US3816121A - Direct positive photographic material containing a color coupler under one micron in size and fogged silver halide grains with substantially no internal sensitivity having absorbed on the surface a desensitizing dye containing a solubilizing group - Google Patents

Direct positive photographic material containing a color coupler under one micron in size and fogged silver halide grains with substantially no internal sensitivity having absorbed on the surface a desensitizing dye containing a solubilizing group Download PDF

Info

Publication number
US3816121A
US3816121A US00286395A US28639572A US3816121A US 3816121 A US3816121 A US 3816121A US 00286395 A US00286395 A US 00286395A US 28639572 A US28639572 A US 28639572A US 3816121 A US3816121 A US 3816121A
Authority
US
United States
Prior art keywords
silver halide
color
group
nucleus
emulsion
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
US00286395A
Other languages
English (en)
Inventor
K Shiba
A Sato
H Amano
H Ueda
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.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
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 Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3816121A publication Critical patent/US3816121A/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
    • G03C1/485—Direct positive emulsions
    • G03C1/48515—Direct positive emulsions prefogged
    • G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser
    • G03C1/4853—Direct positive emulsions prefogged characterised by the desensitiser polymethine dyes
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/141—Direct positive material

Definitions

  • ABSTRACT A color photographic material having at least one silver halide photographic emulsion layer containing chemically fogged direct positive silver halide grains, said silver halide photographic emulsion layer simultaneously satisfying the following criteria:
  • said silver halide photographic emulsion having substantially no free electron trap in said silver halide grains
  • said silver halide photographic emulsion having adsorbed on the surface of said silver halide grains an electron acceptor having a water-soluble anionic group or an anionic group forming a betaine structure;
  • said silver halide emulsion containing droplets of an oil-soluble color coupler dispersed therein, the mean droplets size in diameter of said coupler being smaller than about 1 micron;
  • said silver halide emulsion layer forming a color image on development with a color developing solution containing a phenylenediamine or a derivative thereof as the color developing agent is disclosed.
  • FIG I LOG E (RELATIVE VALUE) LOGE (RELATIVE VALUE) 5 0 I. Is 0 ESE 25$ 6 552%
  • FIG. l5 (RELATIVE VALUE) 5 0 I. Is 0 ESE 25$ 6 552%
  • the present invention relates to a color photographic material for obtaining a color positive image directly by using a color developing solution containing a conventionally used phenylenediamine derivative. More particularly, the invention relates to a direct positive type color photographic material having improved sensitivity-, clearness of the highlight portions, exposure latitude, and color reproducibility as well as an excellent stability.
  • a negative image of an original is obtained by a series of developing procedures including one developing process. Accordingly, in order to obtain a positive image of an original using such an ordinary silver halide photographic light-sensitive material, it is required that the negative image obtained by conducting the above-described series of developing procedures is exposed again for printing and further another series of developing procea washing, a bleaching, a washing, a fixing, a washing, and a stabilization. In general, such a system is quite troublesome and requires a considerable period of time. Therefore, it is frequently advantageous to record or reproduce a positive image directly as the positive image.
  • the direct positive color photographic material of this invention can provide a color positive image directly from an original by processing it using color developing procedures ordinarily used for developing color photographic negative materials and color photographic positive materials and in particular color photographic papers.
  • a color positive image can be obtained from an original rapidly, easily and economically by using conventionally employed color developing procedures.
  • an ordinary direct positive color photographic material has been found at present to have various defects.
  • the production of the direct positive color photographic materials encounters specific technical difficulties. They are as follows:
  • the first difficulty is that the sensitivity is low, in particular, the spectral sensitivity in a specific wave length region is low.
  • the second difficulty is that the clearness at the highlight portions is insufficient.
  • the third difficulty is that in the process of producing photographic sensitive materials, the flowable emulsions are poor in stability and also the maintenance of uniform photographic properties is difficult.
  • the fourth difficulty is that the direct positive color photographic materials are poor in stability.
  • the fifth difficulty is that a sufficient gradation is difficult to obtain.
  • An object of this invention is, therefore, to improve these defects.
  • a silver halide emulsion which contains adsorbed on the surface of the silver halide grains an electron acceptor having a water-soluble anionic group or such an anionic group that can provide a betaine structure in the molecule, in particular at least one sulfo group, carboxyl group, or phosphoric acid group,
  • a silver halide emulsion which contains a hydrophobic color coupler dispersed in a hydrophilic colloid or water, in particular an oil-soluble color coupler in such a condition that the mean particle size thereof is less than about one micron,
  • a silver halide emulsion which can provide a colored dye image by using a color developing solution containing a phenylenediamine derivative (this term includes those compounds which are equivalent to the derivative) as the color developing agent.
  • a color photographic material meeting the objects of this invention is provided according to this invention by applying to an appropriate support at least one layer of the fogged direct positive silver halide photographic emulsion satisfying the aforesaid four criteria.
  • FIGS. 1, 2, 3,and 4 are characteristic curves of the silver halide photographic emulsion of this invention and silver halide photographic emulsions prepared for the purposes of comparison.
  • FIGS. 5 to 14 are spectrophotographs obtained using the silver halide photographic emulsions of this inventron.
  • FIG. 15 is a spectral transmittance curve of Filter K-31 and Wratten 47B Filter. 1
  • the first feature of this invention is in the photosensitive characteristics of the silver halide grains contained in the silver halide photographic emulsion. That is to say, the surface of the silver halide grains in the direct positive type silver halide photographic emulsion has been chemically fogged and the fogged silver halide grains absorb exposed radiations, preferably visible rays, ultraviolet rays, electron beams, gamma-rays, etc., to generate free electrons in the grains, while forming positive holes at the surface of or inside of the silver halide grains. In this case, if electron trap are present in the silver halide grains preferably at the central portion of each silver halide grain, the free electrons are caught by the electron trap.
  • the silver halide photographic emulsion used in this invention comprises silver halide particles having substantially no free electron trap in the particles and a hydrophilic colloid.
  • a direct positive photographic emulsion having electron trap is well known as the internal sensitive emulsion, the core-outershell type emulsion and so on which are disclosed in Japanese Patent Publication No. 4125/68; Japanese Patent Publication No. 29,405l68; the specifications of US. Pat. Nos. 2,401,051; 2,717,833; 2,976,149; and 3,023,102; the specifications of British Pat. Nos. 707,704; 1,097,999; and 690,997; the specifications of French Pat. Nos. 1,520,822; 1,520,824; 1,520,817; and 1,523,626; and the specifications 'of Belgian Pat. Nos. 713,272; 721,567; and 681,768.
  • the direct positive photographic emulsion of the type having electron trap has a comparatively high possibility that the positive holes are recombined with electrons generated in the silver halide grains and since the positive holes are reluctant to react effectively with the fogging specks, such a direct positive emulsion has a characteristic that the provision of high sensitivity to the emulsion is difficult. Furthermore, the important matter in such a direct positive emulsion is that the free electron trap in the silver halide grains become a latent image and if they are positioned comparatively at a surface portion, they act as developing centers and they reduce the highlight clearness. Moreover, they give a negative image in the highlight domain to greatly narrow the exposure latitude.
  • a photographic emulsion having substantially no free electron trap in the silver halide grains does not give a sufficient direct positive image by itself. Therefore, in order to improve the properties of such a photographic emulsion, it has been proposed to adsorb an electron acceptor or a material having a similar function to any electron acceptor on the surface of silver halide grains.
  • a direct positive type silver halide emulsion is a photographic emulsion of the type having substantially no free electron trap in the silver halide grains as in this invention or not can be easily and clearly determined by one skilled in the art according to the following method: That is to say, a fogged direct positive silver halide photographic emulsion is coated on a support such as a glass sheet, a polyethylene terephthalate film base or a cellulose triacetate film base in a dry thickness of less than about 5 microns. In this case it is preferable that the amount of silver halide coated be so selected that the maximum optical density obtained due to development becomes 1.0 to 1.5.
  • the sample thus prepared is exposed behind an optical wedge to a sufficient amount of blue light or white light, developed for 2 minutes at 20C. using a Developer D-72 made by the Eastman Kodak Company, having the following composition:
  • a sample prepared in the same manner as described above is degassed for longer than 17 hours at normal temperature under a reduced pressure of mm/I-Ig and subjected to sensitometry using the same blue light or a white light as described above under reduced pressure to provide a characteristic curve.
  • the characteristic curve obtained by conducting sensitometry in air is compared with the characteristic curve obtained by conducting the sensitometry in vacuo after subjecting the sample to a degassing treatment.
  • the silver halide photographic emulsion of the sample is defined to have substantially no electron trap in the silver halide particles as in this invention.
  • This definition can be applied not only the samples prepared by the preparation method as described above but also to direct positive light-sensitive materials. Even though the degassing treatment as described above is conducted in a vacuum condition higher than 10" mm/Hg, the above defined value is easily obtained and thus even in such case, the results meeting the definition for the photographic emulsion of this invention are frequently obtained.
  • a chemical sensitization or apply iodine ion an ion of a metal belonging to Group II of the periodic table such as a Zn ion or a Sr ion, an ion of a metal of Group VIII, such as an Ir ion, a Rh ion, a Ru ion, or a Pt ion, or an ion of a metal of Group V, such as a Bi ion or an As ion.
  • Example of materials which can be used to provide the above metal ions include zinc chloride, zinc nitrate, strontium chloride, strontium sulfate, hexahalogeno iridate, trihalogeno iridate, hexahalogeno rhodate, hexahalogeno ruthenate, hexahalogeno platinate and the like.
  • zinc chloride zinc nitrate
  • strontium chloride strontium sulfate
  • hexahalogeno iridate trihalogeno iridate
  • hexahalogeno rhodate trihalogeno iridate
  • hexahalogeno ruthenate hexahalogeno platinate and the like.
  • the method of using the degassing effect discovered by the inventors of the present invention is based on the fact that the efficiency of the free electrons which can be accepted on the surface of the silver halide grains or accepted outside the grains are extremely reduced and it is believed to be a very clear, excellent, and reasonable method. This method will be further explained more specifically in Experiment 1.
  • a second feature of this-invention is in the point that an electron acceptor having at least one anionic radical, which is a water-soluble radical such as a sulfo radical, a carboxyl radical or a phosphoric acid radical, and can form a betaine structure in the molecule with a core atom having a positive charge formed by the localized presence of IT-ElCCU'OIlS or by ionization is adsorbed on the surface of the silver halide grains.
  • an electron acceptor having at least one anionic radical which is a water-soluble radical such as a sulfo radical, a carboxyl radical or a phosphoric acid radical, and can form a betaine structure in the molecule with a core atom having a positive charge formed by the localized presence of IT-ElCCU'OIlS or by ionization is adsorbed on the surface of the silver halide grains.
  • the silver halide photographic emulsion of this invention contains the electron acceptor and a color coupler
  • the electron acceptor used in this invention by introducing at least one of the anionic radicals as defined above into the electron acceptor, not only is the reduction of the spectral sensitivity prevented but also the desensitization of the silver halide grains by the adsorption of the color coupler and the reduction of the clearness of the highlight portions are also prevented and further the intrinsic sensitivity of the silver halide grains is also increased.
  • the electron acceptor asdefined in this invention is present together with a color coupler, excellent results meeting the objects of this invention are obtained.
  • the electron acceptor in this invention When the electron acceptor in this invention is used together with a soluble bromine ion, iodine ion, or a mixture thereof, the adsorption of the electron acceptor is further improved, the desensitization by a color coupler is prevented, and in particular the spectral sensitivity is also increased, which give advantageous results to the production of the color photographic materials of this invention.
  • the electron acceptor used in this invention includes many of so-called desensitizers or deor non-sensitizing dyes.
  • the electron acceptor may be a compound capable of catching the free electrons of silver halide grains and having the lowest vacant electron energy level lower than the electron conduction band of the grains.
  • the electron acceptor in this invention is a compound having a maximum occupied electron energy level lower than the valence electron band of the silver halide grains. It is known that those electron energy levels correspond linearly to the cathodic polarographic halfwave potential (E or the anodic polarographic halfwave potential (E).
  • the electron acceptor of this invention is preferably a compound having an E value equal to or more positive than l.0 volt and an E value equal to or more positive than 0.7 volt.
  • An E value equal to or more positive than l.0 volt means that the electron acceptor has an electron affinity capable of sufficiently catching the free electrons.
  • an E value equal to or more positive than 0.7 volt means that the electron acceptor has an ionization potential capable of not too effectively catching the positive holes formed in the silver halide grains.
  • the E value is determined by measuring in an acetonitrile solution containing tetra-n-propylammonium perchlorate as a supporting electrolyte at 25C. using a mercury dropping electrode and further a saturated calomel electrode (SCE) as a reference electrode. Furthermore, the value is measured in an acetonitrile solution of l X 10" mole to l X 10 mole per liter.
  • the E value is determined by using sodium perchlorate as a supporting electrolyte, a rotary platinum electrode as an anode, and a saturated calomel electrode as a reference electrode (see, the specification of German OLS No. 2,010,762).
  • the third feature of this invention is in the point that the silver halide emulsion contains an oil-soluble color coupler in a dispersed state of fine particles having a mean particle size of less than about 1.0 micron.
  • a sulfo radical, a carboxyl radical, a hydroxyl radical, or an amino radical is introduced into the molecule of a color coupler, the color coupler is dispersed in a hydrophilic colloid as an aqueous solution or an alkaline solution thereof, and the dispersion is incorporated in a silver halide emulsion in micelle form.
  • a method of solubilizing the color coupler with the aid of a surface active agent and incorporating the coupler in a silver halide emulsion are also provided.
  • a color coupler which is soluble in an oil such as fat but substantially insoluble in water (for instance, having a solubility in water of less than 1 percent by weight) is dissolved at least partially in a high boiling plasticizer such as tricresyl phosphate, polyethyl acrylate, polybutyl methacrylate, di-
  • butyl phthalate, and a biphenyl ether derivative or an oil such as a fat or an oil it is then dispersed in an emulsion as fine particles with the aid of a surface active agent.
  • oil-soluble color coupler itself is oily or in a liquid state at high temperatures
  • a method is known in which the coupler is directly dispersed in an emulsion with the aid of a surface active agent.
  • the coupler is mechanically ground into fine particles and they are dispersed in an emulsion.
  • a color coupler can be dispersed in an emulsion together with a hydrophilic colloid by utilizing the intramolecular co-action between the coupler and the hydrophilic colloid.
  • a color coupler capable of forming a dye with a color developing solution containing a penylenediamine derivative as a color developing agent in the presence of silver halide grains which have become developable by exposure or chemical fogging can be said to have a certain reducing power, principally, to the oxidation product of the color developing agent.
  • a color coupler When a color coupler is adsorbed on silver halide grains, it frequently forms positive hole traps in the silver halide grains.
  • a magenta couple r for instance, a coupler having a -pyrazolone nucleus, a coupler having an indazolone nucleus, and a coupler having a cyanoacetophenone nucleus has a strong tendency for this. Accordingly, when such a color coupler is incorporated in a direct positive silver halide emulsion, it tends to give adverse effects such as a reduction in sensitivity, a reduction in the cleamess of the highlight portions, and a deterioration of the stability. Thus, when such a color coupler is used for color photographic materials, a specific technique is required.
  • the inventors have discovered that the above disadvantages can be removed by pre-dispersing the oilsoluble color coupler which is substantially insoluble, in water in a sufiiciently fine state corresponding to the size of the silver halide grains, e.g., as fine particles of less than 1 micron and adding the dispersion to a silver halide emulsion.
  • This remarkable phenomenon is not presently known by persons skilled in the art and the surprising effects have not been reported in any of the literature.
  • the fourth feature of this invention is in the point that a direct positive color photographic image having good cleamess of the highlight portions, a wide exposure latitude, and sufficient gradation can be obtained by the developing process in a' color developing solution using a conventional phenylene-diamine type color developing agent.
  • a conventionally employed color developing solution has generally the property of developing even an internal latent image and also-a physical developing property. Therefore, in the case of developing in such a conventional color developing solution, the cleamess of highlight portions is greatly reduced and thus the highlight portion is apt to be developed to form a negative image again in comparison with the case of using a conventional black and white developing solution. Accordingly, a specific improvement has been required in the color developing process. However, as described above, it is extremely economical from the standpoint of simplification in a mono-bath process to employ the conventional color developing process.
  • the fifth feature of the present invention is in the point that the objects of this invention can be first attained by combining the above-described factors of this invention. This will be readily understood from the following description in this specification.
  • the silver halide photographic emulsion used in this invention is one which has previously been fogged chemically.
  • the fogged nuclei are provided by the addition of an inorganic reducing compound such as stannous chloride or a hydrated borate or an organic reducing compound such as a hydrazine derivative, formalin, thiourea dioxide, a polyamine compound, an amine borane, and methyl dichlorosilane.
  • an inorganic reducing compound such as stannous chloride or a hydrated borate
  • an organic reducing compound such as a hydrazine derivative, formalin, thiourea dioxide, a polyamine compound, an amine borane, and methyl dichlorosilane.
  • a combination of a reducing agent and metal ions more noble than silver ions or a combination of a reducing agent and hydride ions can be used for the chemical foggingof silver halide photographic emulsion as described in the specifications of, e.g., US.
  • gelatin is ordinarily used as the protective colloid but the use of inactive gelatin is particularly advantageous.
  • an inactive gelatin derivative or a hydrophilic synthetic polymer such as polyvinyl acrylate, polyvinyl alcohol, polyvinyl pyrrolidone, and polyvinyl alginate may also be used in place of the gelatm.
  • the silver halide photographic emulsion of this invention may contain a mercapto compound, a thion compound, or a tetraazaindene derivative as a stablizer for the fogged nuclei; a stilbene compound or a triazine compound as a modifier for clearness;.a brightening agent; a ultraviolet adsorbent; a fading preventing agent for colored images; chrome alum, a 2,4-dichloros-triazine compound, an aziridine compound; or an epoxy compound as a hardening agent; an anionic surface active agent or an amphoteric surface active agent as a dispersing and spreading agent; a lubricating agent; and a plasticizer.
  • a mercapto compound, a thion compound, or a tetraazaindene derivative as a stablizer for the fogged nuclei
  • a stilbene compound or a triazine compound as a modifier for clearness
  • B represents an atomic group necessary for forming a heterocyclic ring, which is usually selected from the heterocyclic ring nuclei used in cyanine dyes such as 2-quinoline benzoxazole, quinoxaline, indolenine nuclei;
  • R represents an alkyl group (including substituted alkyl groups), an unsaturated aliphatic group or an aryl group, the alkyl groups being preferably a lower alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, methylvinyl, acetoxyethyl, sulfopropyl, carboxymethyl, carboxyethyl and the like;
  • A represents a phenyl group having at least one nitro group, a naphthyl or a heterocyclic ring nucleus such as indole and pyrazol nuclei and the like;
  • m and n each represents an integer of l or 2, the compound forming a betaine
  • Z represents an atomic group necessary for forming a cycloheptatriene ring
  • L, and L each represents a methine group (including a substituted methine group such as those substituted by methyl, phenyl, cyano or the like)
  • Z represents an atomic group necessary for forming a heterocyclic ring, particularly a heterocyclic nucleus usually used in cyanine dyes
  • X, n, and m have the same meaning as described in General Formula I
  • R represents an alkyl group (including a substituted alkyl group (aralkyl group)) having at least one sulfo group, a carboxyl group, or a phosphoric acid group or an unsaturated aliphatic group, such as methyl, ethyl, propyl, carboxyethyl, carboxybutyl, sulfopropyl, sulfoisobutyl and the like.
  • Z represents an indole nucleus, a carbazole nucleus, or a phenothiazine nucleus;
  • Z has the same meaning as described for Z in the General Formula ll;
  • R represents an alkyl group (including a substituted alkyl group), an unsaturated aliphatic group, or an aryl group such as methyl, ethyl, propyl, carboxyethyl, sulfobutyl, phosphopropyl, methylvinyl, p-sulfobenzyl and the like; the alkyl group being preferably a lower alkyl group having 1 to 6 carbon atoms; the Z Z, or R wherein Z and Z, each represents an atomic group necessary for forming a S-membered or 6-membered heterocyclic nucleus, at least one of Z, and Z representing an atomic group necessary for forming a S-membered or 6-membered heterocyclic nucleus having an electron accepting property or a des
  • heterocyclic nuclei usually used in cyanine dyes include an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a selenazole nucleus, a benzoselennucleus, and a pyrrolopyride nucleus.
  • anions usually used in cyanine dyes include halogen ions, chlorate ions, thiocyanate ions, methyl sulfate ions, ethyl sulfate ions, sulfonate ions, and p-toluenesulfonate ions.
  • the mean grain size used in this invention can be easily obtained from the analysis of the wave length dependence of the light scattering of a coupler-containing emulsion. This method is fundamentally based upon the principle described in the report of R. J. Gledhill et 5 al., Journal of Optical Society of America, Vol. 53, 239-246( 1963).
  • color couplers having at the active methylene position a substituent group capable of conducting splitting development imagewise at the step of color development, such as a halogen atom, an aryldiazo group, an arylthio group, an aryloxy group, or a carboxyl group (the compounds described in, e.g., the specifications of US. Pat. Nos. 3,311,476; 3,408,194; and 3,447,928).
  • the color developing solution used in this invention contains as a color developing agent phenylenediamine or a derivative thereof and a small amount of a sulfite and having a pH in an alkaline region or preferably a pH of higher than 9.8.
  • Suitable examples of such color developing agents are p-amino-N-ethyl-N-B- (methanesulfoamidoethyl -m-toluidine sesquisulfate monohydrate, diethylamino-p-phenylenediamine sesquisulfite, p-amino-N,N-diethyl-m-toluidine hydrochloride, p-amino-N-ethyl-N-B-hydroxyethylphenylene sesquisulfate monohydrate, etc.
  • any known color developing solutions for color photographic negative materials, cine-color photographic negative materials, cine-color photographic positive materials, color photographic papers, and instant color photographic materials can be employed.
  • color developing processes which may be employed in this invention are described in the specifications of Japanese Patent Publication No. 35,749/1970; Japanese Patent Application No. 67,798/ 1969, and Japanese Patent Application No. 13,313/ 1971 as well as described in H. Gordon; The British Journal of Photography; pages 558-, published on Nov. 15, 1954; ibid.; pages 440-, published on Sept. 9, 1955, ibid.; pages 2-, published on Jan. 6, 1956, S. Horwitz; ibid.; pages 212-, published on Apr. 22, 1960; E. Gehret, ibid., pages 122-, published on Mar. 4, 1960; ibid., pages 396-, published on May 7, 1965; and
  • Suitable silver halide photographic emulsions which can be used in this invention are a pure silver bromide emulsion, a silver iodobromide emulsion (including silver bromide grains having iodine ions adsorbed on the surface), a silver chlorobromide emulsion, a silver chloroiodobromide emulsion, and mixtures thereof.
  • the grain size of the silver halide in the photographic emulsion ranges from 0.04 micron to 2 microns, in particular 0. 15-07 micron.
  • a pure silver chloride emulsion or a silver halide emulsion containing silver halide grains coarser than 1 micron is undesirable since in this case the internal sensitivity of the silver halide grains becomes too high.
  • bromine ions or iodine ions can be adsorbed on the surface of the silver halide grains or further the ions having an electron-accepting property or a desensitizing action, such as the ions of a metal of Group lb, Group IVb or Group VIII, e.
  • cupric chloride, lead nitrate, lead bromide, hexachloro iridate, hexachloro rhodate, ferricyanate salt can be adsorbed on the surface of the silver halide grains.
  • the electron acceptorin this invention can be used alone as well as used in combination with other dyes in particular as an electron acceptor. It is preferable to use the electron acceptor in an amount of -.from 1 X 10 mole to5 X 10. mole, preferably from 1 X 10' to 5 X 10 mole per mole of the silver halide in the photographic emulsion. Still further, a photographic dye such as an antihalation dye, an dye which prevents light scattering, or a dye for filter layer can also be used. In particular, a water-soluble dye such as a triphenylmethane dye such as those disclosed in F r'ench Patent No. 2,012,545; British Pat. Nos. 1,027,747; 1,025,567; US. Pat. Nos. 3,382,074 and 3,406,069, a diazo dye such as those disclosed in US. Pat. No.
  • an anthraquinone dye such as those disclosedin US. Pat. Nos. 3,575,704 and 2,865,752, a dye having a nitro group, and a metal chelate dye such as those disclosed in US. Pat. No. 3,364,029 is preferably used.
  • the amount of the color coupler can range from 2mole to l/ 100 mole per one mole of silver halide, preferably 1 mole to 1/60 mole.
  • the finished silver halide emulsion in this invention may be applied on any photographic support such as a glass sheet, a cellulose acetate film, a cellulose acetate butyrate film, apolyester film, a photographic paper, a paper coated with baryta or a polyolefin, or a synthetic paper.
  • a suitable coating amount of the silver halide photographic emulsion can range from 5 mg. to 200 mg., preferably from mg. to 100 mg. per 100 cm based on the amount of silver.
  • the color photographic material of this invention may be one having only one silver halide photographic emulsion layer on a support or having multi-layers of silver halide photographic emulsions on a support. Furthermore, an intermediate layer may be disposed betweenthe two silver halide photographic emulsion layers on a support. Still further, an antihalation layer may be formed on the back side of the support of the color photographic material of this invention or a protective layer or a filter layer may be formed on the silver halide photographic emulsion layer of the color photographic material.
  • Example 1 (Emulsion A) To a first liquid prepared by heating to 60C a mixture of 8 g of inactive gelatin, 5 cc of a one normal aqueous solution of potassium bromide, and 500 cc of water were added with stirring over a period of 50 minutes a second liquid prepared by dissolving 100 g of silver nitrate in 500 cc of water under heating to 60C and a third liquid prepared by dissolving 70 g of potassium bromide in 150 cc of water under heating to 60C and then the mixture was subjected to physical ripening for 5 minutes.
  • the pAg of the mixture was adjusted to 6.0 using an aqueous silver nitrate solution. Furthermore, after adding to the mixture hydrazine and potassium chloroaurate, the pH of the resultant mixture was adjusted to 10 using an aqueous sodium hydroxide solution to complete the ripening. Then, the mixture was neturalized with citric acid and washed with water. Thereafter, a fourth liquid prepared by dissolving 75 g of inactive gelatin in 300 cc of water was added to the above-prepared mixture to provide the silver halide emulsion. The mean grain size of the silver halide emulsion thus prepared was about 0.2 micron and the emulsion contained grains of a normal tetragonal system having a (100) plane.
  • the pAg of the melt was adjusted to 7.0 by adding thereto a mixed solution of an aqueous sodium chloride solution and aqueous potassium bromide solution and then a fourth solution prepared by dissolving g of inactive gelatin in 300 cc of water was added to the resultant mixture to provide the comparison silver halide emulsion.
  • the mean grain size of the silver halide emulsion was about 0.15
  • the substantially all of the grains of the silver halide contained the grains of a normal tetragonal system having a plane.
  • Comparison compound b 8 x 10') 4 cc Each of the samples thus prepared was exposed using an optical wedge to blue light through a k.31 Filter made by the Fuji Photo Film Co., Ltd. by using a tungsten lamp of 2854K under a normal temperature and normal pressure. The sample, then, was developed in the following developing solution for 2 minutes at 20C and fixed at 20C for 20 minutes in a fixing solution having the following composition to provide a strip:
  • thesame sample prepared above was allowed to stand under vacuum conditions of about mm Hg using an oil diffusion pump for about l7 hours at normal temperature to conduct the degassing. Thereafter, the sample was exposed using an optical wedge through a window of the vacuum vessel to blue light through the K-31 Filter using a tungsten lamp of At use, the composition was diluted with water in a volume ratio of l l.
  • Emulsion A was the silver halide emulsion of this invention having substantially no free electron trap in the silver halide grains, while the Comparison Emulsion a was not such a silver halide emulsion of this invention.
  • composition of the developing solution used in the above process was as follows:
  • composition of the Developing Solution Water (about 50C) Metol 3 g Potassium Bromide 2 g Water to make 1,000 cc
  • (A) designates normal temperature and normal pressure
  • (B) designates after evacuation degassing
  • D,,,,-, designates minimum optical density
  • D designates maximum optical density
  • Sens. designates sensitivity, the value of logE at the point of D /Z.
  • the dispersion state of the coupler can be controlled by 23 controlling the particle size of the oil droplets of the coupler. That is to say, by using the coupler dispersion containing the oil droplets of a coupler having a mean particle size of less than about 1 micron, the objects of l Thereafter, 500 g of the dispersion of the coupler prepared by the method shown in Experiment 2 of Example was added to the above mixture and melted.
  • the coupler used is shown in Table 4.
  • this invention can be attained. Then, by adding to the mixture cc of a 2 percent
  • aqueous solution of N-tetradecyl-N,N-di-polyoxyethyl to the evacuation treatment or degassing under the betaine and 10cc of a 2 p cent aqu ous ution conditions as shown in Experiment 1 and exposed in 4-dichloro-6-hydroxy-s-trla a finlshed fimulSlOfl vacuo in situ, reversal images were hardly obtained on Was Oblamedcolor development.
  • the finished emulsion thus prepared was applied to EX eriment 4 a transparent cellulose triacetate film in a dry thickness p of about 3 microns.
  • the photosensitive material ob- 40 cc of a 8 X 10 mole 9 of h compognd tained was exposed using an optical wedge to a tung- S-l was added to 100 g of the Comparison Emulsion Sten lamp f 54 under normal temperature d (a) and after further adding to the mixture 50 g of the l 5 normal pressure emulsion of the Coupler (C- I the resultant emulsion
  • the exposed sample was subjected to a sensitometric was apphed to a cellulose macetate film as Expat" .test according to the procedure as described in Exammam 1 or 3 to Provlde sample 9 TWO Sheets of ple l.
  • Example 2 By repeating Example 1, a fogged silver halide Emulsion A was prepared. After adding the electron accep- 5 tor shown in Table 4 to one kilogram of the emulsion prepared, the mixture was stirred for 20 minutesat 40C. I
  • E and E of the dyes used in the experiment are shown in Table 5. It will be understood that the values of E and E of the dyes used satisfied the above-indicated values (E 2 about 1 .0 volt, E about 0.7 volt).
  • the finished emulsions as shown in Table 6 were prepared and each of the emulsions was applied to a polyethylene coated paper, which had been subjected to a corona discharging treatment for improving the ad- -hesivity of the emulsion.
  • a color positive image having good clearness of the highlight portion could be obtained.
  • a color photographic material having at least one silver halide photographic emulsion layer containing chemically fogged direct positive silver halide grains, said silver halide photographic emulsion layer simultaneously satisfying the following criteria:
  • said silver halide photographic emulsion having substantially no free electron trap in said silver halide grains
  • said silver halide photographic emulsion having adsorbed on the surface of said silver halide grains a desensitizing dye electron acceptor having a water-soluble anionic group or an anionic group forming a betaine structure, selected from the class consisting of at least one sulfo group, carboxy group or phosphoric acid group, said electron acceptor having an E value equal to or more positive than l.0 volt and an E value equal to or' more positive than 0.7 volt;
  • said silver halide emulsion containing droplets of an oil-soluble color coupler dispersed therein, the mean droplets size in diameter of said coupler being smaller than about one micron;
  • said silver halide emulsion layer forming a color image on development with a silver halide developing solution containing a phenylenediamine as the color developing agent.
  • said silver halide grains contain at least 50 mole percent bromine ions and less than 2 mole percent iodine ions and further in which said silver halide grains have a mean grain size of less than 0.7 micron.
  • B represents an atomic group necessary for forming a heterocyclic ring
  • R represents an alkyl group, an unsaturated aliphatic group, or an aryl group
  • A represents a phenol group having at least one nitro group, a naphthyl group or a heterocyclic ring nucleus
  • m and n each represents an integer of l or 2
  • X represents an anion, and wherein at least one of R B or A. contains at least one of a sulfo group, a carboxyl group, or a phosphoric acid group;
  • Z represents an atomic group necessary for forming a cycloheptatriene ring
  • A represents a hydrogen atom, an oxygen atom, or a halogen atom
  • L and L each represents a methine group
  • Z represents an atomic group necessary for forming a heterocyclic ring
  • X, n, and m have the same meaning as described above
  • R represents an alkyl group having at least one sulfo group, a carboxyl group or a phosphoric acid group or an unsaturated aliphatic p;
  • I-IIQHZS z.-L, L2o: oH-orr r'-i-m n-l i
  • Z represents an indole nucleus, a carbazole nucleus, or a phenothiazine nucleus
  • Z represents an atomic group necessary for forming a heterocyclic ring
  • R represents an alkyl group, an unsaturated aliphatic group, or an aryl group, at least one of Z Z or R containing at least one of a sulfo group, a carboxyl group, or a phosphoric acid group
  • L and L each repwherein Z, and Z each represents an atomic group I necessary for forming a S-membered or 6-membered heterocyclic nucleus, at least one of said Z and Z representing an atomic group necessary for forming a S-membered or 6-membered heterocyclic nucleus selected from the group consisting of indolc, nitrosubstituted in
  • heterocyclic nucleus is an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, an indolenine nucleus, an indole nucleus, an imidazole nucleus, a benzoimidazole nucleus, an imidazoquinoxaline nucleus, or a pyrrolopyride nucleus.
  • a color photographic element comprising a support having coated thereon a layer of the color photographic materials of claim 1.
  • said support is a glass sheet, a cellulose acetate film, a cellulose acetate butyrate film, a polyester film, a photographic paper, a buryta coated paper, a polyolefin coated paper, or a synthetic paper.
  • the silver halide emulsion layer is coated to a thickness of less than about 5 microns, exposed to blue light and white light, developed for 2 minutes at 20C. using developer D72 or developer D- l 9, and fixed, to obtain a characteristic curve of the direct positive type, a sample prepared in the above manner compared to a sample prepared identically but being degassed for longer than I?
  • the minimal optical density value D of the degassed sample being higher than the optical density corresponding to 30 percent of the maximum optical density value D of the non-degassed sample or the sensitivity of the degassed sample at a point of one-half of the maximum optical density thereof being lower than 65 percent of the sensitivity of the non-degassed sample at the point of one-half of the maximum optical density thereof, such a silver halide photographic emulsion having substantially no electron traps.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00286395A 1971-09-04 1972-09-05 Direct positive photographic material containing a color coupler under one micron in size and fogged silver halide grains with substantially no internal sensitivity having absorbed on the surface a desensitizing dye containing a solubilizing group Expired - Lifetime US3816121A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6825071A JPS5547378B2 (fr) 1971-09-04 1971-09-04

Publications (1)

Publication Number Publication Date
US3816121A true US3816121A (en) 1974-06-11

Family

ID=13368313

Family Applications (1)

Application Number Title Priority Date Filing Date
US00286395A Expired - Lifetime US3816121A (en) 1971-09-04 1972-09-05 Direct positive photographic material containing a color coupler under one micron in size and fogged silver halide grains with substantially no internal sensitivity having absorbed on the surface a desensitizing dye containing a solubilizing group

Country Status (4)

Country Link
US (1) US3816121A (fr)
JP (1) JPS5547378B2 (fr)
DE (1) DE2243421A1 (fr)
GB (1) GB1371580A (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933506A (en) * 1973-05-18 1976-01-20 Agfa-Gevaert N.V. Spectral sensitization of direct-positive silver halide emulsions
US3933501A (en) * 1973-11-28 1976-01-20 Eastman Kodak Company Photographic elements containing color-forming couplers having and inhibiting effect upon the reactivity of competing couplers
US4015989A (en) * 1974-01-30 1977-04-05 Fuji Photo Film Co., Ltd. Color light-sensitive material with spontaneously developable silver halide emulsion containing desensitizing dye
USRE30211E (en) * 1973-11-28 1980-02-12 Eastman Kodak Company Photographic elements containing color-forming couplers having an inhibiting effect upon the reactivity of competing couplers
US5049483A (en) * 1989-06-08 1991-09-17 Konica Corporation Direct positive silver halide photographic light-sensitive material and a processing method therefor
WO2004037814A1 (fr) * 2002-10-25 2004-05-06 Vertex Pharmaceuticals Incorporated Compositions indazolinones utiles en tant qu'inhibiteurs des kinases
CN101125960B (zh) * 2007-06-11 2011-05-04 大连理工大学 一类用于染料敏化太阳能电池的吩噻嗪染料

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5751858A (en) * 1980-09-09 1982-03-26 Asahi Chemical Ind Production of polyolefine nonwoven fabric
JPS599854U (ja) * 1982-07-10 1984-01-21 ライフ株式会社 情報収集カ−ド
JPS5971753U (ja) * 1982-11-08 1984-05-16 三和建物株式会社 デ−タシ−ト

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2322027A (en) * 1940-02-24 1943-06-15 Eastman Kodak Co Color photography
US2801171A (en) * 1954-12-20 1957-07-30 Eastman Kodak Co Photographic color former dispersions
US2870012A (en) * 1955-12-23 1959-01-20 Eastman Kodak Co Microdispersions of photographic color couplers
US3492123A (en) * 1966-03-11 1970-01-27 Eastman Kodak Co Direct positive silver halide emulsions containing carbocyanine dyes having a carbazole nucleus
US3501305A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Monodispersed photographic reversal emulsions
US3501306A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Regular grain photographic reversal emulsions
US3687674A (en) * 1969-11-14 1972-08-29 Fuji Photo Film Co Ltd Direct positive fogged silver halide emulsion sensitized with a cyclo-heptatriene cyanine dye

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE345168B (fr) * 1966-03-11 1972-05-15 Eastman Kodak Co
SE345167B (fr) * 1966-03-11 1972-05-15 Eastman Kodak Co
DE2436598C2 (de) * 1974-07-30 1983-04-07 Boehringer Mannheim Gmbh, 6800 Mannheim Stabiler Teststreifen zum Nachweis von Inhaltsstoffen in Flüssigkeiten

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2322027A (en) * 1940-02-24 1943-06-15 Eastman Kodak Co Color photography
US2801171A (en) * 1954-12-20 1957-07-30 Eastman Kodak Co Photographic color former dispersions
US2870012A (en) * 1955-12-23 1959-01-20 Eastman Kodak Co Microdispersions of photographic color couplers
US3492123A (en) * 1966-03-11 1970-01-27 Eastman Kodak Co Direct positive silver halide emulsions containing carbocyanine dyes having a carbazole nucleus
US3501305A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Monodispersed photographic reversal emulsions
US3501306A (en) * 1966-03-11 1970-03-17 Eastman Kodak Co Regular grain photographic reversal emulsions
US3687674A (en) * 1969-11-14 1972-08-29 Fuji Photo Film Co Ltd Direct positive fogged silver halide emulsion sensitized with a cyclo-heptatriene cyanine dye

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933506A (en) * 1973-05-18 1976-01-20 Agfa-Gevaert N.V. Spectral sensitization of direct-positive silver halide emulsions
US3933501A (en) * 1973-11-28 1976-01-20 Eastman Kodak Company Photographic elements containing color-forming couplers having and inhibiting effect upon the reactivity of competing couplers
USRE30211E (en) * 1973-11-28 1980-02-12 Eastman Kodak Company Photographic elements containing color-forming couplers having an inhibiting effect upon the reactivity of competing couplers
US4015989A (en) * 1974-01-30 1977-04-05 Fuji Photo Film Co., Ltd. Color light-sensitive material with spontaneously developable silver halide emulsion containing desensitizing dye
US5049483A (en) * 1989-06-08 1991-09-17 Konica Corporation Direct positive silver halide photographic light-sensitive material and a processing method therefor
WO2004037814A1 (fr) * 2002-10-25 2004-05-06 Vertex Pharmaceuticals Incorporated Compositions indazolinones utiles en tant qu'inhibiteurs des kinases
US20040167121A1 (en) * 2002-10-25 2004-08-26 Alex Aronov Indazolinone compositions useful as kinase inhibitors
US7262200B2 (en) 2002-10-25 2007-08-28 Vertex Pharmaceuticals Incorporated Indazolinone compositions useful as kinase inhibitors
US20090048250A1 (en) * 2002-10-25 2009-02-19 Alex Aronov Indazolinone compositions useful as kinase inhibitors
US7842712B2 (en) 2002-10-25 2010-11-30 Vertex Pharmaceuticals Incorporated Indazolinone compositions useful as kinase inhibitors
CN101125960B (zh) * 2007-06-11 2011-05-04 大连理工大学 一类用于染料敏化太阳能电池的吩噻嗪染料

Also Published As

Publication number Publication date
DE2243421A1 (de) 1973-03-22
GB1371580A (en) 1974-10-23
JPS4834534A (fr) 1973-05-19
JPS5547378B2 (fr) 1980-11-29

Similar Documents

Publication Publication Date Title
US3501309A (en) Direct positive silver halide emulsions containing halogenated cyanine dyes
US3397060A (en) Supersensitization of green-sensitive silver halide emulsions
US3672898A (en) Multicolor silver halide photographic materials and processes
US3501305A (en) Monodispersed photographic reversal emulsions
US3501307A (en) Photographic reversal materials containing organic desensitizing compounds
US3816121A (en) Direct positive photographic material containing a color coupler under one micron in size and fogged silver halide grains with substantially no internal sensitivity having absorbed on the surface a desensitizing dye containing a solubilizing group
US3822136A (en) Silver halide light-sensitive supersensitized materials
US3615573A (en) Direct-positive composition containing individually and differently fogged silver halide emulsions
US3501306A (en) Regular grain photographic reversal emulsions
US3865598A (en) Photographic silver halide emulsions
US3647463A (en) Direct-positive photographic elements containing multiple layers
US3446619A (en) Radiation sensitive silver-dye complexes
US3583870A (en) Emulsions containing a bipyridinium salt and a dye
US3854953A (en) Direct positive-type multi-layer light-sensitive material
US3933505A (en) Fogged, direct positive silver halide emulsion containing a nitro-substituted fluorene desensitizer
US3637388A (en) Process for the photographic production of equidensities
GB2302411A (en) Silver halide materials
US3582338A (en) Film elements and process of preparing same using electron bombardment
US3765899A (en) Light-sensitive super-sensitized silver halide photographic emulsion
US3679424A (en) Fogged,direct-positive silver halide emulsion containing nitron
JP2802687B2 (ja) ハロゲン化銀写真感光材料
USRE29930E (en) Direct-positive silver halide emulsion fogged with low levels of reduction and gold fogging agents
US6503697B2 (en) Light-sensitive silver halide photographic material for forming direct-positive images and method for making same
USRE28258E (en) Direct positive silver halide emulsions containing halogenated derivatives of cyanine dyes
USRE29575E (en) Cubic regular grain photographic reversal emulsions