US 3615498 A
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United States Patent Inventors Atsuaki Aral;
Mitsugu Tamika; Isao Shimamura, all of Kanagawa, Japan Appl. No. 748,205 Filed July 29, 1968 Patented Oct. 26, 1971 Assignee Fuji Photo Film Co., Ltd.
Nakanuma, Minami Ashigara Machi, Ashigara-Kamigun, Kanagawa, Japan Priority July 29, 1967 Japan 42/48760 COLOR DEVELOPERS CONTAINING SUBSTITUTED N-BENZYL-p-AMINOPHENOL COMPETING DEVELOPING AGENTS  References Cited UNITED STATES PATENTS 3,300,305 1/l967 Pesch et al 96/55 X Primary Examiner-Norman G. Torchin Assistant Examiner-Won l-l. Louie, Jr. Attorney-Sughrue, Rothwell, Mion, Zinn and Macpeak 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 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.
COLOR DEVELOPERS CONTAINING SUBSTITUTED N- BENZYL- -AMINOPIIENOL COMPETING DEVELOPING AGENTS 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 dyeformer; 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 sup pressing 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 wherein X represents a nonmetallic atomic group necessary for forming a member selected from the group consisting of a S-membered heterocyclic ring and a 6-membered heterocyclic ring by the combination thereof with a member selected from the group consisting of CI-l and O, the number of --CH,, 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 l.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 bluesensitive 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 maran hydrochloride.
wherein X represents the nonmetallic atoms necessary for completing a S-membered heterocyclic ring or a 6-membered heterocyclic ring by a suitable combination with -Cl-l and -O, the number of Cl l -groups being from l 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-(phydroxy-anilomethyl) coumaran; 6-(p-hydroxyanilinomethyl) chroman; N-piperonyl-p-aminophenol; 6-(p-hydroxyanilinomethyl)-l 4benzodioxane; S-(p-hydroxyanilinomcthyl) 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 l .0 g./liter.
The compensating developer of this invention is commonly used in the form of a salt, such as the hydrochloride, which is e t sthan he renamin 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-l-naphthol; 2,4-dichlore-5- tolysulfonamido-l-naphthol; l-oxy-2-benzylnaphthamide; 2, -dibromo-l,S-dihydroxynaphthalene; benzoylacetanilide; wbenzoyl-4-(p-toluenesulfonamido )acetanllide; l-phenyl-3-(mnitrobenzoyl-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 I):
A mixture of 16.5 g. of p-aminophenol and 24.5 g. of 2- methyl-S-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 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 lO7-l09 C. The hydrochloride of this coumaran is in the form of colorless leaflets having a melting point of l671 70 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 hydrochloride (Compound 2):
A Schiff base prepared by the reaction of 14.0 g. of paminophenol 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-pamlnophenol in the form of colorless prisms having a melting point of 8384 C. The hydrochloride in this compound is in the form of colorless prisms having a melting point of 165-l 8 0 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 -96 C. The hydrochloride of this compound is in the form of colorless plate crystal having a melting point of l73-l88 C. (decomposed).
Analytlcally determined: C 65.74%; H 6.21%.
Calculated: C 65.84%; H 6.25%.
4. Preparation of 6-(p-hydroxyanilinomethyl)-l, benzodioxane hydrochloride (Compound 4):
A Schiff base (27 g.) prepared by the reaction of 20.1 g. of p-amlnophenol 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 84-84.5 C. The hydrochloride of this compound is a colorless crystal having a melting point of l70l80 C. (decomposed).
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 com pensating developers.
N-piperonyl-p-aminophenol 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' C. 5 min. Washing 24 C. 2 min. Reversal exposure (red) at 200 Wnshlng CMS from the surface 24' C. Cyan color 24 C. 5 min. Washing 24 C. 2 min. Reversal exposure (blue) at 200 CMS from the reverse side. Yellow color development 24 C. 5 min. Washing 24 C. 2 min. Second black and white development 24' C. 2 min. Washing 24 C. 2 min. Reversal exposure (white light) at 2000 CMS from both sides. Magenta color development 24' C. 5 min. Washing 24 C. 8 min. Bleaching 24 C. 2 min.
\Vashihg 24 C. 2 min. Fixing 24 C. 2 min. Washing 24 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 3. Potassium thiocyanate 1.0 g. Water to make 1.000 ml.
Cyan Color Developer Sodium sulfite 5.0 g. 2-Amino-5-N,N-diethylarnino toluene hydrochloride 0.6 g. Sodium carbonate (monohydrate) 15.0 g. Potassium bromide 0.5 5. Potassium iodide (0.1% sq. soln.) ml. l,5-dihydroxy-2,6-dibromonaphthalene 1.2 g. Sodium hydroxide 2.0 g. Water to make 1,000 m1 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. solnt) 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-S-N,N-diethylaminotoluene hydrochloride 2.0 5. Potassium bromide 0.8 g. l-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 l'erricyanide 100.0 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 mlv Exp.
No. Amount Compensating developer l N -benzyl-p-aminophenol hydrochloride 0.85 2 6-(p-hydroxyanilinomethylchroman hydrochloride 0.85 3 2-methyl-5-( p-hydroxyanilino' methyl)coumaran hydrochloride 0.85
(') mmoles/l000 m1. 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,./D,) 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,/D,,) of said portion is also shown. The ratio D,/D, or D,./D, 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,/D,, D,/D. l 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
Exp. Purity of red color No. Reversal sensitivity reproduced Cyan Yellow Magenta DJD, DJD, l 0.68 1.07 0.92 0.38 0.34 2 0.77 1.10 0199 0.34 0.28 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 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 the sum of the c an cou lin densit in the ortion of the h drochloride. The amount and the t e of com ensatin P green-sensitive emulsion layer exposed to red light and the developer used are shown below: cyan coupling density in the portion of the blue-sensitive Example emulsion layer exposed to red light. These two light sensitive cmpensaiing Devehp" Ammm" emulsion layers are ones which will not be developed to any extent in a cyan color development, and hence, cyan coupling 10 'P- ?P hlydrgchlmde these portions causes undesirable developing fogs in the gf sf r 'g y 0 85 green-sensitive emulsion layer to be magenta coupled and un- 3 methyi 5.(pmwmyaniiincmflhyimu. desirable fogs in the blue-sensitive emulsion layer to be yellow maran hydrochloride 0.85 coupled. In other words, the cyan coupling causes color turbidity, which results in a degrading of the quality of the color Photogtaphlc Imagern. moles/1,000 ml. ofdeveloperv Exp. No Compensating developer Amount* (A)** (B)*** l N-benzyl-p-aminophenol hydro chloride. 0.85 1.27 0.33 2 flmhydmxyanmnommhyl) The results obtained are shown in the following table.
chroman hydrochloride. 0.85 1.34 0.34 3 Z-methyl-S-(phydroxy-anilinomethyl)coumara.n hydrochloride. O.8S l.33 0.33 Exp ("l m. mol per 1,000 ml. of developer; reversal sensitivity; ("H cyan con- N' Reversal sensitivity Pumy tamination color density. Reproduced The results show that the compensating developer of this in- Cyan Yellow Magema r),/Di. D,-/D., vention has an excellent effect when compared with a convenl 1.20 1.31 1.26 0.25 0.23 tional compensating developer, N-benzyl-p-aminophenol 5 ii: 8-2 hydrochloride.
EXAMPLE 3 The cyan color developer used in example 2 was forcibly After allowing the three kinds of cyan developers to oxidize degraded by developing 2,800 sq. cm. of a color film with in air for 7 days, the same procedure used above was repeated, 1,000 ml. of the cyan developer in a light room. Thereafter, again using the cyan developers. The effect of the degraded the same basic procedure used in example 2 was repeated cyan developers on the photographic properties was then using the thus degraded cyan developer, the results of which determined, the results of which are shown in the following taare shown in the following table. (In this experiment, the l l amount of compensating developer used was the same as that 40 in example 2.)
Exp. No. Reversal Sensitivity Purity of red color Exp. v Reproduced N0 Compensating developer (AP (3) l N-benzyl-p-aminophenol 1.05 0.63 l 5 g ig; 2 1.05 1.13 1.15 0.32 0.30 2 6-(p-hydroxyanllmomethyl)- 3 103 l u 1 3 032 03 chroman hydrochloride l.l0 0.58 5 2-methyl-5-(p-hydroxyanilinomethyl) coumaran hydrochloride l.l2 0.57
It can be seen that the compensating developer of this inreversalsensmmy, n, cyan wmaminamn colordensny, vention illustrated an excellent effect during this experiment,
when compared with the known compensating developer.
EXAMPLE 5 The cyan developer contaming the compensatmg developer of this invention again gave excellent results in comparison to Th ame basi procedure as was in example 1 was repeated the cyan developer containing the known compensating while incorporating a compensating developer (including a developer. known compensating developer) in each of the cyan color EXAMPLE 4 developers (the types and amounts utilized being shown in the following tables: The same basic procedure as was used in example 1 was repeated while conducting the cyan development for 6 minutes Exp at 24C using the following cyan developer: Nu compensaung Developer Amoum. l N-benzyl-p-aminophenol hydrochloride 0.85 Cyan Color Developer 2 N-piperonyl-p-aminophenol hydrochloride 0 R5 50 3 6-(p-hydroxyanilinomethyl)-l,4- :IIZ; 500 benzodioxane hydrochloride 0.85 N.N-dlethyl-p-phenylenediamine sulfite 2.8 g. il s lzl f's Potassium bromide 2.0 g. y me -85 Potassium 1odidc(0.l7r aq. soln.) 5.0 ml. 2.4-dichloro-5-(p-toluenesulfonamido)-lnaphthol 2.0 g. Sodium hydroxide 2.5 g. Hydroxylamlne sulfate 0.5 g. m. moles/I000 ml. ofdeveloper. Water to make L000 ml 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:
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.
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 wherein X represents a nonmetallic atomic group necessary for forming a member selected from the group consisting of a S-membered heterocyclic ring, an alkyl substituted S-membered heterocyclic ring, and a 6-membered heterocyclic ring by the combination thereof with a member selected from the group consisting of -CH and O, the number of CH, groups in said heterocyclic ring being l, 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-paminophenol, 6-(p-hydroxyanilinomethyl)-l, 4-benzodioxane, 5-(p-hydroxyanilinomethyl) isocoumaron, and 6-(phydroxyanilinomethyl) isochroman.
5. The color developing composition as claimed in claim 1 wherein said competing developer is Z-methyI-S-(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-paminophenol.
8. The color developing composition as claimed in claim 1 wherein said competing developer is G-(p-hydroxyanilinomethyl)-1,4-benzodioxane.
9 The 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.
10 The color developing composition of claim 1 wherein said competing developer is utilized in the salt form thereof.
11. The color developing composition of claim 10 wherein said salt is the hydrochloride.