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
  • G03C1/54—Diazonium salts or diazo anhydrides

Definitions

• a high-speed diazo-type reproduction material suitable for both one-component and two-component diazo-type reproduction processes comprising a diazonium salt of the formula wherein R and R are selected from alkyl, aralkyl, and the atoms necessary to form a heterocyclic ring with the amino nitrogen atom; R is selected from hydrogen, alkoxy, and halogen; n is an integer of up to 4; and Y is an anion.
• Such diazonium salts are especially suited in two-component diazo reproduction processes utilizing ammonia development.
• the present invention is directed to a high speed diazo type reproduction material useful in both one-component and two-component diazo reproduction processes; more particularly, the present invention is directed to such highspeed diazo type reproduction material having cyano alkoxy substitution'meta to the diazo moiety, such high speed diazo type reproduction material being specially suited for twocomponent reproduction processes using ammonia development.
• a carrier or support such as a sheet of paper, plastic, or the like, is provided with a light-sensitive layer or coating which includes a stabilized light-sensitive diazo compound.
• the diazo compound will react with a occidentalo dye coupler to form an intensely colored azoic dye.
• the coupler is either included in the light-sensitive layer or the light-sensitive layer is treated with the coupler during a subsequent step in the process.
• the image is developed by rendering the light-sensitive layer or coating alkaline. It is in this step that the three principal processes differ.
• the formation of the azoic dye is accomplished by contacting the light-sensitive layer with moist ammonia gas.
• the coating composition contains both the diazo as the lightsensitive member and the coupler which is an essentially colorless compound capable of reacting under appropriate conditions with the diazo compound to form the highly colored azoic dye.
• An atmosphere of warm, moist ammonia causes the diazo component and coupler to react.
• the function of the ammonia is to raise the pH level of the sensitive layer.
• the diazo and coupler components must be kept under conditions so as to prevent precoupling.
• Precoupling is prevented by adding certain acids to the light-sensitive layer.
• These acids can include organic acids such as citric, tartaric, etc., or inorganic acids such as sulfuric acid, perchloric acid, etc.
• Other additives that are included in the light-sensitive layer to prevent precoupling include acidic salts such as zinc chloride, magnesium chloride, cadmium chloride, etc.
• the combination of acids and metallic salts tends to create in the paper a reasonably high acidity level. This: acidity must be neutralized by the warm, moist ammonia gas during the development stage so as to allow a basic condition to exist. As was pointed out above, such a basic condition is required if the diazo and coupling components are to combine.
• Modern ammonia developing equipment for diazo systems operates at very high rates of speed, as high as feet per minute. Under these conditions the length of time of contact of the light-sensitive coating or layer with the ammonia vapors is of extremely short duration. For this reason it is essential to increase the rate of neutralization of the acidic stabilizing materials during the development cycle.
• materials such as glycerine, ethylene glycol and other hygroscopic materials have been employed. These compounds accelerate the rate of neutralization *by drawing moisture into the coating during the development cycle. Inasmuch as ammonia has a high afiinity for moisture, it also is drawn into the coating.
• the humectants or hygroscopic materials also serve as a reaction medium in which development can occur.
• the second principal diazotype reproduction process is one in which the diazo-bearing support is immersed in an alkaline or acidic solution of a coupling component.
• the coupling component is selected so that coupling can occur under either acidic or alkaline conditions.
• liquid development system it is important that the development take place across the entire coated surface of the paper or other support.
• the third principal diazotype system is referred to as a heat developable system.
• This system differs from the first system described above in that the development of the azoic dye is effected by applying heat to the lightsensitive layer or stratum.
• the light-sensitive layer or stratum includes a material which produces an alkaline reaction when heated. The heat causes the generation of an alkaline substance which, in turn, neutralizes the acidic stabilizing materials and creates a condition whereby the diazonium compound and the coupler can unite.
• urea The material most commonly used to produce an alkaline reaction when heated is urea.
• ammonia When urea is decomposed by heat, ammonia is generated which neutralizes the acidic materials present in the light-sensitive layer and effects development.
• guanidine, alkylsubstituted ureas and alkyl-substituted guanidines have been used to efiect coupling through the formation of ammonia.
• the properties of the p-amino diazo compounds depend also on substituents attached to the phenylene ring.
• a substituent such as a methyl, methoxy, or carboxyl group in a position ortho to the diazonium group, brings about a considerable improvement in stability and at the same time a color shift toward blue.
• Light sensitivity is, however, lowered by these substituents.
• the presence of an alkoxy group in a position meta to the diazonium group makes the diazo compounds considerably more light sensitive in relation to the unsubstituted compounds, but the keeping qualities become poorer as a result.
• this group of diazo compounds is nevertheless important because of their high light sensitivity and their practical use in cases where copies have to be prepared as quickly as possible.
• a further object of the present invention is to provide novel high speed diazo type sensitizers useful in both onecomponent and two-component diazo reproduction processes, such novel high speed diazo type sensitizers eliminating substantially the inherent thermal instability of metaalkoxy substituted derivatives of diazotized para-phenylene diamine without appreciably effecting the high-speed reproduction properties thereof.
• a still further object of the present invention comprises a novel high speed diazo sensitizer particularly suited for a two-component diazo reproduction process employing ammonia development, such high speed diazo type sensitizer having cyano alkoxy substitution meta to the diazo moiety.
• the desirable balance of properties allowing the production of a high speed diazo type sensitizer having a substantially reduced degree of thermal stability and a high degree of light sensitivity and reproduction at high speeds is achieved by providing a diazonium salt of the following general formula:
• R and R are selected from alkyl, e.g. lower alkyl of 1-4 carbon atoms, aralkyl, e.g. benzyl, or the atoms necessary to form a 5 or 6 member heterocyclic ring with the nitrogen atom; R is selected from the group consisting of hydrogen, alkoxy, e.g. lower alkoxy of 1-4 carbon atoms, or halogen, e.g. chloro, bromo, or fluoro; n is an integer not greater than 4; and Y is an anion.
• the salt forming anions which are conveniently employed as the moiety Y in the above general formula can be any of those conventionally employed in derivatives of diazotized para-phenylene diamine.
• Such anions include, for example, salt forming anions such as sulphate, chloride, phosphate, nitrate, and sulfonate, e.g. para-chlorobenzene sulfonate, as well as preferred double salts of zinc chloride, cadmium chloride, tin chloride, and borofluoride.
• the diazonium salts are utilized as double salts such as chlorostannate, chlorozincate, chlorocadmiate, and brofiuoride. All such anionic species are well known in the art and conventionally employed in diazonium salts of the general nature as those of the instant invention.
• heterocyclic ring which can be formed by the moieties R and R and the amino nitrogen atom can comprise any of the conventional 5 and 6 membered nitrogen containing heterocycles conventionally employed in diazonium salts of the general type embraced by the present invention.
• suitable heterocyclic rings para to the diazonium moiety include morpholino, piperidino, thiomorpholino, piperazino, pyrrolidino, etc.
• diazonium salts falling within the general formula above.
• Such diazium salts can be present as salts of any and all of the above mentioned anions.
• double salts e.g. chlorozincate, chloro stann'ate, chlorocadmiate, and borofiuoride, are preferred.
• Such 5-nitro-2-substituted phenoxy acetonitrile, etc. is converted to the corresponding amine compound by the chemical reduction of the nitro group.
• the amine is subsequently diazotized by convention diazotization with sodium nitrite, etc. to produce the desired cyanoalkoxysubstituted diazo compound.
• the corresponding diazonium salt is produced, for example, by the reaction of the diazo compound with hydrochloric acid and zinc chloride to produce the chlorozincate double salt.
• the diazonium salt sensitizers of the present invention are effectively employed in both one-component and two-component diazo reproduction processes, the diazonium salts of the present invention are particularly suited for two-component dry processes, wherein development is achieved by the utilization of ammonia gas.
• a coupling compound is generally intimately mixed with the diazo sensitizer and stabilized against premature coupling.
• Development is effected by a dry process wherein coupling of the diazo compound and coupling compound is caused by passage of the light exposed material through an alkaline gas, e.g. ammonia.
• an alkaline gas e.g. ammonia.
• Suitable coupling components that can be employed in conjunction with the diazonium salts in the two-component diazo reproduction process include, for example:
• Acid stabilizers which are generally employed to present the precoupling of the diazonium salt and coupling component include organic acids such as citric acid, tartaric acid, boric acid, acetic acid, etc. as well as inorganic acid such as sulfuric acid, perchloric acid, etc.
• Other additives which are generally included in the light sensitive diazo layer to prevent precoupling include acidic salts such as'zinc chloride, magnesium chloride, cadmium chloride, etc.
• additives generally employed in diazo type photo printing can also be employed in conjunction with the diazonium salt of the present invention.
• Such materials include, for example, substances serving to increase the developing speed, such as glycerol, polyethylene glycol and urea, surface improving substances such as finely divided silica (colloidal or non-colloidal), aluminum oxide, barium sulfate, white starch, etc., binders such as gelatin, gum arabic, cellulose ethers, starch derivatives, polyvinyl alcohol, dispersions of synthetic resins such as dispersions of cationic, nonionic and anionic polyvinyl acetate, substances serving to improve the background of the copies such as thiourea, etc.
• diazo compositions can be applied to any conventional support employed in diazo reproduction processes.
• the diazo material can be applied to an opaque support such as white paper or opaque linen, or a transparent support such as tracing paper, tracing linen, cellulose ester foil, polyester foil, transparentized paper; and the like.
• the diazonium salt composition can be applied directly to the surface of the support or may be present in a hydrophilic film layer which may or may not be attached to the support by means of one or more conventional sub-layers.
• the diazonium salts of the present invention are not only applicable to a two-component dry diazo reproduction process, but can also be utilized in a one-component wet process, wherein the diazo composition does not contain a coupling agent or an acid stabilizer to prevent premature coupling, but the coupler is supplied in a solution of developing agent.
• the diazo composition does not contain a coupling agent or an acid stabilizer to prevent premature coupling, but the coupler is supplied in a solution of developing agent.
• any conventional developing solution for example, various conventional developing solutions based upon phloroglucinol are conveniently employed. The following represent Weakly acid phloroglucinol developers and weakly alkaline phloroglucinol developers which are practically employed in the development of one-component diazo compositions.
• Developer A is a solution of:
• Developer B is a solution of:
• Phloroglucinol 6.5 Resorcinol 4 Thiourea Sodium salt of butylnaphthalene sulphonic acid Sorbit P (from Geigy Chem. Corp, Ardsley, N.Y.,
• the pH of this liquid is 6.5.
• Developer C is a solution of Phloroglucinol g 5 Rescorcinol g 1 Dipotassium phosphate g 3 Tergitol O8 m1 3 Maleic anhydride g 3 Potassium hydroxide solution (13.5 N) ml 75 Water ml 1000 The pH of this liquid is 6.9.
• Developer D is a solution of:
• the diazonium salts of the present invention are applicable in diazotype systems wherein the reproduction process utilizes heat development.
• the light-sensitive layer or stratum includes a diazonium compound, a coupler, and acidic stabilizing materials as in the dry two-components system described above.
• the light-sensitive layer includes a material which causes an alkaline reaction when heated, the heat causing the generation of an alkaline substance which in turn neutralizes the acidic stabilizing materials and creates a condition whereby the diazonium compound and the coupler can unite.
• the preferred compounds which produce such an alkaline reaction when heated are those which generally yield ammonia upon decomposition or dissociation.
• Such compounds include, for example, the ureas, i.e. urea and its derivatives, in particular, guanadine, alkyl-substituted urea, and alkyl-substituted guanadines.
• a diazo composition was prepared by admixing the following components:
• the above solution was coated on a suitable paper base, dried, and exposed to light through a translucent original. A clear print was obtained after treatment with ammonia vapor. A bright blue image against a clean background was formed, which image showed resistance to diazo decomposition when printed at high machine speeds.
• the diazonium salt produced below was used in the composition of Example 1, replacing the diazonium salt present therein in an equal amount.
• the diazo 11 solution was coated on a suitable paper base, dried, and exposed to light through a translucent original. After development by treatment with ammonia vapor, a print of good dye density and background was obtained. The print showed a high degree of resistance to thermal decomposition also.
• EXAMPLE 4 A sheet of white base paper suitable for the diazo-type reproduction process was sensitized with a solution of:
• the sheet was developed with the developer A described above according to the so-called thin layer method.
• the diazonium compound showed high coupling activity, and the development of a clear, bright image Without any tendency toward thermal instability or decomposition.
• R and R are selected from the group consisting of alkyl having from 1 to 4 carbon atoms, benzyl, and when taken together with the amino nitrogen atom, the atoms necessary to form a heterocyclic selected from the group consisting of morpholino, piperidino, thiomorpholino, piperazino, and pyrrolidino;
• R is selected from the group consisting of hydrogen, lower alkoxy, and a halogen selected from the group consisting of fluorine, chlorine and bromine;
• n is an integer of from 1 to 4; and Y is an anion.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Indole Compounds (AREA)

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Cited By (1)

• 1968
  • 1968-06-18 US US737854A patent/US3597413A/en not_active Expired - Lifetime
• 1969
  • 1969-06-14 DE DE19691930344 patent/DE1930344A1/de active Pending
  • 1969-06-17 NL NL6909231A patent/NL6909231A/xx unknown
  • 1969-06-17 FR FR6920083A patent/FR2011143A1/fr not_active Withdrawn
  • 1969-06-17 GB GB30612/69A patent/GB1263379A/en not_active Expired

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