US2822272A - Light sensitive diazotype material - Google Patents

Light sensitive diazotype material Download PDF

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Publication number
US2822272A
US2822272A US409521A US40952154A US2822272A US 2822272 A US2822272 A US 2822272A US 409521 A US409521 A US 409521A US 40952154 A US40952154 A US 40952154A US 2822272 A US2822272 A US 2822272A
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US
United States
Prior art keywords
silica
light sensitive
polyvinyl
solution
diazotype
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
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US409521A
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English (en)
Inventor
Joseph F Kosalek
Jr John Sulich
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GAF Chemicals Corp
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General Aniline and Film Corp
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Filing date
Publication date
Priority to NLAANVRAGE8601394,A priority Critical patent/NL188976B/xx
Priority to BE529755D priority patent/BE529755A/xx
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US409521A priority patent/US2822272A/en
Priority to FR66476D priority patent/FR66476E/fr
Priority to CH337726D priority patent/CH337726A/de
Priority to DEG14700A priority patent/DE954392C/de
Priority to GB23942/54A priority patent/GB752422A/en
Application granted granted Critical
Publication of US2822272A publication Critical patent/US2822272A/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/60—Compositions containing diazo compounds as photosensitive substances with macromolecular additives

Definitions

  • the present invention pertains to light sensitive diazotype materials having fast printing speed and being capable of yielding images of high density, and more particularly to such materials in which the light sensitive component is located on the base in a layer comprising a polyvinyl ester having finely divided silica dispersed rherethrough.
  • diazonium compound having such a high light sensitivity that it may be used in a concentration which will give the required image density while still permitting complete burn-out in the whites in the desired period of time.
  • diazos of widely varied chemical structures have been proposed, synthesized and tested in the diazotype process.
  • the stabilized diazos derived from N,N-disubstituted p-phenylenediamines appear to offer the best compromise between high light sensitivity and greater dye density, on the one hand, and the other requisite features such as Water solubility in coating solutions, stability to decomposition and/ or precoupling, fastness properties and the like, on the other hand.
  • Another tack has been the used additives in the diazotype coating solution to increase the burn-out sensitivity of the diazo in the light struck areas.
  • diazotype coating solution For this purpose there have been proposed such compounds as anthraquinone disulfonic acid, ketonic organiccompounds and the like. It is evident that this phenomenon, if successful, would permit more diazo to be used in the sensitized layer and thereby result in a higher density in the image areas with no sacrifice in printing speed. Unfortunately, this approach has met'with but limited" success, the results not being commercially satisfactory on a quality or cost basis.
  • 2,566,709 proposes to produce the same improvement in the diazotype system of photoreproduction by the incorporation of colloidal silica in a dispersed state in a diazotype sensitizing solution.
  • the latter procedure has the very important added economic advantage of eliminating a separate coating step.
  • Rub-off, or powdering-oif, as the name implies involves the tendency of the silica particles to be removed during manufacture and end use of the diazotype materials.
  • the silica layer acts as a chromatographic separator toward the several ingredients present in a typicaldiazo coating solution. This re sults in poorer stability, poorer fade resistance, and, in the case of the black line (which uses a multiplicity of coupling components) off-colored blacks. It has been stated that the use of the silica layers in the above patents enhanced brightness and density. It is to be noted, however, that the degree of improvement when weighed against the aforesaid objections, the increased cost and extra eiforts is disappointingly small.
  • the water insoluble polymers may be a polyvinyl ester per se, such as polyvinyl acetate, polyvinyl chloride or the like, or copolymers of a vinyl ester, suchas vinyl chloride, vinyl acetate or the like with another vinyl compound copolymerizable with such ester, i. e., acrylic acid, styrene or the like.
  • the vinyl ester in such copolymers will range from to 40 parts by weight.
  • These polymers and copolymers are employed in the form of aqueous dispersions in which the solids content is 40-55% by Weight, Such polymers are readily obtainable in the open market.
  • the silica which we use in our dispersions may be either colloidal in character or may be of a coarser grade, i. e., ranging from 1 to 5 microns in. size. We find that we obtain best results with the coarser particles and so prefer their use.
  • diazos examples are those derived from .N,N-diethyl-p-phenylenediamine; N-benzyl N ethyl p phenylenediamine; N-ethyl-p-phenylenediamine; N phenyl p phenylenediamine; N,N-diethyl-2- ethoxy p-phenylenediamine; N-ethyl-Z-methyl-p-phenylenediamine; N,N bis(fl hydroxyethyl) p-phenylenediamine; N fi-hydroxyethyl-N-methyl-p-phenylenediamine and the like. According to customary procedure these diazos are used in the form of salts stabilized with zinc chloride, tin chloride, cadmium chloride and the like.
  • any of the usual coupling components are satisfactory for our purpose.
  • couplers are 2,5- xylenol; 2,3-dihydroxynaphthalene; 1,8-dihydroxynaphthalene; resorcinol, octyl resorcinol; p-methyl-N-phenyl pyrazolone; the amide of u-resorcylic acid; 2-hydroxynaphthalene-3,6'disu1fonic acid; H acid; acetyl acetanilide; 2,3-dihydroxynaphthalene-6-sulfonic acid and the like.
  • Other couplers are mentioned in the Van der Grinten article supra.
  • the coating solution in addition to the polymer, silica and light sensitive diazo may contain the various adjuncts usual in the manufacture of light sensitive diazotype ma terials. These include metal salts for intensification of the dyestuif image, suchas ammonium sulfate, nickel sulfate, zinc chloride and the like; stabilizing agents such as thiourea, thiosinamine, naphthalene trisulfonic acid and the like; acids acting to retard precoupling such as acetic acid,'boric acid, tartaric acid and the like; hygroscopic agents such as glycol, glycerinand the like; and wetting agents such as saponin, lauryl sulfonate, keryl benzene sulfonate, the oleic acid 'amid of N-methyl.taurine and the like.
  • metal salts for intensification of the dyestuif image suchas ammonium sulfate, nickel sulf
  • agents which have the property of accelerating the rate of azo dye color development. particularly under conditions of low ammonia concentration.
  • thiourea derivatives and, particularly those in which either one or both nitrogen atoms are substituted byan aliphatic radi cal. Examples of such compounds are l-allyl-3-p-hydroxyethyl-Z-thiourea; 1-allyl-2-thiourea and the like.
  • the ratio of silica to binder is not as critical in our procedure as in the procedure of U. S. P. 2,662,013.
  • the quantity of binder may range from /6 to 1 part by weight for each part by weight of silica.
  • the quantity of silica on the other hand, based on the weight of the light sensitive diazonium compound is about 1 part of the diazonium compound to 1 to 4 parts of silica.
  • the base to which our coating solution is applied may be any of the bases which have been previously suggested for use in the diazotype field.
  • bases are high grade all-sulfite bond paper, rayon or cotton cloth, starch filled cloth, partially hydrolyzed cellulose acetate film base, regenerated cellulose acetate and the like.
  • the polyvinyl ester dispersion is essentially composed of discrete water insoluble particles of resin with tiny amounts of polyvinyl alcohol in solution. Being in the insoluble state, the concentration used raises viscosity negligibly compared to what a typical water soluble resin in an equally effective concentration would. This permits rapid sensitizing and drying during the coating operation.
  • the low pH of the coating solution in combination with the heating applied during the drying step hydrolyzes a small amount of the polyvinyl ester to polyvinyl alcohol on the surface of the particles thus making these particles more receptive to impregnation by the coating solutioningredients.
  • the low block temperature of the resin permits a portion of the particles to fuse during the drying step.
  • This fusion together with the well-known adhesive qualities of the polyvinyl ester, makes its binding properties upon the silica especially desirable.
  • this polyvinyl ester In the diazotype system in which this polyvinyl ester is used, one can thus visualize the eflfectsof coating solution and resin acting upon one another to produce in a discrete particle, discontinuous film form, a mixture of polyvinyl alcohol and polyvinyl ester, the latter being partially hydrolyzed, unhydrolyzed and partially fused.
  • This mixture represents a very effective manner for receiving the coating solution and enhancing the density of the dye images formed therein.
  • Example I High grade all-sulfite bond paper is coated with a sensitizing solution of the following composition:
  • Example 11 High grade all-sulfite bond paper is coated with a sensitizing solution of the following composition:
  • Example III A high grade, well-sized bond paper is coated with the following solution:
  • Example IV The procedure is the same as in Example I, excepting that there is employed 50% solids cationic type polyvinyl chloride aqueous suspension in lieu of the polyvinyl acetate of Example I.
  • Example V The procedure is the same as in Example II, except ing that there is employed, in lieu of the polyvinyl acetate, 50% solids cationic type vinyl acetateacrylic acid copolymer aqueous dispersion, the content of acrylic acid in said copolymer being 20% by weight.
  • a light sensitive composition for diazo type materials comprising a compatible aqueous dispersion of a light sensitive diazonium compound, a water insoluble polymer of a vinyl ester selected from the class consisting of those which are cationic and non-ionic and finely divided silica.
  • composition as defined in claim 1, wherein the water insoluble polymer is polyvinyl acetate.
  • composition as defined in claim 1, wherein the silica has a particle size ranging from 1 to 5 microns.
  • a water receptive base coated with a light sensitive composition comprising a compatible aqueous dispersion of a light sensitive diazonium compound, a polymer of a vinyl ester selected from the class consisting of those which are cationic and non-ionic and finely divided silica.
  • silica has a particle size ranging from 1 to 5 microns.

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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)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US409521A 1953-06-22 1954-02-10 Light sensitive diazotype material Expired - Lifetime US2822272A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
NLAANVRAGE8601394,A NL188976B (nl) 1954-02-10 Maaimachine.
BE529755D BE529755A (enrdf_load_stackoverflow) 1954-02-10
US409521A US2822272A (en) 1954-02-10 1954-02-10 Light sensitive diazotype material
FR66476D FR66476E (fr) 1953-06-22 1954-06-15 Matériels photosensibles pour la diazotypie
CH337726D CH337726A (de) 1954-02-10 1954-06-22 Sensibilisiergemisch für lichtempfindliche Diazotypiematerialien
DEG14700A DE954392C (de) 1953-06-22 1954-06-23 Mischung zur Sensibilisierung von Diazotypiematerial
GB23942/54A GB752422A (en) 1954-02-10 1954-08-17 Light sensitive diazotype material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US409521A US2822272A (en) 1954-02-10 1954-02-10 Light sensitive diazotype material

Publications (1)

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US2822272A true US2822272A (en) 1958-02-04

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US409521A Expired - Lifetime US2822272A (en) 1953-06-22 1954-02-10 Light sensitive diazotype material

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US (1) US2822272A (enrdf_load_stackoverflow)
BE (1) BE529755A (enrdf_load_stackoverflow)
CH (1) CH337726A (enrdf_load_stackoverflow)
GB (1) GB752422A (enrdf_load_stackoverflow)
NL (1) NL188976B (enrdf_load_stackoverflow)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062644A (en) * 1956-12-28 1962-11-06 Azoplate Corp Diazo printing plates and method for the production thereof
US3113865A (en) * 1960-05-05 1963-12-10 Eastman Kodak Co Heat developable diazo sulfones
US3163535A (en) * 1956-11-14 1964-12-29 Gen Aniline & Film Corp Alkali-soluble resins with non-colloidal silica for precoating diazotype materials
US3169869A (en) * 1958-06-04 1965-02-16 Grinten Chem L V D Diazotype material
US3307949A (en) * 1962-08-15 1967-03-07 Keuffel & Esser Co Diazotype intermediate comprising a layer containing a tri-substituted phenol coupler
US3316092A (en) * 1963-05-09 1967-04-25 Dietzgen Co Eugene Diazotype material comprising a metal sulfate nitrogenous compound and polymeric anhydride
US3406072A (en) * 1964-12-21 1968-10-15 Gaf Corp One-component diazotypes
US3418152A (en) * 1966-08-01 1968-12-24 Eastman Kodak Co Method of making a chromatographic element containing a resinous binder and product produced thereby
US3418158A (en) * 1964-06-17 1968-12-24 Eastman Kodak Co Chromatographic sheets
US3622335A (en) * 1970-01-13 1971-11-23 Norman Thomas Notley Copolymers of an alpha acrylonitrile and a styrene used as vehicles in vesicular materials
JPS4962122A (enrdf_load_stackoverflow) * 1972-10-16 1974-06-17
US3847614A (en) * 1971-09-13 1974-11-12 Scott Paper Co Diazo photopolymer composition and article comprising carboxylated resin
US4272605A (en) * 1975-06-09 1981-06-09 Western Litho Plate & Supply Co. Base plate and lithographic plate prepared by sensitization thereof
US4272604A (en) * 1975-06-09 1981-06-09 Western Litho Plate & Supply Co. Base plate and lithographic plate prepared by sensitization thereof
US4288520A (en) * 1978-08-03 1981-09-08 Hoechst Aktiengesellschaft Process of manufacturing light-sensitive copying material based on diazonium salt condensation products
US4471043A (en) * 1981-11-23 1984-09-11 Oc/e/ -Nederland B.V. Diazotype material
US4495269A (en) * 1982-09-22 1985-01-22 Am International, Inc. Waterborne two component diazo type coating composition with hydrolyzed polyvinyl acetate and hexamethoxy methylmelamine resin
US4522910A (en) * 1975-06-19 1985-06-11 Napp Systems (Usa), Inc. Photosensitive graphic arts article
US4687726A (en) * 1984-05-12 1987-08-18 Hoechst Aktiengesellschaft Photosensitive recording material for use in the production of negative-working planographic printing plates with diazonium polycondensate and inorganic pigment
US4980273A (en) * 1987-01-10 1990-12-25 E. I. Dupont De Nemours And Company Matted photographic imaging materials

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2405523A (en) * 1944-08-09 1946-08-06 Du Pont Light-sensitive photographic compositions and elements
US2522771A (en) * 1944-11-03 1950-09-19 Gen Aniline & Film Corp Photographic silver halide emulsions
US2566709A (en) * 1947-10-30 1951-09-04 Gen Aniline & Film Corp Diazotype photoprinting materials containing colloidal silica
US2611763A (en) * 1948-12-23 1952-09-23 Gen Aniline & Film Corp Amphoteric vinyl interpolymers
US2662013A (en) * 1951-07-18 1953-12-08 Gen Aniline & Film Corp Diazotype photoprinting material
FR1049725A (fr) * 1951-11-07 1953-12-31 Kalle & Co Ag Matériel pour photo-tirages
GB702294A (en) * 1951-09-11 1954-01-13 Ozalid Co Ltd Photographic diazotype layers

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2405523A (en) * 1944-08-09 1946-08-06 Du Pont Light-sensitive photographic compositions and elements
US2522771A (en) * 1944-11-03 1950-09-19 Gen Aniline & Film Corp Photographic silver halide emulsions
US2566709A (en) * 1947-10-30 1951-09-04 Gen Aniline & Film Corp Diazotype photoprinting materials containing colloidal silica
US2611763A (en) * 1948-12-23 1952-09-23 Gen Aniline & Film Corp Amphoteric vinyl interpolymers
US2662013A (en) * 1951-07-18 1953-12-08 Gen Aniline & Film Corp Diazotype photoprinting material
GB702294A (en) * 1951-09-11 1954-01-13 Ozalid Co Ltd Photographic diazotype layers
FR1049725A (fr) * 1951-11-07 1953-12-31 Kalle & Co Ag Matériel pour photo-tirages

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3163535A (en) * 1956-11-14 1964-12-29 Gen Aniline & Film Corp Alkali-soluble resins with non-colloidal silica for precoating diazotype materials
US3062644A (en) * 1956-12-28 1962-11-06 Azoplate Corp Diazo printing plates and method for the production thereof
US3169869A (en) * 1958-06-04 1965-02-16 Grinten Chem L V D Diazotype material
US3113865A (en) * 1960-05-05 1963-12-10 Eastman Kodak Co Heat developable diazo sulfones
US3307949A (en) * 1962-08-15 1967-03-07 Keuffel & Esser Co Diazotype intermediate comprising a layer containing a tri-substituted phenol coupler
US3316092A (en) * 1963-05-09 1967-04-25 Dietzgen Co Eugene Diazotype material comprising a metal sulfate nitrogenous compound and polymeric anhydride
US3418158A (en) * 1964-06-17 1968-12-24 Eastman Kodak Co Chromatographic sheets
US3406072A (en) * 1964-12-21 1968-10-15 Gaf Corp One-component diazotypes
US3418152A (en) * 1966-08-01 1968-12-24 Eastman Kodak Co Method of making a chromatographic element containing a resinous binder and product produced thereby
US3622335A (en) * 1970-01-13 1971-11-23 Norman Thomas Notley Copolymers of an alpha acrylonitrile and a styrene used as vehicles in vesicular materials
US3847614A (en) * 1971-09-13 1974-11-12 Scott Paper Co Diazo photopolymer composition and article comprising carboxylated resin
JPS4962122A (enrdf_load_stackoverflow) * 1972-10-16 1974-06-17
US4272605A (en) * 1975-06-09 1981-06-09 Western Litho Plate & Supply Co. Base plate and lithographic plate prepared by sensitization thereof
US4272604A (en) * 1975-06-09 1981-06-09 Western Litho Plate & Supply Co. Base plate and lithographic plate prepared by sensitization thereof
US4522910A (en) * 1975-06-19 1985-06-11 Napp Systems (Usa), Inc. Photosensitive graphic arts article
US4288520A (en) * 1978-08-03 1981-09-08 Hoechst Aktiengesellschaft Process of manufacturing light-sensitive copying material based on diazonium salt condensation products
US4471043A (en) * 1981-11-23 1984-09-11 Oc/e/ -Nederland B.V. Diazotype material
US4495269A (en) * 1982-09-22 1985-01-22 Am International, Inc. Waterborne two component diazo type coating composition with hydrolyzed polyvinyl acetate and hexamethoxy methylmelamine resin
US4687726A (en) * 1984-05-12 1987-08-18 Hoechst Aktiengesellschaft Photosensitive recording material for use in the production of negative-working planographic printing plates with diazonium polycondensate and inorganic pigment
US4980273A (en) * 1987-01-10 1990-12-25 E. I. Dupont De Nemours And Company Matted photographic imaging materials

Also Published As

Publication number Publication date
GB752422A (en) 1956-07-11
NL188976B (nl)
CH337726A (de) 1959-04-15
BE529755A (enrdf_load_stackoverflow)

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