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Description  |
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BACKGROUND OF THE INVENTION
The present invention relates to a process of replenishing a color
developing solution for a light-sensitive silver halide color photographic
material, more specifically to a process for replenishing a color
developing solution with replenisher compositions which process can
dissolve a poorly soluble alcohol uniformly, easily and in a short time,
and also suitable for the AR system (which will be explained hereinafter).
A color developing solution which is used for processing a light-sensitive
silver halide color photographic material usually contains such developer
components as represented by a p-phenylenediamine derivative or a salt
thereof as a color developing agent; a carbonate, a borate or a phosphate
as an alkaline agent; a sulfite or a hydroxylamine salt as a preservative;
and so on. It further contains, as occasion demands, a poorly soluble
alcohol as a development accelerator, for example, benzyl alcohol or the
like.
When such a color developing solution is used continuously and its use is
over a long period of time, the main component thereof is consumed and an
added component (additive) is dissolved out of a light-sensitive material
to be processed. As the result, the activity of the color developing
solution is lost and the obtained image properties are subject to
deterioration.
Thus, for the purpose of replenishing the developing components which have
been lost by the above-mentioned continuous processing and of diluting the
additive components which have been dissolved out of the light-sensitive
material, there has been taken a procedure in which a color developing
replenisher is prepared and supplemented in necessary portions to the
above-mentioned color developing solution.
Recently, on account of economy and of the social demand to minimize any
pollutive component which is caused by the waste developing solution to be
discharged during the developing process, there is a tendency that the
replenisher for a color developing solution be thickened or concentrated
and the amount thereof reduced. In order to save labor for the mixing and
dissolving operations of chemical agents for a developing solution or to
concentrate and minimize the replenishing amount, the necessity is
expanding for a concentrated supplemental developing solution capable of
easy preparation only by diluting with water.
However, a poorly soluble alcohol, e.g., benzyl alcohol etc., to be used as
a development accelerator has extremely poor solubility in water or a
color developing solution, it has required a fairly long time for the
replenisher composition to dissolve thoroughly, and vigorous stirring and
heating have frequently been required.
In cases where the dissolution of such poorly soluble alcohol is
insufficient, there is observed phenomena of oil-drops being formed in the
developing solution (oil-out) and floating at the surface thereof.
This causes smears in a color developer tank, a replenisher tank or a
mixing tank of an automatic processing machine which is used for the
processing, and further causes a change in a practical composition of a
developing solution to exert an adverse effect upon photographical
processing performance, which has been problematic.
For the purpose of improving the above drawbacks, there are proposed
methods of preparing an aqueous dispersion by using glycols such as
ethylene glycol as described in the specification of U.S. Pat. No.
3,574,615 and so on or by using celluloses such as hydroxyethyl cellulose
as described in the specification of U.S. Pat. No. 3,615,496 and so on to
disperse above-mentioned poorly soluble alcohol.
However, in cases where a glycol mentioned above is used, 10 g or more of
the same is required per 1 lit. of the color developing solution, which
results in remarkable increase of B.O.D. (Biochemical Oxygen Demand) or
C.O.D. (Chemical Oxygen Demand) in the color developing solution. This is
not only undesirable in view of the prevention of pollution but also
disadvantageous economically.
On the other hand, in cases where a cellulose is used as has been done
conventionally, it has a property capable of dispersing and solubilizing
the poorly soluble alcohol with a relatively small amount thereof.
However, a large amount of water is necessary to obtain a uniform
replenisher composition leading to a large volume of a replenisher
composition. Further, since a small amount of water cannot provide any
uniform replenisher composition, there is a drawback in that a part of
such non-uniform replenisher composition cannot be taken out for
replenishment.
There has recently been adopted an AR system (Automatic Replenishing
System) in which various parts of processing agents and a dilution kit are
connected with each other and the solutions are automatically diluted and
mixed with water followed by replenishing a processing tank of an
automatic processing machine, for the purposes of simplifying the
operation for dissolving the processing agents and of labor-saving.
However, since a poorly soluble alcohol, such as benzyl alcohol etc. is
extremely inferior in solubility, a mixing room and a mixing device are
always provided with said AR system. So the AR system carries a problem
that it fails to be compact as a device.
Thus, an object of the present invention is primarily to provide a process
for replenishing a developing solution with a replenisher composition,
which process is capable of dissolving a poorly soluble alcohol uniformly,
easily and within a short time in the replenishment of the color
developing solution, secondarily to provide a process for replenishing a
color developing solution with a replenisher composition, wherein each
part has an excellent solubility to realize a compact AR system without
any necessity of a mixing device and so on.
SUMMARY OF THE INVENTION
The objects of the present invention defined above may be achieved by use
of a process of replenishing a color developing solution with a
replenisher composition, wherein at least two kinds of separate solutions
for a color developing solution, i.e., Solution (A) comprising an alkaline
substance and Solution (B) comprising a water soluble salt of a poorly
soluble alcohol which may be cleaved by an alkali, are supplemented.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic one showing the automatic developing system to be
used in the replenishing process of the present invention;
FIG. 2 is a schematic one of another type of the same system as that of
FIG. 1;
FIG. 3 is a schematic one of an automatic developing system according to
the present invention.
DESCRIPTION OF PREFERRED EMBODIMENT
The present invention will be explained further in detail as follows:
In the first place, the alkaline substance for the replenisher composition
to be used in the present process of replenishing a color developing
solution with a replenisher composition (hereinafter simply referred to as
the replenishing process of the present invention), which is an alkaline
compound usually used as a component for the developing solution for
photography, may include, a carbonate (e.g., potassium carbonate, sodium
carbonate, etc.), a borate (e.g., borax, sodium borate, potassium borate,
etc.), a phosphate (e.g., sodium phosphate, potassium phosphate, etc.), an
organic amine (e.g., ethylenediamine, triethanolamine, polyethyleneimine,
trimethylamine, etc.), a silicate (e.g., sodium silicate etc.), sodium
hydroxide and potassium hydroxide.
Solution (A) of the present invention comprising an alkaline substance
dissolved therein is used as an alkaline solution of pH 7.5 or more,
preferably of pH 9 or more, especially of pH 10.5 or more.
Solution (A) of the present invention comprising an alkaline substance
dissolved therein may contain an organic solvent (e.g., ethylene glycol,
diethylene glycol, hexylene glycol, etc.), a chelating agent (e.g.,
nitridotriacetic acid, diethylenetriaminepentacetic acid,
1-hydroxyethylidene-1,1-diphosphonic acid,
2-propanol-1,3-diamine-tetracetatic acid, etc.), a preservative (e.g.,
potassium sulfite, sodium metahydrogensulfite, etc.), an alkali halide
(e.g., sodium bromide, potassium chloride, potassium iodide, etc.).
Especially when a chelating agent is incorporated, it will exhibit an
effect to prevent the formation of sludge, which is liable to occur in
Solution (A), and this may be mentioned as one of the preferred
embodiments for the present invention.
Next, to describe the water soluble salt of a poorly soluble alcohol which
may be cleaved by an alkali, the water soluble salt of a poorly soluble
alcohol may be represented by the following General Formula (I): General
Formula (I)
A--B
wherein A represents a residue of a poorly soluble alcohol, capable of
releasing said poorly soluble alcohol when the salt is cleaved under an
alkaline condition, may possibly liberate the poorly soluble alcohol. B
represents a water soluble group.
The above-mentioned poorly soluble alcohol which is released by cleavage
under alkaline conditions includes, for example, benzyl alcohol,
o-hydroxybenzyl alcohol, cyclohexanol, t-butyl alcohol, 2-phenoxyethanol,
phenylethyl alcohol, etc.
Benzyl alcohol, which is especially excellent in the acceleration of
development among the above-mentioned poorly soluble alcohols, is most
preferably used in the present invention.
The water soluble group represented by B in said General Formula is a group
which can form a carbonate, a sulfite, a sulfate, a phosphate, a borate,
etc., when it is cleaved by an alkali.
In the present invention, a water soluble salt of a poorly soluble alcohol
represented by said General Formula (I) may preferably be represented by
the following General Formula (II): General Formula (II)
R--(CH.sub.2).sub.n --O--X--O--M
wherein R represents an alkyl group having 1 to 10 carabon atoms or an aryl
group; X represents a --CO-- group, an --SO-- group, an --SO.sub.2 --
group, a --PO.sub.2 -- group or a --BO-- group; M represents an alkali
metal group such as potassium, sodium, lithium, etc. or an ammonium group;
n is an integer of 1 to 4.
Furthermore, in the present invention, the compound represented by said
General Formula (II) may more preferably be represented by the following
General Formula (III) General Formula (III)
##STR1##
wherein R.sub.1 represents a hydrogen atom or an alkyl group having 1 to 4
carbon atoms; Y represents a --CO-- group or an --SO-- group; M has the
same meaning as defined in the General Formula (II); m is an integer of 1
to 3.
Typical examples of the compounds which may be represented by said General
Formula (I) are as follows: (Exemplary Compounds)
##STR2##
C.sub.6 H.sub.13 --CH.sub.2 --O--COON.sub.a (8)
The water soluble salts which may be cleaved by an alkali as exemplified
above may easily be prepared according to the synthesis method described
in U.S. Pat. No. 4,414,307.
Solution (B) used in the present invention, which contains the water
soluble salt of a poorly soluble alcohol, can exhibit good effect of the
invention particularly when it is used as a solution having such a
concentration that can provide a concentration of the poorly soluble
alcohol, released after hydrolysis of the salt under alkaline conditions,
of 40 g/liter or more. When the above-mentioned Solution (B) is more
preferably used as a solution as can provide a concentration of the
released poorly soluble alcohol of 80 g/liter or more, much better effect
of the present invention can be obtained.
Solution (B) of the present invention comprising the water soluble salt of
a poorly soluble alcohol may include an organic solvent (e.g., ethylene
glycol, diethylene glycol, polyethylene glycol, hexylene glycol, etc.), a
buffer (e.g., borate, phosphate, phthalate, glycine, acetate, carbonate,
etc.), a chelating agent (e.g., 1-hydroxyethylidene-1,1-diphosphonic acid,
diethylenetriaminepentacetic acid, etc.) and it is preferred to include
especially above-mentioned organic solvent(s) , since it will exhibit an
effect of further improving the solubility of Solution (B) of the present
invention.
In the present invention the storability of a poorly soluble alcohol is
surprisingly improved when at least two parts of solutions are used--a
water soluble salt of a poorly soluble alcohol as a part of thick solution
and a separate alkaline solution as another part of solution--and there is
another effect of preventing oil-out. Furthermore, the addition of an
organic phosphonate chelating agent (e.g.,
1-hydroxyethylidene-1,1-diphosphonic acid etc.) or an aminopolycarboxylic
acid chelating agent (e.g., diethylenetriaminepentaacetic acid,
2-propanol-1,3-diaminotetraacetic acid, nitrilotriacetic acid
hydroxyethyliminodiacetic acid, etc.) to Solution (A) of the present
invention comprising an alkaline substance dissolved therein, it will not
only prevent the formation of sludge in Solution (A) but also effect
extremely good mixing of Solution (A) with Solution (B) of the present
invention comprising the water soluble salt of a poorly soluble alcohol.
The pH value of 9 or more of Solution (B) is not preferred since a pH of 9
or more cases hydrolysis of the water soluble salt of a poorly soluble
alcohol to oil out the poorly soluble alcohol. Further, a pH of lower than
4 makes the above-mentioned water soluble salt to be unstable or even to
be decomposed. Therefore, it is preferable to store Solution (B) under a
condition of pH 4-9.
According to the replenishing process of the present invention, a more
favorable effect may be obtained by replenishing a color developing
solution with at least two kinds of said separate replenisher compositions
for the color developing solution, i.e., Solution (A) and Solution (B),
with substantially no mixing thereof prior to replenishment.
While the above-mentioned "replenishment of a color developing solution
with substantially no mixing of replenisher compositions" will be
explained specifically by way of FIG. 1, it means a process where any
forced or intentional mixing by using, for example, a mixing device is not
carried out. Even contact of Solutions (A) and (B) within a replenishing
piping or tube may be included in the above-mentioned case of
"substantially no mixing".
FIG. 1 is a constitutional view of an apparatus showing an example of an
automatic developing system to be used in the replenishing process of the
present invention and the part surrounded by the dotted line is the AR
system, wherein 1 is a replenisher tank supplied with said Solution (A); 2
is a replenisher tank filled with said Solution (B), 3 is a replenisher
tank filled with Solution (C), which although described in the
below-mentioned Examples, is, for example, a solution comprising a color
developing agent. 4 is a replenisher tank supplied with Solution (D),
which although described in the below-mentioned Examples, is, for example,
a solution of a preservative (such as hydroxylamine etc.) which is
prohibited to be mixed with the color developing agent. 5 is a water tank;
6 is a bellows pump. 7 is a developer tank of the automatic processing
machine; 8 is a filter; 9 is a circulating pump; 10 is a light-sensitive
material to be processed.
While the replenishing process in the automatic developing apparatus (FIG.
3) as constructed in such a manner as mentioned above will be explained in
detail in the Examples described below, the developer tank 7 is
replenished in the order of water (Tank 5)--Solution (A) (Tank
1)--Solution (B) (Tank 2)--Solution (C) (Tank 3)--Solution (D) (Tank 4),
and for the purpose of attaining further completely substantially no
mixing of of Solution (A) and Solution (B) of the present invention, the
replenishment of the developer tank 7 is carried out in the order of
Solution (A) (Tank 1)--water (Tank 5)--Solution (B) (Tank 2)--Solution (C)
(Tank 3)--Solution (D) (Tank 4).
As can be understood from the above-mentioned orders of feeding solutions,
Solution (A) and Solution (B) are placed separately in different tanks,
and are transmitted or fed into Tank 7 at slightly different times.
Therefore the developer tank 7 is replenished with these solutions with
substantially no mixing thereof. Thus, the effect of the present invention
can be obtained at least by separating Solution (A) and Solution (B).
According to the present invention, each of Solution (A) in which the
alkaline substance of the invention has been dissolved and Solution (B) in
which the poorly soluble alcohol of the invention has been dissolved may
directly be supplemented to the developer tank in an automatic developing
apparatus, or may be supplemented to the tank after they are mixed with
each other while they are thick or concentrated or after they are diluted
and mixed.
However, the developer tank of an automatic developing apparatus may
preferably be replenished directly with the above-mentioned Solutions (A)
and (B) as well as other replenisher compositions in order to enable
adoption of the AR system where no mixing device is needed. The developer
tank referred to in the present invention is constituted not only by a
tank but also by such an appended circulating system as a filter part, a
circulating pump, and a piping for circulation, etc.
The order of adding Solution (A), Solution (B) and other replenisher
compositions is not specifically designated. Either of Solution (A) or
Solution (B) may be added at the beginning or the end of the addition, or
Solutions (A) and (B) may be added simultaneously.
FIG. 2 shows schematically another Example of an automatic processing
apparatus to which the replenishing process of the present invention is
applied.
In the figure, all the symbols and numerals are the same as in FIG. 1. When
such an apparatus as shown in the Figure, the order of the additions of
the replenisher compositions as mentioned above may be controlled in any
optional manner.
It has already been known that the alkali-cleavable water-soluble salt of a
poorly soluble alcohol is employed for the preparation of a developing
solution, as disclosed in Japanese Provisional Patent Publn. No.
156934/1983.
The present invention has improved further the technology disclosed in the
publication mentioned above. It has been found that, when the solid
alkali-cleavable water-soluble salt of a poorly soluble alcohol is
employed as a replenisher composition in the form of a thick solution, the
poorly soluble alcohol may be dissolved in a developing solution uniformly
and in an extremely short time without any generation of oil drops and
hence the replenisher composition according to the present invention is
extremely excellent as a replenisher composition for the AR system.
The replenisher composition for a color developing solution to be used in
the present invention may inlude various additives, which may be used for
an ordinary developing solution, for example, potassium bromide, sodium
chloride, citrazinic acid (development controller), hydroxylamine, sulfite
(a preservative), etc.; it may optionally include various defoaming
agents, various surface active agents and an organic solvent, such as
ethylene glycol, diethylene glycol, methanol, dimethylformamide,
dimethylsulfoxide and the like.
The replenisher composition for a color developing solution to be used in
the present invention may include, as occasion demands, an anti-oxidant,
such as hydroxyurine, tetronic acid, tetronimide, 2-anilinoethanol,
dihydroxyacetone, aromatic secondary alcohol, hydroxam acid, pentose,
hexose or pyrogallolle-1,3-dimethylether, etc.
Furthermore, in the replenisher composition for a color developing solution
relating to the present invention, various chelating agents may be jointly
used as a sequestering agent. Said chelating agents include an
aminopolycarboxylic acid such as ethylenediaminetetracetic acid,
diethylenetriaminepentacetic acid, etc., an organic phosphonic acid such
as 1-hydroxyethylidene-1,1-diphosphonic acid etc., and an
aminopolyphosphonic acid such as aminotri(methylenephosphonic acid),
ethylenediaminetetraphosphonic acid, etc., an oxycarboxylic acid such as
citric acid, gluconic acid, etc., a phosphonocarboxylic acid
2-phosphonobutane-1,2,4-tricarboxylic acid, a polyphosphoric acid such as
tripolyphosphoric acid, hexametaphosphoric acid.
While p-phenylene series color developing agent is used as a replenisher
composition for color developing solution relating to the present
invention, a compound represented by the following General Formula (IV) is
preferred as a color developing agent. General Formula (IV)
##STR3##
wherein, R.sub.4 represents a hydrogen atom, a halogen atom or an alkyl
group, which alkyl group represents a straight-chain or branched-chain
alkyl group having 1 to 5 carbon atoms and may further be substituted by a
substituent. R.sub.2 and R.sub.3 each represent a hydrogen atom, a
substituted or unsubstituted alkyl group or a substituted or unsubstituted
aryl group; and as for the alkyl group, such an alkyl group further
substituted by an aryl group is preferable. And at least one of R.sub.2
and R.sub.3 is an alkyl group which has been substituted by a water
soluble group such as a hydroxyl group, a carboxyl group, a sulfonic acid
group, an amino group, a sulfonamide group, etc., or a ((CH.sub.2).sub.p
O--.sub.q R.sub.5 group. This alkyl group may further be substituted by a
substituent.
R.sub.5 represents a hydrogen atom or an alkyl group, which alkyl group
represents a straight-chain or branched-chain alkyl group having 1 to 5
carbon atoms; p and q are integers of 1 to 5.
Next, typical examples of the compound represented by said General Formula
(IV) are given below, however, such compounds are not restricted to them.
(Exemplary compounds)
##STR4##
These p-phenylenediamine derivatives represented by the General Formula
(IV) may be used as a salt of an organic acid or an inorganic acid, which
may include a hydrochloride, a sulfate, a phosphate, a p-toluensulfonate,
a sulfite, an oxalate, a benzenesulfonate, etc.
In the present invention, the effect of the object of the present invention
may be especially remarkably exhibited when R.sub.2 and/or R.sub.3 is a
((CH.sub.2).sub.p O--.sub.q R.sub.5 (wherein p, q and R.sub.5 have the
same meanings as defined above) among other p-phenylenediamine derivatives
represented by said General Formula (IV).
The color developing agent represented by said General Formula (IV) may be
added to and included in a light-sensitive material.
Light-sensitive silver halide color photographic materials being processed
by means of the replenishing process of the present invention may include
color printing paper, color negative film, color reversal film, color
reversal printing paper, etc.
The replenishing process of the present invention will be explained
concretely by way of Examples given below:
EXAMPLE 1
The following Solutions (A) to (D) were prepared as replenisher
compositions for a developing solution for color printing paper.
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Solution (A)
Potassium carbonate 312.5 g
1-hydroxyethyliden-1,1-diphosfonic acid
12.5 ml
(60% solution)
Potassium sulfite (50% solution)
62.5 ml
Potassium hydroxide 37.5 g
Water to make up 1 liter
Solution (B-1)
Benzyl alcohol 250 g
Ethylene glycol 500 ml
4,4'-diaminostilbenedisulfonic acid
50 ml
(fluorescent brightening agent)
Water to make up 1 liter
Solution (C)
Sulfate of the Exemplary Compound (IV-1)
235 g
Potassium sulfite (50% solution)
30 ml
Water to make up 1 liter
Solution (D)
Hydroxylamine sulfate 160 g
Lithium chloride 80 g
Water to make up 1 liter
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Each solution thus prepared was put into the mixing device 11 of the
automatic developing system shown in FIG. 3 by use of the AR system
according to the following order: Water (825 ml)--Solution (A) (80
ml)--Solution (B-1) (40 ml)--Solution (C) (30 ml)--Solution (D) (25 ml),
followed by complete mixing thereof. The resulting mixture was
supplemented to the developer tank 7 of the automatic processing machine
by use of the bellows pump 6' through the circulation piping. Mixing time
spent for the complete dissolution within the mixing device 11 was
measured to be 3 min. and 3 sec.
Next, the same experiment as mentioned above was repeated, except that
Solution (B-2) relating to the present invention as specified below was
used instead of Solution (B-1).
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Solution (B-2)
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Exemplary Compound (1)
220 g
4,4'-diaminostilbenedisulfonic acid
25 ml
(fluorescent brightening agent)
Water to make up 1 liter
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(The resulting mixture was adjusted to pH 7 by use of sodium hydroxide or
a diluted sulfuric acid.)
However, since potassium carbonate may be formed from the above-mentioned
Exemplary Compound (1) during the mixing for dissolution, the equivalent
amount of potassium carbonate which had been formed thereby was removed
from said Solution (A) and then Solution (A) was condensated to one half
as much to be a 40 ml solution for addition. The addition amount of
Solution (B-2) was 80 ml. With the rest of the conditions having been
exactly the same as those of the previous experiment, the replenisher
compositions were added to the same order as mentioned above, and the
mixing time spent for the complete dissolution within the mixing tank was
measured to be only 28 sec.
From the above-mentioned results of the experiments, according to the
present replenishing process, there can be provided a replenisher
composition which can completely dissolve in an extremely short period of
time, with which an automatic developing apparatus can be replenished.
EXAMPLE 2
The mixing device 11 of the automatic developing system shown in FIG. 3 in
Example 1 was removed, and, instead, the automatic developing system shown
in FIG. 1 to be used in the replenishing process of the present invention
was used to perform several cycles of replenishment as a Comparative
Example in the following order: Water (196.5 ml)--Solution (A) (19
ml)--Solution (B-1) (9.5 ml)--Solution (C)(7.2 ml)--Solution (D) (6 ml)
Several cycles of replenishment were performed in exactly the same manner
as that of the above-mentioned experiment except that Solution (B-2) of
the present invention was used instead of Solution (B-1).
As a result, in the experiment in which Solution (B-1) was used as a
Comparative Example, there was observed floating of benzyl alcohol, which
is a poorly soluble alcohol, on the surface of the developing solution in
the developer tank of the automatic processing apparatus, and the
light-sensitive material and the developer tank were smeared.
In contrast thereto, in the process in which Solution (B-2) of the present
invention was used, there was not observed any floating of benzyl alcohol
in spite of the fact that the mixing device was removed, and the
light-sensitive materials and the developer tank were not smeared.
Thus, it was found that the replenishing process of the present invention
is quite excellent to be used in the AR system, since it does not require
any mixing device, and hence the AR system may be made compact; any
floating of a poorly soluble alcohol, for example, benzyl alcohol etc.
will not occur; and any smear of light-sensitive materials and the
developer tank will be obviated.
EXAMPLE 3
By use of the automatic processing system shown in FIG. 2 instead of the
automatic processing system shown in FIG. 1, simultaneous replenishment
with Solution (A) to (D) of the present invention and water were performed
through the bellows pump. As a result, there was not observed any floating
of benzyl alcohol and any smear of light-sensitive materials and the
developer tank did not occur.
EXAMPLE 4
Experiments were performed in exactly the same manner as in Example 1
except that Exemplary Compound (1) in Replenisher Composition (B) used in
Example 1 was replaced by Exemplary Compounds (2) and (4), respectively.
As the result, there was obtained the same result as in Example 1.
EXAMPLE 5
Experiments were performed in the same manner as in Example 1 except that
Exemplary Compound (IV-1), which was a developing agent of Replenisher
Composition C in Example 1 was replaced by 4-amino-N,N-diethylaminoaniline
hydrochloride of Exemplary compound (A) and p-toluenesulfonate of
Examplary Compound (IV-11) respectively, to measure the time until the
replenisher composition was dissolved in the mixing device. The thus
obtained results are shown in Table 1.
TABLE 1
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Dissolution order
Dissolution order
Color of the solutions
of the solutions
Developing
Water.fwdarw.(A).fwdarw.(B-1).fwdarw.
Water.fwdarw.(A).fwdarw.(B-2).fwdarw.
Agent (C).fwdarw.(D) (C).fwdarw.(D)
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Exemplary
3 min. 30 sec. 28 sec.
Compound
(IV-1)
Exemplary
5 min. 30 sec. 1 min. 18 sec.
Compound
(A)
Exemplary
3 min. 27 sec. 19 sec.
Compound
(IV-11)
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As is clear from the above Table, when a developing agent represented by
the general formula (IV) was used as the replenisher composition according
to the present invention, it was found that the time required for
dissolution was very short, and the effect of the present invention was
further enhanced. It was also found when a p-phenylenediamine color
developing agent, which further has a substituent including an oxyethylene
group such as Exemplary Compound (IV-11) as a substituent for an amino
group, was used, the time required for dissolution was further shortened
and a more favorable effect could be obtained.
EXAMPLE 6
Solutions (B-1) and (B-2) prepared in the above-mentioned Example 1 were
respectively put into a polyethylene container having a capacity of 1.2
liter, and kept at 50.degree. C. for three months, then the quantitative
analysis was performed of the benzaldehyde which have been formed and of
the remaining benzyl alcohol by means of gas chromatography.
As the result, in Comparative Example (B-1), 3.5% of benzaldehyde was
formed; in the case of Example (B-2) of the present invention it was
observed to be merely 0.3%. From this, it will be understood that the
storability of benzyl alcohol may be improved when the composition of the
present invention is used.
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