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
  • G03C1/60—Compositions containing diazo compounds as photosensitive substances with macromolecular additives

Definitions

• the conventional two-component diazotype material is generally developed with the aid of ammonia vapour. This developing method is applied on a large scale, but it has disadvantages which make the application of the two-component diazotype process inconvenient in many cases, for instance .in otfices.
• Such diazotype materials either have poor keeping qualities, for instance because with a view to achieving the required developing speed the pH of the light-sensitive layer has been set too high or the layer has been stabilized insufficiently, or they cannot be developed at a temperature sufficiently low to be acceptable in practice, which is the case, for instance, if the substance elfecting the development is asubstance which splits off ammonia upon heating, such 'as urea, thiourea, and their alkyl derivatives. Developing temperatures of, for instance, 150 C. and higher are not desirable.
• British patent specification 815,005 describes a heatdevelopabl'e diazotype material in which the diazo compound and the azo coupling component are present in separate layers, which are separated by a wax layer melting between 60 and 70 C. The latter is formed from molten wax. If necessary a top layer consisting of a film-forming organic binding agent can be applied.
• the diazo compound preferably is a very actively coupling and thus not particularly stable diazo compound, such as a 4-(4'-tolyl)mercapto-Z,5-diethoxybenzene diazonium salt or a 4-benzoylamino-2,S-diethoxybenzene diazonium salt.
• suitable azo coupling components the actively coupling compounds resorcinol, phloroglucinol, and dimedone are mentioned.
• Such diazotype material has good keeping qualities only if the waxy layer is thick. However, it then develops slowly and incompletely, because, upon heating, the azo coupling component has to dissolve in the molten waxy intermediate layer before penetrating into the diazo layer. All this has to take place during the time which is availice able for development and which, if pyrolysis of the diazo compound is to be avoided, can only be very short.
• the layer containing the azo coupling component may also contain a basic-reacting substance, for instance an amine of a long chain hydrocarbon such as steary-lamine.
• a similar heatdevelopable diazotype paper in which an azo coupling component-containing layer, a wax layer, and a diazo layer are successively applied on a paper support.
• the azo coupling component-containing layer contains an "actively or very actively coupling azo coupling component, such as 2,3-dihydroxynaphthalene, or an azo coupling component of the pyrazolone or acetylacetanilide type with a low melting point.
• a hydrophilic binding agent such as polyvinyl alcohol, and, if necessary, a basic-reacting substance such as hexylamine, laurylamine, and stearylamine.
• polyvinyl acetate may also be present.
• the intermediate layer mainly consists of waxy mate- 'rial, such as paraffin and polyethylene, applied on the azo coupling component layer from an emulsion or an aqueous dispersion. It contains a hydrophilic binding agent, such as polyvinyl alcohol, and melts when the diazoty-pe paper is heated to above C.
• waxy mate- 'rial such as paraffin and polyethylene
• hydrophilic binding agent such as polyvinyl alcohol
• the light-sensitive layer contains a diazo compound p-diazo-N,N-dimethylaniline, a slowly coupling stable diazo compound, and an acid the first dissociation constant of which is greater than 10- such as maleic acid or sulphamic acid.
• an acid the first dissociation constant of which is greater than 10- such as maleic acid or sulphamic acid.
• the waxy intermediate layer still has to be rather thick, so that also with this material the development proceeds comparatively slowly, i.e. if the diazotype material is to be developed as satisfactorily as possible, it has to be kept at an elevated temperature for a long time.
• the content of diazo compound in the light-sensitive layer is high, it yields azo-dyestuff images which are not very dense, due to the pyrolysis of the diazo compound then occurring.
• the present invention is concerned with the production of heat-developable diazotype material, which avoids the disadvantages referred to above.
• a process for the production of heat-developable twocomponent diazotype paper which contains a light-sensitive benzene diazonium compound, an azo coupling component, an acid-reacting compound, a quantity of water of the order of that commonly used in twocomponent 3 diazotype material, and a fusible acid-neutralizing material, the latter material being separated from the layer which contains the diazonium compound by means of an intermediate layer, said process being characterized in that the paper is coated successively with:
• an open-structure light-sensitive layer containing, in addition to the diazonium compound, the azo coupling component, and the acid-reacting compound, a quantity of 1-6 g./m. of a thermoplastic, high-molecular, polymerized substituted vinyl compound, which is applied from an aqueous dispersion;
• a thin hydrophobic thermoplastic film layer having a weight not exceeding 4 g./m. which layer separates the acid-neutralizing material from the light-sensitive layer, but transmits this material upon heating, and in which layer is present a polymeric substance selected from hydrophobic polymerized substituted vinyl compounds and hydrophobic cellulose derivatives, said film layer being formed on the dry light-sensitive [layer from a solution of the polymeric substance in a solvent in which the diazonium compound, the azo coupling component, and the acid-reacting compound present in the lightsensitive layer do not dissolve, or only slightly so; and
• a light-transmitting layer which is dry and solid at room temperature and which contains a filler as well as an acid-neutralizing organic material melting below 100 C. and selected from non-volatile or only slightly volatile organic non-aromatic amines and the salts of those amines with weak acids.
• the invention also relates to heat-developable twocomponent diazotype paper, which is produced by the above-mentioned method.
• heat-developable two-component diazotype paper can be produced which has good keeping qualities under normal atmospheric conditions, and copies on this material can be developed within a few seconds by heating to a temperature not exceeding 120 C., strong azo-dyestuff images thus being formed.
• -It is one of the characteristic qualities of heat-developable two-component diazotype paper according to the invention that the diazo compound and the azo coupling component are present in one layer together with a quantity of an acid or an acid-reacting substance necessary for preventing decomposition of the diazo compound and premature coupling of the-diazo compound and the azo coupling component.
• This layer can be regarded as a normal two-component diazotype layer, which, if desired, can indeed also be developed with the aid of ammonia vapour.
• the paper according to the invention can therefore be developed in two different ways, which may be an advantage for users who already have apparatus for ammonia-development at their disposal, for instance in a drawing office, and who set up a heat-developing machine in the general office, but wish to use the same paper in the two departments.
• the diazotype paper of this invention is preferably placed in such a way that its back is turned to the source of ammonia, because the paper support will generally have greater transmission for ammonia vapour than the combination of layers applied on the light-sensitive layer.
• the structure of the light-sensitive layer of the diazotype paper a-ccording to the invention has to satisfy certain special requirements as compared with normal two-component diazotype paper.
• the liquid acid-neutralizing organic material upon development by heating, the liquid acid-neutralizing organic material has to penetrate via the intermediate layer into the light-sensitive layer, where it has to neutralize the acid-reacting compound present therein, in order to effect the azo-dyestuff formation.
• the lightsensitive layer has to be permeated with the acid-neutralizing material within a few seconds, because otherwise pyrolysis of the diazo I ture and preferably should be present on the surface of the support as a very thin separate layer.
• the support used is preferably paper which has been pre-coated with a so-called surfaceimproving agent, such as colloidal or non-colloidal silica or aluminium oxide or titanium dioxide or baryta (colloidal), clays such as kaolin, bentonite, zeolite, attapulgite, halloysite and the like, or synthetic resins such as polystyrene, polymethylmethacryl-ate, polyvinyl acetate, butadiene-acryl-onitrile copolymers, vinylidene chloride copolymers and the like, or paper which has been lacquered, for instance, with a cellulose acetate lacquer.
• the surface-improving agent may also be added to the sensitizing liquid.
• thermo-' plastic, high-molecular, polymerized substituted vinyl compound is incorporated in this layer from an aqueous dispersion.
• an acid aqueous dispersion of such a polymer is added to the aqueous sensitizing liquid with the aid of which the light-sensitive layer is formed. It is also possible, however, to apply the dispersion before or after sensitization.
• the acid aqueous dispersions of many thermoplastic, high-molecular, polymerized substituted vinyl compounds can be used.
• Polymers the particles of which do not have this quality can be given this quality by addition of plasticizer.
• the particles of such polymers may alternatively be fixed to the paper surface with the aid of a binding agent such as polyvinyl alcohol.
• the polymer must not be markedly adhesive or form a closed film on the paper surface, both of which are qualities of polymers with a relatively low molecular weight ⁇ and/ or high content of plasticizer.
• Polymerized substituted vinyl compounds which are suitable for use in the light-sensitive layer and can be incorporated therein from an acid aqueous dispersion are, for instance, high-molecular polyvinyl acetate, polystyrene, polyvinyl chloride, high-rnolecular copolymers of vinyl acetate with vinyl chloride and of styrene with butadiene, polymethylmethacrylate, polybutylmethacrylate, copolymers of vinylidene chloride, and copolymers of vinyl chloride with vinyl isobutyl ether.
• dispersions with an average particle size between 05 and 3 microns are used. Useful results can also be obtained with finer dispersions.
• dispersions of polymers which soften at relatively high temperatures, such as polystyrene, the average particle size of which 1s about 0.1 micron can be used, although light-sensitive layers which are formed with such dispersions are less readily accessible to the acid-neutralizing material penetrating through the intermediate layer upon development than are light-sensitive layers in the formation of which coarser dispersions have been used.
• the quantity of polymer which the light-sensitive layer should contain, in order that it should possess the desired structure lies between 1 and 6 g. of polymer per m? of sensitized surface. Quantities smaller than 1 g./m. are not very effective, whilst quantities of more than 6 g. cause the light-sensitive layer to become too thick. In both cases the development proceeds too slowly and relatively weak azo-dyestuff images are obtained. Usually quantities of 2 to 4 g./m. are chosen.
• thermoplastic film layer On the light-sensitive layer a thin hydrophobic thermoplastic film layer is applied. This layer separates the acid-neutralizing organic material from the light-sensitive layer, even when the diazotype material is kept under unfavourable conditions, for instance in warm moist surroundings. However, upon development it permits the passage of that material.
• Polymers which are suitable for the formation of the intermediate layer include the non'crystallizing and the non-waxy, hydrophobic, polymeric substituted vinyl compounds, for instance polyvinyl acetates, polyvinyl acetals, polyvinyl butyrals, polystyrenes, polymethylmethacrylates and copolymers thereof, polybutylrnethacrylates, and copolymers of vinyl acetate with vinyl chloride, and cellulose acetates, cellulose acetate butyrates, benzylcelluloses, and ethylcelluloses. Mixtures of these polymers may also be used.
• the solution from which the intermediate layer is formed preferably contains l-3% by weight of the poly mer in a solvent such as ethyl acetate, acetone, trichloroethylene, carbon tetrachloride, benzene, toluene or tetra hydrofur-an.
• a solvent such as ethyl acetate, acetone, trichloroethylene, carbon tetrachloride, benzene, toluene or tetra hydrofur-an.
• the diazo compound, the azo coupling component, and the acid-reacting compound which are present in the light-sensitive layer do not dissolve in these solvents or only slightly so, so that when the intermediate layer is applied, these substances remain in situ and are not mixed with the polymer from which the intermediate layer is formed. Mixtures of these solvents may also be used.
• the intermediate layer may be of very small thickness. Layers of which the weight is considerably less than 0.5 g./m. can still afford good results. But their production calls for a very accurate working method, because, for instance, any impurity in the liquid from which such a layer is formed may cause an opening in the layer, through which the acid-neutralizing material may prematurely penetrate into the light-sensitive layer. Intermediate layers having a weight of more than 4 g./rn. cannot be used very well in practice, because the time which the acid-neutralizing material needs to penetrate through them upon development is too long. Very suitable intermediate layers are those having a weight of 0.3 to 1 g./m.
• the acid-neutralizing organic material is present on the intermediate layer in a light-transmitting layer which is dry and solid at room temperature. It should be substantially non-volatile at temperatures below 140 C. and may consist of a substance that is solid at room temperature and has a low melting point. It may, however, also be liquid at room temperature.
• the non-volatile or slightly volatile organic non-aromatic amines and their salts with weak acids have been found to be very suitable.
• Suitable amines are primary aliphatic amines with a long carbon chain, such as laurylamine, stearylamine, octamethylene diamine, decamethylene diamine; N-(alkylcarbonylamido)ethyl-N-ethanolamines having an alkyl radical of 6-18 C-atoms; triethanolamine. Salts of such amines with weak acids, such as triethanolamine stearate and phosphate, are also suitable.
• Such salts may be formed in the solution or dispersion with the aid of which the layer containing the acid-neutralizing material is applied, for instance from a mixture of a salt of such an amine with a strong acid and a salt of a strong base with a weak acid, for instance from ttriethanolamine chloride and sodium stearate.
• N-(alkylcarbonylamido) ethyl-N-ethanolarnines having an alkyl radical of 6-18 carbon atoms are preferred. Upon development they permeate quickly through the intermediate layer and they hardly evaporate at temperatures of l20-140 C.
• the acid-neutralizing organic material is mixed with finely divided substances, herein referred to as fillers, such as silica, aluminium oxide, kaolin, titanium dioxide, barium sulphate, bentonite, magnesium carbonate, synthetic resin dispersions, for instance dispersions of polyvinylacetate, polyvinyl chloride, polystyrene, polymethylmethacrylate, and copolymers thereof.
• fillers such as silica, aluminium oxide, kaolin, titanium dioxide, barium sulphate, bentonite, magnesium carbonate, synthetic resin dispersions, for instance dispersions of polyvinylacetate, polyvinyl chloride, polystyrene, polymethylmethacrylate, and copolymers thereof.
• Each of the different layers in the two-component diazotype paper according to the invention should have a uniform thickness and structure throughout its plane and should have good anchorage to the support paper and the adjacent layers.
• a preferred embodiment of the process according to the invention is that. in which the intermediate layer is formed from a solution of a suitable polymer in a solvent in which the polymer present in the light-sensitive layer swells or dissolves. quence, upon the formation of the intermediate layer, good adhesion of the polymer that is present in the said solution to the polymer in the light-sensitive layer is obtained, owing to which the two layers are firmly fixed together.
• the polymer in the light-sensitive layer is applied from an aqueous dispersion of polystyrene or poly-n-butylmethacrylate, and, if the intermediate layer is formed with a solution of polystyrene or with a solution of polymethylmethacrylate, in solvents such as trichloroethylene, ethyl acetate, and acetone, two-component diazotype paper according to the invention which has good keeping qualities and develops well at about 120 C. can be produced.
• polyvinyl acetate is present either in the light-sensitive layer or in the solution from which the intermediate layer is formed, or in both.
• the intermediate layer is formed from a solution of polyvinylacetate in a solvent in which the polymer present in the light-sensitive layer swells or dissolves, such as ethyl acetate, acetone, carbon tetrachloride, trichloroethylene, benzene or toluene.
• a solvent in which the polymer present in the light-sensitive layer swells or dissolves such as ethyl acetate, acetone, carbon tetrachloride, trichloroethylene, benzene or toluene.
• Other polymers may also be present in the polyvinyl acetate solution.
• copolyrners thereof can also be used.
• a solution of 13% by weight of polyvinyl acetate having a molecular weight of 500,000 or higher, preferably 1,000,000 or higher, in ethyl acetate, acetone or trichloroethylene is preferred.
• polyvinyl acetate When polyvinyl acetate is used in the light-sensitive layer, the polyvinyl acetate dispersion has to meet the requirements stated above with reference to the polymer in the light-sensitive layer.
• Twocomponent diazotype paper according to the invention which has good structure and good anchor-age of the layers, and which develops rapidly and has good keeping qualities, is that in which the light-sensitive layer contains a quantity between 1 and 6 g./m.
• the intermediate layer is a thin film layer having a weight not exceeding 4 g./m. consisting substantially of polyvinyl acetate with a molecular weight of more than 500,000 and covered with a light-transmitting layer which is dry and solid at room temperature .and contains a filler as well as an acid-neutralizing organic material melting below C. which is a non-volatile or only slightly volatile organic non-aromatic amine or a salt of such an amine with a weak acid.
• Very satis- In consefactory two-component diazotype paper according to the invention is also obtained if, using the said finely divided polyvinyl acetate in the light-sensitive layer the intermediate layer is formed with the aid of a solution of a polymer other than polyvinyl acetate, for instance of a hydrophobic cellulose derivative, such as cellulose acetate, cellulose acetate butyrate, ethylcellulose, benzylcellulose, or with the aid of a solution of polystyrene, polymethylmethacrylate, polyvinyl chloride, or copolymers thereof.
• a solvent for polyvinyl acetate is used in which the diazo compound, the am coupling component, and the acid-reacting compound present in the light-sensitive layer do not dissolve.
• the two-component diazotype paper according to the invention in which the polymer in the light-sensitive layer, or that in the intermediate layer, or both is or are polyvinyl acetate develops rapidly at temperatures between 100 and 130 C. and has good keeping qualities if the acid-neutralizing organic material is a water-soluble N-(alkylcarbonylamido) ethyl-N-ethanolamine the alkyl radical of which contains at least 6 carbon atoms.
• the light-sensitive diazonium compounds commonly used in the two-component diazotype process can be employed.
• Good results are obtained with benzene diazonium salts with a tertiary amino group in p-position, such as 4-diazo N,N-dimethylaniline, 4-diazo N,N-diethylaniline, 4-diazo N-ethyl N-2-hydroxyethylaniline and 4-diazo morpholinobenzene, and also with diazo compounds with a secondary amino group in p-position such as 4-diazo 2-rnethoxy N-rnethylaniline.
• these diazonium compounds are satisfactorily resistant to .temperatures of l-130 C.
• the much less stable 4-diazo 2,S-dialkoxyphenylmorpholines such as 4-diazo 2.,5-diethoxyphenylrnorpholine and 4-diazo 2,5-din-hutoxyphenylrnorpholine, can also be used with a good result.
• the quantity of these latter diazonium compounds converted in a few seconds at a developing temperature of 120 C. into azo-dyestutf is sufficient to obtain strong azo-dyestuff images. Because of their great light-sensitivity a larger quantity of these latter compounds can be used than of the first-mentioned compounds. Nevertheless the diazotype paper produced therewith is much more light-sensitive than the diazotype paper made with the first-mentioned compounds.
• the azo coupling components which are commonly used in the two-component diazotype process, are eminently suitable for use in the heat-developable two component diazo-type material according to the invention.
• Examples are Z-hydroxynaphthalene, 2,3-dihydroxynapthalene, 2,3-dihydroxynaphthalene 6-sulphonic acid, 2,7-dihydroXynaphthalene-3,6-disulphonic acid, 1,6,7-trihydroxynaphthalene-3-sulphonic acid, 7-hydroxy-1,2, 4,5 naphthimidazole, 2 hydroxy 3 (2'hydroxy)ethylamido-carbonylnaphthalene, m-ureidophenol, 2,2,4,4'- diresorcinol, hydroxyethylamide of fl-resorcyclic acid, 4-di-methylamino methyl-2,S-dimethylphenol, dimedone and 1-phenyl-3-amido-carbonylpyrazolone-S.
• actively coupling azo coupling components such as phloroglucinol and resorcinol may be used in combination with relatively slowly coupling diazonium compounds, to avoid premature coupling, whilst slowly coupling azo coupling components such as 2-hydroxy-naphthalene-3,6-disulphonic acid and 7-hydroxy-1,2,4,S-naphthimidazole may be used with relatively actively coupling diazonium compounds.
• the light-sensitive layer further contains a suflicient quantity of an acid-reacting compound, such as tartaric acid, citric acid, maleic acid, succinic acid, alum and the like.
• an acid-reacting compound such as tartaric acid, citric acid, maleic acid, succinic acid, alum and the like.
• auxiliary agents commonly used in two-component diazotype layers, for instance metal salts, such as zinc chloride, magnesium chloride and nickel sulphate; substances which increase the developing speed, such as glycerol, polyethylene glycol, urea, allylthiourea; stabilizers, such as thiourea and naphthalenel,3,6-trisulphonic acid or one of its salts; and substances which improve the shade of the azo-dyestuif formed upon development, such as 2-hydroxymethylbenzimidazole.
• metal salts such as zinc chloride, magnesium chloride and nickel sulphate
• substances which increase the developing speed such as glycerol, polyethylene glycol, urea, allylthiourea
• stabilizers such as thiourea and naphthalenel,3,6-trisulphonic acid or one of its salts
• substances which improve the shade of the azo-dyestuif formed upon development such as 2-hydroxymethylbenzimidazole.
• the heat-developable two-component diazotype paper according to the invention should contain a small quantity of water in order to ensure good development.
• Example I White base-paper of weight g./m. and suitable for the diazotype process, which has been pre-coated with an aqueous silica dispersion and dried, is sensitized with a liquid containing:
• the light-sensitive layer contains about 3 g. of polymer per m.
• the intermediate layer weighs 0.5-0.7 g./m.
• the material obtained is coated with a dry, solid, light-transmitting layer which contains acid-neutralizing material, by applying on the intermediate layer a layer of 10 to 15 g./m. of a liquid containing:
• a sheet of the diazotype paper thus produced is imagewise exposed in contact underneath a transparent ink drawing until underneath the white portions of the drawmg all the diazo compound has bleached out, and is then developed by guiding it round a metal cylinder having a temperature of C., which cylinder rotates with a circumferential speed of about 1.5 m./min., while the sheet lies with its back against the cylinder and is in contact with the cylinder over a distance of about 10 cm. Every part of the sheet is thus heated for about 4 seconds.
• the copy obtain-ed shows a strong violet-blue azo-dyestuff image on a clear white background.
• the image side of the copy can readily be written on with pencil, fountain-pen, and ballpointpen.
• Copies on this diazotype paper can also be developed by exposure to ammonia vapour, the sheet to be developed being turned with the paper side towards the source of ammonia.
• the diazotype paper has good keeping qualities.
• Example 11 White base-paper of weight 80 g./m. and suitable for the diazotype process, which has been pre-co-ated with an aqueous dispersion of polyvinyl acetate and dried, is coated with a light-sensitive layer by treating it on the pre-coated side with a liquid containing:
• the light-sensitive layer contains about 4 g. of polymer per m
• an intermediate layer is now applied by spreading on it a thin layer of a solution of:
• a light-transmitting, dry, solid layer which contains an acid-neutralizing organic material.
• the intermediate layer weighs about 40 g. of the N-(alkylcarbonylamido) ethyl-N-ethanolamine Nalcamine A.12 (melting point 35 C.)
• a sheet of the highly light-sensitive diazotype material thus obtained is imagewise exposed until underneath the white portions of the original all the diazo compound has bleached out, and is then developed by guiding it round a metal cylinder having a temperature of 135 C., which cylinder rotates with a speed of about 1.8 m./min., while the sheet lies with its light-sensitive side against the cylinder and is in contact with the cylinder over a distance of 10 cm. Every part of the sheet is thus heated for about 3 and /3 seconds.
• the copy obtained shows a strong violet-blue azo-dyestuif image on a white background.
• Development with the aid of ammonia vapour also yields a strong violet-blue azo-dyestuff image.
• the diazotype paper has good keeping qualities.
• Example III White base-paper of weight 80 g./m. and suitable for the diazotype process, which has been pro-coated with the aqueous butadiene-acrylonitrile copolymer dispersion Chemigum 245 CH8 and dried, is sensitized with a liquid containing:
• the light-sensitive layer contains g. of polymer per m.
• the diazotype paper has a moisture content of about 2.5%.
• the dry light-sensitive layer is treated with a solution of:
• a dry, solid, light-transmitting layer is formed on the intermediate layer by application of a liquid containing:
• a sheet of the highly light-sensitive diazotype material thus obtained is imagewise exposed and developed as in Example I. It shows a strong dark-blue azo-dyestulf image.
• the diazotype paper has reasonable keeping qualities.
• Example IV White base-paper of weight 70 g./m. and suitable for the diazotype process, which has been pre-c-oated with an aqueous silica dispersion and then dried, is sensitized with a liquid containing:
• the light-sensitive layer contains about 3 g. of polymer per m.
• the diazotype paper has a moisture content of about 4%.
• a thin film of polyvinyl acetate has been formed on the light-sensitive layer, which film firmly adheres to the light-sensitive layer. It weighs about 0.5 g./m.
• a layer which contains an acid-neutralizing organic material from a liquid containing:
• a sheet of the diazotype paper thus obtained is imagewise exposed and developed as in Example II.
• the copy shows a violet image on a white background.
• Development with ammonia vapour also yields a violet image on a white background.
• the diazotype paper has excellent keeping qualities.
• Example V White paper of weight g./m. which is coated on one side with a cellulose acetate film layer (approximately 50% by weight of combined acetic acid) having a thickness of about 10 microns, which is fixed to the paper by means of an adhesive, is coated on the side of the cellulose acetate layer with a light-sensitive'layer by treatment with a solution containing:
• the light-sensitive layer contains about 2 g. of polystyrene per m? and about 2 g. of water per m.
• an intermediate layer is ap- 1 1 plied by spreading on it a thin layer of a solution containing:
• Example I On the intermediate layer, which weighs about 1 g./m. is applied the light-transmitting, dry, solid layer described in Example I, which contains an acid-neutralizing organic material.
• a sheet of the highly light-sensitive diazotype material thus obtained is imagewise exposed and developed as in Example II.
• the copy obtained shows a violet-blue image on a white background.
• the diazotype paper has good keeping qualities.
• Example VI White base-paper of weight 70 g./m. and suitable for the diazotype process, which has been pre-coated with the aqueous n-butyl-methacrylate dispersion Plextol P2n and dried, is sensitized with a liquid containing:
• the light-sensitive layer contains about 3 g. of polymer per m.
• a dry solid layer which contains-an acid-neutralizing organic material, is applied by treatment with a liquid containing:
• a sheet of the diazotype paper thus obtained is imagewise exposed and developed as in Example I.
• the copy shows a violet-blue azo-dyestutf image on a white background.
• the diazotype paper has good keeping qualities.
• Example VII White base-paper of weight 70 g./m. and suitable for the diazotype process, which has been pre-coated with the aqueous polyvinylidene chloride copolymer dispersion Saran F. l22A.15 and then dried, is sensitized with a liquid containing:
• the dry light-sensitive layer contains about 5 g. of polyvinyl acetate per m.
• an intermediate layer is applied by spreading on it a thin layer of a solution containing:
• Example VIII White base-paper of weight 70 -g./m. and suitable for the diazotype process, which has been pre-coated with an aqueous silica dispersion, is sensitized with a liquid containing:
• the dry light-sensitive layer contains about 4 g. of polymer per m.
• Example III On the intermediate layer is applied the dry, solid, light transmitting layer described in Example III, containing acid-neutralizing organic material.
• a sheet of the highly light-sensitive diazotype paper thus obtained is imagewise exposed and developed as in Example I.
• the copy shows a strong violet-blue image on a white background.
• the diazotype paper has reasonable keeping qualities.
• Example IX White base-paper of weight 70 .g./m. and suitable for the diazotype process which has been pre-coated with an aqueous silica dispersion and dried, is sensitized with a liquid containing:
• an intermediate layer is formed by treatment with a solution of 25 g. of the copolymer Plexigum M. 265 containing predominantly polymethylmethacrylate in 1000 ml. of acetone and drying, as a result of which an intermediate layer of about 1 g./m. is formed.
• Example III which contains an acid-neutralizing organic material.
• a sheet of the highly light-sensitive diazotype paper thus obtained is imagewise exposed and developed as in Example I.
• a copy with a strong violet-blue azo-dyestuff l3 image on a white background is obtained, which copy can readily be written on.
• Example X White -base-paper of weight 70 g./n1. and suitable for the diazotype process, which has been pre-ooa ted with an aqueous silica dispersion and dried, is sensitized with a liquid containing:
• an intermediate layer of about 1.5 g. is formed by treatment with a solution of:
• Example III which contains acid-neutralizing organic material, is applied on the intermediate layer.
• a sheet of the satisfactorily light-sensitive diazotype paper thus obtained is imagewise exposed and developed as in Example II.
• the copy shows a violet-blue image on a white background.
• Example XI White base-paper of weight 70 g./tm. and suitable for the diazotype process is sensitized with a liquid containing:
• this intermediate 'layer is coated with a layer in which acid-neutralizing organic material is present, by treatment with a liquid containing:
• a sheet of the diazotype paper thus obtained is imagewise exposed and developer as in Example I.
• the copy shows a violet-blue azo-dyestutf image on a white background.
• Example XII White base-paper of weight 70 g./m. and suitable for the diazotype process, which has been pre-coated with an aqueous silica dispersion and dried, is sensitized with a liquid containing:
• the dry light-sensitive layer contains about 4 g. of polyvinyl acetate per m.
• an intermediate layer of about 1 g./m. is formed by treating it with a solution of:
• a layer containing acidneutralizing organic material is applied by treating it with a liquid containing:
• a sheet of the diazotype paper thus obtained is imagewise exposed and developed as in Example II.
• the copy shows a blue-green image on a white background.
• Example XIII White base-paper of 70 g./m. for the diazotype process, which has been pre-coated with an aqueous dispersion of silica and dried, is sensitized with the sensitizing liquid described in Example XII and dried.
• a sheet of the diazotype paper thus obtained is imagewise exposed and developed as in Example I.
• the copy obtained shows a blue-green image on a white background.
• Example XIV and dried.
• the dry light-sensitive layer contains about 4 g. of polymer per m.
• the dry light-sensitive layer is provided with an intermediate layer and a top layer containing acid-neutralizing material, as described in Example III.
• the diazotype paper has reasonable keeping qualities.
• a heat-developable diazotype material comprising a support carrying in cohering superposed relation on a side thereof (a) a light-sensitive two-component diazotype layer containing a light-sensitive diazo compound, an azo component capable of coupling with said compound to form an azo dyestulf and a substance preventing coupling of said component with said compound,
• thermoplastic film layer holding said agent inaccessible to said substance at normal atmospheric temperatures, said agent being in liquid state upon a heating of said layers insufficient to pyrolyze said diazo compound, and said film layer upon such heating melting and admitting said agent in liquid state into said light-sensitive layer to bring about said coupling.
• a diazotype material according to claim 1 said support being a paper support carrying said light-sensitive layer next to a surface thereof, said support and said light-sensitive layer being permeable by a gas capable of reacting with said substance, to render said substance incapable of preventing said' coupling, whereby after an imagewise exposure of the light-sensitive layer to actinic light an image of said dyestuff may be developed therein either by said heating or by contacting said support with said gas.
• a diazotype material according to claim 1 said support being paper carrying next to and between its surface and said light-sensitive layer a coating inhibiting penetration of said diazo compound and said azo component into the paper.
• a diazotype material according to claim 1 said light-sensitive layer containing, in addition to said diazo compound, said azo component and said substance, -finely divided solid particles rendering said light-sensitive layer quickly permeable by said agent in liquid state.
• a diazotype material according to claim 4 said solid particles lbeing particles having an average size of about 0.1-3 microns, of a thermoplastic high-molecular polymer of an olefinically unsaturaated compound having a terminal methylene group, and being present in a quantity of 1-6 grams per square meter of said lightsensitive layer.
• a diazotype material according to claim 1 said film layer being a continuous thin layer having a weight not exceeding 4 g./rn.. of a polymeric substance selected from the group consisting of hydrophobic polymers of olefinically unsaturated compounds having tenminal methylene group, hydrophobic cellulose esters and ethers, and mixtures thereof.
• a diazotype material according to claim 5 said film layer being a continuous thin layer formed 'by coating and drying upon said light-sensitive layer a solution of a polymeric substance selected from the group consisting of hydrophobic polymers of olefinically unsaturated compounds having terminal methylene groups,
• a diazotype material according to claim 7, the polymer in said light-sensitive layer comprising a polyvinyl acetate and having a molecular weight of at least 500,000 and an average particle size of 0.8-3 microns, and said polymeric substance comprising a polyvinyl acetate and having a molecular weight greater than that of the polymer in said light-sensitive layer.
• a diazotype material according to claim 1 said substance being an acidic compound and said agent being a normally solid organic material that melts at a temperature below C. and is capable in liquid state of neutralizing said acidic compound.
• a diazotype material according to claim 1 said developer layer forming an outer surface of said material, being pervious to the light to which said diazo compound is sensitive, being dry and solid at room temperature, and comprising a mixture of said agent with a finely divided substantially inert solid rendering said outer surface amenable to being written upon.
• a heat-developable two-component diazotype paper comprising a paper support carrying thereon a lightsensitive layer which contains a diazonium compound, an azo component capable of coupling with said compound to form an azo dyestufi and an acidic compound effective at room temperature to prevent coupling of said component with said diazonium compound, the said constit-uents being disposed in a liquid permeable layer structure constituted by 16 grams per square meter of said layer of a finely-divided thermoplastic high-molecular polymer of an olefinically unsaturated compound having a terminal methylene group; superimposed upon the said layer a continuous thin hydrophoibic thermoplastic film layer having a weight not exceeding 4 g./m.
• a layer which is pervious to light to which said diazonium compound is sensitive is dry and solid at room temperature, and comprises a mix ture of a finely-divided substantially inert solid and a normally solid acid-neutralizing organic material that melts at a temperature below 100 C.
• a heat-developable two-component diazotype paper comprising a paper support carrying thereon a lightsensitive layer which contains a diazonium compound, an azo component capable of coupling with said compound to form an azo dyestuif and an acidic com pound effective at room temperature to prevent coupling of said component with said diazonium compound, the said constituents being (disposed in a liquid permeable layer structure constituted by 1-6 grams per square meter of said layer of a finely-divided thermoplastic highrnolecul-ar polymer of an olefinically unsaturated compound having a terminal methylene group which polymer is attacked by a solvent for polyvinyl acetate; superimposed upon the said layer a continuous thin hydrophobic thermoplastic film layer having a Weight not exceeding 4 g./m.
• a layer which is pervious to light to which said diazonium compound is sensitive is dry and solid at room temperature, and comprises a mixture of a finely-divided substantially inert solid and a normally solid acid-neutralizing organic material that melts at a temperature below 100 C.
• a heat-developable two-component diazotype paper said layer structure being a product of the drying of an acid aqueous dispelrison of a finely-divided polyvinyl acetate having a molecular weight of at least 500,000 and an average particle size of 0.8-3 microns; said film layer being a product of the drying of a solution of said polymeric substance in a solvent for polyvinyl acetate in which said diazonium compound, said azo component and said acidic compound do not appreciably dissolve.
• a heat-developable diazotype material comprising a support carrying in cohering superposed relation on a side thereof (a) a light-sensitive two-component diazotype layer containing a light-sensitive diazo compound, an azo coupling component capable of coupling with said compound to form an azo dyestutf, an acidic compound preventing coupling of said component with said diazo compound, and finely divided solid particles rendering said layer quickly permeable by liquid,
• a developer layer over the outer side of said lightsensitive layer, said developer layer being pervious to the light to which said diazo compound is sensitive, being dry and solid at room temperature, and containing a N-(alkylcarbonylamido) ethyl-N-ethanolamine having an .alkyl radical of 6-18 carbon atoms, which amine melts at a temperature below C. and is capable in liquid state of neutralizing said acidic compound to render the latter incapable of preventing said coupling, and
• thermoplastic film layer holding said amine inaccessible to said light-sensitive layer at normal atmospheric temperatures, said film layer being composed essentially of a polymeric substance selected from the group consisting of hydrophobic polymers of olefinically unsaturated compounds having terminal methylene groups, hydrophobic cellulose esters and ethers, and mixtures thereof,

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
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• General Physics & Mathematics (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Heat Sensitive Colour Forming Recording (AREA)

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• 0
  • DE DENDAT1251655D patent/DE1251655B/de active Pending
  • NL NL272831D patent/NL272831A/xx unknown
  • BE BE626167D patent/BE626167A/xx unknown
• 1962
  • 1962-12-14 GB GB47343/62A patent/GB983799A/en not_active Expired
  • 1962-12-19 US US245644A patent/US3284201A/en not_active Expired - Lifetime
  • 1962-12-20 CH CH1497862A patent/CH434974A/de unknown
  • 1962-12-21 ES ES283593A patent/ES283593A1/es not_active Expired
  • 1962-12-21 SE SE13890/62A patent/SE302406B/xx unknown

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