US3281244A - Heat-developable two-component diazotype reproduction material - Google Patents

Heat-developable two-component diazotype reproduction material Download PDF

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Publication number
US3281244A
US3281244A US253646A US25364663A US3281244A US 3281244 A US3281244 A US 3281244A US 253646 A US253646 A US 253646A US 25364663 A US25364663 A US 25364663A US 3281244 A US3281244 A US 3281244A
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heat
hydroxide
reproduction material
developable
substance
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Endermann Fritz
Munder Johannes
Ziegler Hellmut
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Keuffel and Esser Co
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Keuffel and Esser Co
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Assigned to CHASE MANHATTAN BANK, N.A. THE; A NATIONAL BANKING ASSOCIATION, SECURITY NATIONAL BANK, A NATIONAL BANKING ASSOCIATION FOR ITSELF AND AS AGENT FOR CITIBANK, N.A. A NATIONAL BANKING ASSOCIATION, CONTINENTAL ILLINOIS NATIONAL BANK & TRUST CO., OF CHICAGO, A NATIONAL BANKING ASSOCIATION, BANK OF CALIFORNIA N.A. THE; A NATIONAL BANKING ASSOCIATION, CHEMICAL BANK, A BANKING INSTITUTION OF reassignment CHASE MANHATTAN BANK, N.A. THE; A NATIONAL BANKING ASSOCIATION SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KEUFFEL & ESSER COMPANY A.N.J. CORP
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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
    • G03C1/58—Coupling substances therefor
    • 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 relates to diazotype reproduction materials and refers more particularly to heat-developable two-component diazotype reproduction material and to processes for preparing said materials.
  • the so-called dry process the reproduction material contains both a diazo compound and a coupler in the light-sensitive coating, and the development of the exposed reproduction material is effected in ammonia vapour.
  • the semi-wet process the reproduction material contains a diazo compound in the light-sensitive coating and during development in acid or alkaline solution a coupler is brought in contact with the exposed material so that in the parts of the coating unaffected by the light an azo dyestuff is formed as a result of coupling between the diazo compound and the coupler.
  • the coupling component and the diazo compound should be used in two layers separated from each other by a fusible third layer which would prevent premature coupling.
  • the production of such a diazotype material is however very costly from the technical point of view because at least three layers have to be applied one after the other to the sup porting material and the middle one must moreover be absolutely impermeable and free of pores and therefore needs particularly careful attention.
  • one object of the present invention is to provide a diazotype reproduction material which does not have the disadvantages of prior art.
  • Another object is to provide a two-component diazotype reproduction material which is developable without the use of gaseous ammonia or a developer bath.
  • Another object is to provide a diazotype reproduction material which is developable by heat.
  • Another object is to provide a process of making a heatdevel-opable two-component diazotype reproduction material.
  • Another object is to provide a heat-developable two- 3,281,244 Patented Oct. 25, 1966 component diazotype reproduction material which has very good contrast, which has good keeping qualities, and which is easy to produce.
  • Another object is to provide a diazotype reproduction material which, in addition to being heat-developable, is applicable in thermographic processes and, after generation of an image by imagewise heating, can be fixed by exposure to light.
  • the drawing shows a cross-sectional view of a base and a light-sensitive layer on said base.
  • the present invention relates to a heat-developable diazotype reproduction material containing a conp-ler in the light-sensitive coating in addition to a diazo compound, which material has advantages over the known reproduction materials of this type. It is characterized by the fact that the coupling component is a substance which has acid action resulting from a phenolic or enolic hydroxy group and which forms an intimate mixture with an equivalent quantity of alkali hydroxide and/or alkaline earth hydroxide, the mixture being in the form of tiny particles which are enveloped in a water-insoluble organic substance that melts at between 50 and 200 C.
  • the finely pulverized mixture of the coupling component with an equivalent quantity of alkali hydroxide or alkaline earth hydroxide may, for example, be introduced into the melt of a suitable Wax or resin and the melt allowed to solidify with the particles of mixed coupler and alkali or alkaline earth hydroxide suspended therein.
  • the solidified substance is then finely pulverized and the powder washed with a solvent, preferably water, to remove any outwardly adhering coupler and alkali or alkaline earth hydroxide not enveloped.
  • the washed powder may then be applied from an aqueous suspension together with one or more suitable water-s-olu-ble diazo compounds and the additives commonly used in diazotype processes to a suitable base, support, or supporting material, such as paper, viscose foil, cellulose, acetate foil, etc., in a single process to produce a coated material as in the figure which material comprises a base 10 and a layer 11 on said base.
  • a suitable base, support, or supporting material such as paper, viscose foil, cellulose, acetate foil, etc.
  • Another process for the preparation of a heat-developed diazotype reproduction material comprises a finely pulverized intimately mingled mixture of a substance with acid action resulting from a phenolic or enolic hydroxy group with an equivalent quantity of alkali metal hydroxide and/or alkaline earth metal hydroxide being dispersed in a solution of a waterinsoluble organic substance that melts at between 50 and 200 C., the dispersion being atomized and dried, the resultant fine powder being washed with a solvent, preferably water, and suspended in an aqueous solution of the diazo compound and the suspension being coated upon the supporting material.
  • a solvent preferably water
  • the atomizing and drying of the dispersion may, for example, be carried out in a wide vertical shaft into which the dispersion i introduced from above via a jet while a current of hot air or other hot gas is introduced from below to meet the falling atomized droplets.
  • the hot current of gas rapidly evaporates the solvent from the droplets so that the dispersed material falls to the bottom in solid particles in the form of a fine dust.
  • the dispersion is made to drip in a closed container upon an atomizing plate which is rotating very rapidly, e.g., 5000 to 20,000 revolutions per minute, which causes the liquid to become atomized.
  • the atomized particles are dried by a current of hot gas that is passed through the container and the material is then obtained in the form of a fine powder.
  • the said processes can be modified in a multitude of ways. For
  • the spray-drying may be carried out in a medium of very high air or gas pressure.
  • the hot gas is, for example, often passed to the drying dispersion not in a counter-current, but in a current travelling in the same direction.
  • the coupling component in the form of tiny particles enveloped in the coating of wax or resin or similar material is preferably used in a maximum grain size of 30 microns. If coarser powder is used it becomes difficult to obtain evenly coated diazotype reproduction material accordant with the invention. Separation of the fraction with the desired particle size is carried out in known manner, e.g. by screening or air-sifting.
  • the coupling reaction between the coupling component and the diazo compound does not take place until the water-insoluble skin which envelops each particle of the mixture of coupler and alkali hydroxide or alkaline earth hydroxide is melted by the action of heat.
  • water-insoluble organic substance are suitable, provided they have melting range within the region of 50 to 200 C., are colorless or only weakly colored, are fluid in their molten states, and are sufficiently hard and brittle at room temperature to enable them to be finely pulverized and do not react with the diazo compounds used.
  • wax or resin-type substances fulfilling these condiitons may be used.
  • natural resin such as colophony, root resins, and shellac
  • conversion products of natural resins
  • any organic compound with phenolic or enolic hydroxyl groups can be used which in the presence of the alkali hydroxide or alkaline earth hydroxide provided in accordance with the invention is able to couple, at least when heated, with the diazo compound to form a dyestuif.
  • the following example are given:
  • acetoacetic anilide 2,3-dihydroxynaphthalene-6-sulphonic acid, 2-naphthol-3-carboxylic acid, Z-naphthol-S-carboxylic acid methyl ester, 2,4-dihydroxy benzamide, 1-methy13-hydroxy-benzene-4-glutaric acid, phenol-3-urea, 2,4,2,4-tetra-hydroxydiphenyl, l-phenyl-3-methyl-pyrazolone- 5 and resorcinol.
  • diazo compound all diazo compounds used elsewhere in diazotype processes are suitable provided they are sufliciently stable in the temperature region of the heat development and in the presence of the quantity of alkali hydroxide or alkaline earth hydroxide to be used as provided by the invention and couple at least in the heat to form a dyestulf with a coupler of the type to be used as provided by the invention.
  • diazo compounds are: I
  • the additives usually included in diazotype materials such as tartaric acid or citric acid, zinc chloride and thiourea may also be present.
  • a wetting agent such as saponine
  • a binder such as carboxyl methyl cellulose, soluble starch, casein, gelatine or synthetic resin dispersions to be used to ensure that the particles adhere firmly to the supporting material.
  • Base papers such as are commonly used in diazo printing may be used as supports, but also transparent foils made of various materials, e.g., processed cellulose products such as cellulose hydrate or cellulose esters or of synthetics such as polyamides, polyesters, polycarbonates and polyvinyl compounds are suitable. The preference is, however, for paper and similar cellulose products.
  • the reproduction material provided by the inventi-on is exposed under a master in known manner and then brought into contact with a hot body, e.g., a hot roller or plate.
  • a heat image can also be produced by the contact process with the reproduction material provided by the invention if a master with an image on one side only is placed between an infrared source and the reproduction material provided by the invention in such a way that the image-side of the master and the non-sensitized side of the light-sensitive reproduction material are in contact. Under the influence of the infra-red rays the image parts of the master generate more heat than the image-free parts.
  • this heat will be sufiicient to melt the water-insoluble skin enveloping the particles of mixed coupler and alkali hydroxide or alkaline earth hydroxide in the reproduction material in the parts adjacent to the image parts, so that a coupling image is produced in the reproduction material.
  • the images are fixed by exposure to light, the unused diazo compound left in the image-free parts being thereby decomposed.
  • a third method whereby copies can be produced is the reflex process.
  • the reproduction material accordant with the invention is placed between the infra-red source and the master in such a Way that the image side of the master and the non-sensitized side of the light-sensitive material are in contact.
  • the master may in this case have images on both sides.
  • the infra-red rays are then reflected in the image parts and cause heating and consequent formation of a heat-coupling image.
  • the unused diazo compound in the image-free parts of the reproduction coating is decomposed by subsequent exposure to light.
  • Reproduction coatings accordant with the invention have the advantage that they are simple to produce. They can be developed by a mere heating process, i.e., without any adjuvant such as alkali or steam, give prints with very good contrast and have good keeping qualities.
  • Example 14.8 parts by weight of resorcinol and 15.6 parts by weight of potassium hydroxide were Well dried and then finely ground. They were then suspended, with stirring, in 50 parts by weight of melted carnauba wax (melting temperature: 83 to 91 C.) at 140 to 150 C. After complete homogenization the material was cooled rapidly to avoid disintegration and the solidified melt was broken up and ground in a ball mill. Any coupling substance not enveloped which may be adhering to the particles was removed by repeated washing with water. The fraction with the most favourable particle size of not more than 30 microns was separated by drying and subsequent screening or air-sifting.
  • aqueous suspension was then applied to a supporting material of, e.g., paper:
  • a heat-developable two-component diazotype repro duction material which comprises a support and a lightsensitive diazo layer coated on said support, said layer comprising a light-sensitive diazonium compound, an enolic coupling component, an hydroxide selected from the group consisting of alkali hydroxides and alkaline earth hydroxides, and an envelope substance, said coupling component and said hydroxide being enveloped together in the unreacted state in about equivalent amounts without any liquid in said substance and intimately, uniformly dispersed with said diazonium compound throughout said layer in the form of particles having a maximum size of thirty microns, said substance melting between 50 C.
  • said coupling component is selected from the group consisting of: 2,3-dihydroxy-naphthalene; acetoacetic anilide; 2,3- dihydroxy-naphthalene-6-sulfonic acid; 2-naphthol-3-carboxylic acid; 2-naphthol-3-carboxylic acid methyl ester; 2,4-dihydroxy-benzamide; 1-methyl-3-hydroxy-benzene-4- glutaric acid; phenol-3-urea; 2,4,2,4-tetra-hyd.roxy-diphenyl', 1-phenyl-3-methyl-pyrazolone-(5); and resorcinol.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US253646A 1962-01-27 1963-01-24 Heat-developable two-component diazotype reproduction material Expired - Lifetime US3281244A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEK45776A DE1192516B (de) 1962-01-27 1962-01-27 Durch Waerme entwickelbares Zweikomponenten-Diazotypiematerial

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DE (1) DE1192516B (enrdf_load_stackoverflow)
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3360371A (en) * 1962-12-29 1967-12-26 Keuffel & Esser Co Heat-developable two-component diazotype reproduction material
US3539345A (en) * 1967-02-01 1970-11-10 Gaf Corp Thermal diazotype papers
US3620740A (en) * 1968-01-09 1971-11-16 Agfa Gevaert Nv Thermodiazo-type copying
US3779758A (en) * 1969-03-25 1973-12-18 Photocircuits Corp Photosensitive process for producing printed circuits employing electroless deposition
US4529681A (en) * 1982-11-17 1985-07-16 Fuji Photo Film Co., Ltd. Light- and heat-sensitive recording material
US4650740A (en) * 1983-09-13 1987-03-17 Fuji Photo Film Co., Ltd. Heat-sensitive recording material
US5236800A (en) * 1988-04-12 1993-08-17 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive copying material comprising microcapsules having substantially no solvent

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1070625A (en) * 1963-04-27 1967-06-01 Konishiroku Photo Ind Alkali-generating compositions used in developing diazotype materials

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2846309A (en) * 1952-07-17 1958-08-05 Polaroid Corp Photographic products
DE1041980B (de) * 1955-11-05 1958-10-30 Pelikan Werke Wagner Guenther Aufzeichnungs- und Vervielfaeltigungs-verfahren und UEbertragungsblatt hierfuer
GB815005A (en) * 1957-07-03 1959-06-17 Ilford Ltd Improvements in or relating to radiation-sensitive diazotype materials
US2939009A (en) * 1956-02-01 1960-05-31 Jack M Tien Thermotransfer duplicating process
US3016308A (en) * 1957-08-06 1962-01-09 Moore Business Forms Inc Recording paper coated with microscopic capsules of coloring material, capsules and method of making
US3111407A (en) * 1960-02-26 1963-11-19 Ibm Methods for making record materials
US3113865A (en) * 1960-05-05 1963-12-10 Eastman Kodak Co Heat developable diazo sulfones
US3202510A (en) * 1961-07-11 1965-08-24 Frederick Post Co Production of encapsulated light-sensitive diazotype compositions and coatings

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2846309A (en) * 1952-07-17 1958-08-05 Polaroid Corp Photographic products
DE1041980B (de) * 1955-11-05 1958-10-30 Pelikan Werke Wagner Guenther Aufzeichnungs- und Vervielfaeltigungs-verfahren und UEbertragungsblatt hierfuer
US2939009A (en) * 1956-02-01 1960-05-31 Jack M Tien Thermotransfer duplicating process
GB815005A (en) * 1957-07-03 1959-06-17 Ilford Ltd Improvements in or relating to radiation-sensitive diazotype materials
US3016308A (en) * 1957-08-06 1962-01-09 Moore Business Forms Inc Recording paper coated with microscopic capsules of coloring material, capsules and method of making
US3111407A (en) * 1960-02-26 1963-11-19 Ibm Methods for making record materials
US3113865A (en) * 1960-05-05 1963-12-10 Eastman Kodak Co Heat developable diazo sulfones
US3202510A (en) * 1961-07-11 1965-08-24 Frederick Post Co Production of encapsulated light-sensitive diazotype compositions and coatings

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3360371A (en) * 1962-12-29 1967-12-26 Keuffel & Esser Co Heat-developable two-component diazotype reproduction material
US3539345A (en) * 1967-02-01 1970-11-10 Gaf Corp Thermal diazotype papers
US3620740A (en) * 1968-01-09 1971-11-16 Agfa Gevaert Nv Thermodiazo-type copying
US3779758A (en) * 1969-03-25 1973-12-18 Photocircuits Corp Photosensitive process for producing printed circuits employing electroless deposition
US4529681A (en) * 1982-11-17 1985-07-16 Fuji Photo Film Co., Ltd. Light- and heat-sensitive recording material
US4650740A (en) * 1983-09-13 1987-03-17 Fuji Photo Film Co., Ltd. Heat-sensitive recording material
US5236800A (en) * 1988-04-12 1993-08-17 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive copying material comprising microcapsules having substantially no solvent

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DE1192516B (de) 1965-05-06
NL287857A (enrdf_load_stackoverflow)

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Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808

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