an alkylsulfonamido radical (such as, e.g., methanesulfonamido), 
an acylamido radical (such as, e.g., acetylamido), an ureido radical or an 
amino radical; and it is preferred that the R.sub.10 and R.sub.11 each is 
a hydrogen atom and the R.sub.12 is an alkoxycarbonyl, acyalamido or 
alkylsulfonamido radical; and X is as defined in Formula (I), and 
preferably a radical having Formula (III) or (IV), and the more preferred 
one of Formula (III) is one having Formula (V) or (VI). 
In Formula (I), those other preferred yellow couplers of the present 
invention have the following Formula (VIII): 
##STR7## 
wherein R.sub.13 is as defined in the R.sub.9 of Formula (VII); R.sub.14, 
R.sub.15 and R.sub.16 each is a hydrogen atom, a halogen atom (such as, 
e.g., chlorine), an alkyl radical (such as, e.g., methyl, nonyl), an 
alkenyl radical, an alkoxy radical (such as, e.g., methoxy, dodecyloxy), 
an aryl radical (such as, e.g., phenyl), a carboxyl radical, an 
alkoxycarbonyl radical (such as, e.g, methoxycarbonyl, 
decenyloxycarbonyl), a carbamyl radical, a sulfone radical, a sulfamyl 
radical, a sulfonamido radical (such as, e.g., methanesulfonamido), an 
acylamido radical (such as, e.g., acetylamido), an unreido radical or an 
amino radical; and X is as defined in Formula (I), and preferably a 
radical having Formula (III) or (IV), and the more preferred of Formula 
(III) is one having (V) or (VI). 
The following are typical examples of the yellow couplers of the present 
invention, but the yellow couplers of the present invention are not 
limited thereto: 
##STR8## 
These yellow couplers can be synthesized in accordance with those methods 
described in, e.g., U.S. Pat. Nos. 2,778,658, 2,875,057, 2,908,573, 
3,227,155, 3,227,550, 3,253,924, 3,265,506, 3,277,155, 3,341,331, 
3,369,895, 3,384,657, 3,408,194, 3,415,652, 3,447,928, 3,551,155, 
3,582,322, 3,725,072 and 3,894,875; West German OLS Pat. Nos. 1,547,868, 
2,057,941, 2,162,899, 2,163,812, 2,213,461, 2,219,917, 2,261,361 and 
2,263,875; Japanese Patent Examined Publication Nos. 13576/1974, 
33410/1976 and 25733/1977; Japanese Patent O.P.I. Publication Nos. 
29432/1973, 66835/1973, 94432/1973, 1229/1974, 10736/1974, 122335/1974, 
28834/1975, 65231/1975 and 132926/1975; and the like. 
The yellow couplers of the present invention may be used either singly or 
in combination of not less than two thereof. The adding quantity of these 
couplers is usually preferably from 0.05 mole to two moles per mole of 
silver halide, and particularly preferably from 0.1 to mole to 1 mole per 
mole of silver halide. 
In the high-boiling organic solvent having Formula (II) of the present 
invention (hereinafter referred to as the high-boiling organic solvent of 
the invention), each of the R.sub.3 and R.sub.4 of Formula (II) is an 
alkyl radical selected from the group consisting of nonyl, decyl and 
undecyl radicals, and may be either the same or different, but is 
desirable to be the same, and particularly the R.sub.3 and R.sub.4 each is 
desirable to be nonyl radical. Further, the foregoing alkyl radicals 
represented by the R.sub.3 and R.sub.4 may be favorably used in any of the 
cyclic, straight-chain or branched-chain form, but at least either one of 
the R.sub.3 and R.sub.4 is desirable to be a branched-chain alkyl radical, 
and it is particularly desirable that both R.sub.3 and R.sub.4 are the 
same branched-chain radical. 
The following are examples of the suitably-usable high-boiling organic 
solvents of the present invention, but the high-boiling organic solvents 
of the present invention are not limited thereto: 
##STR9## 
Any of the high-boiling organic solvents of the present invention can be 
synthesized by those methods of the prior art; for example, by the 
reaction of phthalic anhydride with an alcohol having alkyl chains 
corresponding to the R.sub.3 and R.sub.4 of the high-boiling organic 
solvent of the present invention in the presence of such an acid catalyst 
as sulfuric acid, or by the reaction of phthalic acid with a halogenated 
alkyl in the presence of a tertiary amine. 
Those compounds similar to the high-boiling organic solvent of the present 
invention are already known to those skilled in the art. For example, U.S. 
Pat. No. 4,146,393 and Japanese Patent O.P.I. Publication No. 4125/1979 
disclose only the use of dinonyl phthalate as an application example of 
the high-boiling organic solvent for cyan couplers and ultraviolet 
absorbing agents. 
Japanese Patent O.P.I. Publication No. 91325/1979 describes a method for 
preventing possible yellow stain on the white area or margin of 
photographic prints by reducing the amount of the residual color 
developing agent remaining in a processed light-sensitive material by 
incorporating a phthalate compound thereinto, but does not refer at all to 
any functional effect of the present invention upon the improvement effect 
on the resistance to light by the use in combination of the high-boiling 
organic solvent of the present invention and the yellow coupler of the 
present invention. 
The present invention provides an unexpectedly surprising light 
resistance-improving effect to a photographic light-sensitive material by 
the use in combination of the yellow coupler having Formula (I) and the 
high-boiling organic solvent having Formula (II), thus accomplishing the 
aforesaid objects of the present invention. 
The adding quantity of the high-boiling organic solvent of the present 
invention depends on the kind of the yellow coupler of the present 
invention used, and, although no special resprictions are to be placed 
thereon, is preferably 0.1-300% by weight, and more preferably 10-70% by 
weight to the weight of the yellow coupler of the present invention. These 
high-boiling organic solvents of the present invention may be used singly 
or in combination of not less than two thereof, or may also be used 
together with some of other high-boiling organic solvents arbitrarily 
selected from the group of conventionally known high-boiling organic 
solvents such as, e.g., dibutyl phthalate, tricresyl phosphate, di-n-octyl 
phthalate, di-n-dodecyl phthalate, di-2-ethylhexyl phthalate, dimethyl 
phthalate, trihexyl phosphate, tri-2-ethylhexyl phosphate, triisononyl 
phosphate, dibenzyl phthalate, N,N-diethyllaurylamide, 
3-pentadecylphenylethyl-ether, 2,5-di-sec-amylphenylbutyl-ether, and the 
like. 
For the purpose of preventing possible occurrence of stain or color fog on 
the photographic light-sensitive material, it is desirable to use a 
hydroquinone derivative together with the yellow coupler of the present 
invention and the high-boiling organic solvent of the present invention. 
Typical examples of the above hydroquinone derivative are as given below: 
HQ-1: 2,5-di-t-octyl-hydroquinone. 
HQ-2: 2-t-octyl-5-methyl-hydroquinone. 
HQ-3: 2,5-di-n-dodecyl-hydroquinone. 
HQ-4: 2-n-dodecyl-hydroquinone. 
HQ-5: 2,2'-methylenebis-5,5'-di-t-butyl-hydroquinone. 
HQ-6: 2,5-di-n-octyl-hydroquinone. 
HQ-7: 2-dodecylcarbamoylmethyl-hydroquinone. 
HQ-8: 2-(.beta.-n-dodecyloxycarbonyl)ethyl-hydroquinone. 
HQ-9: 2-(N,N-dibutylcarbamoyl)hydroquinone. 
HQ-10: 2-n-dodecyl-5-chlorohydroquinone. 
HQ-11: 2-octadecyl-5-methyl-hydroquinone. 
HQ-12: 2,5-di-(p-methoxyphenyl)hydroquinone. 
HQ-13: 2-t-octyl-hydroquinone. 
HQ-14: 2,5-dichloro-3,6-diphenyl-hydroquinone. 
HQ-15: 2,6-dimethyl-3-t-octyl-hydroquinone. 
HQ-16: 2,3-dimethyl-5-t-octyl-hydroquinone. 
HQ-17: 2-{.beta.-(dodecanoyloxy)ethyl}carbamoyl-hydroquinone. 
HQ-18: 2-dodecyloxycarbonyl-hydroquinone. 
HQ-19: 2-{.beta.-(4-octaneamidophenyl)ethyl}hydroquinone. 
HQ-20: 2,5-bis(1',1'-dimethylbutyl)-hydroquinone. 
These hydroquinone derivatives may be used singly or in combination of not 
less than two thereof. Any of these hydroquinone derivatives may be used 
usually in an adding quantity of preferably from 0.001 mole to 2 moles, 
and more preferably from 0.01 mole to 1 mole per mole of the cyan coupler 
of the present invention. 
The incorporation of such an ultraviolet absorbing agent as 
2-(2'-hydroxyphenyl)benzotriazole, 2-hydroxybenzophenone, a salicylic acid 
ester, acrylonitrile, thiazoline or a 2'-hydroxyl-1,3,5-triazine-type 
compound into the layer containing the yellow coupler of the present 
invention and/or other photographic layers is advantageous for the 
prevention of possible discoloration of the yellow dye due to 
short-wavelength active rays and the prevention of possible static marks. 
Above all, the ultraviolet absorbing agents suitably usable for the 
prevention of possible discoloration are those compounds having the 
following Formula (IX): 
##STR10## 
wherein R.sub.17, R.sub.18 and R.sub.19 each is a hydrogen atom, a halogen 
atom, an alkyl radical, an aryl radical, an alkoxy radical, an aryloxy 
radical, an alkenyl radical, a nitro radical or a hydroxyl radical. 
The following are typical examples of the ultraviolet absorbing agents 
having Formula (IX): 
##STR11## 
The yellow coupler of the present invention is dissolved into the 
high-boiling organic solvent, if necessary, combined with use of a 
low-boiling organic solvent as an auxiliary solvent, the solution is then 
finely dispersed by use of an emulsifying agent into such a dispersion 
medium as an aqueous gelatin solution, and the resulting emulsifiedly 
dispersed product is incorporated into an objective hydrophilic colloidal 
layer. In this instance, the yellow coupler of the present invention and 
the high-boiling organic solvent of the present invention are allowed to 
be separately emulsified to be dispersed, and after that both dispersed 
liquids may be mixed. 
To the yellow coupler of the present invention and the high-boiling organic 
solvent of the present invention may be added concurrently other 
hydrophobic compounds (other couplers, ultraviolet absorbing agents, 
antidiscoloration agents, brightening agents, hydroquinone derivatives, 
etc.). The preferred low-boiling organic solvents usable as the auxiliary 
solvent include methyl acetate, ethyl acetate, propyl acetate, butyl 
acetate, butyl propionate, cyclohexanol, cyclohexane, tetrahydrofuran, 
methyl alcohol, ethyl alcohol, acetonitrile, dimethylformamide, dioxane, 
methyl-ethyl ketone, methyl-isobutyl ketone, diethylene-glycol 
monoacetate, acetylacetone, nitromethane, nitroethane, carbon 
tetrachloride, chloroform, and the like. The preferred emulsifying agents 
include anionic surfactants such as alkylbenzenesulfonic acids, 
alkylnaphthalenesulfonic acids, etc. and/or nonionic surfactants such as 
sorbitansesquioleates, sorbitanmonoluarates, etc. As dispersing apparatus 
there may be used simple stirrer, homogenizer, colloid mill, flow-jet 
mixer, ultrasonic disperser, and the like. The dispersed product may be 
incorporated into a hydrophilic colloid, but prior to the incorporation 
there may be inserted a process for removing the low-boiling organic 
solvent. 
The preferred embodiments of the dispersion of the yellow coupler of the 
present invention are given below: 
An yellow coupler of the present invention, a high-boiling organic solvent 
of the present invention, a hydroquinone derivative, and ethyl acetate are 
mixed and dissolved by heating to 60.degree. C. An aqueous gelatin 
solution as a dispersion medium is mixed with an emulsifying agent, and 
the mixture is heated to 60.degree. C. Both the resulting solutions were 
mixed with stirring and then emulsified to be dispersed by a homogenizer 
or equivalent means. 
For the photographic light-sensitive material of the present invention 
there may be used known magenta dye image-forming couplers and/or cyan dye 
image-forming couplers. The suitably usable couplers include those having 
Formulas (X) and (IX). 
The preferred magenta dye image-forming couplers (hereinafter referred to 
as magenta couplers) have the following Formula (X): 
##STR12## 
wherein Ar represents an aryl radical; R.sub.20 is a hydrogen atom, a 
halogen atom, an alkyl radical or an alkoxy radical; R.sub.21 is an alkyl 
radical, an amido radical, an imido radical, an N-alkylcarbamoyl radical, 
an N-alkylsulfamoyl radical, an alkoxycarbonyl radical, an acyloxy 
radical, an alkylsulfonamido radical or an urethane radical; Y is a 
hydrogen atom or a radical that can be split off by the reaction of the 
coupler with the oxidized product of an aromatic primary amine-type color 
developing agent; and W is an amino radical, an acylamino radical or an 
ureido radical. 
Examples of the above magenta couplers having Formula (X) are as given 
below, but it goes without saying that the magenta couplers are not 
limited thereto: 
##STR13## 
These are as described in, e.g., U.S. Pat. Nos. 2,600,788, 3,061,432, 
3,062,653, 3,127,269, 3,311,476, 3,152,896, 3,419,391, 3,519,429, 
3,555,318, 3,684,514, 3,888,680, 3,907,571, 3,928,044, 3,930,861, 
3,930,866 and 3,933,500; Japanese Patent O.P.I. Publication Nos. 
29639/1974, 111631/1974, 129538/1974, 13041/1975, 58922/1977, 62454/1980, 
118034/1980, 38043/1981 and 35858/1982; British Pat. No. 1,247,493; 
Belgian Pat. Nos. 769,116 and 792,525; West German Pat. No. 2,156,111; and 
Japanese Patent Examined Publication No. 60479/1971. 
The preferred cyan dye image-forming couplers (hereinafter referred to as 
cyan couplers) are those compounds having the following Formula (XI): 
##STR14## 
wherein Z is a hydrogen atom or a radical that can be split off by the 
reaction of the coupler with the oxidized product of an aromatic primary 
amine-type color developing agent; and R.sub.22, R.sub.23, R.sub.24, and 
R.sub.25 each is a hydrogen atom, a halogen atom, an alkyl radical, a 
carbamoyl radical, a sulfamoyl radical, an amido radical, a sulfonamido 
radical, a phosphoric acid amido radical or an ureido radical. 
The following are typical examples of the cyan couplers having Formula 
(XI): 
##STR15## 
These are as described in, e.g., U.S. Pat. Nos. 2,369,929, 2,423,730, 
2,434,272, 2,474,293, 2,698,794, 2,706,684, 2,772,162, 2,801,171, 
2,895,826, 2,908,573, 3,034,892, 3,046,129, 3,227,550, 3,253,294, 
3,311,476, 3,386,301, 3,419,390, 3,458,315, 3,476,563, 3,516,831, 
3,560,212, 3,582,322, 3,583,971, 3,591,383, 3,619,196, 3,632,247, 
3,652,286, 3,737,326, 3,758,308, 3,779,763, 3,839,044 and 3,880,661; West 
German OLS Pat. Nos. 2,163,811 and 2,207,468; Japanese Patent Examined 
Publication Nos. 27563/1964 and 28836/1970; Japanese Patent O.P.I. 
Publication Nos. 37425/1972, 10135/1975, 25228/1975, 112038/1975, 
117422/1975, 130441/1975, 109630/1978, 65134/1981 and 99341/1981; and 
Research Disclosure No. 148, p. 14,853 (1976), and the like. 
The silver halide emulsion used in the photographic light-sensitive 
material of the present invention is generally a hydrophilic colloid 
containing silver halide particles dispersed thereinto. The silver halide 
used includes silver chloride, silver bromide, silver iodide, silver 
chlorobromide, silver iodobromide, silver chloroiodobromide and a mixture 
of these silver halides. These silver halides can be prepared by various 
processes such as the ammoniacal process, neutral process, the so-called 
conversion process, simultaneously mixing process, and the like. As the 
hydrophilic colloid into which is to be dispersed the silver halide, 
gelatin or gelatin derivatives such as phthalated gelatin, malonated 
gelatin, or the like, may be used, but these may also be partially or 
wholly replaced by albumin, agar-agar, gum arabic, alginic acid, casein, 
partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl 
acetate, polyacrylamide, imidated polyacrylamide, polyvinyl pyrolidone or 
copolymers of these vinyl compounds. Further, any of these silver halide 
emulsions may be spectrally sensitized by use of various sensitizing dyes 
in order to render it sensitive to any desired wavelength region. As the 
spectrally sensitizing dye for this purpose, there may be used singly or 
in combination cyanine dyes, merocyanine dyes or complex cyanine dyes. 
And, if necessary, there may also be used singly or in combination such 
photographic additives including, for example, chemical sensitizers 
including noble-metallic salts such as compounds of gold, platinum, 
palladium, iridium, rhodium, ruthenium, etc., sulfur compounds, reduction 
materials or thioether compounds, quaternary ammonium compounds or 
polyalkyleneoxide compounds, etc.; stabilizers such as triazoles, 
imidazoles, azaindenes, benzothiazoles, tin compounds, cadmium compounds, 
mercaptans, etc.; hardening agents such as chromium salts, zirconium 
salts, mucochloric acid, aldehyde-type and triazine-type polyepoxy 
compounds, active halogenated compounds, ketone compounds, acryloyl-type, 
triethylenephosamide-type and ethyleneimine-type hardeners, etc.; 
plasticizers of dihydroxyalkanes such as glycerol, 1,5-pentanediol, etc.; 
brightening agents; antistatic agents; coating aids; and the like. 
Into the obtained silver halide emulsion layer is incorporated the 
foregoing dispersed liquid into which is dispersed the aforementioned 
compounds of the present invention. Further, if necessary, into the 
subbing layer, interlayer, yellow filter layer, ultraviolet absorbing 
layer, protective layer, and the like, are incorporated dispersed products 
of the compounds of the present invention. And these layers are coated on 
a support such as of cellulose acetate, nitrocellulose, polycarbonate, 
polyethylene terephthalate, synthetic resin film such as of polyethylene, 
baryta paper, polyethylene-coated paper, glass plates, or the like, thus 
producing a photographic light-sensitive material. These are described in 
detail in Research Disclosure No. 17643 (1978) and the like. 
The above photographic light-sensitive material is particularly 
advantageous for coupler-in-emulsion-type silver halide color photographic 
light-sensitive materials, and, after being exposed imagewise to light, is 
processed by the color development process. Further, the photographic 
light-sensitive material may be of the type that the coupler and a color 
developing agent are present so as not to come into contact with each 
other before exposure and processing in a same layer and, after being 
exposed to light and processed, are able to come into contact with each 
other; or of such the coupler-in-emulsion-type silver halide color 
photographic light-sensitive material type that the coupler-free layer 
thereof contains a color developing agent which moves, when an alkaline 
processing liquid permeates into the light-sensitive material, to come 
into contact with the coupler. 
And in that instance, the support used therefor is desirable to be any of 
baryta paper, polyethylene-coated paper, titanium oxide-containing 
polyethylene terephthalate film, electron beam-setting resin-coated paper 
and polypropylene-synthetic paper. 
Furthermore, the photographic light-sensitive material is desirable to be 
of the type comprising a support, made of any one of the above support 
materials, having thereon in order at least a blue-sensitive emulsion 
layer, a green-sensitive emulsion layer and a red-sensitive emulsion 
layer, and, besides, at least two ultraviolet absorbing agent-containing 
layers provided on the further side than the foregoing green-sensitive 
emulsion layer from the support. 
Referring to the processing of the photographic light-sensitive material of 
the present invention, in the reversal process, the light-sensitive 
material is first processed in a black-and-white developer bath, and then 
the entire area of the material is either exposed to a white light or 
processed in a bath containing such a fogging agent as a boron compound, 
and after that color-developed in an alkaline liquid containing a color 
developing agent. In this instance, the development may also be made in an 
alkaline developer bath containing a fogging agent together with the color 
developing agent. After the color development, the developed 
light-sensitive material is bleached in a bleaching bath containing 
ferricyanide or ferric carboxylate as an oxidizing agent, and then fixed 
in a fixing bath containing such a silver halide solvent as a thiosulfate 
to remove the silver image and residual silver halide, thereby leaving the 
formed dye image. Instead of using the bleaching bath and the fixing bath, 
a bleach-fix monobath may be used for bleaching and fixing the material, 
the monobath containing ferric aminopolycarboxylate as an oxidizing agent 
and a thiosulfate as a silver halide solvent. In combination with the 
color development, bleaching, fixing, or bleach-fixing, there may also 
take place such processings or prehardening, neutralizing, washing, stop, 
stabilizing, and the like. Particularly, the processings by which the 
photographic light-sensitive material of the present invention is 
advantageously processed are, e.g., color development, if necessary, 
bleach-fixing, washing, if necessary, stabilizing, and drying, and these 
processings take place in a very short period of time at as high a 
temperature as not less than 30.degree. C. 
The color developer, as previously described, contains a color developing 
agent and certain necessary additives whose typical examples include, 
e.g., alkali agents such as hydroxides, carbonates, phosphates, etc., of 
an alkali metal or of ammonium, buffer such as acetic acid, boric acid, 
etc., pH control agent, a development accelerator, antifoggant, antistain 
agent, antisludge agent, interlayer effect accelerator, preservative, and 
the like. 
The bleaching agent for use in the bleaching includes ferricyanides such as 
potassium ferricyanide, bichromates, permanganates, hydrogen peroxide, 
chloride of lime; metallic complex salts of such aminopolycarboxylic acids 
as ethylenediaminetetraacetic acid, iminodiacetic acid, and the like; 
metallic complex salts of such polycarboxylic acids as malonic acid, 
tartaric acid, malic acid, and the like; ferric chloride; and the like. 
These may be used singly or in combination at need. To the bleach-fix bath 
may be added, if necessary, various additives including a bleach 
accelerator and the like. 
The fixing agent for use in the fixing process includes thiosulfates such 
as sodium thiosulfate, ammonium thiosulfate, etc., cyanides and urea 
derivatives. To the fixing bath may be added, if necessary, various 
additives including a fixing accelerator and the like. 
The photographic light-sensitive material of the present invention may be 
effectively processed also by use of a color developer solution containing 
both an aromatic primary amine-type color developing agent and an 
oxidizing agent that causes the metallic silver image to take part in a 
redox reaction. 
When such a color developer liquid is used, the color developing agent is 
oxidized by the oxidizing agent, and then effects a coupling reaction with 
photographic couplers to thereby form a dye image. Such the color 
developer liquid is disclosed in, e.g., Japanese Patent O.P.I. Publication 
No. 9729/1973. The preferred oxidizing agents for this purpose are cobalt 
complex salts whose coordination number is 6. The color photographic 
development process including such the color developer liquid is 
particularly useful for silver-saving-type photographic light-sensitive 
materials containing a smaller amount of silver than that of ordinary 
photographic light-sensitive materials. 
The photographic light-sensitive material of the present invention is 
developed in a color developer bath containing an aromatic primary 
amine-type color developing agent, and may also be subsequently processed 
preferably in an amplifying bath containing the foregoing oxidizing agent 
such as, e.g., a cobalt complex salt whose coordination number is six, in 
which the color developing agent which has been permeated into the 
light-sensitive layer during the preceding developing process and which is 
movable into the amplifying bath and, if necessary, a color developing 
agent in advance being present in the amplifying bath come into contact 
with the cobalt complex salt. In addition, another oxidizing agent 
suitably usable for this purpose is an aqueous hydrogen peroxide solution.

The present invention is illustrated further in detail in reference to 
examples below, but the embodiments of the present invention are not 
limited thereto 
EXAMPLE 1 
Samples were prepared which have the construction as given in Table 1. 
TABLE 1 
______________________________________ 
Coupler-dis- 
Coated q'ty 
Coated q'ty 
persed 
of silver 
of gelatin 
liquid 
______________________________________ 
Layer 2 
Protective -- 20 -- 
layer 
Layer 1 
Blue-sensi- 4.0 25 (Table 2) 
tive EM layer 
Polyethylene-coated paper support 
______________________________________ 
*Coated quantity unit: in mg/100 cm.sup.2 
The respective samples were prepared using the blue-sensitive emulsion 
layer's coupler dispersion compositions varied as given in Table 2. The 
coating quantity of the coupler is 10 mg/100 cm.sup.2. The yellow coupler 
dispersion liquids each was prepared in the following procedures (a) to 
(b): 
(a) Thirty-one grams of Exemplified Yellow Coupler Y-7 of the present 
invention, 0.6 g of 2,5-di-t-octylhydroquinone (HQ-1), 22 g of the high 
boiling organic solvent given in Table 2, and 62 g of ethyl acetate were 
mixed and dissolved by heating to 60.degree. C. 
(b) Forty grams of photographic gelatin and 500 ml of pure water were mixed 
at room temperature and swelled spending about 20 minutes, and then 
dissolved by heating to 60.degree. C. After that to this were added 50 ml 
of an aqueous 5% Alkanol B (produced by DuPont) solution, and the mixture 
was stirred until it becomes homogeneous. 
(c) The respective solutions obtained in (a) and (b) were mixed and 
dispersed by means of an ultrasonic disperser for a period of 30 minutes, 
whereby a dispersed liquid was obtained. 
TABLE 2 
__________________________________________________________________________ 
Hi-boiling 
Low-boil- 
Exemplified 
Hydroquinone 
organic 
ing organ- 
Sample 
coupler and 
derivative & 
solvent & 
ic solvent 
No. quantity (g) 
quantity (g) 
quantity (g) 
& q'ty (g) 
__________________________________________________________________________ 
1 (Y-7) 31 
(HQ-1) 0.6 
DBP 22 
EA 62 Comparative 
2 " " DOP 22 
" " 
3 " " (H-8) 22 
" Invention 
4 " " (H-2) 22 
" " 
5 " " (H-19) 22 
" " 
6 " " (H-12) 22 
" " 
7 " " (H-27) 22 
" " 
8 " " (H-21) 22 
" " 
9 " " DLP 22 
" Comparative 
__________________________________________________________________________ 
In Table 2, DBP stands for di-n-butyl phthalate, DOP for di-2-ethylhexyl 
phthalate, DLP for di-n-lauryl phthalate, and EA for ethyl acetate. 
The thus obtained nine samples were subjected to the following tests (1) to 
(3): 
(1) Coupler's dispersion stability tests 
Measurements were made on the turbidities (correlating with the dispersed 
particles; the smaller the value, the smaller the particle size) of the 
respective dispersed liquids obtained in the above procedures (a) to (c), 
and the particle's deposition degrees (deposition starting points of 
time). The measurements took place after allowing the samples to stand 
without stirring at 40.degree. C. for 10 hours. 
(2) Sensitometry tests 
The nine coated samples each was exposed through an optical wedge to light 
by use of a sensitometer (Model KS-7, manufactured by Konishiroku Photo 
Industry Co., Ltd.) and then processed in the following processing liquids 
in accordance with the steps below: 
______________________________________ 
Processing steps 
Time Temperature 
______________________________________ 
Color developing 
3.5 minutes 
33.degree. C. 
Bleach-fix 1.5 minutes 
33.degree. C. 
Washing 3.0 minutes 
33.degree. C. 
Drying -- 80.degree. C. 
______________________________________ 
Color developer composition 
______________________________________ 
Pure water 700 ml 
Benzyl alcohol 15 ml 
Diethylene glycol 15 ml 
Hydroxyamine sulfate 2 g 
N--ethyl-N--.beta.-methanesulfoneamidoethyl- 
4.4 g 
3-methyl-4-aminoaniline sulfate 
Potassium carbonate 30 g 
Potassium bromide 0.4 g 
Potassium chloride 0.5 g 
Potassium sulfite 2 g 
Pure water to make 1 liter (pH = 10.2) 
______________________________________ 
Bleach-fix bath composition 
______________________________________ 
Iron-ammonium ethylenediaminetetraacetate 
61 g 
Diammonium ethylenediaminetetraacetate 
5 g 
Ammonium thiosulfate 125 g 
Sodium metabisulfite 13 g 
Sodium sulfite 2.7 g 
Water to make 1 liter (pH = 7.2) 
______________________________________ 
The thus processed samples each was measured with respect to the relative 
speed and the maximum reflection density by use of a photoelectric 
densitometer (Model PDA-60, manufactured by Konishiroku Photo Industry 
Co., Ltd.). The obtained results are as shown in Table 3. 
(3) Dye image preservability tests 
Each of the nine samples processed in the same way as in (2) was subjected 
to dye image preservability tests in the following procedures (a) and (b): 
(a) Light-discoloration characteristic 
______________________________________ 
Illuminance 
Irradiation 
(Lux) period (hr) 
______________________________________ 
A Xenon fadeometer 3.5 .times. 10.sup.4 
100 
B Fluorescent lamp fadeometer 
1.6 .times. 10.sup.4 
300 
______________________________________ 
(b) Dark-discoloration characteristic 
The samples were aged under the following conditions: 
______________________________________ 
C At 77.degree. C. 
without humidification 
for 14 days 
D At 70.degree. C. 
80% RH (relative humidity) 
for 14 days 
______________________________________ 
In addition, the results of the dye image preservability tests are given in 
Table 3 in percentage (%) of the after-test density (D) to the initial 
density (Do)=1.0. 
All the results obtained in (1) to (3) are as given in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Sensitometric 
Turbidity characteristics 
High 
Right Deposi- Max re- Light 
Dark 
boiling 
after 
After 
Dif- 
tion Rela- 
flec- discolor- 
discolor- 
Sample 
organic 
disper- 
ten fer- 
starting 
tive 
tion Gamma 
ation 
ation 
No. solvent 
sion 
hours 
ence 
time (hr) 
speed 
density 
(.gamma.) 
A B C D 
__________________________________________________________________________ 
1 DBP 28.0 
57.2 
29.2 
7.5 100 2.42 3.32 51 72 
96 
92 Comparative 
2 DOP 28.3 
45.4 
17.1 
8.0 93 2.31 3.11 55 75 
97 
93 " 
3 (H-8) 
28.2 
44.7 
16.5 
Not less 
98 2.36 3.05 64 81 
97 
93 Invention 
than 10 
4 (H-2) 
28.4 
34.3 
5.9 
Not less 
99 2.43 3.31 73 86 
97 
94 " 
than 10 
5 (H-19) 
29.5 
46.4 
16.9 
Not less 
98 2.35 3.03 63 80 
96 
93 " 
than 10 
6 (H-12) 
29.1 
36.2 
7.1 
Not less 
99 2.42 3.33 70 85 
98 
93 " 
than 10 
7 (H-27) 
28.6 
48.3 
19.7 
Not less 
98 2.38 3.08 64 80 
96 
92 " 
than 10 
8 (H-21) 
28.1 
35.6 
7.5 
Not less 
101 2.41 3.32 72 85 
97 
93 " 
than 10 
9 DLP 28.9 
49.5 
20.6 
Not less 
92 2.28 3.03 56 77 
95 
92 Comparative 
than 10 
__________________________________________________________________________ 
As apparent from Table 3, the samples for the present invention (Samples 3 
to 8) are excellent in the sensitometric characteristics as well as in the 
light-discoloration and dark-discoloration characteristics, and 
particularly remarkably improved on the light-discoloration 
characteristic. 
Of these samples for the present invention, Samples 4, 6 and 8 which use 
the branched-chain alkyl-having high-boiling organic solvents of the 
present invention show better improved light-discoloration characteristic, 
and also improved so that increase in the turbidity after a passage of 
time is repressed, thus showing much improved dispersion stability. 
EXAMPLE 2 
Similar samples were prepared in the same manner as in Example 1 with the 
exception that DBP and Exemplified Compound (H-2) of the present invention 
as high-boiling organic solvents and those couplers as shown in Table 4 
were used. These samples were subjected to the same dye image 
preservability tests as in Example 1. The obtained results are as given in 
Table 5. 
TABLE 4 
______________________________________ 
High-boiling or- 
Coupler ganic solvent 
______________________________________ 
1A (Y-7) DBP Comparative 
1B (H-2) Invention 
2A (Y-21) DBP Comparative 
2B (H-2) Invention 
3A (Y-23) DBP Comparative 
3B (H-2) Invention 
4A (Y-30) DBP Comparative 
4B (H-2) Invention 
5A (Y-35) DBP Comparative 
5B (H-2) Invention 
6A Comparative DBP Comparative 
6B coupler-1 (H-2) " 
7A Comparative DBP " 
7B coupler-2 (H-2) " 
______________________________________ 
Comparative Coupler-1 and Comparative Coupler-2 in the above table are 
given below: 
Comparative Coupler-1 
The magenta coupler described in U.S. Pat. No. 3,684,514 
##STR16## 
Comparative Coupler-2 
The cyan coupler described in U.S. Pat. No. 2,423,730 
##STR17## 
TABLE 5 
______________________________________ 
Light dis- Dark dis- 
coloration coloration 
A B A B 
______________________________________ 
1A 51 72 96 92 Comparative 
1B 73 86 97 94 Invention 
2A 46 68 96 93 Comparative 
2B 70 82 97 94 Invention 
3A 40 61 96 92 Comparative 
3B 68 77 96 93 Invention 
4A 52 72 96 93 Comparative 
4B 75 88 97 94 Invention 
5A 43 64 95 90 Comparative 
5B 56 71 95 91 Invention 
6A 37 52 95 91 Comparative 
6B 38 53 95 92 " 
7A 80 93 65 71 " 
7B 80 94 67 72 " 
______________________________________ 
As apparent from Table 5, only the samples using the yellow couplers of the 
present invention are largely improved on the light-resistant effect. 
Particularly this effect is conspicuous in the case where the yellow 
coupler having Formula (VII) is used. 
EXAMPLE 3 
A sample was prepared which has the layer construction as given in Table 6. 
This was regarded as Sample 1. 
TABLE 6 
__________________________________________________________________________ 
Coated 
Coated 
Coated 
q'ty of High- 
q'ty of 
q'ty of 
UV absorb- 
Coated q'ty 
boiling 
Layer No. 
Layer silver 
gelatin 
ent of coupler 
solvent 
__________________________________________________________________________ 
Layer 7 
Protective 
-- 7 -- -- -- 
layer 
Layer 6 
Third -- 10 4.0 -- DOP 
interlayer 3.0 
Layer 5 
Red-sensitive 
3.0 15 -- Comparative 
DOP 
EM layer coupler-2 
3.0 
6.0 
Layer 4 
Second -- 15 8.0 -- DOP 
interlayer 6.0 
Layer 3 
Green-sensitive 
3.0 15 -- Comparative 
TCP 
EM layer coupler-1 
5.0 
6.1 
Layer 2 
First -- 7 -- -- DOP 
interlayer 0.5 
Layer 1 
Blue-sensitive 
4.0 15 -- (Y-7) DBP 
EM layer 10.0 6.0 
Polyethylene-coated paper support 
__________________________________________________________________________ 
Note: 
*In the above table, TCP stands for tricresyl phosphate. 
*DOP stands for di2-ethylhexyl phthalate. 
*Coated q'ty stands for coated quantity: mg/cm.sup.2 
Sample 2 was prepared in the same manner as in Sample 1 with the exception 
that the DBP of Layer 1 given in Table 6 was replaced by the high-boiling 
organic solvent (H-2) of the present invention. 
The obtained samples each was exposed in the same way as in Example 1 but 
to a blue light alone. The obtained yellow color formed samples were 
subjected to dye image preservability tests under the same conditions as 
previously described. The results are as given in Table 7. 
TABLE 7 
______________________________________ 
Light dis- Dark dis- 
coloration coloration 
Sample A B C D 
______________________________________ 
1 (Comparative) 
63 65 96 92 
2 (Invention) 78 85 97 93 
______________________________________ 
From Table 7, it is apparent that also in the case of the multilayered 
samples using an ultraviolet absorbing agent, the sample for the present 
invention has still largely improved effect on both light-discoloration 
and dark-discoloration characteristics.