US3585036A - Photographic silver halide light-sensitive element - Google Patents

Photographic silver halide light-sensitive element Download PDF

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Publication number
US3585036A
US3585036A US702171A US3585036DA US3585036A US 3585036 A US3585036 A US 3585036A US 702171 A US702171 A US 702171A US 3585036D A US3585036D A US 3585036DA US 3585036 A US3585036 A US 3585036A
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US
United States
Prior art keywords
silver halide
photographic
plumming
emulsion
sensitive element
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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
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US702171A
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English (en)
Inventor
Kazuya Sano
Kinji Ohkubo
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3585036A publication Critical patent/US3585036A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/35—Antiplumming agents, i.e. antibronzing agents; Toners
    • 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
    • Y10S430/13—Antibronze agent or process

Definitions

  • the present invention relates to a photographic silver halide light-sensitive element having a layer containing an anti-plumming agent, and more particularly, it relates to a photographic silver halide light-sensitive element having a layer containing fine dispersions of a solution of an antiplumming agent in a hydrophobic solvent.
  • Silver halide emulsions are often subject, on processing, and especially on hot glazing, to a form of image discoloration and a reduction of its reflection density. That is, when a blueblack silver image formed by development is subjected to drying by a glazer at high temperature, the silver image is discolored purple or lead-gray and at the same time the reflection density of the silver image is reduced. This phenomenon is usually called plumming.
  • anti-plumming additives for photographic silver halide light-sensitive emulsions.
  • anti-plumming agents are 1-phenyl-5-mercaptotetra- Zole, potassium salt of endothiophenylthiadiazolinethiol, and derivatives of 2,3a,5,6a-tetrazaperhydropentalene-1,4- dithione, and so forth.
  • the anti-plumming agent is incorporated in a coating composition of a sliver halide light-sensitive emulsion layer or other layers by the following method.
  • the anti-plurnming agent is dissolved into an organic solvent such as methanol, and the resulting solution is added to a silver halide light-sensitive emulsion or an aqueous gelatin solution.
  • the anti-plumming agent is added to a silver halide light-sensitive emulsion or an aqueous gelatin solution directly or as an aqueous solution thereof.
  • an object of this invention is to provide a photographic light-sensitive element causing no plumming, that is, causing neither discoloration not density reduction when dried at a high temperature.
  • Another object of this invention is to provide a photographic silver halide light-sensitive element having a layer containing an anti-plumming agent substantially unaccompanied by the reduction of the sensitivity thereof.
  • a photographic silver halide light-sensitive element having a layer containing an anti-plumming agent, said antiplumming agent having been incorporated in said layer as a fine dispersion of a solution thereof in a non-volatile organic solvent which is sparingly soluble (less than 0.5 in solubility) in water under the condition of preparation of photographic light-sensitive elements where the pH is below 7 but is dissolved out of the layer under the condition of development where the pH is greater than 8.
  • the photographic silver halide light-sensitive element of the present invention is prepared by dissolving an anti-plumming agent in the organic solvent having the properties mentioned above (hereinafter such an organic solvent shall be called alkali-philic hydrophobic solvent) directly or by the aid of an auxiliary solvent, dispersing the solution thus prepared into a silver halide emulsion or an aqueous gelatin solution to make a coating composition, and applying it to a support followed by drying.
  • the anti-plumming agent is dispersed in an emulsion layer as particles of the solution thereof in an alkali-philic hydrophobic solvent.
  • the anti-plumming agent is in a protected state in the emulsion layer. The agent is, therefore, prevented from diflfusing into the other layers.
  • the anti-plumming agent is isolated from the photographic light-sensitive silver halide grains in the photographic light-sensitive element,
  • the photographic light-sensitive element containing an anti-plumming agent does not result in deterioration of the photographic properties when it is stored in a non-processed state, and after development, does not show a plumming phenomenon when it is dried by glazing at high temperature.
  • DETAILED DESCRIPTION OF THE INVENTION vent used in this invention is one represented by the general Formula I NCHCHCOOH RCO X wherein X represents a hydrogen atom or a methyl group and R and R each represents an alkyl group or a substipletely into the alkaline aqueous solution.
  • auxiliary solvent a solvent used for facilitating the dissolution of the anti-plumming agent in the alkali-philic hydrophobic solvent, reducing the viscosity of the solution, and facilitating the preparation of the dispersion.
  • the auxiliary solvent may be water-soluble or volatile and can be removed from the system during the production of the photographic light-sensitive elements, or may be water-insoluble and non-volatile, and hence be left in the lightsensitive element together with the alkali-philic hydrophobic solvent during the production of the light-sensitive elements, provided that it is solublized by the solvent and is dissolved out with the latter during development. If necessary, both types of the auxiliary sol-vent may be employed simultaneously.
  • auxiliary solvents there are mentioned methanol, acetone, dimethylformamide, ethyl acetate, methylethylketone and so on.
  • phosphoric acid esters or a phthalic acid ester examples of the latter type are mentioned phosphoric acid esters or a phthalic acid ester, but a methyl ester or an ethyl ester of the alkali-philic hydrophobic solvent having beforementioned general Formula I (that is, a compound represented by general Formula II RCO X (II) wherein X, R and R have the same meanings as in Formula I and R" represents a methyl group or an ethyl group) is particularly suitable owing to its desirable dissolving power and viscosity.
  • auxiliary solvents represented by general Formula II are shown below, which may be obtained as intermediates in the preparation of (I).
  • any compound may be used as long as it has a desired anti-plumming effect and requisite solubility in the solvent.
  • Typical examples of the anti-plumming agents usable in this invention are shown below, although the invention is not limited thereto.
  • the product thus obtained was mixed with 450 ml. of an aqueous 2 N sodium hydroxide solution containing 45 ml. of methanol and the mixture was shaken at room temperature, whereby the heat was generated and the solution soon became clear. After further shaking of the system, the resulting solution was cooled and acidified with concentrated hydrochloric acid to separate an oily material. This was extracted with ether, washed with water, dried over sodium sulfate, and then the solvent was distilled off under vacuum to provide 120 g. of Compound 1.
  • the fraction was mixed with 500 ml. of an aqueous 2 N sodium hydroxide solution followed by shaking to cause hydrolysis and to make the solution clear.
  • the resultant product was acidified with hydrochloric acid.
  • the oily product thus formed was extracted with ether, washed with water and dried, and thereafter the solvent was distilled 01f under a reduced pressure to provide 155 g. of Compound 2.
  • the whole amount of the addition product was treated with 58 g. of freshly distilled acetic anhydride as in Example 1 and then distilled under a reduced pressure to provide 94 g. of a fraction having a boiling point of 142 145 C./l mm. Hg.
  • the fraction was hyrolyzed in 250 ml. of an aqueous 2 N sodium hydroxide solution containing 30 ml. of methanol and then treated in the same manner as Example 1 to provide 78 g. of Compound 3.
  • EXAMPLE 1 After addition of suitable amounts of an antifoggant, a stabilizer and a hardening agent, a photographic silver halide emulsion containing 4.0 g. of a silver halide (silver chloro-bromide consisting of 50 mol percent of silver chloride and 50 mol percent of silver bromide) and 11.0 g. of gelatin per 100 g. of the emulsion was applied to a photographic baryta paper and dried. (Emulsion I).
  • a photographic emulsion was mixed with 10 ml. (per 100 g. of said emulsion) of a 0.3% methanol solution of Compound 11. 3,6-diphenyl-2,3a,5, 6a-tetrazaperhydropentalene 1,4 dithione and suitable amount of additives and was applied to a photographic baryta paper and dried (Emulsion II).
  • Emulsion H showed a high anti-plumming effect as compared with Emulsion I, but the sensitivity thereof was reduced to about 40% of that of Emulsion I.
  • Emulsion III of this invention the plumming effect sufficiently prevented and also the reduction in sensitivity was only about that of Emulsion I.
  • EXAMPLE 2 After adding suitable amounts of an antifoggant, a stabilizer and a hardening agent, a photographic emulsion containing 4.5 g. of a silver halide per 100 g. of emulsion was applied to a photographic baryta paper and dried. (Emulsion IV).
  • Emulsion V the plumming effect was prevented as compared with the case of using Emulsion 'IV, but the sensitivity was reduced to about 40% of Emulsion IV.
  • Emulsion VI of the present invention the plumming was sufficiently prevented and the sensitivity thereof was reduced to only about 15% of Emulsion IV.
  • a photographic silver halide light-sensitive element comprising a support having a silver halide emulsion layer and said support bearing at least one layer containing at least one anti-plumming agent and a non-volatile organic solvent having the formula:
  • R and R are each alkyl groups or R is an alkoxyalkyl group, the total carbon atoms contained in R and R being 7 to 11, said solvent being substantially sparingly soluble in water at a pH lower than 7, but which is dissolved out of said at least one layer at a pH higher than 8, said at least one layer being applied from a coating composition wherein said agent is present in said composition as a fine dispersion of a solution thereof in the said solvent.
  • auxiliary solvent is selected from the group consisting of methanol, acetone, dimethylforrnamide, ethyl acetate, methylethylketone, and a compound of the following general Formula II:
  • RCO X wherein X represents a hydrogen atom or a methyl group, R and R each represents an alkyl group or R is an alkoxyalkyl group, the total carbon number of R and R being from 7 to 11, and R" represents a methyl group or an ethyl group.
  • said compound represented the general Formula II is selected from the group consisting of ethyl 2-methyl-3-(N-n-hexylacetamido)propionate, ethyl 3- [N- (Z-ethylhexyl) acetamido] -propionate, methyl 2-methyl-3-(N-n-octylacetamido)-propionate, methyl 3-(n-n-butyloctanamido)-propionate, and methyl 3-[N-(3-hexyloxypropyl) acetamido] -propionate.

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  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US702171A 1967-02-01 1968-02-01 Photographic silver halide light-sensitive element Expired - Lifetime US3585036A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP651867 1967-02-01

Publications (1)

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US3585036A true US3585036A (en) 1971-06-15

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US (1) US3585036A (is")
BE (1) BE710216A (is")
DE (1) DE1622279C3 (is")
GB (1) GB1211577A (is")
NL (1) NL6801493A (is")

Also Published As

Publication number Publication date
BE710216A (is") 1968-06-17
DE1622279A1 (de) 1970-10-29
NL6801493A (is") 1968-08-02
GB1211577A (en) 1970-11-11
DE1622279C3 (de) 1974-10-17
DE1622279B2 (de) 1974-02-28

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