US3647458A - Solarization of silver halide photographic emulsions - Google Patents

Solarization of silver halide photographic emulsions Download PDF

Info

Publication number
US3647458A
US3647458A US14454A US3647458DA US3647458A US 3647458 A US3647458 A US 3647458A US 14454 A US14454 A US 14454A US 3647458D A US3647458D A US 3647458DA US 3647458 A US3647458 A US 3647458A
Authority
US
United States
Prior art keywords
emulsion
silver halide
solarizing
agent
aldehyde
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
US14454A
Other languages
English (en)
Inventor
Giovan Battista Tagliafico
Ferdinando Grazzino
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.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing 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 Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Application granted granted Critical
Publication of US3647458A publication Critical patent/US3647458A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485Direct positive emulsions
    • G03C1/48515Direct positive emulsions prefogged

Definitions

  • ABSTRACT Silver halide is solarized by treatment with an aldehyde having more than one carbon atom or a ketone to provide direct positive photographic emulsions.
  • the present invention relates to photographic emulsions of the direct positive type and to a method for the preparation of such emulsions.
  • a solarized silver halide emulsion i.e., an emulsion which has attained this reversal point, yields directly a positive image of a subject which is photographed, and accordingly is called a direct positive emulsion.
  • One known solarization process involves exposing to a light source of suitable intensity a photographic emulsion obtained by precipitating silver halide in a gelatin solution. This process is performed prior to spreading of the emulsion on a support, and is difficult to carry out on an industrial scale because of the difficulty of uniformly exposing all the silver halide grains.
  • Another process comprises heating a silver halide emulsion in the presence of materials which promote fogging of the emulsion, such as AgNO decomposition product of animal or vegetable proteins, thiazoles, and photographic developers such as hydroquinone, paraphenylene diamine, amidol (diaminophenol hydrochloride), etc.
  • materials which promote fogging of the emulsion such as AgNO decomposition product of animal or vegetable proteins, thiazoles, and photographic developers such as hydroquinone, paraphenylene diamine, amidol (diaminophenol hydrochloride), etc.
  • Such treatments may cause hydrolysis of the gelatin emulsion since, for example, the emulsion may require heating at 100 C. for half an hour or at 45 C. for -24 hours.
  • the present invention provides a solarization process for silver halide which comprises treating silver halide with a solarizing agent selected from the group consisting of an aldehyde having more than one carbon atom and a ketone.
  • Such aldehydes and ketones may be aliphatic or aromatic, and may contain one or more aldehyde or ketone functions.
  • the aldehydes and ketones of the aliphatic series are generally more effective and hence are preferred.
  • those aldehydes and ketones which contain hydroxyl or halogen (e.g., chloro) substitution since such substituted aldehydes and ketones have been found to be especially effective in solarizing silver halide emulsions.
  • Glycol aldehyde for example, is more effective than acetaldehyde, and monochloro acetone is more effective than acetone.
  • the aldehydes of the present invention can be used also in the form of their bisulfite derivatives.
  • Aliphatic aldehydes which may be used in the present invention include, for example, acetaldehyde, chloral, glycol aldehyde, glyceraldehyde, glyoxal, glutaraldehyde, ribose, etc.
  • Aromatic aldehydes include benzaldehyde, salicylaldehyde, terephthalic aldehyde, 3,5-dioxybenzaldehyde, 2,4-dioxybenzaldehyde (resorcylic aldehyde), 2,4,6-trioxybenzaldehyde (phloroglucinaldehyde), o-chloro-benzaldehyde, ooxy-p-chlorobenzaldehyde, etc.
  • the aldehyde or ketone groups may also be found in a macromolecule, for example, the oxidized starch commercially available under the name of Sumstar" and manufactured by the Miles Chem. Co., Division of Miles Laboratories Inc. (U.S.A.).
  • Ketones useful in the present invention include acetone, monochloroacetone, acetylacetone, diacetyl (i.e., 2,3-butanone), sorbose, benzophenone, phenylacetone, 2,4-dihydroxy-benzophenone, etc.
  • the amount of solarizing agent which is utilized depends upon the method of preparation of the emulsion and upon the desired solarization effect. ln general, the contrast of the solarized emulsion increases as the amount of solarizing agent is increased.
  • the solarizing agents of the present invention preferably are employed in an amount of from about 0.2 to about 500 mg. of solarizing agent per gram-atom of silver.
  • the solarizing treatment of the present invention wherein silver halide is contacted with a solarizing agent, may be carried out at any stage of preparation of the emulsion.
  • the solarizing agent maybe added all at once or in successive stages in the course of emulsion preparation.
  • the solarizing agent is added in solution during the silver halide precipitation step of the emulsion preparation.
  • the silver halides employed in the present invention include the chloride, the bromide, the iodide and mixtures thereof.
  • the silver halide emulsions of the present invention may contain any of the hydrophilic, water-permeable colloids suitable for this purpose such as gelatin, hydrophilic polyvinyl copolymers, acrylamide polymers, polyvinyl alcohol. etc., and may contain the usual photographic additives such as coating aids and the like.
  • the emulsions. may be coated on a wide variety of supports such as cellulose triacetate film, poly (ethylene terephthalate) film and other films, glass, paper, metal, etc., to provide photographic elements.
  • the present invention may be more easily understood by reference to the following illustrative examples.
  • the graphs referred to in the examples are sensitometric curves for various emulsions wherein the ordinate D represents optical density and wherein the abscissa log E represents the logarithm of the exposure.
  • the mass is stirred for additional 10 minutes at 65 C. and then the emulsion is adjusted to a pH of 3.0 by the addition of 45 percent sulfuric acid solution while cooling the whole to 30 C. At this point the silver salts and the gelatin are precipitated by the addition of a saturated solution of sodium sulfate.
  • the precipitate is washed with water and is redissolved at about 50 C. in a solution of 30 g. of gelatin in 600 ml. of water. After addition of the usual coating additives, the emulsion is spread on a transparent support and dried.
  • Curve 1 After exposure and development in a photographic developer for 5 minutes at 20 C a characteristic curve is obtained which is shown as Curve 1 in FIG. 1.
  • Curve ll of FIG. 1 represents data for the same emulsion prepared without the glycol aldehyde
  • Curve lll represents data for this emulsion (without glycol aldehyde) prepared at 80 C.
  • the solarization effect afforded by the glycol aldehyde far surpasses the effect afforded by preparing the emulsion at 80 C., thereby providing for higher maximum densities with less risk of hydrolysis.
  • Example 1 The whole is kept at 60 C. for minutes and the pH is adjusted to a value of 3.0. The emulsion preparation is then continued as in Example 1.
  • Curve I of FIG. 2 represents the characteristic curve obtained with this emulsion.
  • Curve II OF FIG. 2 represents the characteristic curve obtained from the same emulsion prepared without the use of glyceric aldehyde.
  • Curve No. VIII refers to the emulsion prepared without the addition of solarizing agents.
  • Example lO-benzaldehyde for the emulsion (Curve I)
  • Example I I-salicylaldehyde for the emulsion (Curve II)
  • Example l2-phloroglucinaldehyde for the emulsion (Curve III)
  • Curve IV refers to the emulsion prepared without the addition of solarizing agents.
  • a silver halide emulsion is treated with a solarization agent the improvement wherein, said material is selected from the group consisting of an aldehyde having more than one carbon atom and a ketone.
  • the step which comprises treating silver halide during preparation of said emulsion with a solarizing agent which is an aldehyde having more than one carbon atom or a ketone.
  • said solarizing agent is an aldehyde having more than one carbon atom and which contains a halide or hydroxyl substituent.
  • the step which comprises treating silver halide during preparation of said emulsion with a solarizing agent selected from the group consisting of an aldehyde having more than one carbon atom and a ketone, said solarizing agent containing hydroxyl or halogen substitution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US14454A 1969-03-11 1970-02-26 Solarization of silver halide photographic emulsions Expired - Lifetime US3647458A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT3562569 1969-03-11

Publications (1)

Publication Number Publication Date
US3647458A true US3647458A (en) 1972-03-07

Family

ID=11242046

Family Applications (1)

Application Number Title Priority Date Filing Date
US14454A Expired - Lifetime US3647458A (en) 1969-03-11 1970-02-26 Solarization of silver halide photographic emulsions

Country Status (7)

Country Link
US (1) US3647458A (https=)
JP (1) JPS4920088B1 (https=)
BE (1) BE747040A (https=)
CH (1) CH533849A (https=)
DE (1) DE2011072A1 (https=)
FR (1) FR2037724A5 (https=)
GB (1) GB1305423A (https=)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259438A (en) * 1978-07-03 1981-03-31 Polaroid Corporation Method for preparing photosensitive silver halide emulsions
US5814123A (en) * 1991-08-02 1998-09-29 Ecologel Usa, Inc. Method for improving survival of plants in conditions of reduced watering
US9877434B2 (en) 2013-05-30 2018-01-30 Ecologel Solutions, Llc Granular compositions and methods for drought mitigation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE977553C (de) * 1963-07-19 1967-02-02 Bundesrep Deutschland Schutzvorrichtung in Form sogenannter Graetings fuer OEffnungen an gepanzerten Objekten

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1221407A (fr) * 1959-03-25 1960-06-01 Kodak Pathe Nouvelle émulsion photographique positive directe et procédé pour sa préparation
FR1405108A (fr) * 1963-08-28 1965-07-02 Ilford Ltd Matière photographique fournissant directement des images positives et son procédé de fabrication

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1221407A (fr) * 1959-03-25 1960-06-01 Kodak Pathe Nouvelle émulsion photographique positive directe et procédé pour sa préparation
FR1405108A (fr) * 1963-08-28 1965-07-02 Ilford Ltd Matière photographique fournissant directement des images positives et son procédé de fabrication

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Mees, The Theory of Photographic Process, 3rd Ed. ed. 1966, Macmillan Co. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259438A (en) * 1978-07-03 1981-03-31 Polaroid Corporation Method for preparing photosensitive silver halide emulsions
US5814123A (en) * 1991-08-02 1998-09-29 Ecologel Usa, Inc. Method for improving survival of plants in conditions of reduced watering
US9877434B2 (en) 2013-05-30 2018-01-30 Ecologel Solutions, Llc Granular compositions and methods for drought mitigation
US10798885B2 (en) 2013-05-30 2020-10-13 Ecologel Solutions, Llc Granular compositions and methods for drought mitigation

Also Published As

Publication number Publication date
GB1305423A (https=) 1973-01-31
FR2037724A5 (https=) 1970-12-31
BE747040A (fr) 1970-09-09
JPS4920088B1 (https=) 1974-05-22
CH533849A (it) 1973-02-15
DE2011072A1 (de) 1970-10-08

Similar Documents

Publication Publication Date Title
US3930867A (en) Macrocyclic polyamines as sensitizers for silver halide emulsions
US3772031A (en) Silver halide grains and photographic emulsions
US3892574A (en) Controlled reduction of silver halide grains formed during precipitation
US3033682A (en) Radiation-sensitive emulsions, elements, and processes for making same
US3647458A (en) Solarization of silver halide photographic emulsions
US4059450A (en) Direct positive silver halide elements
US3690891A (en) Infrared-sensitized silver halide systems
US4067740A (en) Trithiocarbonates as sensitizers for silver halide emulsions
US3539353A (en) Poly(sulfoalkyl) gelatin
US3260605A (en) Method for preparing light-sensitive silver halide emulsions suitable for print-out recording materials
US5240828A (en) Direct reversal emulsions
JPS6147941A (ja) ハロゲン化銀写真感光材料
EP0300631A2 (en) Direct-positive silver halide emulsion
US3782959A (en) Polyhedral borane fogged direct-positive silver halide emulsion containing an organic sulfoxide
US3409437A (en) Silver halide emulsions containing antibronzing agents
US4065312A (en) Process for the production of photographic vesicular images in photographic silver halide material
US3419396A (en) Print-out emulsions and process
US3963497A (en) X-ray film with hydrophillic layer containing developing and fixing agents
US3441412A (en) Photographic silver halide material containing carboxyalkylated dextrin
US3110597A (en) Composition comprising gelatin and a potential hardener therefor
US3804632A (en) Metalloboranes as fogging agents in direct positive emulsions
US4260674A (en) Silver salt photographic material for the production of silver and bubble photographic images with 80% transparency
US3547647A (en) Photographic systems comprising silver halide particles with occluded metal ions therein,a halogen acceptor,and an organic aldehyde
US3573915A (en) Photographic silver halide emulsions containing nitrosubstituted or unisubstituted cinnamic acid or cinnamaldehyde
US3598597A (en) Speed and contrast of a silver halide photographic emulsion obtained by addition of silver chloride emuldion to silver bromide emulsion