US3615501A

US3615501A - Color photographic developing process

Info

Publication number: US3615501A
Application number: US868583A
Authority: US
Inventors: Reiichi Ohi; Isao Shimamura; Tadao Shishido
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1968-10-22
Filing date: 1969-10-22
Publication date: 1971-10-26
Anticipated expiration: 1988-10-26
Also published as: DE1952253A1; DE1952253B2; DE1952253C3; GB1249531A

Abstract

A process for developing exposed multilayer color photographic silver halide light-sensitive elements which comprises processing said color photographic element in a processing composition containing a compound represented by the general formula: WHEREIN R represents an alkyl group having four to 7 carbon atoms or a compound represented by the general formula: WHEREIN R'' represents an alkylene group having one to eight carbon atoms.

Description

United States Patent F nn 3,615,501

[72] lnventors Reiichiphi; j

v lsao S hi narnura;Tadab Shishido, all of KanagawaJapari [21] Appl. No. 868,583 v [22] Filed Oct.22, 1969 [45] Patented, -Oct l26, 1971" [73] Assignee: Fyji Photofilm Co. Ltd.

Nakanuma,Minami-Ashigara Machi, A'shigara-Kami'gun, Kinagavva, Japan) [32] Priority Oct. 22, 1968 i [33] Japan [31] 43/76923 54 COLOR'PHOTOOilAPHICDEVELOP-INC'PROCESS 6 Claims, No Dra'vvings.

[52] US. Cl 96/55, 96/66-.5, 96/l09 [51-] lnt.Cl G03c 5/30, -GD3c 7/30 [50] Fieldofsearch .96/55,66.5, .56.5,109,22

[56] References Cited UNITED STATES PATENTS 2,324,123 7/1943 Weissberger 96/66.5X 2,384,593 9/1945 Bean 96/66.5 X 2,939,789 6/1960 Dersch eta]. 96/66.5 3,137,578 6/1964 De Selms 96/109 3,165,407 l/1965 McCarthy 96/55 X 3,271,154 9/1966 DersCh etal 96/66.5

3,495,981 2/1970 Nagae et a], 96/55 Primary Examiner-John T. Goolkasian AssistantExaminer-Joseph C. Gil

Attorr'tey-Sughrue, Rothwell, Mion, Zinn Macpeak ABSTRACT; A prdcss for-developing'exposed multilayer color photographic silver-halide light-Sensitive elements which comprisespr'oc'essing said color photographic element in a processing composition containing a compound represented by the general formula:

N I i I R O;N

wherein R represents an alkyl group having four to 7 carbon atoms or a compound represented by the general fonnula:

(II) H i H WQL N0,

wherein R represents an alkylene group having one to eight carbon atoms.

COLOR PHOTOGRAPIIIC DEVELOPING PROCESS The present invention relates to a process for developing 5 color photographic light-sensitive elements and more particularly to a process for developing color photographic light-sensitive elements using an additive which is effectively employed in the case of conducting development at a high temperature.

2. Description of the Prior Art A multilayer color photographic element generally has at least three difl'ercnt sensitive silver halide emulsion layers superimposed on a support, for example, a lowermost red-sensitive emulsion layer, a green-sensitive emulsion layer, a yellow filter layer, and an uppermost blue-sensitive emulsion layer. These are generally formed on a support in this order.

Recently, development of color photographic elements has tended to be carried out at high temperatures, i.e., higher than 30 C., to reduce the developing time. Such a developing process is usually called a high temperature process or a high temperature rapid process." Hereinafter, the term high temperature processing in this specification means color photographic developing processing at a temperature higher than 30 C.

One of the troubles encountered in high temperature processing is the phenomenon that the development of fog becomes dominant over image development due to a high activation energy for fog development. Hence the image developability, which is the ratio of the image developing density to the fog developing density, is reduced.

To improve this point, one would think it would be easy to add a developing inhibitor to a processing solution, but even if conventionally known developing. inhibitors, such as 5- nitrobenzimidazole and the like, are employed, the antifogging effect by the additive is less when high-temperature processing is used. In this case, although the antifogging effect may be increased by using a large quantity of the developing inhibitor, image development is also inhibited, and hence'the use of a large amount of developing inhibitor is not very useful for the avowed purpose.

SUMMARY OF THE INVENTION general formula:

R OzN N} wherein R represents an alkyl group having 4 to 7 carbon atoms or a compound represented by the general formula:

H H l om wherein R represents an alkylene group having 1 to 8 carbon atoms. 1

2 Therefore, one object of the present invention is to provide a process for efi'ectively preventing the formation of fogs in a high temperature developing process for color photographic light-sensitive elements.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The compound used in the present invention is represented by the general formula:

r N N R! 0m No- N N s wherein R represents an alkyl group having 4-7 carbon atoms and R represents an alkylene group having 1-8 carbon atoms.

According to the present invention, by adding the above compound to a developing solution used in high-temperature processing, the formation of development fog can be effectively prevented to provide a development balance, and the total color balance of the image and the quality thereof are further improved. Thus, on merit of the present invention is in enabling the processing of photographic light-sensitive elements at a temperature of from 30 to C. (at least in the case of using the compound of this invention).

The compound of the present invention is particularly effective in the so-called coupler-in-developer type reversal development, in which color developments are conducted in three steps, i.e., cyan development, yellow development, and magenta development. In other words, when the aforementioned reversal development is conducted at a high temperature without using the compound of this invention, the cyan development provides cyan fogs in the blue-sensitive emulsion layer and the green-sensitive emulsion layer which are to be color developed in a yellow color developer and a magenta color developer, respectively. This gives severe color mixing or color stain and provides an image having a bad color balance.

Further, the abovementioned compound of the present invention may effectively be incorporated in a first black and white developing solution in a coupler-in-developer type color reversal developing process, as well as a coupler-in-emulsion layer type color reversal developing process. Essentially as over development of the uppermost layer due to a high-temperature development is prevented and the formation of development fogs therein is suppressed by the use of the compound of this invention, the reversal color image thus obtained has an excellent image quality with good color balance and high reversal color density. Moreover, when the reversal color development process involves a pretreatment step, such as a prehardening step, before the first black and white development, the compound of this invention can effectively be incorporated in the pretreatment bath.

By incorporating the compound of this invention in a color developing solution in the development process for color negative films or color papers, the reduction in the gamma value caused by the increase in the formation of fogs in the high-temperature process can be prevented, and an image having good color balance is obtained with a good development balance.

A coupler-in-developer type color developing solution in which the above-mentioned compound of the present invention is incorporated contains, in addition to a colordeveloping agent and a coupler, an alkali such as sodium hydroxide or sodium carbonate, a salt such as sodium sulfate, a developing inhibitor such as an alkali halide, and an antioxidant such as sodium sulfite or hydroxylamine sulfate.

As the color developing agent, there are employed p-phenylene-diamine derivatives, such as N,N-diethyl-p-phenylenediamine sulfite N,N-diethyl-3-methyl-p-phenylenediamine hydrochloride, 4-amino-3-methyl-N-ethyl-N- methanesulfonamide ethylaniline sulfate, 4-amino-3-methyL N-ethyl-NJiydroxyethyl aniline sulfate, and N-ethyl-N- hydroxyethyl p-phenylene-diamine sulfate.

As the couplers, there are used cyan couplers, such as 2,4- dichlorol -naphthol, 2,4dichloro-5 -tolysulfonamidol naphthol, l-hydroxy-Z-benZylnaphthamide, 2,6-dibromo-l,5- dihydroxynaphthaline, etc., and yellow couplers such as benzoylacetanilide, w-benzoyl-4-(p-toluenesulfonamide)acetanilide, etc. Other couplers soluble in the developing solution in general use can be employed.

As the first black and white developer for developing color reversal films, an aqueous solution containing at least one developing agent such as hydroquinone, phenidone and Metol is generally used. The developer further usually contains a salt such as sodium sulfate, a pH adjusting agent and a buffer agent such as borax, boric acid, sodium hydroxide, sodium carbonate, etc., and a developing inhibitor such as an alkali halide. To a color developer for color negative films or color papers there are usually added a color developing agent such as a p-phcnylene-diamine derivative, a salt such as sodium sulfate, a pH-adjusting agent, and a bufier agent such as sodium hydroxide, sodium carbonate, and sodium phosphate, a developing inhibitor such as alkali halide and an antioxidant such as sodium sulfite and hydroxylamine sulfate.

The above mentioned objects of the present invention can be achieved by adding to the aforesaid processing solutions the Smitrobenzimidazole compound represented by the general formula described above.

The preferred concentration of the compound of this invention is from about 1X10 mole/liter to about 1X10" -mole/liter. However, the optimum concentration thereof deinvention shall not be limited only to them.

Compound 1.M.P. 139 C.

2)a a Q Compound 2.-M.P. 235 C.

Compound 3.M.P. 231 C.

. Compound 4.M.P. 300 0.

Compound 5.-M.P. 290 C.

Compound 6.

Compound 7.M.P. 136 C.

H 1 1 l N The aforesaid compounds represented by the general formulas can be prepared by known methods using orthophenylenediamines as the raw materials (cf: fNippon Yakugaku Zasshi," Vol. 78, 242-244 (1958); "Journal of the Chemical Society, 2389-2398 (1952); and Journal of the Chemical Society," 2238-2240 (1953)).

Examples of preparing the compounds'represented by the above-mentioned general formula are shown below. Preparation of Compound 1 A mixture of 22 g. of orthophenylenediamine and 30 g. of valeric acid was refluxed by heating for 2 hours and the product was poured into ethanol and neutralized with an aqueous solution of potassium hydroxide. The crystal was collected by filtration and recrystallized from a mixed solvent of ethanol and water to provide 14 g. of product as needles. Ten grams (10 g.) of the crystal was added to 60 ml. of concentrated sulfuric acid and to the mixture there was added dropwise 6.5 ml. of nitric acid (gradually) with stirring under ice cooling. Thereafter, the system was stirred for 2 hours under ice cooling, and the product was poured in ice water, neutralized with aqueous ammonia, and then the crystal thus formed was recrystallized from a mixed solvent of ethanol and water to provide a white crystal of compound I having a melting point of 139 C.

Preparation of Compound 2 A mixture of g. of orthophenylenediamine and g. of caproic acid was refluxed under heating for 2 hours, and the product was poured in ethanol and neutralized with aqueous ammonia. The crystal thus formed was collected and recrystallized from ethyl acetate to provide 8 g. of product as needles melting at 160 C. Four grams (4 g.) of the crystal was dissolved in 30ml. of concentrated sulfuric acid and to the solution was added 3 g. of potassium nitrate, with stirring, under ice cooling. Thereafter, the system as stirred for 3 hours under ice coolingand the product was poured in ice water and neutralized with aqueous ammonia. The crystal thus formed was recrystallized from a mixed solvent of ethanol and water to provide the crystal of Compound 2 having a melting point of 235 C.

Preparation of compound 4 ln 30 ml. of ethylene glycol were refluxed, under heating, 2l

y g. of 'orthophenylenediamine and 10.2 g. of malonamide for4 hours. Then, 200 ml. ofwater was'added to the solution. The

- crystal thus obtained was collected and recrystallized from ethanol to'provide 6 g. of yet another crystal. The crystal was dissolved in 25 ml. of concentrated sulfuric acid and then 5 g. of potassium nitrate was added graduallyto the solution,'with stirring, under ice cooling. Thereafter, the system was stirred.

for 2 hoursunder ice colling, poured in ice water and neutralized with-sodium carbonate. When the crystal thus obtained was recrystallized from methanol, the crystal of Compound 4 having a melting point of above 300 C. was obtained.

Preparation of Compound 6 A mixture of 22 g. of orthophenylenediamine and 15 g. of adipic acid was refluxed under heating for 6 hours in 200 ml. of hydrochloric acid. The crystal obtained by cooling the product was collected, dissolved in water, and the solution was neutralized'with sodium carbonate to provide 18 g. of a crystal having a melting point. of 259 C. Six grams (6 g.) of the crystal'was dissolved in 40 ml. of concentrated sulfuric acid and to the solution there was gradually added 5 g. of potassium nitrate, with stirring, under ice cooling. Thereafter, the mixture was stirred for 2 hours under ice cooling. The reaction product was poured into ice water, neutralized with aqueous ammonia, and the crystal thus formed was collected and recrystallized from methanol to provide the crystal of Cornpound 6, as needles, melting at 259 C. The following examples are given in order to illustrate the invention in more detail.

EXAMPLE 1 A multilayer color photographic film was preparedfby applying, in this order, a silver iodobromide emulsion having red sensitivity, a silver iodobromide emulsion having green sensitivity, a yellow filter layer composed of colloidal silver, and a silver iodobromide emulsion having blue sensitivity to a cellulose triacetate film. The color photographic film was exposed by means of a sensitometer and then subjected to the following procedures: The processing temperature, including water washing, was 40 C.

Time

Water washing The compositions used for the processing solutions used above were as follows:

Prehardening solution:

Sodium hexamethaphoaphate l.0 g. Sodium bisultite 5.0 g. Sodium pyrophosphate l5.0 g. Sodium sulfate l50.0 g. Potassium bromide 2.0 g. Sodium hydroxide 0.l g. Formalin (37%) l5.0 ml. Water to make L000 ml.

First black dt white developer:

N-Methyl-p-aminophenol 5.0 g. Sodium sull'ite I 70.0 g. Hydroquinone 2.0 g., Sodium carbonate (monohydralc) 4|.0 g. Potassium bromide 4.0 g. Potassium thiocyanate [.6 g. Potassium iodide (01% sq. soln.) l0.0 ml. Water to make L000 ml.

Cyan color development:

Potassium bromide 3.0 g. Potassium iodide 0.1% a soln.) 10.0 ml. Sodium sulfite l0.0 g. Sodium sulfate 60.0 g. Potassium thiocyanate v LO Q. LAmino-J-rnethyl-N-ethyl-N- hydroxyethyl aniline sulfate 2.5 g. Sodium hydroxide 3.0 g. l.S-dihydroiy-Lbdibromonaphthalene 2.0 g. Monohenzyl-paminophenol 0.4 g. pAminophenoI hydrochloride 0.! g. Water to make L000 ml.

Yellow color developer:

Sodhirrrsulfite 10.0 g. Potassium bromide 0.5 g. Potassium iddide (0.l% aq. aoln.) 25.0 ml.

2.5 g. Sodium hydroxide 2.5 g. W-Ben aoyl-4(p-toluenesulfoamido)- acetanilide L8 g Water to make L000 ml.

Second black & white developer:

N-Methyl-p-aminophenol sulfate L0 g. Sodium sulfit' e 50.0 g. Hydroquino ne l.0 Sodium carb'ona'te limiterams 41.0 Potassium bromide 2.5 3. Water toj'nake 1.000 ml.

Magenta color developer:

Sodium sulfi te 5.0 g. Potassium bromide H) g. Potassium th'iocyanate l .0 g. Sodium si'ilfate 6010 g. nflaieiiiyi-a-mem i- 'ph enylenediamine hydrochloride 2.5 g. Sodium hydroxide 2.0 g. l-pheny|-3 (m-nitrobenzoylarnino)- 5-pyrazolone 1.4 g. Ethylene'diamine 8.0 ml. Water to make L000 rnl.

Bleaching solution:

Potassium terricyanide I00 g. Potassium bromide 30 g.

Water to m'alre 1,000 ml.

Fixing solution:

Sodiurn'thiosulfate Sodium sulfite Water to make [,000 ml.

In the above-mentioned coupler-in-developer type color reversal'processing, the compound of the present invention was added in the cyan color developer as shown in the following table:

The photographic properties obtained as the result of the above color-development processings are shown in the following table. As the photographic properties selected for the table, the blue density (D, max) and the red density (D max) at the maximum density portion (D max) were shown. Furthermore, as the red color purity, the ratio (D,/D of the red filter light density to the blue filter light density at the portion exposed to red light, and the ratio (DJD,) of the red filter light density to the green filter light density at the red exposed portion, were shown.

These values relate to evaluating the purity of the reproduced color when a red object is reproduced as a color photograph The lower these ratios are, the better the purity of the red color on photographic material reproduced from an object.

Test No. D,max D,max D,/D, D,/D,

l 1.87 1.63 0.95 [.12 2 3.35 3.2] 0.30 0.32 3 3.30 3.28 0.17 0.34 4 3.29 3.08 0.3l 0.39 5 3.02 2.7l 0.35 0.42 6 2.9l 2.40 0.48 0.63

EXAMPLE 2 The processing of example I were followed while adding to the cyan color developer the compound of the present invention as shown in the following table.

For comparison, comparative examples using 5- nitrobenzimidazole and other developing inhibitors are also shown in the table.

Test No. Additive Amount l S-nitrobenzimidazole l.34 l0" mole/liter 2 2-methyl-5-nitrobenzimidazole 134x10" mole/liter 3 Z-ethyl-S-ntrobenzimidazolc LIMXIO" mole/liter 4 5-nitro-2'propyl benzimidazole l.34 l 0" mole/liter 5' Compound I I .34XIO" mole/liter 6' Compound 2 1.34200" mole/liter 7' Compound 3 1 34x10" mole/liter 8 Z-nonyl-S-nitrobenzimidazole I.34Xl0" mole/liter 9 s'nitro-z-undecylbenzimidazole IJ4XIO" mole/liter Present invention:

The photographic properties obtained by the processings shown are given in the following table, in which the same evaluations as in example 1 were made.

Test No. D, max D, max DJ D,/D

As shown in the above table. only in the case of using the compounds of this invention (test Nos. 5, 6 and 7) were good results obtained.

Example 3 A multilayer color photographic reversal film having three differentially sensitized silver halide emulsion layers, each containing a color coupler. was exposed by means of a sensitomcter and subjected, at 37 C to the following 40 procedures:

Processing Time First hlaclt A while development 3 min. First stopping 30 sec. Water washing l min. (nlur development 2l0 sec Second stopping 30 sec. Water washing 1 min. Bleaching sec. Fixing l min. Water washing l min.

The compositions of the processing solutions used in the above procedures were as follows:

First black and white developer Water to make 1.000 ml.

in the above-mentioned coupler-in-emulsion layer-type reversal processing, the compound of the present invention was incorporated in the first black and white developer as shown in the following table. For comparison, comparative experiments were conducted without incorporating the compound in the developer and, in another case, by adding a conventional developing inhibitor, -nitrobenzimidazole, to the developer.

Telt No. Additive Amount 1 none 2 Compound 5 0.50Xl0" mole/liter 3 Compound 2 1.00X l0" mole/liter 4 S-nitrobenzimidazole 1.00Xl0 mole/liter The results obtained are shown in the following table, in which the photographic properties shown are the blue density (D max) and the red density (1 ),max) at the maximum density (D max) portion of the image.

Test No. D,max D,max

As shown in the above table, by the addition of the compound of the present invention, the blue density (D max) is sufficiently increased and a better image quality (showing a good balance with the red density (D,max)) was obtained.

EXAMPLE 4 A multilayer color photographic negative film having three differently sensitive silver halide emulsion layers each containing therein a color coupler was exposed by means of a sensitometer and subjected to the following processings. The processing temperature was 35 C.

Procesing Time Color development 3 min. Stopping 30 sec. Water washing 30 sec. Bleaching l min. Fixing 90 sec. Water washing 1 min.

The compositions of the processing solutions in the above processings were as follows:

Color developer:

Sodium hexalnethaphoephate 1.0 g. Benzyl alcohol 5.0 g. Sodium aulfite 3.0 g. Sodium carbonate 41.0 g. Sodium hydroxide 1.0 g. 4-Amino-3 methy1-N-ethyl-N- I methane-sulfoamidoethylaniline sulfate 5.0 g. Potassium bromide 0.5 Water to make 1.000 ml.

Stopping solutionf Acetic acid 25 ml.

Sodium acetate 3 g. Potassium alum 10 g. Water to make 1,000 ml.

Bleaching solution:

Potassium ferricyanide g. Potassium bromide 20.0 Water to make 1.000 ml.

Fixing solution:

Sodium thiosull'ate g. Sodium sulfite 10 g. 1

The results obtained by the above coupler-in-emulsion layer type negative color developing procedure were compared with the results obtained by adding Compound 2 of the present invention to the color developer in an amount of 5X10mole/liter. By the addition of Compound 2 of this invention, the uppermost blue-sensitive emulsion layer of the color film was prevented from being excessively developed and each of the blue-sensitive emulsion layers, the green-sensitive emulsion layer, and the red-sensitive emulsion layer could be developed with good balance.

What we claim is:

l. A process for developing exposed multilayer color photographic silver halide light-sensitive elements which comprises processing said color photographic element in a processing composition containing a compound represented by the general formula:

OiN

wherein Rrepresents an alkylene group having 1 to 8 carbon atoms.

2. The process according to claim 1 wherein the concentration of said compound in said processing solution is from about 1X10""mole/liter to about 1X10" mole/liter.

3. The process according to claim 1 wherein said multilayer color photographic element is a coupler-in-developer type color photographic element and said compound is incorporated in the'cya'n color developer.

MAL fills 4. The process according to claim 1 wherein said multilayer type color photographic element and said compound is incorcolor photographic element is a coupler-in-developer type porated in the black and white developer. c0101 P l element and said compound is incor 6. The process according to claim 1 wherein said process is porated in the first black and white developer or in a pretreatment bath before the black and white development 5 zfgsg process conducted at a temperature usher 5.'The process according to claim 1 wherein said multilayer color photographic element is a coupler-in-emulsion layer-

Claims

2. The process according to claim 1 wherein the concentration of said compound in said processing solution is from about 1 X 10 6 mole/liter to about 1 X 10 2 mole/liter.
3. The process according to claim 1 wherein said multilaYer color photographic element is a coupler-in-developer type color photographic element and said compound is incorporated in the cyan color developer.
4. The process according to claim 1 wherein said multilayer color photographic element is a coupler-in-developer type color photographic element and said compound is incorporated in the first black and white developer or in a pretreatment bath before the black and white development.
5. The process according to claim 1 wherein said multilayer color photographic element is a coupler-in-emulsion layer-type color photographic element and said compound is incorporated in the black and white developer.
6. The process according to claim 1 wherein said process is a high temperature process conducted at a temperature higher than 30* C.