US3881931A - Method for developing black diazotype photographic light-sensitive materials - Google Patents

Method for developing black diazotype photographic light-sensitive materials Download PDF

Info

Publication number
US3881931A
US3881931A US362722A US36272273A US3881931A US 3881931 A US3881931 A US 3881931A US 362722 A US362722 A US 362722A US 36272273 A US36272273 A US 36272273A US 3881931 A US3881931 A US 3881931A
Authority
US
United States
Prior art keywords
hydroxy
naphthamide
naphthyl
naphthanilide
morpholino
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US362722A
Other languages
English (en)
Inventor
Motohiko Tsubota
Taiichi Nishimura
Kinji Ohkubo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3881931A publication Critical patent/US3881931A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G03C1/58—Coupling substances therefor

Definitions

  • ABSTRACT A method for developing a diazo-type photographic light-sensitive material containing at least one lightsensitive diazonium compound (Component A) selected from the compounds represented by the general formula;
  • R represents (wherein R and R each represents a hydrogen atom, a halogen atom or an alkyl group having 1-4 carbon atoms), COR (wherein R represents an alkyl group having l4 carbon atoms, or a substituted or unsubstituted phenyl group or (wherein n represents 1 or 2) or from the compounds represented by the general formula;
  • R and R 0 each represents an alkyl group having l-4 carbon atom
  • R9 and R each represents a hydrogen atom or a halogen atom
  • the present invention relates to a method for developing a diazo-type photographic light-sensitive material.
  • One system is a method for forming a dye image by coating a light-sensitive diazo composition containing, of a light-sensitive diazonium compound and a coupler, only the former (mono component type) to prepare a light-sensitive material and, after imagewise exposure, subjecting the material to a development wherein the light-sensitive material is processed with a coupler-containing developer to thereby react both compounds with each other.
  • the other system is a method for forming a dye image by preparing a light-sensitive material in the same manner as in the above-described method using a light-sensitive diazo composition containing both a light-sensitive diazonium compound and a coupler (binary type) and, after imagewise exposure, subjecting the material to a development wherein the light-sensitive material is exposed to an alkaline atmosphere, such as ammonia gas or ammonia vapor, to thereby react the diazonium compound and the coupler with each other.
  • a light-sensitive diazo composition containing both a light-sensitive diazonium compound and a coupler (binary type)
  • an alkaline atmosphere such as ammonia gas or ammonia vapor
  • the latter system includes a method wherein a visible image is formed by adding an alkali-generating agent capable of being decomposed by heat to produce an alkaline substance to the light-sensitive material in addition to the above-described two components, and, after imagewise exposing the light-sensitive material, heating the material. If desired, the resulting image can then be stabilized by decomposing the light-sensitive diazonium compound remaining in the light-sensitive material with actinic light.
  • the photographic methods of these systems are superior in function, reliability, ease of operation, economic advantages, speed, diversity in color, and the like, at least to silver halide photographic methods as have hitherto widely been conducted.
  • the color of the images obtained by the aforesaid two methods is not a neutral black, and hence there have often been encountered problems with such images in practical use. That is, in connection with the light absorbability of the resulting image and the accompanying distinctness of the image, a neutral black tone image is optimal in hue since a neutral black tone image appears so distinct to the eye. Further, and importantly, a black tone image has advantages such as in the case of use as an original for duplication, the large difference in light transmittance between the image areas and the non-image areas due to the large light absorbance of the image areas enables one to duplicate distinct images. Thus, a black tone is considered to be the most distinct images. Thus, a black tone is considered to be the most desirable hue.
  • the inventors after long investigations relating to forming a neutral black image showing no dichroism with a diazo-type photographic material utilizing the reaction between a light-sensitve diazonium compound and a coupler, have now discovered a diazo-type photographic method which removes the above-described defects, more particularly, a diazo-type photographic method which is characterized by its developing step.
  • the present invention relates to a method for developing a diazo-type photographic light-sensitive material, which comprises developing a photographic light-sensitive material containing at least one lightsensitivee diazonium compound (Component A) selected from compounds represented by the general formula;
  • R represents a hydrogen atom, an alkyl group having l-4 carbon atoms or (wherein n represents 1 or 2); and at least one coupler (Component C capable of forming a yellow dye, se lected from compounds represented by the general formulae;
  • FIG. 1 is a triangular diagram showing the range of the molar ratio of the amounts of components B, C and C used, wherein boundary abcd and the interior thereof show the ratio of the amounts of the respective components to each other suitable for obtaining the desired effects of the present invention, and the boundary wxyz and the interior thereof show the ratio of the amounts of the respective components to each other to be used where particularly preferable results can be obtained.
  • FIG. 3 is a u-v chromaticity diagram wherein the chromaticity values calculated by means of a color computer are plotted.
  • FIGS. 2, 4 and 5 are u-v chromaticity diagrams showing chromaticity values determined in the same manner as for FIG. 3 with respect to diazo-type photographic images formed on the diazotype photographic lightsensitive materials in the Examples of the invention, with the u value on the horizontal axis and the v value vertically.
  • the point C in the Figures shows theoretical neutral black.
  • R and R are a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, t-pentyl group, cyclopentyl group, cyclohexyl group, etc, where R, and R, may be the same of different from each other, and X represents an anion such as a metal salt, halide, sulfate, tetrafluoroborate, hexafluorophosphate, etc.
  • Component A there can be illustrated 4-morpholino-2,5-dimethoxybenzenediazonium tetrafluoroborate, 4-morpholino-2- methoxy-S-sec-butoxybenzenediazonium sulfate, 4- morpholino-2-ethoxy-5-n-pentoxybenzenediazonium hexafluorophosphate, 4-morpholino-Z-iso-propoxy-S- cyclopentyloxybenzenediazonium chloridezinc chloride double salt, 4-morpholino-2,5-di-nbutoxybenzenediazonium tetrafluoroborate, 4- morpholino-2-t-butoxy-5-cyclohexylbenzenediazonium tetrafluoroborate, 4-morpholino-2-npentoxy-S-sec-butoxybenzenediazonium tetrafluoroborate, 4-morpholino-2-cyclopentyloxy-5-npropoxybenzenediazonium hexafluorophosphat
  • Component B represented by general formula (ll) or (Ill) is a coupler capable of forming a blue dye.
  • general formula (11) specific examples of R are:
  • R represents a hydrogen atom; an alkyl group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, etc.; a benzyl or phenethyl group, and the substituent OR containing these atoms may be located at any position of the naphthalene nucleus of Com- *UZQ M3 Br Cl 400 -co -c1, -c0
  • pound (Ill) As specific examples of the Compound 60 (Hi), there can be illustrated N-(2'-hydroxy-l'- naphthyl)-2-hydroxy-3-naphthamide, N-(4'-methoxy- I'-naphthyl)-2-hydroxy-3-naphthamide, N-(5-ethoxyl'-naphthyl)-2-hydroxy-3-naphthamide, N-( 6 benzyloxy-l'-naphthyl)-2-hydroxy-3-naphthamide, N-
  • Component B represented by general formula (11) or (111) can be synthesized by condensing 2- hydroxynaphthoic acid and a l-aminonaphthalene derivative or an aniline derivative.
  • the synthesis of Component B is described in Japanese Patent Applications No. 46-79187 and 45-82695. Several specific synthesis examples are described below.
  • Component C is a compound capable of coupling with Component A to form a yellow dye and is, particularly, represented by the general formula (IV) or (V).
  • R and R each represents an alkyl group having 1-4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secbutyl, t-butyl, etc.
  • R and R each represents a hydrogen atom or a halogen atom such as chlorine, bromine or iodine.
  • Component C there can be illustrated 2,2, 4,4'-tetrahydroxy-3,3'- dimethyldiphenyl sulfide, 2,2, 4,4-tetrahydroxy-3,3'- di-isopropyl-5,5'-dichlorodiphenyl sulfide, 2,2, 4,4- tetrahydroxy-3,3'-dimethyl-5,5'-dichlorodiphenyl sulfide 2,2, 4,4'-tetrahydroxy-3,3'-dimethyl-5,5'- dichloro-diphenylsulfoxide, and the like.
  • the present invention relates to a method for developing a diazotype photographic light-sensitive material, which comprises imagewise exposing a lightsensitive material containing Component A and developing the material in the presence of Components B and C,.
  • the term "in the presence of the Components B and C means to incorporate those components in the light-sensitive material or in the development processing solution, or in both of them.
  • the photographic light-sensitive material and the composition of the developer to be used in the invention are known, and conventional arts may be applied per se to the production thereof, e.g., see Photosensitive Diazo Compounds by M. S. Dinaburg, Focal Press (1964).
  • a light-sensitive diazo-type material capable of providing neutral black color images can be obtained by providing on a support of the light-sensitive diazo-type material the above-described light-sensitive aromatic diazonium Compound (A), the blue coupler Component (B) and the first yellow coupler Component (C,).
  • the second yellow coupler Component (C) can be used with the diazonium compound, which Component is suitable for the invention for the following reason, i.e., the addition of the second yellow coupler component can provide a black color over a wider density range as compared with the use of the combination of the light-sensitive aromatic diazonium Compound (A), the blue coupler Component (B) and the first yellow coupler Component (C).
  • both the combination of the light-sensitive aromatic diazonium Compound (A), the blue coupler Component (B) and the first yellow coupler Component (C and the combination of the light-sensitive aromatic diazonium Compound (A), the blue coupler Component (B), the first yellow coupler Component (C,) and the second yellow coupler Component (C provide a practically sufficient neutral black images over a wide density range.
  • amounts of the Components (A), (B) and (C or of the Components (A), (B), (C,) and (C2) are of importance. That is, the light-sensitive aromatic diazonium Component (A) must be coated on a support in an amount of at least 0.001 m mol/m Component (A) is preferably added in an amount of about l0 m mol to about 10 m mol/m most preferably, l0 m mol to ID m mol/m.
  • PK]. 1 is a triangular coordinate showing the molar ratio of the coupling Components (B), (C and (C to each other. In this triangular diagram, the area surrounded by W, X and Y shows the range where prefered black coloring is attained.
  • the molar ratio of diazonium salt to coupler is diazo/ coupler (total) about 10' to about 10 /1, preferably l0-l0'/l.
  • the molar ratio of A to B and C is A/B+C, about 10' to about 10 preferably, 10* 10
  • a light-sensitive diazo-type material using Components (B), (C,) and (C,) at a molar ratio within the area surrounded by X, Y and Z provides neutral black images over such a wide density range that they cannot be discriminated from the black tone images obtained by silver halide photography. This characteristic is not illustrated by conventional light-sensitive diazo-type materials.
  • the novel blue coupler Component (B) exhibits sufficient solubility in commonly used coupler solvents.
  • composition of the invention can, if desired, contain any auxiliary agent used for producing a diazo-type light-sensitive materials as well as the light-sensitive aromatic diazonium Compound (A), the novel blue coupler Component (B), the yellow coupler Component (C and the yellow coupler Component (C,).
  • auxiliary agent used for producing a diazo-type light-sensitive materials as well as the light-sensitive aromatic diazonium Compound (A), the novel blue coupler Component (B), the yellow coupler Component (C and the yellow coupler Component (C,).
  • a pre-coupling restrainer to prevent precoupling between the diazonium salt and the coupling components there can be used citric acid, sulfosalicylic acid, tartaric acid, boric acid, acetic acid, hydroxypyridine, hydroxybenzotriazole, sulfuric acid, phosphoric acid and the like.
  • the composition ammonium sulfate, zinc chloride, magnesium chloride and nickel sulfate. Also, in order to prevent discoloration of the background of a print obtained by development, there can be added to the composition thiourea and thiosinamine. As development accelerators, there can be added to the composition l-allyl-3B-hydroxyethylthiourea, l-allyl-thiourea, and the like.
  • a hygroscopic agent such as glycol, glycerin, etc.; wetting agent such as saponin, aleyl-N-methyltaurine, etc.; binding agent such as polyvinyl alcohol, starch, polyvinyl acetate, etc.; pigments such as silica, aluminum, etc. can also be added to the composition.
  • films made from polycarbonate, regenerated cellulose, polyesters such as polyethylene terephthalate, cellulose esters such as cellulose acetate butyrate, cellulose diacetate, cellulose triacetate, etc., or like plastics, or papers.
  • This diazo-type light-sensitive material finds wide industrial application in the field of diazo-type microfilming for use in duplicating microfilm, in forming second originals for industrial use, as a copying diazo-type paper and the like.
  • EXAMPLE 1 1.20 Grams of sulfosalicylic acid was dissolved in a mixed solvent composed of 60 cc of methanol, cc of methyl ethyl ketone, 30 cc of methylene chloride, 5 cc of glacial acetic acid and 5 cc of phenol. In this solution there was then dissolved l.0 g of N-(2'-hydroxy-1 naphthyl)-2-hydroxy-3-naphthamide.
  • the thus obtained light-sensitive diazo-type film was exposed for 5 seconds to a i500 W mercury lamp spaced a distance of 5 cm through an original superposed on the film.
  • Step wedge No. 3 made by Eastman Kodak Co. was used as the original.
  • the thus exposed film was developed for ID seconds in an atmosphere prepared by vaporizing aqueous ammonia at about 80C.
  • the visual density of each step of the resulting print film was measured by means of a TD-l02 type densitometer made by Macbeth Instruments wherein a Wratten 93 filter (made by Eastman Kodak Co.) was used.
  • the chromaticity of the azo dye at each step of the resulting print film was calculated by a color computer made by Tokyo Shibaura Electric Co., Ltd., and plotted on a u-v chromaticity diagram.
  • the resulting u-v chromaticity diagram is shown in FIG. 2.
  • the condensation values which are measured by Macbeth TD-l02 are written in the u-v chromaticity diagrams.
  • Point C in FIGS. 2 and 3 is the point which shows theoretical neutral gray in the case of measuring the sample with light source C.
  • the numerical value at each point represents the visual density of the wedge printed on the diazo-type film. The larger the numerical value, the higher the visual density. The further the points plotted on the u-v chromaticity diagram deviate from point C, the greater, the color tone varies from a neutral black color.
  • the combination of the diazonium compound and the coupling components used for FIG. 1 shows a smaller change in chromaticity with a change in the density of the diazo-type film on which the step wedge was printed than in the combination of the diazonium compound and the coupling components used for FIG. 3, and, in addition, the points showing the chromaticity of the former gather more in the vicinity of point C, i.e., the point of theoretical neutral gray, as compared with the latter. Therefore, the diazo-type film provided by the combination of the diazonium compound and the coupling components used for FIG. 2 is capable of providing a neutral black image over a wider density range than in the diazo-type film obtained with the formulation employed for FIG. 3.
  • EXAMPLE 2 A coating solution was prepared in the same manner as in Example I using l.00 g of 2-hydroxy-2'-(4"- methylbenzenesulfonyloxy)-3-naphthanilide instead of 1.00 g of the novel blue coupler component, N-(2'- hydroxy-l '-naphthyl)-2-hydroxy-B-naphthamide, as the yellow coupler components, 0.40 g of 1,3-di-(3- hydroxyphenyU-urea and 0.20 g of 2,2, 4,4- tetrahydroxy-3,3'-dimethylphenylsulfide, and, as the aromatic diazonium compound, 2.
  • Example I The chromaticity of the azo dye at each step of the resulting print film was calculated by means of a color computer made by Tokyo Shibaura Electric Co., Ltd. and shown on a u-v chro' maticity diagram as in Example 1.
  • FIG. 4 shows the u-v chromaticity diagram. From the results obtained, it can be seen that neutral black images can be obtained over a wide density range as in Example I.
  • EXAMPLE 3 A coating solution was prepared as in Example l using 0.60 g of 2-hydroxy2'-benzyloxy-3- naphthanilide in place of 1*.00 g of the novel blue cupler component, N-( 2 -hydroxyl '-naphthyl )-2- hydroxy-3-naphthamide, as the yellow coupler components, 0.20 g of 2,2',4,4'-tetrahydroxy-3,3'-dimethyldiphenylsulfide and l.20 g of l,3-di-( 3- hydroxyphenyl)-urea, and, as the aromatic diazonium compound, 2.00 g of 2,5-di-isopropoxy-4- morpholinobenzenediazonium chloride-zinc chloride double salt in place of the 2,5-dibutoxy-4- morpholinobenzenediazonium tetrafluoroborate used in Example I, and coated and dried as in Example 1. The resulting light-sensitive film was exposed and developed
  • EXAMPLE 4 0.8 Gram of sulfosalicylic acid was dissolved in a mixture solvent composed of cc of methanol, 20 cc of methyl ethyl ketone, 30 cc of methylene chloride, 5 cc of glacial acetic acid, and 3 cc of phenol. In this solution there was dissolved 1.00 g of N-(2'-hydroxy-l naphthyl)-2-hydroxy-3-naphthamide.
  • EXAMPLE 5 A coating solution was prepared as in Example 1 using 0.60 g of 2-hydroxy-2'-benzyloxy-3- naphthanilide in place of 1.00 g of the novel blue coupler component, N-( 2'-hydroxy-l '-naphthyl )-2- hydroxy-3-naphthamide, used in Example I, as the yellow coupler components, 020 g of 1,3-di-(3- hydroxyphenyhurea and 0.40 g of 2,2',4,4- tetrahydroxy-3,3'-dimethyl-5,5- dichlorodiphenylsulfide, and, as the aromatic diazonium compound, 2.00 g of 2,5-dipentoxy-4- morpholinobenzenediazonium fluoroborate was used in place of 2,5-dibutoxy-4- morpholinobenzenediazonium tetrafluoroborate used in Example 1, and coated and dried as in Example 1. Thereafter, the resulting light-sensitive film was exposed and developed
  • EXAMPLE 6 A coating solution was prepared in the same manner as in Example I using 1.00 g of the same novel blue coupler component as was used in Example 4, N,-(2'- hydroxy-l '-naphthyl )-2-hydroxy-3-naphthamide, as the yellow coupler components, 0.20 g of 2,2'4,4,4'- tetrahydroxy-3,3'-dimethyldiphenylsulfide and l.50 g of l,3-di-(3-hydroxyphenyl)-urea, and, as the aromatic diazonium compound, 2.20 g of 2,5-dihexyloxy-4- morpholinobenzenediazonium hexafluorophosphate in place of the 2,5-dibutoxy-4- morpholinobenzenediazonium tetrafluoroborate used in Example 1, and, after adding thereto 0.5 g of 1,2,3- triphenylimidazolidine, coated and dried as in Example 4. There
  • EXAMPLE 7 A coating solution was prepared in the same manner as in Example 1 using 1.00 g of 2-hydroxy-2'-(4"- methylbenzenesulfonyloxy)-3-naphthanilide in place of the novel blue coupler component, N-(2'-hydroxy-l naphthyl)-2-hydroxy-3-naphthanilide, used in Example 1, as the yellow coupler component, 0.40 g of 2,2',4,4- tetrahydroxy-3,3 -dimethyldiphenylsulfide, and, as the aromatic diazonium compound, 2.00 g of 2,5-dibutoxy- 4-morpholinobenzenediazonium tetrafluoroborate as was used in Example I, and coated and dried as in Example l.
  • Example 1 The chro maticity of the azo dye of each step of the resulting print film was calculated by means of a color computer made by Tokyo Shibaura Electric Co., Ltd., and the results obtained were plotted on a u-v chromaticity diagram as in Example I.
  • FIG. shows the u-v chromaticity diagram. it can be seen from the results that neutral black images can be obtained over a wide density range as in Example 1.
  • R is selected from the group consisting of R and R each representing a hydrogen atom, a halogen atom or an alkyl group having 1-4 carbon atoms, C0R wherein R represents an alkyl group having 1-4 carbon atoms or a substituted or unsubstituted phenyl group and wherein n represents 1 or 2 or from the compounds represented by the general formula:
  • R represents a hydrogen atom, an alkyl group having 1-4 carbon atoms or wherein n represents 1 or 2, as a coupler designated Component B capable of coupling with said light-sensitive diazonium compound Component A to form a blue dye;
  • Coupler designated Component C capable of forming a yellow dye, at least one compound selected from the compounds represented by the general formula:
  • R and R each represents an alkyl group having 1-4 carbon atoms. and R, and R each represents a hydrogen atom or a halogen atom;
  • the molar ratio of diazonium compound A to the total of coupler Components B and C is about l0" to about 10 of A to l of B plus C the molar ratio of Component B: Component C, is 95.0 5.0 37.5:62.5 and the amount of Component A coated is at least 0.001m mol/m.
  • NI-ICONH as a coupler designated Component C capable of coupling with said light-sensitive diazonium compound Component A to form a yellow dye is present in addition to the Components B and C wherein the molar ratio of diazonium Compound A to the total of coupler Components B, C, and C is about 10 to about l of A to l B plus C, plus C Components B, C, and C are present in a molar ratio within the triangular area formed by coordinants W, X and Y of the triangular diagram of FIG.
  • the molar ratios of B: C,: C at each point W, X and Y being for W125: 5.0: 82.5, for X 95.0: 5.0: 0.0 and for Y 37.5: 62.5:0.0, and the amount of Compound A coated is at least 0.00lm mol/m 3.
  • R, and R are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, tpentyl, cyclopentyl and cyclohexyl, wherein R, and R may be the same or different and X represents an anion selected from the group consisting of a metal salt, halide, sulfate, tetrafluoroborate and hexafluorophosphate.
  • R, and R are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl sec-butyl, t-butyl, tpentyl, cyclopentyl and cyclohexyl, wherein R, and R may be the same of different and X represents an anion selected from the group consisting of a metal salt, halide, sulfate, tetrafluoroborate and hexafluorophosphate.
  • X is selected from the group consisting of salts of zinc-chloride, boron tetrafluoridc, hydrogen sulfate and phosphorous hexafluoride.
  • X is selected from the group consisting of salts of zinc-chloride, boron tetrafluoride, hydrogen sulfate and phosphorous hexafluoride.
  • Component A is selected from the group consisting of 4-morpholino- 2,5-dimethoxybenzenediazonium tetrafluoroborate, 4-morpholino-2-methoxy-5-secbutoxybenzenediazonium sulfate, 4-morpholino-2- ethoxy-S-n-pentoxybenzenediazonium hexafluorophosphate, 4-morpholino-2-iso-propoxy-5-cyclopentyloxybenzenediazonium chloride-zinc chloride double salt, 4-morpholino-2,5-di-n-butoxybenzenediazonium tetrafluoroborate, 4-morpholino-2,4-t-butoxy-5- cyclohexylbenzenediazonium tetrafluoroborate, 4- morpholino-2-n-pentoxy-5-secbutoxybenzenediazonium tetrafluoroborate, morpholino-Z-cyclopentyloxy-S-npropoxybenzenediazon
  • Compound A is selected from the group consisting of 4-morpholino- 2,5-dimethoxybenzenediazonium tetrafluoroborate, 4-morphoolino-2-methoxy-5-secbutoxybenzenediazonium sulfate, 4-morpholino-2- ethoxy-S-n-pentoxybenzenediazonium hexafluoropphosphate, 4-morpholino-2-iso-propoxy-5-cyclopentyloxy-benzenediazonium chloride'zinc chloride double salt, 4-morpholino-2,5-di-nbutoxybenzenediazonium tetrafluoroborate, 4- morpholino-2-t-butoxy-S-cyclohexylbenzenediazonium tetrafluoroborate, 4-morpholino-2-npentoxy-S-sec-butoxybenzenediazonium tetrafluoroborate, 4-morpholino-2-cyclopentyloxy-5-npropoxybenzenediazonium
  • R is selected from the group consisting of:
  • a pre-coupling restrainer selected from the group consisting of citric acid, sulfosalicylic acid, tartaric acid, boric acid, acetic acid, hydroxypyridine, hydroxybenzotriazole, sulfuric acid and phosphoric acid is present to prevent preconpling between the diazonium compound and the coupling components.
  • a pre-coupling restrainer selected from the group consisting of citric acid, sulfosalicylic acid, tartaric acid, boric acid, acetic acid, hydroxypridine, hydroxybenzotriazole, sulfuric acid and phosphoric acid is present to prevent precoupling between the diazonium compound and the coupling components.
  • said development accelerator is l-allyl -3-62 -hydroxyethylthiourea or l-allyl-thiourea; said hygroscopic agent is glycol or glycerin; said wetting agent is saponin or oleyl-N-methyl-taurine; said binding agent is polyvinyl alcohol, starch or polyvinyl acetate and said pigment is silica or aluminum.
  • polyester is polyethylene terephthalate and said cellulose ester is cellulose acetate butyrate, cellulose diacetate or cellulose triacetate.
  • Component B is N-(2'-hydroxy-l '-naphthyl)-2-hydroxy-3- naphthamide, 2-hydroxy-2-(4"- methylbenzenesulfonyloxy)-3-naphthanilide, or N-(2'- hydroxy-l '-naphthyl)-2-hydroxy-3-naphthamide.
  • Component B is 2'hydroxy-l '-naphthyl )-2-hydroxy-3-naphthamide.
  • Component B is Z-hydroxy-Z 4 '-methylbenzenesulfonyloxy )-3- naphthanilide.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US362722A 1972-05-22 1973-05-22 Method for developing black diazotype photographic light-sensitive materials Expired - Lifetime US3881931A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP47050539A JPS5213741B2 (ja) 1972-05-22 1972-05-22

Publications (1)

Publication Number Publication Date
US3881931A true US3881931A (en) 1975-05-06

Family

ID=12861799

Family Applications (1)

Application Number Title Priority Date Filing Date
US362722A Expired - Lifetime US3881931A (en) 1972-05-22 1973-05-22 Method for developing black diazotype photographic light-sensitive materials

Country Status (4)

Country Link
US (1) US3881931A (ja)
JP (1) JPS5213741B2 (ja)
DE (1) DE2325999A1 (ja)
GB (1) GB1413183A (ja)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4304831A (en) * 1978-08-08 1981-12-08 Ricoh Co., Ltd. Black-color forming two-component type diazo copying material
US4642383A (en) * 1982-09-30 1987-02-10 James River Graphics, Inc. Fast coupling lemon-yellow phenolic couplers

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS576571B2 (ja) * 1974-05-27 1982-02-05
JPS5520211B2 (ja) * 1974-05-31 1980-05-31
DE2746551A1 (de) * 1977-10-17 1979-04-26 Hoechst Ag Diazotypiematerial
JPS5540471A (en) * 1978-09-18 1980-03-21 Kaneo Yamamoto High speed binary black line diazo photosensitive paper
JPS60198533A (ja) * 1984-03-23 1985-10-08 Oji Paper Co Ltd ジアゾ第二原図用シ−ト
JPH0585473U (ja) * 1992-04-21 1993-11-19 昭和精機工業株式会社 携帯用塗装装置
US20060014949A1 (en) * 2004-07-13 2006-01-19 Supergen Inc. Compositions and formulations of decitabine polymorphs and methods of use thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2405523A (en) * 1944-08-09 1946-08-06 Du Pont Light-sensitive photographic compositions and elements
US2717832A (en) * 1954-09-08 1955-09-13 Gen Aniline & Film Corp Diazotype materials for black line images containing diresorcyl sulfide or sulfoxide as a subsitiute for resorcinol
US2893866A (en) * 1954-03-15 1959-07-07 Cinetechnik A G Photosensitive material and a process of making same
US3052542A (en) * 1958-07-24 1962-09-04 Gen Aniline & Film Corp Intermediate master for use in the diazotype process and a process for producing same
US3113025A (en) * 1960-03-02 1963-12-03 Gen Aniline & Film Corp Diazotype materials for the production of black images
US3248220A (en) * 1961-11-22 1966-04-26 Grinten Chem L V D Two-component diazotype material
US3373021A (en) * 1964-01-29 1968-03-12 Harris Intertype Corp Presensitized positive working lithographic plate
US3585033A (en) * 1967-09-13 1971-06-15 Tecnifax Corp The Diazotype composition employing 3'-substituted 2-hydroxy-3-naphthanilides as couplers
US3591381A (en) * 1967-07-31 1971-07-06 Eastman Kodak Co Stabilized diazotype composition
US3619191A (en) * 1967-09-13 1971-11-09 Tecnifax Corp The Diazo-type materials
US3679421A (en) * 1969-08-26 1972-07-25 Eastman Kodak Co Azo dye-forming system including a boric acid ester

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2405523A (en) * 1944-08-09 1946-08-06 Du Pont Light-sensitive photographic compositions and elements
US2893866A (en) * 1954-03-15 1959-07-07 Cinetechnik A G Photosensitive material and a process of making same
US2717832A (en) * 1954-09-08 1955-09-13 Gen Aniline & Film Corp Diazotype materials for black line images containing diresorcyl sulfide or sulfoxide as a subsitiute for resorcinol
US3052542A (en) * 1958-07-24 1962-09-04 Gen Aniline & Film Corp Intermediate master for use in the diazotype process and a process for producing same
US3113025A (en) * 1960-03-02 1963-12-03 Gen Aniline & Film Corp Diazotype materials for the production of black images
US3248220A (en) * 1961-11-22 1966-04-26 Grinten Chem L V D Two-component diazotype material
US3373021A (en) * 1964-01-29 1968-03-12 Harris Intertype Corp Presensitized positive working lithographic plate
US3591381A (en) * 1967-07-31 1971-07-06 Eastman Kodak Co Stabilized diazotype composition
US3585033A (en) * 1967-09-13 1971-06-15 Tecnifax Corp The Diazotype composition employing 3'-substituted 2-hydroxy-3-naphthanilides as couplers
US3619191A (en) * 1967-09-13 1971-11-09 Tecnifax Corp The Diazo-type materials
US3679421A (en) * 1969-08-26 1972-07-25 Eastman Kodak Co Azo dye-forming system including a boric acid ester

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4304831A (en) * 1978-08-08 1981-12-08 Ricoh Co., Ltd. Black-color forming two-component type diazo copying material
US4642383A (en) * 1982-09-30 1987-02-10 James River Graphics, Inc. Fast coupling lemon-yellow phenolic couplers

Also Published As

Publication number Publication date
DE2325999A1 (de) 1973-12-13
GB1413183A (en) 1975-11-12
JPS5213741B2 (ja) 1977-04-16
JPS4916435A (ja) 1974-02-13

Similar Documents

Publication Publication Date Title
US4260677A (en) Thermographic and photothermographic materials having silver salt complexes therein
US4155763A (en) Color photographic processing method
US2313586A (en) Hydroxynaphthoic acid amide coupler
US4126461A (en) Black-and-white photographic elements and processes
US4009035A (en) Process for forming cyan dye photographic images
US3365294A (en) Photographic material containing yellow fog-preventing agents
US4138265A (en) Antifoggants in certain photographic and photothermographic materials that include silver salts of 3-amino-1,2,4-mercaptotriazole
US3954478A (en) Silver halide emulsion containing an alkenyl benzothiazolium salt as stabilizer
US3881931A (en) Method for developing black diazotype photographic light-sensitive materials
US4012258A (en) Process for forming color photographic images
US3679415A (en) Diazotype photographic elements having extended exposure latitude with specific u-v absorber
US3503741A (en) Silver-dye-bleach process utilizing formazan dyes
US3910794A (en) Imidazole couplers for two component diazotype systems
US3056674A (en) Color formers for producing yellow dye images by color development
US3250617A (en) Photographic elements protected against ultraviolet radiation
JPS6113748B2 (ja)
US3775128A (en) Silver halide emulsion containing a triazine as antifoggant
US3770436A (en) Process for forming cyan image in light-sensitive color photographic material
US3573051A (en) Two-component diazotype composition
US3585033A (en) Diazotype composition employing 3'-substituted 2-hydroxy-3-naphthanilides as couplers
US2728660A (en) Salicylic acid ester and amide photographic coupler compounds
US2976152A (en) Photographic gelatin layers containing triazine hardeners
US2289804A (en) Sulphonic ester coupler
EP0029837B1 (en) Photothermographic stabilizers
US3642482A (en) Photographic element and process