US3480433A - Thermally activatable diazotype compositions - Google Patents

Thermally activatable diazotype compositions Download PDF

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Publication number
US3480433A
US3480433A US624991A US3480433DA US3480433A US 3480433 A US3480433 A US 3480433A US 624991 A US624991 A US 624991A US 3480433D A US3480433D A US 3480433DA US 3480433 A US3480433 A US 3480433A
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Prior art keywords
diazotype
triazino
tetrahydro
composition
light
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Expired - Lifetime
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US624991A
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English (en)
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Grant M Haist
James R King
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C1/58—Coupling substances therefor
    • G03C1/585—Precursors

Definitions

  • This invention relates to photography and in particular to light-sensitive, thermally activatable diazotype compositions, to heat-developable photographic elements wherein such diazotype compositions constitute the light-sensitive material, and to a thermal process for producing images upon such photographic elements.
  • diazotype compositions are useful for image reproduction purposes, such utility being derived from the fact that diazo compounds (aromatic diazonium salts in particular) are lightsensitive. When exposed to light, diazo compounds are destroyed to the extent that they can no longer form a dye by reacting with a coupling component. It is currently believed that where light energy impinges upon a surface coated with a diazotype composition, the diazo compound reacts to form a compound having the corresponding hydroxylated moiety at the sight of the diazo moiety. In those areas where light energy is prevented from striking the surface, this diazo destruction reaction does not take place. During the development of an imagewise exposed photographic element in which a diazotype composition constitutes the lightsensitive component, the unexposed diazo compound reacts with the coupling component under alkaline conditions to form a dye image which is a positive reproduction of the original.
  • diazo compounds aromatic diazonium salts in particular
  • photographic elements incorporating diazotype compositions as the light-sensitive material typically require development according to one of two well-known types of processes, the miost (or semi-dry) process and the dry process.
  • the moist process involves a one-component system.
  • the light-sensitive photographic element is prepared by coating a support material with a diazo compound and other materials such as an acidic stabilizing agent. There is no coupling component present in the coating.
  • a photographic element so prepared is exposed to a light source through the original which is to be copied. Development is accomplished by treating the exposed element with an alkaline solution comprising a coupling component and a pH adjusting agent, which development produces a dye image in the unexposed areas.
  • Such developing solutions are generally corrosive and difficult to handle.
  • the above mentioned dry process avoids the corrosive nature of the alkaline medium developing solution of the semi-dry process and also provides a significant advantage by forming dry reproductions.
  • a support material is coated with a diazo compound or compounds in combination with one or more coupling comice ponents and preferably with other known additives, such as acidic stabilizing agents.
  • the photographic element is developed by exposing it to an alkaline atmosphere.
  • a typically utilized atmosphere is moist ammonia fumes.
  • the dry process sutfers from the limitation that noxious ammonia fumes must be adequately stored, transported and vented out of the developing machine.
  • heat activated alkali-releasing agents have been included in the diazotype composition.
  • Such a. composition, incorporating a heat activated alkali-releasing agent can be coated onto a support material.
  • such an alkali-releasing agent can be used independently in the developing machine. In either case, the application of heat causes the agent to decompose with the attendant formation of an alkaline material, thus triggering the coupling reaction.
  • ammonium carbonate, bicarbonate, acetate and formate generate ammonia when heated.
  • Another object of this invention is to provide, for photographic purposes, a new diazotype composition which couples upon the application of heat.
  • Still another object of the present invention is to provide, for photographic purposes, a new diazotype composition which when coated on a support is' susceptible of extended storage and is transparent, free from haze, nontacky and non-crystalline.
  • An additional object of this invention is to provide a novel photographic element which incorporates a diazotype composition in a light-sensitive layer and which photographic element is developable without either a separate alkaline atmosphere or a separate alkali-releasing agent.
  • Yet another object of the instant invention is to provide a new photographic element which incorporates a diazotype composition in the light-sensitive layer and which photographic element is developable solely upon the application of heat.
  • an additional object of the present invention is to provide a novel photographic element which incorporates a diazotype composition as the light-sensitive component, and which diazotype composition is transparent, free from haze, and resistant to deterioration upon storage.
  • Still an additional object of the present invention is to provide a new thermal process for producing photographic images.
  • diazotype compositions containing a light-sensitive diazo compound and a S-Substituted s-triazine as the coupler component.
  • S-Substituted s-triazines which can be employed in the practice of the present invention include compounds having the formula:
  • R is a monovalent radical such as a lower alkyl radical, a lower alkoxy radical or a lower cycloalkyl radical; and Z is a divalent atom such as sulfur or oxygen.
  • lower alkyl radicals have 1 to 8 carbon atoms and include substituted alkyl radicals such as hydroxyalkyl radicals, for example, methyl, ethyl, npropyl, t-butyl, n pentyl, n-hexyl, n-heptyl, n-octyl, hydroxyethyl, l-hydroxyoctyl, etc.
  • lower alkoxy radicals have 1 to 8 carbon atoms such as methoxy, ethoxy, n-propoxy, n-butoxy, n-octoxy, etc.
  • lower cycloalkyl radicals have 4 to 8 carbon atoms and include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, with cyclohexyl being particularly useful.
  • Typical S-Substituted s-triazines used as couplers in the invention include:
  • This 5-substituted-s-triazine coupling component precludes the need for either separate alkaline material or alkaline-release material in the developing process. Although the actual mechanism is not completely understood, it is believed that under the heating conditions of the developing process, the saturated triazine coupling component is rearranged or reacted into a molecular structure which is alkaline in character. Given such a shift, however, the coupling compound is not destroyed with respect to its coupling potential with the diazonium salt. Without rendering an exacting description of the kinetics of the reaction, it has been found that thermal activation of this coupling component in a diazotype composition results in a clear positive image developed on the support material without added alkaline materials.
  • the diazotype compositions of this invention comprise any of the usual diazo compounds (diazonium salts) suitable for producing images, which diazonium salts are well known in the art. They are light-sensitive and are stable at ambient temperatures and under conditions of mechanical agitation. Suitably, they are soluble in water or other common solvents. Additionally, the diazo compound should devolop into a dye having a sufliciently dark color to contrast with the background surface of the support.
  • the diazonium salts are preferably aromatic compounds having a diazo moiety attached directly to a carbon atom of the aromatic nucleus.
  • the remaining valence bond of the diazo moiety is filled by a suitable cation such as halogen, phosphate, nitrate, borate, oxalate, citrate, and the like.
  • the diazonium salts can be employed to advantage as the stabilized double salts such as metal halides and non-metallic fluorides.
  • zinc chloride, cadium chloride, stannic chloride, boron trifluoride and fiuoboric acid double salts are used.
  • Exemplary of diazonium compounds useful in diazotype compositions of the invention are the diazonium salts resulting from diazotization of the following amines:
  • an acidic stabilizing agent is included in the diazotype composition to prevent premature coupling.
  • Acidic stabilizing agents are used to control the pH of the diazonium salt-coupling component admixture. Although elevated temperatures are required to fully activate the coupling reaction, it has been found that some coupling does take place after extended storage at ambient temperatures. The acidic agent restrains such premature coupling.
  • Examples of useful organic and inorganic acidic stabilizing agents commonly employed for this purpose include citric acid, acetic acid, tartaric acid, oxalic acid, boric acid, succinic acid, crotonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, 3-nitrophthalic acid, phosphoric acid, sulfamic acid, and other sulfamic acid derivatives such as cyclohexylsulfamic acid.
  • diazotype compositions of the invention can be incorporated in the diazotype compositions of the invention, for example, background stabilizers or materials for inhibiting discoloration of the image reproductions after they are made.
  • background stabilizers include thiourea, thiocinnamine, napthalene trisulfonic acid and the like.
  • additives which can also be added are substances that are intended to reduce the tendency of the paper to curl, such as ethylene glycol, glycerol, or a polyethylene glycol; dyestutf image intensifiers such as metal salts, including, for example, zinc chloride, ammonium sulfate, nickel sulfate, and the like; coating aids such as colloidal silica and the like; a small amount of a wetting agent such as saponin, lauryl sulfonate, cetyl benzene sulfonate, the oleic acid amide of N-methyl taurine, and the like; and other known additives useful for known purposes in the present art.
  • dyestutf image intensifiers such as metal salts, including, for example, zinc chloride, ammonium sulfate, nickel sulfate, and the like
  • coating aids such as colloidal silica and the like
  • a wetting agent such as saponin, lauryl s
  • the components of the present diazotype compositions can be admixed with a carrier or binder material prior to coatlng on a support material.
  • the carrier is capable of forming a film on the support after drying.
  • EX- amples of such carriers include cellulose acetate, ethyl cellulose trimellitate, cellulose acetate phthalate, ethyl cellulose hexahydrophthalate, cellulose ether phthalate, cellulose acetate butyrate, cellulose butyrate, cellulose bu tyrate hexahydrophthalate, ethyl cellulose, cellulose propionate and the like.
  • the carrier is generally dissolved in .5 a volatile solvent for ease of handling, such as methanol, acetone, dichloromethane and other well-known organic solvents.
  • a base or support material can be widely. varied; it is usually made on the basis of the requirements to be served.
  • paper and plastics or resins in the form of films have found wide acceptance especially where the reproduction itself is to be used as a master.
  • Particularly useful for work where the reproduction is to be used as a master are transparent polymeric films, such as polyethylene terephthalate, cellulose, cellulose triacetate, cellulose acetate butyrate, cellulose propionate, polycarbonates, polystyrenes, polysulfones, polyphenylene oxides, etc.
  • Wood, metals, such as steel, copper, zinc, and aluminum, and ceramics, glass, and textiles are also useful as supports for the diazotype compositions of the invention.
  • the components of the diazotype compositions namely, the diazonium salt, the coupling component described, and other additives, are combined with the carrier as by mixing the components.
  • the admixture may be coated onto the base in conventional manner as, for example, doctor blade, air knife, roller, or hand painting, followed by drying. It is noted that the dried coating typically forms a transparent, continuous film free of crystallization.
  • Coating proportions of the diazotype composition can be varied in accordance with usual practice. Useful results have been obtained in the range of between about .013.0 grams of dry diazotype composition per square foot of coated base surface.
  • the coated support is imagewise exposed through an original pattern to a light source which pattern is disposed between the light and the sensitized base.
  • the light energy is in the wavelength range of about 3,500- 4,500 A.
  • the base is heated within the temperature range sufiicient to cause a dye image to appear in the unexposed areas, giving a positive reproduction of the original pattern.
  • Processing temperatures can be widely varied and are largely dependent on the materials used. However, usual operation is within the range of about ZOO-400 F.
  • the upper temperature limit is essentially fixed by the deformation and decomposition temperature of the support material and the coating composition present thereon. Special care should be exercised when the support material is a plastic film such as cellulose acetate.
  • the lower temperature is fixed by practical development time available, since lower temperatures reduce the activity of the coupling component.
  • EXAMPLE 1 A solution of 10 parts of cellulose acetate, 12 parts of methyl alcohol, and 56 parts of acetone is prepared. Into 25 ml. of this solution are admixed 0.5 gram of p-diazodiethylaniline zinc chloride, 0.5 gram of cyclohexylsulfamic acid, and 0.5 gram of -n-propyl-tetrahydro-s-triazino-2 (1H) thione. The admixture is coated onto a poly (ethyleneterephthalate) film base-to a wet thickness of about .003 inch, or about 1.5 grams dry weight per square foot and dried at about 20 C.
  • the dry coating is transparent, clear (free from haze), hard (free from tack), and no crystallization is observed thereon.
  • the dried coated film is image-wise exposed through a master to a light source rich in ultraviolet energy, and passed through a belt processor over a heated drum with a 10-second cycle. The drum temperature is kept at 330 F. A brown dye image of good quality is formed in the unexposed areas, giving a positive reproduction of the master.
  • EXAMPLE 3 In a modification of Example 1, a paper sheet is used in place of the polyester film. A dye image of good quality is obtained in the paper, which dye image corresponds to the unexposed image area-s.
  • EXAMPLE 4 An image is made as in Example 1 except that the triazinyl compound used is 5-n-butyl-tetrahydro-s-triazino-Z- (1H) thione. This image-bearing film is in turn used as a master on a new second sample prepared as in Example 1. The resulting second generation dye image has characteristics essentially the same as the dye image of Example 1.
  • a thermally activatable light-sensitive diazo-type composition comprising:
  • R is a monovalent radical selected from the group consisting of a lower alkyl radical, a lower alkoxy radical, and a lower cycloalkyl radical, and Z is selected from the group consisting of a sulfur atom and an oxygen atom;
  • a thermally activatable diazotype light-sensitive composition comprising:
  • R is an alkyl radical having 1 to 8 carbon atoms; and, (3) an acidic compound employed to prevent the composition from precoupling.
  • R is an alkyl radical having 1 to 8 carbon atoms; and, (3) an acidic compound employed to prevent the composition from precoupling.
  • composition as described in claim 2 wherein the R substituent is an n-butyl radical.
  • a thermally activatable diazotype light-sensitive composition comprising:
  • R is a hydroxyalkyl radical having 1 to 8 carbon atoms
  • a thermally activatable diazotype light-sensitive composition comprising:
  • R is an alkoxy radical having 1 to 8 carbon atoms
  • a thermally activatable diazotype light-sensitive composition comprising:
  • R is a cycloalkyl radical having 4 to 8 carbon atoms
  • a thermally activatable diazotype light-sensitive composition comprising:
  • R is an alkyl radical having 1 to 8 carbon atoms
  • a thermally activatable diazotype light-sensitive composition comprising:
  • R is a hydroxyalkyl radical having 1 to 8 carbon atoms
  • a thermally activatable diazotype light-sensitive composition comprising:
  • R is an alkoxy radical having 1 to 8 carbon atoms
  • a thermally activatable diazotype light-sensitive composition comprising:
  • a photographic element comprising a support having a layer coated thereon said layer comprising a thermally activatable light-sensitive diazotype composition as described in claim 1.
  • a photographic process for treating an imagewise exposed photographic element comprising a support having a layer coated thereon said layer being a thermally activatable light-sensitive diazotype composition compris- (1) a light-sensitive diazonium salt;
  • R is a monovalent radical selected from the group consisting of a lower alkyl radical, a lower alkoxy radical, and a lower cycloalkyl radical, and
  • Z is selected from the group consisting af a sulfur atom and an oxygen atom;

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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)
US624991A 1967-03-22 1967-03-22 Thermally activatable diazotype compositions Expired - Lifetime US3480433A (en)

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US62499167A 1967-03-22 1967-03-22

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US (1) US3480433A (enrdf_load_stackoverflow)
BE (1) BE712580A (enrdf_load_stackoverflow)
DE (1) DE1622930A1 (enrdf_load_stackoverflow)
FR (1) FR1558148A (enrdf_load_stackoverflow)
GB (1) GB1182861A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607275A (en) * 1967-11-29 1971-09-21 Keuffel & Esser Co Diazo-type material
US5834299A (en) * 1994-12-21 1998-11-10 Novo Nordisk A/S Method for dehairing of hides or skins by means of enzymes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4776879A (en) * 1987-05-07 1988-10-11 Triazone Corporation Water insoluble triazone fertilizer and methods of making and use

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2016521A (en) * 1935-10-08 Condensation product of the cya
US2536398A (en) * 1947-10-10 1951-01-02 Gen Aniline & Film Corp Pyrazolone diazotype couplers
DE864951C (de) * 1944-06-26 1953-01-29 Kalle & Co Ag Azokomponenten fuer die Diazotypie
US2688543A (en) * 1950-12-20 1954-09-07 Gen Aniline & Film Corp Poly-acetoacetyl derivatives of polyamines as azo components in diazotype photoprinting material
US2826500A (en) * 1954-12-30 1958-03-11 Hercules Powder Co Ltd Use of cationic-modified urea-formaldehyde resins in the manufacture of wet strengthpaper
US3039872A (en) * 1958-07-16 1962-06-19 Lichtdrukpapierfabriek De Atla Material for diazotype processes
US3140180A (en) * 1959-04-29 1964-07-07 Keuffel & Esser Co Heat developable diazotype reproduction coatings comprising thermolabile carboxylic tertiary alkyl esters
GB983665A (en) * 1961-06-29 1965-02-17 Jean Jacques Dorel Improvements relating to diazotype papers
US3199982A (en) * 1963-03-19 1965-08-10 Keuffel & Esser Co Diazotype reproduction material
GB1115496A (en) * 1965-07-01 1968-05-29 Oce Van Der Grinten Nv Heat-developable diazotype material

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2016521A (en) * 1935-10-08 Condensation product of the cya
DE864951C (de) * 1944-06-26 1953-01-29 Kalle & Co Ag Azokomponenten fuer die Diazotypie
US2536398A (en) * 1947-10-10 1951-01-02 Gen Aniline & Film Corp Pyrazolone diazotype couplers
US2688543A (en) * 1950-12-20 1954-09-07 Gen Aniline & Film Corp Poly-acetoacetyl derivatives of polyamines as azo components in diazotype photoprinting material
US2826500A (en) * 1954-12-30 1958-03-11 Hercules Powder Co Ltd Use of cationic-modified urea-formaldehyde resins in the manufacture of wet strengthpaper
US3039872A (en) * 1958-07-16 1962-06-19 Lichtdrukpapierfabriek De Atla Material for diazotype processes
US3140180A (en) * 1959-04-29 1964-07-07 Keuffel & Esser Co Heat developable diazotype reproduction coatings comprising thermolabile carboxylic tertiary alkyl esters
GB983665A (en) * 1961-06-29 1965-02-17 Jean Jacques Dorel Improvements relating to diazotype papers
US3199982A (en) * 1963-03-19 1965-08-10 Keuffel & Esser Co Diazotype reproduction material
GB1115496A (en) * 1965-07-01 1968-05-29 Oce Van Der Grinten Nv Heat-developable diazotype material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3607275A (en) * 1967-11-29 1971-09-21 Keuffel & Esser Co Diazo-type material
US5834299A (en) * 1994-12-21 1998-11-10 Novo Nordisk A/S Method for dehairing of hides or skins by means of enzymes

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Publication number Publication date
GB1182861A (en) 1970-03-04
DE1622930A1 (de) 1970-12-23
FR1558148A (enrdf_load_stackoverflow) 1969-02-21
BE712580A (enrdf_load_stackoverflow) 1968-07-31

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