US3820996A - Process for development of two component diazotype photosensitive materials - Google Patents

Process for development of two component diazotype photosensitive materials Download PDF

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US3820996A
US3820996A US00275071A US27507172A US3820996A US 3820996 A US3820996 A US 3820996A US 00275071 A US00275071 A US 00275071A US 27507172 A US27507172 A US 27507172A US 3820996 A US3820996 A US 3820996A
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acid
development
photosensitive
activating
carboxylic
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K Nihyakumen
T Yokoyama
Y Kamezawa
T Aizawa
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Kyocera Mita Industrial Co Ltd
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Mita Industrial Co Ltd
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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
    • G03C1/61—Compositions containing diazo compounds as photosensitive substances with non-macromolecular additives

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  • ABSTRACT A process for development of two-component diazotype photosensitive materials comprising exposing image-wise to light a photosensitive material having a two-component diazotype photosensitive layer comprising a photosensitive diazonium salt, a coupler capable of coupling with said diazonium salt and an acidic stabilizer, applying a small amount of an activating liquor to the photosensitive layer of the exposedphotosensitive material and thereafter heating the activating liquor-applied photosensitive material according to need, said activating; liquor being a solution or dispersion of a carboxylic acid salt selected from the group consisting of alkali metal carboxylates, alkaline earth metal carboxylates and mixtures thereof.
  • a so-called dry development method using a gaseous mixture of ammonia and vapor has been broadly used in diazotype reproduction employing a two-component diazotype photosensitive material having a photosensitive layer comprising a photosensitive diazonium salt, a coupler and an acidic stabilizer.
  • this dry development method since the contact of a gaseous mixture of ammonia and vapor acting as a developer with the photosensitive layer is a contact between the gas phase and the solid phase, it is necessary to supply the gaseous mixture in an amount such that the amount of ammonia is such greater than the amount required for coupling the coupler with the diazonium salt. As a result, excessive ammonia is discharged from the developing device and its nasty smell causes trouble.
  • Japanese Patent Publication No. 39-8 141/64 or No. 45235 /70 has proposed a process comprising applying a small amount of an activating liquid comprising an organic amine such as mono, diand tri-ethanolamines to an light-exposed two-component diazotype photosensitive layer, and developing the photosensitive layer by or without heating.
  • an activating liquid comprising an organic amine such as mono, diand tri-ethanolamines
  • This development method is advantageous in that the development can be accomplished, as in the dry development method, without substantial wetting of the diazotype photosensitive layer.
  • this method has a fatal defect in the point that an organic amine which is highly irritative to skins and mucous membranes and which is readily absorbed in human bodies to give harmful effects thereto must be employed.
  • ethanolamines which are amines giving the least nasty smell among organic amines, are considered to give high irritation to skins and mucous membranes and exhibit high absorption in human bodies when they are heated. Therefore, according to The Food and Drug Administration of U.S.A., it is stipulated that in ethanolamines the tolerance should be 3 ppm or less.
  • U.S.A. it is stipulated that in ethanolamines the tolerance should be 3 ppm or less.
  • the alkali metal salt or alkaline earth metal salt to be contained in the activating liquor to be used in this invention is a neutral salt (normal salt) and it is relatively stable at high temperatures, and in this point the activating liquid of this invention can be clearly distinguished from conventional aqueous solutions of organic amines or inorganic alkalis. Further, the mecha- I nism of development by the activating liquor of this invention is quite different from the development mechanism in the conventional development methods.
  • any of two-component diazotype photosensitive materials having a photosensitive layer comprising a photosensitive diazonium salt and a coupler capable of coupling with the diazonium salt may optionally be used in this invention.
  • Such photosensitive materials are readily commercially available as dry diazotype photosensitive papers.
  • the photosensitive layer of such twocomponent diazotype photosensitive material comprises as essential ingredients a light-decomposing diazonium salt, a coupler capable of coupling with said diazonium salt and an acidic stabilizer.
  • any of diazonium salts which decompose under irradiation and are capable of coupling with a coupler under the developing conditions adopted may be used in the process of this invention.
  • Typical instances of such diazonium salts are as follows:
  • X stands for an anion such as a halogen ion, a sulfuric ion or a fluoroboric ion
  • R and R which may be the same or different, designate an alkyl group which may be substituted by a halogen atom or a hydroxyl or amino group
  • Z and Y are substituents known in the art of dyestuffs as substituents on the benzene nucleus, e.g., hydrogen, halogens, alkyl groups and alkoxy groups. Specific examples of compounds of this type are as follows:
  • Para-diazodiphenylamine 4-Diazo-2,5,4-triethoxydiphenylamine 4-Diazo-2,5,4-triethoxydiphenyl 4,4 -Bis-diazo-2,2 ,5 ,5 '-tetrahydroxydiphenylmethane Bis-diazo-3 ,3 dichloro-S ,5 '-dimethoxybenzidine 4-Diazo-2,5dimethoxyphenylethylsulfide 4-Diazo-2,5-diethoxy-4-methyldiphenylsulfide Diazonium salts of the heterocyclic amine type expressed by the following general formula wherein X, Y and Z are as defined above, and B stands for O (morpholine type), -S- (thiomorpholine type), CH (phenylpiperidine type) or a direct bond (phenylpyrolidine type).
  • diazo-4-methylmercapto-N,N-dimethylaniline 2-Diazo-5-benzoylamino-N,N-dimethylaniline
  • Z-Diazo-lnaphthol-S-sulfonic acid The above-mentioned diazo compounds are used in the form of relatively stable diazonium salts, such as sulfates or hydrochlorides. They may also be used in the form of double salts with zinc chloride, tin chloride, aluminum sulfate or the like.
  • diazotates stabilized by aryl sulfonates diazonium salts of aromatic sulfonic acids
  • diazosulfonates diazonium salts of sulfonic acid acids or their alkali metal salts.
  • diazonium salts may be used singly, or mixtures of two or more of them may also be used.
  • any of couples capable of coupling with a diazonium salt such as exemplified above under development conditions adopted in this invention may be used.
  • phenol derivatives, naphthol derivatives and active methylene group-containing compounds are used.
  • Specific examples of such couplers are as follows:
  • Phenol derivatives such as pyrocatechol, resorcine, phloraglucinal, pyrogallol, resorcine monoglycol ether, meta-aminophenol, para-aminophenol, diethylaminophenol, 2,5,6-trimethylphenol, 2- hydroxymethylphenol, B-(Z-hydroxyphenyl)-propionic acid, Z-(w-phenylaminomethyl)-phenol, B-(4-methyl- 2-hydrophenol)-glutaric acid, 2,5dimethyl-6-(N- dimethylaminomethyl)-phenol, the l,3-dimethyl ether of pyrogallol, a-resorcyclic acid ethanolamine, N-lauryl-para-aminophenol, B-resorcylic acid ethanolamine, N-acyl-meta-aminophenol, meta-hydroxyacetoanilide, ortho-Nhydroxydiphenol-monoguanidine, para-N- hydroxydip
  • Hydroxynaphthalene derivatives such as 2,3-dihydroxynaphthalene, B-naphthol, a-naphthol, l,6 dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3- dihydroxynaphthalene-6-sulfonic acid, 2-naphthol-3,6- disulfonic acid, 2,7-dihydroxynaphthalene-3-sulfonic acid, 2,8-dihydroxynaphthalene-6-sulfonic acid, 1,8- dihydroxy-naphthalene-8-sulfonic acid, l,8aminonaphthol-5-sulfonic acid, 2,7-dihydroxy-3,6- disulfonic acid, 1,8-benzolyl-aminonaphthol-2-sulfonic acid, l,8-dihydroxynaphthalene-6-sulfonic acid, 2- hydroxy-3-naphthonic-acid-
  • Active methylene group-containing compounds such as l-phenyl-3-methyl-pyrazolone (5), acetoacetic acid anilide, l-phenyl-3-carboxypyrazolone, acetoacetic acid cyclohexylamide, acetoacetic acid benzylamide, cyanoacetoanilide, cyanoacetomorpholine, l (3 sulfonamide)-phenyl-3-methylpyrazolone-5, and H4- carboxy-ethylphenyl)-3-dodecyl-pyrazolone-5.
  • Couplers may be used singly, or mixtures of two or more of these compounds may be used.
  • Non-volatile or difficulty volatile, organic or inorganic acids are generally used as the acidic stabilizer (precoupling inhibitor) to be contained in the diazotype photosensitive material to be used in this invention.
  • non-volatile or difficulty volatile acid there are mentioned, for example, citric acid, tartaric acid, oxalic acid, maleic acid, malic acid, succinic acid, sulfamic acid, boric acid, phosphoric acid, etc.
  • such composition constituting the photosensitive layer of the diazotype photosensitive material to be used in this invention may further comprise an extender for improving the bondability of the composition to the substrate, the coating uniformity and water resistance. It is also possible to incorporate into such photosensitive composition additives orginarily used in the art, such as development promotors and coloring materials.
  • the extender there may be employed, for example, dextrin, polyvinyl alcohol, gum arabic, colloidal silica, and polyvinyl borate emulsion.
  • dextrin polyvinyl alcohol
  • gum arabic gum arabic
  • colloidal silica colloidal silica
  • polyvinyl borate emulsion As the development 2,5dimethyl-4- 2-methyl-5-isopropyl-4- monomethyl ether,
  • promotor there may be used, for example, glycerine,
  • coloring materials are used for the purpose of indicating the surface to be exposed to light and increasing the whiteness of the background.
  • coloring material there may be preferably used blue dyes such as Methylene Blue, Patent Blue, etc.
  • Blue dyes such as Methylene Blue, Patent Blue, etc.
  • Water and organic solvents such as alcohols, e.g., methanol and ethanol, ketones, e.g., acetones and methylethylketone, aro- 4-morpholine-.
  • matic hydrocarbons e.g., toluene and xylene
  • esters e.g., ethyl acetate and butyl acetate are used for dissolving the above ingredients of the photosensitive composition constituting the photosensitive layer.
  • Two-component diazotype photosensitive compositions suitable for attaining the objects of this invention generally contain ingredients at ratios illustrated below, through the scope of this invention is not at all limited by such illustration:
  • the above photosensitive composition is coated on a substrate such as paper, plastic film, woven fabric, nonwoven fabric or metal foil, whereby a two-component diazotype copying material is formed.
  • a two-component diazotype photosensitive material having a photosensitive layer formed by application of the abovementioned two-component diazotype photosensitive composition is exposed image-wise to light emitted from a known light source used in the diazotype reproduction, such as from a fluorescent lamp, tungsten lamp, mercury lamp, arc lamp, xenon lamp, sun-light, etc. through an original having opaque image areas and transparent or semi-transparent non-image areas; whereby a pattern consisting of a latent image composed of the undecomposed diazonium salt and a background is formed on the photosensitive layer.
  • a known light source used in the diazotype reproduction such as from a fluorescent lamp, tungsten lamp, mercury lamp, arc lamp, xenon lamp, sun-light, etc.
  • a pattern consisting of a latent image composed of the undecomposed diazonium salt and a background is formed on the photosensitive layer.
  • an activating liquor composed of a solution or dispersion of an alkali metal or alkaline earth metal salt of a carboxylic acid is applied to the photosensitive layer having a latent image consisting of the undecomposed diazonium salt.
  • Alkali metal and alkaline earth metal salts of organic compounds having at least one carboxyl group are used as far as they are soluble or dispersible in solvents to be used, and it does not matter whether they are volatile or not. In some cases, however, it is preferred that carboxylic acids are volatile and carboxylic acid salts are soluble in water.
  • carboxylic acids are volatile and carboxylic acid salts are soluble in water.
  • the alkali metal for forming a salt with such carboxylic acid there may be mentioned, for instance, potassium, sodium, lithium and rubidium, and use of sodium and potassium is especially preferred.
  • the alkaline earth metal there may be exemplified magnesium, calcium, barium, beryllium and strontium, and use of magnesium and calcium is especially preferred.
  • alkali metal and alkaline earth 'metal salts of carboxylic acids are as follows:
  • Alkali metal and alkaline earth metal salts e.g., so-
  • R is a saturated or unsaturated, straight, branched or cyclic mono-valent aliphatic groups which may have such substituents as halogen, hydroxyl, amino or sulfonic groups, M is an alkali metal or alkaline earth metal, and n is 1 or 2 indicating the valency of M;
  • alkali metal and alkaline earth metal salts of such aliphatic monocarboxylic acids as formic acid, acetic acid, propionic acid, acrylic acid, aconic'acid, acetoacetic acid, valdric acid, crotonic acid, butyric acid, undecanoic acid, butyric acid, capric acid, caprylic acid, chloroacetic acid, bromoacetic acid, trichloroacetic acid, chlorofumaric acid, cyclobutane-carboxylic acid, quinic acid, sulfoacetic acid, sorbic acid, tiglic acid.
  • aliphatic monocarboxylic acids as formic acid, acetic acid, propionic acid, acrylic acid, aconic'acid, acetoacetic acid, valdric acid, crotonic acid, butyric acid, undecanoic acid, butyric acid, capric acid, caprylic acid, chloroacetic acid, bromoacetic acid,
  • tetrolic acid vinylacetic acid, pyruvic acid, methacrylic acid, levulinic acid, caproic acid, isovaleric acid, pelargonic acid, palmitic acid, lauric acid, myristic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, tridecanoic acid, morganic acid, behenic acid, stearclic acid, glycolic acid, citric acid, tartaric acid, adipic acid, arabonic acid, alloxanic acid, saccharic acid, isovanillic acid, hydroxybutyric acid, glyceric acid, gluconic acid, diglycolic acid, citramanic acid, thioglycolic acid, desoxalic acid, lactic acid, racemic acid, mannonic acid, malic acid, leucic acid, glycine, alanine, leucine, serine, threonine, cyste
  • Sodium and potassium salts of formic acid and acetic acid are especially preferably among the abovementioned alkali metal or alkaline earth metal salts of carboxylic acids.
  • Alkali metal and alkaline earth metal salts e.g., so-
  • aliphatic polycarboxylic acids expressed by the following general formula wherein R is a saturated or unsaturated, straight, branched or cyclic poly-valent aliphatic group which may have such substituents as halogen, hydroxyl, amino or sulfonic groups, m is the valency of the aliphatic group, and M and n are as defined above;
  • alkali metal and alkaline earth metal salts of Sodium and potassium salts of oxalic acid and malonic acid are especially preferred among these alkali metal and alkaline earth metal salts of carboxylic acids.
  • Alkali metal and alkaline earth metal salts e.g., so-
  • Ar stands for a mono-valent or polyvalent aryl or aliphatic groups which may have such substituents as halogen, amino, hydroxyl, mercapto, alkyl, alkenyl, hydroxyalkyl, acyl and sulfonic groups, p is the valency of the Ar group, and M and n are defined above;
  • alkali metal and alkaline earth metal salts of such aromatic carboxylic acids as benzoic acid, phthalic acid, terephthalic acid, trimellitic acid.
  • salicylic acid acetophenone-carboxylic acid, anisic acid, aminobenzoic acid, aminocinnamic acid, propylbenzoic acid, hydroxyphthalic acid, hydroxyphenylacetic acid, cinnamic acid, chlorobenzoic acid, chlorophthalic acid, dimethoxyphthalic acid, sulfosalicylic acid, thiosalicylic acid, toluic acid, truxillic acid, tropic acid, naphthalic acid, vanillic acid, biphenyl-carboxylic acid, phenyl-acetic acid, phenylsuccinylacetic acid, phenyl-lactic acid, benzenetetracarboxylic acid, phenylbutyric acid, benzoylbenzoic acid, benzoylglucoli
  • Sodium and potassium salts of benzoic acid and salicylic acid are especially preferred among the above-mentioned alkali metal and alkaline earth metal salts of aromatic carboxylic acids.
  • Alkali metal and alkaline earth metal salts of heterocyclic monoand poly-carboxylic acids such as sodium, potassium, lithium, magnesium, calcium and barium salts of 2,4-dimethyl-3-furancarboxylic acid, thiophenecarboxylic acid, terpenylic acid, paraconic acid, furanacarboxylic acid, alginic acid, coumarinic acid, and pyridine-carboxylic acid.
  • one or more of the above-mentioned carboxylic acid salts need not be completely dissolved, but a dispersion (or suspension) of such salt may also be used.
  • Water is most preferred as a medium for dissolving such carboxylic acid salt, but it is also possible to use aqueous mixtures of water-miscible organic solvents such as polyhydric alcohols, e.g., methanol, ethanol and propanol, ketones, e.g., acetone and methylethylketone, and polyhydric alcohols, e.g., ethylene glycol and glyceral.
  • polyhydric alcohols e.g., methanol, ethanol and propanol
  • ketones e.g., acetone and methylethylketone
  • polyhydric alcohols e.g., ethylene glycol and glyceral.
  • organic solvents capable of dispersing therein carboxylic acid salts can be used in this invention.
  • solvent there may be exemplified alcohols such as methanol, ethanol and propanol, ketones such as acetone and methylethylketone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, ethers such as butyl ether, propyl ether, dioxane and trioxane, and halogenated hydrocarbons such as chloroform and carbon tetrachloride.
  • alcohols such as methanol, ethanol and propanol
  • ketones such as acetone and methylethylketone
  • aromatic hydrocarbons such as toluene and xylene
  • esters such as ethyl acetate and butyl acetate
  • ethers such as butyl ether, propyl ether, dioxane and
  • the activating liquor to be used in this invention contains the alkali metal or alkaline earth metal salt of a carboxylic acid at a concentration generally ranging from 5 to 60 percent by weight, preferably 10 to 40 percent by weight, based on the amount of the activat above-mentioned range. Since the activating liquor is applied to the two-component diazotype photosensitive material, it is important that the activating liquor should not contain a coupler.
  • the activating liquor may further comprise small amounts of assistants as optional components. Examples of such assistants include dye-insolubilizing agents such as disclosed in Japanese Patent Publication No.
  • 45-27680/70 e.g., quaternary ammonium compounds and amines; penetrants such as monoand poly-hydric alcohols, or non-ionic surface active agents; and extenders such as dextrin, starch, and polyvinyl alcohol.
  • a whitening agent such as fluorescent dyes and blue dyes.
  • composition of an activating liquor to be used preferably in this invention is as follows:
  • a small amount of the activating liquor is applied to the exposed twocomponent diazotype photosensitive material, and it is preferred that the activating liquor is applied uniformly to the light-exposed photosensitive layer.
  • the amount of the activating agent is such that the photosensitive layer is wetted with the activating liquor, and it is generally unnecessary to drench the photosensitive layer with the activating liquor.
  • it is possible to apply a considerable amount of the activating liquor to the photosensitive layer but any particular advantage is not attained by application of the activating liquor in a great amount.
  • a diazonium salt or coupler contained in the photosensitive layer is readily soluble in water, use of a great amount of the activating liquor results frequently in such defects as flow and blot of a copied image.
  • the amount applied of the activating liquor liquor varies considerably depending on the kind of the carboxylic acid salt contained in the activating liquor, but generally speaking, it is preferred that the activating agent is applied in an amount of l to g, especially 4 to 10 g, per square meter of the photosensitive layer.
  • Application of the activating liquor can be accomplished by means known per se, for instance, roller coating, spraying and other liquid-applying methods.
  • roller coating spraying and other liquid-applying methods.
  • the abovementioned amount of the activating liquor is at first applied on the coating roll and then a thin layer of the activating liquor on the coating roll is transferred onto the photosensitive layer.
  • coating roll there may be employed, for instance, a smooth metal roll, a mesh roll, a rubber roll, a sponge roll and the like.
  • a latent image formed on the photosensitive layer can be developed into a visible image without any particular heating (namely allowing it to stand still at temperatures approximating room temperature). In such case, however, it takes time to develop the latent image into a visible image. Therefore, in general, heating is used to develop the latent image consisting of the undecomposed diazonium salt and coupler and obtain a copy sheet in the dry state.
  • the heating temperature varies greatly depending on the kind of the activating liquor or combination of the diazonium salt and coupler.
  • the heating is effected at 50 to 250C, preferably 60 to 200C, especially to C.
  • the heating is effected with use of steam or the photosensitive layer is wetted with water by some means prior to heating.
  • the heating of the photosensitive material can be conducted with ease by optional heating means, for instance, a heating roll, infrared irradiation, hot air, heated steam or the like.
  • the alkali metal or alkaline earth metal carboxylate promotes development in the twocomponent diazotype photosensitive material in this invention have not been completely elucidated.
  • the alkali metal or alkaline earth metal carboxylate is a neutral salt and is stable at high temperatures, it is readily presumed that the car boxylate or its thermal decomposition product may neutralize the acidic stabilizer in the two-component diazotype photosensitive composition and initiate coupling of the diazonium salt with the coupler.
  • the reason why the alkali metal or alkaline earth metal carboxylate enables coupling of the diazonium salt with the coupler at relatively low temperatures is not that the carboxylate acts on the acidic stabilizer but that the carboxylate activates the diazonium salt by synergetic activity with the heat thereby initiating initiate coupling of the diazonium salt with the coupler regardless of the presence of the acidic stabilizer.
  • the ingredient of the activating liquor is a salt stable. Even at high temperatures, one obvious advantage is that development can be accomplished easily without formation of a nasty or irritative decomposition gas. Further, since the ingredient of the activating liquor to be applied on the two-component diazotype photosensitive material is a non-volatile salt, it is sufficient that the activating liquor is applied only in a very small amount. Accordingly, the process of this invention is advantageous also from the economical viewpoint, and any special opera tion need not be effected to dry a copy sheet.
  • the process of this invention is generally advantageous in that copy sheets excellent in the image density and water resistance can be obtained.
  • copy sheets excellent in the image density and water resistance can be obtained.
  • dihydroxynaphthalene sulfonic acid and a diazonium salt which is most commonly used in two-component diazotype photosensitive copying papers for the dry development
  • copied images are relatively faintly blue and poor in water resistance when the development is conducted by the dry development method using a gaseous mixture of ammonia and vapor.
  • the activating liquor of this invention for instance, an aqueous solution of sodium acetate is applied to such photosensitive papers, images of a dense violet color excellent in water resistance can be obtained.
  • the process of this invention can be effectively applied not only to ordinary diazotype reproduction processes but also to multi-color reproduction processes such as disclosed in German Patent Application Laid- Open Specification No. 2,007,690.
  • EXAMPLE 1 A composition of the following recipe was coated on a substrate paper for a photosensitive copying sheet by means of an ordinary coating device such as an air knife coater, and dried to form a two-component diazo type photosensitive paper for heat development:
  • Example 2 A composition of the following recipe was coated on a substrate paper for a photosensitive copying sheet by means of an ordinary coating device such as air knife coater, and dried to form a two-component diazotype photosensitive paper for heat development:
  • Example 3 A composition of the following recipe was coated on a substrate paper in the same manner as in Example 1 and dried to obtain a diazotype photosensitive copying sheet for heat development and black coloration:
  • Example 4 A composition of the following recipe was applied on a substrate for a copying sheet in the same manner as in Example 1 and dried to obtain a two-component diazotype copying sheet for heat development and red coloration:
  • Example 5 A composition of the following recipe was coated on a substrate paper for a copying sheet in the same manner as in Example 1 and dried to obtain a twocomponent diazotype phososensitive copying sheet for heat development:
  • Example 6 A solution of the following recipe was coated on a 5 semi-transparent tracing paper and dried to obtain a two-component diazotype copying sheet for heat development and for formation of a second original:
  • Example 7 A solution of the following recipe was coated on a substrate paper for a photosensitive copying sheet according to a customary coating method using an air knofe coater and dried at a relatively low temperature (80- 90C.) to obtain a two-component diazotype photosensitive sheet for heat development:
  • Example 8 A composition of the following recipe was coated on a polyester film by means of a rod coater and dried by hot air maintained at about 100C. to obtain a twocomponent diazotype photosensitive film for heat development:
  • Example 9 A solution of the following recipe was coated by means of an air knife coater on a substrate paper which had been treated in advance with a percent solution of a butadiene-methyl methacrylate copolymer resin emulsion, and dried to obtain a two-component diazotype photosensitive copying sheet for heat development and multi-color reproduction:
  • thermovolatile couplers were transferred to the copying sheet at parts corresponding with the treated portions of the original sheet.
  • An activating liquor of the following recipe was applied to the copying sheet in an amount of about 7 g per square meter of the copying sheet surface:
  • the activating liquor-applied copying sheet was instantaneously contacted with a heating roll maintained at about C. to obtain a three-color copy sheet in which the part corresponding with the portion of the original treated with the red-color-forming liquor was colored red, the part corresponding with the portion of the original treated with the yellow-color-forming liquor was colored yellow and the part corresponding with the untreated portion of the original was colored blue.
  • Example 10 A solution of the following recipe was coated on a substrate paper in the same manner as in Example 1 and dried to obtain a photosensitive copying sheet for heat development and for twocolor reproduction:
  • a two-color copy sheet in which the part corresponding with the image portion drawn with the drafting ink was colored blue and the part corresponding with the image portion drawn with the pencil colored red was thus obtained.
  • Example 1 l A solution of the following recipe was coated on an ordinary substrate paper for a copying sheet by means of an air knife coater and dried to obtain a two- 3 5 component diazotype photosensitive copying sheet for heat development:
  • the activating liquor-applied copying sheet was instantaneously contacted with a heating roll maintained at about 100C. thereby obtaining a copy sheet having a blue-colored image.
  • EXAMPLE 13 A solution of the following recipe was coated on a substrate paper for a copying sheet by a customary coating method employing an air knife coater and dried izggg z' 15 g 40 at a relatively low temperature (80 90C.) to obtain Glycerine 50 g a two-com onent diazot e hotosensitive co in Tartaric acid 30 g yp p py g Sodium 2,3-dihyclroxy-6-sulfonate 40 g sheetfor heat development: Zinc chloride 50 s Thiourea 30 g Patent Blue 0.1 g 4) -N t l A water balance franlzfizg 181:; dime hy aniline ZnCl, 1; 5 Tom] 1 met Sodium 2,S-dihydroxynaphthalene-6-sulfonate 40 g Trichloroacetic acid g The so formed copying sheet was overlapped with an g fifg 52 8 original sheet having an image thereon,
  • the activating liquor-applied copying sheet was instantaneously heated at about C. by infrared irradiation thereby to obtain a copy sheet having an image of a clear blue color.
  • Triethanolamine I0 100 The so treated copying sheet was instantaneously contacted with a heating roll maintained at about C. to effect the development.
  • Development Process Using Aqueous Solution of Alkali In accordance with the teachings of Japanese Patent Publication No. 43-13815/68, an aqueous solution of the following recipe was coated on the above lightexposed copying sheet by means of a coating roll in an amount of about 7 g per squre meter of the copying sheet surface:
  • the development process of this invention is not substantially different from the conventional dry development method using a gaseous mixture of ammonia and water with respect to the development efficiency and the process of this invention is superior to the said conventional dry development method with respect to the water resistance of the copied image. It is also seen that the process of this invention is superior to the conventional method employing a nitrogen-containing organic base in that the concentration of the colored image is higher in the process of this invention and such fatal effects of the conventional method as contamination and discoloration of the copied image are prominently overcome in the process of this invention. Further, in the method employing an aqueous alkali slution it can be seen that, the flow of the image was extreme with the copy lacking accuracy. Clearly, there is no comparison with such process and the process of the instant invention.
  • polycarboxylic acids heterocyclic monocarboxylic acids and heterocyclic polycarboxylic acids.
  • aliphatic monocarboxylic acid is one selected from the group consisting of formic acid, acetic acid, propionic acid, acrylic acid, aconic acid, acetoacetic acid, valerianic acid, crotonic acid, butyric acid, undecanoic acid, enanthic acid, capric acid, caprylic acid, chloro-acetic acid, bromacetic acid, trichloracetic acid, chlorofumaric acid, cyclobutane-carboxylic acid, quinic acid, sulfoacetic acid, sorbic acid, tiglic acid, tetrolic acid, vinylacetic acid, pyruvic acid, methacrylic acid, levulimic acid, caproic acid, isovaleric acid, pelargonic acid, palmitic acid, lauric acid, myristic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, erucic
  • a process for wet developing two-component diazotype photosensitive materials comprising exposing image-wise to actinic light a photosensitive material having a two-component diazotype photosensitive layer consisting essentially of a photosensitive diazonium salt, a coupler capable of coupling with the diazonium salt and an acidic stabilizer, and developing said photosensitive material by applying a small amount of an activating liquid to the photosensitive layer of the exposed photosensitive material, the improvement characterized in that the activating liquid consists essentially of:
  • carboxylic acid is one selected from the group consisting of aliphatic monocarboxylic acids, aliphatic polycarboxylic acids, aromatic monocarboxylicacids, aromatic saccharic acid, isovanillic acid, hydroxybutyric acid, glyceric acid, gluconic acid, diglycolic acid, citramanic acid, thioglycolic acid, desoxalic acid, lactic acid, racenic acid, mannonic acid, malic acid, leucic acid, glycine, alanine, leucine, serine, threonine, cysteine, methionine, lysine and arginine.
  • the aliphatic polycarboxylic acid is one selected from the group consisting of malonic acid, acetonedicarboxylic acid, citraconic acid, oxalic acid, acrylmalonic acid, isocamphoronic acid, ethylmalonic acid, glutaric acid, succinic acid, camphoric acid, sebacic acid, pimelic acid, brassylie acid, maleic acid, muconic acid, mesaconic acid, adipic acid, axelaic acid, suberic acid, aspartic acid and glutamic acid.
  • aro matic monoor poly-carboxylic acid is one selected from the group consisting of benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, salicylic acid, acetophenone-carboxylic acid, anisic acid, aminobenzoic acid, aminocinnamic acid, propylbenzoic acid, bydroxy-phthalic acid, hydroxyphenylacetic acid, cinnamic acid, chlorobenzoic acid, chlorophthalic acid, dimethoxyphthalic acid, sulfosalicylic acid, thiosalicylic acid, toluic acid, truxillic acid, tropic acid, naphthalic acid, vanillic acid, biphenyl-carboxylic acid, phenyl-acetic acid, phenylsuccinylacetic acid, phenyllactic acid, benzene tetracarboxylicl acid, phenylbutyric acid

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  • Chemical & Material Sciences (AREA)
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  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US00275071A 1971-07-31 1972-07-25 Process for development of two component diazotype photosensitive materials Expired - Lifetime US3820996A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3950171A (en) * 1970-07-27 1976-04-13 Mita Industrial Co. Ltd. Diazotype multicolor reproduction process
US3981730A (en) * 1973-04-18 1976-09-21 Mita Industrial Company, Ltd. Diazo-type multicolor reproduction process

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB294972A (en) * 1927-05-03 1928-08-03 Frans Van Der Grinten Improvements in the manufacture of diazo-types

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3950171A (en) * 1970-07-27 1976-04-13 Mita Industrial Co. Ltd. Diazotype multicolor reproduction process
US3981730A (en) * 1973-04-18 1976-09-21 Mita Industrial Company, Ltd. Diazo-type multicolor reproduction process

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JPS5414497B1 (enrdf_load_stackoverflow) 1979-06-07

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