Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/10—The polymethine chain containing an even number of >CH- groups
  • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
• • 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
• • 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

Definitions

• the present invention relates to a silver bromoiodide emulsion comprising crystalline grains containing mixed crystals of silver bromoiodide having iodide ions and one or more sensitizing dyes absorbed on the surface thereof and, more particularly. it relates to an improved silver bromoiodide photographic emulsion suitable for spectral sensitization to green light.
• the spectral sensitivity of a photographic emulsion can be extended from the spectral sensitivity intrinsic to the silver halide (mainly ranging from the near ultraviolet region to the blue light region) to visible light of longer wavelengths or to the infrared region by the addition of dyes of the cyanine series to the photographic emulsion. This procedure is termed spectral sensitization.
• a variety of combinations of dyes and photographic emulsions have been developed in order to use the above-mentioned spectral sensitization, depending on the purpose of the particular photographic lightsensitive material.
• the dye/emulsion combination is the main factor that determines in which spectral region the emulsion is sensitized, and how much sensitivity the emulsion is provided.
• a number of inventions have been made to improve the emulsions with respect to other desirable characteristics such as rapid processing capability, good storage capability of the light-sensitive material and latent images thereon, lowered color stain in the processed light-sensitive materials and the like, by the use of a specific dye/emulsion combination.
• a difficulty arises from the fact that the main spectral reflection region of the green of the leaves of natural plants usually lies at about 550 nm, while the main spectral reflection region ofartificial green (such as the green of artificial plants, e.g., Hung-Kong flowers, and that of different types of printed material) lies in the range of from 510 to 530 nm.
• the main spectral reflection region ofartificial green such as the green of artificial plants, e.g., Hung-Kong flowers, and that of different types of printed material
• the object of the present invention is to provide a silver halide photographic emulsion capable of markedly improving the above-described difficulties, more specifically, an object of the present invention is to provide a photographic emulsion in a gelatino-silver bromoiodide photographic light-sensitive material wherein spectral sensitization in the green region is provided in a desired spectral wavelength region with- DETAILED DESCRIPTION OF THE INVENTION It could not have been expected from the prior art that the spectral sensitivity region could be precisely adjusted as desired without encountering the aforesaid difficulties, i.e., changes in sensitivity, etc., as described above.
• the present invention makes it extremely easy to design a lightsensitive material according to the desired end use of the element.
• iodide ions are, of course, included in the grains as a mixed crystal, and hence it would naturally be supposed that a certain amount of iodide ions exist on the surface of the grains. It is therefore a surprising discovery that, in spite of the above fact, a certain addition amount of iodide ions provides marked effects from the viewpoint of spectral sensitization.
• iodide ions can sometimes be added accidentally to a photographic emulsion together with spectral sensitizing dyes. That is, many of the cyanine dyes frequently employed as spectral sensitizing dyes are cationic dyes, and when these dyes have an iodide ion as a counter ion, iodide ions are added to the photographic emulsion together with the dye cations without any intention of doing such, and they sometimes adsorb on the silver halide grains.
• the molar amount of iodide ions added in such a situation is equal to that of the dye(s) added (That is, conventionally, this amount is very small, as compared with that of the present invention.
• spectral sensitizing dyes used in the present invention are known, for example, they are described in Japanese Pat. publication No. 22884/68. West German Pat. OLS No. 2,030,326. etc.
• spectral sensitivity can be changed by altering the characteristics of the emulsion, above all, by a change in the silver ion concentration. It is true that the adsorption of iodide ions will naturally cause some change in the silver ion concentration. but the effect of the adsorbed iodide ions in a silver bromoiodide system could not be expected from prior art as described above. ln addition, the present invention tends in the direction of reducing the silver ion concentration, which is quite opposite to the direction of increasing the silver ion concentration to raise the spectral sensitivity as is described in the known literature cited above.
• the silver halide photographic emulsion contains silver bromoiodide mixed crystals preferably containing about 0.5 to about mol percent of iodide ions and, as a protective hydrophillic colloid, a major proportion of gelatin.
• a protective hydrophillic colloid conventionally used in the art, such as phthalated gelatin, polyacrylic amide, polyvinylalcohol, polyvinylpyrrolidone, may be used, of course.
• the ratio of silver iodobromide to protective colloid is from about 3:1 to about 1:3, by weight. This is not overly critical, however, and greater and lesser proportions can be used.
• the mean grain size ofthe silver bromoiodide usually ranges from 0.2 to 2 3 p. in diameter, of course, finer or larger grain size silver halide may be used in the present invention.
• These grains are usually subjected to various sensitizing processes usually known as chemical ripening (such as sulfur sensitization, noble metal sensitization, reduction sensitization and the like).
• the iodide ions are usually added to the system as a water-soluble iodide ion compound, generally added to the silver bromoiodide photographic emulsion sol in the form of an aqueous solution.
• the water-soluble iodide ion compound is prefered to be completely soluble or substantially soluble in water.
• the term watersoluble implies at least 10 weight percent solubility as a practical matter.
• salts for example, alkali metal salts such as sodium iodide and potassium iodide; Col amine salts such as ammonium iodide; and alkali earth metal such as Znl Cdl Cal Srl and Bal
• the proportion of iodide ions added, based on the silver bromoiodide, is at least 0.01 mol percent and preferably no more than l.0 mol percent, most preferably 0.05 to 0.3 mol percent, which is suitably adjusted depending upon the kind of the sensitizing dye and emulsion.
• an iodide ion compound and a bromide ion compound may be mixed to form an aqueous solution, and added to a sol-state silver bromoiodide emulsion.
• This concentration of iodide and/or bromide is in addition to any bromide or iodide present throughout the grains as mixed silver halide. This procedure may give more reproduceable results with the invention than the single addition of iodide.
• the aqueous solution containing iodide ions is added to the emulsion and sufficiently stirred. Substantially all of the iodide ions added are believed to immediately absorb on the silver bromoiodide grains. This is easily recognized by an immediate change in color of the grains.
• an organic solution of a spectral sensitizing dye which provides green sensitivity is added to the resulting silver bromoiodide photographic emulsion (maintained in the sol state) to which iodide ions have been added there is added an organic solution of a spectral sensitizing dye which provides green sensitivity.
• a spectral sensitizing dye which provides green sensitivity.
• a substantially lesser amount may provide lessened effects, whereas no overly significant increase is encountered by using substantially greater amounts.
• green sensitizing dye includes both an anionic dye and a cationic dye with or without an iodide ion as a counter anion.
• cyanine dyes comprising an oxacarbocyanine skeleton, such as benzoxacarbocyanine, naphthoxacarbocyanine, etc.
• group I cyanine dyes comprising a benzimidazolocarbocyanine skeleton, a henzimidazoloxacarbocyanine skeleton or a benzimidazoloindocarbocyanine skeleton, such as benzimidazolonaphthoxacarbocyanine, etc.
• cyanine includes cyanine dyes and merocyanine dyes, e.g., monomethine cyanine dyes and carbocyanine dyes.
• cyanine dyes feature the amidinium ion chromophore system wherein each nitrogen atom is contained in a beterocyclic ring.
• dyes represented by the following general formula (I) are used among the dyes belonging to group (I):
• aryl group nucleus results in. for example, an a-naphthoxazole nu- 5 (eg. phenyl. tolyl group. etc.). cyano group. carbamcleus.
• B.B-naphthoxazole nucleus or B-naphthoxazole oyl group (carbamoyl. methylcarbamoyl. phenylcarnucleus)
• R represents a hydrogen atom. lower alkyl bamoyl. dimethylcarbamoyl. diethylcarbamoyl. morgroup (e.g., methyl. ethyl, n-propyl group. etc.), aryl pholinocarbamoyl, piperidinocarbamoyl group. etc), group (eg. phenyl, tolyl group. etc.) etc.
• R and R alkylsulfonyl group (e.g.. methylsulfonyl group. etc.). each represents an alkyl group (such as methyl. ethyl, ll! alkylaminosulfonyl group (e.g.. methylaminosulfonyl. n-propyl group), hydroxyalkyl group (e.g.. 2- ethylaminosulfonyl. dimethylaminosulfonyl. morhydroxyethyl. 3-hydroxypropyl, 4-hydroxybutyl group. pholinosulfonyl, piperidinosulfonyl.
• alkyl group such as methyl. ethyl, ll! alkylaminosulfonyl group (e.g.. methylaminosulfonyl. n-propyl group)
• hydroxyalkyl group e.g.. 2- ethylaminosulfonyl. dimethylaminosul
• B and B can represent the atoms necessary kyl group (e.g., 2'methoxyethyl, B-methoxypropyl to form a bengene ring. Y represe ts group, etc.).
• alkyl group containing a carboxyl group e.g., carboxymethyl, 2carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2-(2-carboxyethoxy)ethyl group, etc.
• an alkyl group containing a sulfo group e.g.. 2- 8 sulfoethyl 3 Sulfompy] 4 sulfobutyl, wherein R and R each represents an alkyl group (e.g.. sulfopropyl.
• R4 and s represent the Same alkyl nate. methylsulfate, ethyl-sulfate, perchlorate.
• p-tolgroups as R or R 0 represents a y rog n a m r uenesulfonate ion, etc), and n represents l or 2.
• A,, A A R, R and R may be the kylene group (e.g.. dimethylene. trimethylene group.
• iodide ions and the green sensitizing dyes are added to a sol-state photographic emulsion to adsorb them onto the surface of the silver the exposure surface for 1/100 second through a yellow filter and a neutral continuous wedge, the yellow filter cutting blue light and thus enabling one to measure only the sensitivity of the spectrally sensitized region.
• the exposed samples were developed in the followof a water-soluble iodide to a green sensitizing dye ing developer at C for 6 minutes. added is preferred to be within a range of from more Developer Composition: than 1 to about 6.
• the green sensitizing dye employed is preferably a dye without an iodide counter anion Monol (Trade name used by Fuji Photo Film when the ratio is near 1.
• the sol-state photographic emulsion is appotassium bromide 3 g plied to a support film comprising cellulose triacetate,
• the de- EXAMPLE 1 A negative-working photographic emulsion comprising silver bromoiodide grains having a mean grain diameter of 0.7 u and containing 7.1 mol percent of 10- Immediately after the development. the materials were processed in a stopping bath (0.3 percent glacial acetic acid soln.), then in a fixing bath (Kodak F-5 solution; Kodak" is a registered trade mark), washed and dried. The optical density of the silver image formed was measured, and the sensitivity was determined from the reciprocal of the exposure required to obtain an optical density of 0.5 above fog. The results obtained are shown in Table 4.
• the resulting emulsions (sol state) were applied on to a cellulose triacetate film base in a coating amount of 15 mg of silver/dm to a thickness of 5 #(after drying), and then dried.
• the materials thus obtained were exposed to light of 4.800K (a tungsten lamp provided with a prescribed pected by increasing the amount of the dye (1) added, a further increase in sensitivity can be obtained by using potassium iodide together with the dye(s).
• the suitable amount lies between 50 and mg of potassium iodide per mol of silver.
• Such a dye combination is andye as the major constituents of this layer).
• other embodiment of the present invention Onto the resulting green sensitive layer were applied successively a colloidal silver yellow filter layer, a blue EXAMPLE sensitive layer (containing 4-dodecyl-benzoyl-2- Dyes given in Table 5 were added to the same silver methoxy-acetanilide yellow coupler), and a protective bromoiodide photographic emulsion as in Example 1. film layer to obtain a color light-sensitive material.
• the amount of potassium iodide added The sensitivity of the light-sensitive material thus obwas fixed.
• EXAMPLE 3 light-sensitive material was directly exposed to the light 0
• lightsensitive material is shown below.
• EXAMPLE 4 The same silver bromoiodide photographic emulsion as in Example I was maintained in a sol state at 35C. and an aqueous solution of potassium iodide and a methanol solution of dye(s) were added thereto as shown in Table 7 to adsorb the dye(s) and iodide onto the grains. The resulting emulsions were applied and dried in the same manner as in Example I, and subsequently subjected to sensitometry measurements to thereby obtain the sensitivity data shown in the following Table. In the case of using these dyes too. the same effect of potassium iodide as was illustrated in the foregoing Examples can clearly be recognized.
• a silver bromoiodide negative-working photographic emulsion of the developing out type which is subjected to only one exposure followed by wetdeveloping, said emulsion containing at least one green sensitizing dye to effect green sensitization thereof
• a silver bromoiodide photographic emulsion wherein at least 0.01 mol percent of iodide ion based on silver halide adsorbs on the surface of silver bromoiodide grains contained in the emulsion.
• said iodide ion being in addition to iodine present in said silver iodobromide grains and said green sensitizing dye intensely sensitizing said emulsion to green without substantially deteriorating its photographic properties
• said green sensitizing dye is represented by one of the following general formulae wherein A, and A,-, each represents a hydrogen atom or halogen atom.
• a and A represent a hydrogen atom. halogen atom, hydroxy group. alkoxy group. amino group, acylamido group, acyloxy group, alkoxycar-.
• B represents a hydrogen atom or halogen atom.
• B 8;, and B each represents a hydrogen atom, halogen atom, lower alkyl group. amino group, acylamido group, acyloxy group, alkoxycarbonyl group, carboxyl group. alkoxy group, aryl group, cyano group, carbamoyl group. alkylsulfonyl group. alkylaminosulfonyl group or aminosulfonyl group, or. when taken together, 8,, and B, can represent the atoms necessary to form a benzene ring.
• Y represents O- wherein R and R each represents an alkyl group,
• R represents an alkyl group
• R R and R represent the same alkyl groups as R or R R represents a hydrogen atom or R and R may combine with each other through an alkylene group.
• m represents l or 2.
• the photographic emulsion as claimed in claim 1 comprising silver bromoiodide mixed crystals with about 0.01 to about 1.0 mol percent of iodide ions adsorbed on the surface thereof.
• the halogen atom in A,, A or B is chlorine, bromine, iodine or fluorine; wherein the alkoxy group is methoxy or ethoxy, the amino group is amino, methylamino or dimethylamino, the acylamido group is acetoamido or propionamido, the acyloxy group is acetoxy, the alkoxycarbonyl group is methoxycarbonyl, ethoxycarbonyl, propioxycarbonyl or butoxycarbonyl in A A B B or B the lower alkyl group is methyl, ethyl or isopropyl in A or A wherein the lower aklyl group is methyl, ethyl or n-propyl, and' the aryl group is phenyl or tolyl in R wherein the alkyl group is methyl, ethyl or n-propyl, the hydroxyalkyl group is
• said green sensitizing dye is a cyanine dye selected from the group:
• the photographic light-sensitive silver halide material which comprises a support having thereon at least one layer comprising a photographic emulsion as claimed in claim 1.
• a process for spectrally sensitizing a negativeworking silver bromoiodide photographic emulsion of the developing out type which is subjected to only one exposure followed by wet-developing said emulsion containing at least one green sensitizing dye which effects the green sensitization of said emulsion, the improvement comprising adsorbing at least0.l mol percent iodide ions on the surface of the silver halide grains in the emulsion, said iodide being in addition to iodine present in said silver iodobromide, whereby the emulsion is intensely sensitized to green without substantially deteriorating its photographic properties
• said green sensitizing dye is represented by one of the following general formulae wherein A, and A, each represents a hydrogen atom or halogen atom, A and A, represent a hydrogen atom, halogen atom, hydroxy group, alkoxy group, amino group.
• acylamido group can be the atoms necessary to form a benzene nucleus
• R respresents a hydrogen atom, lower alkyl group, or aryl group
• R and R each represents an alkyl group, hydroxyalkyl group, acetoxyalkyl group, alkoxyalkyl group, alkyl group containing a carboxyl group, alkyl group containing sulfo group, benzyl group, phenethyl group or a vinylmethyl group;
• B represents a hydrogen atom or halogen atom
• B B and 8 each represents a hydrogen atom, halogen atom, lower alkyl group, amino group, acylamino group, acyloxy group, alkoxycarbonyl group, carboxyl group, alkoxy group, aryl group, cyano group, carbamoyl group, alkylsulfonyl group, alkylaminosulfonyl group or aminosulfonyl group, or, when taken together, B and B can represent the atoms necessary to form a benzene ring
• Y represents O wherein R, and R, each represents an alkyl group
• R represents an alkyl group
• R represents an alkyl group
• R represents the same alkyl groups as R, or R R,, represents a hydrogen atom or R,-, and R may combine with each other through an alkylene group
• m represents l or 2.
• bromide ion in an amount of from l to 30 times of the molar concentration of the iodide ion added is also adsorbed on the surface of silver bromoiodide grains contained in the emulsion.
• said emulsion comprises silver bromoiodide mixed crystals with about 0.01 to about 1.0 mol percent of iodide ions adsorbed on the surface thereof.
• the halogen atom in A,, A, or B is chlorine, bromine, iodine or fluorine; wherein the alkoxy group is methoxy or ethoxy, the amino group is amino, methylamino or dimethylamino, the acylamido group is acetoamido or propionamido; the acyloxy group is acetoxy, the alkoxycarbonyl group is methoxycarbonyl, ethoxycarbonyl, propioxycarbonyl or butoxycarbonyl in A A B 8,, or 8,; the lower alkyl group is methyl, ethyl or isopropyl in A or A wherein the lower alkyl group is methyl, ethyl or n-propyl, and the aryl group is phenyl or tolyl in R, wherein the alkyl group is methyl, ethyl or n-propyl, the hydroxyalkyl group is
• the alkyl group containing a carboxy group is carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl or 2-(2-carboxyethoxy)ethyl
• the alkyl group containing a sulfo group is 2- sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 2-hydroxy-3- sulfopropyl, 2-(3-sulfopropoxy) ethyl, 2-acetoxy-3- sulfopropyl, 3-methoxy-2-(3-sulfopropoxy)propyl, 2- [2-(3-sulfopropoxy)-ethoxylethyl, p-sulfobenzyl, psulfobenzyl or p-sulfophenethyl in R,.
• R R,,. R, or R,-,' wherein the lower alkyl group is methyl, ethyl or trifluoromethyl, the aryl group is phenyl or tolyl, the carbamoyl group is carbamoyl, methylcarbamoyl, phenylcarbamoyl, dismethylcarbamoyl, diethylcarbamoyl morpholinocarbamoyl or piperidinocarbamoyl, the alkyl sulfonyl group is methyl sulfonyl, the alkylaminosulfonyl group is methylaminosulfonyl, ethylaminosulfonyl, dimethylaminosulfonyl, morpholinosulfonyl, piperidinosulfonyl or pyrrolidinosulfonyl in B B or 8,; wherein the alkyl group in R, or R, is methyl, ethy
• said green sensitizing dye is a cyanine dye selected from the group:

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• 1971
  • 1971-10-28 JP JP46085835A patent/JPS4851627A/ja active Pending
• 1972
  • 1972-10-26 FR FR7237990A patent/FR2157975B1/fr not_active Expired
  • 1972-10-26 DE DE2252585A patent/DE2252585A1/de active Granted
  • 1972-10-27 GB GB4977672A patent/GB1413826A/en not_active Expired
  • 1972-10-30 US US301912A patent/US3864134A/en not_active Expired - Lifetime

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