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
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
  • B65B19/00—Packaging rod-shaped or tubular articles susceptible to damage by abrasion or pressure, e.g. cigarettes, cigars, macaroni, spaghetti, drinking straws or welding electrodes
  • B65B19/02—Packaging cigarettes
  • B65B19/04—Arranging, feeding, or orientating the cigarettes
  • B65B19/10—Arranging cigarettes in layers each comprising a predetermined number

Definitions

• This invention relates to photographic emulsions and more particularly to photographic emulsions of the silver halide type.
• a difficulty encountered with the aforesaid method is that the surface active substances appear to diffuse to a greater or lesser degree from the emulsions into the film supports upon which the emulsions are usually coated, i. e., the ordinary film supports of plastic materials, such as cellulose nitrate, cellulose acetate or polyvinyl acetate resin for example, with the result that their effect on the photographic emulsion may be decreased.
• plastic materials such as cellulose nitrate, cellulose acetate or polyvinyl acetate resin for example
• polyonium salts whether of the surface active type or not
• the group consisting of quaternary ammonium, quaternary phosphonium and ternary sulfonium salt groups sensitize photographic silver halide emulsions (whether spectrally sensitized or not) and have the added advantage of not diffusing appreciably from the emulsions into the film support upon which the emulsions are usually coated.
• the polyonium salts act on the emulsion in unknown manner to increase its effective sensitivity.
• the sensitivity is increased by about the same amount at any wavelength within the range of its spectral sensitivity, although in spectrally sensitized emulsions there is frequently observed an appreciable increase in relative sensitivity for longer wavelengths.
• the supersensitizing effect is confined more or less to a single spectral region, the supersensitization attained in our new emulsions extends throughout I the entire region in which the spectral sensitizer acts, (and is fairly uniform in degree throughout the entire region), while at the same time the sensitivity in the violet and blue region (where the spectral sensitizer does not act) it is also enhanced to about the same degree.
• An object of our invention is to provide new photographic emulsions.
• R2 represent alcohol radicals, such as methyl, ethyl, n-primarybutyl, isoamyl, lauryl, or benzyl for example
• Q represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus, such as a pyridine nucleus, 9.
• X represents an anion (or acid radical), such as halide, p-toluenesulfonate, alkylsulfate or perchlorate for example and Z represents a bivalent organic radical such as the following for example:
• vis. bis is used for like molecules united by a bivalent organic radical.
• the compound is a bis compound whether the bivalent organic radical is, in itself, symmetrical or unsymmetrical.
• R and R represent alkyl groups and X represents an acid radical.
• the polyammonium salts are superior to the polyphosphonium and polysulfonium salts.
• the bis pyridinium quaternary salts, the his dimethylbenzylammonium quaternary salts and the bis diethylbenzylammonium quaternary salts are especially advantageously employed.
• the anion of the salt may be any anion, such as chloride, bromide, iodide, p-toluenesulfonate, perchlorate or alkylsulfate for example.
• halide anions introduction of halide anions into photographic silver halide emulsions alters the halide concentration in the emulsion and compensating changes in the emulsion may be desirable, if such ammonium salts are employed.
• polyonium salts containing anions other than halides Perchlorates and .p-toluenesulfonates are advantageously employed.
• the polyonium salts are incorporated in the emulsions in any suitable form, e. g. in the form of a solution in a suitable solvent, such as water or methyl alcohol.
• a suitable solvent such as water or methyl alcohol.
• the polyonium salts should be thoroughly incorporated in the emulsion.
• the polyonium salt can .be incorporated in the emulsion before, simultaneously with or after the sensitizing dye, although in some cases as hereinafter set forth, it is advantageous to incorporate the sensitizing dye before incorporating the polyonium salt.
• the methods of incorporating sensitizing dyes in emulsions are, of course, well known to those skilled in the art. Ordinarily, it is advantageous to employ a solution of the sensitizing dye in a suitable solvent, e. g. methyl alcohol; ethyl alcohol or acetone may be employed in cases where the solubility of the sensitizing dye in methyl alcohol is very low.
• sensitizing dyes are ordinarily incorporated in the washed, finished emulsions, and in accordance with our invention, the polyonium salts are advantageously also incorporated in the washed, finished emulsions.
• onium salts can be added to the emulsion during the preparation thereof, i. e. during the precipitation, the first digestion or the second digestion (ripening). After preparing the emulsions in the presence of the polyonium salts, the sensitizing dyes can be incorporated in the so-prepared emulsions.
• polyonium salts which may be used in our invention, as apparent from the foregoing generic description of these salts, may specifically include various elements and be. of several different chemical structures. Also, these polyonium salts may be produced by a number of However, the poly-- methods. The polyonium salts of this invention may be obtained from various sources, assuming, of course, they are of high purity and are otherwise satiaiactory for photographic use.
• Bis quaternary ammonium and phosphonium salts of the character set forth above can be prepared by reacting a tertiary amine or a tertiary phosphine with an ester of a dihydric alcohol as the ester of halogen acids, p-toluene sulfonic acid, etc., halides or di-p-toluenesulfonates being advantageously employed.
• Typical dihalides are those corresponding to the above bivalent radicals, e. g.
• Typical tertiary amines which can be reacted readily with such alkyl salts of dihydric alcohols are pyridines (including the ordinary pyridine as well as substituted pyridines, e. g., e-picoline and a-(n-110Ily1) -pyridine) N-methylpiperidine, 1-,
• 2.Tetramethylene-bis-orymethyl-triethylphosphonium bromide 6 parts of triethylphosphine and 6 parts of decamethylene bromide were mixed together and the mixture warmed slightly. A vigorous reaction set in and a white solid separated. After cooling, the reaction product was dissolved in 20 'parts of methyl alcohol and the resulting solution allowed to stand until the bulk of the alcohol had evaporated. The residue was diluted with 20 parts of diethyl ether and the white crystal,- line material which formed was filtered off and dried in the air. It melted at 158 C.
• Ethylenedioxymethyl-a picolinium perchlorate is an oil which fails to solidify. It was separated from the aqueous-alcoholic mother liquors, washed with ether to remove any unchanged reactants and the last traces of ether removed by heating for a few minutes on the steam bath.
• the useful salts of such type compounds would preferably be the perchlorate or sulfonate, as already described. However, other derivatives. such as the bromide and the like may be employed. Examplesof useful salts are as follows:
• EXAMPLE 6 Ethylene-bis-Z-methylpyrinzidazolium p-toluenesullonate Two and seven tenths parts of Z-methylpyrimidazole and 3.7 parts of bis-ethylene-p-toluenesulfonate were heated for 2 hours at 125 to 130 C. During this heating the reaction mixture solidified. At the end of this time, the reaction mixture was dissolved in hot alcohol, flltered-and precipitated from the cold filtrate by the gradual addition of ether. The yield of solid was 4.5 parts, melting at 268 to 270 C.
• the perchlorates may be obtained by reacting a solution, as, for example, an alcoholic solution of the salt to be converted, with an alkali perchlorate, such as sodium perchlorate.
• the quantity of polyonium salt which is most advantageously employed varies with the nature of the polyonium salt and with the nature of the emulsion. In most instances, a satisfactory concentration was found to be between about 20 mg. and 200 mg. of the polyonium salt per grammole of silver halide in the emulsion, although greater or smaller concentrations could be employed. We have found, however, that too large quantities of the polyonium salts are advantageously avoided, since excesses tend to produce fog in the emulsions. For our polyonium salts containing a bivalent organic radical having a chain of 1-6 members, we have found that the larger quantities, as for example, even 400 mg., of our polyonium salts could be employed without encountering excessive fog. In the instance of polyonium salts havinga bivalent organic radical containing a chain of 7 to 14 or more members, we have found that the lowerquantities, as for example, less than 200 mg., of the compound per mol of silver halide would be preferable.
• the upper range of concentration for any particular one of our polyonium salts in any particular type of emulsion can be determined by employing a series of concentrations of the polyonium salt separately in several batches of the same emulsion, and determining the sensitivity of the several emulsions before and after incorporation of our polyonium salt or salts.
• This method of determining the optimum concentration may be carried out in any conventional manner. Briefly, the method we would employ would comprise coating the aforementioned emulsion in suitable thickness onto glass plates and then testing the resultant photographic plates in a wedge spectograph and a sensitcm eter, whereby the spectral sensitivity and speed of the emulsion on the plate may be determined.
• the spectral sensitizers are advantageously employed in about their optimum concentration, which, for most purposes may be considered as lying between about 3 mg. and 20 mg. of spectral sensitizer per liter of emulsion containing about 0.25 mole of silver halide, although it is to be understood that these values are merely set forth for purposes of illustration and the concentrations above or below the aforementioned concentrations can be employed.
• the ratio of the sensitizing dye to the concentration of the silver halide inthe emulsion may advantageously be larger than in the coarser-grained emulsions, where smaller amounts of sensitizing dye will, in many instances, give satisfactory or optimum sensitization.
• the optimum concentration, as discussed herein, of a sensitizing dye, namely the concentration at which the apparently greater sensitivity occurs, can also be determined in any conventional manner known to those skilled in the art by measuring the sensitivity of a series of emulsions containing different concentrations of the sensitizing material.
• spectral sensltizers sensitizing dyes
• non-acidic sensitizing dyes we include all the known neutral and basic sensitizing dyes, and it is to be understood that our invention is not restricted in this respect. Examples of some.
• the non-acidic sensitizing dyes are the sensitizing cyanine dyes (see, for example, United States Patents 1,846,- 300; 1,846,301; 1,846,302; 1,846,303 and 1,846,304, each dated February 23; 1932', United States Patent 1,861,836, dated June 7, 1932, United States Patent 1,939,201, dated December 12, 1933, United States Patent 1,942,854, dated January 9, 1934, United States Patent 1,957,869, dated May 8, 1934, United States Patent 1,962,124, dated June 12, 1934, United States Patent 1,969,446, dated August 7, 1934, United States Patent 1,973,462,
• EXAMPLE 7 To an emulsion optionally sensitized with at least one cyanine dye, as for example, 2,2'-diethyl-8-methyl thiocarbocyanine bromide, there is added thio-bis-ethylene pyridinium perchlorate.
• cyanine dye as for example, 2,2'-diethyl-8-methyl thiocarbocyanine bromide.
• the emulsion was not greatly changed in distribution of spectral sensitivity.
• the absolute value of sensitivity at any wavelength was increased by 25 to As the concentration of the polyonium salt was increased, its effect increased up to a certain point where there was also an undesirable increase in fog. Increase in concentration of the polyonium salt beyond this point did not improve the sensitivity.
• EXAMPLE 8 In accordance with this example, compounds were prepared and added to the emulsion wherein the chain included a nitrogen atom.
• An example of such a compound is as follows:
• novel compounds may be prepared by reacting a diamide of the formula NHzCOYCONI-Iz with formaldehyde and, for example, hydrochloric acid.
• amide it is to be understood that we refer not only to simple amides, but to any derivatives obtainable by replacing one of the hydrogen atoms on the nitrogen atom by other groups, in particular, OH, NIH and also by varying the nature of the radical Y, which may be aliphatic, alkyl, aralkyl, or aromatic, and may or may not contain atoms other than carbon as a part of the chain.
• a compound containing nitrogen in the chain in accordance with this example was incorpo rated into a silver halide emulsion as described in Example 7, and also found to increase the sensitivity 25-50%.
• heterocyclic nuclei may be, for example, pyridine, piperid-ine, pyrazcles or pyriminazoles and" the like, 1 1
• Our invention is useful for all types of optically sensitized emulsions, and even useful in unsensitized emulsions, especially unsensitized emulsions of relatively low iodide content.
• a photographic silver halide emulsion containing a polyonium salt which contains an onium salt group, selected from the groupcon another onium salt group, selected from the group consisting. of quaternary ammonium, quaternary phosphonium and ternary sulfonium salt groups.
• a photographic-silver-halide emulsion containing aquat'ernary ammonium salt which contains a quaternary ammonium salt group linked through its ammonium atom, by at least one bivalent organic radical, to the ammonium atom of another quaternary ammonium salt group.
• R, R and R" represent alcohol radicals, X represents an acid radical and Z represents a bivalent organic radical.
• a photographic gelatino silver halide developing-out emulsion containing a polyonium salt which contains an onium salt group selected from the group consisting of quaternary ammonium, quaternary phosphonium and ternary sulfonium salt groups, linked through its onium atom by at least one bivalent organic radical to the onium atom of another onium salt group selected from the group consisting of quaternary ammonium, quaternary phosphonium and ternary sulfonium salt groups.
• Aphotographic gelatino silverhalide devel oping-out emulsion containing aquaternary ammonium salt which contains a quaternary ammonium salt group linked through its ammonium atom by at least one bivalent organic radical to the ammonium atom of another quaternary ammonium salt group.
• Q represents the non-metallic atoms necessary to complete an organic heterocyclic nuclei
• X represents'an acid radical
• Z represents a bivalent organic radical
• a photographic gelatino silver halide developing-out emulsion containing, in a concentration of not more than 400 milligrams per grammole of the silver halide in the emulsion, a polyonium salt which contains an onium salt group selected from the group consisting of quaternary ammonium, quaternary phosphonium, and ternary sulfonium salt groups, linked through its onium atom by a bivalent organic radical consisting of a chain' of from 1 to 6' members, to the onium atom of another onium salt group selected from the group consisting of quaternary ammonium, quaternary phosphonium and ternary sulfonium salt groups.
• Q represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from the group consisting oi pyridine, pyrazole and pyriminazole nuclei, X
• a photographic gelatino silver halide developing-out emulsion containing, ina concentration equal to not more than'400 milligrams per gram-mole of the silver halidein the emulsion, a polyonium salt of the following general formula: I
• Q represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from the group consisting of pyridine, pyrazole and pyriminazole nuclei
• X represents anacid.
• radical and Z represents a bivalent organic radical consisting of a chain of from 1 to 6 members.
• a photographic gelatino silverhalide developing-out emulsion containing, in a concentration of not more than 200 milligrams per gram-mole of the silver halide in the emulsion,
• Q represents the non-metallic atoms necessary to complete a pyridine nucleus
• X represents an acid radical
• Z represents a bivalent organic radical consisting of from 7 to 14 members.
• polyonium salt which contains an onium salt group selected from the group consisting of quaternary ammonium, quaternary phosphonium and ternary sulfonium salt groups, linked through its onium atom by a bivalent organic radical consisting of a chain of from 7 to 14 members, to the onium atom of another onium salt group selected from the group consisting of quaternary ammonium, quaternary phosphoni- 5 um and ternary sulfonium salt groups.
• Patent No. 2,288,226 June 50, 19!;2.

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• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Pyridine Compounds (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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Cited By (23)

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• 0
  • BE BE463680D patent/BE463680A/xx unknown
• 1940
  • 1940-02-29 US US321594A patent/US2288226A/en not_active Expired - Lifetime
• 1942
  • 1942-01-07 GB GB272/42A patent/GB557178A/en not_active Expired
  • 1942-01-07 GB GB271/42A patent/GB558710A/en not_active Expired
• 1945
  • 1945-08-11 FR FR949230D patent/FR949230A/fr not_active Expired
• 1947
  • 1947-05-05 FR FR949680D patent/FR949680A/fr not_active Expired

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