US3620741A - Diazo-type copying - Google Patents

Diazo-type copying Download PDF

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Publication number
US3620741A
US3620741A US790150A US3620741DA US3620741A US 3620741 A US3620741 A US 3620741A US 790150 A US790150 A US 790150A US 3620741D A US3620741D A US 3620741DA US 3620741 A US3620741 A US 3620741A
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United States
Prior art keywords
methylene
compound
indoline
heat
transfer material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US790150A
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English (en)
Inventor
Albert Lucien Poot
Rene Alois Van Brandt
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Agfa Gevaert NV
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Agfa Gevaert NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/58—[b]- or [c]-condensed
    • C07D209/60—Naphtho [b] pyrroles; Hydrogenated naphtho [b] pyrroles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D293/00—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms
    • C07D293/10—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D293/12—Selenazoles; Hydrogenated selenazoles

Definitions

  • the heat can be applied to the transfer material directly in the form of an image or the diazonium carrying receiving material can be preliminarily exposed to light imagewise to decompose the diazonium compound in the exposed areas with heat being uniformly applied to the transfer material to transfer the coupling compound for reaction with residual undecomposed diazonium compound.
  • Heat in the temperature range of 80-140 C. can be used with these specific coupling compounds and the coupling can take place under acid as well as alkaline conditions.
  • the present invention relates to compounds, materials and processes for recording and reproducing information. More particularly the present invention is concerned with diazotype copying.
  • a number of diazo-type processes is known from which one of the more recently developed is described and claimed in the U.S. Pat. Spec. No. 2,789,904 of Charles H. Benbrook and Clifford E. l-lerreck issued Apr. 23, 1957. in such a process a diazonium compound in a sheet material is exposed and afterwards contacted with a sheet material impregnated with a coupler capable of thermal transfer.
  • the coupler may be selected from the group consisting of phenols, naphthols and compounds containing a reactive methylene group but being free of primary amino groups.
  • the thermal transfer takes place at temperatures between 140 and 225 C. At these temperatures, the layers containing the light-sensitive diazocompounds can be developed within a fraction of a minute in the absence of ammonia, dilute alkali or volatile amines.
  • the said class of compounds is represented by the following general formula:
  • Z represents the necessary atoms to close an aromatic ring or aromatic ring system including a substituted aromatic ring or aromatic ring system, e.g. a benzene nucleus, a naphthalene nucleus or a substituted benzene nucleus, e.g. a benzene nucleus substituted with a C -C alkyl group, a phenyl group, an acetyl group, a nitro group, a cyano group, a hydroxyl group or an acetoxy group, and
  • a substituted aromatic ring or aromatic ring system e.g. a benzene nucleus, a naphthalene nucleus or a substituted benzene nucleus, e.g. a benzene nucleus substituted with a C -C alkyl group, a phenyl group, an acetyl group, a nitro group, a cyano group,
  • R represents an aliphatic group including a saturated, un-
  • cycloaliphatic and substituted aliphatic group such as an alkyl group, e.g. a C C alkyl group, a cyclohexyl group, a cyclopentyl group, an allyl group, a substituted alkyl, e.g. an alkyl group substituted with a phenyl group or a hydroxy group, or an aromatic group, e.g. a phenyl group.
  • Light-sensitive diazonium compounds suited for the coupling with the above active methylene compounds may be of the low as well as of the high-reactivity type, so diazonium compounds used in a common wet as well as those used in a common dry diazo-type process are considered.
  • the diazocompound one of the commonly used stabilized diazonium salts, preferably the zinc chloride double salt.
  • Other stabilized derivatives may be used too, e.g. the fluoborates and oxalates.
  • Exemplary diazocompounds are the diazonium salts obtained by diazotization of the following amines:
  • suitable supports or carriers for the diazonium salts or compositions containing them are mentioned absorbent material, e.g. grained aluminum, ordinary wood pulp paper or rag-type paper but also textiles including fabrics made from cotton, cellulose acetate, regenerated cellulose, in other words all types of woven or felted materials that can be impregnated with a solution containing a diazonium compound or mixture of diazonium compounds.
  • absorbent material e.g. grained aluminum, ordinary wood pulp paper or rag-type paper but also textiles including fabrics made from cotton, cellulose acetate, regenerated cellulose, in other words all types of woven or felted materials that can be impregnated with a solution containing a diazonium compound or mixture of diazonium compounds.
  • transparent resin supports e.g. a polyester resin sheet
  • the diazonium salt is applied in a hydrophilic binder, e.g. in gelatin.
  • the coating composition for applying the diazonium compounds may contain a substance increasing the storage stability, e.g., an acid such as citric acid, tartaric acid, boric acid, sulfosalicyclic acid, phosphoric acid, trichloroacetic acid, tribromoacetic acid or l,3,5 -naphthalene trisulfonic acid in an amount of l to 10 percent by weight in respect of the diazonium salt.
  • the coating may further contain antioxidizing agents improving the whiteness of the areas wherein the diazonium compound has been destroyed.
  • suitable antioxidants may be mentioned urea, thiourea, ascorbic acid and allyl isothiocyanate in concentrations ranging from 25 to 15 percent by weight in respect of the diazonium salt.
  • Thermally transferable couplers are preferably incorporated into a material (hereinafter called "transfer material") with absorbent nature or porous character.
  • transfer material a material with absorbent nature or porous character.
  • absorbent materials for carrying the thermally transferable substance are particularly mentioned cloth, felt, paper, e.g. blotting paper, foamed rubber, sponge porous stone, porous porcelain and sintered glass.
  • the thermal transfer can be realized by distilling the coupler from the transfer material to the receiving sheet or layer containing the diazonium compound, which sheet or layer hereinafter is called receiving material.
  • the coupler is transferred in liquid or dissolved state, in the latter case with the aid ofa noncoupling liquid substance or substance being transformed in liquid state during heating.
  • the coupler may also be applied as a dry powder (toner) either or not mixed with carrier particles.
  • the coupler can be transferred to the receiving material by means of a substance or substances applied in layer form, which substance(s).in heated state stick(s) to the receiving material, e.g. a thermoplastic polymer or colloid, e.g. a polyoxyalkylene compound, poly-N-vinylpyrrolidone, gelatin, animal glue, a watersoluble melamine resin or thermoplastic latex polymer.
  • a thermoplastic polymer or colloid e.g. a polyoxyalkylene compound, poly-N-vinylpyrrolidone, gelatin, animal glue, a watersoluble melamine resin or thermoplastic latex polymer.
  • Preferred active methylene compounds which can thermally be transferred without the aid of an auxiliary substance, i.e., can be volatilized or sublimed in the temperature range of 8 to C., are listed hereinafter:
  • the methylene base is extracted with ether and the extract dried on anhydrous sodium sulfate
  • the ether is removed by evaporation and the methylene base is further purified by vacuum distillation or recrystallization.
  • Solvents that can be used for applying the coupler to the transfer material are, e.g., alcohols and ketones having a boiling point lower than 100 C.
  • the couplers are used in combination with humectants.
  • Suitable humectants for the active methylene compounds of the general formula, which play a part in the thermal transfer of the said compounds, are found in the class of polyols, e.g., diethylene glycol, glycerol, and hexitols such as sorbitol.
  • Surfactants of the nonionic type e.g.
  • polyoxyalkylene glycols such as polyethylene glycols having an average molecular weight from 2,000 to 6,000, are also of interest for speeding up the transfer and coupling reactions.
  • weight of humectant, solvent or surfactant in the transfer material is not higher than 200 percent by weight in respect of the coupler.
  • the way, however, of applying the coupler to the exposed receiving material is not necessarily restricted to dry or semidry transfer systems.
  • the coupler may be applied as has already been said in dissolved or finely dispersed state from a liquid. On applying that technique, however, as less liquid as possible should be used in order to produce touch-dry copies.
  • the solution or dispersion is applied by spraying, by means of a lickroller, or a porous or absorbent material, eg a felted or woven material impregnated with a solution of the coupler.
  • a heating after treatment e.g. by contact with a hot roller or irradiation with infrared light, surplus liquid can be removed.
  • An absorbing or porous carrier impregnated with the coupler can be reused for making several prints.
  • the heat necessary for a thermally nondifferential transfer of coupler to the receiving material can be supplied by a hot roller as is used, e.g., in a Dry Silver Process equipment manufactured by Minnesota Mining and Manufacturing Company, St. Paul, Minn., U.S.A., or by nondifferential infrared expo sure.
  • the transfer material should preferably contain (a) finely divided infrared-absorbing substance(s) transforming absorbed infrared light into heat. Said substance(s) can also make part of an auxiliary sheet held in intimate heat-conductive contact with the sheet material containing the active methylene compound.
  • a diazo-type copy is commonly prepared by imagewise exposing a sheet containing a diazonium salt to UV. radiation and coupling the nonexposed diazonium salt with a coupler nondifferentially applied thereto or contained therein, it is also possible to produce an azo dye image by imagewise transferring a coupler to a nonexposed sheet containing a diazonium salt Said imagewise transfer can be realized by imagewise heating a transfer material containing the heat-transferable coupler. According to one embodiment, imagewise heating proceeds by the accumulation of heat in the image markings of an original as is done in classical thermography.'For that purpose the coupler is preferably coated onto a thin heat-conductive sheet, e.g.
  • the sheet containing the diazonium salt is held in contract with the coupler-releasing side of the transfer sheet while the other side stands in heat-conductive relationship with the infrared absorbing image markings of the original.
  • the 0 heat produced in said imagemarkings is conducted to the coupler, which as a' consequence thereof is imagewise and thermally transferred so as to form an azo-dye image on the receiving sheet.
  • imagewise heating can proceed by imagewise irradiating a sheet material containing colored oxides, sulfides or carbonates of heavy metals, particularly of those heavy metals having an atomic weight between 45 and 210, such as manganese or lead sulfide, or these heavy metals themselves in finely divided state such as silver, bismuth, lead, iron, cobalt or nickel.
  • Carbon black being an excellent heat-generating product when irradiated with infrared and/or visible light is preferably used.
  • the powdery substances absorbing infrared and/or visible light have a grain size preferably lower than 0. l
  • the light-absorbing substance visible and/or infrared light-absorbing
  • the transfer layer e.g., is dissolved or dispersed in a binder for the coupler or in the paper mass of a paper sheet.
  • a pattern of radiation-absorbing substances conform to the image to be reproduced is formed in the transfer sheet.
  • a pattern can be obtained by starting from a light-sensitive substance or composition which on exposure forms an infrared-absorbing substance converting absorbed light into heat. If required by the nature of the light-sensitive substance or composition, the exposure may be followed by a suitable development.
  • Preferably light-sensitive silver halide is used as the substance from which infrared-absorbing silver can be formed imagewise.
  • a silver halide emulsion applied in the present invention may be of the negative as well as of the positive type.
  • the silver halide is preferably combined with a suitable developing agent, e. g. hydroquinone, so that the development may be carried out with a so-called activating bath, which is an alkaline aqueous solution containing no developing agent.
  • An alternative way of bringing about an informationwise distribution of infrared-absorbing substance in the recording material is to form a silver image in situ from complexed silver halide introduced into the recording material and deriving from unexposed portions of an informationwise exposed silver halide emulsion layer as known per se in silver salt diffusion transfer process.
  • the transfer of the coupler can proceed by a nondifferential exposure of the transfer material to infrared radiation. Suitable radiation sources emitting infrared light are commercially available.
  • the heat-generating exposure of a silver image can also be effected by visible light, which is preferably of high in- Example A transfer paper (A) and a light-sensitive paper (B) were prepared as follows:
  • A. l0 g. of an active methylene indoline of the list in the description were dissolved in 200 cc of acetone and coated on a document paper at a rate of 100 cc. per sq.m.
  • B. g. of a diazonium compound corresponding with one of the amines particularly described were dissolved in 1,000 cc. of water and coated on a document paper at a rate of 100 cc. per sq.m.
  • the light-sensitive material (B) was exposed for 10 sec. to U.V. radiation through a positive silver image transparency by means of an ultraviolet high-pressure mercury vapor bulb of 80 w. placed at a distance of cm.
  • the exposed paper was heated in contact with material (A) in a thermographic copying apparatus with a heating roller whose temperature was maintained between 8 and 100 C. On the material (B) a visible image was formed.
  • the material (A) could be used 10 times before it became necessary to apply a fresh amount of active methylene compound.
  • R represents a lower alkyl or hydroxyalkyl group 2.
  • the active methylene compound is one that can be volatilized or sublimed in the temperature range of to C. and said transfer material is heated to a temperature in said range.
  • thermoadhesive layer 6.
  • imagewise heating is effected by imagewise exposing the transfer material containing the active methylene compound to infrared and/or visible light, which is absorbed and converted into heat in substances nondifferentially distributed in said transfer material or making part of an auxiliary sheet material being in heatconductive contact with the transfer material.
  • n C CH3 Z CH7 N Signed and sealed this 232% day of May EDWIARD L LFLE'ICHER, JR. attesting Officer DRM PC4050 USCOMM-DC scam-ps9 U 5v GOVERNMENT PRlhTlNG OFFICE 1969 0-326 334

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US790150A 1968-01-09 1969-01-09 Diazo-type copying Expired - Lifetime US3620741A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB0320/68A GB1245261A (en) 1968-01-09 1968-01-09 Improvements relating to diazotype copying

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US3620741A true US3620741A (en) 1971-11-16

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CH (1) CH511124A (de)
GB (1) GB1245261A (de)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2532744A (en) * 1945-07-04 1950-12-05 Gen Aniline & Film Corp Diazotype containing as the azo component a quaternary salt of 2-methyl-6-methoxy-benzoselenazole
FR1123399A (fr) * 1955-03-11 1956-09-20 Perfectionnements aux produits photosensibles pour diazotypie
US2789904A (en) * 1953-09-17 1957-04-23 Gen Aniline & Film Corp Diazo print process
US2815338A (en) * 1954-05-13 1957-12-03 Ciba Ltd Basic azo dyestuffs
GB907724A (en) * 1960-02-01 1962-10-10 Dietzgen Co Eugene Diazotype reproduction material and method of using the same
US3076707A (en) * 1959-04-22 1963-02-05 Nashua Corp Heat developable copy sheet and compositions useful therefor
US3318699A (en) * 1963-10-12 1967-05-09 Keuffel & Esser Co Process and material for the development of diazotype copies
US3392020A (en) * 1956-05-14 1968-07-09 Eastman Kodak Co Photo-thermographic process and element

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2532744A (en) * 1945-07-04 1950-12-05 Gen Aniline & Film Corp Diazotype containing as the azo component a quaternary salt of 2-methyl-6-methoxy-benzoselenazole
US2789904A (en) * 1953-09-17 1957-04-23 Gen Aniline & Film Corp Diazo print process
US2815338A (en) * 1954-05-13 1957-12-03 Ciba Ltd Basic azo dyestuffs
FR1123399A (fr) * 1955-03-11 1956-09-20 Perfectionnements aux produits photosensibles pour diazotypie
US3392020A (en) * 1956-05-14 1968-07-09 Eastman Kodak Co Photo-thermographic process and element
US3076707A (en) * 1959-04-22 1963-02-05 Nashua Corp Heat developable copy sheet and compositions useful therefor
GB907724A (en) * 1960-02-01 1962-10-10 Dietzgen Co Eugene Diazotype reproduction material and method of using the same
US3318699A (en) * 1963-10-12 1967-05-09 Keuffel & Esser Co Process and material for the development of diazotype copies

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Publication number Publication date
CH511124A (de) 1971-08-15
GB1245261A (en) 1971-09-08

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