US3881931A

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

Info

Publication number: US3881931A
Application number: US362722A
Authority: US
Inventors: Motohiko Tsubota; Taiichi Nishimura; Kinji Ohkubo
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1972-05-22
Filing date: 1973-05-22
Publication date: 1975-05-06
Anticipated expiration: 1992-05-06
Also published as: JPS4916435A; GB1413183A; DE2325999A1; JPS5213741B2

Abstract

WHEREIN R7 represents a hydrogen atom, an alkyl group having 1-4 alkyl group or

(WHEREIN N REPRESENTS 1 OR 2), AS A COUPLER (Component B) capable of coupling with said light-sensitive diazonium compound (Component A) to form a blue dye; and, as a coupler (Component C1) capable of forming a yellow dye, at least one compound selected from the compounds represented by the general formula;

(WHEREIN N REPRESENTS 1 OR 2) OR FROM THE COMPOUNDS REPRESENTED BY THE GENERAL FORMULA;

(WHEREIN R4 and R5 each represents a hydrogen atom, a halogen atom or an alkyl group having 1-4 carbon atoms), -COR6 (wherein R6 represents an alkyl group having 1-4 carbon atoms, or a substituted or unsubstituted phenyl group or

WHEREIN R3 represents

WHEREIN R1 and R2 each represents an alkyl group having 1-6 carbon atoms or a cycloalkyl group having 5-6 carbon atoms, and X represents an anion, which comprises developing the lightsensitive material in the presence of: at least one compound selected from the compounds represented by the general formula;

A method for developing a diazo-type photographic lightsensitive material containing at least one light-sensitive diazonium compound (Component A) selected from the compounds represented by the general formula;

WHEREIN R8 and R10 each represents an alkyl group having 1-4 carbon atom, and R9 and R11 each represents a hydrogen atom or a halogen atom.

D R A W I N G

Description

Tsubota et a1.

May 6, 1975 METHOD FOR DEVELOPING BLACK DIAZOTYPE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS [75] Inventors: Motohiko Tsubota; Taiichi Nishirnura; Kinji Ohkubo, all of Minami Ashigara, Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Minami Ashigara, Kanagawa, Japan [22] Filed: May 22, 1973 [21] Appl. No.: 362,722

[30] Foreign Application Priority Data May 22, 1972 Japan 47-50539 [52] US. Cl 96/49; 96/91 R; 96/75;

[51] Int. Cl. G030 1/58; G03c 5/34; G03c H54 [58] Field 01 Search 96/91 R, 75, 49; 260/560 [56] References Cited UNlTED STATES PATENTS 2,405,523 8/1946 Sease et a1. 96/91 R 2,717,832 9/1955 Sulich 96/91 R 2,893,866 7/1959 Haefeli 96/91 R 3,052,542 9/1962 Sulich 96/91 R 3,113,025 12/1963 Bialczak 96/91 R 3,248,220 4/1966 VanRhijn......... 96/91 R 3,373,021 3/1968 Adams et a1 96/75 3,585,033 6/1971 Desjarlais 96/91 R 3,591,381 7/1971 Gray et al. 96/91 R 3,619,191 11/1971 Desjarlais 96/91 R 3,679,421 7/1972 Kasper 96/91 R FORElGN PATENTS OR APPLICATIONS 1,229,299 4/1971 United Kingdom 96/91 R OTHER PUBLlCATlONS Dinaburg, M. 5., "Photosensitive Diazo Compounds," The Focal Press, 1965, p. 105. Landau, R., Fascicules 9 and 17," Andrews Paper & Chem. Co. Inc., 1962, p. 65.

Primary Examiner-Charles L. Bowers, Jr. Att0rney,Agent, or F irm-Sughrue, Rothwell. Mion, Zinn & Macpeak [57] 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;

XN N o (I) wherein R, and R each represents an alkyl group having l-6 carbon atoms or a cycloalkyl group having 5-6 carbon atoms, and X represents an anion, which comprises developing the light-sensitive material in the presence of: at least one compound selected from the compounds represented by the general formula;

011 OR} (II) @3 0010-1 3 wherein 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;

on @CK coma (III) wherein R1 represents a hydrogen atom, an alkyl group having 1-4 alkyl group or (wherein n represents 1 or 2), as a coupler (Component B) capable of coupling with said light-sensitive diazonium compound (Component A) to form a blue dye; and, as a coupler (Component C capable of forming a yellow dye, at least one compound selected from the compounds represented by the general formula;

wherein R and R 0 each represents an alkyl group having l-4 carbon atom, and R9 and R each represents a hydrogen atom or a halogen atom.

41 Claims, 5 Drawing Figures PATENTEMY ems SHEET 1 BF 2 METHOD FOR DEVELOPING BLACK DIAZOTYPE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a diazo-type photographic light-sensitive material.

2. Description of the Prior Art In photographic methods for forming a dye image utilizing a light-sensitive diazonium compound, the diazonium compound is uniformly distributed on a support, imagewise destroyed by exposure, and the lightsensitive diazonium compound remaining in unexposed areas is subjected to a coupling reaction with a compound, called a coupler, capable of reacting with the diazonium compound in an alkaline atmosphere to form a dye, whereby a dye image is formed in the photographic material.

It is the step of forming a dye image in such a photographic material by development processing that is the primary subject of the present invention.

Such photographic methods can roughly be classified into two systems. 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. 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.

However, 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.

However, none of the dyes formed between a conventionally known light-sensitive diazonium compound and a coupler has a black tone. Therefore, in order to obtain a neutral black tone image, two or more couplers have heretofore been used in combination to thereby mix the colors thereof. However, in the dye images formed using a diazonium derivative of a dialkoxysubstituted p-phenylenediamine, which have so far been most widely used, the above-described defects are particularly serious and a neutral black tone cannot be obtained over a wide range of image density, often re sulting in serious dichroism. The term dichroism" as used herein means the phenomenon that the hue of an image becomes different at portions having a different image density. This phenomenon is due to the fact that since two or more couplers are used in combination so as to form a neutral black image, and each coupler does not react with the diazonium salt at the same ratio at all portions due to the coupling activity of each coupler being different at portions having a different image density, there results a difference in image hue. Also, it should be taken into consideration that the hue of the resulting dye can shift depending upon the pH of the processing solution used in developing.

SUMMARY OF THE INVENTION 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.

That is, 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;

XN 1i 0 t I) wherein R and R, each represents an alkyl group or a cycloalkyl group having l-6 carbon atoms, and X represents an anion, in the presence of at least one coupler (Component 8) capable of coupling with the lightsensitive diazonium compound to form a blue dye, selected from compounds represented by the general formula;

OR (ID Q7 CONE wherein R represents (wherein n represents 1 or 2) or from compounds represented by the general formula;

H 0 (III) CONH wherein 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;

R8 on on R8 -{3% OH R I I 9 R ing l-4 carbon atoms, and R and R each represents a hydrogen atom or a halogen atom; and optionally at least one coupler (Component C capable of coupling with the light-sensitive diazonium compound (Component A)) to form a yellow dye, selected from the compounds represented by the formulae;

OH OH 1 (VI) NHCONH/\ OH OH NHCSN and (VIII) NHCONHZ For the groups R, and R R and R R and R and R and R in every instance the pairs of the groups may be the same but can be different from each.

BRIEF DESCRIPTION OF THE DRAWINGS 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.

DETAILED DESCRIPTION OF THE INVENTION Component A used in the invention is a lightsensitive diazonium compound represented by the foregoing general formula (I). In general formula (I), specific examples of 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. Anions as are discussed in Photosensitive Diazo Compounds" by M. S. Dinabury, Focal Press (1964), or Light Sensitive Systems" by J. Kosar, John Wiley & Sons (1965), are useful in general. Preferred are salts of zinc.chloride, boron tetrafluoride, hydrogen sulfate and phosphorus hexafluoride. Compound (I) is stabilized (rendered harder to decompose) by the presence of X. As specific examples of 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 hexafluorophosphate, 4- morpholino-2-cyclohexyloxy-5- ethoxybenzenediazonium sulfate, and 4-morpholino- 2,5-dicyclohexyloxybenzenediazonium hexafluorophosphate and the like.

Component B represented by general formula (ll) or (Ill) is a coupler capable of forming a blue dye. ln general formula (11), specific examples of R are:

6 2-hydroxy-2'-(4"-methylbenzenesulfonyloxy)-3- naphthanilide, 2-hydroxy-3 '-(2 ethylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy- 4-( 2' '-chloro-4 '-methylbenzenesulfonyloxy )-3- naphthanilide, 2-hydroxy-2'-acetoxy- 3-naphthanilide, 2-hydroxy-3'-butyroyloxy-3-naphthanilide, 2-hydroxy- 4'-(2"-hydroxybenzoyloxy)-3-naphthanilide, 2-

hydroxy-4'-benzoyloxy-3-naphthanilide, 2-hydroxy-3-' On the other hand, in general formula (III), 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

000,3 QQQ,

--CO CH -CH CH and the like.

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-

65 (5 n-butoxy-l '-naphthyl )-2-hydroxy-3-naphthamide,

N-(5 '-hydroxy-l '-naphthyl)-2-hydroxy-3- naphthamide, N-( 7-phenethyloxy-l '-naphthyl)-2- hydroxy-3-naphthamide, N-(7'-hydroxy-l -naphthyl)- 2-hydroxy-3-naphthamide, N-( 8 '-hydroxy-1 naphthyl)-2-hydroxy-3-naphthamide, and the like.

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.

SYNTHESIS EXAMPLE 1 0.1 M01 of l-amino-2-naphthol hydrochloride and 0.1 mol of triethylamine were refluxed in 400 ml of acetonitrile, and 400 ml of benzene solution containing 0.1 mol of Z-hydroxynaphthoyl chloride was added thereto and the system further refluxed for 4 hours at the boiling point of the solvent and at 1 atmosphere. Thereafter, the solvent was distilled off, and the residue formed put into an ether-ethyl acetate solution (1:1 volume). After washing the solution with water, an organic layer was separated. The solvent was removed therefrom to crystallize the system, and the crystals formed were filtered out. The thus obtained crystals were N-(2 '-hydroxy-1'-naphthyl)-3-hydroxy-2- naphthamide having a melting point of 240242C.

SYNTHESIS EXAMPLE 2 0.1 M01 of 2-benzyloxyaniline was dissolved in 400 ml of acetonitrile, and 400 ml of benzene solution containing 0.1 mol of 3-hydroxy-2-naphthoyl chloride was added thereto while refluxing and then refluxing was continued for 5 hours. Thereafter, solvent was distilled off to crystallize the system, and the crystals formed were recrystallized from dioxane. The resulting crystals were 3-hydroxy-2'-benzyloxy-2-naphthanilide having a melting point of 184C.

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). In these general formulae, 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., and R and R each represents a hydrogen atom or a halogen atom such as chlorine, bromine or iodine. As specific examples of 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.

Methods of synthesizing several compounds used as Component C are described below. The synthesise is known from Japanese Patent Application No. 45-40756. 1. Production of 2,2, 4,4'-tetrahydroxy-3,3'-

dimethyldiphenyl sulfide:

18.7 Grams of Z-methylresorcinol was dissolved in 48 ml of ethyl acetate while stirring. Thereafter, 7.8 g of sulfur dichloride dissolved in 58 ml of ethyl acetate was gradually added to the ethyl acetate solution of 2- methylresorcinol, and the reaction mixture was stirred at a room temperature for 30 minutes while introducing dry nitrogen in order to remove hydrogen chloride generated by the reaction. Then, the reaction mixture was washed with water and extracted with ethyl acetate. The organic layer was separated and vacuum distilled. The ethyl acetate layer was vacuum distilled. The residual yellowish, solid reaction product was made Elemental analysis:

Calculated: C: 60.41% H: 5.07%

Found: C: 60.32 H: .20

2. Production of 2,2',4,4'-tetrahydroxy-3,3'-

dimethylphenyl sulfoxide:

13.9 Grams of 2,2,4,4'-tetrahydroxy-3,3-dimethyl diphenylsulfide was added to 100 ml of glacial acetic acid while stirring. Thereafter, 5.65 g of 30 percent hydrogen peroxide was gradually added thereto while continuing the stirring. The temperature of the mixture rose to 40C, and then gradually lowered to 25C. After continuing the stirring for 24 hours, the reaction mix ture was diluted with 250 ml of water. The thus diluted reaction mixture was stirred for 1 hour more during which a precipitate separated out from the reaction mixture. The precipitate thus formed was filtered out, washed with water and dried to obtain 8.5 g of the product having a decomposition point of 145C. Results of elemental analysis of the resulting 2,2',4,4'- tetrahydroxy-3,3-dimethyldiphenylsulfoxide product were as follows.

3. Production of 2,2',4,4'-tetrahydroxy-3,3'-dimethyl- 5 ,5 -dichlorodiphenylsulfide:

1 1.5 Grams of 2-methyl-4-ch1ororesorcinol was dissolved in ml of ethyl acetate, and to this solution was added 3.75 g of sulfur dichloride over a 30 minute period with stirring. During the addition of sulfur dichloride, the temperature of the reaction mixture was maintained at 15C and, after the completion of the addition of sulfur dichloride, the reaction mixture was stirred for 1 hour more. Thereafter, ethyl acetate was evaporated off from the reaction mixture, and the residue was washed with ml of toluene. The white solid formed was filtered out and dried to obtain 7.2 g of the product having a melting point of 198 to 200C. Results of elemental analysis of the resulting 2,2 ',4,4'-tetrahydroxy- 3,3'-dimethy1-5,5-dichlorodiphenylsulfide were as follows.

Calculated: Found:

Results of IR analysis were as follows.

middle OH absorption weak OH absorption strong phenyl absorption strong sulfur-phenyl absorption strong chlorine absorption 1 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,. To be specific, 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,).

Furthermore, in addition to the 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 However, 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.

As the second yellow coupler Component (C at least one compound selected from among the following three compounds is used.

1 ,B-di- '-hydroxyph enyl urea OH OH I NHCOHN 1 2 3 l B-di- (3 '-hydroxyph enyl -thiourea OH on NHCSHN B-hydro xy phenylurea NHCO NH When a light-sensitive diazo-type material having on a support a light-sensitive layer comprising the three Components (A), (B) and (C,) or the light-sensitive diazo-type material having on a support a lightsensitive layer comprising the Components (A), (B), (C and (C is used with carefully combined amounts of each component, there are provided neutral black images over a wide density range, which images are difficult to discriminate from the black tone images obtained by silver halide photography.

in this case, 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.

Furthermore, coupling Components (B), (C,) and (C are added in a molar ratio shown in FIG. 1. 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 ratios of Components (B) (C (C at each point are as follows.

W; (12.5 5.0 80.5), X; (95.0 5.0 0.0) Y; (37.5 62.5 0.0)

The molar ratio of diazonium salt to coupler is diazo/ coupler (total) about 10' to about 10 /1, preferably l0-l0'/l.

The molar ratios of Components (B) and (C,) when Component (C is not present is clear from the FIG. I.

The molar ratio of A to B and C, is A/B+C, about 10' to about 10 preferably, 10* 10 In addition, 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. ln addition to providing neutral black images over a wide range of density, the novel blue coupler Component (B) exhibits sufficient solubility in commonly used coupler solvents.

The 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,). For example, as 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. In order to prevent part of the diazo compound from being dissolved and spreading out to lower the contrast or blur the lines, there can be added to 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. Furthermore, 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.

These materials are used in amounts as are common in the art, e.g., in moles per mole of diazonium salt intensifer: S X 10 5 x 10 mole; stabilizer: l X 10" 9.2 X mole; development accelerator: l0 l0 mole; moisture absorbant: 10 l0 mole; wetting agent: l0 l0 mole.

As the support used in the invention, there can be used 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.

The present invention will now be described in greater detail by several examples, which, however, should not be construed to limit the scope of the invention in any way.

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. After confirming the dissolution, 0.20 g of 2,2, 4,4'-tetrahydroxy-3,3- dimethyldiphenylsulfide and 1.60 g of l,3-di-(3 hydroxyphenyl)-urea were then dissolved therein. Furthermore, immediately before coating the resulting solution, 1.70 g of 2,5-dibutoxy-4- morpholinobenzenediazonium tetrafluoroborate was added thereto to prepare a light-sensitive coating solution. The resulting light-sensitive coating solution was uniformly applied to a 150 p. thick transparent cellulose triacetate film in an amount of 27 cc/m, the cellulose triacetate film having been saponified to a depth of 20 microns by an alkali processing in an NaOH/al cohol/water bath at 80C for 30 seconds. The film thus coated with the coating solution was immediately fed to a drying zone heated at 60-80C, through which the film was passed in 5 minutes. The film having thereon the dried coating solution was allowed to remain in another drying station at 80-l00C for about minutes to thereby substantially completely remove any organic solvent remaining on the film. There was thus obtained a light-sensitive diazo-type film.

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. Furthermore, 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.

A light-sensitive diazo-type film prepared in the same manner as above using I g of 2.5-dibutoxy-4- morpholinobenzenediazonium tetrafluoroborate as the light-sensitive diazonium compound, 0.9 g of N-l naphthyl-2-hydroxy-3-naphthamide as the blue coupler component, 0.20 g of 2,2',4,4'-tetrahydroxy-3,3'- dimethyldiphenylsulfide and 1.60 g of l,3-di-(3- hydroxyphenyl)-urea as the yellow coupler components was processed as above and the visual density and the chromaticity were determined in the same manner as above. The results obtained are shown in FIG. 3.

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.

Comparing FIG. 2 with FIG. 3, it is seen that 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.

Images having a neutral black color over a similar wide density range were obtained when N-(2'-hydroxyl-naphthyl)-2-hydroxy-3-naphthamide used in the above formulation was replaced by N-(7'- phcncthyi'oa'y-l -naphthyl)-2-hydroxy-B-naphthamide, N-(4-methoxy-l -naphthyl)-2-hydroxy-3- naphthamide, N-(S -eth0xy-l '-naphthyl)-2-hydroxy-3- naphthamide, N-(6'-benzyloxy-l '-naphthyl)-2- hydroxy-3-naphthamide of N-(8 '-hydroxy-l naphthyl)-2-hydroxy-3-naphthamide.

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. l0 g of 2,5-dibutoxy- 4-morpholinobenzenediazonium tetrafluoroborate, coated on a cellulose triacetate film subjected to saponification processing as in Example 1, and dried. Thereafter, the resulting light-sensitive film was exposed and developed as in 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.

Images having a neutral black color over a similar wide density range were obtained when Z-hydroxy-T- (4"-methylbenzenesulfonyloxy)-3-naphthanilide used in the above formulation was replaced by 2-hydroxy-2'- benzenesulfonyloxy-3-naphthanilide, 2-hydroxy-4'- (2 ",4 '-dimethylbenzenesulfonyloxy )-3-naphthanilide, 2-hydroxy-2 3' "bromobenzenesulfonyloxy )-3- naphthanilide, 2-hydroxy-3-(4"- methylbenzenesulfonyloxy)-3-naphthanilide, 2- hydroxy-4'-(4'-t-butylbenzenesulfonyloxy)-3 naphthanilide or 2-hydroxy-3'-(2"- ethylbenzenesulfonyloxy)-3-naphthanilide.

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 as in Example 1. It was found that the thus obtained print film has a neutral black image over a wide density range as in Example 1.

Images having neutral black color over a similar wide density range were obtained when 2-hydroxy-2'- benzyloxy-3-naphthanilide used in the above formulation was replaced by 2-hydroxy-3'-butyroyloxy-3- It was found that the thus obtained print film has i formed thereon a neutral black image over a wide dennaphthanilide, 2-hydroxy-4 2 "-hydroxybenzoyloxy 3-naphtl1anilide, 2-( hydroxy-4 -benzoyloxy.)-3- naphthan ilide 2-hydroxy-3 4 '-chlorobenzoyloxy )-3- naphthanilide, 2-hydroxy-2 3 "-nitrobenzoyloxy )-3- naphthanilide or 2-hydroxy-4-phenethyloxy-3- naphthanilide.

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. After confirming the dissolution, 0.80 g of l,3-di-(3 hydroxyphenyl)- thiourea and 0.30 g of 2,2',4,4'-tetrahydroxy-3,3'- dimethylphenylsulfide were dissolved therein. Furthermore, 2.00 g of 2,5-dibutoxy-4- morpholinobenzenediazonium chloride'zinc chloride double salt was added to this solution immediately before coating in place of 2,5-dibutoxy-4- morpholinobenzenediazonium tetrafluoroborate to prepare a light-sensitive coating solution. Thereafter, the resulting coating solution was coated and dried as in Example I to form a light-sensitive film, which was exposed and developed as in Example I.

sity as in Example 1.

images having a neutral black color over a similarly wide density range were obtained when l,3-di'(3- hydroxyphenyD-thio-urea was replaced by 3hydroxyp'henylurea.

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 as in Example 1.

it was found that the thus obtained print film has formed thereon a neutral black image over a wide density range as in Example I.

images having a neutral black color over a similar wide density range were obtained when 2,2',4,4- tetrahydroxy-3 ,3 -d'imethyl-5 ,5 dichlorodiphenylsulfide used in the above formulation was replaced by 2,2',4,4'-tetrahydroxy-3,3-dipropyldiphenylsulfide or 2,2',4,4'-tetrahydroxy-3 ,3 dimethyl-5,5 '-dibromodiphenylsulfide.

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. Thereafter, the thus obtained light-sensitive film was exposed and developed as in Example 1. The resulting print film was found to have formed thereon a neutral black image over a wide density range as in Example l.

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. Thereafter, the resulting light-sensitive film was exposed and developed as in 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.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is:

l. A method for developing a diazo-type photographic light-sensitive material to form a neutral black image substantially showing no dichroism wherein said material contains a coating on a support of at least one light-sensitive diazonium compound designated Component A selected from the compounds represented by the general formula:

wherein 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:

CONH (m) wherein 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;

and, as a coupler designated Component C, capable of forming a yellow dye, at least one compound selected from the compounds represented by the general formula:

mo H OH a HO Is OH wherein 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;

wherein 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.

2. A method for developing a diazo-type photographic light-sensitive material as described in claim 1, wherein at least one compound selected from the compounds:

3 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. 1 of the drawing, 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. The process of claim 1 wherein the molar ratio of diazonium Compound A to the total of coupler Components B and C, is about to about 10 of A to l of B plus C, and the amount of Compound A coated is 10"m mol to 10m mol/m 4. The process of claim 2 wherein the molar ratio of diazonium Compound A to the total of coupler Components B, C, and C is about l0 l0' ofA to l of B plus C, plus C and the amount of Compound A coated is about l0"m mol to 10m mol/m 5. The process of claim 1 wherein 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.

6. The process of claim 2 wherein 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.

7. The process of claim 5 wherein X is selected from the group consisting of salts of zinc-chloride, boron tetrafluoridc, hydrogen sulfate and phosphorous hexafluoride.

8. The process of claim 6 wherein X is selected from the group consisting of salts of zinc-chloride, boron tetrafluoride, hydrogen sulfate and phosphorous hexafluoride.

9. The process of claim 1 wherein 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-npropoxybenzenediazonium hexafluorophosphate, 4- morpholin0-2-cyclohexyloxy-5- ethoxybenzenediazonium sulfate, and 4-morpholino- 2,5-dicyclohexyloxybenzene-diazonium hexafluorophosphate.

10. The process of claim 2 wherein 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 hexafluorophosphate, 4- morpholino-Z-cyclohexyloxy-5- ethoxybenzenediazonium sulfate, and 4-morpholino- 2,5-dicyclohexyloxybenzenediazonium hexafluorophosphate.

11. The process of claim 1 wherein R is selected from the group consisting of:

21 the group consisting of N-(2'-hydroxy-l'-naphthyl)-2- hydroxy-3-naphthamide, N-(4'-methoxy-l '-naphthyl)- 2-hydroxy-3-naphthamide, N-(5'-ethoxy-l '-naphthyl)- Z-hydroxy-B-naphthamide, N-( 6'-benzyloxy-l naphthyl)-2-hydroxy-3-naphthamide, N-(5'-n-butoxyl '-naphthyl)-2-hydroxy-3-naphthamide, N-( S hydroxy-l '-naphtyl-2-hydroxy-3-naphthamide, N-(7'- phenethyloxy-l '-naphthyl)-2-hydroxy-3-naphthamide, N-(7-hydroxy-l '-naphthyl)-2-hydroxy-3-naphthamide, N-(7 '-hydroxyl '-naphthyl)-2-hydroxy-B-naphthamide and N-( b 8'-hydroxy-l '-naphthyl)-2-hydroxy-3- naphthamide.

18. The method of claim 2 wherein the compound represented by the general Formula III is selected from the group consisting of N(2'-hydroxy-l '-naphthyl)-2- hydroxy-3-naphthamide, N-(4-methoxy-l '-naphthyl)- 2-hydroxy-3-naphthamide, N-( 5 '-ethoxy-l '-naphthyl)- 2-hydroxy-3-naphthamide, N-(6'-benzyloxy-l naphthyl)-2-hydroxy-3-naphthamide, N-(5'-n-butoxyl'-naphthyl)-2-hydroxy-I i-naphthamide, N-( 5 hydroxy-l'-naphthyl)-2-hydroxy-3-naphthamide, N- (7 '-phenethyloxy-l '-naphthyl)-2-hydroxy-3- naphthamide, N-(7'-hydroxy-l'-naphthyl)-2-hydroxy- B-naphthamide and N-(8-hydroxy-l'-naphthyl)-2- hydroxy-3-naphthamide.

19. The method of claim 1 wherein 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.

20. The method of claim 2 wherein 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.

21. The method of claim 1 wherein a compound selected from the group consisting of ammonium sulfate, zinc chloride, magnesium hloride and nickel sulfate is present to prevent the dia Z compound from being dissolved and spreading out on the photographic material.

22. The method of claim 2 wherein a compound selected from the group consisting of ammonium sulfate, zinc chloride, magnesium chloride and nickel sulfate is present to prevent the diazo compound from being dissolved and spreading out on the photographic material.

23. The method of claim 1 wherein thiourea oor thiosinamine is present to prevent discoloration of the background of a print obtained by development.

24. The method of claim 2 wherein thiourea or thiosinamine is present to prevent discoloration of the background of a print obtained by development.

25. The method of claim 1 wherein a development accelerator, hygroscopic agent, wetting agent, binding agent or pigment is present in the light-sensitive material.

26. The method of claim 2 wherein a development accelerator, hygroscopic agent, wetting agent, binding agent or pigment is present in the light-sensitive material.

27. The method of claim 25 wherein said development accelerator is l-allyl-3-/3-hydroxyethyl-thiourea 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.

28. The method of claim 26 wherein 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.

29. The method of claim 25 wherein based on moles per mole of diazonium salt, said development accelerator is present in a concentration of 10 1Cl mole, said hygroscipic agent is present in a concentration of 10 l() mole and said wetting agent is present in a concentration of l010 mole.

30. The method of claim 26 wherein based on moles per mole of diazonium salt, said development accelerator is present in a concentration of l0"--l0 mole, said hygroscopic agent is present in a concentration of 10" 10 mole.

31. The method of claim 1 wherein said support is made from polycarbonate, regenerated cellulose, polyester, a cellulose ester or paper.

32. The method of claim 2 wherein said support is made from polycarbonate, regenerated cellulose polyester, a cellulose ester or paper.

33. The method of claim 31 wherein said polyester is polyethylene terephthalate and said cellulose ester is cellulose acetate butyrate, cellulose diacetate or cellulose triacetate.

34. The method of claim 32 wherein said polyester is polyethylene terephthalate and said cellulose ester is cellulose acetate butyrate, cellulose diacetate or cellulose triacetate.

35. The method of claim 1 wherein 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.

36. The method of claim 1 wherein Component B is 2'hydroxy-l '-naphthyl )-2-hydroxy-3-naphthamide.

37. The method of claim 1 wherein Component B is Z-hydroxy-Z 4 '-methylbenzenesulfonyloxy )-3- naphthanilide.

38. The method of claim 19 wherein said precoupling restrainer is present in a concentration of l X 10 to 9.2 X l0 mole per mole of diazonium salt.

39. The method of claim 20 wherein said precoupling restrainer is present in a concentration of l X 10 to 9.2 X 10 mole per mole of diazonium salt.

40. The method of claim 21 wherein said compound to prevent dissolving and spreading of the diazo compound is present in a concentration of 5 X l0 to 5 X 10 mole per mole of diazonium salt.

41. The method of claim 22 wherein said compound to prevent dissolving and spreading of the diazo compound is present in a concentration of 5 X 10' to 5 x 10 mole per mole of diazonium salt.

Claims

1. A METHOD FOR DEVELOPING A DIAZO-TYPE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL TO FORM A NEUTRAL BLACK IMAGE SUBSTANTIALLY SHOWING NO DICHROISM WHEREIN SAID MATERIAL CONTAINS A COATING ON A SUPPORT OF AT LEAST ONE LIGHT-SENSITIVE DIAZONIUM COMPOUND DESIGNATED COMPONENT A SELECTED FROM THE COMPOUNDS REPRESENTED BY THE GENERAL FORMULA:

2. A METHOD FOR DEVELOPING A DIAZO-TYPE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL AS DESCRIBED IN CLAIM 1 WHEREIN AT LEAST ONE COMPOUND SELECTED FROM THE COMPOUNDS:

3. The process of claim 1 wherein the molar ratio of diazonium Compound A to the total of coupler Components B and C1 is about 10 1 to about 10 of A to 1 of B plus C1 and the amount of Compound A coated is 10 1m mol to 10m mol/m2.

4. The process of claim 2 wherein the molar ratio of diazonium Compound A to the total of coupler Components B, C1 and C2 is about 10 1 -101 of A to 1 of B plus C1 plus C2 and the amount of Compound A coated is about 10 1m mol to 10m mol/m2.

5. The process of claim 1 wherein R1 and R2 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, t-pentyl, cyclopentyl and cyclohexyl, wherein R1 and R2 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.

6. The process of claim 2 wherein R1 and R2 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, t-pentyl, cyclopentyl and cyclohexyl, wherein R1 and R2 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.

7. The process of claim 5 wherein X is selected from the group consisting of salts of zinc.chloride, boron tetrafluoride, hydrogen sulfate and phosphorous hexafluoride.

8. The process of claim 6 wherein X is selected from the group consisting of salts of zinc.chloride, boron tetrafluoride, hydrogen sulfate and phosphorous hexafluoride.

9. The process of claim 1 wherein Component A is selected from the group consisting of 4-morpholIno-2,5-dimethoxybenzenediazonium tetrafluoroborate, 4-morpholino-2-methoxy-5-sec-butoxybenzenediazonium sulfate, 4-morpholino-2-ethoxy-5-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-sec-butoxybenzenediazonium tetrafluoroborate, 4-morpholino-2-cyclopentyloxy-5-n-propoxybenzenediazonium hexafluorophosphate, 4-morpholino-2-cyclohexyloxy-5-ethoxybenzenediazonium sulfate, and 4-morpholino-2,5-dicyclohexyloxybenzene-diazonium hexafluorophosphate.

10. The process of claim 2 wherein Compound A is selected from the group consisting of 4-morpholino-2,5-dimethoxybenzenediazonium tetrafluoroborate, 4-morphoolino-2-methoxy-5-sec-butoxybenzenediazonium sulfate, 4-morpholino-2-ethoxy-5-n-pentoxybenzenediazonium hexafluoropphosphate, 4-morpholino-2-iso-propoxy-5-cyclopentyloxy-benzenediazonium chloride.zinc chloride double salt, 4-morpholino-2,5-di-n-butoxybenzenediazonium tetrafluoroborate, 4-morpholino-2-t-butoxy-5-cyclohexylbenzenediazonium tetrafluoroborate, 4-morpholino-2-n-pentoxy-5-sec-butoxybenzenediazonium tetrafluoroborate, 4-morpholino-2-cyclopentyloxy-5-n-propoxybenzenediazonium hexafluorophosphate, 4-morpholino-2-cyclohexyloxy-5-ethoxybenzenediazonium sulfate, and 4-morpholino-2,5-dicyclohexyloxybenzenediazonium hexafluorophosphate.

11. The process of claim 1 wherein R3 is selected from the group consisting of:

12. The process of claim 2 wherein R3 is selected from the group consisting of:

13. The method of claim 1 wherein the compound represented by the general Formula II is selected from the grouop consisting of 2-hydroxy-3''-(4''''-methylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-2''-hydroxy-2''-benzenesulfonyloxy-3-naphthanilide, 2-hydroxy-4''-(2'''', 4''''-dimethylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-2''-(3''''-bromobenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-4''-(4''''-butylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-2''-(4''''-methylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-3''-(2''''-ethylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-4''-(2''''-chloro-4''''-methylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-2''-acetyloxy-3-naphthanilide, 2-hydroxy-3''-butyroyloxy-3-naphthanilide, 2-hydroxy-4''-(2''''-hydroxybenzoyloxy)-3-naphthanilide, 2-hydroxy-4''-benzoyloxy-3-naphthanilide, 2-hydroxy-3''-(4''''-chlorobenzoyloxy)-3-naphthanilide, 2-hydroxy-2''-benzyloxy-3-naphthanilide, 2-hydroxy-4''-phenethyloxy-3-naphthanilide, 2-hydroxy-4''-(2''''-chloro-4''''-methylbenzenesulfonyloxy)-3-naphthanilide, N-(2''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(4''-methoxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''ethoxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(6''-benzyloxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-butyloxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-hydroxy-5''-1''-naphthyl)2-hydroxy-3-naphthamide, N-(7''-phenethyloxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N (7''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide and N-(8''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide.

14. The method of claim 2 wherein the compound represented by the general Formula II is selected from the group consisting of 2-hydroxy-3''-(4''''-methylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-2''-benzenesulfonyloxy-3-naphthanilide, 2-hydroxy-4''-(2'''', 4''''-dimethylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-2''-(3''''-bromobenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-4''-(4''''-t-butylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-2''-(4''''-methylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-3''-(2''''-ethylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-4''-(2''''-chloro-4''''-methylbenzenesulfonyloxy)-3-naphthanilide, 2-hydroxy-2''-acetyloxy-3-naphthanilide, 2-hydroxy-3''-butyroyloxy-3-naphthanilide, 2-hydroxy-4''-(2''''-hydroxybenzoyloxy)-3-naphthanilide, 2-hydroxy-4''-benzoyloxy-3-naphthanilide, 2-hydroxy-3''-(4''''-chlorobenzoyloxy)-3-naphthanilide, 2-hydroxy-2''-benzyloxy-3-naphthanilide, 2-hydroxy-4''-phenethyloxy-3-naphthanilide, 2-hydroxy-4''-(2''''-chloro-4''''-methylbenzenesulfonyloxy)-3-naphthanilide, N-(2''-hydroxy-1''-naphthy)-2-hydroxy-3-naphthamide, N-(4''-methoxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-ethoxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(6''-benzyloxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-butyloxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-naphthyl)-2-hydroxy-3-naphthamide, N-(7''-phenethyloxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N (7''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide and N-(8''-hydroxy-1''-naphthy)-2-hydroxy-3-naphthamide.

15. The method of claim 1 wherein R7 is a group selected from the class consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, benzyl and phenethyl.

16. The method of claim 2 wherein R7 is a group selected from the class consisting of hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, benzyl and phenethyl.

17. The method of claim 1 wherein the compound represented by the general Formula III is selected from the group consisting of N-(2''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(4''-methoxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-ethoxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(6''-benzyloxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-n-butoxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-hydroxy-1''-naphtyl)-2-hydroxy-3-naphthamide, N-(7''-phenethyloxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(7-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(7''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide and N-(b 8''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide.

18. The method of claim 2 wherein the compound represented by the general Formula III is selected from the group consisting of N-(2''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(4-methOxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-ethoxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(6''-benzyloxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-n-butoxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(5''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(7''-phenethyloxy-1''-naphthyl)-2-hydroxy-3-naphthamide, N-(7''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide and N-(8''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide.

19. The method of claim 1 wherein 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 precoupling between the diazonium compound and the coupling components.

20. The method of claim 2 wherein 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 pre-coupling between the diazonium compound and the coupling components.

21. The method of claim 1 wherein a compound selected from the group consisting of ammonium sulfate, zinc chloride, magnesium chloride and nickel sulfate is present to prevent the diazo compound from being dissolved and spreading out on the photographic material.

25. The method of claim 1 wherein a development accelerator, hygroscopic agent, wetting agent, binding agent or pigment is present in the

27. The method of claim 25 wherein said development accelerator is 1-allyl-3- Beta -hydroxyethyl-thiourea or 1-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.

28. The method of claim 26 wherein said development accelerator is 1-allyl -3-62 -hydroxyethyl-thiourea or 1-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.

29. The method of claim 25 wherein based on moles per mole of diazonium salt, said development accelerator is present in a concentration of 10 3 -102 mole, said hygroscipic agent is present in a concentration of 10 5-10 mole and said wetting agent is present in a concentration of 10 4-102 mole.

30. The method of claim 26 wherein based on moles per mole of diazonium salt, said development accelerator is present in a concentration of 10 3-102 mole, said hygroscopic agent is present in a concentration of 10 4-102 mole.

35. The method of claim 1 wherein Component B is N-(2''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide, 2-hydroxy-2''-(4''''-methylbenzenesulfonyloxy)-3-naphthanilide, or N-(2''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide.

36. The method of claim 1 wherein Component B is -(2''-hydroxy-1''-naphthyl)-2-hydroxy-3-naphthamide.

37. The method of claim 1 wherein Component B is 2-hydroxy-2''-(4''''-methylbenzenesulfonyloxy)-3-naphthanilide.

38. The method of claim 19 wherein said pre-coupling restrainer is present in a concentration of 1 X 10 2 to 9.2 X 102 mole per mole of diazonium salt.

39. The method of claim 20 wherein said pre-coupling restrainer is present in a concentration of 1 X 10 2 to 9.2 X 102 mole per mole of diazonium salt.

40. The method of claim 21 wherein said compound to prevent dissolving and spreading of the diazo compound is present in a concentration of 5 X 10 3 to 5 X 102 mole per mole of diazonium salt.

41. The method of claim 22 wherein said compound to prevent dissolving and spreading of the diazo compound is present in a concentration of 5 X 10 3 to 5 X 102 mole per mole of diazonium salt.