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
• • 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
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/42—Developers or their precursors

Definitions

• This invention relates to high-contrast, silver-halidesensitized photographic materials for graphic arts use and particularly to lith-type silver halide emulsion layers of improved physical and photographic properties.
• lith films are processed in hydroquinone-type developers which contain relatively low concentrations of sulfite ion.
• the dot quality and the development contrast obtained in processing lith emulsions in such developers can be improved by processing in the presence of certain water-dispersible polymers containing substantial proportions of ethylene oxide units, such as polyethylene oxides, their terminally substituted derivatives, block copolymers containing ethylene oxide units, etc. These can be added either to the photographic element or the developing solution or both.
• colloid binder for lith type emulsions a colloid-compatible vinyl polymer, the presence of which improves the dimensionable stability of the resulting lith film.
• the marked improvement resulting from the use of the ethylene oxide polymer on the contrast and dot quality of the emulsion and that of the vinyl polymers on the dimensional stability of the element may result in certain unwanted effects on other properties such as decreasing the developing rate, impairing the emulsion speed, and narrowing the development latitudes.
• Our invention provides an improved photographic lithtype film material comprising a radiation sensitive hydrophilic colloid silver halide emulsion, an alkyleneoxy polymer, and a S-pyrazolidone.
• an aqueous silver chlorobromoiodide lithographic emulsion containing at least 50% silver chloride and a reduced amount of gelatin is prepared in a manner familiar to those skilled in the art.
• a gelatin-compatible vinyl polymer a polyalkyleneoxy compound and a pyrazolidone silver halide developing agent.
• This preparation is then coated on a suitable film support, dried, sensitometrically exposed, processed in a lith-type developing solution, fixed and dried.
• the fine grain silver halide emulsions used to advantage have silver halide crystals preferably containing at least 50 mole percent chloride.
• the emulsions 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 ortho-sensitized or panchromaticallysensitized.
• 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 Clavier et al. in US. Pat. 2,949,442, issued Aug. 16, 1960, polyvinyl alcohe], 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 Clavier et al. in US. Pat. 2,949,442, issued Aug. 16, 1960
• polymeric gelatin substitutes examples include copolymers of allylamine and methacrylic acid; copolymers of allylamine, acrylic acid and acrylamide; hydrolyzed copolymers of allylamine, methacrylic acid and vinyl acetate; the copolymers of allylamine, acrylic acid and styrene; the copolymers of allylamine, methacrylic acid and acrylonitrile; alkyl acrylate-acrylic acid copolymers, e.g., copolymers of butyl acrylateacrylic acid; etc., and etc.
• Useful compatible vinyl polymers include the following:
• the vinyl polymers are incorporated in the photographic elements of our invention at quantities ranging from approximately 30 to 80 percent of the total emulsion vehicle. In one embodiment in which a gelatin emulsion is employed, the ratio of gleatin to vinyl polymer ranges from 20:80 to 80:20 parts by weight.
• vinyl polymers useful in our invention may include those disclosed in U.S. Pats. No. 1,933,052, patented Oct. 31, 1933 and No. 2,140,048, patented Dec. 13, 1938 and US. AlienProperty Custodian Ser. No. 397,138, published May 11, 1943.
• alkyleneoxy polymers useful in tihs invention are:
• Water-dispersible polyethylene oxides having molecular weights of from approximately 400 to approximately 4,000 are particularly useful polyethylene oxides.
• Particularly useful polyethylene oxides include the following:
• polyglycols include, for example, polyethylene glycol oleyl ether, polyethylene glycol ether, as well as the polyethylene glycols disclosed in US. Pats. Nos. 2,531,832, 2,423,549, and 2,886,437.
• Water-dispersible alkyleneoxy block copolymers containing at least about 30 percent by weight of ethyleneoxy units include those block polymers in which the polyoxypropylene chain (or moiety) has an average molec- 4 ular weight between 800 and 3,000 and in which the polyoxyethylene units constitute from about 10 to about 70 percent by weight of the polymer.
• Y represents an organic radical having a valence of x, said radical being the residue of an organic compound containing atoms selected from the class consisting of carbon, hydrogen, oxygen, nitrogen and sulfur with x active hydrogen atoms, such as, the residue of polyhydroxy compounds, e.g., ethylene glycol, 1,2-propanediol, 1,5 pentanediol, 1,2,3 propanetriol, sucrose etc., the residue of a polybasic acid, e.g., oxalic acid, malonic acid, succinic acid, maleic acid, citric acid, etc.,
• a polyamine e.g., ethylenediamine, 1,3-diaminopropylene, etc.
• the residue of a polyamide e.g., malonamide, succinamide, etc.
• the residue of a polythiol e.g., 1,2-ethylenedithiol, 1,3-propylenedithiol, etc.
• 11 is an integer greater than 1
• x is an integer greater than 1, so that the values of n and x are such that the molecular weight of the said polymer exclusive of Y, E and R is between 800 and 3,000
• E represents a polyoxyethylene chain constituting from about 10 to about 70 percent by weight of said block polymer
• R represents the hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, (such as methyl, propyl, decyl, dodecyl, octadecyl, etc.), an alkyl carbonyl group in which the alkyl groups has from 1 to
• b represents an integer of from 14 to 42; a and c are each integers such that the sum of a+c has a total of from 4 to 48 and the polyoxyethylene groups constitute between 10 and 70 percent by weight of the block polymer.
• the block polymers of Formula II and of Formula I where R represents the hydrogen atom are described in Lundsted US. Pat. 2,674,619, issued Apr. 6, 1954 and Lundsted US. Pat. 3,022,335, issued Feb. 20, 1962.
• the block polymers of Formula I in which R is hydrogen are readily converted to compounds where R represents an organic residue by reaction with the appropriate reagent in a suitable inert organic solvent that is preferably anhydrous.
• alkyl halides such as alkyl chlorides, alkyl bromides, etc., are used to advantage to replace the terminal hydrogen atom of the block polymer with an alkyl group.
• Alkyl-p-toluenesulfonates are also used to advantage to place an alkyl group at the end of the block polymers.
• the appropriate acid chloride or acid anhydride such as, acetyl chloride, propionyl chloride, stearoyl chloride, benzoyl chloride, acetic anhydride, etc., are used to advantage to prepare block polymers of Formula I in which R is an alkyl carbonyl or an aryl carbonyl group.
• Water dispersi ble alkyleneoxy block copolymers containing at least about 30 percent by weight of ethyleneoxy units and containing in their main chain up to approximately 15 percent by Weight silicone atoms.
• Particularly useful water-soluble organosilicone polyalkylene oxide polymers include those disclosed in US. Pat. No. 2,917,480, issued Dec. 15, 1959.
• Polymers used to advantage are of the type which are prepared by reacting a dialkyl siloxane with a compound of the following structure:
• Y is the residue of an organic compound containing therein, x active hydrogen atoms
• n is an integer
• x is an integer greater than 1
• the values of n and x are such that the molecular weight of the compound exclusive of E and R is between 800 and 3,000, and E is a polyoxyethylene chain constituting 70% by weight of the compound
• R is hydrogen or the residue of an organic compound containing an active hydrogen atom; e.g., alcohols, amines. acids, amides, phenols, etc.
• the above alkyleneoxy block copolymers (2 and 3) have molecular weights ranging from approximately 600 to about 10,000.
• the alkyleneoxy polymers may be added to the photographic element at any stage in the preparation. They may be added as such or from an aqueous solution or from an organic solvent, e.g., ethanol, but are advantageously added from solutions in water. They are added to the aqueous hydrophilic colloid (either with or without the silver halide) before it is coated.
• the alkyleneoxy polymers can be used to advantage over a wide. range of concentrations. The operable range of concentrations is from 0.01 to 3.00 gram of polymer per mole of silver, while the particularly useful range is from 0.010 to 1.0 gram per mole of silver.
• the optimum concentration of a given alkylene oxide-containing 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 known in the art. The determination of the optimum concentration is preferably made by employing the alkyleneoxy polymer in the silver halide emulsion layer or in an adjacent hydrophilic colloid layer according to the element that is desired.
• onium Salts such as, quaternary ammonium salts, sulfonium salts and phos phonium salts
• onium Salts such as, quaternary ammonium salts, sulfonium salts and phos phonium salts
• quaternary ammonium salts include nonyl pyridinium perchlorate, hexoxymethyl pyridinium perchlorate, ethylene bis-dioxymethyl pyridiniurn perchlorate and others described by Carroll U.S. 2,271,623, issued Feb.
• 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. U.S. 2,275,727, issued Mar. 10, 1942, such as, n-decyl dimethyl sulfonium p-toluene sulfonate, n-nonyl dimethyl sulfonium p-toluene sulfonate, etc., and the phosphonium salts of Carroll et al. U.S. 2,271,622, issued Feb. 3, 1942, such as, tetramethylene bis-triethyl phosphonium bromide, lauryltriethylphosphonium bromide, etc.
• the onium salts are added to the photographic materials at concentrations ranging from approximately 0.01 to approximately 2.0 gram per mole of silver in the light sensitive emulsions.
• the preferred range is from approximately 0.035 gram to approximately 0.65 gram per mole of silver.
• 3-pyrazolidone to the emulsion containing the onium salt, however, gives a very surprising increase in emulsion speed and this is enhanced further by some apparent synergism between the 3-pyrazolidone and an onium compound.
• the pyrazolidones used to advantage 6 include those disclosed in U.S. Pat. No. 2,751,297 and represented by the following general formula:
• the preferred range is from 0.01 to 1.0 gm./mole of silver.
• Optimum concentrations of the alkyleneoxy polymers and the pyrazolidones can be determined readily by actual tests in the emulsion and will vary with the formulation of thephotographic emulsion and the developer used.
• both the alkyleneoxy polymer and the pyrazolidone are incorporated in the light-sensitive silver halide emulsion. While this is a particulary useful form of the invention, either or both the alkyleneoxy polymer and pyrazolidone may alternatively be present in an adjoining insensitive layer, or one or both can be imbibed from a processing bath, it being required only that both are present during development.
• Our light-sensitive emulsions can be coated to advantage on any of the conventional photographic supports, including glass, cellulose acetate, polystyrene, polyalkyleneterephthalate, etc.
• a typical lith-type developing solution which may be used contains as the only developing agent, hydroquinone or a hydroquinone derivative and having a very low sulfite ion content, the sulfite ion content being maintained by the presence in the solution of formaldehyde.
• Lith-type developing solutions are used for developing lithographic film materials which contain photographic emulsions having an emulsionsof uniform and fine-grain silver halide crystals. Such emulsions are developed in lith-type developing solutions to yield a contrast of 10 and above.
• a typical lith-type developing solution is Kodak De-
• the film samples were then fixed, washed and dried, and the speed, contrast, fog and dot quality evaluated.
• a dot quality scale from 1 to 10 represents increasing quality of half-tone dot with increasing number, 6 being a first acceptable quality of half-tone dot. The results are illustrated in Table I.
• Fog proximately 1 mole percent silver iodide was prepared and split into separate portions. The following compounds were added to the individual portions in the indicated amounts per mole of silver halide:
• EXAMPLE III An emulsion was prepared as described in Example I. The following compounds were added to the individual portions in the indicated amounts per mole of silver halide.
• EXAMPLE V An emulsion was prepared as in Example IV and split into two portions, (a) and (b). To each portion were added, per mole of silver halide, .030 gm. of organosilicone, coply(polyethyleneoxypolypropyleneoxy dimethylsiloxane), mol weight 2000, PPG-PEG 6040, 9.5% by weight silicone. To portion (b) was added, in addition, .015 gm. of 4-methyl-1-pheny1-3-pyrazolidone per mole of silver halide. Each sample was processed and evaluated as in Example I. The results are shown in Table V.
• EXAMPLE VI An emulsion was prepared as in Example IV and split into two portions, (a) and (b). To each portion were added, per mole of silver halide, 0.100 gm. of an organosilicone, a water-soluble polysiloxane made up of dimethyl silicone sections and polyether sections and containing 6.5% by weight of silicone, and .5 gm. of w-hydroxydecylpyridinium-perchlorate. To portion (b) were added, in addition, .015 gm. of 4-methyl-l-phenyl-3-pyrazolidone. Each sample was processed and evaluated as in Example I. The results are shown in Table VI.
• EXAMPLE VllII An emulsion was prepared as in Example IV and split into three portions, (a), (b), and (c). To portion (a) were added per mole of silver halide, .025 gm. of a block copolymer of polyethyleneoxide and polypro'pyleneoxide units having a total molecular weight of 2000 and wherein the molecular weight of the polypropyleneoxide constituent is 1200 and wherein the ratio by weight of the polyethyleneoxide to polypropyleneoxide is 60 to 40; to portion (b), .025 gm.
• EXAMPLE IX An emulsion was prepared as in Example I wherein the vehicle comprised, per mole of silver halide, 70 gm. of gelatin and 70 gm. of copoly(butyl acrylateacrylic acid- 4,4,9 trimethyl 8-oxo-7-oxa-4--azonia-9-decene-l-sulfonate). The emulsion was split into two portions, (a) and (b). To each portion were added, per mole of silver halide, .075 gm. of the block polymer A of Example VIII and .500 gm. of w-hydroxydecyl pyridinium-perchlorate. To portion (b) were added, in addition, .015 gm. of 4- methyl-1-pheny1-3-pyrazolidone. Each sample was processed and evaluated as in Example I. The results are shown in Table IX.
• the advantageous efifeot of the 3-pyrazolidone with respect to speed and contrast is retained when the vinyl polymer concentration in the emulsion vehicle is increased to constitute 50 percent of the total vehicle.
• EXAMPLE XI One film sample of each coating made with emulsion portions A and B of Example X was incubated for 1 week at 120 F. and 50% relative humidity. Each of the incubated samples was, together with a nonincubated corresponding sample, immersed at a temperature of 68 F. for 4 minutes into a developing solution of the following composition:
• film strips were prepared according to the procedures described in the preceeding examples. They comprised, in addition to silver halide and other common addenda, the following compounds per mole of silver halide:
• Block polymer A of Example VIII grams Developer Strip A 0. 025 4-methyl-l-phenyl-3-pyrazolidone,
• Strips A, B, and C were developed in the developer solution of Example I.
• Strip D- was developed in the developer soution of Example I to which were added 5 gm. of 4-methyl-1-phenyl-3-pyrazoidone per liter of solution. The development time was in each case 1% minutes.
• Fog Effective Contrast of a developed photographic material differs from the conception of contrast which is in the photographic art generally synonymous with only the slope of the straightline portion of the characteristic curve, in that the slope of the characteristic curve in the toe region is also taken into account.
• two diiferent photographic materials may exhibit identical contrasts, but the one whose characteristic curve shows also a more acute shape of the curve in the toe region has a higher effective contrast.
• the quality of the silver images produced in lithtype emulsion layers is conveniently measured in terms of efiective contrast and dot quality.
• Dot quality is a measure of the quality of the reproduction of a halftone image lith-type photographic elements exposed to a half-tone image, and developed, produce areas commonly referred to as shadow dots and areas known as highlight areas. Intermediate between these two extremes are areas of varying size.
• the dot quality used herein is a measure of the areas referred to as 50% dots Ge, /2 clear, and V2 developed denisty) and is expressed in a progressive scale where 9 is excellent and 1 is extremely poor. A 50% dot quality below 6 is generally not acceptable.
• Typical olymeric vinyl compounds useful in our invention are disclosed in.U. S. P at; 3,142,568, issued July 28, 1964, incorporated herein 'byL-ref erence'.
• a light-sensitive photographic element comprising a support having thereon at least one light-sensitive silver halide emulsion in which the chloride comprises at least 50 mole percent of the halide, containing a hydrophilic colloid binder, a polyalkyleneoxy polymer in amount of about 0.01 gram to about 3.0 grams per mole of silver halide, and a 3-pyrazolidone silver halide developing agent in an amount of about 0.005 gram to about 2.0 grams per mole of silver halide.
• a light sensitive photographic containing an onium salt 4.
• a light sensitive photographic element of claim 2 containing an aqueous dispersion of a polymerized vinyl compound.
• a light sensitive photographic element of claim 2 comprising an aqueous dispersion of a polymerized vinyl compound and an onium salt.
• a light sensitive photographic element of claim 2 in which said support is a dimensionally stable polymeric support and said element comprises an aqueous dispersion of a polymerized vinyl compound and an onium salt.
• the vinyl polymer comprises an acrylic acid-ester polymeric compound selected from the group consisting of a homopol mer of an acrylic acid-ester and a copolymer of ac. lic acid-ester and acrylic acid, said copolymer containing at least 80% by weight of units of said acrylic acid esters.
• the vinyl polymer comprises an interpoly-mer selected from the group consisting of acrylic acid, unsaturated carboxylic acid esters and sulfobetaines, said interpolymer containing (1) up to about by weight, of acrylic acid, (2) at least about 75%, by weight of a monomer having the formula:
• R is hydrogen or methyl and R is an alkyl radiions and modifications 14 cal, containing 1-12 carbon atoms, with (3) up to about 10%, by weight, of a monomer having the formula:
• R- is hydrogen or alkyl
• R and R are each divalent saturated aliphatic hydrocarbon radicals, containing up to 12 carbon atoms, and R and R are each hydrogen or alkyl.
• polyalkyleneoxy polymer is a block polymer of polyoxypropylene" and polyoxyethylene represented by the formula: p
• Y represents an organic radical having a valence of x
• n is an integer
• x is an integer'greater than 1, so that the values of n and x are such that the molecular weight of the said polymer exclusive of Y, E and R is between 800 and 3,000
• B represents a polyoxyethylene chain constituting from about 10 to about 70 percent by weight of said polymer
• R is a member selected from the class consisting, of the hydrogen atom, an alkyl group, an alkyl carbonyl group, and an aryl carbonyl group.
• polyalkyle'neoxy polymer is a block copolymer of polyoxypropylene and polyoxyethylene represented by the formula:
• b represents an integer of from 14 to 52; and a and c each represent integers such that the sum of a+c represents an integer of from 4 to 48 and the polyoxyethylene groups constitute between 10 and 70 percent by weight of said polymer.
• a photographic element of claim 11 in which the copolymer of polyoxypropylene and polyoxyethylene contains in the main chain silicone atoms at concentration ranges to approximately 15% by weight, of the polymer compound.
• a photographic element of claim 12 in which the copolymer of polyoxypropylene and polyoxyethylene contains in the main chain silicone atoms at concentrations ranging up to approximately 15%, by weight, of the polymer compound.
• R represents a heterocyclic group or an aryl group of the benzene or naphthalene series and R represents hydrogen, an aryl group of the benzene or naphthalene series, or an alkyl group, and R and R each represents hydrogen or an alkyl group.
• the polymerized vinyl compound comprises an acrylic acidester polymeric compound selected from the group consisting'of a homopolymer of an acrylic acid-ester, and a copolymer of acrylic acid-ester and acrylic acid, said copolymer containing at least 80% :by weight of units of said acrylic acid-esters.
• a photographic element of claim 5 in which the polymerized vinyl compound comprises an interpolymer selected from the group consisting of acrylic acid, unsaturated carboxylic acid-ester and sulfobetaines, said interpolymer containing (1) up to about 15%, by weight, of acrylic acid, (2) at least about 75%, by weight, of a monomer having the formula:
• R is hydrogen or methyl and R is an alkyl radical, containing 1-12 carbon atoms, with (3) up to about by weight, of a monomer having the formula:
• R is hydrogen or alkyl, R; and R are each divalent saturated aliphatic hydrocarbon radicals, containing up to 12 carbon atoms and R and R are each hydrogen or alkyl.
• a photographic element of claim 15 in which the concentration of said polyethyleneoxy polymer present in said emulsion ranges from 0.001 to 3.0 grams per mole of silver halide.
• a process of developing an exposed photographic silver halide emulsion in which the halide comprises at least mole percent chloride comprising imbibing into the said emulsion about 0.01 gram to 3.0 grams per mole of silver halide of a polyalkyleneoxy polymer and about 0.005 gram to about 2.0 grams per mole of silver halide of a 3-pyraz0lidone silver halide developing agent, and reducing the exposed silver halide to silver.

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Cited By (10)

Citations (5)

• 1965
  • 1965-09-23 US US489736A patent/US3518085A/en not_active Expired - Lifetime
• 1966
  • 1966-09-13 BE BE686827D patent/BE686827A/xx unknown
  • 1966-09-22 DE DE1547734A patent/DE1547734C3/de not_active Expired
  • 1966-09-23 GB GB42689/66A patent/GB1164494A/en not_active Expired

Patent Citations (5)

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