US2813792A - Photosensitive material - Google Patents

Photosensitive material Download PDF

Info

Publication number
US2813792A
US2813792A US343502A US34350253A US2813792A US 2813792 A US2813792 A US 2813792A US 343502 A US343502 A US 343502A US 34350253 A US34350253 A US 34350253A US 2813792 A US2813792 A US 2813792A
Authority
US
United States
Prior art keywords
silicate
suspension
paper
carrier layer
light
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
US343502A
Other languages
English (en)
Inventor
Sus Oskar
Neugebauer Wilhelm
Bottger Hans
Endermann Fritz
Schafer Werner
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.)
Keuffel and Esser Co
Original Assignee
Keuffel and Esser 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 Keuffel and Esser Co filed Critical Keuffel and Esser Co
Application granted granted Critical
Publication of US2813792A publication Critical patent/US2813792A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/61—Compositions containing diazo compounds as photosensitive substances with non-macromolecular additives

Definitions

  • This invention relates to light sensitive material of the type usually sensitized with Water soluble light sensitive substances such as used for making diazotypes, blueprints and Vandyke prints or brownprints.
  • the invention relates to a carrier layer for these light sensitive substances applied to the surface of an absorbent base material and made up of particles formed of silicates of metals of the second group of the periodic system.
  • Patent No. 2,433,515 discloses that a layer of silica particles applied as a precoat for blueprint paper and similar light sensitive materials greatly improves the prints obtained from these materials.
  • the objects of the present invention are to achieve all the advantages of the silica precoated material and at the same time produce prints which have greater fastness to ink and India ink and which are more receptive to water colors.
  • the ink or color does not bleed or feather and the India ink will not peel or crack oif.
  • the light sensitive materials to which the present invention relates are conventionally applied to an absorbent base material, generally paper, although other absorbent bases such as cardboard, cloth and other textile fabrics and the like may be employed.
  • the layer of metal silicate particles applied to the absorbent base material according to the present invention should not be confused with a sizing. Sizing is ordinarily applied to paper for example as a step in the paper making process before the Web is fully matted into a sheet. Thus these sizings penetrate through the entire thickness of the sheet whereas the discrete particles applied according to the present invention form a layer at the surface of the sheet.
  • the absorbent sheet treated according to the present invention will have been previously sized since the papers conventionally used for diazotype prints, blueprints and the like are normally sized papers.
  • diazotype materials have been made by coating a light sensitive diazo compound from an aqueous solution onto the surface of an absorbent base material such as described in the previous paragraph.
  • an azo dye coupling component is coated with the light sensitive diazo compound and after exposure through a pattern an image is formed by exposing the sheet to ammonia fumes which causes the undecomposed diazo compound to couple with the coupling component to form an azo dye image.
  • the azo component is not coated on the sheet with the light sensitive diazo compound but is applied after exposure in an alkaline solution.
  • Blue print coatings consist essentially of a light sensitive ferric salt and a water soluble complex iron cyanide salt.
  • Exposure to actinic light results in reduction of the ferric salt to a ferrous salt in the light struck areas.
  • Application of water after exposure results in the formation of an insoluble blue complex from the ferrous salt and the water soluble iron cyanide salt. Vandyke or brownprints also depend on States Pate t the light reduction of light sensitive ferric salts but in this case the ferrous salt which is formed reduces a Water soluble silver salt such as silver nitrate to metallic silver which forms a brown or black image.
  • a layer of metal silicate particles may be applied to the base material used for making photosensitive materials of any of the types previously described in order to obtain prints of improved color and contrast with the additional advantages previously noted.
  • the metals of the second group of the periodic system magnesium and the alkaline-earth metals are particularly suitable.
  • the particles applied to the paper are preferably of colloidal size and are dispersed in water or an aqueous solution which may be coated onto the surface of the absorbent base material by known methods and dried.
  • minutely dispersed and particles of colloidal size as used herein are intended to include particles having a size up to 5;, the best size being between .la and In.
  • silicate layer according to the present invention on the base material by means of minutely dispersed aqueous suspensions of the silicates which have been prepared by causing a reaction to take place in an aqueous medium.
  • Silicate suspensions which give good results can be obtained for example by mixing, while thoroughly stirring, dilute sodium silicate solutions with dilute aqueous solutions of the salts of elements belonging to the second group of the periodic system.
  • Silicates of elements in the 3rd group in the periodical system which may function as metals and are able to form salts on reaction with acids may also be used according to the invention.
  • the mother liquor can be centrifuged off. By adding water to the moist remainder of silicate the fluid component of the suspension can be restored.
  • This suspension is suitable for coating on paper or the like.
  • the dispersion or suspension used for coating should contain 1 to 10% solids, preferably 3 to 5%, of the particular silicate.
  • the silicate suspension is obtained by the following process: 400 parts of an approximately 55% solution of crude sodium silicate (a suitable product of this kind is sold under the trade name Natronwasserglas 58/60 B by the firm Rheinische Wasserglasfabriken at Ludwigshafen on Rhine) are diluted with 2,400 parts of water. This solution is thoroughly swirled around by means of an electric mixer (i. e. a high-speed mixer for example of 2800 R. P. M.) and 480 parts of commercial magnesium chloride-6-hydrate dissolved in 2,000 parts of water are added at room temperature as quickly as possible, within a few seconds. The magnesium silicate thus formed is deposited as a very fine-grained, uniformly distributed sediment which is ready for use in this form.
  • an electric mixer i. e. a high-speed mixer for example of 2800 R. P. M.
  • 480 parts of commercial magnesium chloride-6-hydrate dissolved in 2,000 parts of water are added at room temperature as quickly as possible, within a few seconds.
  • the magnesium silicate thus formed is
  • 600 parts of crude magnesium chloride-G-hydrate are dissolved in 5,000 parts of hot water (60 C.) and, while intensively stirring, within 5 minutes 500 parts of an approximately 55% sodium silicate solution dissolved in 4,000 parts of hot water (60 C.) are added.
  • the magnesium silicate precipitates in a very finely dispersed state and is separated from the mother liquor by means of a centrifuge.
  • the residual white paste is treated with fresh water to make 5,620 parts.
  • a 4% magnesium silicate suspension having a thixotropic character is formed which may be used for coating paper.
  • the coated paper may be made sensitive to light by coating it with a conventional blueprint sensitizing solution including a light sensitive ferric salt and a water soluble iron cyanide salt such as potassium ferricyanide.
  • a conventional blueprint sensitizing solution including a light sensitive ferric salt and a water soluble iron cyanide salt such as potassium ferricyanide.
  • the light-sensitive blue-print paper aifords prints prepared in this manner of excellent contrast and excellent legibility even from poor originals, such as bad pencil drawings. Such prints have a rich deep blue color.
  • Either of the aforementioned magnesium silicate dispersions may also be added directly to the sensitizing solution and applied to the paper therewith. This procedure results in prints having similar properties to those described above.
  • an aqueous calcium silicate sus pension can also be used for the production of the precoat layer applied directly on the paper stock.
  • the calcium silicate suspension is prepared by diluting 225 parts of a technical sodium silicate solution of 58/60 B with 2,000 parts of water and, by adding very quickly, while stirring thoroughly as described in Example 1, a solution of 111 parts of calcium chloride in 1,000 parts of Water.
  • the calcium silicate deposits in a gel-like state which is separated from the mother liquor in a centrifuge.
  • the paste thus obtained is treated with fresh water to make 2,870 parts and made suitable for coating purposes by stirring this intensively.
  • Paper precoated with this suspension and subsequently rendered sensitive to light by means of a diazo-type sensitizing solution of the usual type for forming blue images which may be developable by either the dry or semiwet method has proved to afford, upon exposure to light under a master, prints that show a deeper and stronger color shade than those produced on paper which is not provided with the calcium silicate layer.
  • paper stock may be coated with an aqueous zinc silicate suspension and made sensitive to light with any of the water soluble light sensitive substances after drying the silicate layer.
  • This paper too, produces prints of excellent contrast. Inscriptions with ink and India ink will not bleed when applied to this type of paper.
  • Production of the zinc silicate suspension is analogous to that of the calcium silicate, described in Example 2. 140 parts of the Zinc chloride are mixed with 225 parts of the sodium silicate solution 58/ 60 B. The gel-like zinc silicate deposit is centrifuged from the mother liquor and transformed into a coatable suspension by adding 3,750 parts of fresh water and stirring vigorously.
  • Transparentized paper or paper stock which can be used for intermediate reproductions or duplicate originals and which transmits long wave ultraviolet rays in the production of subsequent prints, is precoated with a magnesium silicate suspension prepared as follows:
  • a paste which is dispersed in fresh water (3750- 3800 g.) and mixed in a high-speed mixer (3000 R. P. M.) to form a suspension (total weight 5600 g.).
  • the suspension which still has a pH-value of 10 is brought down to a pH-value of 8.0 to 8.2, by slowly adding an 18% solution of hydrochloric acid free from iron. Then process, for which about -105 cc. of an 18% solution of hydrochloric acid are used, takes place in a high-speed mixer under steady control.
  • a water-soluble cellulose-ether of high viscosity e. g. methyl-cellulose or oxethylmethylcelluose. After the cellulose-ether is dissolved, the suspension is ready for coating.
  • silicate suspension it may be advantageous to add to the silicate suspension also other natural or synthetic organic colloidal substances, such as gelatine, casein, dextrin, water soluble synthetic resins, e. g. polyvinyl-alcohol or polyvinyl-pyrrolidone, or water insoluble synthetic resins, suitably in finely dispersed state.
  • water soluble synthetic resins e. g. polyvinyl-alcohol or polyvinyl-pyrrolidone
  • water insoluble synthetic resins suitably in finely dispersed state.
  • the transparentized paper thus pretreated is coated with one of the usual diazotype preparations which develops brown azo dyes.
  • the paper is then dried.
  • the prints thus obtained yield better contrasts than those obtained from notpretreated papers, and their printing density is higher, which is very important when the print is intended as an intermediate for the production of subsequent copies.
  • the magnesium-silicate-gel is separated from the salt-bearing mother liquor by means of a centrifuge with at least 3000 R. P. M. Approximately 5200 to 5500 g. of a paste is agitated with 9500-9800 g. of water to yield 15 kg. of a homogeneous suspension.
  • This suspension (which is now ready for coating) has a pH value of 8.0 to 8.4 (potentiometrically measured).
  • an ordinary diazotype base material (paper) is pre-coated with this silicate suspension and subsequently coated with a lightsensitive layer diazo preparation.
  • Prints obtained from material thus prepared show distinctly better contrasts than those made with material which was not pre-treated.
  • Finely dispersed silica may be added to this silicate suspension, as well as to all silicate suspensions covered by the present invention.
  • a silica suspension of the kind described in U. S. Patent 2,433,515 may be used.
  • prints obtained from diazotype material prepared with such suspensions show an inferior fastness to ink.
  • coupling components are used in the light-sensitive preparation which have a tendency to form aluminum lakes, e. g. compounds containing hydroxyl-groups in ortho-position to each other, such as 2,3-dihydroxynaphthalene and derivatives thereof, formation of an aluminum silicate layer beneath the light-sensitive layer is less advisable.
  • resorcinol 2 hydroxynaphthalene 3,6 disodiurnsulfonate or 2,7-dihydroxynaphthalene-3,6-disodiumsulfonate is used as a coupling component, good prints with excellent contrasts are obtained.
  • Photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of a silicate of a metal of the second and third groups of the periodic system, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive compound selected from the group consisting of diazo compounds and ferric salts.
  • Photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of a silicate of a metal of the second group of the periodic system selected from the group consisting of magnesium and the alkaline earth metals, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive compound selected from the group consisting of diazo compounds and ferric salts.
  • Photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of a silicate of a metal of the second group of the periodic system selected from the group consisting of magnesium, calcium and zinc, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive compound selected from the group consisting of diazo compounds and ferric salts.
  • Photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of magnesium silicate, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive compound selected from the group consisting of diazo compounds and ferric salts.
  • Photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of calcium silicate, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive compound selected from the group consisting of diazo compounds and ferric salts.
  • Photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of zinc silicate, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive compound selected from the group consisting of diazo compounds and ferric salts.
  • Photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of aluminum silicate, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive compound selected from the group consisting of diazo compounds and ferric salts.
  • Diazotype photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of a silicate of a metal of the second and third groups of the periodic system, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive diazo compound.
  • Diazotype photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of a silicate of a metal of the second and third groups of the periodic system, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive diazo compound and an azo dye coupling component.
  • Blueprint photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of a silicate of a metal of the second and third groups of the periodic system, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive ferric salt and a complex iron cyanide salt.
  • Photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles formed of a silicate of a metal of the second and third groups of the periodic system, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive ferric salt and :a water soluble silver salt.
  • Photoprinting material comprising an absorbent base coated with a carrier layer consisting essentially of particles of collodial size formed of a silicate of a metal of the second and third groups of the periodic system, said carrier layer being sensitized with a photosensitive solution comprising a light sensitive compound selected from the group consisting of diazo compounds and ferric salts.
  • the method of making photoprinting material comprising the steps of coating an absorbent base with a carrier layer consisting essentially of particles formed of a silicate of a metal of the second and third groups of the periodic system and coating said layer of particles on said base with a photosensitive solution comprising a light sensitive compound selected from the group consisting of diazo compounds and ferric salts.
  • the method of making photoprinting material comprising the step of applying to an absorbent base a coating consisting of an aqueous solution containing a light sensitive compound selected from the group consisting of diazo compounds and ferric salts and dispersed particles formed of a silicate of a metal of the second and third groups of the periodic system.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US343502A 1952-03-27 1953-03-19 Photosensitive material Expired - Lifetime US2813792A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEK13677A DE973579C (de) 1952-03-27 1952-03-27 Verfahren zur Herstellung von Lichtpausmaterial

Publications (1)

Publication Number Publication Date
US2813792A true US2813792A (en) 1957-11-19

Family

ID=7214122

Family Applications (1)

Application Number Title Priority Date Filing Date
US343502A Expired - Lifetime US2813792A (en) 1952-03-27 1953-03-19 Photosensitive material

Country Status (7)

Country Link
US (1) US2813792A (en(2012))
BE (1) BE518233A (en(2012))
CH (1) CH314941A (en(2012))
DE (1) DE973579C (en(2012))
FR (1) FR1075711A (en(2012))
GB (1) GB742407A (en(2012))
NL (2) NL89036C (en(2012))

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4258125A (en) * 1975-11-14 1981-03-24 Edhlund Ronald D Method of making hand proofs of color prints

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2178771A (en) * 1934-10-10 1939-11-07 Philips Nv Light-sensitive layer and method of making same
US2626867A (en) * 1947-12-04 1953-01-27 Du Pont Light-sensitive photographic element

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1989879A (en) * 1932-01-19 1935-02-05 Bruning Charles Co Inc Photographic line printing
US2121205A (en) * 1936-11-07 1938-06-21 Bancroft & Sons Co J Blueprint, photo-vellum, and similar sensitized cloths
USRE22579E (en) * 1941-10-22 1944-12-19 Sensitizer containing a gel-forming
FR896644A (fr) * 1942-08-05 1945-02-27 Ig Farbenindustrie Ag Procédé pour augmenter la résistance à l'eau de papiers, tissus ou analogues comme supports de couches pour applications photographiques ou photomécaniques
GB647197A (en) * 1945-04-18 1950-12-06 H P Andrews Paper Company Improvements relating to the coating of paper
USRE23510E (en) * 1945-04-18 1952-06-10 Method of making photographic
NL142417B (nl) * 1947-10-30 Sumitomo Chemical Co Werkwijze voor het stabiliseren van cyclische fosforesters van salicylalcohol.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2178771A (en) * 1934-10-10 1939-11-07 Philips Nv Light-sensitive layer and method of making same
US2626867A (en) * 1947-12-04 1953-01-27 Du Pont Light-sensitive photographic element

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4258125A (en) * 1975-11-14 1981-03-24 Edhlund Ronald D Method of making hand proofs of color prints

Also Published As

Publication number Publication date
BE518233A (en(2012))
CH314941A (de) 1956-07-15
GB742407A (en) 1955-12-30
NL89036C (en(2012)) 1958-04-15
DE973579C (de) 1960-03-31
NL176611B (nl)
FR1075711A (fr) 1954-10-19

Similar Documents

Publication Publication Date Title
US3353984A (en) Method for the preparation of lightsensitive diazotype materials and improved materials prepared by such method
US2662013A (en) Diazotype photoprinting material
US3996056A (en) Diazotype reproduction layer formed from matrix of spheric particle polystyrene pigment and diazotype components
US2566709A (en) Diazotype photoprinting materials containing colloidal silica
US3113025A (en) Diazotype materials for the production of black images
US3027256A (en) Production of light-sensitive diazotype materials
US2196950A (en) Photographic printing process
US2813792A (en) Photosensitive material
US2659672A (en) Diazotype photoprinting materials
US3345168A (en) Diffusion transfer receiving sheet containing china clay and an aliphatic amine
US3207603A (en) Diazotype and blueprint photoprinting materials having a coating of waterinsoluble metallic fatty acid soap thereon
US3653903A (en) Diazo-type multicolor reproduction process
US3950171A (en) Diazotype multicolor reproduction process
US2822271A (en) Photosensitive material
US2536398A (en) Pyrazolone diazotype couplers
US3944422A (en) Photosensitive material in use for diazo-type multicolor reproduction
US3529964A (en) Heat developable diazo compositions and diazotype reproduction media
US3367776A (en) Heat sensitive diazotype materials
US2172307A (en) Process for the manufacture of colored photographic materials and material therefor
US3052542A (en) Intermediate master for use in the diazotype process and a process for producing same
US2746863A (en) Light sensitive diazotype material
US3155511A (en) Precoated diazo reproduction paper
US3907567A (en) Waxy crayon or ink-like diazotype developer composition comprising heat transferrable azo coupler and transfer promotor
US2523889A (en) Diazotypes containing dialkoxy phenols
US3191030A (en) Process of making and using thermographic reproduction paper