Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
  • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
  • C07D213/20—Quaternary compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
  • C07D213/30—Oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/72—Nitrogen atoms
  • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
• • 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

Definitions

• Emulsions containing the compounds of the ,invention are appreciably more stable than emulsions containing the mentionedquarternary compounds. Accordingly, upon the aging ofemulsions containing the new sensitizing agents, less fog is developed and the emulsion speed is maintained.
• photographic emulsions containing the new quaternary nitrogen compounds maintain their speed over awiderrange of development conditions than do emulsions sensitized with previously .known alkylene-bis-pynidiniurnsalts such as decamethylene- LIO-b-is-pyridinium perchlorate
• alkylene-bis-pynidiniurnsalts such as decamethylene- LIO-b-is-pyridinium perchlorate
• the quaternary salts of the praent invention when employed in .the emulsions as sensitizing agents unexpectedly do not retard the development rate whendevelopment carried out with a pphenylenediamine.type developing'agent.
• T q t rn y a n i n ents, o t e i entin 2,944,898 Patented July 12, 1960 2. are bis-quaternary salts having Formulas A and B:
• n represents the integers 1 or 2, and therefore includes tetraand bis-urethanes of the general structures I and'II, respectively.
• R R2 R n the following two general
• Q and Q represent the smear different organic radicals containing quaternary nitrogen atoms such as trialkyl ammonium salt radicals, and eyelarnrn'onium.
• salt radicals e.-g. pyridinium salt radicals or quino-linium salt radicals.
• R and R represent the same or different, radicals, which may be alkylene, such as (CH and including a carbon chain separated by other atoms suchas O or S, e.g., --(CH ),,O(CH or (CH ),,S(CH n and n" being integers of from about -1' to 10.
• the total chain length of R and R' must be such that the number of atoms in the linear .chain joining-Q toQ' doesfinot exceed about 30.
• atoms as used herein refers solely to the actual elements that compose the chain and not to any groups that these elements may carry. For example, -(CH is considered to be a 10-atom chain, the
• the compounds contain from about 14 to about 30 atoms in the chain.
• group A represents a linear chain of one or more atoms of carbon which may or may not contain sulfur, oxygen or nitrogen as an intermediate linkage.
• the number of atoms comprising group A is limited by the number of atoms in R and R since as mentioned above the total number of atoms in the chain connecting Q to Q must not exceed about 30.
• A may contain as many as 22 atoms in a linear chain when R and R are methylene groups.
• the linear chain of group A can contain only 2 to about 22 carbon atoms since it has not been possible to synthesize compounds in which A equals a CH group because the diisocyanate OCNCI-I --NCO required in the synthesis is not available.
• V (cm) "1,l6 bis(pyridiniumperchlorate) -'(II)' 5,12-dia'za 3,14 dioxa 4,13 dioxohexadecane- 1 1 6-bi s (trimethylammonium-p-toluene sulfon ate) (III) 6,l3-diaza-4,15 dioxa 5,14 dioxo-octadecane- 1,18 bis(N-niethylpyridinium-p-toluene sulfonate) (IV) 8,15diaZa-6,17-dioxa-7,l6-dioxodooosane 1,22- bis (trimethylamrnoniurn-p-itoluene sulfonate) j "(V) 9,16 -diaza-7,18.- dioxa-8,17 dioxotetracosane- -1, 2
• Ether 4 [(CH3)2N(CH2)5OOCNH(CH2)3]Z 'IOa solution of 5.2 g. (0.04 mole) of dimethylamino- -amyl alcohol in 100 m1. of'dry ether was added a solution of 3.4g. (0.02 mole) of.hexarnethylene diisocyanate; a exothermic reaction occurred. The mixture was refluxed for. three. hours and then pooled. A white solid (5.9" g., 69 percent); M.P.
• the appropriate diisocyanate is reacted first with 1 mol of a dialkylamino- .alkyl alcohol followed by reaction with 1 mol of a different dialkylarninoalkyl alcohol, and the product subsequently quaterniz ed by treatment with, for example, methyl-p-toluene sulfonate.
• V COMPOUND V 9,16#diaza-7,I8-dioxa-8,17-dioxotetracosane-1,24-dichloride 2c1 c,H, ,oH -OcN cH, ,NcO-
• Ethanol was added and removed in the above manner to remove last traces of pyridine.
• the oily salt was redissolved in 25 ml. of ethanol and added to a solution of 6.3 g. (0.045 mole) of sodium perchlorate monohydrate in 25 ml. of acetone.
• the mixture was concentrated on the steam bath to about 30 ml., and the precipitated sodium chloride filtered off.
• the ether was decanted total solid (7.5 g.) was recrystallized first from acetone and then from methanol-ether. In all cases of recrystallization the product first separated as a guru which set to a solid on chilling. Final yield, 5 g.
• symmetrical tetra-urethanes having the general Formula I above may be prepared using the appropriate alcohols and isocyanates.
• the diol compound is first reacted with 1 mol of the appropriate haloalkyl isocyanate followed by reaction with 1 mol of a different haloalkyl isocyanate.
• COMPOUND IX 3-aza-5-0xa-4-0x0pentadecane-I,15-dichl0ride Cl(CH NCO-[-HO(CH Cl- Cl(CH NHCOO(CH Cl Decamethylene chlorohydrin (19.3 g, 0.10 mole) and 10.5 g. (0.10 mole) of 2-chloroethyl isocyanate were added together giving a mildly exothermic reaction. After the exotherm had subsided, the oil was heated on the steam bath for five hours. Upon cooling, 2. white crys- This solutraces of inorganic salt removed by filtration.
• tetrazaeic'osane-l,20-dichloride was heated to reflux for two hours. The solvents were removed on the steam bath under vacuum. The .oil was slurried several times with ether and the ether decanted in order to remove traces of pyridine.
• the pyridinium chloride was dissolved in ml. of., 'methanol, and a solution of 5.0 g. (0.036 mole) of sodium perchlorate monohydrate in 25 ml. of acetone added.
• the mixture was heated on the steam bath; immediately a dense solid consisting of bis-pyridinium perchlorate and .s odium chloride separated.
• Example 3 An emulsion was provided as in Example 1 but with the addition to samples of the emulsion of the compounds shown in Table, 3. Processing was carried out as in Example 1 for evaluating the emulsion sensitivity and other characteristics of the emulsion.
• Example 4 An 'ernulsion was prepared and tested as" shown in Example r nsing" the bis-quaternary compound shown in Table 4. The dataof this example shows that additional speed increase'can beetfected by using a combination of a bis-quaternary compound of the invention such as 'lllaan'd' a polyethylene glycol XXXI, i.e., a polyethylene oxide or average molecular weight of 1500 (PEG 1500).
• a bis-quaternary compound of the invention such as 'lllaan'd' a polyethylene glycol XXXI, i.e., a polyethylene oxide or average molecular weight of 1500 (PEG 1500).
• octadecane-l 18-bis(' -pyridinium J1; m/ethti-p-toluenesulfonate) (III) 0.3 1 r, g. 1110 146245.... 4-Hydroxy-6-methyl-1, 3, 3a, 7-tetra- 328 1.35 .16
• a fast bromoiodide emulsion was chemically sensitized with sulfur andgoldcompounds and optically sensitized with-a combination of cyanine dyes.
• 3.0 gramsp'ermole of silver halideof 4-hydroxy-6-methyl- 1,3,3a,-7-'tetrazaindene and 0.75 gram per mole of silver halide of a polyethylene oxide of average molecular weight 1500 were added.
• the amounts of the compounds shown in Table 7 were then added and the .ernulsions coated. Testing was carried out as in Example .ljupon'the' freshlycoated emulsion samples and other v samples of each'emulsion werejincubated for 1 Week at f. 120 and percent relative humidity.
• a sulfur and gold sensitized gelatino silver bromoiodide emulsion was ripened to maximum sensitivity.
• an optical sensitizing dye that extended the light sensitivity to 6000-7000 A. and a hydrophobic cyan 'color former suitably dispersed in a high boiling organic solvent.
• a hydrophobic cyan 'color former suitably dispersed in a high boiling organic solvent.
• Both portions were coated on film support, and the dry films were -'exposed--to red light in an intensity scale sensitometer.
• the exposed films were processed inthe reversal Color Process land the-5248 negative Color ProcessZ' with the assess 11 results shown in the follq jng table.
• the Color Process 2 was carried out as described 'by Hanson and Kisner JSMPTE 61 667-701 (1953) forthe Color Negative Film, Type 5248-,invol-ving the steps of color 'developmenflfixation, silver bleaching and final fixation.
• Color Process 1 was carried out at 75 F.-as follows:
• Negative development 10 (2) Reversal flash exposure (3) Color development l (4) Silver bleaching 8 (5) Fixing Y 3
• the negative developer had the following composition: Water, 90 F. (32 CL) 'liter 1.0 Sodium hexametaphosphate "grams" 2.0 N-methyl p-aminophenol sulfate do 6.0 Sodium sulfite, desiccated d0; 50.0 Hydroquinone ...d0 6.0 Sodium carbonate,monohydrated do 35.0 Potassium bromide d0 2.0 Sodium thiocyanate do 1.5 0.5% solution (6-nitrobenzimidazole nitrate) cc 12.0 0.1% solution of potassium iodide ..cc 10.0
• a stabilizing agent into the emulsion sensi- 12 Process 2 of Example 8 and a multilayer color film having couplers in the emulsion layers was developed therein,
• the preparation of silverhalide emulsions involves three separate operations: (1) the emnlsification and digestion or ripening of the silver halide, (2) the freeing of the emulsion from aqueous soluble salts usually by washing, (3) the second digestion or after ripening to obtain increased sensitivity (Mees, The Theory of the Photographic Process, 1942, page 3).
• the sensitizing agents may be added at any stage, preferably after the final digestion.
• the emulsions are chemically sensitized by any of the accepted procedures in addition to sensitizing with the bis-quaternary salts of the invention.
• the emulsions may be digested with naturally active vgelatimor sulfur. compounds may be added such as those described in Sheppard U.S. Patents 1,574,944 and 1,623,499, and Sheppard and Brigham U.S. Patent 2,410,689.
• the emulsions may also be treated with salts of the noble metals such as .ruthenium, rhodium, palladium,
• Representative compounds are ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, and as anti-foggants in higher amounts, as
• the silver'bleaching solutionabove had'th'e following composition: I Water 90 F. (32 C.) liter 1.0 Potassium dichronrate grams 5.0 Potassium ferricyanide ..;...do 70.0 Potassium bromide i do.... 20.0
• the fixing baths above had the following composition Water, 80 F. (27 C.) liter.. 1.0 Sodium thiosulfate grarns 150.0 Sodium bisulfite V g I do 20.0
• the bis-quaternary salts described above can be used in emulsions in the manner of the above examples in concentrations of the order of about0.02 to 4 grams per mol of 1silver halide. l i"? *1 Y a; he emulsions may also be developed inthe presence of '.the bis-quaternary salts by; incorporating the salts into .a 'edeveloper-a solutionz; For example, when; compound VI described in Trivelli and Smith U.S. Patents 2,566,245 and 2,566,263.
• the emulsions may also be chemically sensitized with gold salts as described in Waller and Dodd U.S. Patent 2,399,083 or stabilized with gold salts as described in Damschroder U.S. Patent 2,597,856 and Yutzy and Leermakers U.S. Patent 2,597,915.
• Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride andZ-aurosulfobenzo-thiazole methochloride.
• the emulsions may also be chemically sensitized with reducing agents such, as stannous salts (Carroll U.S. Patent 2,487,850), polyamines such as diethylene triamine Lowe and Jones U.S. Patent 2,518,698), polyamines such as spermine (Lowe and Allen U.S. Patent 2,521,925), or bis-(Beaminoethyl) sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,926).
• reducing agents such, as stannous salts (Carroll U.S. Patent 2,487,850), polyamines such as diethylene triamine Lowe and Jones U.S. Patent 2,518,698), polyamines such as spermine (Lowe and Allen U.S. Patent 2,521,925), or bis-(Beaminoethyl) sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,926).
• the emulsions may also contain polyalkylene oxides and derivatives thereof such as the polyethylene glycols, in addition to the bis-quaternary compounds of the invention.
• polyalkylene oxides and polyalkylene oxide derivatives are described in Blake U.S. Patent 2,441,389,, Mayl1, 1948, Blake et a1.
• stabilizing agents may be added to the emulsions containing the bis-quaternary salts such as the metalinorganic salts of U.S. Patent application Serial No. 493,-
• the chemicalsensitizing agents and other addenda which we have describedmay be used in various kinds of photographic emulsions, e.g., various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide or silver bromoiodide.
• various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide or silver bromoiodide.
• the dispersing agent for the silver halide may be gelatin or other hydrophilic material such as collodion, albumin, cellulose derivatives or synthetic resins.
• the coupler-containing emulsions sensitized as described with the bis-quaternary salts are adapted particularly for use in color photography, they will ordinarily comprise the emulsion layers of multilayer color films which emulsion layers are customarily differentially sensitized to the primary regions of the visible spectrum and contain coupler compounds producing dye images of colors complementary to the sensitivity of the emulsion layers.
• one or more of the differentially sensitized emulsion layers may be sensitized with the bis-guaternary salts, and in a typical example emuls'ionssensitizedto the red, green and blue regions of the spectrum are super-imposed on the support in that order and contain cyan, magenta and yellow colorforming coupler compounds respectively.
• a yellow filter layer such as yellow colloidal silver is advantageously interposed between the blue and green-sensitive emulsion layers.
• the emulsion layers sensitizedwith the bisquatcrnary salts of the invention may contain coupler com ounds they can be readily processed by well known methods to yield color negatives directly or positive images bymeans of well known reversal processes. That is, after initial exposure of the emulsion to a subject a developer of the p-phenylenediamine type Will produce a .colored image negative in respect to the subject. Like- ⁇ wise,'if development of theemulsion layer is first carried --out with a non-color-forming developer followed by reversal exposure'of the residual silver halide and then color development, a colored positive is obtained as described in the examples above.
• the coupler compounds used in the emulsion layers sensitized with the ionic polyalkylene oxide derivatives are any of the well known compounds which combine with the oxidation product of primary aromatic amino (p-phenylenediamines) silver halide color developing agents to form dyes, for example, the phenolic couplers of U.S. Patents 2,266,452, 2,362,598, 2,589,004, 2,474,- 293, 2,521,908, 2,423,730 and Fierke U.S. patent application 476,561; the pyrazolone couplers of U.S.
• the emulsions may contain colored color-forming couplers as described in U.S. Patents 2,521,908, 2,706,684, 2,455,169, 2,694,703, 2,455,- 170 and 2,453,661.
• the couplers may be dispersed in the emulsion layers by means of an oily coupler solvent according to the methods of U.S. Patents 2,304,940 and 2,322,027.
• the couplers may contain solubilizsoluble in alkaline solution, the oily coupler solvent may be dispensed with and the couplers can be added to the emulsion from aqueous solutions as their alkali metal salts.
• R represent lower alkyl groups
• R R and represents the atoms necessary to complete a heterocyclic t-nucleus' of the class consisting of pyridinium and quinoli- I QRNHCOOAQf I wherein Q and Q each representpradicals of the class conwherein R R and R represent lower alkyl groups, Z
• .T' represents the atoms necessary to complete a heterocyclic .nucleus of the class consisting of pyridinium and quinolinium, R and A each'represent alkylene groups, there being. from about 14' to about 30 atoms present in the shortest linear chain of atoms linking the quaternary lnitrogen atoms of said radicals.
• n and n' represent positivejintegers of from jabout'l to -10,' therebeing from aboutli14 to"about 3 0 atoms presentin the shortest linear chain of atoms linking said'qua'ternary nitrogen atoms.
• Z 7' A photographic silver halide femulsioncontaining the.
• a method of increasing the speed of a silver halide emulsion layer which comprises developing said emulsion in the presence of a quaternary ammonium salt having a formula of the class consisting of wherein R R and R represent llower allryl groups, Z represents the atoms necessary to complete a heterocyclic nucleus of the class consisting of pyridinium and quinoto the quaternary nitrogen atoms of said radicals, R represents a member of the class consistingpf a hydrogen atom and an alkyl group of from 1 to 4 carbon atoms,
• a americanum silver halide-emulsion containing thevcompround 3,10,17,24-tetrazai-5,8,l9,22atetroxa-4,9,l8, 23-tet'roxohexacosane-1,26-bis(pyridinium perchlorate) 10.
• ,ll.' The emulsion of claini'2 further containing a cou- ,pler compound reactive with theoxidation products of a .phenylenediamine silver halide developing agent to form a' dye. 7
• the emulsion of claini 3 further containing a con- ,pler compound reactive with the oxidation products of a phenylenediamin silver halide developing agent to forin 13.
• the emulsion ofclairn-4 further-containing a coutpler compound reactive with the oxidation products of a -,phenylenediamine silver halidedeveloping agent to form .radye. ::14

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• 1957
  • 1957-11-27 US US699198A patent/US2944898A/en not_active Expired - Lifetime
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• 1958
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