Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings

Definitions

• ABSTRACT The physical properties and storage stability of color photographic papers are improved by processing them in a stabilization bath containing a water-soluble zirconium salt and a polycarboxylic acid.
• the present invention relates to a stabilization pro cess for color photographic materials and, more particularly, it relates to a process for improving the physical properties of color photographic materials and the storage stability of color photographic images.
• a stabilization bath containing a watersoluble aluminum salt and a polycarboxylic acid can improve simultaneously the image stability and physical properties of photographic materials as described in US. Pat. 3,666,468 but the improvement by the process is not satisfactory.
• the reaction of physical properties of photographic materials after processing includes the following various matters.
• Photographic papers which have been subjected to photographic processingare usually stored by mounting them on a pasteboard mat or in an album having a transparent film cover or by placing them directly in a bag or box.
• the temperature and humidity in the storage of the processed photographic papers depend on the season, the climate, and the location but in any case, if the storage conditions are at low temperature and low humidity, physical difficulties such as adhesion or stickiness is less and they increase as the temperature and humidity increases.
• the storage conditions are at low temperature and low humidity, physical difficulties such as adhesion or stickiness is less and they increase as the temperature and humidity increases.
• tons rings are formed or dissolved matter in the cover film, such as plasticizers, causes sticking.
• electrostatic charges are frequently formed in an ordinary processing step, in particular the drying step for photographic papers, and if such electrostatic charges are formed on photographic papers, the stacked photographic papers after cutting will be disordered or the photographic papers will stick to each other complicating counting or checking them.
• the steps for processing photographic papers having a baryta-coated paper as the support include a drying step using a ferrotype dryer.
• the hardening bath and stabilization bath becomes frequently questions since they are subjected to various processings before drying.
• the color photographic paper processed in the manner as described in The British Journal of Photography, Sept. 27, 1968, pages 838840 and the specification of British Pat. No. 736,881 is subjected, as it is, to high-temperature high-speed ferrotype drying, the photographic paper sticks to the ferrotype plate.
• An object of this invention is, therefore, to provide a stabilization process for color photographic materials for improving the physical properties of the color photographic materials.
• Another object of this invention is to provide a stabilization process for improving the storage stability of color photographic images.
• Still another object of this invention is to provide a processing bath for color photographic materials for improving the above-mentioned physical properties and storage stability, in which the bath itself is also quite stable.
• the aforesaid object of this invention can be attained by processing color photographic materials with a processing bath containing a water-soluble zirconium salt and a polycarboxylic acid.
• the present invention provides a process of processing color photographic materials which comprises processing color photographic materials with a bath containing a water-soluble zirconium salt and a polycarboxylic acid.
• Suitable water-soluble zirconium salts which can be used in this invention, are zirconium salts such as zirconium sulfate, zirconium nitrate, zirconium chloride, zirconium oxysulfate, zirconium oxynitrate, and zirconium oxychloride. Of these zirconium salts as illus trated above, zirconium oxysulfate is particularly effective.
• the zirconium salts can be used individually or as a mixture of two or more salts and the amount of the zirconium salt generally used 1 to g/liter, preferably 2 to 6 g/liter.
• suitable polycarboxylic acids which can be used in this invention are acids such as oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, citric acid, glutaric acid, adipic acid, lactic acid, crotonic acid, aconitic acid, itaconic acid, diglycolic acid, and citraconic acid and the salts of these acids, such as the alkali metal salts, e.g., the sodium and potassium salts, ammonium salts, etc.
• Suitable polycarboxylic acids which can be used in this invention are disclosed, for example, in U.S. Pat. Nos. 2,515,121; 2,518,686; 3,140,177; 3,582,332; and 3,676,136.
• the polycarboxylic acids or the salts thereof can be used individually or as a mixture of them and the amount of the polycarboxylic acid generally used 1 to 15 g/liter, preferably 2 to 10 g/litcr.
• the stabilization bath of this invention is used at a pH of 2.7 to 4.5, preferably 3.3 to 4.0.
• the pH of the stabilization bath of this invention can be adjusted using an alkali such as sodium hydroxide, sodium metaboratc, borax, amine, etc.,'or an acid such as boric acid, acetic acid, sulfuric acid, etc., as disclosed in U.S. Pat. Nos. 2,515,121; 2,518,686; 3,140,177; 3,582,322, 3,676,136 and 2,647,057.
• Another manner of using a zirconium salt which is different from the present invention is in a hardening bath containing a zirconium salt as disclosed in the specification of British Pat. No. 1,271,025.
• a known bath may be effective for hardening during processing, the bath is not effective for improving the image stability and the physical properties of photographic materials after processing and hence it is clear that this is different from the process of this invention is effect and the manner of using.
• the objects of this invention as described before are not attained by using a bath containing a zirconium salt or a zirconium salt and an aldehyde.
• the objects of this invention are attained by processing color photographic papers with a bath containing simultaneously a water-soluble zirconium salt and a polycarboxylic acid or a salt thereof, with the pH of the bath having been adjusted to 2.7 to 4.5, as a final step in the color process for the color photographic papers.
• the processing bath of this invention containing the water-soluble zirconium salt and the polycarboxylic acid or a salt thereof can further contain at least one of a compound having an aldehyde group and a compound capable of forming formaldehyde.
• R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a carboxyl group, or a heterocyclic ring residue, said'R may have been sub stituted, and when R is a hydrogen atom, n represents an integer and when R is a substituent other than a hydrogen atom, n is l.
• compounds represented by the general formula (I) are formaldehyde, paraformaldehyde, acetaldehyde, aldol, propionaldehyde, acrolein, crotonaldehyde, salicylaldehyde, glyoxylic acid, muco,-. chloric acid, mucobromic acid, furfural, diglycolaldehyde, etc. Also, precursors of compound of the general formula (I) can be used as the water-soluble compound having an aldehyde group.
• dialdehyde compounds represented by the general formula (II) can be used as the compound having an aldehyde group.
• R Cl-IO wherein R represents a divalent aliphatic residue or a divalent aromatic residue, and m is O or 1.
• Examples .of compounds represented by the general formula (III) and the Nmethylol compounds are ,N- methylolurea, thylenebismonoethylurea,
• aldehydes which can be used in the stabilizing bath are disclosed in US Pat. Nos, 2,518,686 and 3,140,177.
• the water-soluble aldehyde compound or the compound capable of forming formaldehyde as described above can be used in an amount sufficient'to attain the objects of this invention but the amount of the aldehyde compound generally used is about 1.2 X to 1.8 X 10 mol/liter, preferably 4.2 X 10 to 1.1 X 10 mol/liter and the amount of the compound forming formaldehyde generally used is 1.0 X10 to 1.7 X 10, preferably 4.1 X 10 to 1.2 X 10 mol/liter.
• the dialdehyde compounds better results can be obtained by using it in an amount of 1.0 X 10' to 1.7 X 10" mol/litcr.
• a method of improving the stability of a magenta image by processing a photographic material containing a pyrazolone coupler with a stabilization bath containing a polycarboxylic acid and an aldehyde is known as disclosed in the specification US. Pat. No. 3,140,177.
• the method may be excellent in image stability, when the polycarboxylic acid and the aldehyde are used in the amounts disclosed in the specification of this US. patent, the photographic materials thus processed are greatly reduced in physical properties.
• the amount of the aldehyde is increased, the physical prop erties of the processed photographic material are greatly degraded and the use of these compounds is unpleasant because'of their irritative smell. Further stains are readily formed depending on the storage conditions.
• the objects of this invention can not be attained using such a known method.
• the processing bath of this invention containing the water-soluble zirconium salt and the polycarboxylic acid or a salt thereof can further contain a water? soluble organic acid such as benzoic acid or an alkali metal salt of benzoic acid.
• a suitable level of use ranges from about 0.01 to 10 g/l, preferably 0.1 to 1 g/l, for the benzoic acid or its alkali metal salt.
• the stabilization bath of this invention be used fundamentally after finishing the develop ment steps of color photographic materials, that is to say, after finishing the development, bleaching, and fixing. After processing with the stabilization bath of this invention, the photographic material can be rinsed.
• the development steps for color photographic materials which are employed prior to the use of the stabili zation bath of this invention can be conventional color processes for color photographic materials as disclosed in US. Pat. Nos. 2,515,121; 2,518,686; 2,647,057; 3,140,177; 3,582,322 and 3,676,136.
• the steps include basically the steps of development, bleaching, and fixing as described in, e.g., the publications as described above.
• other embodiments of development steps including a blix step or a stopfix step can be employed.
• any of these steps in the development can be followed by a wash step or another step.
• the stabilization process of this invention can be applied to any color photographic materials but it is preferably applied to color photographic paper which have photographic emulsions containing at least one 4- equivalent or Z-equivalent coupler.
• the pyrazolone couplers giving a magenta dye represented by the following general formula are particularly useful.
• R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group and R represents an alkyl group, a carbamyl group, an amino group, or an amide group.
• Suitable examples of pyrazolones which are suitable are disclosed, for example, in US. Pat. No. 3,582,322.
• the 2-equivalent couplers as disclosed in the specifications of US. Pat. No. 3,582,322 can be used as couplers for color photographic papers processed by the process of this invention.
• the phenolic couplers giving cyan dyes as disclosed in the specifications of U.S. Pat. No. 2,423,730 and US. Pat. No. 2,801,171 can be effectively used.
• the color photographic emulsions for the color photographic materials processed by the process of this invention are those prepared by dispersing a silver halide such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, etc., in a natural or synthetic water-soluble polymer such as gelatin, gelatin derivative (e.g., phthalated gelatin, malonated gelatin, etc.,), colloidal albumin, cellu lose derivatives, etc., for example, as disclosed in US. Pat. No. 3,582,322.
• a silver halide such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, etc.
• a natural or synthetic water-soluble polymer such as gelatin, gelatin derivative (e.g., phthalated gelatin, malonated gelatin, etc.,), colloidal albumin, cellu lose derivatives, etc., for example
• silver halide photographic emulsions can contain, in addition to the aforesaid couplers, conventional additives well known in the photographic art, such as dye sensitizers, antifoggants, stabilizers, hardening agents, coating aids, etc., as desclosed in US. Pat. No. 3,582,322.
• the silver halide emulsion as described above is coated on conventional support such as a barytacoated paper, a polymer-coated paper such as polyolefin coated paper (as disclosed in, eg, the specifications of Japanese Pat. publication No. 19,164/1968 and British Pat. Nos. 1,314,196 and 1,134,197), and a so-called synthetic paper prepared by making opaque a transparent film of a polymer such as polyolefin, cellulose derivative, etc. Furthermore, when the process of this invention is applied to, in particular, color photographic papers, excellent advantages are obtained.
• the stabilization bath used in this invention has the following advantages:
• the stabilization bath does not get musty.
• the stabilization bath has a higher buffer action.
• An extremely important advantage of the color photographic paper processed by the stabilization process of this invention is that the photographic paper shows excellent physical properties when the photograph is stored under various conditions and additionally photographs processed by the stabilization process of this invention have stable images as described above is also an excellent advantage of this invention. That is to say, according to the process of this invention, a color photograph having not only a stable magenta color image but also cyan and yellow color images is obtained. Also, when the photographic papers are preserved under various conditions, less formation of stains is observed.
• the image stability of the photograph processed by the stabilization process of this invention is particularly excellent when the photograph is exposed to hightemperature and high-humidity conditions and also to light. The effects or advantages of this invention are confirmed by referring to the method of Photographic Science and Engineering; 1 l, (5), 295-305 (1967).
• electrostatic charges are formed on the photographic paper to a lesser extent and thus the occurrence of difficulties caused by the formation of static charges can be prevented.
• the photographic paper thus processed can be subjected to hightemperature high-speed ferrotype drying directly and without the necessity of predrying. Furthermore, the drying speed of the color photographic paper processed by the process of this invention is higher than that with pretype-drying a photographic paper processed by the aforesaid known development process and dried in a predrying step. Moreover, the color photographic paper thus dried after processing by the process of this invention has superior gloss to the conventionally processed paper. Also, while electrostatic charges are formed even if the color photographic paper processed by the known development processing is dried by ferrotype drying at a low speed, almost no electrostatic charges are formed in drying the color photographic paper processed by the process of this invention.
• the stabilization bath used in this invention has sufficiently high buffer capacity, satisfactory results can be obtained by conducting the process in any vessel such as a tank, vat, drum, etc.
• the stabilization bath of this invention is particularly suitable for the continuous processing of a large amount of photographic papers.
• a color photographic paper was prepared by applying to a polyethylene-coated paper a silver bromide emulsion containing a yellow coupler emulsified dispersion, a silver chloride emulsion (silver chloride 70 mol percent) containing a magenta coupler emulsified dispersion, a silver chlorobromide emulsion (silver chloride 70 mol percent) containing a cyan coupler emulsified dispersion, and then a gelatin solution containing a ultraviolet absorbent.
• the coupler emulsified dispersion used in the preparation of the color photographic paper was prepared by dissolving each coupler in a mixture of dibutyl phthalate and tricresyl phosphate and then dispersing the solution in a gelatin solution in an o/w type using sorbitan monolaurate, Turkey oil, and sodium dodecylbenzenesulfonate as an emulsifying dispersing agent.
• the color photographic paper thus prepared was exposed using i dIor p r iii ter and then subjected to the following colo rgd ev elopment at temperatures lower than 30.0c.-
• the adjustment of the pH was conducted using sodium hydroxide.
• the fading percentage of the portion having a density of 1.0 and an increased yellow stain density (AD, l) of the color photographic paper when it was stored for 14 days in the dark at 37.8C and a relative humidity of 90% were measured.
• the results obtained are shown in the following table.
• the stabilization baths of this invention was superior in image stability to the known stabilization baths (DF). Also, when the color photographic papers thus processed were preserved for 7 days at 76.7C (the same condition as the drying step), the color photographic papers processed with the stabilization baths of :known stabilization-bath F stuck to each other but no such phenomenon was observed in the other samples.
• this invention showed less in fading of the cyan color under high humidity Conditions image and iess increase in yeiiow Stains as Compared Also, the samples processed'with the known stabilizawith the Color Photographic P p Processed iii the tion bath F became sticky and it was easy to leave finkhowh Stabiiizatioh baths- Furthermore when the gerprints on the samples but no such difficulties were Coior Photographic P p Processed were exposed to encountered with the other samples.
• the time required for finishing the drying scribed in Example 1 for 3 minutes-and 30 seconds at procedure in this case is shown in the following table. 3 c and then Phocessed in h bhx bath having the The ferrotype dryer MR 3D made by japo was lowing composition for 1 minute and 30 seconds: used in this step.
• the amount of electrostatic charges formed in the process- Bath iv Am unt ing with the stabilization baths (A-C) of this invention v G Formaldehyde 5.0g/l was almost same as or less than that of the processing H Acetaidchydc LS /l with the known stabilization baths. Also, the amount i yf y y was the same as that of the processing with the bath 1 tglgs 335: containing zirconium oxysulfate alone.
• the period of time required for finishing the drying step, the degreeof formation of electrostatic charges, and the sticking state under the condition of REFERENCE EXAMPLE A color photographic paper prepared in the same manner as described in Example l was processed ina solution having the following composition for 80 seconds at 38C.
• the color paper was washed for 2 minutes, processed for 2 minutes in a bleach bath having the same composition as described in Example 1, washed for 2 minutes, processed for 4 minutes in a hardening-fix bath having the same composition as described in Ex ample l, and then washed for 4 minutes.
• a stabilization process for a color photographic material having silver halide emulsion layers containing color couplers which react with an oxidation product of a color developer to form color images which comprises processing said color photographic material, after developing and bleaching, with a bath having a pH of 2.7 to 4.5 containing (1) a water-soluble zirconium salt and (2) a polycarboxylic acid or a salt thereof, said stabilization process being the final step in a color development process except for rinsing.
• a stabilization process for a color photographic paper having silver halide emulsion layers containing color'couplers which react with an oxidation product of a color developer to form color images comprises processing said color photographic paper, after developing and bleaching, with a bath having a pH of 2.7 to 4.5 containing a water-soluble zirconium salt and a polycarboxylic acid or a salt thereof, said sta bilization process being the final step in color development process except for rinsing.
• R represents a divalent aliphatic residue, or a divalent aromatic residue
• m is O or 1
• said watersoluble compound having a group capable of forming formaldehyde being a compound represented by the formula R crnon wherein R represents an aliphatic residue, an aromatic residue, or a heterocyclic ring residue.
• polycarboxylic acid is oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, citric acid, glutaric acid, adipic acid, lactic acid, crotonic acid, aconitic acid, itaconic acid, diglycolic acid, citraconic acid, an alkali metal salt of said acid, or an ammonium salt of said acid.
• a stabilization bath for a color photographic paper containing a water-soluble zirconium salt, a polycarboxylic acid, and at least one of a water-soluble compound having an aldehyde group and a watersoluble compound having a group capable of forming formaldehyde.
• the stabilization bath of claim 10 wherein the bath has a pH of 2.7 to 4.5, the water-soluble compound having an aldehyde group is present in the amount of 1.2 X 10 to 1.8 X 10" mol/liter, the watersoluble compound having a group capable of forming formaldehyde is present in an amount of 1.0 X 10 to 1.7 X 10 mol/liter, said water-soluble compound having an aldehyde group is selected from the group consisting of a monoaldehyde compound represented by the formula (R CH0),
• R represents a divalent aliphatic residue, or a divalent aromatic residue
• m is O or 1
• said watersoluble compound having a group capable of forming formaldehyde is represented by the formula R CH OH wherein R represents an aliphatic residue, an aromatic residue, or a heterocyclic ring residue.

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Citations (6)

• 1972
  • 1972-12-13 JP JP47124915A patent/JPS4983441A/ja active Pending
• 1973
  • 1973-12-06 GB GB5671073A patent/GB1411190A/en not_active Expired
  • 1973-12-11 DE DE2361668A patent/DE2361668A1/de not_active Withdrawn
  • 1973-12-13 US US424253A patent/US3909267A/en not_active Expired - Lifetime

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