US3615537A - Heat-developable diazotype material - Google Patents

Heat-developable diazotype material Download PDF

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US3615537A
US3615537A US685287A US3615537DA US3615537A US 3615537 A US3615537 A US 3615537A US 685287 A US685287 A US 685287A US 3615537D A US3615537D A US 3615537DA US 3615537 A US3615537 A US 3615537A
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diazo
coupling
compound
heat
type material
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Leonardus Jacobus Anton Giesen
Hubertus Wilhelmus Hen Roncken
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Van der Grinten NV
Canon Production Printing Holding BV
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Oce Van der Grinten NV
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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
    • G03C1/58—Coupling substances therefor

Definitions

  • Diazo-type material readily developable by heat, having good keeping quality, and producible economically by aqueous coating techniques, comprises a light-sensitive layer containing, with a diazo compound, an acid-reacting stabilizer and a water-soluble hydrophilic organic binder, a substantially water insoluble acylacetamide as azo-coupling component and a substantially water insoluble developing agent, each dispersed as particles of .01-10 microns average size, the developing agent when heated above 100C.
  • acylacetamide melting above 50 C. and having solubility of less than 1X10 mol/liter in water at 20 C.
  • the acylacetamide is yellow-coupling. Its use with a blue-coupling compound provides material that develops a black image, as by the use of dispersed particles of a N,N'-bis(acylacet)-alkyl-enediamine with 2,3-dihydroxynaphthalene-6-sulfonic acid or a salt thereof.
  • This invention relates to new and improved heat-developable diazo-type material.
  • a light-sensitive layer formed on a support contains a diazo compound, an azo-coupling component, a stabilizing acid or similar acid-reacting component (which counteracts decomposition of the diazo compound as well as premature coupling of diazo compound and azo-coupling component), and a substance which promotes the coupling reaction upon heating of the material-called the developing agent, all of which are present on the support in such a condition that the coupling reaction proceeds readily only if the material is heated to 100 l 50 C.
  • Heat-developable one-layer materials are known the light sensitive layer of which contains, in the form of dispersed finely divided particles, a developing agent which dissolves less than 2 g./liter in water of 20 C. and upon heating creates a medium in which coupling of the diazo compound and the azo-coupling component is possible.
  • the salt contains at least two cations derived from an amine conforming to the above definitron.
  • Japanese Pat. application 7832/6l mentions wax-enveloped barium hydroxide particles as a developing agent for heatdevelopable diazo-type material.
  • lrish Pat. application 1265/63 proposes the use, as a dispersed developing agent in heat-developable diazo-type material, of water-insoluble particles obtained by adding a base or a basic-reacting salt to a melt or a solution of a resin or a wax (which resin or wax may carry carboxyl groups) and isolating the product thus obtained in the form of fine particles.
  • Dutch Pat. application 6,600,540 describes the use of complex compounds of a substance having an amine function with a substance having an acid function as water-insoluble developing agents in heat-developable diazo-type material.
  • the substance having the amine function may be a resis (e.g. an aminoplast), a copolymer of styrene with divinylbenzene into which aminogroups have been introduced, or an aliphatic or aromatic amine.
  • the substance having the acid function may be a polymer carrying carboxyl groups, a fatty acid, a synthetic wax carrying carboxyl groups, an aliphatic or aromatic dicarboxylic acid, or a resin of the phenolformaldehyde type, capable of cation-exchange.
  • a hydrophilic organic binder is used in addition to the developing agent, the diazo compound, the azo-coupling component, and an acid-reacting compound. It may also be advantageous to incorporate in such materials other auxiliary agents known to be useful in one and two-component diazo-type materials.
  • black-developing diazo-type materials areproduced by incorporating in the material a yellow-coupling azo-component (a so-called shading component) in addition to a blue-coupling azo-component.
  • the shading component as a rule, possesses a considerably higher coupling activity than the blue-coupling azocomponent.
  • the outstanding blue-coupling azo-component is 2,3-dihydroxynaphthalene--sulfonic acid which may or may not be in the form of a water-soluble salt).
  • 2,3- dihydroxynaphthalene, 2,7-dihydroxynaphthalene-3,6-disulfonic acid, and the B-ethanolamide of Z-hydroxynaphthalene- 3-carboxylic acid are blue'coupling azo-components of practical importance.
  • a shading component frequently used in the two-component diazo-type process is acetoacetanilide.
  • Heat-developable one-layer diazo-type material which, upon development, yields black azo-dyestuff images has usually been composed in the same way as black-developing conventional two-component diazo-type material. Up to the present, however, such a heat-developable diazo-type material which, as to light-sensitivity, keeping quality, and cost, can bear comparison with conventional black-developing twocomponent diazo-type material is neither known from the literature nor commercially available.
  • French Pat. Specification 1,249,913 described heatdevelopable diazo-type material which contains an acid having a dissociation constant greater than 1X10 as the stabilizer, with urea, thiourea or an alkyl derivative thereof as the developing agent.
  • the azo-coupling component may be, for instance, 2,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene-6-sulfonic acid, l-hydroxynaphthalene-4-sulfonic acid, phlorogucinol, acetoacetanilide, or l-(4'-ethoxycarbonylphenyl)-3-dodecylpyrazolone(5).
  • the azo-coupling components 2,3-dihydroxynaphthalene and l-(4'-ethoxycarbonyl-phenyl)-3-dodecylpyrazolone(5) are not readily water soluble. They are therefore dissolved in an organic solvent and this solution is suspended in an aqueous pretreatment or sensitizing liquid. Material prepared according to French Pat. Specification 1,249,9l3 with application of the said nonreadily soluble azo-coupling components has insufficient keeping quality.
  • the object of the present invention is to provide a diazotype material which readily develops upon heating and has good keeping quality, and whose light-sensitive layer contains an acylacetamide of high coupling activity as a yellowcoupling azo-component.
  • the heat-developable diazo-type material of this invention comprises a support carrying thereon a light-sensitive layer which contains'a diazo compound, an azo-coupling component, an acid-reacting compound, a water-soluble hydrophilic organic binder, and a developing agent; the developing agent being a compound (advantageously, a reaction product of an organic amine and an organic dicarboxylic acid, such as products of this nature disclosed in the aforementioned Dutch Pat. Application 6,402,452 or Belgian Pat.
  • d. is present in the layer in the form of dispersed particles having an average size between 0.1 and 10 microns. 4
  • the present invention furnishes the possibility of producing in a simple and consequently inexpensive way heat-developable diazo-type material having good keeping quality.
  • This diazo-type material if it contains only the acylacetamide as its azo-coupling component, yields upon imagewise exposure and heating to IOU-150 C. copies having a yellow azo-dyestuff image which has high absorption for the U.V.-radiation (3,6004,400 AU) commonly applied in the diazo-type process. If, however, a quantity of a further azocoupling component is used in the material, the copies may shown azo-dyestuff images of a different shade.
  • a diazotype material according to the invention which develops black upon heating can be obtained by incorporating an appropriate quantity of a blue-coupling azo-component in the material.
  • acyl group of the acylacetamides which are suitable for application in the diazo-type material according to the invention may be widely varied.
  • Practical acyl groups to be mentioned are, for instance: acetyl, propionyl, butyryl, pivaloyl, chloroacetyl, phenacetyl, stearoyl, benzoyl, naphthoyl, furoyl, 2,5-diethoxybenzoyl, Z-methoxybenzoyl, benzofuroyl. and thiophenylcarbonyl.
  • the amido residue is derived from a primary amine having a molecular weight of at least I50. (If the amine is polyvalent and carries more than one acylaceto group, for the calculation of the molecular'weight of the amine from which the amido residue has been derived the further acylacetamino groups are looked upon as substituents to the hydrocarbon radical combined with the first amino group).
  • Suitable amines are, for instance: decylamine, dodecylamine, hexadecylamine, octadecylamine, 9-octadecenylamine, 9,l2-octadecadienylmaine, 6-(phenyl)hexylamine, aniline derivatives carrying an acylamino group and possibly one or more alkyl, alkoxy, or halogen substituents to the phenyl nucleus, 4-dodecylaniline, 4-phenyland 4-tolylthio-anilines the phenyl nuclea of which may carry further substituents, such as alkoxy, alkyl or acylamino, heterocyclic amines such as 2-amino-6ethoxybenzothiazole.
  • Polyvalent amines such as hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, p-menthane-l,8-diamine, and 3,3 -diamino-dipropylamine, are also eminently suitable for the preparation of water-insoluble acylacetamides which can be applied in the diazo-type material according to the invention, provided that in all the amino groups an acylaceto radical is introduced or that in one of the groups an acylaceto radical is present and the other amino groups are substituted in such a way that they show no longer a marked basic character, for instance because they carry an electronegative substituent such as an acyl group or a phenyl group.
  • Suitable acylacetamides can be obtained from the amines mentioned above by reacting them with an alkyl ester of an acylacetic acid or with diketene.
  • acetoacetamides which can be obtained very easily by reacting a suitable primary amine with diketene.
  • the acylacetamides have to melt above 50 C., preferably above C., because otherwise the particlelike division in which they have to be present in the light-sensitive layer is lost too easily during the drying process(es) which is (are) required in making the diazo-type material.
  • the diazo-type material according to the invention has better keeping quality according as the acylacetamide has lower water-solubility and lower coupling activity.
  • acylacetamide does not dissolve completely or does not give a clear solution
  • a new solution is prepared which contains lXiO mol of the acylacetamide per liter of ethanol. All the acylacetamides, so far known to the applicants, dissolve more than 1X10" moi/litre in ethanol. If, on dilution of 1 ml. of this solution to 100 ml with distilled water, the acylacetamide precipitates, it may be assumed to dissolve less than lXlO mol/liter in water. Successively, l 2, and 3 ml. of the alcoholic solution of the acylacetamide are diluted to I ml. with distilled water.
  • the mixture is further diluted with distilled water until the concentration falls within the desired range. From the E- max value thus obtained the molarity of the undiluted solution is calculated with the formula.
  • d represents the optical density found of the dilute saturated solution of the azo-coupling component
  • a is the dilution factor
  • M is the molecular weight of the azo-coupling component
  • E is the molar extinction
  • l is the thickness of the layer of the liquid measured (i.e. the length of the path of the measuring light trough the cell).
  • acylacetamide shows no selective spectrum
  • its watersolubility can be determined as follows, provided its solubility in ethanol (96 percent) amounts to at least 1X10 mol/liter. Three solutions are prepared:
  • the nondissolved substance is filtered off with a porcelain filter crucible having an average pore-size of 6 microns.
  • 5 ml. of the filtrate is mixed with 20 ml. of solution B and 2 ml. of solution C., and kept in the dark for 20 hours at a temperature of 20 C. Then the volume of the reaction mixture is brought up to 50 ml. with solution D and the optical density (O.D.2) at the A max is determined.
  • diethoxy-aniline 28 I70- l 74 N-acetoacet-4-benzolamino-2,5-di-nbutoxyaniline l5 l30-l 32 N-acetoacet-4-benzoylamino-S-methoxy- Z-chloroaniline 78 174-170 N-acetoacett-benzoylamino-S-methoxy- 2N-methyl-N-ethoxycarbony laminoaniline 200 lbl-lott N-scetoucet-5-benzoylnminc-2.4-
  • acetoacetamides which can be applied in the diazo-type material according to the invention must, as a rule, be free from groups which highly promote the solubility in water, such as sulfonic acid groups and sulfonyl radicals.
  • Diazo-type material according to the invention which contains an acylacetamide dissolving less than 0.25X20 10" mol/liter in water of 20 C. always shows acceptable keeping quality, if the coupling activity of the acylacetamide, measured in vitro at 20 C. according to the usual method, is.not more than 20 times greater than the coupling activity of acetoacetanilide. Diazo-type materials having excellent keeping quality can also be obtained using acylacetamides with higher coupling activity, provided their water-solubility is less than lXlO mol/liter.
  • the acylacetamides are applied in the diazo-type material according to the invention in the form of dispersed particles having an average size between 0.1 and 10 microns.
  • the azo-coupling component is dispersed, preferably in an aqueous liquid.
  • a hydrophilic organic binder such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, hydrolysed starch, or high molecular epoxyethane polymers is added.
  • a hydrophilic organic binder such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, hydrolysed starch, or high molecular epoxyethane polymers is added.
  • binders can also be used.
  • the treatment of the diazo-type material with the dispersion of the acylacetamide can be effected before or after sensitization. However, it is preferred to form the light-sensitive layer in a single treatment with the aid of a liquid which contains all the required ingredients.
  • acylacetamides which can be applied in the diazo-type material according to the invention with good results
  • the following compounds stand out as being particularly suitable: N-acetoacet-Z,4,6-tribromoaniline, N- acetoacet-4-acetoacet-2-methylaniline, N-benzoylacet-4- benzoylamino-2,S-dimethoxyaniline, N-acetoacet-4- benzoylamino-2,S-diethoxyaniline, N-benzoylacet-42,5-
  • the most attractive compounds are the N,N-bis(acetoacet) derivatives of alkylene diamines with an alkylene group having at least eight carbon atoms. They are fairly accessible, show good dispersibility in water, and the materials made with them have very good keeping quality.
  • azo-coupling components can be employed in addition to the acylacetamide. These components may be water-soluble or water-insoluble, and may or may not be present in the form of dispersed particles.
  • a blue-coupling azo-component is used besides the acylacetamide.
  • This blue-coupler is preferably 2,3-dihydroxy-naphthalene-6sulfonic acid or a salt thereof.
  • fairly black-developing diazo-type materials according to the invention may also be prepared using other blue-couplers, such as the B-ethanolamide of 2-hydroxynaphthalene-3-carboxylic acid.
  • N ,N-bis(acetoacet)alkylene diamines referred to above with 2,3-dihydroxynaphthalene-6-sulfonic acid may lead to a very fine black-developing material.
  • diazo compounds which are useful in the conventional two-component diazo-type process can be taken.
  • Very suitable diazo compounds are e.g.: 4-diazo-N,N- dimethyl-aniline, 4-diazo-N,N-diethylaniline, 4-diazo-N-ehtyl- N-2-hydroxyaethylaniline, 4-diazo-3-ethoxy-N,N- diethylaniline, 4-diazo-N-methyl-N-cyclohexylaniline, 4- diazo-N-ethyl-N-benzylaniline, 4-diazo-5-chloro-2ethoxy-N- methyl-N-benzylaniline, 4-diazo-2,S-diethoxy-N-ethyl-N- benzylaniline, 4-diazo-2,5-diethoxy-N.N-bis(2'-acetoxyehtyl)-aniline
  • acids and acid-reacting salts such as tartaric acid, citric acid, boric acid, maleic acid, gluconic acid, oxalic acid, phosphoric acid, benzene sulfonic acid, potassium hydrogen sulfate, malic acid, aluminum sulfate, and zinc chloride can be used in the diazotype material according to the invention.
  • a stabilizer of the naphthalene sulfonic acid type can advantageously be added to the light-sensitive layer, e.g, naphthalene-l-sulfonic acid, naphthalene-2-sulfonic acid, naphthalene-l,S-disulfonic acid, naphthalene-2,6-disulfonic acid, naphthalene-2,7-disulfonic acid, naphthalene-1,3,6- trisulfonic acid, l-hydroxynaphthalene-Z-sulfonic acid, 1- hydroxynaphthalene 3-sulfonic acid, l-hydroxynaphthalene- 4-sulfonic acid, l-hydroxynaphthalene-5-sulfonic acid, 1- hydroxynaphthalene-8-sulfonic acid, Z-hydorxynaphthalenel-sulfonic acid, 2-hydroxynaphthalene-fi-sulfonic
  • these stabilizers are used as watersoluble salts, e.g. as sodium salts.
  • the substance which upon heating creates the medium in which coupling of the diazo compound and the azo-coupling component can occur is preferably a developing agent according to the Belgian Pat. Application No. 29,782.
  • good materials can also be prepared using other water-insoluble developing agents.
  • the support of the diazo-type material according to the invention may be paper, tracing paper, tracing linen, opaque linen, synthetic paper, metal foils, glass fabric, polyester film, and the like.
  • the diazo-type material according to the invention may also contain mixtures of water-insoluble acylacetamides and that, besides the acylacetamide, very different diazo compounds, azo-coupling components, acidreacting compounds, developing agents, binders, and further auxiliary agents can be used.
  • binders polyvinyl alcohol, polyvinyl pyrrolidone, and hydrolysed potato starch are chiefly used in the examples. These binders are always added to the coating liquids in the form of an aqueous solution. Unless otherwise mentioned, it is to be understood that:
  • P.V.A.-solution is an aqueous solution which contains g./l. of a low-viscous polyvinyl alcohol having a degree of hydrolysis of 98.5 percent;
  • P.V.P.-solution is an aqueous solution which contains 200 g./l. ofa polyvinyl pyrrolidone with K-value 30 (mol. weight about 40,000);
  • starch solution is an aqueous solution which contains 100 g./l. of hydrolysed potato starch.
  • wetting agent a solution which contains I00 ml./l. of a condensate of one mole of an aromatic amine with l0 moles of epoxyethane.
  • Dispersions can be prepared in many ways.
  • the dispersions according to the examples have always been prepared by grinding the given mixture of substances in a ball-mill for 24 hours. Thus finely divided particles having an average size of l-7 microns are obtained, dependent, inter alia, on the substance to be ground and the auxiliary agents which are present in the grinding liquid.
  • an azo-coupling component dispersion means an aqueous dispersion which contains per litre 100 g. of the insoluble yellow-coupling azo-components mentioned in the example 20 g. of polyvinyl alcohol (low-viscous, degree of hydrolysis 98.5 percent) and 40 g. of polyvinyl pyrrolidone K-value 30).
  • a strip of both sheets is kept for 24 hours in a light-tight room with a temperature of 35 C. and a relative humidity of 75 percent. Then the strips are exposed until all the diazo compound has bleached out. On strip A a light violet fog is observed as a result of a small premature azo-dyestuff formation. On strip B a conspicuous yellow-brown fog is present because of a rather strong premature coupling between the yellowcoupling azo-component and the diazo compound. Light-sensitive paper B thus has considerably lower keeping quality than light-sensitive paper A.
  • a second strip of the sheets A and B is imagewise exposed underneath a transparent original until underneath the transparent portions of the original all the diazo compound has bleached out.
  • the copy is developed by bringing its face in contact for ID seconds with a metal surface with a temperature of l50 C.
  • the copies show a brown-black image on a clear white background.
  • silica (2-4 microns) 200 ml. of starch solution 250 ml. of P.V.P.-solution and 300 ml. of water 400 ml. of this dispersion is diluted with water to make 700 After the dispersion has been made homogeneous again,
  • white base-paper of 80 glm for the diazo-type process is sensitized. Per m O,4 millimole of diazo compound is used. After the sensitization the paper is dried to a moisture content of 4 percent. A sheet of the diazo-type paper thus obtained is imagewise exposed underneath an ink drawing on tracing paper until underneath the transparent portions of the drawing all the diazo compound has bleached out, and is then developed as described in example I. The copy shows a black image on a white background.
  • a dispersion is prepared from a mixture 150 g. of melamine sebacate 5 g. of oxalic acid 200 ml. of P.V.A.-solution 240 ml. of P.V.P.-solution and 375 ml. ofwater To 500 ml. of this dispersion 200 ml. of water is added,
  • the dispersion thus obtained is made homogeneous. and thin translucent base paper of 60 g/m for the diazo-type process is sensitized with the dispersion. After the sensitization the paper is dried. A sheet of the diazo-type paper thus prepared is imagewise exposed underneath a pencil drawing on tracing paper until underneath the transparent portions of the drawing the diazo compound has largely bleached out.
  • the copy is developed by guiding it with the back over a surface with a temperature of l50 C., the contacting time being 10 seconds.
  • the copy shows an intensive yellow image on a foggy yellow background. It is eminently suitable as an intermediate original for making further copies on diazo-type material.
  • a dispersion is prepared from a mixture containing:
  • the light-sensitive dispersion thus prepared is made homogeneous, after which white base paper of g/m for the diazo-type process is sensitized with the dispersion. After the sensitization the paper is dried. A sheet of the diazo-type diazonium paper thus prepared is imagewise exposed and developed as described in Example Ill. The copy shows a yellow-brown image on a foggy background.
  • the light-sensitive dispersion thus prepared is made homogeneous, after which white base paper of 80 g/m2 for the diazo-type process, which has been pretreated with noncolloidal silica, is sensitized with the dispersion. After sensitization the paper is dried. A sheet of the diazo-type paper thus obtained is imagewise exposed underneath an ink drawing on tracing paper until underneath the transparent portions of the drawing all the diazo compound has bleached out, and is then developed as described in example Ill. The copy shows a black image on a clear white background.
  • a dispersion is prepared from a mixture containing:
  • melamine sebacate g. of tartaric acid 50 g. of the sodium salt of 2-hydroxynaphthalene-hthalenc- 3,6disulfonic acid 30 g. of silica (2-4 microns) 500 ml. of P.F.A.-solution 200 ml. of a solution of 50 g. of polyvinyl pyrrolidone K-90 in 1,000 ml. of water 150 ml. ofwater 500 ml. of the dispersion thus obtained is diluted with water to make 700 ml. and then ml. of wetting agent 5 g. of diethylaminobenzene diazonium chloride/zinc chloride double salt 5 g.
  • the light-sensitive dispersion thus prepared is made homogeneous, after which white base paper of 80 g/m for the diazo-type process is sensitized with the dispersion.
  • a sheet of I the diazo-type paper thus obtained is imagewise exposed underneath an ink drawing on tracing'paper until underneath the transparent portions of the drawing all the diazo compound has bleached out, and is then developed as described in Example Ill.
  • the copy shows an orange-yellow image on a foggy background.
  • EXAMPLE vn A dispersion is prepared from a mixture containing: triazinesebacate Egg. of 2,4- dia mino-6-methyl-l ,3,5,-triazinesebacate 5 g. of citric acid v I 50 g. of the sodium salt of 2,3-dihydroxynaphthalene-6-sul- I fonic acid 12 sFi Efthioiirea 30 g. ofsilica (2-4 microns) 200 ml. ofstarch solution 250 ml. of RV .P.-solution and 250 ml. ofwater 500 ml.
  • this dispersion is diluted with water to make 750
  • white base paper of g/m for the diazo-type process a thin layer containing about 5 g. of developing agent per m is formed.
  • the paper side thus treated is sensitized with a solution containing 8 g. of 4-morpholino-2,S-diethoxybenzene diazonium chloride/zinc chloride double salt 1 g. of citric acid 250 ml. of starch solution 250 ml. ofP.V.A.-solution ml. of an azo-coupling dispersion on the basis of N- acetoacetoctadecylamine and 380 ml. of water and dried.
  • a sheet of the diazo-type paper thus obtained is imagewise exposed underneath an ink drawing on tracing paper until underneath the transparent portions of the drawing all the diazo compound has bleached out, and is then developed as described in example Ill.
  • the copy shows a blue-black image on a white background.
  • a dispersion is prepared from a mixture containing g. of melamine sebacate 5 g. of citric acid 50 g. of the sodium salt of 2,3-dihydroxynaphthalene-6-sulfonic acid 200 ml. of P.V.A.-solution 250 ml. of P.V.P.-solution 1 ml. of wetting agent 10 g. of 4-diethylaminobenzene diazonium chloride/zinc chloride souble salt and 300 ml. of water To the dispersion, thus prepared, 200 ml. of an aqueous dispersion containing 100 g./l. of N-acetoacet-4- benzolylamino-Z,S-di-n-butoxyaniline and 20 g./l. of gum arabic is added, after which the liquid thus obtained is made homogeneous.
  • V aqueous dispersion containing 100 g./l. of N-acetoacet-4- benzolylamino
  • Sized natural tracing paper of 80 g/m for the diazo-type process is sensitized with the sensitizing liquid thus prepared. After sensitization the paper is dried. A sheet of the diazotype paper thus obtained is imagewise exposed underneath an ink drawing on tracing paper until underneath the transparent portions of the drawing all the diazo compound has bleached out, and is then developed as described in example Ill. The copy shows a yellow-brown image on a white background and is eminently suitable asan intermediate original for making further copies on diazo-type material.
  • EXAMPLE lX A dispersion is prepared from a mixture containing: 200 g. of di(octadecylammonium )oxalate 15 g. of oxalic acid 400 ml. ofP.V.A.-solution 400 ml.;of water With this dispersion white base paper of 80 g/m for the diazo-type process is coated with a layer containing about 6 g. of developing agent per m2. After drying, the treated side of the paper is sensitized with a liquid containing 10 g. of 4-N,N-bis(2'-acetoxyethyl)amino-2,S-diethoxybenzene diazonium chloride/zinc chloride double salt 30 g.
  • a sheet of the diazo-type paper thus obtained is iamgewise exposed underneath an ink drawing on tracing paper until underneath the transparent portions of the drawing all the diazo compound has bleached out, and is then developed as described in example Ill.
  • the copy shows a dark violet-brown image on a white background.
  • a sheet of the diazo-type paper thus obtained is imagewise exposed underneath an ink drawing on tracing paper until underneath the transparent portions of the drawing all the diazo compound has bleached out, and is then developed as described in example Ill.
  • the copy shows a dark brown image on a clear background.
  • a sheet of the diazo-type paper thus obtained is imagewise exposed underneath an ink drawing on tracing paper until underneath the transparent portions of the drawing all the diazo compound has bleached out, and is then developed as described in example [I].
  • the copy shows a green image on a white background.
  • EXAMPLE Xll To a developing agent dispersion prepared as described in example IX 10 ml. of wetting agent and 40 ml. of an azo-coupling component dispersion on the basis of N-benzoylacet-4-benzoylamino-2,5-dimethoxyaniline are added. After homogenization of the dispersion, white base paper of 80/g/m for the diazo-type process is treated therewith. After drying, the treated side is sensitized with a sensitizing liquid as described in example XI, from which the azo-coupling component dispersion has been omitted.
  • a sheet of the diazo-type paper thus obtained is imagewise exposed underneath an ink drawing on tracing paper until underneath the transparent portions of the drawing all the diazo compound has bleached out, land is then developed as described in example Ill.
  • the copy shows a violet-brown image on a white background.
  • a heat-developable diazo-type material comprising a sheet shaped support having coated thereon so as be accessible one to another during heating a light sensitive diazo compound, an azo-coupling component, an acid-reacting compound, and a finely-divided developing agent that is substantially water-insoluble
  • said developing agent comprises a reaction product of an organic amine and an organic dicarboxylic acid, which has a solubility of less than 2 g./liter in water at 20 C.
  • the azo-coupling component comprises an acylacetamide which has the general formula R,CH,CO R R being an acyl group and R being an amido residue derived from a primary amine having a molecular weight of at least 150, and which melts above 50 C., has a solubility of less than l l0 mol/liter in water at 20 C., and is present in the form of dispersed particles having an average size between 0.l and 10 microns.
  • Heat-developable diazo-type material according to claim 1, wherein the acylacetamide is one having a solubility of less than 0.25 XlO mol/liter in water at 20 C.
  • acylacetamide is a N,N-bis(acylacet)-alkylenediamine having an alkylene group containing at least 8 C-atoms.
  • the azo-coupling component comprises, besides the acylacetamide, a quantity of a compound capable of forming a blue dyestuff by coupling with said diazo compound so that said layer when developed will give a substantially black image.
  • Heat-developable diazo-type material according to claim 1, said developing agent being a salt of melamine and an alkane dicarboxylic acid having 9-12 C atoms.
  • a heat-developable diazo-type material comprising a support carrying a light-sensitive layer which contains a lightsensitive diazo compound, an azo-coupling component capable of coupling with said diazo compound to form dyestuff giving a substantially black color, an acid-reacting compound as a stabilizer, a water-soluble hydrophilic organic binder. and as a developing agent dispersed particles of a compound which kylenediamine having an alkylene group containing at least 8 C-atoms and having a solubility of less than 0.25 l0 mol/liter in water at 20 C., said developing agent and said yellow-coupling compound each being present in said layer in the form of dispersed particles of between 0.l and 10 microns in average size.

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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)
US685287A 1966-12-02 1967-11-24 Heat-developable diazotype material Expired - Lifetime US3615537A (en)

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NL6617031A NL6617031A (enrdf_load_stackoverflow) 1966-12-02 1966-12-02

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US (1) US3615537A (enrdf_load_stackoverflow)
BE (1) BE707092A (enrdf_load_stackoverflow)
DE (1) DE1597520A1 (enrdf_load_stackoverflow)
FR (1) FR1570461A (enrdf_load_stackoverflow)
GB (1) GB1193987A (enrdf_load_stackoverflow)
NL (1) NL6617031A (enrdf_load_stackoverflow)
ZA (1) ZA6706969B (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4275137A (en) * 1974-09-13 1981-06-23 Oce-Van Der Grinten N.V. Light-sensitive diazotype material
US4400456A (en) * 1980-08-29 1983-08-23 Ricoh Co., Ltd. Thermo-developable type diazo copying material
US4497887A (en) * 1981-06-09 1985-02-05 Ricoh Compay, Ltd. Thermal development type diazo copying material with hydrophobic resin encapsulated coupler particle
US4929534A (en) * 1987-08-31 1990-05-29 Hoechst Aktiengesellschaft Positive-working photosensitive mixture and photolithographic copying material produced therefrom with o-quinone dialide sulfonyl ester and azo coupler
US5354366A (en) * 1993-09-27 1994-10-11 Deluxe Corporation Ink composition and resins and methods relating thereto
WO2002096884A3 (de) * 2001-05-25 2003-02-27 Bayer Ag Substituierte benzoylketone als herbizide wirkstoffe zur verwendung asl pflanzenbehandlungsmittel
US20030073025A1 (en) * 2001-06-01 2003-04-17 Fuji Photo Film Co., Ltd. Recording material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54136319A (en) * 1978-04-14 1979-10-23 Ricoh Co Ltd Coupling component for diazo photosensitive paper

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4275137A (en) * 1974-09-13 1981-06-23 Oce-Van Der Grinten N.V. Light-sensitive diazotype material
US4400456A (en) * 1980-08-29 1983-08-23 Ricoh Co., Ltd. Thermo-developable type diazo copying material
US4497887A (en) * 1981-06-09 1985-02-05 Ricoh Compay, Ltd. Thermal development type diazo copying material with hydrophobic resin encapsulated coupler particle
US4929534A (en) * 1987-08-31 1990-05-29 Hoechst Aktiengesellschaft Positive-working photosensitive mixture and photolithographic copying material produced therefrom with o-quinone dialide sulfonyl ester and azo coupler
US5354366A (en) * 1993-09-27 1994-10-11 Deluxe Corporation Ink composition and resins and methods relating thereto
WO2002096884A3 (de) * 2001-05-25 2003-02-27 Bayer Ag Substituierte benzoylketone als herbizide wirkstoffe zur verwendung asl pflanzenbehandlungsmittel
US20030073025A1 (en) * 2001-06-01 2003-04-17 Fuji Photo Film Co., Ltd. Recording material
US6720124B2 (en) * 2001-06-01 2004-04-13 Fuji Photo Film Co., Ltd. Recording material

Also Published As

Publication number Publication date
BE707092A (enrdf_load_stackoverflow) 1968-04-01
NL6617031A (enrdf_load_stackoverflow) 1968-06-04
DE1597520A1 (de) 1970-05-21
GB1193987A (en) 1970-06-03
FR1570461A (enrdf_load_stackoverflow) 1969-06-13
ZA6706969B (enrdf_load_stackoverflow)

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