US3123472A - Material comprising a diazomum com- - Google Patents

Material comprising a diazomum com- Download PDF

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US3123472A
US3123472A US3123472DA US3123472A US 3123472 A US3123472 A US 3123472A US 3123472D A US3123472D A US 3123472DA US 3123472 A US3123472 A US 3123472A
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diazotype
diazo
acid
light
azo
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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
    • G03C1/54—Diazonium salts or diazo anhydrides

Definitions

  • the invention relates to one-component diazotype material and more particularly to such material in which the light-sensitive layer has an acid reaction and contains a p-amino benzene diazo compound which has a greater coupling activity than p-diazo ethyl benzylaniline, which is derived from a tertiary amine with only one aryl radical attached directly to the tertiary nitrogen atom, and which carries in the 4-position the diazo group, in the 2-position an alkoxy, aralkoxy or aryloxy group, and in the 5-position a hydrogen atom, a halogen atom, a methyl group or an alkoxy group.
  • diazo compounds are known. They are very sensitive to the light of the mercury vapour lamps commonly used in the modern diazotype process. Compounds in which the substituent in the 2-position is an alkoxy group are known, for example, from the Belgian Patent No. 564,343. Diazotype material sensitized with such a diazo compound is extremely suitable for the visual observation of the endpoint of the exposure when copies are made in the light of actinically fluorescent mercury vapour lamps.
  • diazo compounds of the type described above couple more actively than p-diazo ethyl benzylaniline.
  • Their coupling activity, in comparison with that of p-diazo ethyl benzylaniline, can be determined in vitro by measuring the time in which a given proportion for instance) of the diazo compound to be examined will have coupled in a given molar concentration (0.1 milli-' molar, for instance) with the coupling component 1- phenyl 3-methyl-5-pyrazolone in a given molar concentration (1.0 millimolar, for instance) in a buffer mixture of a given composition and a given pH at a given temperature.
  • the compounds coupling more actively than p-diazo ethyl benzylaniline are very suitable for the manufacture of one-component diazotype material which can be developed according to the so-called semi-Wet process.
  • imagewise exposed one-cornponent diazotype material is developed by spreading a thin layer (a layer of 8 g. square meter for instance) of developing liquid, containing one or more azo components and one or more buffer salts, evenly over the surface of the diazotype material.
  • a thin layer a layer of 8 g. square meter for instance
  • developing liquid containing one or more azo components and one or more buffer salts
  • the azo dyestuffs formed should have the same colour even under the said varying conditions.
  • alkaline phloroglucinol developers of a pH between 8.5 and 10.5 which have been buffered sufliciently. They yield browncoloured azo-dyestuffs in the semi-wet development of one-component diazotype materials which have been manufactured with diazo compounds according to the above definition and the light-sensitive layer of which has the composition that is usual for one-component diazotype materials, containing inter alia a small quantity of acid, such as citric aid, tartaric acid or alum.
  • acid such as citric aid, tartaric acid or alum.
  • the desired pH value and the desired bufl'er capacity of the phloroglucinol developers in question are achieved with the aid of buifer salts such as carbonates, borates, citrates, phosphates, tartrates, and the like.
  • buifer salts such as carbonates, borates, citrates, phosphates, tartrates, and the like.
  • the borate developers described in the United States Patents Nos. 2,657,137 and 2,657,141 are especially suitable.
  • Phloroglucinol developers showing a stronger or weaker alkaline reaction than those with pH between 8.5 and 10.5 are less suitable, the first because they have poor keeping qualities owing to oxidation upon exposure to the air, the latter because they often fail to bring about a complete conversion of the diazo compound into azo dyestutf in the semi-wet development of diazotype material manufactured wtih diazo compounds according to the above definition and with a light-sensitive layer of normal composition.
  • the azo component In the diazotype process with semi-wet development phloroglucinol is the azo component most widely used.
  • This compound can form mono-, bisand tris-azo dyestuffs which are of different colours.
  • the colours of the trisazo dyestuffs are darkest and those of the mono-azo dyestuffs lightest.
  • a large visible image contrast in the developed diazotype copies is often desirable and the image contrast in general is larger according as the colour of the azo dyestuff formed during development is darker, the formation of as dark as possible an azo dyestufi is often desirable.
  • the acid-reacting light-sensitive layer contains a quantity of alkali metal and/or ammonium orthophosphates in the amount of the stoichiometric equivalent of at least 0.15 g. and at most 0.9 g. of P per m? (i.e., per square meter) of said material.
  • One-component diazotype material according to the invention yields, by semi-wet development with the said alkaline-reacting phloroglucinol developers, darker azo dyestuifs than corresponding diazotype material which contains no orthophosp'hate but only a larger quantity of one of the commonly used acids or acid salts. Moreover, the colours of the azo dyestuffs show considerably smaller deviations, or none at all, in consequence of the said deviations in the concentration and the application of the developer.
  • Quantities of orthophosphate which are the stoichiometric equivalents of less than 0.15 g. of P 0 per m? are of little utility, because the effect of the invention is not achieved with them, or not to a suflicient degree. Quantities which are the stoichiometric equivalents of more than 0.9 g. of P 0 per m? cause difliculties in the sensitization.
  • the spreading of solutions containing such large quantities of phosphate over the surface of the di azotype material is not suificiently uniform; they penetrate too far into some supports, such as paper.
  • the desired content of orthophosphate can be obtained by dissolving a suitable quantity of alkali metal or ammonium orthophosphate, e.g., primary sodium phosphate, in the sensitizing liquid, the magnitude of the quantity of sensitizing liquid which in the manufacture of the diazotype material is applied on the support per unit area naturally being taken into account.
  • a suitable quantity of alkali metal or ammonium orthophosphate e.g., primary sodium phosphate
  • the desired content of orthophosphate can also be obtained by treating the surface of the support to be sensitized, before the sensitization, with a solution of a suitable quantity of phosphate or by subjecting the sensitized surface to an after-treatment with such a solution.
  • Primary, secondary or tertiary orthophosphates or mixtures of them can be used.
  • mixtures of orthophosphoric acid with alkali metal or ammonium salts of acids which are weaker than orthophosphoric acid may be employed.
  • the phosphate-containing light-sensitive layer must always show an acid reaction.
  • the pH of the light-sensitive layer or rather the pH of the light-sensitive surface (the light-sensitive layer of many diazotype materials, amongst others diazotype paper, is too thin for pH-determined inside the layer), is partly dependent on the pH and the acid and/or the bufler content of the support, but especially On the pH and the acid and/or the buffer content of the liquid(s), which is (are) used for the manufacture of the lightsensitive material.
  • a suitable composition of this (these) liquid(s) it can easily be given a certain value. In practice this is not chosen below 2, since many diazotype materials, e.g., diazotype paper, become brittle at such a high degree of acidity of the light-sensitive layer and the sizing of the paper is adversely affected. It will preferably not be chosen higher than about 6.5 because the keeping qualities of the lightsensitive layers are then too small.
  • the surface-pH of the light-sensitive layers of the common one-component diazotype materials in most cases is between 3.5" and 4.5.
  • a pH below 3.5 is sometimes chosen, particularly when above this pH value the keeping qualities would still leave much to be desired and if the application of stabilizers such as naphthalene-1.3.6-trisulphonic acid and its salts is not possible, for example owing to the formation of precipitates in the sensitizing liquids. If, however, stabilizers can be applied, a higher pH, e.g., between 4.5 and 6.5, may be chosen in many cases.
  • a higher pH e.g., between 4.5 and 6.5
  • diazotype material according to the invention Upon comparison of diazotype material according to the invention with corresponding diazotype material which contains instead of phosphate a larger quantity of the commonly used acids or acid salts, it therefore has to be taken into account that it is not necessary for the surface-pH which is measured for the comparable diazotype materials before the development to be exactly the same.
  • the comparability is determined in the first place by the results of the development, in other words by the question of whether in the development the same quantity of diazo molecules is converted into azo dye-stuff in about the same time.
  • the surface-pH can easily be determined by wetting the ligh-sensitive surface locally with distilled water with the aid of the so-called surface-electrodes of an electric pH- meter that has been adjusted to the measurement, e.g. the surface glass electrode 613 14/ and the surface calomel electrode 6B 15/100 of the pH-meter type 6C of N.V. Electrofact, Amsterdam, Holland, in such a way that between the two electrodes via the wetted surface an electrical contact is effected, and by subsequently reading the deflection of the meter.
  • One-component diazotype material is known in which a diazo film layer contains as diazo compound p.p'-tetrazoo.o'-dianisidine and also contains a large quantity of primary sodium phosphate.
  • the phosphate serves to prevent the bleeding of the azo dyestuff during bath-development, and can therefore be replaced by an equal quantity of common salt.
  • no favourable effect of the phosphate with regard to deviations in the shade of the azo dyestufls owing to deviations in the concentration and the application of the developers is observed.
  • Another known one-component diazotype paper is that sensitized with the actively coupling 4-diazo-2,5-diethoxy benzoylanilide, the light-sensitive layer of which contains a small quantity of primary sodium phosphate. This quantity is smaller than that which corresponds to 0.15 g. of P 0 per 111.
  • the paper is suitable for develop ment with an acid, buffered phloroglucinol developer. In this case the deviations in shade owing to development fluctuations, as described above, do not arise.
  • diazo film layers contain very small quantities of the acids commonly used in the diazotype process such as tartaric acid, citric acid, and alum.
  • the diazo compounds are not suited for the sensitization of some supports commonly used in the diazotype process, e.g. paper, because their solutions penetrate too far into them. They are aslo less light-sensitive than the diazo compounds which can be applied in the diazotype material according to the invention.
  • Diazotype materials which have been sensitized with actively coupling diazo compounds such as 4-diazo-2.5- dialkoxy-acylanilides, 4-diazo-2.5-dialkoxy-aryl-mercaptd benzene compounds, and 4-diazo-2.5-dialkoxy diphenyl compounds, and which are usually developed with acid, strongly buffered developers, can be developed, as is known, according to the semi-wet process with alkalinereacting phloroglucinol developers, and may then yield azo deystutf shades as pure or neutral and as dark as those obtained by development with the said strongly buffered developers, if their light-sensitive layer contains a large quantity of a saturated aliphatic dicarboxylic acid, in which the carboxyl groups are attached to carbon atoms which form part of a saturated hydrocarbon radical with at least 2 carbon atoms which may or may not be branched and may or may not be provided with other substituents, the dissociation constants of said acid being smaller than 1X Examples
  • diazotype material according to the present invention has better keeping qualities.
  • the diazo compounds which are used in the diazotype material according to the invention it is not only the substituents in the phenyl radical carrying the diazo group, but also the other groups besides that phenyl radical which are attached to the tertiary nitrogen atom which affect the colour of the azo dyestuffs formed from the diazo compounds by semi-wet development.
  • the azo dyestuffs are darker accordingly as the tertiary nitrogen atom carries heavier groups.
  • diazo compounds of which the tertiary nitrogen atom carries two ethyl groups when used in diazotype material according to the present invention, do not yield blackcoloured, but lighter, more or less brown to dark brown azo dyestuffs upon development of the diazotype material with phloroglucinol developer.
  • Corresponding diazo compounds with heavier alkyl groups, e.g. n-butyl groups, or with an aralkyl group, e.g. a benzyl group, on the tertiary nitrogen atom often yield fine black azo dyestufis.
  • Such diazo compounds are often less readily soluble in the sensitizing liquids which are used for the manufacture of the diazotype material according to the present invention, while their light-decomposition products often cause rather serious discolouration of the diazotype copies. Both the said solubility and the said discolouration are worse accordingly as the quantity of phosphate used is larger.
  • Fine black azo dyestuffs are obtained with one-component diazotype material according to the present invention which contains a p-diazo-2.5-dialkoxy phenylrnorpholine.
  • the diazo compounds used in such onecomponent diazotype mate-rial do not have the disadvantages which corresponding diazo compounds with heavier groups on the tertiary nitrogen atom present.
  • One-component diazotype material sensitized with p- 6 diazo 2.5-diethoxy-phenylmonpholine is known. It does not contain orthophosphate.
  • the diazotype material according to the present invention may of course also contain mixtures of diazo compounds.
  • additives commonly used in one-component diazotype materials such as stabilizers, e.g. naphthalene-1.3.-trisulphonic acid or one of its salts, anti-discolouration agents, e.g. thiourea, means for improving the surface, eg. fine particles of silica, aluminium oxide, synthetic resins or rice starch.
  • stabilizers e.g. naphthalene-1.3.-trisulphonic acid or one of its salts
  • anti-discolouration agents e.g. thiourea
  • means for improving the surface eg. fine particles of silica, aluminium oxide, synthetic resins or rice starch.
  • the diazo compounds used in the diazotype material according to the present invention can be prepared in several ways, erg. as described in Belgian Patent No. 564,343.
  • Compounds with an aralkoxy group can be prepared from o-nitro-phenyl-aralkyl ethers in the manner described in the said Belgian patent for the preparation of alkoxy compounds.
  • Compounds with an aryloxy group can be prepared in a corresponding way from o-nitro-diphenyl ethers.
  • Example 1 White balse-paper of weight gm. as used for the diazotype process is sensitized with a solution of:
  • the sensitized surface contains approximately 0.38 millimole of diazo compound per m? and a quantity of phosphate Which is the stoichiometric equivalent of 0.18 g. of P 0 per m. and has a ph 3.85.
  • the light-sensitive side of, a sheet of the diazotype paper thus prepared is covered with a sheet of tracing paper on which a pencil drawing has been made, and exposed in an exposure apparatus equipped with actinically fluorescent low-pressure mercury vapour lamps. Exposure is continued until, in the portions which are in contact with the blank parts of the drawing, only a small quantity of diazo compound is left.
  • the moment at which the exposure has to be terminated can be determined very well by visual observation (from the direction of the light-source, for instance) of the change or colour which occurs in the light-sensitive layer during the exposure. This moment is soon reached.
  • the latent diazotype copy thus obtained is developed by applying on its image surface a layer of approximately 8 g./-rn. of a developing liquid of the following composrtion:
  • the developing liquid has a pH 9.8.
  • the developed copy shows a strong black positive image on a uniform foggy background.
  • the developing liquid is diluted, erg. by addition of 200 em. of water, the copy developed with it shows an image which is less strong but still black.
  • Example II White base-paper of weight 80 g./m. as used for the diazotype process is sensitized with a solution of:
  • the sensitized surface contains approximately 0.38 millimole of diazo compound per m2 and a quantity of phosphate which is the stoichiometric equivalent of 0.29 g. of P per m. and has a pH 3.6.
  • a sheet of the diazotype paper thus prepared is imagewise exposed as described in Example I. The moment at which the exposure has to be terminated can be observed very well and is soon reached.
  • the latent diazotype copy thus obtained is developed in a developing apparatus as described in Dutch Patent No. 67,009 at a speed of 5 m./min., 8.5 g./m. of a developing liquid of the following composition being applied:
  • the developing liquid has a pH 9.4 A strong black image on a foggy background is obtained.
  • Example III White base-paper of weight 80 g./m. as used for the diazo-type process is pre-sensitized with about 10 g./m. of the following liquid:
  • colloidal silica dispersion Satessa 14 2 g. of polyvinyl alcohol, Rhodoviol BS 10 in 900 cm? of Water and dried.
  • the sensitized surface contains approximately 0.5 millimole of diazo compound per rn. and a quantity of phosphate which is the stoichiornetric equivalent of 0.28 g. of P 0 per m. and has a pH 3.5.
  • a sheet of the diazotype paper thus prepared is imagewise exposed as described in Example I.
  • the moment g at which the exposure has to be terminated can be observed very well and is soon reached.
  • the latent diazotype copy thus obtained is developed by applying approximately 9 g./m. of the following developing liquid:
  • the developing liquid has a pH 9.4.
  • the developed copy shows a strong black positive image on a foggy background, which does not show deviations in shade due to vibrations and mechanical irregularities of the developing apparatus.
  • Example IV White base-paper of weight g./rn. as used for the diazo-type process is sensitized with a solution of:
  • the light-sensitive surface contains approximately 0.55 millimole of diazo compound per m and a quantity of phosphate which is the stoichiometric equivalent or" 0.18 g. of P 0 per m. It has a pH 3.3.
  • a sheet of the diazotype paper thus prepared is image- Wise exposed as described in Example I. The moment at which the exposure has to be terminated can be observed very well and is soon reached.
  • the latent diazotype copy thus obtained is developed by applying approximately 8.5 g./rn. of the following developing liquid:
  • the developing liquid has a pH 9.
  • the developed copy shows a strong black positive image on a foggy background.
  • Example V White base-paper of weight 80 g./m. as used for the diazo-type process is sensitized with a solution of:
  • the sensitized surface contains approximately 0.5 millimole of diazo compound per m? and a quantity of phosphate which is the stoichiometric equivalent of 0.41 g. of P per m. and has a pH 3.5.
  • a sheet of the diazotype paper thus prepared is imagewise exposed as described in Example I. The moment at which the exposure has to be terminated can be observed very well and is soon reached.
  • the developed copy shows a grey-black positive image on a foggy background and shows only small variation of shade due to development fluctuations.
  • Example VI A cellulose acetate layer of weight approximately 20 g./m. applied on natural tracing paper of weight approximately 80 g./m. is superficially hydrolyzed to a depth of approximately 4 1. and, after removal of the chemicals used for the hydrolysis by washing with water, is sensitized with a solution of 1 24 g. of 4-dimethylamino-3-p-chlorophenoxy-6-chlorobenzene diazonium chloride, zinc chloride double salt 80 g. of primary sodium phosphate (2 aq.)
  • the light-sensitive hydrolyzed layer contains approximately 0.75 millimole of diazo compound per m. and a quantity of phosphate which is the stoichiometric equivalent of 0.46 g. of P 0 per m. and has a surface pH 3.2.
  • a sheet of the diazotype material thus prepared is image-wise exposed as described in Example I. The moment at which the exposure has to be terminated can be observed very well and is soon reached.
  • the latent diazotype copy thus obtained is developed by applying approximately 8 g./m. of the following developing liquid:
  • the developing liquid has a pH 9.4.
  • the developed copy shows a brown-black image on a foggy background which shows little variation of shade due to development fluctuations.
  • the copy produced according to this example can be used as an intermediate original for making further copies on diazotype paper.
  • Example VII A baryta-coated paper of weight g./m. is sensitized with a solution of:
  • the sensitized surface contains approximately 0.7 millimole of diazo compound per m. and a quantity of phosphate which is the stoichiometric equivalent of 0.38 g. of P 0 per m. and has a pH 4.3.
  • a sheet of the diazotype paper thus prepared is imagewise exposed as described in Example I. The moment at which the exposure has to be terminated can be observed very well and is soon reached.
  • the latent diazotype copy thus obtained is developed as described in Example II.
  • the developed copy shows a grey-black positive image on a grey foggy background, which shows little or no deviation in shade due to vibrations and mechanical irregularities of the developing apparatus.
  • the copy shows an image with considerable dilferences in azo dyestuff shade due to vibrations and mechanical irregularities of the developing apparatus, in the form of alternating brown and grey-black lines.
  • Example VIII White base-paper of weight 80 g./m. as used for the diazotype process is sensitized with a solution of:
  • the sensitized surface contains approximately 0.5 millimole of diazo compound per 111. and a quantity of phosphate which is the stoichiometric equivalent of 0.56 g. of P 0 per m. and has a pH 3.5.
  • a sheet of the diazotype paper thus prepared is imagewise exposed as described in Example I. The moment at which the exposure has to be terminated can be observed very Well and is soon reached.
  • the latent diazotype copy thus obtained is developed as described in Example VI.
  • the developed copy shows a grey-black positive image on a violet-grey foggy background, which shows little or no deviation in shade due to vibrations and mechanical irregularities of the developing apparatus.
  • the copy shows a dark-brown image on a red-brown foggy background with considerable differences in azo dyestulf shade due to vibrations and mechanical irregularities of the developing apparatus, for example in the form of alternating green-brown, dark-brown and red brown lines.
  • Example IX White base-paper of Weight 80 g./m. as used for the diazotype process is sensitized with a solution of:
  • the sensitized surface contains approximately 0.45 millimole of diazo compound per m? and a quantity of phosphate which is the stoichiometric equivalent of 0.23 g. of P per m2, and has a pH 3.4.
  • a sheet of the diazotype paper thus prepared is imagewise exposed as described in Example I. The moment at which the exposure has to be terminated can be observed very well and is soon reached.
  • the latent diazotype copy thus obtained is developed as described in Example II.
  • the developed copy shows a strong black positive image on a foggy background which shows little variation of shade due to development fluctuations.
  • Example X ⁇ Vhite base-paper of weight 80 g./m. as used for the diazotype process is sensitized with a solution of:
  • the sensitized surface contains approximately 0.45 millimole of diazo compound per m. and a quantity of phosphate which is the stoichiometric equivalent of 0135 g. of P 0 per m. and has a pH 5.4.
  • a sheet of the diazotype paper thus prepared is imagewise exposed as described in Example I. The moment at which the exposure has to be terminated can be observed very well and is soon reached.
  • the latent diazotype copy thus obtained is developed as described in Example H.
  • the developed copy shows a strong black positive image on a foggy background which shows little variation of shade due to development fluctuations.
  • One-component diazotype material comprising a support carrying a light-sentive layer containing a lightsensitive diazo compound in the absence of an azo coupling component, said light-sensitive layer having an acid reaction and said diazo compound being a p-amino ben zene diazonium salt which has a greater coupling activity than p-diazo ethyl benzylaniline, which is derived from a tertiary amine with only one aryl radical attached directly to the tertiary nitrogen atom, and which carries in the 4-position the diazo group, in the 2-position a member selected from the class consisting of alkoxy, aryloxy and aralkoxy groups, and in the 5-position a member selected from the class consisting of a hydrogen atom, a halogen atom, a methyl group and an alkoxy group, the said lightsensitive layer containing a quantity of orthophosphate selected from the class consisting of alkali metal and ammonium orthophosphates in the
  • a process for the production of a diazotype print which comprises imagewise exposing a diazotype material as defined in claim 1 and developing the exposed material by the semi-Wet method using a developer containing phloroglucinol.
  • diazonium salt being a diazonium salt of 4- di-n-propylamino-3-ethoxybenzene.
  • diazonium salt being a diazonium salt of 4-dimethylamino 3 p-chlorophenoxy 6 chlorobenzene.
  • diazonium salt being a diazonium salt of 4-morpholino-2,S-di-n-propoxybenzene.

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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)
US3123472D 1958-11-10 Material comprising a diazomum com- Expired - Lifetime US3123472A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3382070A (en) * 1964-01-02 1968-05-07 Gen Aniline & Film Corp Black-line moist diazotype process
US3389996A (en) * 1964-10-15 1968-06-25 Gen Aniline & Film Corp Two-component heat developable diazotypes
US3409434A (en) * 1965-10-28 1968-11-05 Gaf Corp Resin precoated diazotype papers
US3650750A (en) * 1968-12-28 1972-03-21 Ricoh Kk Heat-developable diazo-type light-sensitive material
US3873316A (en) * 1970-06-11 1975-03-25 Kalle Ag Process for the production of a light-sensitive copying material having a copper-containing support, and copying material so produced

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2217189A (en) * 1938-12-05 1940-10-08 Kalle & Co Ag Process of preparing photographic prints
US2405523A (en) * 1944-08-09 1946-08-06 Du Pont Light-sensitive photographic compositions and elements
CA476718A (en) * 1951-09-04 Charles Slifkin Sam Diazotype photoprinting

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA476718A (en) * 1951-09-04 Charles Slifkin Sam Diazotype photoprinting
US2217189A (en) * 1938-12-05 1940-10-08 Kalle & Co Ag Process of preparing photographic prints
US2405523A (en) * 1944-08-09 1946-08-06 Du Pont Light-sensitive photographic compositions and elements

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3382070A (en) * 1964-01-02 1968-05-07 Gen Aniline & Film Corp Black-line moist diazotype process
US3389996A (en) * 1964-10-15 1968-06-25 Gen Aniline & Film Corp Two-component heat developable diazotypes
US3409434A (en) * 1965-10-28 1968-11-05 Gaf Corp Resin precoated diazotype papers
US3650750A (en) * 1968-12-28 1972-03-21 Ricoh Kk Heat-developable diazo-type light-sensitive material
US3873316A (en) * 1970-06-11 1975-03-25 Kalle Ag Process for the production of a light-sensitive copying material having a copper-containing support, and copying material so produced

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