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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides

Definitions

• Photographic films used in the graphic arts for making halftone or line images should be capable of producing extremely high contrast and good image sharpness. These factors contribute in the case of half-tone images to high dot quality, that is, to the production of halftone dots of high density and sharpness.
• Photographic elements of the lith-type typically comprise fine-grain, high-contrast silver halide emulsions whose halides contain at least 50 mole percent chloride, and which are processed customarily in alkaline hydroquinone developing solutions having very low concentration of free sulfite ion in order to produce the high contrast and high dot quality required for good quality halftone reproduction.
• Such developing solutions are unstable, having very short tray or tank life during exposure to air, so the solutions must be prepared fresh before they are to be used for processing.
• suflicient free sulfite ion can be added to the developer to give a stable single solution; yet the contrast and halftone dot quality are as high as normally seen in emulsions containing polyethylene glycol and developed in a low sulfite, hydroquinone developer.
• an object of my invention to provide a photographic film which produces high contrast and high halftone dot quality even when developed with a developer solution having sufiiicently high free-sulfite content to insure good stability upon prolonged exposure to air in tray or tank.
• Another object is to provide a photographic element which is capable of producing high contrast, high quality halftone images over a relatively broad range of film exposure and development times.
• Another object is to provide a photographic element which develops evenly.
• photographic elements comprising a support, at least one hydrophilic colloidal fine-grain photographic silver halide emulsion layer whose halide is comprised of at least mole percent of chloride, and either contiguous to the silver halide or integral therewith, certain water-soluble silicone-containing polyalkylene block polymers.
• Water-soluble organosilicone polyalkyleneoxide polymers used to advantage according to my invention include those disclosed in US. Pa'tent No. 2,917,480, issued December 15, 1959, assigned to Union Carbide Corporation.
• Y is an organic radical having a valence of x
• n is an integer
• x is an integer greater than 1
• the values of n and x are such that the molecular weight or the compound, exclusive of E, Y and R is between 800 and 3,000
• E is a polyoxyethylene chain constituting about 1070 percent by weight of the compound
• R is a hydrogen atom or the residue of an organic compound containing an active hydrogen atom, such as, an alkyl, carbonyl, or aryl carbonyl group, e.g., alcohols, amines, acids, amides, phenols, etc.
• the conventional alkaline, pure hydroquinone, low free-sulfite developer may be used to develop my exposed element.
• a developer having from 10 to about 30 grams of an alkali sulfite per liter of the developer solution.
• My elements are particularly valuable when developed with a stable dihyd-roxybenzene developer with a high free sulfite ion concentration in an alkaline solution. My elements provide the following advantages:
• the organosilicone block polymers used according to my invention are water soluble and are advantageously added in a water solution to the aqueous hydrophilic colloid (either with or without the silver halide) before it is coated.
• the organosilicone block polymers are used to advantage over a wide range of concentrations.
• operable range of concentrations is from .001 to 1.00 gram of block polymer per mole of silver, while the preferred range is from 0.010 to 0.200 gram per mole of silver.
• the optimum concentration of a given block polymer used in my elements depends upon the results desired, the particular silver halide emulsion, the developer solution, etc., and is readily determined by methods well known in the art. The determination of the optimum concentration is preferably made by employing the organosilicone block polymer in the silver halide emulsion layer or in an adjacent hydrophilic colloid layer according to the element that is desired.
• Typical fine grain silver halide emulsions used to advantage can be prepared as described by MacWilliam US. 2,756,148 issued July 24, 1956. These emulsions may be used without being sensitized; however, it is advantageous to spectrally sensitize them according to methods well known in the art to make them orthochromatically-sensitized or panchromatically-sensitized.
• the silver halide is dispersed in hydrophilic colloid materials used as binders, including gelatin, collodion, gum arabic, cellulose ester derivatives, such as alkyl esters of carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose, synthetic resins, such as the amphoteric copolymers described by C'lavier et al. in US. Patent 2,949,442, issued August 16, 1960, polyvinyl alcohol, and others well known in the art.
• hydrophilic colloid materials used as binders including gelatin, collodion, gum arabic, cellulose ester derivatives, such as alkyl esters of carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose, synthetic resins, such as the amphoteric copolymers described by C'lavier et al. in US. Patent 2,949,442, issued August 16, 1960, polyviny
• any of the hydrophilic colloids described hereinbefore may be used to advantage as a binder for coating my polymers.
• quaternary ammonium salts examples include nonyl pyridinium perchlorate, hexoxymethyl pyridinium perchlorate, ethylene bis-dioxymethyl pyridinium perchlorate and others described by Carroll U.S.
• 2,288,226, issued June 30, 1942 such as bis(lauryl methyl sulfonium p-toluene sulfonate) 1,2-ethane, N,N'-trimethylene dioxymethyl pyridinium perchlorate, etc., the sulfonium salts of Carroll et al. US. 2,275,727, issued March 10, 1942, such as n-decyl dimethyl sulfonium ptoluene sulfonate, n-nonyl dimethyl sulfonium p-toluene sulfonate, etc., and the phosphonium salts of Carroll et al. US. 2,271,622, issued February 3, 1942, such as tetramethylene bis-triethyl phosphonium bromide, lauryltriethylphosphonium bromide, etc.
• My light-sensitive emulsions can be coated to advantage on any of the conventional photographic supports, including glass, cellulose acetate, polystyrene, polyalkyleneterephthalate, etc.
• the organosilicone block polymers can be coated advantageously in the silver halide emulsion layer or in a hydrophilic colloid layer that is either under or over the silver halide emulsion layer so that the block polymer is contiguous to the silver halide.
• organosilicone block polymers used to illustrate my invention are those which may be prepared by reacting a polypropylene oxide-polyethylene oxide block polymer with dimethyl siloxane to give a copolymer having the following general structure:
• M is a polyethyleneoxy chain constituting approximately 10-70% by weight of [(M),,(N) N is a polypropyleneoxy chain having a molecular weight between approximately 800 and 3000, and wherein x, y and n arepositive integers as shown in Table A.
• Organosilicone l and polyether sections containing 6.5% by Weight of silicone.
• PE G Oleyl ether of polethyleneglyeol having a molecular weight of 1,540.
• Organosilicone II A water-soluble polysiloxane composed of dimethyl siloxane sections and block polymers of ethylene oxide and propyleneoxide, containing 8.2% by weight of silicone.
• TTlalitone Dot Quality-Dot quality is a measure of the quality of the reproduction of a halltone image. and developed, highlight areas.
• dot quality used herein is a measure of the areas referred to as dots (i.e., clear and developed density) and is expressed extremely poor. A dot quality below 6 is generally not acceptable.
• Example II By varying the concentration of the water-soluble polyalkylene oxide-dialkyl siloxanes, it also is possible to make materials having relatively small changes in speed with development time. This characteristic is particularly advantageous in automatic processing equipment where the activity of the developer may vary with aging or other variables may be present which affect the devel- K against time.
• Example III The coatings in the following examples were prepared like those previously described and were processed in a high sulfite pure hydroquinone lith developer of the following type which is more stable to oxidation than the low uulfite developers normally used, but which usually gives poorer dot quality.
• Example VI ots 5
• An emulsion as described in Example I was divided PEG n5 6 6 6 2 into two portions one of which was retained as a control, Block DCIVI I'ICIZTIII 1020 7 7% 714 while to the other portion were added, per mole of silver orgmllslncone n 7 8 8A halide, .200 gm. of the organosilicone I of Example 1. Both portions were then coated and processed according Polyethyleneglycol of Example 1.
• Example 3 A copolymer composed of blocks of polyethylene oxide to the procedures In Example I and poly propyleneoxide having a total molecular weight of The results are shown in Table VI. 2,000 and wherein the ratio by weight of said blocks is 60 to 40, respectively. TABLE VI Organosilicone II (see Example I).
• Example IV Efiective Contrast Dot Quality I Dev. Time Fog
• the coatings in this example were prepared like those Control Sam 16 1 Contr 1 Sam 1 1 previously described and were processed in the developp0 ing solution of Example I.
• the results tabulated in Table 8 0 10 0 6 8 0 01 IV below illustrate how the image quality obtained with 5 3 8 1 coatings containing a silicone-containing polyethyleneoxy -2 12-3 1 8.8 ⁇ copolymer remains good over a long development range 1 1 and that it is better than that obtained with the related block copolymer from which it was synthesized.
• Example V The following example illustrates the improvement obtained from the addition of a quaternary ammonium salt to a high-contrast silver chlorobromide emulsion containing 10 gm. of a water-soluble polyalkylene-oxideinto equal parts.
• a quaternary ammonium salt to a high-contrast silver chlorobromide emulsion containing 10 gm. of a water-soluble polyalkylene-oxideinto equal parts.
• Each sample was coated and tested as in Examcontrast, they tend to reduce speed. It has been found, pie I. The results obtained are shown in Table VII.
• Example VIII This is a repeat of Example VII. The results are recorded in Table VIII.
• Example X In each case, the polymers were add-ed to separate portions of a silver chlorobromoi-odide emulsion containing approximately 90 mole percent chloride, 9 mole percent TABLE VIII Effective Contrast Dot Quality Fog Development Time 1.75 2.75 3.75 4.75 1.75 2.75 3.75 4.75 4.75 4.75
• Copolymer A copolymer of Carbowax 4000 and polydimethyl siloxane.
• Copolymer B copolymer of Carhowax 1000 and polydimethyl siloxane.
• Example I a control containing mg. of the oleyl ether of polyethylene glycol per silver mole were each developed to optimum contrast in a developer containing a high level of sulfite ion of the following composition:
• Example XI The following coatings were prepared and processed as described in previous examples. The coatings were developed for 3% minutes in the developing solution of Ex ample I.
• block copolymers of this invention are usefully incorporated in the photographic emulsion or in an adjoining insensitive layer, the block copolymers can be imbibed from a processing bath, it being required only that the block copolymer be present during development.
• a photographic silver halide emulsion in which the halide comprises at least 50 mole percent chloride said emulsion containing a block copolymer comprising blocks of polyoxyethylene and polyoxypropylene, about 10 to about 70%, by Weight, of said copolymer being polyoxyethylene and the average molecular weight of polyoxypropylene in said copolymer being in the range of about 800 to about 3,000, said block copolymer containing up to about percent, by weight, of silicon atoms in the main polymer chain.
• a photographic silver halide emulsion in which the halide comprises at least 50 mole percent chloride said emulsion containing a polymer prepared by reacting a dialkyl siloxane with a block copolymer comprising blocks of polyoxyethylene and polyoxypropylene, about 10 to about 70% by weight of said copolymer being polyoxyethylene and the average molecular weight of the polyoxypropylene in said copolymer being in the range of about 800 to about 3,000, said block copolymer having the formula:
• Y is an organic radical having a valence of x; n is an integer; x is an integer greater than 1, the values of n and x being such that the molecular weight of said copolymer exclusive of Y, E and R is in the range of about 800 to about 3,000; B being a polyoxyethylene chain constituting from about 10 to about 70% by weight of said copolymer and R is a hydrogen atom, an alkyl group, an alkyl carbonyl group or an aryl carbonyl group.
• Y is an organic radical having a valence of x; n is an integer; x is an integer greater than 1, the values of n and x being such that the molecular weight of said copolymer exclusive of Y, E and R is in the range of about 800 to about 3,000; E being a polyoxyethylene chain constituting from about 10 to about 70% by weight of said copolymer and R is a hydrogen atom, an alkyl group, an alkyl carbonyl group or an aryl carbonyl group.
• M is a polyethyleneoxy chain constituting about 10 to about 70% by weight of wherein a and b are positive integers
• M is a polyethyleneoxy chain constituting about 10 to about 70% by weight of
• N is a polypropylene chain having a molecular weight between about 800 and 3,000, and wherein x, y and n are positive integers, and n has a value of 1 to 8.
• M is a a poly- 13 ethyleneoxy chain consistuting about to about 70% by weight of N is a polypropyleneoxy chain having a molecular weight between about 800 and 3,000, and wherein x, y and n are positive integers, and the ratio of xzy is from 2:1 to 1:1.
• a photographic element comprising a support having thereon a photographic silver halide emulsion layer in which the halide comprises at least 50 mole percent chloride, said emulsion containing a water-soluble block copolymer comprising blocks of polyoxyethylene and polyoxypropylene, about 10 to about 70% by weight of said copolymer being polyoxyethylene and the average molecular weight of the polyoxypropylene in said copolymer being in the range of about 800 to 3,000, said block copolymer containing up to about percent by weight of silicon atoms in the main polymer chain.
• a photographic element comprising a support having thereon a photographic silver halide emulsion layer in which the halide comprises at least 50 mole percent chloride, said emulsion containing a polymer prepared by reacting a dialkyl siloxane With a water-soluble block copolymer comprising blocks of polyoxyethylene and polyoxypropylene, about 10 to about 70% by weight of said copolymer being polyoxethylene and'the average molecular Weight of the polyoxypropylene in said copolymer being in the range of about 800 to 3,000, said block copolymer having the formula:
• Y is an organic radical having avalence of x; n is an integer; x is an integer greater than 1, the values of n and x being such that the molecular weight of said copolymer exclusive of Y, E and R is in the range of about 800 to 3,000; E being a polyoxethylene chain consituting from about 10 to about 70% by weight of said copolymer and R is a hydrogen atom, an alkyl group, an alkyl carbonyl group or an aryl carbonyl group.
• a photographic element comprising a support having thereon a silver halide emulsion in which the halide comprises at least 50 mole percent chloride, said emulsion containing about .001 to about 1 gram per mole of silver halide, of a polymer prepared by reacting a dialkyl siloxane with a water-soluble block copolymer comprising blocks of polyoxyethylene and polyoxypropylene, about 10 to about 70% by weight of said copolymer being polyoxyethylene and the average molecular weight of the polyoxypropylene in said copolymer being in the range of about 800 to about 3,000, said water-soluble block copolymer having the formula:
• Y is an organic radical having a valence of x; n is an integer; x is an integer greater than 1, the values of n and x being such that the molecular weight of said copolymer exclusive of Y, E and R is in the range of about 800 to about 3,000; E being a polyoxyethylene chain constituting from about 10 to about 70% by weight of said copolymer and R is a hydrogen atom, an alkyl group, an alkyl carbonyl group or an aryl carbonyl group.
• a photographic element comprising a support having thereon a photographic silver halide emulsion layer in which the halide is at least 50 mole percent chloride, said support having thereon at least one other layer, and incorporated in at least one layer of said element, a watersoluble block copolymer comprising blocks of polyoxyethylene and polyoxypropylene, about 10 to about 70% by weight of said copolymer being polyoxyethylene and the average molecular weight of polyoxy-propylene in said copolymer being in the range of about 800 to about 3,000, said block copolymer containing up to about 15% by weight of silicon atoms in the main polymer chain.
• a photographic element comprising a support having thereon a photographic silver halide emulsion in which the halide comprises at least 50 mole percent chloride, said support having thereon at least one other layer, and incorporated in at least one layer of said element, about .001 to about 1 gram, per mole of silver halide, of a water-soluble block copolymer comprising blocks of polyoxyethylene and polyoxypropylene, about 10 to about 70% by weight of saidl copolymer being polyoxethylene and the average molecular Weight of polyoxypropylene in said copolymer being in the range of about 800 to about 3,000, said block copolymer containing up to about 15% by weight of silicon atoms in the main polymer chain.
• a photographic element comprising a support having thereon a photographic silver halide emulsion layer in which the halide comprises at least 50 mole percent chloride, said support having thereon at least one other layer, and incorporated in at least one layer of said element a polymer prepared by reacting a dialkyl siloxane with a Water-soluble block copolymer comprising blocks of polyoxyethylene and polyoxypropylene, about 10 to about 70% by weight of said copolymer being polyoxyethylene and the average molecular weight of the polyoxypropylene in said copolymer being in the range of about 800 to about 3,000, said block copolymer having the formula:
• Y is an organic radical having a valence of x; n is an integer; x is an integer greater than 1, the values of n and x being such that the molecular weight of said copolymer exclusive of Y, E and R is in the range of about 800 to about 3,000; E being a polyoxyethylene chain constituting from about 10 to about 70% by weight, of said copolymer and R is a hydrogen atom, an alkyl group, an alkyl carbonyl group or an aryl carbonyl group.
• a photographic element comprising a support having thereon a photographic silver halide emulsion layer in which the halide comprises at least 50 mole percent chloride, said support having thereon at least one other layer, and incorporated in at least one layer of said element, about .001 to about 1 gram, per mole of silver halide, of a polymer prepared by reacting a dialkyl siloxane with a water-soluble block copolymer comprising blocks of poly oxyethylene and polyoxypropylene, abuot 10 to about 70% by weight of said copolymer being polyoxyethylene and the average molecular weight of the polyoxypropylene in said copolymer being in the range of about 800 to about 3,000, said block copolymer having the formula:
• Y is an organic radical having a valence of x; n is an integer; x is an integer greater than 1, the values of n and x being such that the molecular weight of said copolymer exclusive of Y, E and R is in the range of about 800 to about 3,000; B being a polyoxyethylene chain constituting from about 10 to about 70% by weight of said copolymer and R is a hydrogen atom, an alkyl group, an alkyl carbonyl group or an aryl carbonyl group.
• a photographic silver halide emulsion in which the halide comprises at least 50 mole percent chloride said emulsion containing a polymer prepared by reacting a dialkyl siloxane with a water-soluble block copolymer comprising blocks of polyoxyethylene and polyoxypropyl- 15 ene, about to about 70% by weight of said copolymer being polyoxyethylene and the average molecular weight of the polyoxypropylene in said copolymer being in the range of about 800 to about 3,000, said water-soluble block copolymer having the formula:
• Y is an organic radical having a valence of x; n is an integer; x is an integer greater than 1, the values of n and x being such that the molecular weight of said copolymer exclusive of Y, E and R is in the range of about 800 to about 3,000; E being a polyoxyethylene chain constituting from about 10 to about 70% by weight of said copolymer and R is a hydrogen atom, an aklyl group, an alkyl carbonyl group or an aryl carbonyl group, said emulsion containing a compatible speed-increasing onium salt.
• a photographic element comprising a support having thereon a silver halide emulsion in which the halide comprises at least 50 mole percent chloride, said emulsion containing about .001 to about 1 gram per mole of silver halide, of a water-soluble block copolymer having the wherein a and b are positive integers, M is a polyethyleneoxy chain constituting about 10 to about 70% by weight N is a polypropyleneoxy chain having a molecular weight between about 800 and 3,000, and wherein x, y and n are positive integers.
• a photographic element comprising a support having thereon a photographic silver halide emulsion in which the halide comprises at least 50 mole percent chloride, said support having thereon at least one other layer, and incorporated in at least one layer of said element, about .001 to about 1 gram per mole of silver halide of a water-soluble block copolymer having the formula:
• M is a polyethyleneoxy chain constituting about 1070% by weight of N is a polypropyleneoxy chain having a molecular weight between about 800 and 3,000, and wherein x, y and n are positive integers.
• a photographic element comprising a support having thereon a silver halide emulsion in which the halide comprises at least 50 mole percent chloride, said emulsion containing about .001 to about 1 gram per mole of silver halide, of a water-soluble block copolymer having the following formula:
• a process of developing an exposed photographic silver halide emulsion in which the halide comprises at least 50 mole percent chloride comprising imbibing into the said emulsion a block copolymer comprising blocks of polyoxyethylene and polyoxypropylene, about 10 to about by Weight, of said copolymer being polyoxyethylene and the average molecular weight of polyoxypropylene in said copolymer being in the range of about 800 to about 3,000, said block copolymer containing up to about 15 percent, by weight of silicon atoms in the main polymer chain, and reducing the exposed silver halide to silver by means of a silver halide reducing agent.
• a photographic silver halide emulsion in which the halide comprises at least 50 mole percent chloride, said emulsion containing saponin and a block copolymer comprising blocks of polyoxyethylene and olyoxypropylene, about 10 to about 70% by weight of said copolymer being polyoxyethylene and the average molecular weight of polyoxypropylene in said copolymer being in the range of about 800 to about 3,000, said block copolymer containing up to about 15% by weight of silicon atoms in the main polymer chain.

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• Physics & Mathematics (AREA)
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Cited By (5)

• 1965
  • 1965-09-17 US US488244A patent/US3294537A/en not_active Expired - Lifetime
• 1966
  • 1966-09-05 BE BE686438D patent/BE686438A/xx unknown
  • 1966-09-16 DE DE19661547732 patent/DE1547732A1/de active Pending
  • 1966-09-16 GB GB41502/66A patent/GB1163726A/en not_active Expired

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