Color photographic developing composition

Color developers represented by the following general formula are useful as color developing agents: ##STR1## R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are defined herein.

This invention relates to a color photographic developing composition for 
developing light-sensitive silver halide color photographic materials. 
More particularly, the invention pertains to a color photographic 
developing composition which, when used for color development of a 
light-sensitive silver halide color photographic material, can form a 
color photographic image excellent in quality and can provide quite 
effective use of silver. 
For formation of a color photographic image by processing a light-sensitive 
silver halide color photographic material, there is ordinarily adopted 
such method that the said photographic material is image-wise exposed and 
then developed with a color photographic developing solution containing a 
p-phenylenediamine type developing agent, whereby the silver halide is 
reduced to silver and, at the same time, the developing agent is oxidized, 
and the resulting oxidation product combines with a coupler to form an 
image-wise dye corresponding to the developed silver. The above-mentioned 
color image-forming method includes, for example, such methods as 
described below. 
An internal development method in which a light-sensitive silver halide 
color photographic material containing non-diffusing couplers is 
image-wise exposed, processed with a color photographic developing 
solution, and then subjected to desilvering and fixing to form a color 
negative image. An external development method in which a light-sensitive 
silver halide photographic material containing no coupler is image-wise 
exposed, processed with a color photographic developing solution 
containing a color photographic developing agent and diffusing couplers, 
and then subjected to desilvering and fixing to form a color negative 
image. A method in which a light-sensitive silver halide color 
photographic material is image-wise exposed, subjected to black-white 
first development, uniformly exposed to excite the remaining silver halide 
emulsion layers, processed with an internal or external type color 
photographic developing solution, and then subjected to desilvering and 
fixing to form a reversal color photographic image. A method in which a 
multicolor reflection type photographic material prepared by forming color 
photographic emulsion layers on an opaque support is printed with the 
color negative image formed by the above-mentioned method, and subjected 
to color photographic development, desilvering and fixing to form a color 
positive image. 
In any of such various color image-forming methods, an active 
p-phenylenediamine type developing agent is used. In forming a color 
photographic image by processing a light-sensitive silver halide color 
photographic material with such conventional p-phenylenediamine type 
developing agent, not all of silver halide particles, which have formed a 
latent image due to sensitization, are effectively converted into silver 
and dyes, but considerable quantities of said silver halide particles are 
dissolved in a fixer and are discarded without being effectively utilized. 
If the silver halide particles are effectively converted into silver and 
dyes without any loss, there ought to be obtained many such advantages 
that an excellent color image high in contrast can be obtained, the amount 
of silver may be reduced to make the photographic material thinner, and 
thus the photographic material can be subjected to rapid processing to 
make it possible to obtain a color image high in resolving power. Such 
advantages are more strongly demanded since rapid processing of large 
quantities of photographic materials has come to be effected in recent 
years by use of an automatic developing machine. Further, benzyl alcohol, 
which has heretofore been used as a development aid in the color 
photographic developing solution in practicing such method as above, is 
demanded to be reduced in amount or removed, since it increases the BOD of 
waste liquor and is undesirable from the standpoint of environmental 
sanitation. Still further, a color photographic image formed by use of a 
conventional developing agent is low in heat resistance, humidity 
resistance and light fastness, and is frequently discolored and faded 
during storage. For the above reasons, the advent of a color photographic 
developing agent, which is free from the above-mentioned disadvantages and 
which can form a color photographic image high in stability, is strongly 
demanded. 
An object of the present invention is to provide a novel color photographic 
developing composition which, when used for color development of a latent 
image silver halide obtained by image-wise exposure of a light-sensitive 
silver halide color photographic material, can form reduced silver with 
high efficiency and leaves no uselessly wasted silver halide. 
Another object of the invention is to provide a novel color photographic 
developing composition which, when used for color development of a latent 
image, can show such effect that the ratio of the density of formed dye to 
the density of developed silver is far greater than a value obtained in 
the case where a known developing composition is used. 
A further object of the invention is to provide a novel color photographic 
developing composition which is excellent in penetrability or osmic 
ability into silver halide emulsion layers and affinity with silver 
halide, and is high in color development speed. 
A still further object of the invention is to provide a novel color 
photographic developing composition which, when used for color 
development, can give a color image capable of maintaining excellent 
stability even when exposed to high temperature, high humidity and light 
over a long period of time. 
Another object of the invention is to provide a novel color photographic 
developing composition which brings about no disadvantage even when benzyl 
alcohol, which has heretofore been incorporated into a color photographic 
developing solution and which becomes a cause for public pollution, is 
reduced in amount or removed. 
We have found that the above-mentioned objects can be accomplished by 
using, for processing of a light-sensitive silver halide photographic 
material, a developing composition comprising as a color developing agent 
a compound, or its salt, represented by the general formula 
##STR2## 
wherein R.sub.1 is --R.sub.6 O--R.sub.9 or (R.sub.7 O).sub.n.sbsb.1 
--(R.sub.8 O).sub.n.sbsb.2 --R.sub.9 (where R.sub.6 is a substituted 
alkylene group having 1 to 6 carbon atoms, R.sub.7 and R.sub.8 are 
individually a substituted or unsubstituted alkylene group having 1 to 6 
carbon atoms (the substituent of the substituted alkylene group 
represented by each of R.sub.6, R.sub.7 and R.sub.8 may be one which has 
further been substituted by other group, and is, for example, an alkyl 
group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl or nonyl 
group; an aralkyl group such as benzyl group, a halogen-substituted alkyl 
group; an aryl group such as phenyl or naphthyl group; an alkoxy group 
such as methoxy, ethoxy, pentyloxy or octyloxy group; an aryloxy group 
such as phenoxy group; or a halogen atom), n.sub.1 and n.sub.2 are 
individually 0 or an integer of 1 or more, the sum of n.sub.1 and n.sub.2 
being 2 or more, R.sub.9 is a substituted or unsubstituted alkyl group, an 
aryl group or an aralkyl group); R.sub.2 is a hydrogen atom, a substituted 
or unsubstituted alkyl group (the substituted alkyl group is, for example, 
a hydroxyalkyl, aminoalkyl, alkoxyalkyl, acylamidoalkyl, carbamylalkyl, 
alkylsulfonamidoalkyl or aryloxyalkyl group) or R.sub.1 ; and R.sub.3, 
R.sub.4 and R.sub.5 are individually a hydrogen or halogen atom, or a 
hydroxy, amino, alkoxy, sulfonamido, acylamido, or substituted or 
unsubstituted alkyl group (the substituent of the substituted alkyl group 
is, for example, a hydroxyalkyl, aminoalkyl, acylamidoalkyl or 
alkylsulfonamidoalkyl group), provided that the alkyl group represented by 
each of R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.9 has 1 to 6 carbon 
atoms. 
That is, when a light-sensitive silver halide color photographic material 
is processed with a developing solution containing the above-mentioned 
color photographic developing agent of the present invention, the color 
development proceeds effectively to form silver and dyes with high 
efficiency. The reason therefor has not been clarified yet. However, the 
color photographic developing agent of the present invention has, bonded 
to its nitrogen atom, a substituted monoalkylene oxide group or a 
substituted or unsubstituted polyalkylene oxide group. Furthermore, the 
terminal hydrogen atom of said alkylene oxide group has been substituted 
by a substituted or unsubstituted alkyl group, an aryl group or an aralkyl 
group. Accordingly, it is inferred that by virtue of the above-mentioned 
structure, the developer of the present invention is increased in both 
hydrophilic and oleophilic properties, and thus is enhanced in affinity 
with silver halide and couplers and in penetrability into emulsion layers, 
whereby the action of the developing agent is promoted. 
As mentioned above, the developing agent of the present invention is high 
in affinity with silver halides and couplers in silver halide emulsion 
layers and in penetrability into emulsion layers, so that the color 
development effectively proceeds to form silver and dyes with high 
efficiency. Accordingly, not only the amounts of silver and couplers can 
be reduced, but also the silver halide emulsion layers can be made 
thinner. When a light-sensitive silver halide color photographic material 
is processed by use of the color photographic developing composition of 
the present invention, therefore, it is possible to attain such effect 
that a color image high in resolving power and sharpness can be obtained. 
Further, due to its excellent properties, the developing agent of the 
present invention is increased in penetrability into emulsion layers. 
Accordingly, it is also possible to obtain such important effect from the 
standpoint of prevention of public pollution that benzyl alcohol, which is 
injurious to environmental sanitation and which is generally contained as 
a development aid in a developing solution, can be reduced in amount or 
removed. Furthermore, the developing agent of the present invention has 
such structure as mentioned previously, and hence can give such effect 
that a color image formed by the color development of latent image silver 
halide with the developing agent of the present invention is fast and is 
excellent in heat resistance, humidity resistance and light resistance. 
Still further, it is observed that an increase in number of the 
alkyleneoxide units in the developing agent used in the present invention 
results in increased solubility of the developing agent in water, thereby 
facilitating the action of the developing solution obtained. This means 
such advantages that the residual amount of the developing agent in a 
light-sensitive emulsion layer after development is quite so small that 
undesidered formation of color stains during the subsequent step of an 
oxidizing bath treatment can be minimized to yield a good image free from 
color stains. 
The color photographic development composition of the present invention 
contains a color photographic developing agent, and is a free base of a 
p-phenylenediamine type compound or an organic or inorganic salt of said 
compound. 
Typical examples of the color photographic developing agent of the present 
invention are shown below, with mass spectrum M.sup.+ and calculated 
molecular weight which is shown in parentheses. 
##STR3## 
Salts, which are obtained by treating the above-mentioned compounds with an 
organic or inorganic acid such as sulfuric hydrochloric, phosphoric, 
oxalic, alkylbenzenesulfonic, benzenesulfonic, naphthalenesulfonic or 
alkylsulfonic acid, may also be effectively used like the above 
exemplified compounds. 
The developing agent used in the present invention may be synthesized 
according to, for example, such procedures as described below. 
As starting material, there is used a monoalkyl N-substituted aniline such 
as N-alkylaniline, N-alkyl-3-alkylaniline, N-alkyl-3-alkoxyaniline, 
N-alkyl-3-alkylsulfonamidoaniline, N-alkyl-3-acylamidoaniline, 
N-alkyl-3-hydroxyaniline, N-alkyl-3-acylamidoalkylaniline, 
N-alkyl-3-hydroxyalkylaniline or N-alkyl-3-alkylsulfonamidoalkylaniline. 
In this case, the said monoalkyl-N-substituted aniline is reacted with a 
.omega.-halide such as 1-halogeno-2-(2-methoxyethoxy)ethane, 
1-halogeno-1-methyl-2-methoxyethane, 
1-halogeno-2-(1-methyl-2-methoxyethoxy)ethane, 
1-halogeno-2-[2-(2-methoxyethoxy)ethoxy]ethane, 
1-halogeno-1-methyl-2-[2-(2-methoxyethoxy)ethoxy]ethane or 
1-halogeno-2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethane to synthesize a 
corresponding N,N-disubstituted aniline. Alternatively, a monoalkyl ether 
of an alkylene glycol such as diethylene glycol, triethylene glycol, 
tetraethylene glycol, propylene glycol, dipropylene glycol or tripropylene 
glycol is reacted with a p-toluenesulfonic acid halide to synthesize a 
corresponding p-toluenesulfonic acid ester. Subsequently, this ester is 
reacted with the aforesaid monoalkyl-N-substitued aniline to synthesize a 
corresponding N,N-disubstituted aniline. Still alternatively, an aniline 
such as 3-alkylaniline, 3-alkoxyaniline, 3-alkylsulfonamidoaniline, 
3-acylamidoaniline, 3-hydroxyaniline, 3-hydroxyalkylaniline, 
3-alkylsulfonamidoalkylaniline or 3-acylamidoalkylaniline is reacted with 
the aforesaid .omega.-halide or p-toluenesulfonic acid ester to synthesize 
a corresponding N,N-disubstituted aniline. 
Using the thus synthesized N,N-disubstituted aniline, the color 
photographic developing agent of the present invention may be synthesized 
in the manner described below. 
In the first place, a diazonium compound obtained by diazotizing a 
substituted or unsubstituted aniline is coupled with the aforesaid 
N,N-disubstituted aniline to form an azo dye. Subsequently, this azo dye 
is hydrogenated in the presence of a palladium-carbon or nickel catalyst 
to synthesize a corresponding p-phenylenediamine type compound. 
Alternatively, the aforesaid N,N-disubstituted aniline is nitrosoated and 
then reduced to synthesize a corresponding p-phenylenediamine type 
compound. 
The thus obtained p-phenylenediamine type compound may be used as the color 
photographic developing agent of the present invention. Alternatively, a 
salt formed by treating the said compound with an organic or inorganic 
acid may also be used as the developing agent of the present invention. 
For the synthesis of the latter developing agent in the form of salt, the 
said p-phenylenediamine type compound can be reacted with a required 
amount of an organic or inorganic acid such as hydrochloric, sulfuric, 
oxalic, phosphoric, alkylbenzenesulfonic, benzenedisulfonic, alkylsulfonic 
or naphthalenedisulfonic acid to deposit crystals of a corresponding salt 
of the p-phenylenediamine type compound.

Typical procedures for synthesizing some color photographic developing 
agents of the present invention are explained below with reference to 
synthesis examples. 
SYNTHESIS EXAMPLE 1 
Synthesis of the Exemplified Compound (19) and its salt 
(a) Synthesis of intermediate (1), 
2-[2-(2-Methoxyethoxy)ethoxy]ethyl-p-toluenesulfonic acid ester: 
To a solution of 49 g. (0.3 mole) of triethylene glycol monomethyl ether in 
96 g. of pyridine, 62.7 g. (0.33 mole) of p-toluenesulfonyl chloride was 
gradually added. The resulting mixture was poured into ice-water 
containing hydrochloric acid to deposit an oily substance. The oily 
substance was extracted with ethyl acetate, and the extract was dried with 
Glauber's salt and then concentrated under reduced pressure to obtain a 
colorless transparent liquid, yield about 95%. 
(b) Synthesis of intermediate (2), 
N-Ethyl-N-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-3-methylaniline: 
To a solution of 12.5 g. (0.09 mole) of N-ethyl-m-toluidine in 6 ml. of a 
40% aqueous sodium hydroxide solution, 29 g. (0.09 mole) of the 
intermediate (1) synthesized in (a) was added with vigorous stirring, and 
the resulting mixture was reacted at 110.degree. C. for 3 hours. The 
reaction liquid was poured into water to deposit an oily substance. The 
oily substance was extracted with ethyl acetate, and the extract was dried 
with Glauber's salt, concentrated under reduced pressure and then 
subjected to distillation under reduced pressure. Subsequently, the low 
boiling N-ethyl-m-toluidine was evaporated to obtain the intermediate (2), 
b.p. 115.degree. C./0.5 mmHg, yield about 60%. 
(c) Synthesis of end compounds, 
N-Ethyl-N-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-3-methyl-4-aminoaniline and 
its salt: 
To a liquid comprising 16 ml. of concentrated hydrochloric acid and 15 ml. 
of water, 5 g. (0.022 mole) of the intermediate (2) synthesized in (b) was 
added with ice-cooling. Into this liquid, a solution of 1.8 g. of sodium 
nitrite in a small amount of water was dropped at about 5.degree. C. to 
nitrosate the intermediate (2). Subsequently, about 5 g. of iron powder 
was added to the liquid to reduce the nitrosate intermediate. Thereafter, 
the liquid was neutralized by addition of a proper amount of a 10% aqueous 
sodium carbonate solution at below 10.degree. C. to deposit an oily 
substance. The oily substance was extracted with ethyl acetate, and the 
extract was dried and then concentrated to obtain the desired 
N-ethyl-N-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-3-methyl-4-aminoaniline 
(the exemplified compound (19)). 
In order to prepare a salt of the above-mentioned compound, a solution of a 
calculated amount of p-toluenesulfonic acid in a small amount of methyl 
alcohol was added to the compound, and then ethyl acetate was gradually 
added thereto to obtain white powdery crystals, m.p. 
134.degree.-136.degree. C., yield about 65%. 
SYNTHESIS EXAMPLE 2 
Synthesis of the Exemplified Compound (2) and its Salt: 
(a) Synthesis of intermediate (1), 
(1-Methyl-2-methoxy)ethyl-p-toluenesulfonic acid ester: 
To a solution of 45 g. (0.5 mole) of propylene glycol-.alpha.-monomethyl 
ether in 180 g. of pyridine, 104.5 g. (0.55 mole) of p-toluenesulfonyl 
chloride was gradually added with stirring at below 20.degree. C. The 
resulting mixture was reacted for 3 hours and then poured into ice-water 
containing hydrochloric acid to deposit an oily substance. The oily 
substance was extracted with ethyl acetate, and the extract was dried with 
Glauber's salt and then concentrated to obtain the intermediate (1) in the 
form of a pale yellow liquid, yield about 95%. 
(b) Synthesis of intermediate (2), 
N-Ethyl-N-(1-methyl-2-methoxy)ethyl-3-methylaniline: 
To a solution of 50 g. (0.37 mole) of N-ethyl-m-toluidine in 25 ml. of a 
40% aqueous sodium hydroxide solution, 91 g. (0.37 mole) of the 
intermediate (1) synthesized in (a) was added with vigorous stirring, and 
the resulting mixture was reacted at 110.degree. C. for 3 hours. The 
reaction liquid was poured into water to deposit an oily substance. The 
oily substance was extracted with ethyl acetate, and the extract was dried 
with Glauber's salt, concentrated under reduced pressure and then 
subjected to distillation under reduced pressure. Subsequently, the low 
boiling N-ethyl-m-toluidine was evaporated to obtain the intermediate (2), 
b.p. 76.degree.-78.degree. C./1 mmHg, yield about 55%. 
(c) Synthesis of end compounds, 
N-Ethyl-N-(1-methyl-2-methoxy)ethyl-3-methyl-4-aminoaniline and its salt: 
To a liquid comprising 17 ml. of concentrated hydrochloric acid and 15 ml. 
of water, 5 g. (0.048 mole) of the intermediate (2) synthesized in (b) was 
added with ice-cooling. Into this liquid, a solution of 2 g. of sodium 
nitrite in a small amount of water was dropped at about 5.degree. C. to 
nitrosated the intermediate (2). Subsequently, about 5 g. of iron powder 
was added to the liquid to reduce the nitrosated intermediate. Thereafter, 
the liquid was neutralized by addition of a proper amount of a 10% aqueous 
sodium carbonate solution at below 10.degree. C. to deposit an oily 
substance. The oily substance was dried with Glauber's salt and then 
concentrated under reduced pressure to obtain the desired 
N-ethyl-N-(1-methyl-2-methoxy)ethyl-3-methyl-4-aminoaniline (the 
exemplified compound (2)). 
In order to prepare a salt of the above-mentioned compound, a calculated 
amount of p-toluenesulfonic acid was added to the compound, and then ethyl 
acetate was gradually added thereto to obtain white powdery crystals, m.p. 
178.degree.-189.degree. C., yield about 65%. 
SYNTHESIS EXAMPLE 3 
Synthesis of the Exemplified Compound (20) and its Salt: 
(a) Synthesis of intermediate (1), 
2-[2-(2-ethoxyethoxy)ethoxy]ethyl-p-toluenesulfonic acid ester: 
To a solution of 36 g. (0.2 mole) of triethylene glycol monoethyl ether in 
64 g. of pyridine, 42 g. (0.22 mole) of p-toluenesulfonylchloride was 
gradually added at 20.degree. C. while stirring. After reaction of the 
mixture for 3 hours, the resultant was poured into ice-water containing 
hydrochloric acid to obtain an oily substance. The oily substance was 
extracted with ethyl acetate. The extract was dried with Glauber's salt 
and then concentrated under reduced pressure to obtain a colorless 
transparent liquid, yield about 90%. 
(b) Synthesis of intermediate (2), 
N-ethyl-N-[2-[2-(2-ethoxyethoxy)ethoxy]ethyl]-3-methylaniline: 
45 g. of N-ethyl-m-toluidine was added to 55 g. (0.17 mole) of the 
intermediate (1), and the resulting mixture was reacted under 140.degree. 
to 150.degree. C. for 2 to 3 hours. The reaction liquid was extracted with 
ethyl acetate. The extract was subjected to pH adjustment with a 5% 
solution of sodium hydroxide, washed with water, dried with Glauber's salt 
and then concentrated under reduced pressure. Subsequently, the low 
boiling N-ethyl-m-toluidine was evaporated to obtain the intermediate (2) 
having a boiling point of 138.degree. C./1.5 mmHg, yield about 75%. 
(c) Synthesis of end compounds, 
N-ethyl-N-[2-[2-(2-ethoxyethoxy)ethoxy]ethyl]-3-methyl-4-aminoaniline and 
its salt: 
35 g. (0.12 mole) of the intermediate (2) was added to a mixture of 85 ml. 
of concentrated hydrochloric acid and 80 ml. of water under ice-cooling. 
To the resulting liquid mixture, a solution of 10.5 g. of sodium nitrite 
in 200 ml. of water was dropped at about 5.degree. C. to nitrosate the 
intermediate (2). Subsequently, 30 g. of iron powder was added to the 
reaction liquid to reduce the nitrosate intermediate. Thereafter, the 
reaction liquid was neutralized by addition of a proper amount of a 10% 
aqueous sodium carbonate solution at 10.degree. C. to deposit an oily 
substance. The oily substance was extracted with ethyl acetate and then 
dried and concentrated to obtain an end compound, 
N-[2-[2-(2-ethoxyethoxy)ethoxy]ethyl]-3-methyl-4-aminoaniline (exemplified 
compound (20)). 
In order to prepare a salt of the above-mentioned compound, a solution of a 
calculated amount of p-toluenesulfonic acid in methyl alcohol was added to 
the compound, and then ethyl acetate was gradually added thereto to obtain 
white powdery crystals, m.p. 140.degree. to 142.degree. C., yield about 
70%. 
SYNTHESIS EXAMPLE 4 
Synthesis of the Exemplified Compound (48) and its salt: 
(a) Synthesis of intermediate (1), 
2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl-p-toluenesulfonic acid ester: 
The intermediate was prepared in the same manner as in the Synthesis 
Examples 1 to 3. 
(b) Synthesis of intermediate (2), 
N-ethyl-N-[2-[2-(2-(2-methoxyethoxy)ethoxy)ethoxy]ethyl]-3-methylaniline: 
The intermediate (2) was synthesized by using N-ethyl-m-toluidine in the 
same manner as in the Synthesis Example 3. 
The resulting intermediate had a melting point of 140.degree. to 
145.degree. C./1 mmHg, yield about 50%. 
(c) Synthesis of end compounds, 
N-ethyl-N-[2-[2-(2-(2-methoxyethoxy)ethoxy)ethoxy]ethyl]3-methyl-4-aminoan 
iline and its salt: 
The above-mentioned aniline compound was prepared by nitrosoating and then 
reducing the intermediate (2) in the same manner as in the Synthesis 
Example 3. 
Further, to this compound, a calculated amount of p-toluenesulfonic acid 
was added to obtain its salt as white powdery crystals, m.p. 120.degree. 
to 123.degree. C., yield about 60%. 
SYNTHESIS EXAMPLE 5 
Synthesis of the Exemplified Compound (23) and its salt: 
(a) Synthesis of intermediate (1), 
2-[2-(2-methoxyethoxy)ethoxy]ethyl-p-sulfonic acid ester: 
6.3 g. (0.033 mole) of p-toluenesulfonylchloride was slowly added to a 
solution consisting of 5 g. (0.03 mole) of triethylene glycol monomethyl 
ether and 9.5 g of pyridine at 20.degree. C. while stirring to react. The 
reaction was continued for 3 hours. The resulting liquid was poured into 
ice-water to obtain an oily substance. The oily substance was extracted 
with ethyl acetate, further extracted using mirabilite and thereafter 
dried. The resulting substance was concentrated under reduced pressure to 
obtain a colorless transparent liquid, yield of 85%. 
(b) Synthesis of intermediate (2), 
N-ethyl-N-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-aniline: 
To 3.2 g (0.01 mole) of the intermediate (1) obtained above, 2.5 g. (0.02 
mole) of N-ethylaniline was added, and then the resulting mixture was 
reacted at 140.degree. to 150.degree. C. for 2 hours. The resulting liquid 
was extracted using ethyl acetate, rendered basic with a 5% sodium 
carbonate solution and then washed with water. The resulting liquid was 
extracted with mirabilite, concentrated under reduced pressure and 
distilled. Low boiling N-ethylaniline was distilled off to leave the 
intermediate (2), b.p. 110.degree. to 115.degree. C./2 mmHg, yield 70%. 
(c) Synthesis of end compounds, 
N-ethyl-N-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-4-aminoaniline and its 
salt: 
To a solution consisting of 21 ml. of concentrated hydrochloric acid and 20 
ml. of water, 8 g. (0.03 mole) of the intermediate (2) was added. An 
aqueous solution consisting of 2.5 g. of sodium nitrite and a small amount 
of water was dropped to the resulting liquid at about 3.degree. C. to 
nitrate. The resulting liquid was added with 9 g. of iron powder, added 
with a 10% sodium carbonate solution to neutralize and thereafter 
extracted using ethyl acetate. The extracted mass was dried to obtain the 
end compound (the exemplified compound (23)). 
In order to prepare the salt of this compound, the compound was added to a 
calculated amount of p-toluenesulfonic acid in methyl alcohol to react. To 
the resulting liquid, ethyl acetate was slowly added to obtain white 
powdery crystals, b.p. 128.degree. C., yield 65%. 
SYNTHESIS EXAMPLE 6 
Synthesis of the Exemplified Compound (71) and its Salt: 
(a) Synthesis of intermediate (1), 
2-(2-methoxyethoxy)ethyl-p-toluenesulfonic acid ester: 
To a solution of 96 g. of pyridine in 36 g. (0.3 mole) of diethyleneglycol 
monomethyl ether, 62.7 g. (0.33 mole) of p-toluenesulfonyl chloride was 
slowly added to react. The reaction was continued for 3 hours. The 
resulting liquid was dropped to ice water containing hydrochloride to 
obtain a solid substance. The solid substance was filtrated, washed with 
water and dried to obtain a white solid substance of the intermediate (1), 
m.p. 25.degree. C., yield 95%. 
(b) Synthesis of intermediate (2), 
N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-3-methyl-aniline: 
To 25 g. (0.18 mole) of N-ethyl-m-toluidine, 25 g. of the intermediate (2) 
was added and heated at 140.degree. to 150.degree. C. for 2 hours to 
react. The reacted mass was extracted using ethyl acetate, made basic with 
an aqueous solution of 3% sodium carbonate, washed with water, extracted 
using mirabilite and dried. The resulting liquid was concentrated under 
reduced pressure and distilled under reduced pressure. Low boiling 
N-ethyl-m-toluidine was distilled off to obtain the intermediate (2), b.p. 
107.degree. C./0.5 mmHg, yield 75%. 
(c) Synthesis of end compounds, 
N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-3-methyl-4-aminoaniline and its salt: 
5 g. (0.022 mole) of the intermediate (2) was added to a solution 
consisting of 16 ml of concentrated hydrochloric acid and 15 ml. of water. 
To the resulting liquid, an aqueous solution of 1.8 g. of sodium nitrite 
in a small amount of water was dropped to nitrate. The resulting liquid 
was added with 5 g. of iron powder to reduce and added with a suitable 
amount of an aqueous solution of 10% sodium carbonate to neutralize to 
obtain an oily substance. The oily substance was extracted using ethyl 
acetate, dried and concentrated to obtain the end compound, 
N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-3-methyl aniline (the exemplified 
compound (71)). 
In order to prepare the salt of the end compound, the end compound was 
added to a solution of a calculated amount of p-toluenesulfonic acid in a 
small amount of methyl alcohol to react. To the resulting liquid, ethyl 
acetate was slowly added to obtain white crystals, m.p. 184.degree. to 186 
C., yield 65%. 
The color photographic developing agent of the present invention are used 
in the form of free bases of p-phenylenediamine type compounds or of salts 
thereof with organic or inorganic acids, e.g. in the form of 
hydrochlorides, sulfates, phosphates, oxalates, alkylbenzenesulfonates, 
benzenedisulfonates, alkylsulfonates or naphthalenedisulfonates. Although 
some free bases of said compounds are stable, the compounds are preferably 
formed, in general, into the above-mentioned salts in view of the 
solubility in aqueous alkaline solutions and of the developing actions. 
Particularly, hydrochlorides, sulfates, alkylsulfonates and 
p-toluenesulfonates are preferable from the standpoint of solubility. 
For formation of a salt of p-phenylenediamine type compound by use of an 
acid, it is preferable to combine about 1 to 4 moles of the acid with 1 
mole of the base of p-phenylenediamine type compound. In order to prepare 
a developing solution by use of the color photographic developing agent of 
the present invention, the developing agent is preferably used in a 
proportion of 0.001 to 0.02 mole, particularly 0.002 to 0.01 mole, per 
liter of the developing solution. 
Examples of additives, other than the developing agent, to be incorporated 
into the developing solution include alkali metal chlorides, alkali metal 
bromides, alkali metal iodides, alkali metal sulfites, alkali metal 
sulfates, alkali metal carbonates, alkali metal hydroxides, alkali metal 
metaborates, alkali metal phosphates, ethylenediamine and citrazinic acid; 
5-nitrobenzimidazoles as antifoggants; 1-phenyl-3-pyrazolidone and benzyl 
alcohol as development aids; diethylhydroxyamine, hydroxylacetone, 
glycolaldehyde, glycelaldehyde and dihydroxymaleic acid as stabilizers; 
and sodium hexametaphosphate. Further, external type color developing 
solutions contain diffusing phenol or naphthol type cyan couplers, 
ketomethylene type yellow couplers and 5-pyrazolone type magenta couplers. 
A typical internal type color photographic developing solution is, for 
example, as follows: Color photographic developing solution: 
______________________________________ 
Benzyl alcohol 0-12 ml. 
Alkali metal hexametaphosphate 
0-3 g. 
Trialkali metal phosphate, 12H.sub.2 O 
10-60 g. 
Alkali metal bromide 0-5 g. 
Alkali metal iodide (0.1% solution) 
0-15 ml. 
Color photographic developing agent 
0.001-0.02 mole 
Ethylenediamine sulfate 
0-20 g. 
Citrazinic acid 0-5 g. 
Dioctanediol 0-5 g. 
Water to make 1 liter 
Adjusted to Ph 10.0-14.0 with, for example, an alkali 
metal hydroxide or an alkali metal carbonate. 
______________________________________ 
In order to process a light-sensitive silver halide color photographic 
material with such color photographic developing solution, there is 
adopted, for example, such procedure as described below. 
The photographic material after exposure is dipped in a developing tank 
containing the developing solution. 
Alternatively, the developing solution is contacted, by use of a roll 
applicator or a coating hopper, with the emulsion layer surface of said 
photographic material, preferably at a temperature of 15.degree. to 
50.degree. C. In this case, the silver halides, which have formed a latent 
image due to exposure, are reduced to silver. At the same time, couplers 
contained in the emulsion layers combine with an oxidation product of the 
developing agent to form dyes corresponding to the reduced silver. 
Subsequently, the color-developed photographic material is processed with 
a bleaching solution to convert the reduced silver into a silver salt, 
which is then removed by use of a fixing solution. These bleaching and 
fixing operations comprising the two processing steps may be carried out 
in one step using a mono-bath bleach-fixing solution. 
The color photographic developing compositions of the present invention are 
applicable to the color development of substantially all of 
light-sensitive silver halide color photographic materials including 
internal type silver halide color photographic materials containing 
dye-forming couplers in the silver halide emulsion layers, external type 
silver halide color photographic materials containing no couplers in the 
emulsion layers, reversal color photographic materials and printing color 
photographic materials. The color photographic developing compositions of 
the present invention are further applicable to the color development of 
diffusion transfer type photographic light-sensitive materials disclosed 
in U.S. Pat. Nos. 3,227,550, 3,347,671 and 3,443,940, Japanese Patent 
Publication No. 39165/1973 and Japanese Patent Pre-Publication Nos. 
64436/1974 and 37538/1972. 
The emulsion layers of the above-mentioned light-sensitive silver halide 
color photographic materials may contain optical sensitizers such as 
cyanine, merocyanine or hemicyanine dyes, chemical sensitizers such as 
sulfur, gold or palladium sensitizers, and stabilizers, antifoggants, 
hardeners, etc. which are ordinarily incorporated into silver halide 
photographic emulsion layers. The internal type color photographic 
material contain Agfa type or oil protect type couplers, e.g. phenol or 
naphthol type cyan couplers, ketomethylene type yellow couplers and 
5-pyrazolone type magenta couplers. These couplers may be any of 
2-equivalent or 4-equivalent couplers. 
Further, the silver halide contained in the silver halide emulsion layers 
to be processed with the color photographic developing composition of the 
present invention may be any of silver chloride, silver chlorobromide, 
silver chloriodobromide, silver bromide and silver iodobromide. 
The present invention is illustrated in more detail below with reference to 
examples, but the modes of practice of the present invention are not 
limited to the examples. 
EXAMPLE 1 
On a paper support laminated with TiO.sub.2 -colored polyethylene, the 
below-mentioned three emulsion layers were successively formed. 
A blue-sensitive gelatin emulsion layer containing 6 mg/100 cm.sup.2 of 
silver iodobromide and the non-diffusing .alpha.-pivalylacetanilide type 
2-equivalent yellow coupler [i.e. 
.alpha.-(3-benzyl-2,4-dioxoimidazolidine-3-yl)-.alpha.-pivaroyl-5-[.gamma. 
'-(2,4-di-tert-amylphenoxy)butylamido]-2-chloroacetanilide]. A 
green-sensitive gelatin emulsion layer containing 4 mg/100 cm.sup.2 of 
silver chlorobromide and the non-diffusing 5-pyrazolone type magenta 
coupler [i.e. 1-(2,4,6-trichlorophenyl)-3-(3-dodecylsuccinimido 
benzamido)-5-pyrazolone]. A red-sensitive gelatin emulsion layer 
containing 3 mg/100 cm.sup.2 of silver chlorobromide and the non-diffusing 
phenol type cyan coupler [i.e. 
2-[.alpha.-(2,4-ditert-amylphenoxy)butylamino]-4,6-dichloro-5-methyl-pheno 
l]. 
In the above manner, a silver halide color photographic paper was prepared 
as a development sample. This sample was exposed through a wedge and 
through blue, green and red filters. The exposed sample was processed with 
each of developing solutions (A), (B), (C), (D) and (E) according to the 
present invention individually containing the exemplified compounds shown 
below, and developing solutions (F) and (G) containing the control 
developing agents shown below, and then processed with the below-mentioned 
bleach-fixing solution and stabilizing solution to prepare seven kinds of 
color image-bearing samples. 
______________________________________ 
Processing steps (31.degree. C.) 
Processing time 
______________________________________ 
Color development 
3 minutes and 30 seconds 
Bleach-fixing 1 minute and 30 seconds 
Water-washing 2 minutes 
Stabilization 1 minute 
______________________________________ 
Color photographic developing solution: 
______________________________________ 
Benzyl alcohol 5.0 ml. 
Sodium hexametaphosphate 
3.00 g. 
Anhydrous sodium sulfite 
1.85 g. 
Sodium bromide 1.40 g. 
Potassium bromide 0.05 g. 
Borax (Na.sub.2 B.sub.4 O.sub.7 . 10H.sub.2 O) 
39.10 g. 
Color photographic developing agent 
0.01 mole 
Water to make 1 liter 
______________________________________ 
Adjusted to pH 10.3 with sodium hydroxide Color photographic developer: 
______________________________________ 
Developing solution (A) 
p-Toluenesulfonate of the 
exemplified compound (2) 
Developing solution (B) 
p-Toluenesulfonate of the 
exemplified compound (19) 
Developing solution (C) 
p-Toluenesulfonate of the 
exemplified compound (21) 
Developing solution (D) 
p-Toluenesulfonate of the 
exemplified compound (48) 
Developing solution (E) 
p-Toluenesulfonate of the 
exemplified compound (71) 
Developing solution (F) 
N-Ethyl-N-[2-(methyl- 
sulfonamido)ethyl]-3- 
methyl-4-aminoaniline 
sulfate 
Developing solution (G) 
N-Ethyl-N-(2-methoxyethyl)- 
3-methyl-4-aminoaniline-p- 
toluenesulfonate 
______________________________________ 
Bleach-fixing solution: 
______________________________________ 
Iron ammonium ethylenediamine- 
61.0 g. 
tetraacetate 
Diammonium ethylenediamine- 
5.0 g. 
tetraacetate 
Ammonium thiosulfate 124.5 g. 
Sodium metabisulfite 13.3 g. 
Sodium bisulfate 2.7 g. 
Water to make 1 liter 
Adjusted to pH 6.5 1 liter 
______________________________________ 
Stabilizing solution: 
______________________________________ 
Glacial acetic acid (trihydrate) 
20 ml. 
Water 800 ml. 
Adjusted to pH 3.5-4.0 with 
sodium acetate trihydrate 
Water to make 1 liter 
______________________________________ 
The thus prepared samples were measured in densities of yellow, magenta and 
cyan colors by use of PD-7R Densitometer (manufactured by Konishiroku 
Photo Industry Co., Ltd.). The photographic properties obtained were as 
shown in Table 1. 
Table 1 
__________________________________________________________________________ 
Photographic 
properties 
Yellow Magenta Cyan 
Developing Maximum Maximum Maximum 
solution 
Speed 
Fog 
density 
Speed 
Fog 
density 
Speed 
Fog 
density 
__________________________________________________________________________ 
A 117 0.13 
2.40 121 0.15 
2.33 120 0.11 
2.30 
B 120 0.15 
2.44 127 0.16 
2.42 129 0.12 
2.28 
C 124 0.13 
2.50 127 0.16 
2.47 133 0.12 
2.38 
D 120 0.12 
2.44 123 0.14 
2.40 126 0.10 
2.30 
E 122 0.13 
2.44 125 0.15 
2.33 132 0.11 
2.30 
F 95 0.11 
2.18 93 0.11 
2.13 94 0.09 
2.14 
G 100 0.13 
2.21 100 0.14 
2.28 100 0.10 
2.20 
__________________________________________________________________________ 
From Table 1, it is understood that the samples processed with the 
developing solutions (A), (B), (C), (D) and (E) according to the present 
invention containing the exemplified compounds (2), (19), (21), (48) and 
(71) are far more excellent in speeds and maximum densities of yellow, 
magenta and cyan colors than the samples processed with the developing 
solutions (F) and (G) containing the control developing agents. 
In Table 1, the speed is a relative value measured when the speed of the 
sample processed with the developing solution (G) was assumed as 100. 
EXAMPLE 2 
The same samples as in Example 1 were processed in the same manner as in 
Example 1, except that benzyl alcohol contained in the seven kinds of 
color photographic developing solutions was removed, to prepare seven 
kinds of positive color image-bearing samples. These samples were compared 
with each other in photographic properties of yellow, magenta and cyan 
colors. As the result, it was found that the samples processed with the 
developing solutions (A), (B), (C), (D) and (E) were more excellent in 
photographic properties of positive color images than those processed with 
the developing solutions (F) and (G), like in Example 1. 
EXAMPLE 3 
On a cellulose triacetate film support were successively formed an 
antihalation layer and a gelatin layer in this order. Thereafter, a 
red-sensitive silver iodobromide emulsion containing 0.12 mole, per mole 
of silver halide, of certain cyan coupler [i.e. 
1-hydroxy-2-N-[.delta.-(2,4-di-tert.-amylphenoxy)-n-butyl]naphthamide] 
and containing 6 mole% of silver iodide was coated on the aforesaid 
gelatin layer to an amount of 16 mg. per 100 cm.sup.2. On the resulting 
layer, a green-sensitive silver iodobromide emulsion containing 0.10 mole, 
per mole of silver halide, of certain magenta coupler [i.e. 
1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-tert.-amylphenoxyacetamido)-benzami 
do]-5-pyrazolone] was coated to an amount of 17 mg. per 100 cm.sup.2, and 
then a yellow filter layer was formed on the resulting layer. On the said 
yellow filter layer, a blue-sensitive silver iodobromide emulsion 
containing 0.15 mole, per mole of silver halide, of certain yellow coupler 
[i.e. 
.alpha.-benzoyl-2'-chloro-5'-[.alpha.-(dodecyloxycarbonyl)ethoxycarbonyl]- 
acetanilide] was coated to an amount of 20 mg. per 100 cm.sup.2, and then a 
protective layer was formed on the resulting emulsion layer to prepare a 
reversal silver halide color photographic film. 
This color photographic film was exposed through a wedge according to an 
ordinary procedure, and then processed in the below-mentioned processing 
steps with each of developing solutions (H), (I), (J) and (K) containing 
the developing agents of the present invention shown below and developing 
solutions (L) and (M) containing the control developing agents shown below 
to prepare six kinds of positive color image-bearing samples. 
______________________________________ 
Processing steps (38.degree. C.) 
Processing time 
______________________________________ 
First development 
3 minutes 
Stopping 30 seconds 
Water-washing 1 minute 
Color development 
4 minutes 
Stopping 30 seconds 
Water-washing 1 minute 
Bleaching 1 minute and 30 seconds 
Water-washing 1 minute 
Fixing 1 minute and 30 seconds 
water-washing 2 minutes 
Stabilization 30 seconds 
______________________________________ 
Color photographic developing solution: 
______________________________________ 
Sodium tetrapolyphosphate 
5.0 g. 
Benzyl alcohol 4.5 ml. 
Sodium sulfite (anhydrous) 
7.5 g. 
Trisodium phosphate (dodecahydrate) 
36.0 g. 
Potassium iodide 90.0 ml. 
(0.1% aqueous solution) 
Sodium bromide (anhydrous) 
0.9 g. 
Sodium hydroxide 3.25 g. 
Citrazinic acid 1.5 g. 
Ethylenediamine 3.3 ml. 
t-Butylaminoborane 0.07 g. 
Color photographic developing 
0.02 mole 
agent shown below 
Water to make 1 liter 
Adjusted to pH 11.65 
______________________________________ 
Color photographic developing agent: 
______________________________________ 
Developing solution (H) 
Methylsulfonate of the 
exemplified compound (20) 
Developing solution (I) 
p-Toluenesulfonate of the 
exemplified compound (2) 
Developing solution (J) 
Methylsulfonate of the 
exemplified compound (27) 
Developing solution (K) 
p-Toluenesulfonate of the 
exemplified compound (39) 
Developing solution (L) 
N-Ethyl-N-[2-(methyl- 
sulfonamido)ethyl]-3- 
methyl-4-aminoaniline 
sulfate 
Developing solution (M) 
N-Ethyl-N-(2-hydroxyethyl)- 
3-methyl-4-aminoaniline 
sulfate 
______________________________________ 
The maximum densities of yellow, magenta and cyan colors of the six kinds 
of positive color images formed in the above manner were measured by use 
of PD-7R Densitometer to obtain such results as shown in Table 2. 
Table 2 
______________________________________ 
Photographic 
Maximum Light fastness 
properties 
density (%) 
Developing 
solution Yellow Magenta Cyan Yellow 
Magenta 
Cyan 
______________________________________ 
H 2.93 3.00 2.87 88 91 91 
I 2.83 2.95 2.69 86 90 91 
J 2.43 2.79 2.63 86 88 91 
K 2.80 2.97 2.77 88 89 92 
L 2.24 2.45 2.45 78 82 87 
M 2.51 2.69 2.50 80 83 89 
______________________________________ 
In Table 2, the light fastness is the percentage (%) of the density of each 
color image after irradiation of light with a Xenon Fade-Ometer to the 
maximum density of the original color image at the same point. 
From Table 2, it is understood that the color images formed by processing 
with the developing solutions (H), (I), (J) and (K) containing the 
developing agents of the present invention are far higher in maximum 
density and more excellent in light fastness than those formed by 
processing with the developing solutions (L) and (M) containing the 
control developing agents. 
EXAMPLE 4 
Sakura Color II Film (produced by Konishiroku Photo Industry Co., Ltd.) was 
exposed through blue, green and red filters, and then processed in the 
below-mentioned processing steps with each of developing solutions (N), 
(O), (P), (Q) and (R) containing the developing agents of the present 
invention shown below and developing solutions (S) and (T) containing the 
control developing agents shown below to prepare seven kinds of color 
image-bearing samples. 
______________________________________ 
Processing steps (38.degree. C.) 
Processing time 
______________________________________ 
Color development 
3 minutes and 15 seconds 
Bleaching 6 minutes and 30 seconds 
Water-washing 3 minutes and 15 seconds 
Fixing 6 minutes and 30 seconds 
Water-washing 3 minutes and 15 seconds 
Stabilization 1 minute and 30 seconds 
______________________________________ 
Color photographic developing solution: 
______________________________________ 
Anhydrous sodium sulfite 0.14 g. 
Hydroxyamine.1/2 sulfate 1.98 g. 
Sulfuric acid 0.74 g. 
Anhydrous potassium carbonate 
28.85 g. 
Anhydrous potassium hydrogen carbonate 
3.46 g. 
Anhydrous potassium sulfite 
5.10 g. 
Potassium bromide 1.16 g. 
Sodium chloride 0.14 g. 
Trisodium nitrilotriacetate 
1.20 g. 
(monohydrate) 
Potassium hydroxide 1.48 g. 
Color photographic developing 
0.01 mole 
agent shown below 
Water to make 1 liter 
______________________________________ 
Color photographic developing agent: 
______________________________________ 
Developing solution (N) 
p-Toluenesulfonate of the 
exemplified compound (20) 
Developing solution (O) 
p-Toluenesulfonate of the 
exemplified compound (19) 
Developing solution (P) 
p-Toluenesulfonate of the 
exemplified compound (47) 
Developing solution (Q) 
p-Toluenesulfonate of the 
exemplified compound (64) 
Developing solution (R) 
p-Toluenesulfonate of the 
exemplified compound (71) 
Developing solution (S) 
N-Ethyl-N-(2-hydroxyethyl)- 
3-methyl-4-aminoaniline 
sulfate 
Developing solution (T) 
N-Ethyl-N-[2-[2-(2- 
hydroxyethoxy)ethoxy]- 
ethyl]-4-aminoaniline 
hydrochloride 
______________________________________ 
The densities of yellow, magenta and cyan colors of the color images formed 
in the above manner were measured by use of PD-7R Densitometer. The 
photographic properties of each sample were as shown in Table 3. 
Table 3 
__________________________________________________________________________ 
Photographic 
properties 
Yellow Magenta Cyan 
Developing Dc/ Dc/ Dc/ 
solution 
Speed 
Fog 
DAg 
Speed 
Fog 
DAg 
Speed 
Fog 
DAg 
__________________________________________________________________________ 
N 185 0.60 
7.7 
172 0.42 
6.0 
170 0.09 
5.3 
O 190 0.64 
7.9 
177 0.43 
6.3 
175 0.10 
5.5 
P 164 0.59 
7.0 
162 0.43 
5.3 
165 0.10 
5.0 
Q 170 0.50 
7.2 
167 0.43 
5.5 
169 0.10 
5.2 
R 178 0.60 
7.7 
170 0.42 
5.7 
163 0.09 
5.1 
S 100 0.59 
5.8 
100 0.40 
4.6 
100 0.08 
4.2 
T 24 0.67 
5.3 
55 0.51 
4.4 
59 0.10 
4.1 
__________________________________________________________________________ 
In Table 3, the speed is a relative value measured when the speed of the 
film processed with the control developing solution (S) was assumed as 
100, and "Dc/DAg" shows the ratio of the density of consumed silver to 1.0 
of the color density. 
From Table 3, it is understood that the samples processed with the 
developing solutions (N), (O), (P), (Q) and (R) containing the developing 
agents of the present invention are far higher in speed and are greater in 
Dc/DAg, i.e. more excellent in color developing efficiency, than the 
samples processed with the developing solutions (S) and (T) containing the 
control developing agents. 
EXAMPLE 5 
Developing solutions (U), (V), (W), (X), (Y) and (Z) were perpared in the 
same manner as in Example 1, except that the benzylalcohol was removed and 
the following developing agents were used. 
______________________________________ 
Developing solution (U) 
p-Toluenesulfonate of the 
exemplified compound (19) 
Developing solution (V) 
p-Toluenesulfonate of the 
exemplified compound (26) 
Developing solution (W) 
p-Toluenesulfonate of the 
exemplified compound (48) 
Developing solution (X) 
p-Toluenesulfonate of the 
exemplified compound (49) 
Developing solution (Y) 
p-Toluenesulfonate of the 
exemplified compound (71) 
Developing solution (Z) 
p-Toluenesulfonate of 
N-ethyl-N-(2-methoxyethyl)- 
3-methyl-4-aminoaniline 
______________________________________ 
Unexposed photographic color papers which were prepared in the same manner 
as in Example 1 were processed with the above-mentioned developing 
solutions and the bleach-fix solution used in Example 1 according to the 
following sequence. 
______________________________________ 
Processing steps Processing time 
______________________________________ 
Color developing 3 minutes and 30 seconds 
Water washing 15 seconds 
White light exposure 
10 minutes 
Bleach-fixing 2 minutes 
Water washing 2 minutes 
______________________________________ 
The resulting samples were subjected to measurement of densities of cyan 
and yellow dyes using red and blue filters. The result are shown in Table 
4. 
Table 4 
______________________________________ 
Developing Fog 
solution Cyan Yellow 
______________________________________ 
U 0.8 0.50 
V 0.88 0.55 
W 0.70 0.45 
X 0.65 0.43 
Y 0.9 0.60 
Z 1.0 0.68 
______________________________________ 
In Table 4, the values of cyan and yellow densities represent fog caused by 
a residual amount of the developing agent in the emulsion layers. 
It is understood that all the samples according to the present invention 
are less in the residual developing agent and hence in fog than the 
control sample.