US2953471A - Photosensitive materials - Google Patents

Photosensitive materials Download PDF

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Publication number
US2953471A
US2953471A US700725A US70072557A US2953471A US 2953471 A US2953471 A US 2953471A US 700725 A US700725 A US 700725A US 70072557 A US70072557 A US 70072557A US 2953471 A US2953471 A US 2953471A
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United States
Prior art keywords
fluoride
diazotype
zinc
solution
paper
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Expired - Lifetime
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US700725A
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English (en)
Inventor
Landau Raphael
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ALSACIENNE DE PAPIERS HELIOGRA
ALSACIENNE DE PAPIERS HELIOGRAPHIQUES Ste
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ALSACIENNE DE PAPIERS HELIOGRA
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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
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/60—Compositions containing diazo compounds as photosensitive substances with macromolecular additives

Definitions

  • This invention relates to diazotype processes and specifically provides photosensitive diazotype materials, coated with substantially insoluble metal fluorides in finely d1- vided form, prior to or concurrently with the application of a conventional sensitizing composition to said materials.
  • the invention further relates to a method of preparing such diazotype materials.
  • Photosensitive diazotype materials generally comprise a support or base which may be paper, cardboard, cellulose film, textile fabric, or other suitable sheet material, coated with a diazonium salt composition sensitive to light and actinic rays.
  • a support or base which may be paper, cardboard, cellulose film, textile fabric, or other suitable sheet material, coated with a diazonium salt composition sensitive to light and actinic rays.
  • the salt is converted to a dye through the action of a bonding or coupling agent which may be mixed with the salt composition or through the action of a developer.
  • diazotype materials One typical feature of diazotype materials is the high optical density of the lines in the image (hereinafter designated triefly by the term density), which is a function of the concentration of diazonium salt. Increased density results in greater contrast and hence more legible final picture or print. 7
  • the maximum density of a diazo material depends directly on the exposure time which has to be used in order to get a satisfactory print.
  • the sensitivity of conventional diazo materials decreases with increase in the maximum density of the material.
  • the finely divided condition of the metal fluorides of the invention makes possible a much more thorough division of the dye formed-on printing and development of the diazotype material, so that a given quantity of absorptive material coating a given surface area will absorb to a greater degree due to its more finely divided state.
  • finely divided pigment such as zinc oxide, barium sulfate, titanium white, and the like, are not suitable for the purposes of the invention since they will coat the surface of the carrier with 2 white coating which reduces the maximum density of i rather than premanently bonding the'dye to the surfacr of the carrier in a form capable of absorbing the inci dent light and hence reducing the degree of specular re flection of the fibres.
  • the density increase is comparativel low, and said increase is particularly high when the grain are within a range of average diameter from about 0.0 micron to about 0.50 micron. Below this range, i.e. witl grain size less than about 0.01 micron the increase i: absorption still remains quite high but the surface become less mat.
  • any metal fluoride may b used providing it is substantially insoluble in water, an especially the fluorides of the following metals: calciurr barium, strontium, magnesium, aluminium, zinc, all in finely divided state.
  • Such finely divided insoluble metal fluorides can b prepared by reacting a compound of the metal dissolve or suspended in water, e.g. a chloride, a sulfate, a nitratr a hydroxide etc. with a compound containing a fluorid anion such as sodium fluoride, potassium fluoride, arr monium fluoride, hydrofluoric acid gas or solution an the like. Alternatively one or more of the constituent may be reacted in gaseous form.
  • a compound of the metal dissolve or suspended in water, e.g. a chloride, a sulfate, a nitratr a hydroxide etc.
  • a compound containing a fluorid anion such as sodium fluoride, potassium fluoride, arr monium fluoride, hydrofluoric acid gas or solution an the like.
  • one or more of the constituent may be reacted in gaseous form.
  • the preferred method of my invention is to precip tate the metal fluoride in water and regulate the reactio conditions in regard to temperature, time and concer trations, in such a manner as to obtain a suspension c a particle-size largely within the preferred range spec fied above, that is 0.01 to 0.50 micron. If necessary th resulting reaction product may be purified by filtratior dialysis, settling or other suitable procedure. A COll0i1 'indiug mill may be used if desired in order to disperse 1y agglomerates of the particles that may tend to form.
  • the metal fluorides may be used separately or in adixture, e.g.
  • the metal fluorides may be used t solid form, as powders, and dispersed in the sensitiztg solution by means of a colloid grinder mill for exnple.
  • sensitizing )llltlOl'l may be added in the form of a con- :ntrated colloidal aqueous solution to the sensitizing )llltlOl'l, also in a concentrated solution, so that the adition of the fluorides will permit a readjustment of the )ncentration of said sensitizing solution to the desired alue.
  • Another procedure is to deposit the metal fluorides on ie carrier or base of the diazotype material in an inial pre-coating step prior to exposure.
  • the otherwise Jnventional pre-coating solution used may then contain 'om about 1% to about 25% of metal fluorides dependlg on the strength of the desired effect, the convenience f using a concentrated solution and on economical conitions. Solutions containing from about 3 to about y weight of fluoride appear to be most satisfactory in iese various respects.
  • the solution used may further contain in addition to ie fluorides other substances such as stabilizers, e.g. aio-urea, naphthalene trisulfonic acid, 1, 3, 6; citric cid; tartric acid, boric acid, phosphoric acid, etc.; it my contain a part of the coupling or bonding agents, .g. diazonium salts, wetting agents, e.g. saponine; col- )ids, e.g. gelatine, gum-arabic, starch; developing-accelrators, e.g. glycerine, glycol; and dispersed resins e.g. rea-formol, thio-urea formol, dicyanodiamine-formol, olyvinyl acetate, and the like.
  • stabilizers e.g. aio-urea, naphthalene trisulfonic acid, 1, 3, 6
  • citric cid e.g.
  • the sensitizing composition may include the iazonium salts described in French Patents Nos. ,096,363, 1,096,744 and 1,097,264, which salts include 1e diazonium derivatives of the compounds derived from my of the folowing compounds: para-hydroxyethyl-ethl-amino-aniline; para-ethyl-amino-ortho-toluidine; paraiethyl-amino-aniline; para-amino-diphenyl-amineg paraenzyl-ethyl-amino-aniline; and others. These comounds may be used in their stabilized form, e.g. in the orm of double salts of zinc chloride, tin chloride, chloobenzenic sulfonate, and the like.
  • any various coupler or bonding compounds may be sed to form the dyes with the diazonium salts on deelopment.
  • any of the following may be used ingly or in admixture: R-salt,; Schaeflers salt, 2,3-diiydroxy-naphthalene-6 sulfonic acid; chloroglucinol, esorcinol, acetylacetanilide, and them.
  • the metal fluorides may, an alternative procedure, e incorporated in the finely divided state, to the celluose pulp in the manufacture of the carrier paper sheet, ireferably together with the loading substances and in ,ny suitable proportions depending on the desired reults.
  • the proportion may vary over the full range of rom l to 100% on the basis of the usual loading subtances (such as kaolin derivatives, barium sulfate, tianium oxide).
  • a comparatively great proporion, say 20 to 90%, of the loading should preferably be etained in view of its function in opacifying the paper.
  • the divided metal fluorides nay be incorporated during any suitable stage of the paier-making process from the forming of the sheet to he final calendering step, by any suitable means such is surface treatment, or full immersion of the formed rheet in a colloidal solution of the metal fluorides.
  • carrier material is paper
  • other :arrier sheet materials may be used such as cardboard
  • tracing paper gelatine paper, coated paper, cellulose film, surface-saponified cellulose ester film and others.
  • metal fluorides in the manner specified above imparts to photosensitive diazotype materials superior density and print-sensitivity as compared to identical materials when prepared without the incorporation of insoluble finely-divided metal fluorides or with such metal fluorides used in proportions outside the ranges specified.
  • the use of the metal fluorides according to the invention increases the rate of the developing operation. Further, such use makes it possible to accomplish a greater uniformity of the bonding mixture where it is desired, for example, to obtain black. This is because the presence of the fluorides results in an attenuation in the colour variations with ambient conditions such as temperature obtaining during the ammonia developing process.
  • Example 1 Calcium fluoride is dispersed in water by the following procedure. Equal volumes are mixed together of a first solution containing 5% anhydrous calcium chloride and a second solution containing 3.5% sodium fluoride. Instead of the second solution, there may be used a solution of 3% ammonium fluoride, or a 4.5% potassium fluoride solution. The resulting calcium fluoride precipitate is filtered off and is dispersed in water to obtain a concentration of 5% of'calcium fluoride.
  • a sheet a base paper of a type conventionally used in diazotype process is coated with the dispersion in a diazotype coating machine.
  • the sheet is allowed to dry and is then treated with any of the following sensitizing solutions conventionally used in diazotype processes:
  • Sensitizing solution I (providing blue lines):
  • Glycerol 3 Tartric acid g 3 Thio-urea g 3 Zinc chloride g 3 2,3-dihydroxynaphthaline-6-sulfonic acid g 2 2,3 dihydroxynaphthalene-6-sulfonic acid.. g 0.8 Acetoacetaniline .g 0.7 Phloroglucinol .g 0.1 P-diazo-(N-hydroxyethyl-N-ethyl)-aniline g 2.8 Water q.s. cc.
  • Example 2 The procedure is identical with that in Example 1 eicept that an equimolecular quantity of zinc chloride (or alternatively zinc sulfate) is used in place of the calcium chloride.
  • Example 3 The same procedure is followed as in Example 1 except that one half the calcium chloride used is replaced by a molecularly equivalent quantity of zinc chloride (alternatively: zinc sulfate).
  • Example 4 The same procedure is followed as in Example 1 except that an aqueous suspension of calcium fluoride is used obtained by grinding a commercial grade of calcium q ride i h water in a colloid mill to produce a suspension wherein a majority of the particles have a diameter smaller than one micron.
  • Example 5 A base paper sheet of thetype used in diazotype processes is sensitized with either of the compositions indicated in Example 1, but modified by addition thereto of 5% zinc fluoride and/ or calcium fluoride in fine powder form, and the solution is dispersed in a colloid grinder mill to a particle size of less than 1 micron.
  • Example 6 A base paper sheet of the type used in diazo-type processes is sensitized with a composition as indicated in Example 1, except that 75 cc. water are used instead of the 100 indicated in preparing the sensitizer solution and the solution is completed to 100 cc. by adding thereto a dispersion of zinc fluoride (and/or calcium fluoride) containing 20% metal fluoride, so as to obtain in fine a sensitizing solution containing 5% metal fluoride.
  • Example 7 The same procedure is used as in any of the Examples 1 to 6 except that the carrier or base used in a sheet of pigment-coated paper, e.g. baryta paper.
  • Example 8 One or more metal fluorides, such as calcium fluoride and/or zinc fluoride and/or magnesium fluoride, having a particle size within the above specified range are incorporated in a ratio of from to 50% of dry extract in the conventional baryta-coating composition used in preparing so-called baryta paper. The resulting sheet of baryta paper is coated with a sensitizing solution as specified in Example 1.
  • metal fluorides such as calcium fluoride and/or zinc fluoride and/or magnesium fluoride
  • the image is developed with a developer of the following composition:
  • Example 10 Paper of the type used in the semi-wet developing Lab-aunt process is sensitized by immersion in a bath of the fol lowing composition:
  • a 6% water dispersion of calcium fluoride having The image is developed with a developer having the following composition:
  • a method of preparing a diazotype photosensitive material comprising first applying to a base material z finely divided water-insoluble fluoride of a metal selected from the group consisting of calcium, barium, strontium magnesium, aluminum and zinc, and then coating the base material with a diazo salt and coupling agent.
  • a method of preparing a diazotype photosensitive material comprising first dispersing in a base material 2 finely divided water-insoluble fluoride of a metal :6- lected from the group consisting of calcium, barium strontium, magnesium, aluminum and zinc, and then coat ing the base material with a diazo salt and coupling agent 3.
  • a method of preparing a diazotype photosensitive material comprising first coating on the surface of a base material a finely divided water-insoluble fluoride of 2 metal selected from the group consisting of calcium barium, strontium, magnesium, aluminum and zinc, and then coating the base material with a diazo salt and .coupling agent.

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  • 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)
US700725A 1956-12-06 1957-12-04 Photosensitive materials Expired - Lifetime US2953471A (en)

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FR1081760X 1956-12-06

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US (1) US2953471A (enrdf_load_stackoverflow)
BE (1) BE562916A (enrdf_load_stackoverflow)
DE (1) DE1081760B (enrdf_load_stackoverflow)
FR (1) FR1163200A (enrdf_load_stackoverflow)
GB (1) GB828386A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3052542A (en) * 1958-07-24 1962-09-04 Gen Aniline & Film Corp Intermediate master for use in the diazotype process and a process for producing same
US3228769A (en) * 1961-05-04 1966-01-11 Minnesota Mining & Mfg Photosensitive copy-sheet comprising zinc oxide and a diazonium compound and method of copying
US3904414A (en) * 1971-09-24 1975-09-09 Gaf Corp Precoated diazotype photocopying materials
US3980478A (en) * 1974-07-05 1976-09-14 Eastman Kodak Company Method of making an ultraviolet light image recording using a visible-light reflective intermediate element

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2205991A (en) * 1935-12-28 1940-06-25 Kalle & Co Ag Diazotype process
DE922390C (de) * 1952-12-06 1955-01-13 Erich Spang G M B H Lichtempfindliche Schicht fuer das Diazotypieverfahren
GB749034A (en) * 1953-06-22 1956-05-16 Gen Aniline & Film Corp Light sensitive diazotype material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2205991A (en) * 1935-12-28 1940-06-25 Kalle & Co Ag Diazotype process
DE922390C (de) * 1952-12-06 1955-01-13 Erich Spang G M B H Lichtempfindliche Schicht fuer das Diazotypieverfahren
GB749034A (en) * 1953-06-22 1956-05-16 Gen Aniline & Film Corp Light sensitive diazotype material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3052542A (en) * 1958-07-24 1962-09-04 Gen Aniline & Film Corp Intermediate master for use in the diazotype process and a process for producing same
US3228769A (en) * 1961-05-04 1966-01-11 Minnesota Mining & Mfg Photosensitive copy-sheet comprising zinc oxide and a diazonium compound and method of copying
US3904414A (en) * 1971-09-24 1975-09-09 Gaf Corp Precoated diazotype photocopying materials
US3980478A (en) * 1974-07-05 1976-09-14 Eastman Kodak Company Method of making an ultraviolet light image recording using a visible-light reflective intermediate element

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Publication number Publication date
BE562916A (enrdf_load_stackoverflow)
FR1163200A (fr) 1958-09-23
GB828386A (en) 1960-02-17
DE1081760B (de) 1960-05-12

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