U.S. patent number 3,615,498 [Application Number 04/748,205] was granted by the patent office on 1971-10-26 for color developers containing substituted n-benzyl- -aminophenol competing developing agents.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Atsuaki Arai, Isao Shimamura, Mitsugu Tanaka.
United States Patent |
3,615,498 |
Arai , et al. |
October 26, 1971 |
COLOR DEVELOPERS CONTAINING SUBSTITUTED N-BENZYL- -AMINOPHENOL
COMPETING DEVELOPING AGENTS
Abstract
Improved results are obtained upon using a color developing
composition which contains an aromatic primary amino developing
agent, a color coupler and an alkali if there is incorporated
therein a water-soluble compensating developer represented by the
general formula ##SPC1## X represents an atomic group necessary to
form a heterocyclic ring, and is specifically defined in the
specification. Typically, the compensating developer shown is
incorporated into a cyan magenta or yellow developing
composition.
Inventors: |
Arai; Atsuaki (Kanagawa,
JA), Tanaka; Mitsugu (Kanagawa, JA),
Shimamura; Isao (Kanagawa, JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Nakanuma, Minami Ashigara Machi, Ashigara-Kamigun, Kanagawa,
JA)
|
Family
ID: |
26389072 |
Appl.
No.: |
04/748,205 |
Filed: |
July 29, 1968 |
Foreign Application Priority Data
|
|
|
|
|
Jul 29, 1967 [JA] |
|
|
42/48760 |
|
Current U.S.
Class: |
430/468; 430/470;
430/473; 430/379 |
Current CPC
Class: |
C07D
311/58 (20130101); G03C 5/3021 (20130101); C07D
317/58 (20130101); C07D 307/79 (20130101); C07D
319/18 (20130101); G03C 7/4136 (20130101) |
Current International
Class: |
C07D
307/00 (20060101); C07D 311/00 (20060101); C07D
307/79 (20060101); C07D 319/00 (20060101); C07D
311/58 (20060101); C07D 317/58 (20060101); C07D
319/18 (20060101); C07D 317/00 (20060101); G03C
5/30 (20060101); G03C 7/413 (20060101); G03c
001/00 () |
Field of
Search: |
;96/55,66.3,66,22 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Louie, Jr.; Won H.
Claims
What is claimed is:
1. In a color developing composition containing (1) an aromatic
primary amino developing agent (2) a color coupler, and (3) an
alkali, the improvement wherein said composition contains a
water-soluble competing developer represented by the general
formula ##SPC5##
wherein X represents a nonmetallic atomic group necessary for
forming a member selected from the group consisting of a 5-membered
heterocyclic ring, an alkyl substituted 5-membered heterocyclic
ring, and a 6-membered heterocyclic ring by the combination thereof
with a member selected from the group consisting of --CH.sub.2 --
and --O--, the number of --CH.sub.2 -- groups in said heterocyclic
ring being 1, 2 or 3, and the number of --0-- groups in said
heterocyclic ring being 1 or 2.
2. The color developing composition as claimed in claim 1 wherein
said color coupler is a cyan color coupler.
3. The color developing composition as claimed in claim 1 wherein
the amount of said competing developer is from about 0.01 to about
5.0 g./liter of the color developing composition.
4. The color developing composition as claimed in claim 1 wherein
said competing developer is selected from the group consisting of
2-methyl-5-(p-hydroxyanilinomethyl) coumaran,
6-(p-hydroxyanilinomethyl)-chroman, N-piperonyl-p-aminophenol,
6-(p-hydroxyanilinomethyl)-1, 4-benzodioxane,
5-(p-hydroxyanilinomethyl) isocoumaran, and
6-(p-hydroxyanilinomethyl) isochroman.
5. The color developing composition as claimed in claim 1 wherein
said competing developer is 2-methyl-5-(p-hydroxyanilinomethyl)
coumaran.
6. The color developing composition as claimed in claim 1 wherein
said competing developer is 6-(p-hydroxyanilinomethyl)-chroman.
7. The color developing composition as claimed in claim 1 wherein
said competing developer is N-piperonyl-p-aminophenol.
8. The color developing composition as claimed in claim 1 wherein
said competing developer is
6-(p-hydroxyanilinomethyl)-1,4-benzodioxane. 9The color developing
composition as claimed in claim 1 wherein the amount of said
competing developer is from about 0.1-1.0 g./liter of the color
developing composition. 10The color developing composition of claim
1 wherein said competing developer is utilized in the salt form
thereof.
The color developing composition of claim 10 wherein said salt is
the hydrochloride.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a developing composition for color
photography, and more particularly, to a color-forming developing
composition containing a novel water-soluble compensating
developer.
2. Description of the Prior Art
In general, reversal color photographic light-sensitive elements
which are to be developed in a coupler-containing developer are,
after exposure, subjected to black and white development, and then,
after being subjected to a reversal exposure, are processed in a
color developer which contains couplers. This type of element
usually has multiple emulsion layers which will include three
selective light-sensitive emulsion layers.
For example, in one such color photographic element, a support will
carry the following layers: a lowermost red-sensitive emulsion
layer, a green-sensitive emulsion layer, a yellow filter layer, a
blue-sensitive emulsion layer, and an upper protective layer
(formed on the support in the order given).
A color-forming developer used for developing such a reversal color
photographic light-sensitive element usually comprises: an alkaline
aqueous solution containing a p-phenyl-enediamine-type developing
agent which has at least one primary amino group, a color-forming
coupler; and additives, such as sodium sulfite, sodium bromide and
the like. Usually, in such a color-forming developing composition,
there will generally be employed a phenolic or naphtholic coupler
as a cyan dye-former; a pyrazolone coupler as a magenta dye-former;
and an open-chain ketomethylene coupler as a yellow dye-former.
When subjecting a reversal color photographic element to cyan
development using a color-forming developer containing a color
former or coupler, to suppress the formation of cyan fogs in the
green-sensitive and the blue-sensitive emulsion layers, a
compensating developer is incorporated into the cyan developer.
N-benzyl-p-aminophenol is widely used as one such "compensating
developer." It is generally known that the compensating developer
will reduce an oxidized color developing agent to the state of the
original developing agent, and will reduce an exposed silver halide
into metallic silver. The compensating developer will thus
contribute to suppressing cyan contamination in the blue-sensitive
emulsion layer and, in particular, in the green-sensitive emulsion
layer, therefore yielding a correct red reproduction of the subject
photographed. This is due to the fact that the compensating
developer and the color developer will both compete for reaction
with the exposed silver halide.
A compensating developer which may be employed in photographic
processing must be capable of increasing the red contrast by
removing cyan contamination, and must be capable of also increasing
the sensitivity of the red-sensitive emulsion layer. Furthermore,
the compensating developer must not reduce the maximum density of
the red-sensitive emulsion layer; must not reduce the high degree
of clarity of the cyan color developing agent; and must not reduce
the photographic properties of the emulsion without also reducing
the stability of the cyan developer.
However, to date, when a conventional color developer containing a
compensating developer for use in color reversal processing has
been employed, the red contrast and the fog prevention have been
insufficient. In particular, sensitivity has been greatly reduced
as time passes, as well as a marked increase in fog formation,
yielding unsatisfactory results. Cyan contamination in the
green-sensitive emulsion layer becomes greatly increased with the
use of a conventional developer and it becomes necessary to
increase the amount of developer needed which greatly lowers the
utility of the color developing process and leads to increased
expense.
SUMMARY OF THE INVENTION
It has been found that greatly improved results are obtained upon
incorporating a water soluble compensating developer represented by
the general formula ##SPC2##
wherein X represents a nonmetallic atomic group necessary for
forming a member selected from the group consisting of a 5-membered
heterocyclic ring and a 6 -membered heterocyclic ring by the
combination thereof with a member selected from the group
consisting of --CH.sub.2 -- and --O-- , the number of --CH.sub.2
--groups in said heterocyclic ring being 1, 2 or 3, and the number
of -- O-- groups in said heterocyclic ring being 1 or 2, in a color
developing composition which contains an aromatic primary amino
developing agent, a colorformer and an alkali.
Generally, the compensating developer of this invention is
incorporated in at least one of the following color developing
compositions: a cyan developing composition, a magenta developing
composition or a yellow developing composition.
The concentration of the compensating developer of this invention
will vary depending upon the type and concentration of the color
developing agent and coupler utilized and the pH of the color
developer. However, most often concentrations of about 0.01 to
about 5.0 g./liter of developer is employed, and most preferably
from about 0.1 to about 1.0 g./liter.
It is preferred to utilize the compensating developer of this
invention in the form of a salt.
It is an object of the present invention to provide a developing
composition which contains a novel compensating developer which
will suppress the formation of fogs in photographic emulsion
layers, and most especially which will suppress the formation of
cyan fogs in green-sensitive and blue-sensitive emulsion
layers.
It is a further object of the present invention to provide a color
developing composition containing a novel compensating developer
which will yield a highly pure red reproduction, and which will
also increase the sensitivity of a red-sensitive emulsion
layer.
Additional objects of the present invention are to provide a
compensating developer which will not reduce the maximum density of
a red-sensitive emulsion layer, will not reduce the clarity of a
cyan color developing agent and which will not reduce the
photographic properties of the emulsion, such as reversal
sensitivity, red purity and the red filter density-blue filter
density ratio, without reducing the stability of the cyan
developer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The aforesaid object of the present invention can be attained by
incorporating, in at least one of the following: a cyan, magenta or
yellow developing composition containing: (1 ) an aromatic primary
amino developing agent, (2 ) a color former, and (3 ) and alkali,
at least one novel water-soluble compensating developer represented
by the following general formula: ##SPC3##
wherein X represents the nonmetallic atoms necessary for completing
a 5 -membered heterocyclic ring or a 6 -membered heterocyclic ring
by a suitable combination with --CH.sub.2 -- and --0 --, the number
of --CH.sub.2 --groups being from 1 -3 and the number of --0 --
groups being 1 or 2, respectively.
Among the most excellent color developers of this invention, is a
cyan developing composition comprising an alkaline aqueous solution
which contains a p-phenylenediamine type color developing agent,
any well-known phenolic or naphtholic cyan-former, and the
aforesaid compensating developer. In particular, when compared with
conventional cyan color developing compositions, the compensating
developer of this invention exhibits an excellent fog-preventing
property, greatly reduces cyan-contamination, exhibits excellent
red reproduction, and reduces the degradation of photographic
properties as time passes.
The following materials are illustrative of the water-soluble
compensating developer used in this invention: 2 -methyl-5
-(p-hydroxy-anilomethyl) coumaran; 6 -(p-hydroxyanilinomethyl)
chroman; N-piperonyl-p-aminophenol; 6 -(p-hydroxy-anilinomethyl)-1,
4 -benzodioxane; 5 -(p-hydroxyanilinomethyl) isocoumaran; 6
-(p-hydroxyanilinomethyl) isochroman and the like. However, the
compensating developer of this invention is not to be considered
limited by the above enumeration.
The concentration of the compensating developer of this invention
will vary, depending upon the type and concentration of the color
developing agent and coupler used in the color developer, and will
also vary with the pH of the color developer. However, in general,
a concentration of 0.01 - 5.0 g./liter of developer is preferably
employed. Further, it has been found that the most effective
concentration utilized is about 0.1 - 1.0 g./liter.
The compensating developer of this invention is commonly used in
the form of a salt, such as the hydrochloride, which is more stable
than the free amine.
The compensating developer of this invention can be effectively
used in any cyan color developer, magenta color developer or yellow
color developer, but it is most effectively used in a cyan color
developer.
The color developing agent used in the color developing composition
of this invention is a general p-phenylene diamine derivative, such
as: N, N-diethyl-p-phenylenediamine sulfite; N,N-diethyl-3
-methyl-p-phenylenediamine hydrochloride; 4 -amino-3
-methyl-N-ethyl-N-methanesulfonamido ethylaniline sulfate; 4
-amino-3 -methyl-N-ethyl-N-hydroxyethylaniline sulfate;
N-ethyl-N-hydroxyethyl-p-phenylenediamine sulfate and the like.
Moreover, illustrative of the color formers used in this invention,
there are: 2, 4 -dichloro-1 -naphthol; 2,4 -dichlore-5
-tolysulfonamido-1 -naphthol; 1 -oxy-2 -benzylnaphthamide; 2, 6
-dibromo-1,5 -dihydroxynaphthalene; benzoylacetanilide; w-benzoyl-4
-(p-toluenesulfonamido)acetanilide; 1 -phenyl-3
-(m-nitrobenzoyl-amino)-5 -pyrazolone; and cyanoacetyl coumaron.
However, other color formers which are conventionally utilized may
be employed in this invention.
The preparation of the novel compensating developers used in this
invention may be illustrated by the examples shown below.
1. Preparation of 2 -methyl-5 (p-hydroxyanilinomethyl)-coumaran
(Compound 1 ):
A mixture of 16.5 g. of p-aminophenol and 24.5 g. of 2 -methyl-5
-formylcoumaran was refluxed for 30 minutes in 100 ml. of ethanol,
and the product was concentrated to provide 30 g. of a Schiff base.
This Schiff base was mixed with 150 ml. of methanol and, while
stirring the mixture at room temperature 4.5 g. of sodium
borohydride was slowly added to the mixture over a 10 minute
period. Thereafter, the product was poured into 300 ml. of ice
water containing a small amount of acetic acid. Crystals were thus
formed, and were recovered by filtering and then were
recrystallized from benzene to provide 25 g. of 2 -methyl-5
-(p-hydroxyanilinomethyl) coumaran, having a melting point of
107.degree. - 109.degree. C. The hydrochloride of this coumaran is
in the form of colorless leaflets having a melting point of
167.degree. - 170.degree. C. (decomposed). The elementary analysis
of this compound was as follows:
Analytically determined: C 66.12 %; H 6.41 %; and N 4.57 %.
Calculated: C 65.84 %; H 6.25 %; and N 4.80 %.
2. Preparation of N-piperonyl-p-aminophenol hydrochloride (Compound
2 ):
A Schiff base prepared by the reaction of 14.0 g. of p-aminophenol
with 19.4 g. of piperonal in 240 ml. of ethanol was reduced with
sodium borohydride as in the preparation of Compound 1. The amine
compound thus obtained was recrystallized from benzene to provide
23 g. of N-piperonyl-p-aminophenol in the form of colorless prisms
having a melting point of 83.degree. - 84.degree. C. The
hydrochloride in this compound is in the form of colorless prisms
having a melting point of 165.degree. - 180.degree. C.
(decomposed). Elementary analysis:
Analytically determined: C 59.77 %; H 5.14 %; and N 5.24 %.
Calculated: C 59.80 %; H 5.10 %; and N 5.06 %.
3. Preparation of 6 -(p-hydroxyanilinomethyl)-chroman hydrochloride
(Compound 3 ):
A Schiff base (23.0 g.) prepared by the reaction of 10.3 g. of
p-aminophenol with 15.3 g. of 6 -formylchroman, as in the
preparation of Compound 1, was dispersed in 150 ml. of an 18 %
aqueous sodium hydroxide solution and reduced by adding 12.0 g. of
zinc dust in small increments. The product obtained was neutralized
and extracted with ether. The extract was concentrated to provide
crystals, which were recovered by filtration and recrystallized
from benzene to give 18.0 g. of the colorless crystals of 6
-(p-hydroxyanilinomethyl) chroman, having a melting point of
95.degree. - 96.degree. C. The hydrochloride of this compound is in
the form of colorless plate crystal having a melting point of
173.degree. - 188.degree. C. (decomposed).
Elementary analysis:
Analytically determined: C 65.74 %; H 6.21 %.
Calculated: C 65.84 %; H 6.25 %.
4. Preparation of 6 -(p-hydroxyanilinomethyl)-1, 4 -benzodioxane
hydrochloride (Compound 4 ):
A Schiff base (27 g.) prepared by the reaction of 20.1 g. of
p-aminophenol and 13.4 g. of 3,4 -ethylenedioxybenzaldehyde was
reduced with zinc dust and sodium hydroxide, as in the preparation
of Compound 3. The product thus formed was recrystallized from
benzene to provide 20 g. of the colorless crystals of the objective
amine, having a melting point of 84.degree. - 84.5.degree. C. The
hydrochloride of this compound is a colorless crystal having a
melting point of 170.degree. - 180.degree. C. (decomposed).
Elementary analysis:
Analytically determined: N 4.19 %.
Calculated: N 4.77 %.
The following examples show that a color developer containing the
compensating developer of this invention is quite superior to color
developers which contain conventional compensating developers.
EXAMPLE 1
A multilayer color photographic film was formed of the following
layers (in the order given) on a photographic support: A
red-sensitive gelatino silver iodo-bromide emulsion layer, a
green-sensitive gelatino silver iodo-bromide emulsion layer, a
blue-absorbing yellow filter layer comprising colloidal silver, and
a blue-sensitive gelatino silver iodo-bromide emulsion layer. This
film was exposed by means of a sensito-meter and subjected to the
following processings:
Process Temp. Time
__________________________________________________________________________
First black and white development 24.degree. C. 5 min. Washing
24.degree. C. 2 min. Reversal exposure (red) at 200 Washing CMS
from the surface 24.degree. C. Cyan color 24.degree. C. 5 min.
Washing 24.degree. C. 2 min. Reversal exposure (blue) at 200 CMS
from the reverse side. Yellow color development 24.degree. C. 5
min. Washing 24.degree. C. 2 min. Second black and white
development 24.degree. C. 2 min. Washing 24.degree. C. 2 min.
Reversal exposure (white light) at 2000 CMS from both sides.
Magenta color development 24.degree. C. 5 min. Washing 24.degree.
C. 8 min. Bleaching 24.degree. C. 2 min. Washing 24.degree. C. 2
min. Fixing 24.degree. C. 2 min. Washing 24.degree. C. 2 min.
__________________________________________________________________________
The compositions of the processing baths used in the above
processings are as follows:
Black and White Developer
__________________________________________________________________________
N-methyl-p-aminophenol sulfate 2.0 g. Sodium sulfite 9.0 g.
Hydroquinone 8.0 g. Sodium carbonate (monohydrate) 52.5 g.
Potassium bromide 5.0 g. Potassium thiocyanate 1.0 g. Water to make
1,000 ml.
Cyan Color Developer
__________________________________________________________________________
Sodium sulfite 5.0 g. 2-Amino-5-N,N-diethylamino toluene
hydrochloride 0.6 g. Sodium carbonate (monohydrate) 15.0 g.
Potassium bromide 0.5 g. Potassium iodide (0.1% aq. soln.) 5 ml.
1,5-dihydroxy-2,6-dibromonaphthalene 1.2 g. Sodium hydroxide 2.0 g.
Water to make 1,000 ml.
Yellow Color Developer
__________________________________________________________________________
Sodium sulfite 5.0 g. N,N-diethyl-p-phenylenediamine sulfite 2.5 g.
Potassium bromide 1.0 g. Potassium iodide (0.1% aq. soln.) 5.0 ml.
W-benzoyl-4-(p-toluenesulfonamido) acetanilide 1.2 g. Sodium
hydroxide 2.5 g. Water to make 1,000 ml.
Magenta Color Developer
__________________________________________________________________________
Sodium sulfite 5.0 g. 2-Amino-5-N,N-diethylaminotoluene
hydrochloride 2.0 g. Potassium bromide 0.8 g.
1-Phenyl-3-(m-nitrobenzoylamino)-5- pyrozolone 1.4 g. Sodium
hydroxide 2.0 g. n-Butylamine 5.0 ml. Water to make 1,000 ml.
Bleaching solution
__________________________________________________________________________
Potassium ferricyanide 100.0 g. Potassium bromide 10.0 g. Borax
20.0 g. Boric acid 1.0 g. Water to make 1,000 ml.
Fixing Solution
__________________________________________________________________________
Sodium thiosulfate 150.0 g. Sodium sulfite 10.0 g. Water to make
1,000 ml.
__________________________________________________________________________
In the aforesaid reversal color developing process, the
compensating developers shown in the following table were
(individually) added to the cyan color developer, and the effect of
the compensating developer on the photographic properties of the
film was measured.
Exp. No. Compensating developer Amount*
__________________________________________________________________________
1 N-benzyl-p-aminophenol hydro- chloride 0.85 2
6-(p-hydroxyanilinomethyl- chroman hydrochloride 0.85 3
2-methyl-5-(p-hydroxyanilino- methyl)coumaran hydrochloride
0.85
(*) mmoles/1000 ml. of developer.
__________________________________________________________________________
The photographic properties of the film processed are shown in the
following table, with each of the three compensating developers, in
which: (1) the reversal sensitivity is shown by the inverse
logarithm of the amount of exposure at which the coupling density
obtained corresponds to 1.0; (2) the purity of the red color
reproduction is shown by the ratio of the red filter density to the
green filter density (D.sub.r /D.sub.g) of a portion of the film
exposed to red light (called red patch); and (3) the ratio of the
red filter density to the blue filter density (D.sub.r /D.sub.b) of
said portion is also shown. The ratio D.sub.r /D.sub.g or D.sub.r
/D.sub.b is a value which illustrates the color purity of a
reproduced color when a red object is reproduced in a color
photograph, and the smaller that this value is, the better the
processing.
---------------------------------------------------------------------------
Exp.
Purity of red color No. Reversal Sensitivity reproduced
__________________________________________________________________________
Cyan Yellow Magenta D.sub.r /D.sub.g D.sub.r /D.sub.b 1 1.13 1.27
1.20 0.33 0.27 2 1.18 1.29 1.25 0.29 0.23 3 1.20 1.30 1.24 0.28
0.23
__________________________________________________________________________
These results show clearly that by the incorporation of the
compensating developer of this invention, a high reversal
sensitivity and a preferred red purity can be obtained, when
compared with the conventionally known N-benzyl-p-aminophenol
hydrochloride.
After allowing the cyan color developers to age for 7 days in open
state to the atmosphere to cause air oxidation, the above procedure
was repeated using the now degradated color developers, and the
extent of degradation was measured. The results of the degradation
measurement are shown in the following table.
---------------------------------------------------------------------------
Exp. Purity of red color No. Reversal sensitivity reproduced
__________________________________________________________________________
Cyan Yellow Magenta D.sub.r /D.sub.g D.sub.r /D.sub.b 1 0.68 1.07
0.92 0.38 0.34 2 0.77 1.10 0.99 0.34 0.28 3 0.78 1.12 0.99 0.35
0.29
__________________________________________________________________________
These results show that by the addition of the compensating
developer of this invention, the cyan color developer will exhibit
a more constant effect, even when it is degradated by air
oxidation, when compared with the case of adding a conventional
compensating developer. This particular advantage of the
compensating developer of this invention was not anticipated, and
it shows even more clearly the excellent usefulness of the
compensating developer of the present invention.
EXAMPLE 2
Using the same basic procedures as in example 1, the three color
developments were replaced with a cyan color development. After
being washed with water for 8 minutes after cyan development, the
cyan-developed color film was subjected to bleaching, washing and
fixing, as in example 1, to provide cyan-colored images. In this
case, the photographic properties of the color photographs which
were improved by the compensating developer of this invention were
measured, the results of which are shown in the following table. In
the table, the reversal sensitivity (A) relates to the
red-sensitive emulsion layer, and the cyan contamination density
(B) is shown by the sum of the cyan coupling density in the portion
of the green-sensitive emulsion layer exposed to red light and the
cyan coupling density in the portion of the blue-sensitive emulsion
layer exposed to red light. These two light sensitive emulsion
layers are ones which will not be developed to any extent in a cyan
color development, and hence, cyan coupling these portions causes
undesirable developing fogs in the green-sensitive emulsion layer
to be magenta coupled and undesirable fogs in the blue-sensitive
emulsion layer to be yellow coupled. In other words, the cyan
coupling causes color turbidity, which results in a degrading of
the quality of the color photographic image. ##SPC4##
The results show that the compensating developer of this invention
has an excellent effect when compared with a conventional
compensating developer, N-benzyl-p-aminophenol hydrochloride.
EXAMPLE 3
The cyan color developer used in example 2 was forcibly degraded by
developing 2,800 sq. cm. of a color film with 1,000 ml. of the cyan
developer in a light room. Thereafter, the same basic procedure
used in example 2 was repeated using the thus degraded cyan
developer, the results of which are shown in the following table.
(In this experiment, the amount of compensating developer used was
the same as that in example 2.)
---------------------------------------------------------------------------
Exp. No. Compensating developer (A)* (B)**
__________________________________________________________________________
1 N-benzyl-p-aminophenol 1.05 0.63 hydrochloride 2
6-(p-hydroxyanilinomethyl)- chroman hydrochloride 1.10 0.58 3
2-methyl-5-(p-hydroxyanilinomethyl) coumaran hydrochloride 1.12
0.57
---------------------------------------------------------------------------
(*): reversal sensitivity; (**): cyan contamination color
density.
The cyan developer containing the compensating developer of this
invention again gave excellent results in comparison to the cyan
developer containing the known compensating developer.
EXAMPLE 4
The same basic procedure as was used in example 1 was repeated
while conducting the cyan development for 6 minutes at 24.degree.
C. using the following cyan developer:
---------------------------------------------------------------------------
Cyan Color Developer
Sodium sulfite 5.0 g. Sodium sulfate 50.0 g.
N,N-diethyl-p-phenylenediamine sulfite 2.8 g. Potassium bromide 2.0
g. Potassium iodide (0.1% aq. soln.) 5.0 ml.
2,4-dichloro-5-(p-toluenesulfonamido)-1-naphthol 2.0 g. Sodium
hydroxide 2.5 g. Hydroxylamine sulfate 0.5 g. Water to make 1,000
ml.
__________________________________________________________________________
The photographic properties obtained by adding the compensating
developer of this invention to the cyan developer were compared
with those obtained by adding thereto a conventional compensating
developer, N-benzyl-p-aminophenol hydrochloride. The amount and the
type of compensating developer used are shown below:
Example No. Compensating Developer Amount*
__________________________________________________________________________
1 N-benzyl-p-aminophenol hydrochloride 0.85 2
6-(p-hydroxyanilinomethyl)-chroman hydrochloride 0.85 3
2-methyl-5-(p-hydroxyanilinomethyl)cou- maran hydrochloride
0.85
The results obtained are shown in the following table:
---------------------------------------------------------------------------
Exp. No. Reversal sensitivity Purity of red color Reproduced
__________________________________________________________________________
Cyan Yellow Magenta D.sub.r /D.sub.g D.sub.r /D.sub.b 1 1.20 1.31
1.26 0.25 0.23 2 1.24 1.37 1.30 0.23 0.21 3 1.26 1.36 1.31 0.21
0.20
__________________________________________________________________________
After allowing the three kinds of cyan developers to oxidize in air
for 7 days, the same procedure used above was repeated, again using
the cyan developers. The effect of the degraded cyan developers on
the photographic properties was then determined, the results of
which are shown in the following table:
---------------------------------------------------------------------------
Exp. No. Reversal Sensitivity Purity of red color Reproduced
__________________________________________________________________________
Cyan Yellow Magenta D.sub.r /D.sub.g D.sub.r /D.sub.b 1 0.97 1.08
1.10 0.35 0.33 2 1.05 1.13 1.15 0.32 0.30 3 1.03 1.11 1.13 0.32
0.31
__________________________________________________________________________
It can be seen that the compensating developer of this invention
illustrated an excellent effect during this experiment, when
compared with the known compensating developer.
EXAMPLE 5
The same basic procedure as was in example 1 was repeated while
incorporating a compensating developer (including a known
compensating developer) in each of the cyan color developers (the
types and amounts utilized being shown in the following tables:
Exp. No. Compensating Developer Amount* 1 N-benzyl-p-aminophenol
hydrochloride 0.85 2 N-piperonyl-p-aminophenol hydro- chloride 0.85
3 6-(p-hydroxyanilinomethyl)-1,4- benzodioxane hydrochloride 0.85
6-(p-hydroxyanilinomethyl)-isochroman hydrochloride 0.85
The multilayer color photographic films thus prepared were
processed as in example 1, using the aforesaid cyan developers, the
results of this processing being as follows:
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Exp. No. Reversal Sensitivity Purity of red color Reproduced
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Cyan Yellow Magenta D.sub.r /D.sub.g D.sub.r /D.sub.b 1 1.13 1.27
1.20 0.33 0.27 2 1.16 1.29 1.24 0.28 0.24 3 1.18 1.30 1.26 0.29
0.23 4 1.16 1.29 1.24 0.30 0.24
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These results show that the compensating developers of this
invention will give a high reversal sensitivity and a high red
color reproduction purity in the red-sensitive emulsion layer in
comparison with the conventional compensating developer.
* * * * *