EP0174018B1 - Emulsions d'halogénure d'argent à distribution de grain uniforme préparées suivant la méthode à jet unique - Google Patents

Emulsions d'halogénure d'argent à distribution de grain uniforme préparées suivant la méthode à jet unique Download PDF

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Publication number
EP0174018B1
EP0174018B1 EP19850111158 EP85111158A EP0174018B1 EP 0174018 B1 EP0174018 B1 EP 0174018B1 EP 19850111158 EP19850111158 EP 19850111158 EP 85111158 A EP85111158 A EP 85111158A EP 0174018 B1 EP0174018 B1 EP 0174018B1
Authority
EP
European Patent Office
Prior art keywords
splash
added
silver
emulsions
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
Application number
EP19850111158
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German (de)
English (en)
Other versions
EP0174018A2 (fr
EP0174018A3 (en
Inventor
Douglas Lee Wilhite
Daniel James Mickewich
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0174018A2 publication Critical patent/EP0174018A2/fr
Publication of EP0174018A3 publication Critical patent/EP0174018A3/en
Application granted granted Critical
Publication of EP0174018B1 publication Critical patent/EP0174018B1/fr
Expired legal-status Critical Current

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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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/0357—Monodisperse emulsion

Definitions

  • This invention relates to the field of silver halide emulsion manufacture and particularly to silver halides made by the so-called “splash-precipitation" methods. Still more particularly, this invention relates to a method for making splash-prepared silver halide emulsions with a uniform particle size distribution of the silver halide crystals.
  • the silver halide crystals or grains can be prepared by two well-known methods: the single jet or “splash” method or the double jet or balanced double jet (BDJ) method.
  • the splash method all of the alkali halide solution is placed in the mixing vessel together with the protective colloid (e.g., gelatin) right from the start and the silver nitrate solution is then added to this mixture.
  • the silver nitrate can be added all at once, gradually over a period of time or in several, finite "splashes”.
  • the halide solution and the silver nitrate solution are added simultaneously to a solution of gelatin in the mixing vessel.
  • the splash precipitation process usually creates an increased number of so-called "crystal lattice defects" in which a number of ions are not positioned correctly in the silver ion - halide ion network.
  • Emulsions made from these crystals can be used to make films which exhibit improved sensitometry, especially improved speed, as compared with films made from silver halide emulsions with crystals that have few or no lattice defects or disorientation.
  • it is difficult to make splash-prepared emulsions with a uniform distribution of particle sizes.
  • a high gradient is necessary and a wide distribution of particle sizes is not tolerable.
  • the DE-B-1162685 discloses a process for making silver halide emulsions which include employing prenucleus emulsion.
  • the final emulsion is prepared in the presence of this emulsion e.g. by BDJ precipitation.
  • the US-A-4,339,532 discloses a monodisperse, negative working silver halide emulsion having grains with uniform habit and a relatively high degree of crystal disorder made by BDJ precipitation in the presence of a seed emulsion.
  • This invention is directed to a process for preparing silver halide emulsions with a narrow grain size distribution, wherein silver nitrate is added to an aqueous solution containing (a) one or more alkali halides in a protective colloid, and (b) monodisperse silver halide seed crystals, characterized in that the silver nitrate is added by a splash method.
  • the process of this invention is applicable to the manufacture of any of the conventionally prepared silver halides such as silver bromide, chloride, iodide, or mixtures thereof.
  • Any of the conventional colloid binder systems such as gelatin may also be used, as well as water-permeable or water-soluble polyvinyl alcohol and its derivatives, partially hydrolysed polyvinyl acetates, polyvinyl ethers, etc.
  • Other useful colloid binding agents include partially hydrolysed gelatin, poly-N-vinyl lactam, etc. among others.
  • Gelatin is preferred since it is well known that it is the protective colloid of choice during precipitation of the silver halides and the formation of the crystals thereof.
  • the desired alkali metal halides (salts) are added to an aqueous dispersion of gelatin.
  • aqueous silver nitrate is added by the splash method. This may be accomplished with two quick splashes of about 30 seconds each in duration, by one long first splash followed by a quick splash, or by a single long splash. These procedures are well known to those skilled in the art.
  • some of the alkali metal halide can be added to the gelatin in the reaction vessel and the remainder added after some of the silver nitrate has been added.
  • the seed crystals are made by the BDJ process following those well-known procedures. By varying those procedures it is possible to make grains of any average particle size distribution and select one to be used as desired in the ambit of this invention.
  • the seed crystals can be also made of any of the conventional halides such as silver bromide, silver iodobromide, silver bromo-chloride and silver iodide, for example, Additionally, these seed crystals may be doped with other metals such as rhodium and lead, for example, as is well known.
  • the emulsion is further "bulked" with colloid binder, and chemical and spectral sensitization can be accomplished as is well known.
  • hardeners, wetting agents, antifoggants, stabilizers, coating aids, etc. may be added.
  • the emulsion can then be coated on any of the well-known photographic substrates such as, for example, polyethylene terephthalate film, suitably subbed (subcoated) to receive the silver halide emulsion coating.
  • the coated emulsion may be overcoated with a protective antiabrasion layer, such as hardened gelatin.
  • These films may be used in any of the conventional ways, for example, as X-ray or graphic arts films or as direct positives. It all depends on the way the product structure is manufactured.
  • Example 6 is considered to represent the best mode.
  • the coagulant was then added to coagulate the gelatino-silver halide as "curds" and these curds were then washed to remove excess soluble salts by adding deionized water and decanting to remove the water and salts.
  • the G solution was available to adjust the pH to 3.0.
  • Samples of the emulsion were then analyzed using the Particle Size Analyzer. Additionally, electron micrographs were taken of each emulsion. These results indicate that the final emulsion in each case had crystals of approximately the same volume as the control and, more importantly, that these emulsions were more uniform than the control.
  • the control emulsion was not uniform and had a wider distribution of grain sizes.
  • Example 1 To demonstrate the photographic utility of emulsions prepared according to the teachings of this invention, four more splash-prepared emulsions were prepared as described in Example 1. The seeds used in three of these emulsions were identical to those of Example 2. The addition of the silver nitrate solution to the emulsions was varied as described below: These emulsions were then brought to their optimum sensitivity with gold and sulfur sensitization as is well known to those skilled in the art. After the addition of the usual wetting agents, antifoggants, hardeners, etc. each emulsion was then coated on polyethylene terephthalate film supports suitably coated with a subbing layer and a thin anchoring substratum of gelatin.
  • Example 1 Four splash-prepared emulsions were made for this example as taught in Example 1.
  • the three emulsions representing this invention used seed grains identical to those of Example 2 added at 0.2 mole/mole of added AgNO3. Variations in the making procedures were as follows: Silver halide composition AgIBr (4% iodide). Added ammonia to A solution alone. Iodide addition - 1/2 to A solution, 1/2 added after 1st silver nitrate splash. The % silver in the first splash was varied as shown below. A Control (no seeds) was also employed. The emulsions were redispersed, sensitized, coated, overcoated, dried, exposed and processed as described in Example 3.
  • Results were as follows: Exposure, development conditions: Kodak Model 101 process and control sensitometer, 1/5 sec. exposure through 2 ⁇ 2 stepwedge; developed in HSD at 28.9°C (84°F) for 90 seconds. Besides showing better digestion latitude, the product shows equivalent speed with higher gradient.
  • a direct positive emulsion was made from silver iodobromid precipitated by splash procedures in the presence of Ag(I)Br seed crystals. Three emulsions were made. One, the control, had no seeds; number two had seeds of 0.0086 ⁇ m3. present; and number three had seeds of 0.0378 ⁇ m3. These emulsions were redispersed in gelatin, fogged with tetraazaundecane, and the usual wetting agents, antifoggants and coating aids added thereto. Each emulsion was coated on a support as previously described and strips from the coatings were exposed with an EG and G sensitometer to a tungsten flash for 10 ⁇ 2 seconds. These strips were then developed in DP-2 for 90 seconds followed by fixing, washing and drying. Sensitometric results show that speed equivalent to the control with higher gradients was obtained.
  • a sample of BDJ prepared seeds (AgIBr, 2.5% I ⁇ - with a grain size of ca. 0.0378 ⁇ m3) was placed in a mixing kettle and sufficient potassium iodide added to convert the entire sample to AgI. A splash-precipitation process (see Example 1) was then run on these seeds. Films made from this emulsion, after sensitization and coating as previously described, were processed with equivalent sensitometric results. The grains were analyzed and found to be uniform in size and shape.
  • the emulsion prepared in this manner was then redispersed in gelatin, sensitized with gold and sulfur, wetting agents, antifoggants, etc. added, and coated and overcoated as previously described.
  • an element was made, sensitized, and coated under the same conditions but without the addition of the seed crystals of silver halide.
  • Samples from the coatings were exposed, developed fixed, washed and dried as previously explained with the following sensitometry: One can see that the film prepared from the emulsion made following the teachings of this invention had excellent gradient and top density, though somewhat lower speed than the control.
  • the grains, when examined under an electron microscope, were uniform in size and shape.
  • Example 2 Following the procedures of Example 1 two additional splash-prepared emulsions were made varying the size of the seed emulsion or grains used.
  • the BDJ prepared seeds were AgIBr seeds of about 0.06 ⁇ m3 (ca. 2.5% I ⁇ ) and in the second case were AgIBr seeds of about 0.039 ⁇ m3 (ca 2.5%I ⁇ ).
  • the emulsions were analyzed by particle size analyzer and by electron micrograph and found to contain uniform particle sizes, indicating that one can use fairly large seed grains within the ambit of this invention.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Colloid Chemistry (AREA)

Claims (4)

  1. Procédé de préparation d'émulsions d'halogénures d' argent d'une étroite distribution du calibre des grains, conformément auquel on ajoute du nitrate d'argent à une solution aqueuse contenant (a) un ou plusieurs halogénures de métaux alcalins dans un colloïde protecteur et (b) des cristaux d'ensemencement en halogénures d'argent monodispersés, caractérisé en ce que l'on ajoute le nitrate d'argent par un procédé à projection.
  2. Procédé suivant la revendication 1, caractérisé en ce que l'on prépare les cristaux d'ensemencement monodispersés par un procédé à double jet équilibré.
  3. procédé suivant la revendication 1, caractérisé en ce que l'on ajoute initialement une partie de l'halogénure de métal alcalin et on ajoute le reste après l' addition d'une partie du nitrate d'argent.
  4. Emulsion de gélatino-halogénure d'argent produite par mise en oeuvre du procédé suivant la revendication 1.
EP19850111158 1984-09-06 1985-09-04 Emulsions d'halogénure d'argent à distribution de grain uniforme préparées suivant la méthode à jet unique Expired EP0174018B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US64780884A 1984-09-06 1984-09-06
US647808 1984-09-06

Publications (3)

Publication Number Publication Date
EP0174018A2 EP0174018A2 (fr) 1986-03-12
EP0174018A3 EP0174018A3 (en) 1988-02-17
EP0174018B1 true EP0174018B1 (fr) 1991-04-24

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19850111158 Expired EP0174018B1 (fr) 1984-09-06 1985-09-04 Emulsions d'halogénure d'argent à distribution de grain uniforme préparées suivant la méthode à jet unique

Country Status (3)

Country Link
EP (1) EP0174018B1 (fr)
JP (1) JPS6172229A (fr)
DE (1) DE3582633D1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06105339B2 (ja) * 1986-06-18 1994-12-21 コニカ株式会社 ハロゲン化銀写真感光乳剤及びその製造方法及び該乳剤を用いたハロゲン化銀写真感光材料
US4794070A (en) * 1987-06-09 1988-12-27 Minnesota Mining And Manufacturing Company Automatically processible photographic element comprising a non-silver halide layer containing bromide
EP0632321B1 (fr) * 1993-07-02 1999-12-08 Minnesota Mining And Manufacturing Company Procédé pour préparer des émulsions monodispersés à l'halogénure d'argent

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1162689B (de) * 1962-11-15 1964-02-06 Perutz Photowerke G M B H Verfahren zur Herstellung von lichtempfindlichen photographischen Emulsionen
DE1597587A1 (de) * 1966-11-12 1970-06-25 Fuji Photo Film Co Ltd Verfahren zur Herstellung einer photographischen lichtempfindlichen Halogensilberemulsion
JPS5448521A (en) * 1977-09-16 1979-04-17 Konishiroku Photo Ind Co Ltd Manufacture of silver halide crystais
JPS5542739A (en) * 1978-09-20 1980-03-26 Nippon Telegr & Teleph Corp <Ntt> Cylinder cutting method and device with multi blade
US4339532A (en) * 1981-01-08 1982-07-13 Polaroid Corporation Novel photosensitive silver halide emulsion and method of preparing same
JPS581408A (ja) * 1981-06-25 1983-01-06 小堀　しづ ヘヤ−ブラシ及びクシ

Also Published As

Publication number Publication date
EP0174018A2 (fr) 1986-03-12
DE3582633D1 (de) 1991-05-29
EP0174018A3 (en) 1988-02-17
JPH0443569B2 (fr) 1992-07-17
JPS6172229A (ja) 1986-04-14

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