US1846301A - Photographic emulsion - Google Patents

Photographic emulsion Download PDF

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Publication number
US1846301A
US1846301A US435104A US43510430A US1846301A US 1846301 A US1846301 A US 1846301A US 435104 A US435104 A US 435104A US 43510430 A US43510430 A US 43510430A US 1846301 A US1846301 A US 1846301A
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US
United States
Prior art keywords
dye
methyl
alkyl
silver
photographic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US435104A
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English (en)
Inventor
Leslie G S Brooker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
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Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US184630D priority Critical patent/USB184630I5/en
Priority to BE378116D priority patent/BE378116A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US435104A priority patent/US1846301A/en
Priority to FR712995D priority patent/FR712995A/fr
Priority to GB7642/31A priority patent/GB378885A/en
Application granted granted Critical
Publication of US1846301A publication Critical patent/US1846301A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/18—Diazo-type processes, e.g. thermal development, or agents therefor

Definitions

  • This invention relates to a new composition of matter and particularly to a new class of photographic sensitizing dyes and a method for their preparation.
  • this restricted sensitivity can be varied at will within certain limits; for example, the emulsion can be rendered strongly sensitive to rays of a particular wave length at the expense of other wave bands or it can be rendered sensitive to all the visual rays in substantially equal proportions.
  • this particular dye has an exceedingly strong maximum at 660 and continues strong even to 690 This dye also gives an exceptionally uniform sensitivity from 520 to 690 which is an unusual range of high sensitivity.
  • This S-methyl dye may be carried out in the followingmanner
  • a 2-methyl beta naphthothiazole is first converted into an alkyl quarternary salt, such as the metho or etho paratoluene sulfonate by heating with a suitable substance at an elevated temperature for a considerable time and this salt is then treat- .ed with 2 molecular proportions of trialkyl ortho acetate in a suflicient-amount of boiling dry pyridine; After several hours boiling, the dye is allowed to crystallize out or may be precipitated by adding to the reaction mixture a salt having a suitable anion, such, for
  • the dye may then be recrystallized to obtain it in a pure form.
  • Example 1 The 8-methyl 2:2 diethyl 314:3'Z4;.dl-'
  • benzo thiocarbocyanine bromide may be prepared in the following manner by the three- I step process Step A: One molecular proportion of 2- methyl beta naphthothiazole which may be prepared by well known methods and whica has the following structural formula is condensed with one molecular proportion of ethyl paratoluene sulfonate by heating the substances together at 130 C. for several days. The crude quartcrnary salt is freed from unchanged starting materials by dissolving these out with acetone.
  • A- dye derived from 2-methyl beta naphthothiazole for instance, will have the following struc- ⁇ N t .0. I
  • 8-alkyl, aryl or aralkyl- 2 2-dialkyl similar or dissimilar 3: 1:23 :4- dibenzothiocarbocyanine salt, and is obtained by using the ortho-esters of carboxylic acids with these various alkyl or aryl groups directly linked to the carbon atom of the trialkyloxy-methyl group (e. g. trialkyl ortho phenyl acetate, trialkyl ortho propionate, methyl diethyl ortho iso caproate, etc.)
  • the R grouping may represent similar or dissimilar alkyl groups while X may rep resent any suitable acid radical that may be used to precipitate the dye, for example, a halide, paratoluene, sulfonate, or alkylo sulfate or, in fact, any suitable acid radical Which will not greatly decrease or destroy the sensitizing properties of the dye, this radical being necessary to give electrical neutrality to the molecule.
  • a suitable acid radical- is employed 'to designate this group of acid radicals.
  • the A position in the above configuration may represent alkyl, aryl, aralkyl or similar groupings. These groupings may be linked to the carbon atom in the 8 position by efi'ect- I
  • Example 2 8 grams (1 mol.) of 2-methyl beta napthathiazole etho-ptoluene sulfonate, 5.4 grams (2 mol.) of trimethyl-ortho-propionate are refluxed with 35 cc. of dry pyridine for approximately one hour. A hot aqueous solution of potassium iodide is added. After allowing this solution to cool, the precipitate is filtered out. The product is digested in hot acetone and again filtered.
  • the dye is then boiled with successive portions of water until tree from the ethiodide of the base.
  • the crude dye obtained in one reaction weighed .36 grams and consisted of a purplish-black powder. Upon crystallization from methyl alcohol minute dark green crystals of the dye were obtained, which give a purplish solution in this solvent.
  • This dye is called 2 2 8- triethyl 3 4 3 4'-dibenzothiocarbocyanine iodide.
  • the structure of this dye is similar to that give above, the Rs and A being replaced by ethyl groups.
  • Example 3 7.7 grams (1 mol.) of 2-methyl beta naphthothiazole metho-p-toluene sulfonate, 8.2 grams (2 mol.) of methyl-diethyl-ortho-isocaproate are refluxed for about 45 minutes in 40 cc. of dry pyridine. To the resultant solution 10 grams of potassium iodide dissolved in 50 cc. of hot Water is added to precipitate the dye Which after standing for about 10 to 12hours is filtered, washed with ,boiling water and then warm acetone to remove the impurities. Theproduct Weighs 1.5 grams and is an olive green color. Upon crystallization from methyl alcohol green felted needles are produced.
  • This dye is called 2:2 dimethyl 8 iso-amyl 354:3'z4' di berizo thiocarbocyanine iodide. Its structural formula is similar to that given above except that the Rs are replaced by methyl groups and the A by .an iso-amyl group.
  • any thio carbocyanine dye in which the 8 position is occupied by an alkyl, aryl or aralkyl group and the 3:4 and 3' :4'positions by fused-on benzene rings, substituted or unsubstituted, and in which the Rs attached to the nitrogen atoms in the thiazole rings' denote similar or dissimilar alkyl groups and X denotes a suitable acid radical will come within the scope of this invention as well as the employment of such dyes as sensitizers in the photographic emulsion.
  • a photographic gelatino-silver-halide emulsion containin a cyanine dye which confithothiazole nuclei linked together by 'a tri-methen'yl chain the h drogen of the central carbon atom of whic has been substituted b an ethyl group.
  • a photograp ic gelatino-silver-halide emulsion containing an 8-alkyl-3:4 :3 :4- dibenzo-thiocarbocyanine salt, the nitrogen atoms of which are each linked to an alkyl radical while one is linked to radical.
  • Patent No. 1,846,301 Granted February23, 1932, to

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Plural Heterocyclic Compounds (AREA)
US435104A 1930-03-12 1930-03-12 Photographic emulsion Expired - Lifetime US1846301A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US184630D USB184630I5 (xx) 1930-03-12
BE378116D BE378116A (xx) 1930-03-12
US435104A US1846301A (en) 1930-03-12 1930-03-12 Photographic emulsion
FR712995D FR712995A (fr) 1930-03-12 1931-03-10 Sensibilisateur photographique
GB7642/31A GB378885A (en) 1930-03-12 1931-03-12 Improved process of sensitising photographic emulsions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US435104A US1846301A (en) 1930-03-12 1930-03-12 Photographic emulsion

Publications (1)

Publication Number Publication Date
US1846301A true US1846301A (en) 1932-02-23

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US184630D Pending USB184630I5 (xx) 1930-03-12
US435104A Expired - Lifetime US1846301A (en) 1930-03-12 1930-03-12 Photographic emulsion

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US184630D Pending USB184630I5 (xx) 1930-03-12

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US (2) US1846301A (xx)
BE (1) BE378116A (xx)
FR (1) FR712995A (xx)
GB (1) GB378885A (xx)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0573650A1 (en) * 1991-12-18 1993-12-15 Fuji Photo Film Co., Ltd. Silver halide photographic material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1132796B (de) * 1961-06-03 1962-07-05 Adox Fotowerke Dr C Schleussne Verfahren zur optischen Sensibilisierung fotografischer Halogensilberemulsionen
JPS5221366B2 (xx) * 1971-11-29 1977-06-10

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0573650A1 (en) * 1991-12-18 1993-12-15 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0573650B1 (en) * 1991-12-18 1999-03-31 Fuji Photo Film Co., Ltd. Silver halide photographic material

Also Published As

Publication number Publication date
GB378885A (en) 1932-08-12
BE378116A (xx)
FR712995A (fr) 1931-10-16
USB184630I5 (xx)

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