US3322556A - Method for preparing heat-developable two-component diazotype reproduction sheet - Google Patents

Method for preparing heat-developable two-component diazotype reproduction sheet Download PDF

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US3322556A
US3322556A US332288A US33228863A US3322556A US 3322556 A US3322556 A US 3322556A US 332288 A US332288 A US 332288A US 33228863 A US33228863 A US 33228863A US 3322556 A US3322556 A US 3322556A
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coupler
particles
heat
water
developable
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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 CONTINENTAL ILLINOIS NATIONAL BANK & TRUST CO., OF CHICAGO, A NATIONAL BANKING ASSOCIATION, SECURITY NATIONAL BANK, A NATIONAL BANKING ASSOCIATION FOR ITSELF AND AS AGENT FOR CITIBANK, N.A. A NATIONAL BANKING ASSOCIATION, BANK OF CALIFORNIA N.A. THE; A NATIONAL BANKING ASSOCIATION, CHASE MANHATTAN BANK, N.A. THE; A NATIONAL BANKING ASSOCIATION, CHEMICAL BANK, A BANKING INSTITUTION OF reassignment CONTINENTAL ILLINOIS NATIONAL BANK & TRUST CO., OF CHICAGO, 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

Definitions

  • the present invention relates to diazotype reproduction materials and refers more particularly to heat-developable two-component diazotype reproduction materials and to processes for preparing said materials.
  • the reproduction materials In the diazotype process, two methods of development are used: the dry process and the semi-wet process.
  • the dry process the reproduction materials contain both diazo compound and coupler, and development of the exposed material is effected by means of gaseous ammonia.
  • the semi-wet process the reproduction materials contain only diazo compound and development is effected by applying a solution of coupler to form an azo dyestuff in the unexposed parts of coating.
  • the coupler and the diazo compound have been used in layers separated from each other by a fusible third layer to prevent premature coupling.
  • a diazotype material is costly because three layers are applied to the supporting material; the middle one being free of pores and thus requiring careful attention.
  • One object of the present invention is to provide a method for the preparation of a two-component diazotype reproduction material developable, without the use -of gaseous ammonia or a developer bath, by heat.
  • Another object is to provide a method for the preparation of a heat developable two-component diazotype reproduction material which has good contrast, good keeping qualities, and ease of manufacture.
  • the water-soluble coupler is dissolved in water and then the solution is finely dispersed in a solution of water-insoluble wax or resin to produce a water-in-oil emulsion.
  • the aqueous solution may be formed by dissolving in water the base-less coupler and the equivalent quantity of the corresponding inorganic or organic base.
  • Emulsification can be effected by means of a high speed mixer (Ultra-Turrax-Mixer), or vibration mixer (Vibro Mixer). Then the water in-oil-emulsion is spray-dried. In the resulting fine powder, the water-insoluble organic substance encloses the azo coupling component in a protective film, and when necessary, the fine powder may be washed with a solvent in which the protective film is not soluble, to remove any unenclosed azo coupling component adhering to the particles. Water or dilute acid can be used. When an emulsion of a sufficiently fine division and a suitable atomizing spray nozzle are used, a powder having a particle size of about 25 microns is obtained directly. If, however, fractionation should be necessary to obtain the desired powder of a particle size of not more than 30 microns, screening or wind shifting is done.
  • a high speed mixer Ultra-Turrax-Mixer
  • vibration mixer Vibro Mixer
  • the coupling component in the form of tiny particles enveloped in the wax or resin is preferably used in a maximum grain size of 30 microns. If coarser particles are used it becomes difiicult to obtain evenly coated diazotype material in accordance with the invention.
  • the coupler or coupling component is inorganic due to its phenolate or enolate form, the necessary conditions for the coupling reaction to take place are already present. It does not occur, however, until the water-insoluble skin which envelops each individual particles of the coupler is melted by the action of heat.
  • any water-insoluble organic substance is suitable provided it has a narrow melting range Within the region of 50 to 200 C., is colorless or only weakly colored, is fluid in its molten state, is suiiiciently rigid at room temperature to afford continuing isolation, and does not react with the diazo compound used.
  • Substances fulfilling these conditions include natural resins such as colophony, root resins and shellac; conversion products of natural resins, such as hydrogenated resins, calcium and zinc resinates, resin esters and synthetic resins modified with natural resins; maleic resins; oil-free alkyd resins; light colored phenol resins of the novolac type; alkyl phenol resins and terpene phenol resins; coumarone resins; vinyl polymers such as polyvinyl acetals, polyvinyl acetates, polyvinyl chloride, polyvinylidene chloride, polyvinyl ether polyacrylic acid ester, polystyrene and interpolymers of the vinyl compounds with one another and with other polymerizable compounds; polymers of aliphatic, unsaturated, hydrocarbons; ketone resins; chlorodiphenyl resins; epoxy resins and silicone resins.
  • natural resins such as colophony, root resins and shellac
  • conversion products of natural resins
  • any alkali metal, alkaline earth metal, ammonium or amine salt of a phenolic or enolic hydroxy compound that can couple with a diazo compound to form a dyestuff under the influence of heat can be used.
  • the following can be used: 2,3-dihydroxynaphthalene; acetoacetic acid anilide; 2,3-dihydroxy- 1 naphthalene-o-sulfonic acid; 2-naphthol-3-carboxylic acid;
  • diazo compounds examples include 2,5-diethoxy-4- benzoylamino-benzene diazonium chloride; 4-phenylaminobenzene diazonium hydrogen sulfate; 4-diazo-2,S- dimethxy-4'-methyldiphenyl sulfide (HCl-salt); 4-morpholino benzene diazonium fluoborate; 4-morphilino-2,5- diethoxy benzene diazonium chloride; 4-morpholino-2,5- dimethoxy-benzene diazonium chloride; 4-dimethyl-aminobenzenediazonium chloride; 4 (4 ethoxyphenyl)2,5- diethoxy-benzene diazonium chloride; 4-ethyl-benzylamino-benzene diazonium chloride; 2-e-thoxy-4-diethylamino benzene
  • additives usually included in diazotype materials may also be present.
  • Common additives are tartaric acid, citric acid, zinc chloride and thiourea.
  • a wetting agent such as saponine to aid dispersion of coupler particles in an aqueous solution of the diazo compound.
  • a binder such as carboxymethyl cellulose, solution starch, casein, gelatine or synthetic resin dispersions to be used to ensure firm ad- 'hesion of the particles to the supporting material.
  • Base papers commonly used in diazo printing can be used as sheet-like supports, and transparent foils of cellulose hydrate, cellulose esters, polyamides polyester, polycarbonates, polyvinyl compounds and the like are suitable. The preference, however, is for paper and similar cellulose products.
  • the reproduction material of the present invention is exposed under a master to actinic radiation to decompose diazo compound in the exposed areas. It is then brought into contact with a hot body such as a hot roller or plate to melt the protective film and thus permit coupling to occur.
  • a copy can also be produced by the contact process if a master with an image on one side only is placed between an infrared source and the reproduction material 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 infrared rays, the image parts of the master generate more heat than the image-free parts.
  • this heat is sufficient to melt the water-insoluble skin enveloping the coupler particles in the parts adjacent to the image parts, and thus permits the coupling to occur in the image areas.
  • 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 is placed between the infrared 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 infrared rays are converted to heat in the image parts to form a 'heat image.
  • the heat image melts the portective film on the coupler particles and permits coupling to occur.
  • the unused diazo compound in the imagefree parts is decomposed by subsequent exposure to light.
  • Reproduction coatings in accordance with the present 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 50 grams of the sodium salt of 2-naphthol-3,6-disulfonic acid were dissolved in 175 grams of water and the solution emulsified by means of a high speed mixer (Ultra- Turrax-Mixer) in a solution of 200 grams of a maleinate resin having a melting range between 69 and 77 C., such as Hobimal P 59, in 1800 grams of trichloroethylene.
  • the emulsion was sprayed by an air stream at about 30 atmospheres at the rate of 12 ml./min. into a conic vessel heated to to C. so that the main part of the water and all of the trichloroethylene was evaporated and removed by the air.
  • the resin enclosed the particles of the moist sodium salt as a protective film. Any unenclosed coupling substance which adhered to the particles was removed by several washings with water. The resultant particles had an average particle size of 20 microns, and were used directly after drying at 40 C.
  • the above mentioned resin sold under the trade name Hobimal P 59 is a polyester resin prepared by condensing maleic acid, rosin, and a polyhydric alcohol.
  • the support coated with the suspension was dried in an air stream at 30 to 40 C.
  • a method for the preparation of a heat-developable two-component diazotype reproduction material comprising the steps of: emulsifying an aqueous solution of a coupler in a solution of water-insoluble organic substance melting between 50 and 200 C., said coupler being a salt of a base of the group consisting of alkali metals, alkaline earth metals, ammonia and amines, and are acid organic hydroxy compound of the group consisting of phenols and enols; spray-drying the emulsion at a temperature below the boiling point of water to form fine moist particles of coupler enclosed in said substance, said particles of enclosed coupler having a maximum particle size of 30 microns; washing said particles with water to remove unenclosed coupler from the surface of said particles; suspending said particles in an aqueous solution of light-sensitive diazo compound capable of coupling with said said coupler under the influence of heat; coating a sheet-like support uniformly with the suspension; and drying the coated support at 30 to 40 C. to produce
  • said coupler is selected from the group consisting of alkali metal, alkaline earth metal, ammonium and amine salts of: 2,3-dihydroxy naphthalene; acetoacetic acid anilide; 2,3-dihydroxynaphthalene-fi-sulfonic acid; 2-naphthol-3- carboxylic acid; 2-naphthol-3-carboxylic acid methyl ester; 2,4-dihydroxy benzamide; l-methyl-3-hydroxy-benzene-4- glutaric acid; phenol- 3 -urea; 2,4,2',4-tetrahydroxy diphenyl; 2-naphthol-3,6-disulfonic acid; an 1-phenyl-3- methyl-pyrazolone- (5) 3.
  • said diazo compound is a member selected from the group consisting of: 2,5-diethoxy-4-benzoylaminobenzene diazonium chloride; 4-phenylaminobenzene diazonium hydrogen sulfate; 4-diazo-2,5-dimethoxy-4-methyl diphenyl sulfide (HQ-salt); 4-morpholino-benzene diazonium References Cited UNITED STATES PATENTS 2,680,062 6/1954 Sus l1736.8 2,939,009 5/1960 Tien 1l736.1 3,016,308 1/1962 Macaulay l173 6.1 3,202,510 8/1965 Hollmann 11734 OTHER REFERENCES Kosar: Photo. Sci. & Eng, volume 5, N0. 4, July- August 1961, pages 239-243.

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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)
  • Heat Sensitive Colour Forming Recording (AREA)
US332288A 1961-12-22 1963-12-20 Method for preparing heat-developable two-component diazotype reproduction sheet Expired - Lifetime US3322556A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEK48553A DE1207793B (de) 1961-12-22 1961-12-22 Verfahren zur Herstellung eines waermeentwickelbaren Diazotypiematerials

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549406A (en) * 1968-04-26 1970-12-22 Eastman Kodak Co Process of coating polymer surfaces activated by corona discharge
US4389315A (en) * 1981-07-24 1983-06-21 Frank Crocket Filter device with permeable corrugated grid panel
US4400456A (en) * 1980-08-29 1983-08-23 Ricoh Co., Ltd. Thermo-developable type diazo copying material
US4497887A (en) * 1981-06-09 1985-02-05 Ricoh Compay, Ltd. Thermal development type diazo copying material with hydrophobic resin encapsulated coupler particle
US4758495A (en) * 1985-03-26 1988-07-19 Fuji Photo Film Co., Ltd. Diazo microcapsule recording material prepared using ion exchange treatment
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2680062A (en) * 1949-07-23 1954-06-01 Keuffel & Esser Co Process for the production of azo dyestuff images
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
US3202510A (en) * 1961-07-11 1965-08-24 Frederick Post Co Production of encapsulated light-sensitive diazotype compositions and coatings

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2680062A (en) * 1949-07-23 1954-06-01 Keuffel & Esser Co Process for the production of azo dyestuff images
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
US3202510A (en) * 1961-07-11 1965-08-24 Frederick Post Co Production of encapsulated light-sensitive diazotype compositions and coatings

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549406A (en) * 1968-04-26 1970-12-22 Eastman Kodak Co Process of coating polymer surfaces activated by corona discharge
US4400456A (en) * 1980-08-29 1983-08-23 Ricoh Co., Ltd. Thermo-developable type diazo copying material
US4497887A (en) * 1981-06-09 1985-02-05 Ricoh Compay, Ltd. Thermal development type diazo copying material with hydrophobic resin encapsulated coupler particle
US4389315A (en) * 1981-07-24 1983-06-21 Frank Crocket Filter device with permeable corrugated grid panel
US4758495A (en) * 1985-03-26 1988-07-19 Fuji Photo Film Co., Ltd. Diazo microcapsule recording material prepared using ion exchange treatment
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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DE1207793B (de) 1965-12-23
NL301888A (enrdf_load_stackoverflow)

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Owner name: SECURITY NATIONAL BANK, A NATIONAL BANKING ASSOCIA

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

Effective date: 19820323

Owner name: CHASE MANHATTAN BANK, N.A. THE; A NATIONAL BANKING

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

Effective date: 19820323

Owner name: CHEMICAL BANK, A BANKING INSTITUTION OF NY.

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

Effective date: 19820323

Owner name: CONTINENTAL ILLINOIS NATIONAL BANK & TRUST CO., OF

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Effective date: 19820323

Owner name: BANK OF CALIFORNIA N.A. THE; A NATIONAL BANKING AS

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

Effective date: 19820323

Owner name: CHEMICAL BANK, A BANKING INSTITUTION OF, NEW YORK

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

Effective date: 19820323