US3754916A - Heat developable diazo type sheets - Google Patents

Heat developable diazo type sheets Download PDF

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Publication number
US3754916A
US3754916A US00203011A US3754916DA US3754916A US 3754916 A US3754916 A US 3754916A US 00203011 A US00203011 A US 00203011A US 3754916D A US3754916D A US 3754916DA US 3754916 A US3754916 A US 3754916A
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United States
Prior art keywords
acid
diazonium salt
layers
heat
sheet
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Expired - Lifetime
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US00203011A
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English (en)
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J Winslow
B Sagawa
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3M Co
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Minnesota Mining and Manufacturing 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
    • G03C1/60—Compositions containing diazo compounds as photosensitive substances with macromolecular additives
    • 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
    • G03C1/61—Compositions containing diazo compounds as photosensitive substances with non-macromolecular additives

Definitions

  • Heat-developable diazotype sheets commonly employ diazonium salts, acidic compounds for inhibiting premature coupling or self-coupling reactions, and acid-neutralizing components for neutralizing the acidic compounds, thereby allowing coupling to occur.
  • the acid-neutralizing compounds commonly are made available for neutralization by the application of heat to the diazotype sheets; e.g., heat may cause evolution of acid-neutralizing components, as taught by U. S. Pat. No. 2,732,299; or may permit migration of acidneutralizing components into other components of diazotype sheets by heat-softening of hinder or barrier materials as taught by British Pat. No. 1,032,508.
  • diazotype sheets which exhibit good storage properties are also capable of development by exposure to reasonable temperatures for short periods of time.
  • diazotype sheets which are capable of development by exposure to reasonable temperatures for short periods of time commonly exhibit relatively poor storage properties. Poor storage properties are evidenced by pre-reaction between diazonium salts and 'azo-couplei' compounds to form dy'es prior to light exposure or by self-coupling of diazonium salt compounds, causing the development of background fog and reducing contrast between the image and background. These phenomena are frequently attributable to highly basic acid-neutralizer components which are normally required to overcome the acidstabilization of diazonium salts and to provide rapid coupling reaction rates.
  • the primary object of this invention is to provide a heat-developable diazotype sheet which exhibits excellent storage properties and is capable of development by exposure to reasonable temperatures for short periods of time.
  • Another object of this invention is to provide a heatdevelopable diazotype sheet capable of utilizing a great variety of diazonium salts.
  • the present invention relates to a heatreactive diazotype sheet having at least two layers.
  • One of the layers comprises an acid-stabilized diazonium salt capable of reacting with an azo-coupler compound to form a dye.
  • Another of the layers comprises an acidneutralizer component capable of providing basic equivalents in an amount at least sufficient to render the acid-stabilized diazonium salt reactive with the azocoupler compound.
  • At least one weakly basic benzimidazole acid-neutralizer compound contributes at least half of the basic equivalents provided by the acidneutralizer component. Minor amounts of basic ingredients other than weakly basic benzimidazoles may often be advantageously incorporated into the diazotype sheet of the present invention.
  • a weakly-basic benzimidazole compound is the sole acid-neutralizer component of the diazotype sheet.
  • the diazotype sheet of the present invention may additionally contain azo-coupler compounds although the azocoupler may be contained in a separate sheet or may be brought into contact with the diazotype sheet.
  • benzimidazole compounds and diazonium salts be kept in separate layers prior to heatdevelopment of the diazotype sheets of the present in vention because of the deleterious effect of benzimid azole compounds upon the storage properties of diazonium salts.
  • Acidic compounds may often be advantageously incorporated in layers containing diazonium salts to prevent premature coupling or self-coupling.
  • Diazonium compounds which are acid-salts or to which acid compounds have been added are herein referred to as acidstabilized.
  • Benzimidazole compounds have heretofore been utilized in heat-developable diazotype sheets to enhance dye colors, as taught by British Pat. Nos. 967,899 and 1,032,508. Such diazotype sheets, however, have always utilized such strongly basic compounds as ammonia or other organic, non-aromatic amines or salts of such amines as acid-neutralizer components. Benzimidazole compounds in general are but weakly basic in comparison to such amines and to other basic compounds commonly used in diazo processes. In fact, benzimidazole and many of its derivatives exhibit pseudoacidic characteristics, reflected by their ability to form salts with metals.
  • benzimidazole compounds are useful as acidneutralizers without significantly increasing the severity of development conditions normally required for diazotype sheets.
  • Perhaps the greatest advantage realized from the utilization of benzimidazole compounds as the predominant, and preferably the sole acid-neutralizer components of such diazotype sheets is the heretofore seldom attainable excellent storage properties now obtained with the present invention without significant sacrifice in coupling reaction rates during heatdevelopment.
  • the weakly basic nature of benzimidazole compounds is explained and exemplified in Hofmann, The Chemistry of Heterocyclic Compounds, Part 1, pp. 248-252, lnterscience Pub. N.Y., 1953.
  • the weakly basic benzimidazole compounds of the present invention are defined as benzimidazole compounds which are sufficiently basic to neutralize acids but which are less basic than imidazole.
  • Such benzimidazole compounds include the following: benzimidazole; 6-
  • nitrobenzimidazole 2-chlorobenzimidazole; 2- methylbenzimidazole; Z-ethylbenzimidazole; 2-npropylbenzimidazole; Z-n-butylbenzimidazole;
  • benzimidazole compounds used in the present invention preferably are non-coupling.
  • the preferred benzimidazole compounds are benzimidazole, 2- methylbenzimidazole, Z-phenylbenzimidazole and 5,6- dimethylbenzimidazole. Of these compounds, benzimidazole is especially preferred.
  • the weakly basic benzimidazole compounds be separated from the diazonium salts in the present invention, since benzimidazole compounds generally have an unfavorable influence on the storage properties of diazonium salt.
  • This unfavorable influence can often be obviated by including acidic compounds such as tartaric or oxalic acids within the layer containing the benzimidazole compound and the diazonium salts. Difficulty is then often experienced, however, in promoting the coupling reaction, e.g., an unusually large amount of benzimidazole compound is required.
  • Separation of the benzimidazole compounds from the diazonium salts may be effected by incorporating these compounds in different layers or by introducing a barrier layer between layers containing these compounds.
  • Diazonium salts which find utility in this invention are those which are capable of coupling with azocoupler compounds in weakly basic environments to form dyes.
  • diazonium salts which may be used in this invention, the following have given good results: p-amino-N-benzyl-N-ethylbenzenediazonium chlorostannate, p-amino-N-benzyl-N- ethylbenzenediazonium chloro-zincate, 3chloro-4- diethylaminobenzenediazonium chlorozincate, pdiethylaminobenzenediazonium fluoroborate, pdiethylamino-2-ethoxybenzenediazonium chlorozincate, 4-diethylamino-2-methylbenzenediazonium chlorozincate, p-morpholinobenzenediazonium fluorobo- 2-methylcarbonylbenrate, p-diazo-N-methyl-N-hydroxyethylaniline zinc chloride, p-d
  • Preferred diazonium salts include: p-diazomorpholino-2,5- dibutoxybenzene borofluoride,p-diazomorpholino-2,5- dibutoxybenzene zinc sulfate, 4-diazophenylmorpholine zinc chloride.
  • Light-sensitive diazonium salts are preferably used.
  • Azo-coupling compounds which find utility in this invention are those which will couple with diazonium salts in weakly basic environments to form dyes.
  • Such couplers include: 2,3-dihydroxy naphthalene, 2,3- dihydroxynaphthalene-6-sulfonic acid sodium salt, 2,7-dihydroxynaphthalene, l,7-dihydroxynaphthalene, phloretin, acetoacetanilide, aceto-ace't-o-ansidide, 3- methyl-p-sulfophenyl-S-pyrazolone, aceto-acet-2,5- dimethoxyanilide, aceto-acet-p-toluidide, aceto-acet- 2,4-xylidide, 2,6-dihydroxy toluene, 3-methyl-l-phenyl-S-pyrazolone, 2-chloroacetanilide, ethylenediaminebisacetoacetamide, N,N
  • spectral absorption characteristics For example, in a.
  • the dyes resulting from the coupling of p-diazomorpholino 2,5-dibutoxy boro fluoride with acetoacetanilide, 2,7-dihydroxy-naphthalene, and 3-hydroxy-Z-naphtho-o-toluidide are yellow, reddishpurple, and cyan, respectively, and together form substantially black images.
  • diazotype sheets which contain highly-reactive diazonium salts for the purpose of inhibiting self-coupling reactions.
  • Diazotype sheets which contain less highly-reactive diazonium salts generally require proportionately reduced amounts of acidic compounds, and many diazonium acid-salts exhibit sufficient stability without the addition of other acidic compounds.
  • a binder material normally polymeric, is preferably used to contain the reactive components in layers in the diazotype sheets of the present invention.
  • the binder materials and barrier materials are preferably thermoplastic and soften sufficiently at reasonable development temperatures to permit benzimidazole compounds to readily migrate therethrough.
  • Thermoplastic binder materials in addition should be sufficiently rigid at normal storage temperatures to hinder such migration. It is desirable that the binder materials used in the present invention be capable of forming continuous films. Examples of such polymeric binder materials include polyvinyl chloride acetate, polystyrene, polymethylmethacrylate, etc.
  • binder materials are preferably chosen to be compatible with the components incorporated therein, i.e., capable of forming a single phase system with such components, and permit the ready migration of benzimidazole compounds therethrough upon heating.
  • polymeric binder materials which are incompatible with the components contained therein, such as polymeric latices, may often be advantageously utilized.
  • Non-thermoplastic and non-continuous binder materials such as paper and cloth may also be used in this invention to yield desirable results. Binder materials which permit the migration therethrough of chemical compounds such as benzimidazole compounds, couplers, and the like are generally known to the art, and the selection therefrom is not critical to the present invention.
  • the supporting substrates for the layers of the present invention may be of any suitable material such as plastic film, glass, paper, metal, cloth, wood, etc. Plastic films, such as polyester and cellulose triacetate, are preferred.
  • the substrates desirably should have a heatdistortion temperature sufficiently high to permit reasonable development temperatures to be used without damage thereto. It is contemplated, however, that substrates having lower heat-distortion temperatures may be desirable, as, for example, when a wrinkled design pattern is desired. It is further contemplated that a separate supporting layer may be advantageously eliminated in some cases, as when at least one of the binder materials is a self-supporting film.
  • the diazotype sheets of the present invention may be prepared by a variety of methods, such as consecutively coating polymer emulsions containing reactive components upon a substrate to form layers; laminating together reactive component-containing layers, etc.
  • the reactive components and polymeric binder material for each layer are combined in a solution which is coated and dried to form a layer.
  • the solvent for each solution is preferably a nonsolvent for the binder material of the preceding layer, thereby avoiding the migration which might otherwise occur should a solvent be capable of dissolving the binder material of the preceding layer to liberate the reactive components contained therein.
  • the densities of the lightstruck background (D,,,,,,) and the non-light-struck imaged areas (D,,,,,,,) of diazotype sheets of the present invention were measured with a MacBeth Quantalog Densitometer Model OT20 using the green filter (Mac- Beth Corporation).
  • the diazotype sheet thus prepared was exposed for 16 seconds through a test negative having a density gradient ranging from D,,,,,, of 0. 10 to D of 2.16 to radiation from a 250 watt mercury-vapor lamp positioned 3.18 cm. from the recording element.
  • the exposed sheet was developed by exposure for 30 seconds to a temperature of 121 C. A bluish-purple image exhibiting a D of 1.20 was obtained.
  • the D of the lightstruck background areas was 0.06.
  • the diazotype sheet thus prepared was exposed and developed as in Example 1.
  • the resulting reddish-black image exhibited a D of 1.70.
  • the D of the lightstruck background was 0.06.
  • a sample of the unexposed was aged for 6 months at 23 C., 50 percent R.H., and was then exposed and developed as above, yielding a D, value of 0.11 and a D of 1.30.
  • EXAMPLE 3 A solution of: 25 g. polyvinyl chloride acetate copolymer (Bakelite VYHH, Union Carbide Corp.)
  • the diazotype sheet thus prepared was exposed and developed as in Example 1. A green image was obtained having a D of 1.30. The background exhibited a D of 0.14.
  • EXAMPLE 4 A solution of: 10 g. polyamide resin (Elvanol 8061, E. l. DuPont de Nemours) 2.2 g. benzimidazole 0.60 g. aceto-acet-p-toluidide 10 g. butanol 80 g. methanol was coated on the surface of polyester film. The coating weight of this layer after drying for 2 minutes at 96 C. was 6.46 g./m
  • the diazotype sheet thus prepared was exposed for 16 seconds through a suitable negative to radiation from a 140 ampere carbon are positioned 0.915 m from the element.
  • the sheet was then developed as in Example l, yielding a reddish-black image having a D of 1.65.
  • the D of the background was 0.07.
  • Example 4 Upon exposure and development as in Example 4, a cyan image was obtained which exhibited a B of 1.00. The D of the background was 0.08.
  • the diazotype sheet thus produced was exposed and developed as in Example 1, yielding a bluish-purple image having a D of 0.07.
  • the background exhibited a D of 1.30.
  • a sample of the unexposed diazotype sheet was aged for 6 months at 23 C., 50 percent R.l-l., and then was exposed and developed as above. D and D,,,,, values of 0.15 and 1.00 respectively were obtained.
  • the diazotype sheet thus obtained was exposed and developed according to Example 1, yielding a bluishblack image having a D of 1.20.
  • the 1),, of the non-imaged areas was 0.15.
  • EXAMPLE 8 A sheet of paper (80 lb. SP-l, Lee Schoeller Company) was saturated with a solution of:
  • a second paper substrate (80 lb. SP-l Lee Schoeller Company) was divided into two portions X and Y which were treated as follows:
  • Portion X was saturated with a solution of 4.0 grams of benzimidazole in 96 ml. of methanol. Upon drying for 2 minutes at 49 C., a coating weight of 1.65 grams (0.0014 g. moles) of benzimidazole per square meter was obtained.
  • Portion Y was saturated with a solution of 2.61 grams of ammonium acetate in 97.4 ml. of methanol to give a coating weight of 0.065 gram (0.00845 g. moles) of ammonium acetate per square meter upon drying for 2 minutes at 49 C.
  • Portion A was placed in facing contact with portion X (containing benzimidazole) and was heated at 121 C. for 10 minutes.
  • portion B was placed in facing contact with portion Y (containing ammonium acetate) and was heated at 121 C. for 10 minutes.
  • Portion C was exposed to a saturated atmosphere of ammonia at 60 C. for 10 minutes in a commercial diazo developing unit (Uniprinter 086, Model No. 49BG, Minnesota Mining and Manufacturing Co.).
  • Example 2 Upon exposure and heat-development as in Example 1, a light-blue image upon a clear background was obtained.
  • Example 10 Z-methylbenzimidazole
  • Example 11 2-phenylbenzimidazole
  • Example 12 5,6-dimethylbenzimidazole
  • Example 13 Z-hydroxybenzimidazole In each case, a light-blue image upon a clear background was obtained.
  • a heat reactive diazotype sheet having at least two layers, one of said layers comprising a heat-softenable component capable of providing basic equivalents in an amount at least sufficient to neutralize said acid stabilization of said diazonium salt, to provide a weakly basic environment for the diazonium salt in the sheet, and to render said acid-stabilized diazonium salt reactive with said azo-coupler compound, at least one of said layers containing an azo-coupler, and greater than percent of said basic equivalents being provided by at least one weakly-basic benzimidazole acid-neutralizer compound.
  • a heat reactive diazotype sheet having at least three layers, one of said layers comprising a heatsoftenable binder material and an acid-stabilized diazonium salt capable of reacting with an azo-coupler compound to form a dye, another of said layers comprising 5 a heat-softenable binder material and an acidneutralizer component capable of providing basic equivalents in an amount at least sufficient to neutralize said acid stabilization of said diazonium salt to render said diazonium salt reactive with said azo-coupler compound by providing a weakly basic environment for the diazonium salt in the sheet, greater than 75% of said basic equivalents being provided by benzimidazole, at least one of said heat softenable binder layers additionally including an azo-coupler compound, and between said diazonium salt containing layer and said benzimidazole-containing layer a barrier layer, permeable, upon heating, to benzimidazole.
  • a light-sensitive, storage-stable diazotype sheet capable of rapid heat development, said sheet comprising a support bearing at least two layers, one of said layers comprising a heat-softenable polymeric binder and a dye-forming composition including an azo-coupler compound and a light-sensitive acid-stabilized diazonium salt capable of reacting with said coupler compound to form a dye, and another of said layers comprising a heat-softenable polymeric binder and an acid neutralizer capable of neutralizing said acid stabilization of said acid-stabilized diazonium salt in sufficient quantity to provide a weakly basic environment for the diazonium salt in the sheet, and to render said diazonium salt reactive with said coupler compound, greater than 75 percent of the basic equivalents of said acid neutralizer being provided by benzimidazole.
  • said dye-forming composition comprises p-diazomorpholino-2,5- dibutoxy benzene borofluoride, acetoacetanilide, 2,7-dihydroxynaphthalene and 3-hydroxy-2-naphthoo-toluidine.
  • a light-sensitive, storage-stable diazotype sheet capable of rapid heat development comprising a support bearing at least two layers, one of said layers comprising a first heat-softenable polymeric binder containing a dye-forming composition including an azo coupler compound and a light-sensitive acid-stablized diazonium salt capable of reacting therewith to form a dye, and another of said layers comprising a second heatsoftenable polymeric binder which contains, as the sole acid neutralizer component of said sheet, a sufficient quantity of benzimidazole to neutralize said acid stabilization of said diazonium salt and to render said diazonium salt reactive with said azo coupler compound, by providing a weakly basic environment for the diazonium salt in the sheet.
  • a heat-reactive diazotype sheet having at least two layers, one of said layers comprising a heat-softenable binder material and an acid-stabilized diazonium salt capable of reacting with an azo-coupler compound to form a dye, and another of said layers comprising a heat-softenable binder material and an acid-neutralizer component capable of providing basic equivalents in an amount at least sufficient to neutralize said acid stabilization of said diazonium salt and to render said diazonium salt reactive with said azo-coupler compound by providing a weakly basic environment for the diazonium salt in the sheet, greater than of said basic equivalents being provided by benzimidazole, at least one of said layers additionally including an azo-coupler compound.
  • Thesheet of claim 7 additionally comprising, in said layer containing said diazonium salt, an acid stabilizing compound.

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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)
  • Heat Sensitive Colour Forming Recording (AREA)
US00203011A 1968-04-22 1971-11-29 Heat developable diazo type sheets Expired - Lifetime US3754916A (en)

Applications Claiming Priority (2)

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US72326368A 1968-04-22 1968-04-22
US20301171A 1971-11-29 1971-11-29

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US3754916A true US3754916A (en) 1973-08-28

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US (1) US3754916A (enrdf_load_stackoverflow)
AT (1) AT300553B (enrdf_load_stackoverflow)
CH (1) CH529367A (enrdf_load_stackoverflow)
DE (1) DE1920196C3 (enrdf_load_stackoverflow)
FR (1) FR2006670A1 (enrdf_load_stackoverflow)
GB (1) GB1271713A (enrdf_load_stackoverflow)
NL (1) NL6905657A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3910794A (en) * 1972-04-20 1975-10-07 Cellophane Sa Imidazole couplers for two component diazotype systems
US4168171A (en) * 1977-08-05 1979-09-18 Minnesota Mining And Manufacturing Company Light-sensitive thermal developable diazotype sheets with imidazoles
US4230789A (en) * 1978-03-13 1980-10-28 Minnesota Mining And Manufacturing Company Thermal diazotype sheets
US4370397A (en) * 1979-04-24 1983-01-25 Rhone-Poulenc Systemes Presensitized plastic card, tamperproof identification card prepared therefrom, and process for manufacture of tamperproof identification card
US4575479A (en) * 1982-06-30 1986-03-11 Ricoh Company, Ltd. Diazo-type thermosensitive recording material with imidazole compound
US4584256A (en) * 1980-12-02 1986-04-22 Rhone-Poulenc Systemes Diazotype materials which can be developed by heat and contain an activator precursor having 2-carboxy carboxamide group releasing a strong base during heating
US4705736A (en) * 1985-12-05 1987-11-10 Minnesota Mining And Manufacturing Company Thermal diazo composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59185691A (ja) * 1983-04-06 1984-10-22 Ricoh Co Ltd ジアゾ系感熱記録材料

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3910794A (en) * 1972-04-20 1975-10-07 Cellophane Sa Imidazole couplers for two component diazotype systems
US4168171A (en) * 1977-08-05 1979-09-18 Minnesota Mining And Manufacturing Company Light-sensitive thermal developable diazotype sheets with imidazoles
US4230789A (en) * 1978-03-13 1980-10-28 Minnesota Mining And Manufacturing Company Thermal diazotype sheets
US4370397A (en) * 1979-04-24 1983-01-25 Rhone-Poulenc Systemes Presensitized plastic card, tamperproof identification card prepared therefrom, and process for manufacture of tamperproof identification card
US4584256A (en) * 1980-12-02 1986-04-22 Rhone-Poulenc Systemes Diazotype materials which can be developed by heat and contain an activator precursor having 2-carboxy carboxamide group releasing a strong base during heating
US4575479A (en) * 1982-06-30 1986-03-11 Ricoh Company, Ltd. Diazo-type thermosensitive recording material with imidazole compound
US4705736A (en) * 1985-12-05 1987-11-10 Minnesota Mining And Manufacturing Company Thermal diazo composition

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DE1920196C3 (de) 1979-02-15
DE1920196B2 (de) 1974-08-08
GB1271713A (en) 1972-04-26
CH529367A (de) 1972-10-15
DE1920196A1 (de) 1969-11-06
FR2006670A1 (enrdf_load_stackoverflow) 1970-01-02
NL6905657A (enrdf_load_stackoverflow) 1969-10-24
AT300553B (de) 1972-07-25

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