US3702251A - Light-sensitive silver halide photographic emulsion for microfilm use - Google Patents

Light-sensitive silver halide photographic emulsion for microfilm use Download PDF

Info

Publication number
US3702251A
US3702251A US782169A US3702251DA US3702251A US 3702251 A US3702251 A US 3702251A US 782169 A US782169 A US 782169A US 3702251D A US3702251D A US 3702251DA US 3702251 A US3702251 A US 3702251A
Authority
US
United States
Prior art keywords
group
light
silver halide
microfilm
lower alkyl
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
US782169A
Other languages
English (en)
Inventor
Shui Sato
Kaiichiro Sakazume
Tsuneo Suga
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.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Application granted granted Critical
Publication of US3702251A publication Critical patent/US3702251A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed

Definitions

  • R R R and R are independently selected from the group consisting of lower alkyl group, a carboxyalkyl group or a sulfoalkyl group, with the proviso that at least one of R R R and R is a carboxyalkyl, sulfoalkyl or sulfalkoxyalkyl group;
  • R is hydrogen atom or a lower alkyl group;
  • R is a lower alkyl group;
  • Y is hydrogen atom, chlorine atom, a lower alkyl group or a lower alkoxy group;
  • Y is hydrogen atom or a lower alkyl group with the proviso that when Y is chlorine, Y, is methyl;
  • Z is a group capable of forming, together with the adjacent nitrogen and carbon atoms, a heterocyclic ring;
  • X is an anion; and 1, n and m are each 1 or 2.
  • This invention relates to sensitized light-sensitive silver halide photographic emulsions for microfilm use. More particularly this invention relates to a light-sensitive silver halide photographic emulsion suited for microfilm, which comprises two or more sensitizing dyes of the general Formula (I) in combination with one sensitizing dye of the general Formula II:
  • R R R and R are independently selected from the group consisting of a lower alkyl radical, a carboxy- 3,702,251 Patented Nov. 7, 1972 alkyl group, a sulfoalkyl group and a sulfoalkoxyalkyl group;
  • R is hydrogen atom or a lower alkyl group;
  • R is an alkyl group, with the proviso that at least one of R R R and R is a carboxyalkyl, sulfoalkyl or sulfoalkoxyalkyl group;
  • Y is hydrogen atom, chlorine atom, an alkyl group or an alkoxy group;
  • Y is hydrogen atom or an alkyl group, with the proviso that Y is methyl when Y; is chlorine atom;
  • Z is an atomic grouping capable of forming, together with the adjacent nitrogen and carbon atoms, a heterocyclic ring such as thiazoline, benzothiazole, benzose'l
  • the joint use of two or three compounds of the general Formula I with a compound of the general Formula II enables one to obtain such particular spectral sensitization of a light-sensitive silver halide emulsion as has never been observed by the sale use of the individual compounds.
  • the photographic emulsion can be imparted with sufiicient spectral sensitivity over the entire visible spectrum, so that the said emulsion is excellent in photo- .graphic reproductviity.
  • this emulsion when used for a microfilm can show good photographic characteristics.
  • a still further advantage of this invention is that the distribution of sensitivity maxima can be optionally determined by varying the types and proportions of the compounds of the general Formulas I and 11.
  • sensitizing compounds used in this invention do not cause any adverse interaction with other photographic additives which may be present in the emulsion.
  • a microfilm prepared from the emulsion of the invention is entirely free from deterioration of photographic properties (e.g. decrease of spectral sensitivity, etc.) during storage.
  • Addition of the compounds of the general Formulas I and II to a silver halide photographic emulsion may be made in a conventional manner.
  • these compounds are dissolved into a water-miscible organic solvent such as methanol, ethanol, etc., to give a solution which is then added to a photographic emulsion.
  • a water-miscible organic solvent such as methanol, ethanol, etc.
  • any types of light-sensitive silver halide emulsions can be sensitized according to the present invention and typically include silver chloride, silver bromide, silver iodo'bromide, silver chlorobromide and silver chloroiodide emulsions.
  • the light-sensitive silver halide photographic emulsion sensitized according to this invention may contain gold sensitizer, sulfur sensitizer, reductive sensitizer or polyalkyleneoxide sensitizer, and further may contain any known photographic additives such as stabilizer, coating aid, hardener, etc.
  • EXAMPLE 1 A silver chlorobromide solution for copying use is prepared, which contains 50 mol. percent of this emulsion, just before the completion of the second ripening, the indicated amount of various compounds set forth in Table 1 is added in the form of an 0.1% methanol solution at a high temperature. Then, the emulsion is coated on a film base and dried.
  • the light-sensitive silver halide photographic film thus obtained has good spectral sensitivity over the entire visible spectrum and is particularly excellent in spectral sensitivity at long wavelengths.
  • This photographic film does not suffer from any interaction due to the coexistence of the sensitizers and photographic additives and is entirely free from color staining after development.
  • this film is used in copying, it is possible to obtain good reproduction from an original having spectral absorptions over the entire visible spectrum even by using a. tungsten lampas light source.
  • the photographic film is exposed to light according to the JIS method K-7609 and then treated at 20 C. for 4 minutes with a developer of the following formulation:
  • the microfilms of the present invention are highly improved in photographic speed to white light in comparison with those prepared by the sole use of the individual compounds of the general Formula I and II. Further, the films of this invention have an increased ratio of both G/W and R/W. Good spectral sensitivity over the entire visible spectrum is obtained.
  • EXAMPLE 2 The same silver chlorobromide emulsion as used in Example 1 is subjected to a second ripening with a gold sensitizer to obtain maximum sensitivity. Just before the completion of said second ripening, each one kilogram portion of the emulsion is added at a high temperature with the indicated amount of varying compound in the form of an 0.1% methanolic solution, as shown in Table 2. After the completion of the second ripening, the emulsion is added with an optimum amount of 4-hydroxy- 6-meth-yl-1,3,3a,7-tetrazaindene. The thus obtained emulsion is coated on a film base and then dried.
  • the light-sensitive silver halide photographic film has good spectral sensitivity over the entire visible spectrum and is particularly excellent in spectral sensitivity at long wavelengths.
  • This photographic film does not sulfer from any adverse effect due to the coexistence of the sensitizers and photographic additives and is entirely free from color staining after development. Further, there is not observed any deterioration of photographic properties even after the storage of the film for a long period of time.
  • this film is used in copying, it is possible to obtain good reproduction from an original having spectral absorptions over the entire visible spectrum even by using a tungsten lamp as light source.
  • the photographic film is exposed to light according to the 118 method K-7609 and then treated with a developer in the same manner as in Example 1. Photographic speed and fog are set forth in Table 2. For comparison, the test results of light-sensitive silver halide photographic films sensitized by the sole use of individual sensitizing 9.0 dyes are also shown.
  • FIG. 1 is a spectral sensitivity curve of the silver chlorobromide emulsion used as the starting material of this example
  • FIG. 2 (I), (II) and MNNMNNNNN (III) are spectral sensitivity curves of the said emulsion when added with each of the compounds No. (1), No. (4) and No. (12) respectively
  • FIG. 3 is a spectral ggg gggg sensitivity curve of the said emulsion when added with the i combination of the compounds No. (l), (4) and (12) according to the present invention.
  • a light-sensitive silver halide photographic emulsion o'de'c'ddc'dc' for microfilm which comprises in combination two or I I three sensitizing dyes of the compounds of the general Q83 5 512382 Formula I:
  • R R R and R are independently selected from the group consisting of a lower alkyl group, a carboxyalkyl group or a sulfoalkyl group, with the proviso that at least one of R R R and R is a carboxyalkyl, sulfoalkyl or sulfalkoxyalkyl group;
  • R is hydrogen atom or a lower alkyl group;
  • R is a lower alkyl group;
  • y is hydrogen atom, chlorine atom, a lower alkyl group or a lower alkoxy group;
  • Y is hydrogen atom or a lower alkyl group with the proviso that when Y is chlorine, Y is methyl;
  • Z is a group capable of forming, together with the adjacent nitrogen and carbon atoms, a heterocyclic ring;
  • a light-sensitive silver halide photographic emulsion for microfilm use as claimed in claim 1, wherein said combination consists of 3,3'-diethyl-thiazolino-carbocyanine iodide, 3,3 sulfoethoxyethyl 9 methyl-thiacarbocyanine triethylamine and (3 carboxyethyl 5 methoxybenzoxazolo) 1,3 diethyl 5,6 dichloro-benzimidazolo)-carbocyanine bromide.
  • a light-sensitive silver halide photographic emulsion for microfilm use as claimed in claim 1, wherein said combination consists of 3,3 dicarboxyethyl-thiazolinocarbocyanine bromide, 3,3 hydroxyethyl 9 methylthia-carbocyanine iodide and (3 ethyl 5 chloro 6- methyl-benzoxazolo) (1 ethyl 3 sulfobutyl 5,6- dichloro-benzimidazolo)-carbocyanine.
  • a light-sensitive silver halide photographic emulsion for microfilm use as claimed in claim 1, wherein said 100 on 30 No. (4). 50 do 50 -d0.- 50 do 40 do 0.1% MeOH solution added to 1 kg. emulsion.
  • a light-sensitive silver halide photographic emulsion for microfilm use as claimed in claim 1, wherein said combination consists of 3,3 diethyl-thiazolino-carbocyanine iodide, 3,3 disulfobutyl 9 methyl-thia-carbocyanine iodide, 3,3'-disulfobutyl-9-methyl-benzselenazolocarbocyanine and (3-ethyl-benzoxazol0)-(1-ethyl-3-ethyl- 5,6-dichloro-benzimidazolo)-carbocyanine iodide.
  • a microfilm which comprises a film base and, supported thereon, a layer of the smulsion as claimed in claim 1.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
US782169A 1967-12-07 1968-12-09 Light-sensitive silver halide photographic emulsion for microfilm use Expired - Lifetime US3702251A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7820567 1967-12-07

Publications (1)

Publication Number Publication Date
US3702251A true US3702251A (en) 1972-11-07

Family

ID=13655510

Family Applications (1)

Application Number Title Priority Date Filing Date
US782169A Expired - Lifetime US3702251A (en) 1967-12-07 1968-12-09 Light-sensitive silver halide photographic emulsion for microfilm use

Country Status (3)

Country Link
US (1) US3702251A (sl)
DE (1) DE1813001A1 (sl)
GB (1) GB1225703A (sl)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853565A (en) * 1972-04-26 1974-12-10 Ilford Ltd Silver halide photographic supersensitising dye combination
US3873324A (en) * 1973-02-28 1975-03-25 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3973969A (en) * 1972-06-21 1976-08-10 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5250692A (en) * 1990-04-20 1993-10-05 Fuji Photo Film Co., Ltd. Water-soluble methine compounds useful in photographic silver halide emulsions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5624938B2 (sl) * 1972-06-21 1981-06-09

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853565A (en) * 1972-04-26 1974-12-10 Ilford Ltd Silver halide photographic supersensitising dye combination
US3973969A (en) * 1972-06-21 1976-08-10 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US3873324A (en) * 1973-02-28 1975-03-25 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US5250692A (en) * 1990-04-20 1993-10-05 Fuji Photo Film Co., Ltd. Water-soluble methine compounds useful in photographic silver halide emulsions

Also Published As

Publication number Publication date
GB1225703A (sl) 1971-03-24
DE1813001A1 (de) 1969-07-17

Similar Documents

Publication Publication Date Title
US3864134A (en) Silver bromoiodide photographic emulsion with improved green sensitivity
JPS59192242A (ja) ハロゲン化銀写真感光材料
JPS5852574B2 (ja) ハロゲン化銀写真乳剤
US3769024A (en) Light-sensitive silver halide photographic material with sensitizing dye combination
US3702251A (en) Light-sensitive silver halide photographic emulsion for microfilm use
US3632349A (en) Silver halide supersensitized photographic emulsion
US3808009A (en) Light-sensitive super-sensitized silver halide photographic emulsions
US3718470A (en) Surface development process utilizing an internal image silver halide emulsion containing a composite nucleating agent-spectral sensitizing polymethine dye
US3953216A (en) Spectrally sensitized silver halide photographic emulsion
US3615610A (en) Silver halide direct positive emulsions spectrally sensitized with a combination of a desensitizing dye with a 2-phenylindole methine dye
US3580724A (en) Light-sensitive supersensitized silver halide color photographic emulsions
US2944901A (en) Multicontrast photographic emulsions
US3971664A (en) Fine grain silver halide emulsions with polyheteronuclear sensitizing dyes
US3782957A (en) Fogged,direct-positive silver halide emulsion layer containing a cyanine dye and a compound containing a metal of group viii of the periodic table
US3369905A (en) Photographic silver halide emulsions containing polyamine sensitizing agents
US3988513A (en) Silver halide emulsions for recording electron rays
US3769025A (en) Spectrally sensitized silver halide photographic emulsion
US3615517A (en) Direct-positive silver halide emulsion containing halogen conductor and electron acceptor developed with polyhydroxy benzene
US3567456A (en) Photographic direct-reversal emulsions
US3367780A (en) Direct-print photographic silver halide emulsions
US3627534A (en) Direct positive photographic emulsion stabilized against development stain
US3364032A (en) Light-developable halide emulsions
US3745015A (en) Spectral sensitization of photodevelopable silver halide emulsions
US3770449A (en) Spectrally sensitized silver halide photographic emulsion
US3745014A (en) Spectrally sensitized silver halide photographic emulsions