US2484451A - Bichromate sensitized photographic material - Google Patents

Bichromate sensitized photographic material Download PDF

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Publication number
US2484451A
US2484451A US37833A US3783348A US2484451A US 2484451 A US2484451 A US 2484451A US 37833 A US37833 A US 37833A US 3783348 A US3783348 A US 3783348A US 2484451 A US2484451 A US 2484451A
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United States
Prior art keywords
resin
light
lead
gelatin
coating
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Expired - Lifetime
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US37833A
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English (en)
Inventor
William H Griggs
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
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Priority to US37833A priority Critical patent/US2484451A/en
Priority to FR983021D priority patent/FR983021A/fr
Priority to GB18131/49A priority patent/GB663430A/en
Application granted granted Critical
Publication of US2484451A publication Critical patent/US2484451A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/66—Compositions containing chromates as photosensitive substances

Definitions

  • This invention relates to, the preparation of photographic resist materials and to methods of forming images therein.
  • One object of my invention is to provide a photographic element of high sensitivity to light. Another object is to provide a method of producing black direct positive relief images from the compositions of my invention. A further object is to provide sensitive compositions having diverse uses. Other objects will become apparent from the following description.
  • the objects of my invention are accomplished in part by incorporating lead sulflte in an aqueous mixture of bichromated hydrophilic colloid, such as gelatin, and an aqueous colloidal dispersion of a soft, water-insoluble polymerized material such as a polyacrylate resin. Other objects are accomplished by processing the sensitive material to direct positive relief images, and if desired, transforming the relief image to a black image.
  • FIG. 1-4 show in enlarged cross-sectional view the appearance of a sensitive element of my invention during the process of exposing it to a subject, forming a direct positive relief image and transforming the relief image to a black relief image.
  • one novel feature of my invention includes using lead sulfite as a means of forming black sulfide relief images.
  • lead sulfite As has been mentioned one novel feature of my invention includes using lead sulfite as a means of forming black sulfide relief images.
  • the use of pigments containing lead should be avoided because they destroy the sensitivity of the bichromated composition.
  • lead salt, lead sulfite is unique in that it does not destroy the light-sensitivity of the emulsions and since it is light in color it eifectively increases the sensitivity of the emulsions compared to emulsions of the type containing colored materials.
  • Example 1 A mixture of 105 gms; lead sulfite, 2.5 grams sodium hexametaphosphate and 52 cc. water is ball-milled for 24 hours. gms. gelatin dissolved in cc. water is added to cc. of an aqueous 25% colloidal dispersion of acrylate resin.
  • the gelatin-resin mixture is then added to the Example 2
  • the coating composition contained gelatin and resin in the ratio of 1 to 1.
  • the support Another suitable ratio of materials includes increasing the gelatin to a ratio of 1.5 parts per part solid resin. This is obtained by substituting in the above example 42 grams gelatin dissolved in resin dispersion and compounding and coating the ballmilled mixture as described.
  • Example 3 When the gelatin/resin ratio is increased substantially beyond 2 to 1 the emulsion tends to become too water-soluble and the resultant relief may turn out to be a negative-rather than a positive. However, a ratio of about 2 to 1 is satisfactory and an emulsion of this range is obtained by substituting in Example 1, 52 grams water and using 104 cc. of 25% resin dispersion and ball-milling and coating the emulsion as before.
  • compositions are very stable and particularly by virtue of the use of the lead sulfite component can be compounded some time prior to actual usage, that is, prior to coating on a support.
  • a variety of supports may be coated or sprayed with the emulsions.
  • nlasticized materials are especially useful for primin any surface capable of being lacquered such as metal. wood. glass. rubber, concrete ,or other refractory materials.
  • Supports such as cellulose acetate or acetate butyrate, polyvinyl butyral resin and polyacrylic ester resins generally require no primin prior to coating with my sensitive emulsions.
  • Phenol-formaldehyde resin surfaces are generally too hard to sensitize without use of a priming coat. Similarly the adhesion of the emulsion to rubber is not good.
  • the bichromate sensitized elements of my invention are exposed under a 35 amp. carbon arc lamp at 18 inches for about 2-4 minutes as is shown in Fig. 1 of the accompanying drawings.
  • the emulsion layer ll of a mixture of dichromated hydrophilic colloid, resin and lead sulfite on a transparent support of for example, polyvinyl acetal or polyacrylic ester resin is shown being exposed to a subject containing an '4 opaque image.
  • the exposure is without effect in region 12 of layer 11 but the balance of layer II has been hardened by exposure and the adhesion to the support so affected that when the element is subsequently treated with water or aqueous solutions containing alkali such as ammonia.
  • the exposed area of the layer breaks away from the support leaving the relief image 13 on support 10 as shown in Fig. 3.
  • the element is then treated with a sulphiding agent such as 2-5% sodium sulfide solution which may contain trisodium phosphate, or treating with hydrogen sulfide solutionor gas.
  • a sulphiding agent such as 2-5% sodium sulfide solution which may contain trisodium phosphate, or treating with hydrogen sulfide solutionor gas.
  • the result is to transform the lead sulfite in image 13 to lead sulfide leaving an opaque.
  • black colloid relief image 14 of high density on support 10 as shown in Fig. 4.
  • thecoating compositions should contain about -40% lead sulfite based on the total weight of solids in the emulsion.
  • the resin compound of my emulsions ⁇ compounded as in the above examples may not only be an acrylate copolymer but acrylic ester and other resins forming aqueous colloidal dispersions are suitable such as polymethyl or polyethyl acrylate, polymethylmethacrylate, as well as polyvinylidene chloride, polystyrene, polyvinyl acetate or natural and synthetic neoprene rubber latex, the natural rubber being preferred to the synthetic.
  • Other desirable characteristics of the resin are that it be soft. that is, aqueous dispersions of the resin do not dry to very hard films. This property can be controlled in part in a wellknown manner by regulatig the degree of polymerization of the resin.
  • the resin must also be water-insoluble and an aqueous colloidal dispersion alone must be capable of drying to a continuous film on glass.
  • the hydrophilic colloid used in my sensitive compositions is preferably a limed or partially hydrolyzed gelatin characterized by low viscosity and jelly strength, or gum arabic. polyvinyl alcohol and the like. It is to be understood that the term gelatin as used herein and in the appended claims includes ordinary gelatins or glues obtained from animal sources as well as gelatin of fish origin such as ordinary fish glues.
  • My sensitive compositions in addition to having all the uses and advantages pointed out herein and in the above copending applications, are particularly useful in processes of decorating ceramic materials such as described in the application Ser. No. 745,737.
  • the fluxing action of lead salts in glazing operations is well known, and when I produced relief designs on ceramic ware by means of the sensitive compositions containing .lead sulfite, the presence of the lead salt in the taken as limited pended claims.
  • a light-sensitive coating composition comprising a mixture of a bichromated hydrophilic colloid, lead sulflte, and an aqueous colloidal dispersion of a water-insoluble soft polymerized material selected from the group consisting of natural and synthetic rubbers, polyvinylidene chloride, polystyrene, polyvinyl acetate and polyacrylates, said composition being adapted to produce a light-sensitive coating in which a direct positive relief image can be formed by exposure to light and development in aqueous solution.
  • a light-sensitive coating composition comprising a mixture of a bichromated hydrophilic colloid, lead sulfite and an aqueous colloidal dispersion of a soft, water-insoluble polyacrylate resin, said composition being adapted to produce a light-sensitive coating in which a direct positive relief image can be formed by exposure to light and development in aqueous solution.
  • a light-sensitive coating composition comprising a mixture of bichromated gelatin, lead sulfite and an aqueous colloidal dispersion of a soft, water-insoluble polyacrylate resin, said composition being adapted to produce a light-sensitive coating in which a direct positive relief image can be formed by exposure to light and development in aqueous solution.
  • a light-sensitive coating composition comprising a mixture of bichromated gelatin, lead sulfite and an aqueous colloidal dispersion of a soft, water-insoluble polyacrylate resin, the relative amount of gelatin and resin present in said composition being of the order of from 0.5 to 2 only by the scope of the apparts gelatin per part resin.
  • a light-sensitive coating composition comprising a mixture of a bichromated hydrophilic colloid, lead sulfite, and an aqueous colloidal dispersion of a water-insoluble soft polymerized material selected from the group consisting of natural and synthetic rubbers, polyvinylidene chloride, polystyrene, polyvinyl acetate and polyacrylates, the relative amount of gelatin and polymerized material present in said composition being of the order of from 0.5 to 2 parts gelatin per part polymeric material, said composition being adapted to produce a light-sensitive coating in which a positive reversal relief image can be formed by exposure to light and development in aqueous solution.
  • a light-sensitive coating composition comprising a mixture of a bichromated hydrophilic colloid, lead sulfite and a rubber latex, said composition being adapted to produce a. light-sensitive coating in which a direct positive relief image can be formed by exposure to light and development in aqueous solution.
  • a light-sensitive coatin composition comprising a mixture of bichromated gelatin, lead sulfite and natural rubber latex, said composition being adapted to produce a light-sensitive coating in which a direct positive relief image can be formed by exposure to light, and development in aqueous solution.
  • a light-sensitive coating composition comprising a mixture of a bichromated hydrophilic colloid, lead sulfite and an aqueous colloidal dispersion of a soft, water-insoluble polyvinyl acetate resin, said composition being adapted to produce a light-sensitive coating in which a direct positive relief image can be formed by exposure to light and development in aqueous solution.
  • a light-sensitive coating composition comprising a mixture of bichromated gelatin, lead sulfite and an aqueous colloidal dispersion of a soft, water-insoluble polyvinyl acetate resin, said composition being adapted to produce a lightsensitive coating in which a direct positive relief image can be formed by exposure to light and development in aqueous solution.
  • a light-sensitive photographic element comprising a support having thereon a layer of a mixture of a bichromated hydrophilic colloid, lead sulfite and a water-insoluble soft polymerized material selected from the group consisting of natural and synthetic rubbers, polyvinylidene chloride, polystyrene, polyvinyl acetate and polyacrylates, drying said coating, exposing said coating to an image, and washing away only the exposed areas of said coating.
  • a light-sensitive photographic element comprising a support hzhzing thereon a layer of a mixture of a bichromated hydrophilic colloid, lead sulfite and a soft, water-insoluble polymerized material selected from the group consisting of natural and synthetic rubbers, polyvinylidene chloride, polystyrene, polyvinyl acetate and polyacrylates, the relative amount of gelatin and polymerized material present in said composition being of the order of from 0.5 to 2 parts gelatin per part polymeric material.
  • a light-sensitive photographic element comprising a support having thereon a layer of a mixture of a bichromated hydrophilic colloid, lead sulfite and a soft, water-insoluble acrylate resin, said element being adapted to produce a direct positive relief image upon exposure to light and development in aqueous solution.
  • a light-sensitive photographic element comprising a support having thereon a layer of a mixture of bichromated gelatin, lead sulfite and a soft, water-insoluble acrylate resin, said element being adapted to produce a direct positive relief image upon exposure to light and development in aqueous solution.
  • a light-sensitive photographic element comprising a support having thereon a layer of a mixture of bichromated gelatin, lead .sulfite and a soft, water-insoluble acrylate resin, the relative amount of gelatin and resin present in said composition being of the order of from 0.5 to 2 parts gelatin per part resin.
  • the method of making a photographic direct positive relief image which comprises coating a support with a mixture of a bichromated hydrophilic colloid, lead sulfite and an aqueous colloidal dispersion of a water-insoluble, soft, polymerized material selected from the group consisting of natural and synthetic rubbers, polyvinylidene chloride, polystyrene, polyvinyl acetate and polyacrylates, drying said coating, exposing said coating to an image, and washing away only the exposed areas of said coating.
  • the method of making a photographic direct positive relief image which comprises coating a support with a mixture of a bichromated hydrophilic colloid, lead sulphite and an aqueous colloidal dispersion of a water-insoluble, soft, polymerized material selected from the group consisting of natural and synthetic rubbers, polyvinylidene chloride, polystyrene, polyvinyl acetate and polyacrylates, drying said coating, exposing said coating to an image, washing away only the exposed areas of said coating, and transforming the lead salt in the resulting relief image to lead sulfide.
  • a photographic direct positive relief image which comprises coatpersion of a water-insoluble, soft, polyacrylate resin, the amount of gelatin present insaid coating being of the order of from 0.5 to 2 parts gelatin per part resin, drying said coating, exposing said coating to an image, washing away only the exposed areas of said coating and transforming the lead salt in the relief image remaining in the unexposed areas of said coating to lead sulfide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US37833A 1948-07-09 1948-07-09 Bichromate sensitized photographic material Expired - Lifetime US2484451A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US37833A US2484451A (en) 1948-07-09 1948-07-09 Bichromate sensitized photographic material
FR983021D FR983021A (fr) 1948-07-09 1948-10-07 Produits photosensibles bichromatés
GB18131/49A GB663430A (en) 1948-07-09 1949-07-08 Improvements in the production of photographic relief images

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US37833A US2484451A (en) 1948-07-09 1948-07-09 Bichromate sensitized photographic material

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US2484451A true US2484451A (en) 1949-10-11

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FR (1) FR983021A (fr)
GB (1) GB663430A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2677091A (en) * 1950-07-22 1954-04-27 Westinghouse Electric Corp Pressure sensitive apparatus
US3352728A (en) * 1963-12-13 1967-11-14 Keuffel & Esser Co Material and method for making stencil masters

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2677091A (en) * 1950-07-22 1954-04-27 Westinghouse Electric Corp Pressure sensitive apparatus
US3352728A (en) * 1963-12-13 1967-11-14 Keuffel & Esser Co Material and method for making stencil masters

Also Published As

Publication number Publication date
FR983021A (fr) 1951-06-18
GB663430A (en) 1951-12-19

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