US3619191A

US3619191A - Diazo-type materials

Info

Publication number: US3619191A
Application number: US667365A
Authority: US
Inventors: Robert C Desjarlais
Original assignee: Tecnifax Corp
Current assignee: Tecnifax Corp
Priority date: 1967-09-13
Filing date: 1967-09-13
Publication date: 1971-11-09
Anticipated expiration: 1988-11-09
Also published as: DE1797322B2; DE1797322A1; DE1793791A1; FR1581357A; GB1248421A; GB1248423A

Abstract

Light-sensitive diazo compositions containing light-sensitive diazonium derivatives of dialkoxy-substituted paraphenylene diamines, at least one coupling component for said diazonium derivatives, and at least one background discoloration inhibitor are disclosed.

Description

United States Patent [72] inventor Robert C. Desjarlais South Hadley Falls, Mass. [21] Appl. No. 667,365 [22] Filed Sept. 13, 1967 [45] Patented Nov. 9, 1971 [73] Assignee The Tecnilax Corporation Holyoke, Mass.

[54] DlAZO-TYPE MATERIALS 39 Claims, No Drawings [52] U.S.Cl 96/75, 96/49, 96/91 [51] 1nt.Cl G03c1/60, G03c l/58,G03c 1/54 [50] Field 01 Search 96/91, 75, 49

[56] References Cited UNITED STATES PATENTS 1,803,906 5/1931 Kreiger et a1. 96/91 2,531,485 11/1950 Van Glohn et a1 96/91 2,617,726 11/1952 Kessels 96/91 X 2,661,291 12/1953 Slifkin. 96/91 X 2,717,832 9/1955 Sulich... 96/91 2,893,866 7/1959 Haefeli 96/91 X 3,069,268 12/1962 Herrick 96/75 X 3,076,707 2/1963 Lawton et a1. 96/75 3,052,542 9/1962 Sulich 96/91 X 3,1 13,025 12/1963 Bialczak 96/49 X 3,248,220 4/1966 Van Rhijn 96/91 3,410,688 11/1968 Weleh 96/91 FORElGN PATENTS 937,510 9/1963 Great Britain 96/91 OTHER REFERENCES Dinaburg, M. S., Photosensitive Diazo Cpds," 1964,

pages 50 53.

Nollev, C. R,, Textbook of Organic Chemistry," 2nd Ed., 1958, page 341 Kosar, J., Light-Sensitive Systems," 296.

Primary Examiner- Norman G. TOrChin Assistant ExaminerCharIes L. Bowers, Jr.

Allorneys- William J. Foley, Stanton T. Hadley and John W.

Kane, Jr.

1965, pages 292- ABSTRACT: Light-sensitive diazo compositions containing light-sensitive diazonium derivatives of dialkoxy-substituted paraphenylene diamines, at least one coupling component for said diazonium derivatives, and at least one background discoloration inhibitor are disclosed.

. BACKGROUND OF THE INVENTION Field of the Invention This invention relates to novel, light-sensitive diazotype materials of the two-component type which contain a diazonium derivative of a dialkoxy-substituted paraphenylene diamine as the diazo component, and which are less susceptible to background discoloration after development than are similar materials of the prior art. Certain diazo compositions within the scope of this invention are useful in preparing black-line prints which are highly resistant to light fading and which exhibit a neutral black-line development over a wide image-density range, as well as being resistant to background discoloration subsequent to their development.

DESCRIPTION OF THE PRIOR ART As is well-recognized by those skilled in the art, the two most widely accepted diazo processes are often referred to as the one-component process or the semi-wet development process, wherein 'the light-sensitive diazotype material contains the diazo compound in the absence of a coupler and the development step in said process consists of applying a developing solution containing a coupler to the diazotype material; and the two-component process or the dry development process, wherein the light-sensitive diazotype material contains both the diazo compound and the coupling component or components and wherein the development step in said process consists of exposing the diazotype material to an alkaline atmosphere, which is usually a mixture of ammonia and water vapors.

Although the two'component or dry development process has certain advantages over the one-component or semi-wet development process, (the major advantage being the one most obvious-the fact that it is essentially a dry process), there has, up until now, been certain serious disadvantages associated with the dry process also. In order to obtain certain desired colors in the developed print, it is necessary to use a relatively specific class of diazonium compounds in combination with a specific class or classes of coupling components; and, although these combinations may result in the color desired in the final print, this print ofttimes exhibits unacceptable background discoloration in the exposed areas wherein the diazo component has been decomposed. This is particularly true in those cases where the diazo component is a diaionium derivative of a dialkoxy-substituted p-phenylene diamine. Although diazonium derivatives of dialkoxy-substituted p-phenylene diamines are known to be useful as diazo components in diazotype materials, particularly in one-component diazotype materials, their use in two-component diazotype materials has been severely limited, due to the pronounced tendency of such materials to discolor after development in the background or burnout areas. Without wishing to be bound to any particular theory as to the cause of this background discoloration, it is believed that this discoloration is due to the subsequent oxidation of the photolysis products of these types of diazo components (i.e., the initially colorless derivatives of these diazo components which are formed in the background or nonimage areas upon exposure of the light-sensitive diazotype material to a light source of sufficient intensity and of the proper wavelength to effect "imaging" of the diazotype material), due to other components and/or impurities which are present in the diazo layer. Until now, this problem of background discoloration which has been observed with these types of diazo components has restricted their use in two-component diazotype materials, despite the fact that they are in most other respects very suitable for use in diazotype materials.

In addition, there is also a well-recognized need in the diazo art for a diazotype material which results upon development in a neutral-black-line print which is neutral black over a wide range of image densities. Although there are diazotypec materials available which may result in a black-line print at a given image density, the color of the print may vary considerably from the desired black at higher or lower image densities. It is believed that this two-toning" is due to a difference in the coupling activities of the various couplers employed to obtain a black-line print, and that if the various couplers are not carefully matched for coupling activity, the difference in coupling rates between or among the coupling components results in images other than neutral black, particularly in the lower image density areas. Another factor which makes the achievement of a neutral black-line image over a wide image density range most difficult is the fact that many resulting azo dyes produced upon coupling or development of many of the previously available diazotype materials are subject to a color-shift or a change in shade with a change in the pH of the diazotype print, resulting in a shift or change in the color of the resulting azo dye from the desired neutral black. It is apparent that in order to obtain a neutral black-line print over a wide image density, the coupling rates of the various couplers employed must be very carefully matched to obtain a mixture of azo dyes in the developed print which is neutral black over a wide range, and the resulting azo dyes must not be subject to a color-shift or change in shade with a change in pH. It is, of course, also highly desirable that the burnout or non-image areas of such a neutral black-line print exhibit little or no background discoloration upon aging. Until now, a two-component diazotype material with these desirable features was unavailable in the diazo art. As indicated above, although the diazonium derivatives of a dialkoxy-substituted p phenylene diamines have heretofore been known to be capable of producing neutral black-line images over at least some ranges of image densities, their inherent tendency to discolor in the background or non-image areas has precluded their extensive use in a two-component diazotype material to form a black-line print.

SUMMARY OF THE INVENTION It has now been found that the incorporation of at least one background discoloration inhibitor into light-sensitive diazo compositions containing a diazonium derivative of a dialkoxysubstituted paraphenylenediamine as the diazo component substantially reduces the background discoloration which one normally obtains with diazo compositions wherein these types of diazo components are employed without such an inhibitor.

7 As has been indicated above, derivatives of dialkoxy-substituted paraphenyl-enediamines have been found to be a potentially very useful class of diazo components, except for their tendency in developed prints to discolor in the background areas. It has been found that this class of diazo compounds is capable of producing azo dyes having excellent light fastness, bright shades, good resistance to color changes due to gas fading; and, with the proper choice of coupling components, dyes which form a neutral black image upon development. By incorporating a background discoloration inhibitor of the type hereinafter disclosed, two-component diazotype materials can be prepared using diazonium derivatives of dialkoxy-substituted p-phenylenediamines, said diazotype materials being essentially free from background discoloration after development.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The Diazo Component As has hereinbefore been indicated, the light-sensitive com positions of this invention employ, as the diazo component, light-sensitive diazonium compounds derived from dialkoxysubstituted p-phenylenediamines. More particularly, these diazonium compounds are compounds formed from a p-phenylenediamine having a general formula selected from the group consisting of:

( ZtR wherein R is an alkyl group or cycloalkyl group containing from about 1 to about 6 carbon atoms, R and R are alkyl groups containing from 1 to about 3 carbon atoms, and the group represented by is a saturated, nitrogen-containing, heterocyclic ring, containing up to about 7 atoms in said ring. Diazonium derivatives of compounds wherein R is a branched alkyl group, such as isopropyl, isobutyl, secondary butyi, tertiary butyl, tertiary pentyl, 2-pentyl, 3-pentyl, and the like; or a cycloalkyl group such as cyclopentyl, cyclohexyl, and the like; and wherein the group represented by diazo compounds are particularly useful in preparing blackline prints when they are employed with the proper coupling components in a one-component process. However, as has been indicated above, the use of these compounds in a twocomponent process has heretofore been limited, due to the fact that the resulting prints exhibited a pronounced degree of background discoloration.

The diazo component employed in the present invention is preferably employed in the form of a stabilized diazo salt, such as a metal halide salt, a sulfate salt, and the like. illustrative of the types of diazonium compounds which may be employed in this invention are compounds such as 4-morpholine-2,5-di

4-1n0rph0lino-2, 5-dl(lsopr0poxy)benzcnc diazoniurn hexafluorophosphate 4-morpholno-2, 5-di(eyc1opentoxy) cenzerie diazonium chloride O N N,Cl

and the like.

The Coupling Component As appreciated by one skilled in the art, the choice of coupler or couplers depends primarily upon the color desired in the resulting diazo print, and the speed required for development. illustrative of the types of couplers which can be employed in preparing the diazotype materials of this invention are couplers such as resorcinol, 2-methyl resorcinol, 4-methyl resorcinol, S-methyl resorcinol, 2-methyl 4-ethyl resorcinol, 2,4 dichloro resorcinol, 4,6 dichloro resorcinol, 4-chloro resorcinol, 4-bromo resorcinol, 4-iodo resorcinol, 4-fluoro resorcinol, N-B-hydroxy-ethyl-a-resorcylamide, a-resorcylamide, N-phenyl a-resorcylamide, resorcinol 5-sulfonic acid, resorcinol 4-sulfonic acid, a-resorcylic acid, resorcinol 4,6 disulfonic acid, resorcinol mono-methyl ether, resorcinol mono benzoate, resorcinol mono acetate, resorcinol mono formate, B-resorcylic acid methyl ester, B-resorcylic acid amide, B-resorcylic acid, a-naphthol B-naphthol 2,3 dihydroxy naphthalene, a-resorcylic acid, a-resorcylic acid methyl ester, a-resorcylic acid amide, 4 bromo-3,5-dihydroxybenzoic acid amide, 4-chloro-3,S-dihydroxybenzoic acid amide, bis- (2 ,4-dihydroxy phenyl sulfide), bis-( 2,4-dihydroxy phenyl sulfoxide), condensation product of S-amino resorcinol and cyanuric chloride, hydroquinone monomethyl ether, phloroglucinol, phloroglucinol mono methyl ether, 1,3,5 trihydroxy-Z-methyl benzene, 0' hydroxy diphenyl, 3,3',5- trihydroxy diphenyl, 2,4,4'-trihydroxy diphenyl, 2,2',4,4'- tetrahydroxy diphenyl, 2,2,4,4'-tetrahydroxy diphenyl sulfide, 3,3',5,5-tetrahydroxy diphenyl, 2,2',4,4-tetrahydroxy 3,3'-dimethyl 5,5-dichlorodiphenyl sulfide, 2,2, 4,4- tetrahydroxy 5,5dichloro diphenyl sulfide, 2,3 dihydroxy naphthalene 6 sulfonic acid, 1 naphthol-2 sulfonic acid, 1 naphthol-3 sulfonic acid, 1 naphthol-4 sulfonic acid, 2 hydroxy naphthalene-3,6 -disulfonic acid, 1,8 dihydroxy naphthalene-3,6 disulfonic acid, 2,7 dihydroxy naphthalene- 3,6 disulfonic acid, 1,8 dihydroxy naphthalene-3,5 disulfonic acid, l,8 dihydroxy naphthalene-4 sulfonic acid, l,8 dihydroxy naphthalene-3 sulfonic acid, 2,8 dihydroxy naphthalene-6 sulfonic acid, 3,8 dihydroxy naphthalene-6 sulfonic acid 8 acetylamino-l -naphthol-5-sulfonic acid, 2 hydroxy naphthalene--sulfonic acid, 2 hydroxy naphthalene-4-sulfonic acid, 2 hydroxy naphthalene-6,8-disulfonic acid, 2 hydroxy naphthalene-7-sulfonic acid, 1 hydroxy naphthalene- 3,8-disulfonic acid,2 hydroxy-3 naphthoic-(3'nitro) anilide, 2 hydroxy-3 naphthoic-(4'chloro) anilide, 2 hydroxy-3 naphthoic-(4chloro) anilide, 2 hydroxy-3 naphthoic- (4methoxy) anilide, 2 hydroxy-3 naphthoic- (Zmethoxy) anilide, 2hydroxy-3 naphthoic-(2 methyl) anilide, 2 hydroxy- 3 naphthoic-(4 methyl) anilide, 2 hydroxy-3 naphthoic-(S' methyl) anilide, 2 hydroxy-3 naphthoic-( 2',5' dimethoxy) anilide, 2 hydroxy-3 naphthoic-(l naphthanilide), 2 hydroxy-3 naphthoic-( 2 naphthanilide), 2 hydroxy-3 naphthoic-(Z methyl, 4' chloro) anilide, 2 hydroxy-3 naphthoic-(Z chloro) anilide, (acetoacetyl amino benzene), (acetoacetyl-benzylamide), (2 acetoacetylamino-l-methoxy benzene), (2 chlorolacetoacetylamino-benzene (4-chlorol -acetoacetylaminobenzene), (2,5-dichlorol -acetoacetylamino-benzene (4 acetoacetylamino-l ,B-dimethoxy benzene), (6 acetoacetylamino-l,4-dimethoxy benzene), (6 chloro-4 R4 OH OH R4 110- -s OH I z z R HO OH R4 0 HO -& OH

wherein R is hydrogen; an alkyl group containing from one to about six carbon atoms, such as methyl, ethyl, propyl, butyl, amyl, hexyl, 2-ethylbutyl, and the like; and unsubstituted aryl group or halo-substituted substituted aryl group such as pchlorophenyl, m-chlorophenyl, phenyl, and the like; an aralkyl group, including alkyl-substituted arlkyl groups and halo-substituted aralkyl groups, such as benzyl p-methylbenzyl, pchlorobenzyl, o-chlorobenzyl and the like; an alkaryl group, including halo-substituted alkaryl groups, such as xylyl, chloroxylyl, tolyl, chlorotolyl, and the like; an alkoxy group containing from one to about six carbon atoms, such as methoxy, propoxy, butoxy, amyloxy, and the like; an aryloxy group including halo-substituted aryloxy groups such as phenoxy, p-chlorophenoxy and the like, an aralkyoxy group including halo-substituted aralkoxy groups such as benzyloxy, p-chlorobenzyloxy, and the like; or a halogen, such as chlorine, bromine or iodine; Z is hydrogen or a halogen, such as chlorine, bromine or iodine, and wherein at least one of the groups represented by R and Z is a group other than hydrogen. The substituted diresorcyl sulfides are particularly preferred.

The substituted diresorcyl sulfides described above onto prepared by reacting sulfur dichloride in the presence of an inert solvent with a resorcinol substituted in the 2-position with an alkyl group, suchas methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a 2-ethyl-butyl group, and the like; an aryl group or halo-substituted aryl group, such as a phenyl group, a p-chlorophenyl group, a mchlorophenyl group, and the like; an aralkyl group, alkyl-substituted aralkyl group, or halo-substituted aralkyl group such as a benzyl group, a p-methylbenzyl group, a p-chlorobenzyl group, an o-chlorobenzyl group, and the like; and alkaryl group or halo-substituted alkaryl group, such as a xylyl group, a chloroxylyl group, a tolyl group, a chlorotolyl group, and the like; an alkoxy group, such as a methoxy group, a propoxy group, a butoxy group, an amyloxy group, and the like; an aryloxy group or halo-substituted aryloxy group, such as a phenoxy group, a p-chlorophenoxy group, and the like; an aralkoxy group or halo-substituted aralkoxy group, such as a benzyloxy group, a p-chlorobenzyloxy group, and the like; or a I halo group, such as a chloro group, an iodo group, a bromo group, and the like; a resorcinol substituted in the 4-position with a halo group, such as a chloro group, an iodo group, a

- bromo group, and the like; or a resorcinol substituted in the 2- position with an alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a 2-ethylbutyl group, and the like; an aryl group or halo-substituted aryl group, such as a phenyl group, a p-chlorophenyl group, a m-chlorophenyl group, and the like; an arlkyl group, alkylsubstituted aralkyl group, or halo-substituted aralkyl group such as a benzyl group, a p-methylbenzyl group, a pchlorobenzyl group, an o-chlorobenzyl group, and the like; and alkaryl group or halo-substituted alkaryl group, such as a xylyl group, a chloroxylyl group, a tolyl group, a chlorotolyl group, and the like; an alkoxy group, such as a methoxy group, a propoxy group, a butoxy group, an aryloxy group, and the like; an aryloxy group or halo-substituted aryloxy group, such as a phenoxy group, a pchlorophenoxy group, and the like; an aralkoxy group or halo-substituted aralkoxy group, such as a benzyloxy group, a p-chlorobenzyloxy group and the like; and in the 4-position with a halo group, such as a chloro group, an iodo group, a bromo group, and the like. lnert solvents such as diethyl ether, dipropyl ether, ethyl acetate, and the like, can be employed, and the reaction temperature can vary, depending on the type of inert solvent which is employed. Temperatures of from about 5 C. to about 35 C. are preferred, with temperatures of from about 5 to about 15 C. being particularly preferred with the lower-boiling inert solvents. It is also preferred to conduct the reaction under an atmosphere of a dry, inert gas, such as nitrogen, helium, and the like, said gas being used to facilitate the removal of the hydrogen chloride which is evolved. The resulting substituted diresorcyl sulfide compounds are easily recovered as crystalline solids having relatively high melting points (in excess of 150 C.) and are readily purified by recrystallization from alcohols or ketones, such as acetone and methylethyl ketone. The sulfoxide derivatives of these substituted diresorcyl sulfides are prepared by treating the sulfide with an oxidizing agent, such as hydrogen peroxide, chromic oxide, potassium permanganate, and the like. Illustrative of the types of compounds within this preferred class of orange or sepia couplers are compounds such as ,4,4-tetrahydroxy-3,3'-dimethyldiphenyl sulfide, ,4,4'-tetrahydroxy-5,5-dichlorodiphenyl sulfide, ,4,4'- tetrahydroxy-3,3-dimethyl-5,5-dichlorodiphenyl sulfide, ,4,4'-tetrahydroxy-3,3,'-dimethyldiphenyl sulfoxide, and the like. It is believed that the diresorcyl sulfides and sulfoxides which are substituted in both the 3,3 positions and the 5,5 positions are novel compositions of matter, and they are claimed as such herein. Quite unexpectedly, they have been found to be excellent yellow shading components for diazo compositions, and they exhibit coupling rates which are highly compatible with the coupling rates of the blue couplers which are usually employed.

The following preparations are provided to illustrate more specifically the methods of preparing the preferred orange or sepia couplers for use in the present invention.

A. PREPARATION OF ,4,4'-TETRAHYDROXY-3,3 DIMETHYL DlPHENYL SULFIDE 18.7 grams of Z-methyl resorcinol were dissolved with stirring in 48 ml. of ethyl acetate. A solution of 7.8 grams of sulfur dichloride in 58 ml. ethyl acetate was then added slowly to the in warm toluene, filtered and dried to yield 7.5 grams (36 percent of theoretical) of a product which was insoluble in cold water, toluene and benzene and soluble in alcohols and ketones and which had a melting point of l68-l70 C. The 2,2-4,4'-tetrahydroxy-3,3'-dimethyl diphenyl sulfide product gave a positive test for sulfur and analyzed as follows: Carbon 59.61(theoretical 60.41 );Hydrogen:5.28(Theoretical: 5.07).

B. PREPARATION OF 2,2',4,4'3,3'-

DIMETHYL DIPHENYL SULFOXIDE 13.9 grams of 2,2,4.4'-tetrahydroxy,3.3-dimet.hyl diphenyl sulfide were added, with stirring, to 100 ml. of glacial acetic acid. 5.65 grams of 30 percent H,O, were then added slowly to the solution while stirring was continued. The temperature rose to 40 C. then slowly subsided to 25 C. Stirring was continued for 24 then the reaction mixture was diluted with 250 ml. of water. The diluted reaction mixture was stirred for an additional hour, during which a precipitate separated from the reaction mixture. The precipitate was filtered, washed with water, and dried to yield 8.5 grams of a product which decomposed at 145 C. The 2.2',4,4'-tetrahydroxy,3,3'-dimethyl diphenyl sulfoxide product analyzed as follows: Carbon:56.98(Theoretical:57.13); 5.15(Theoretical:4.79)

C. PREPARATION OF 2,2',4,4'5,5'-

DICHLORODIPHENYL SULFIDE 21.7 grams of 4-chlororesorcinol were dissolved in 58 cc. of cold ethyl acetate (15 C.), and then to this 4-chlororesorcinolethyl acetate solution was slowly added a solution of 7.8 grams of sulfur dichloride in 58 cc. of ethyl acetate. The temperature during the addition was maintained at 10 to C. Upon completion of the addition of the sulfur dichloride solution to the 4-chlororesorcinol solution, the reaction mixture was stirred overnight. After stirring was completed, the reaction mixture was just washed with 100 cc. of water, and then with 100 cc. of 5 percent sodium bicarbonate solution to neutralize any of the remaining hydrochloric acid which was formed during the reaction. The solvent fraction was separated from the aqueous layer, and the ethyl acetate solvent was evaporated. The solid residue which remained was slurried in water to remove any unreacted 4-chlororesorcinol which may have been present, and the solids were than collected by filtration. The collected solids were slurried with hot toluene, filtered while hot, and then air dried to yield 7.3 grams of a white solid which melted at 220 to 222 c. The 2,2',4,45,5-dichlorodiphenyl sulfide product had the following Carbon-Hydrogen analysis: Carbonz44.80(Theoretical:45.20); Hydrogen 217(Theoretical:2.51 Infrared analysis of the product was as follows:

Medium-OH absorption band at 2.95 microns Strong-OH absorption band at 3.01 microns Phenyl absorption bands at 6.2 microns, 6.26 microns,

and 6.33 microns.

D. PREPARATION OF 2,2',4,4'3,3'-

DIMETHYL-5,5'-DICHLORODIPHENYL SULFIDE l 1.5 Grams of 2-methyl-4-chlororesorcinol were dissolved in 75 cc. of ethyl acetate and 3.75 grams of sulfur dichloride were added, with stirring, to the 2-methyl-4-chlororesorcinolethyl acetate solution over a 30 minute period. During the addition of the sulfur dichloride, the temperature of the reaction mixture was maintained at 15 C. and, upon completion of the addition of the sulfur dichloride, the reaction mixture was stirred for an additional hour. The ethyl acetate was then evaporated from the reaction mixture, and the residue was washed with 100 cc. of toluene. A white solid was collected by filtration and dried to yield 7. 2 grams of a product which had a melting point of 198 to 200 C. The 2,2,4,4'-tetrahydroxy- 3,3-dimethyl-5,5'-dichlorophenyl sulfide product analyzed as follows:

Carbon:48.77(Theoretical:48.4); Hydrogen 5.55(Theoretical:3.46). Infrared analysis was as follows:

Medium-OH absorption band at 2.88 microns Weak-OH absorption band at 290 microns Strong phenyl absorption band at 6.28 microns Strong sulfur-phenyl absorption band at 9.23 microns Strong chlorine absorption band at 13.5 microns.

The substituted diresorcyl sulfide couplers and their sulfoxide derivatives described above, have been found to be fast yellow coupling components for the diazonium derivatives of the dialkoxy-substituted paraphenylene diamines which are used as the diazo components of this invention, and they produce diazo prints which exhibit improved resistance to fade under the influence of ultraviolet radiation and visible light. The use of these couplers with the preferred blue couplers described below produces neutral black-line diazo prints having a wide range of densities. The advantages of such compounds over those presently available will be apparent to those skilled in the art, since it has heretofore been difficult to obtain a neutral black-line diazo print over a wide density range, particularly with only two coupling components.

The preferred blue couplers for use in the present invention are 3'-suhstituted, 2-hydroxy, 3naphthanilides wherein the substituent in the 3'-position is a non-chromophoric, electronwithdrawing substituent in the meta position of the aniline 'nucleus, i.e., compounds having the general formula ((H3OCH;)

a carbethoxy group 0 (("J-OCH,CH;)

a carbopropoxy group H (-co 013,011,031)

a carbobutoxy group and the like; sulfarnyl groups, including N-substituted sulfamyl groups for example, a methylsulfamyl group a benzylsulfamyl group an allylsulfamyl group H s0,N

CH,CH=CH, a morpholinopropylsulfamyl group a benzylcarbamyl group a morpholinocarbamyl group and the like; and acyl groups, for example, an acetyl group O (OH L) a propionyl group (CH3CH:( a butyryl group and the like. Compounds wherein X is a trifiuoromethyl group, an unsubstituted sulfamyl group, or an aliphatic acyl group, such as an acetyl group are particularly preferred. Those 3'-substituted 2-hydroxy, 3-naphthanilides wherein the non-chlomophoric and electron-withdrawing substituent represented by X contains a sulfonyl group or carbonyl group attached directly to the aniline nucleus are believed to be novel compositions of matter, and are claimed as such in a separate application filed on even date as the present application, U.S. Serial No. 667,372. g

The preferred 3-substituted, 2-hydroxy, B-naphthanilides described above can be prepared either by reacting a metasubstituted aniline having the formula a benzoyl group wherein X is as hereinbefore defined with 2-hydroxy, 3- naphthoyl chloride in the presence of a suitable solvent, or by reacting such a meta-substituted aniline with 2-hydroxy-3- naphthoic acid in the presence of an inert solvent and phosphorus trichloride. Illustrative of the meta-substituted anilines which can be employed in preparing these preferred blue couplers are compounds such as m-(trifluoromethyl) aniline (HMO-C a) methyl m-aminobenzoatc ethyl n-aminobenzoato propyl m-mninobcnzoatc butyl m-aminobcnzontc m-aminobenzenesulfonamidc (I-IZN 40 N11 N-me thyl-m-aminoben zenesulfonamide /H --s OgN N-benzyl-m-aminobenzenesulfonamide N-allyl-m-aminobenzenesulfonamide /H s0,N

C H; C H2 N-morpholinopropyl-m-aminobenzene-sulfonamide HgN CH CII CII N O m-aminobenzamide N -methyl-m-aminobenzamide o H II N-benzyl-m-aminobenzamide m-aminobenzmorpholide prpy1m-aminophenyl ketone phenyl-m-aminophenyl ketonc and the like.

When the preferred 3'-substituted, 2-hydroxy, 3-naphthanilides are prepared by reacting a meta-substituted aniline with 2-hydroxy, 3-naphthoyl chloride, the meta-substituted aniline is first dissolved in a solvent such as toluene, dioxane, methylene chloride, pyridine, and the like, and then 2-hydroxy, 3-naphthoy1 chloride is added to the aniline solution. The resulting reaction mixture is stirred overnight, and then the desired 3'-substituted, 2-hydroxy, 3-naphthanilide reaction product is isolated in the usual manner. The reaction between the meta-substituted aniline and Z-hydroxy, 3-naphthoyl chloride can be accelerated by refluxing the reaction mixture,

and the yield of the desired 3'-substituted, 2-hydroxy, 3-'

naphthanilide can be improved by incorporating an acid acceptor in the said reaction mixture. In many instances the solvent used to dissolve the meta-substituted aniline reactant can also serve as an acid acceptor (e.g., solvents such as pyridine, picoline, triethylamine, and the like), or the m-substituted aniline can itself serve as an acid acceptor, if it is employed in amounts in excess of the theoretical amount necessary to react with all of the 2-hydroxy, 3-naphthoyl chloride present in the reaction mixture.

When the preferred 3'-substituted, Z-hydroxy, B-naphthanilides are prepared by reacting a meta-substituted aniline with 2-hydroxy, 3-naphthoic acid in the presence of an inert solvent and phosphorus trichloride, 2-hydroxy, B-naphthoic acid and the m-substituted aniline are first dissolved or slurried in a relatively inert solvent such as toluene, methylene chloride, dichloroethane, and the like; and then phosphorus trichloride is added at a controlled rate in order to prevent the temperature of the reaction mixture from exceeding about 55 C. Upon completion of the addition of the phosphorus trichloride the reaction mixture is then refluxed until substantially all of the hydrochloric acid formed from the reaction is driven off. The desired 3'-substituted, 2-hydroxy, 3-naphthanilide reaction product can be isolated from the reaction mixture by direct filtration if it has precipitated from solution during the course of the reaction; otherwise it can be isolated by cooling, or by the addition of solvents in which the desired product is known to be insoluble.

1 2 Illustrative preparations of the preferred 3'-substituted, 2- hydroxy, B-naphthanilides are as follows:

A. PREPARATION OF Z-HYDROXY, 3-NAPHTHOIC ACID.

3'-(SULFONAMIDO) ANILIDE SIOQNIII BY REACTING m-AMINOBENZENESULPONAM IDE WITH Z-HYDROXY, B-NAPHTHOYL CHLORIDE 17.2 grams of m-aminobenzenesulfonamide were dissolved in ml. of dry pyridine. 20.6 grams of 2-hydroxy, 3- naphthoyl chloride which was prepared by refluxing Z-hydroxy, 3-naphthoic acid and thionyl chloride in methylene chloride, were then added to the aminobenzenesulfonamidepyridine solution. Upon completion of the addition of napththoyl chloride to the aminobenzenesulfonamidepyridine solution, the resulting reaction mixture was refluxed for 2 hours at 1 18 C. The reaction mixture was then cooled to room temperature and 500 ml. of water were added. The 2- hydroxy, 3-napthoic acid, 3'(sulfonamido) anilide reaction product precipitated in the form of a cream colored solid. After filtering, the solids were washed with water, slurried in isopropanol, and then re-filtered. The yield was 21.5 grams of a white solid having a melting point of 276 to 280 C. Carbonhydrogen-nitrogen analysis of the product was as follows:

Found Theoretical Hydrogen 4.31% 0% Nitrogen 7.64% 8.20% Carbon 62.21% 59.60%

Infrared analysis was as follows:

Strong amide absorption bands at 6.0 and 6.5 microns. Strong sulfonamide absorption bands at 6.98, 7.55 and 8.67

microns. Medium-NH and absorption bands at 3.0 microns.

Weak-NH: bands absorption at 3.1 microns. B. PREPARATION OF Z-HYDROXY, B-NAPHTHOIC ACID 3'-(TRIFLUOROMETHYL)ANILIDE BY REACTING 2-HYDROXYL, B-NAPI'ITHOIC ACID WITH m-(TRIFLUOROMETHYL)ANILINE IN THE PRESENCE OF PHOSPHORUS TRICHLORIDE Found Theoretical Hydrogen 3.39% 3.64% i Nitrogen 3.49% 4.24% 1 Carbon 64,57% 65.l%

lnfrared analysis was as follows:

Amide absorption bands at 7.60 and 14.35 microns. I

Trifluoromethyl absorption bands at 7.50, 8.54 and 8.90 0

microns.

preparations set forth above are compounds such as 2-hydroxy, 3-naphthoic acid, 3-(acetyl)anilide OH O=C-CH3 2-hydroxy,3-naphthoic acid,3 (N-allylsulfonamido) anilide H A OH S|O N CHgCH=CHg JiH Q 2-hydroxy, 3-naphthoic acid, 3(N-benzylsulfonamid0) anilide H OII SIOQN Q WQ 0 H 2-hydr0xy, 3-naphbhoic acid, 3 (N-morpholinopropylsulfonamido) anilide H on SIOZN/ OILCH OH N b w n-Q w 0 H 2-hydroxy, 3naphthoic acid, 3(N-methylsulfonamido) anilide H OH SJO N c N 1Q 0 H and the like.

THE BACKGROUND DISCOLORATION INHIBITORS The background discoloration inhibitors which have been found to be useful in preventing discoloration in the burnout or background areas of the developed diazotype materials of this invention are N,N'Diaryl-substuted alkylene diamines, including N,N methylene bridge tertiary amino derivatives thereof. These inhibitors have a general formula selected from the class consisting and A1NR NAr wherein Ar is a group selected from the class consisting of a phenyl group and a hydrocarbyl-substituted phenyl group wherein said hydrocarbyl substituents are in either the meta or para position; R is a divalent hydrocarbon radical having a chain of either two r0 three carbon atoms separating the nitrogen atoms of the diamine; R is a group selected from the class consisting of hydrogen, alkyl groups containing from one to five carbon atoms, aralkyl groups containing from seven to about 10 carbon atoms, and groups represented by Ar; and R is selected from the class consisting of a methylene group and hydrocarbyl-substituted methylene groups. Compounds wherein Ar is a phenyl group, m-tolyl group or p-tolyl group;

' R is an ethylene group, a methyl-substituted ethylene group. a

1,2-dimethyl-substituted ethylene group or an ethyl-substituted ethylene group, a phenyl-substituted ethylene group; R is hydrogen; and R is a methylene group or a phenyl-substituted methylene group are preferred. Illustrative of such compounds are compounds such as N,N'-diphenylethylenediamine N,N'di (m-tolyl) ethylene diamine CH3 (3H3 N,N di(p-to1yl) ethylene diamine N,N-diphenyl, 1,2-bubylenediamine HgCH:

N,N-diphenyls tyrenediamine 1 2 ,8-triphenylimidazolidine e 1 ,3-di (p-tolyl) -2-phenylimidazolidine 1,2,3-tripheny1, 4 -methy1imidazo1idine 1,2,3-triphenyl, 4,5 dimebhylimidazolidine r CH; CH;

1,2,3-triphenyl, 4-ethylimidazolidiue 1,2,3,4,tetraphenylimidazolidine and the like.

Although the amount of inhibitor which is employed in a coating composition has not been found to be narrowly critical from about 0.10 part by weight of inhibitor per parts by volume of the coating mixture to about 2.0 parts by weight of inhibitor per 100 parts by volume of the coating mixture is preferred, with about from 0.25 part by weight to about 1.0 part by weight being particularly preferred. Mixtures of these background discoloration inhibitors may also be employed, as well as mixtures of these types of inhibitors with other types of inhibitors or antioxidants.

Inhibitors having the general formula:

wherein Ar, R and R are as hereinbefore defined can be prepared by reacting an aromatic amine such as aniline, para toluidine, meta-toluidine, and the like, with a dihalo-substituted alkane or aralkane, such as ethylene dichloride; 1,2, dibromobutane; 2,3 dibromobutane; 1,2 dibromopropane; styrene dibromide and the like. This reaction is a known reaction (of, for example, Bennett, G.M. Journal of the Chemical Society" 1919, 115, 577), and can be illustrated by the general equation:

wherein Ar, R and R are as hereinbefore defined and X represents a halogen, such as bromine, chlorine, and the like. The reaction is more specifically illustrated by the following preparation:

PREPARATION OF N,N'Dl-( p-TOYL) ETHYLENE DlAMlNE 42.8 Grams of para-toluidine,

(0.4 mole) were added to 9.9 grams of ethylene dichloride, C1-CH -Cl-l -Cl, (0.1 mole); and the mixture was heated to reflux with stirring. At C. a heavy precipitate began to form, and the mixture reached reflux temperature at C. After refluxing at 150 C. for 2 hours, the mixture was cooled to room temperature, at which temperature the reaction mixture was a solid. The solid reaction mass was then stirred with 200 ml. of water and filtered. A brownish-yellow solid as recovered and recrystallized from hexane to yield 13 grams of a white solid which melted at 89 to 92 C. The N,N'di(ptolyl)ethylenediamine product had the following carbonhydrogen-nitrogen analysis:

tolyl)ethylenediamine product was as follows:

Strong secondary amine absorption band at 2.95 microns.

Strong absorption band at 6.56 microns.

Very Strong-Cl-Q-absorption band at 6.85 microns. Para-substituted doublet absorption bands at 12.34 microns l and 12.42 microns. inhibitors having the general formula wherein Ar, R and R are as hereinbefore defined can be prepared by reacting an aldehyde of the formula R"CHO wherein R is a hydrocarbyl group with an N,N'-diaryl-substituted alkylene diamine of the general formula:

Ar-Nl-l-R -NH-Ar wherein Ar and R are as hereinbefore defined. For example, as disclosed by Moos in Berichte Der Deutchen Chemischen 1 Gesellschaft, Vol. 20, page 732, l,2,3-triphenylimidazolidine i can be prepared by heating benzaldehyde with N,N-diphen-i ylethylenediamine to boiling temperatures. The resulting imidazole derivative can be purified by recrystallization from alcohol, petroleum ether, benzene or other suitable solvents. inhibitors such as l,3-di(m-toyl)-2-phenylimidazolidine andi l,3-di(p-toyl)-2-phenylimidazolidine can be prepared in an! analogous manner by substituting N,N-di(m- 1' tolyl)ethylenediamine and N,N'-di(p-tolyl)ethylenediamine I for N,N'-diphenylethylenediamine in the procedure set forth above. A general equation for the reaction is as follows: i

Ar Ar NR5-N\ R3CH0 ArN R NAr H2O H II CH 1 40 wherein Ar, R and R" are as hereinbefore defined and the divalent group is equivalent to the group R as hereinbefore defined. The reaction is more specifically illustrated by the following preparation:

PREPARATION OF l,2,3,-TRIPHENYL1M1DAZOLIDENE 21.2 Grams of diphenylethylenediamine,

Found Theoretical Nitrogen 9.38 9.33 Carbon 83.71 84.0 Hydrogen 6,84 6.66

The infrared analysis of the product was as follows: N o

absorption bands.

Strong phenyl ring absorption band at 6. 25 microns.

Very Strong phenyl ring absorption band at 6.64 microns.

The light-sensitive diazo compositions of this invention can also contain any of the additional components which are often employed in such compositions, such as stabilizers for the diazo compound present in said compositions. The diazo composition is usually applied to a suitable base support in the form of a solution of various components in a solvent or solvents, which is then dried to form a coated support material which can be imaged and developed in the well-known manner of the diazotype art. The support may be any of the well-known support materials employed for diazo compositions, such as paper, cloth, transparentized paper, cellulose ester and ether films and polyester films having a subcoat thereon, such as mylar film having a subcoat of cellulose acetate butyrate.

The diazo coating compositions of this invention can be used to prepare light-sensitive diazotype materials, which are new and useful products for use in the fields of engineering drawing reproduction, microfilm visual communications and the graphic arts.

The following examples will serve to further illustrated this invention, but they are not intended to limit the scope thereof in any way.

EXAMPLE I A light-sensitive coating formulation was prepared containing the following components:

This coating formulation was coated onto a clear, cellulose diacetate base and dried. The dried, light-sensitive film was then exposed under a mercury vapor lamp light-source in a diazo duplicating machine using a silver halide master. The exposed film was then developed with ammonia vapor. A neutral black print over a wide range of image densities was obtained, and the resulting print exhibited excellent light-fade resistance and aging characteristics. Similar results are obtained when compounds such as N,N-diphenylethylenediamine, N,N- di(p-tolyl)ethylenediamine, N,N-di(m-tolyl) ethylene diamine, l,3-di(p-tolyl)-2-phenylimidazolidine imidazolidine and 1,3,-di(m-tolyl)-2-phenylimidazolidene are substituted for l,2,3-triphenylimidazolidine in the formulation set forth above. However, if the N,N'-diaryl-substituted alkylene diamine background inhibitors are omitted from the formulation set forth above, an objectionable, reddish background appears in the background or burn-out areas of the developed print upon aging of the print. The amount of background discoloration which was observed with the above formulations was measured with a photovolt brightness meter, using White Cararra glass as the brightness standard. The background discoloration due to natural aging of the films prepared from the above formulations was as follows:

Initial After 5 Formulations (identified by inhibitor) brightness months 1.2 3-triplmnylimidszolidine 75. 72. "-dimcthylethylene diainine... 75.0 73.0 N, -di(p-tol vl)ethylone diainino 75. 0 74. 0 N,N'-di(m-t0lyl)ethyleno diamlno. 75.0 73.0 1,3-di p-tolyl)-2-phenylimidazolldi1 75.5 73. 5 l.3-di(n1-tolyl)-2pht nylimidazolidino. 75.0 72.5 (ontrol (no N,N-dinryl-substitut0d nlkylono (limninc inhibitor) T5. 5 l til. 0

I With rod discoloration observed.

The results set forth above clearly indicate that the N,N-diaryl-substituted alkylene diamine inhibitors substantially reduce the amount of background discoloration which is normally obtained with two-component diazo-type materials wherein a diazonium derivative of a dialkoxy-substituted paraphenylene diamine is employed as the diazo component.

EXAMPLE 2 A light-sensitive coating formulation was prepared containing the following components:

This coating formulation was coated onto a clear cellulose diacetate film base and dried. The dried, light-sensitive film was then exposed and developed in a manner similar to that set forth in example i. A neutral black print was obtained from this film over a wide range of image densities, and the resulting print exhibited excellent light-fade resistance and aging characteristics.

EXAMPLE 3 A light-sensitive coating formulation was prepared containing the following components:

COMPONENT AMOUNT Methanol 52 cc.

Acetone 38 cc. Methyl ethyl ketone cc. Hexafluorophosphuric acid 0.6 cc. Thiourea 0.6 g.

2 Hydroxy-3-naphthoic acid (J'acctyUanilide 0.99 g. 2,2.4.4'-Tctrahydroxy-3.3'-dimethyldiphenyl sulfide 0.75 g. l.2,."i triphcnylimidazolidine 0.75 g. 4 Murpholino-2.5-diisopropoxybenzene diazonium hexafluorophosphute 13 g.

This coating formulation was coated onto a clear, cellulose diacetate film base and dried. The dried, light-sensitive film was then exposed and developed in a manner similar to that set forth in example 1. A neutral black print was obtained from this film over a wide range of image densities, and the resulting print exhibited excellent light-fade resistance and aging characteristics. When the 2,2',4,4'-tetrahydroxy-3,3'- dimethyldiphenyl sulfide coupler is replaced with either 2,2,4,4'3,3'-dimethyldiphenyl sulfoxide or 2,2',4,43.3-dimethyl5,5'-dichlorodiphenyl sulfide in the above formulation, similar results are obtained, in that an excellent black print from the film is obtained over a wide range of image densities, and s aid print is resistant to subsequent background discoloration in the burn-out" areas.

Similarly, when the 4-morpholino-2,5-diisopropoxybenzene diazonium hexafiuorophosphate is replaced with either 4- morpholino-2 ,S-dicyclopentyloxybenzene diazonium hexafiuorophosphate or 4-morphoIino-2,5-di(secondary-butoxy) benzene diazonium hexafluorophosphate in the above formulation, the desirable properties are also observed in the prints resulting from films prepared from said formulations. When the 2,2',4.4-tetrahydroxy-3.3-dimethyl dlphenyl suliide coupier in the above formulation is replaced with dlresorcyl sultide, dlresorcyl suli'oxlde or dlresorclnol. the prints resulting from the films prepared these formulations are also resistant to background discoloration. but blue, violet, or blue-black prints having reddish violet hues are obtained. rather than the neutral 1 5 blacks which are obtained from formulations containing the preferred orange or sepia couplers.

We claim:

1. A light-sensitive diazo composition which comprises:

A. at least one light-sensitive 2,5-dialkoxy-4-aminobenzene diazonium compound [derived from a dialkoxy-substituted-p-phenylene diamine] having the general formula selected from the class consisting of:

1 O R R I and g g R JN -N,Y 3 5 wherein Y is an inorganic acid anion; R is an alkyl group or a cycloalkyl group containing five or six carbon atoms; R and R are alkyl groups containing from one to three carbon atoms, and the group represented by is a saturated, nitrogen-containing, heterocyclic ring containing six atoms in said ring;

B. at least one azo coupling component for said diazonium compound;

C. at least one background discoloration inhibitor having a general formula selected from the class consisting of:

5 5 Ar Ar \N-R5-N Rs u Ar-N-R-NAr wherein Ar is a phenyl group or an alkyl-substituted phenyl group wherein said alkyl substituents are in either the meta or para position, R" is a divalent hydrocarbon radical having a chain of two or three carbon atoms separating the nitrogen atoms in said inhibitor, wherein R is a hydrogen atom, an alkyl group containing from one to five carbon atoms, an aralkyl group containing from seven to 10 carbon atoms.

2. A light-sensitive diazo composition as claimed in claim 1 wherein the light-sensitive diazonium compound is [derived from 4-morpholino-2,5-diisopropoxyaniline, 4-morpholino- 2,5-di(tertiary butoxy) aniline; 4-morpholino-2,5-di,(secondary butoxy) aniline; or 4-morpholino-2,5'dicyclopent0xyaniline] a 4-morpholin0-2,5-di(isopropoxy) benzene diazonium salt, a 4-morpholino-2,5-di(tertiary butoxy) benzene diazonium salt, a 4-morpholino-2,5-di(secondary butoxy) benzene diazonium salt or a 4-morpholino-2,5-di(cyclopentoxy) benzene diazonium salt.

3. A light-sensitive diazo composition as claimed in claim 2 which comprises as a background discoloration inhibitor at least one compound selected from the class consisting of N,N'-diphenylethylenediamine, N,Ndi(m-tolyl) ethylene diamine, N,Ndi(p-tolyl) ethylenediamine, N,Ndiphenylpropylenediamine, N,Ndiphenyl-2,3-butylenediamine, N,N- diphenyl-l ,Z-butylenediamine, N,N-diphenylstyrenediamine, l,2,Striphenylimidazolidene, l,3-di-(m-tolyl)-2-phenylimidazolidene, and l,3-di(p-tolyl)-2-phenylimidazolidene, l ,2,3-triphenyl-4-methylimidazolidene, l,2,3triphenyl4,5- dimethylimidazolidine, l,2,3-triphenyl-4-ethylimidazolidine, and l,2,3,4-tetraphenylimidazolidine.

4. A light-sensitive diazo composition as claimed in claim 3, wherein at least one of the compound is a compound having the general formula selected from the class consisting of:

wherein R is selected from the class consisting of hydrogen alkyl groups containing from one to six carbon atoms, unsubstituted aryl groups, halo-substituted aryl groups; unsubstituted aralkyl groups, aralkyl groups having alkyl substituents on the aryl portion thereof, aralkyl groups having halo substituents on the aryl portion thereof, unsubstituted alkaryl groups, alkaryl groups having halo substituents on the alkyl portion thereof, alkoxy groups containing from one to six carbon atoms, unsubstituted aryloxy groups, halo-substituted aryloxy groups, unsubstituted aralkoxy groups, aralkoxy groups having halo substituents on the aryl portion thereof, and halogen atoms; Z is selected from the class consisting of hydrogen and halogen atoms; and wherein at least one of the groups represented by R and Z is a group other than hydrogen.

5. A light-sensitive diazo composition as claimed in claim 4 wherein R is methyl.

6. A light-sensitive diazo composition as claimed in claim 3 wherein at least one of the coupling components for the diazonium compound is a compound having the general formula:

wherein X is a non-chromophoric, electron-withdrawing substituent and is selected from the class consisting of trifluoroalkyl groups, carbalkoxy groups, the sulfamyl group, N-substituted sulfamyl groups, the carbamyl group, N-substituted carbamyl groups and acyl groups.

7. A light-sensitive diazo composition as claimed in claim 3 wherein the coupling component for the diazonium compound is a mixture of A) a compound having the general formula selected from the class consisting of:

and

wherein R is selected from the class consisting of hydrogen, alkyl groups containing from one to six carbon atoms, unsubstituted aryl groups, halo-substituted aryl groups; unsubstituted aralkyl groups, aralkyl groups having alkyl substituents on the aryl portion thereof, aralkyl groups having halo substituents on the aryl portion thereof, unsubstituted alkaryl groups, alkaryl groups having halo substituents on the alkyl portion thereof, alkoxy groups containing from one to six carbon atoms, unsubstituted aryloxy groups, halo-substituted aryloxy groups, unsubstituted aralkoxy groups, having halo substituents on the aryl portion thereof, and halogen atoms; Z is selected from the class consisting of hydrogen and halogen atoms; and wherein at least one of the groups represented by R and Z is a group other than hydrogen and B) a compound having the general formula:

I -OH X ll 0 H W wherein X is a non-chromophoric, electron-withdrawing substituent and is selected from the class consisting of trifluoroalkyl groups, carbalkoxy groups, the sulfamyl group, N-substituted sulfamyl groups, the carbamyl group, N-substituted carbamyl groups and acyl groups.

8. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholino-2.5-diisopropoxybenzenediazonium hexafluorophosphate; the coupling components are 2,2,4,4'- tetrahydroxy-3,3-dimethyldiphenyl sulfide, 2,2,4,4'- tetrahydroxy-5,5'-dichlorodiphenyl sulfide, and 2-hydroxy-3- naphthoic acid-(3-acetyl)anilide; and the background discoloration inhibitor is l,2,3-triphenylimidazolidine.

9. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholino-2,S-diisopropoxybenezenediazonium hexafluorophosphate; the coupling components are 2,2,4,4'- tetrahydroxy-3,3'-dimethyldiphenyl sulfide, 2,2,4,4'- tetrohydroxy-5,5'-dichlorodiphenyl sulfide, and 2-hydroxy-3- naphthoic acid-(3-acetyl)anilide; and the background discoloration inhibitor is N ,N'-diphenylethylene diamine.

10. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholino-2,5-diisopropoxybenzenediazonium hexafluorophosphate; the coupling compounds are 2,2,4,4'- tetrahydroxy-3,3'-dimethyldiphenyl sulfide, 2,2,4,4'- tetrahydroxy-5,5'-dichlorodiphenyl sulfide, and 2-hydroxy-3- naphthoic acid-(3'-acetyl)anilide, and the background discoloration inhibitor is N ,N-di( p-tolyl)ethylene diamine.

11. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholino-2,5-diisopropoxybenzenediazonium hexafluorophosphate; the coupling components are 2,2,4,4'- tetrahydroxy-3,3-dimethyldiphenyl sulfide, 2,2,4,4'- tetrahydroxy-5,5-dichlorodiphenyl sulfide, and 2-hydroxy-3- naphthoic acid-(3-acetyl)anilide; and the background discoloration inhibitor is N ,N-di( m-tolyl)ethylene diamine.

12. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholino-2,S-diisopropoxybenezenediazonium hexafluorophosphate; the coupling components are 2,2,4,4'- tetrahydroxy-3 ,3 '-dimethyldiphenyl sulfide, 2 ,2 ,4 ,4 tetrahydroxy-5,5-dichlorodiphenyl sulfide, and 2-hydroxy-3- naphthoic acid-(3'-acetyl)anilide; and the background discoloration inhibitor is 1,3-di(p-tolyl )-2-phenylimidazolidine.

13. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4morpholino-2,5-diisopropoxybenzendiazonium hexafluorophosphate; the coupling components are 2,2',4,4- tetrahydroxy-3 ,3 -dimethyldiphenyl sulfide, 2,2 tetrahydroxy-5,5' -dichlorodiphenyl sulfide, and 2-hydroxy-3- naphthoic acid-(3'-acetyl)anilide; and the background discoloration inhibitor is l,3-di( m-tolyl )-2-phenylimidizolidine.

14. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholino-Z,S-diisopropoxybenzenediazonium hexafluorophosphate; the coupling components are 2,2,4,4'- tetrahydroxy-3 ,3 -dimethyldiphenyl sulfide; 2,2 ,4 ,4 tetrahydroxy-5,5-dichlorodiphenyl sulfide, 2-hydroxy-3- naphthoic acid (3'-sulfonamide) anilide; and 2-hydroxy 3 naphthoic acid (3[N-methyl]sulfonamido)anilide; and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.

15. A lightsensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compounds is 4- morpholino-2,5-diisopropoxybenzenediazoniurn hexafluorophosphate, the coupling components are 2,2,4,4'- tetrahydroxy-3,3-dimethyldiphenyl sulfide and 2-hydroxy-3- naphthoic acid (3-acetyl)anilide, and the background discoloration inhibitor is l,2,3-triphenylimidazolidine.

16. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholino-2,5-diisopropoxybenezenediazonium hexafluorophosphate, the coupling components are 2,2',4,4- tetrahydroxy-3,3'-dimethyl sulfoxide and 2-hydroxy-3- naphthoic acid (3-acetyl)anilide, and the background discoloration inhibitor is l,2,3-triphenylimidazolidine.

17. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholino-2,5-diisopropoxybenzene diazonium hexafluorophosphate, the coupling components are 2,2',4,- tetrahydroxy-3,3'-dimethyl-5,5-dichlorodiphenyl sulfide and 2-hydroxy-3naphthoic acid (3-acetyl)anilde and background discoloration inhibitor is 1,2,3-triphenylimidazoliclne.

18. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholino-2,5-disopropoxybenaenediazonium hexafluorophosphate, the coupling components are diresorcyl sulfide and 2-hydroxy-3 naphthoic acid (3'-acetyl)anilide, and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.

19. A light-sensitive diazo composition as claimed in claim 7, wherein the light sensitive diazonium compound is 4 morpholineo-2,5-diisopropoxybenzenediazonium hexafluorophosphate, the coupling components are diresorcyl sulfoxide and 2-hydroxy-3-naphthoic acid (3'-acetyl)anilide, and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.

20. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholino-2,S-diisopropoxybenzenediazpmoi, hexafluorophosphate, the coupling components are diresorcinol and 2-hydroxy-3-naphthoic acid(3'-acetyl) anilide, and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.

21. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4- morpholineo-2,5dicyclopentyloxybenzene diazonium hexafluorophosphate, the coupling components are 2,2',4,4'- tetrahydroxy-3,3'-dimethyl-5,5'-dichlorodiphenyl sulfide and 2-hydroxy-3-naphthoic acid( 3 -acetyl )lide, and the background discoloration inhibitor is l,2,3-triphenylimidazolidine.

22. -tetrahydroxylight-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium comthe pound is 4-morpholineo- 2,5-di(secondary-butoxy)benzene diazonium hexafluorophosphate, the coupling components are 2,2,4,4-tetrahydroxy-3,3-diemthyl 5,5'-dichlorodiphenyl sulfide and 2-hydroxy-3-naphthoic acid (3-acetyl)anilide, and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.

23. A diaztotype material comprising a support and a diazo layer coated on said support, said layer comprising the lightsensitive diazo composition claimed in claim 1.

24. A diazotype material as claimed in claim 23, wherein the support is selected from the class consisting of paper, cloth, transparentized paper, a cellulose ether film a cellulose ester film and a polyester film having a subcoat thereon of cellulose acetate butyrate.

25. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 8.

26. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 9.

27. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 10.

28. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 11.

29. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 12.

30. A diazotype material comprising a cellulose diacetate film as a support and diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 13.

31. A diazotype material comprising a cellulose diacetate film as a support and a daizo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 14. I

32. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 15.

33. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 16.

34. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 17.

35. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 18.

36. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 19.

37. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 20.

38. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 21.

39. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 21.

zg gy UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,619,191 Dated November 9, 1971 I Robert C. Desjarlais Page 1 of 9 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Specification:

Column 1, line 75, "diazotypec" should read diazotype-.

Column 3, line 48, "4-morpholine" should read --4morpholino--.

Column 3, line 49, insert the following: (isopropoxy) benzene-diazonium chloride-.

Column 4, line 7, "cenzene" should read --benzene--.

Column 4, line 70, after "acid," and before "2 hydroxy" insert 2 hydroxy-B naphthoic anilide--.

Column 4, lines 71 and 72, delete "2 hydroxy-3 naphthoic- (4 chloro) anilide,".

Column 5, line 16, "l-(Benzen 4' sulfonic acid)" should read l- (Benzene-4' sulphonic acid) Column 5, line 19, delete "N,Ndiaryl-substituted" and insert therefor --in.

Column 5, line 21, delete "diazotype" and insert therefor -general-.

Cont. J

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Pacgnt n 3,619,191 Band November 9, 1971 nventor) Robert C. Desjarlais P 2 f 9 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 5, line 56, delete "onto" and insert therefor --are-.

Column 6, line 44, after "as" and before ",4,4"', insert Column 6, line 45, before ",4,4'" (both occurrences) insert -2,2'.

Column 6, line 46, "5,5' should read -5,5'--.

Column 6, line 47, before ",4,4"', insert --2,2'-.

Column 6, line 60, after "of" and before ",4,4" insert Column 7, line 6, after "2,2',4,4'" and before "3,3'-",

insert tetrahydroxy Column 7, line 14, after "24" and before "then", insert -hours.

Column 7, line 19, "22',4,4'-tetrahydroxy" should read -2,2,4,4'-tetrahydroxy--.

Column 7, line 21, after and before "5.15," insert "'Hydrogen-- Cont J 3,619 ,191 November 9, 1971 Patent No. Dated Robert C. Desjarlais Page 3 of 9 Inventofls) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 7, line 23, after "2,2',4,4"' and before "5,5',"

insert tetrahydroxy- Column 7, line 44, after "'2,2',4,4"' and before "5,5'",

insert tetrahydroxy- Column 7, line 53, after "2,2',4,4'" and before "3,3'",

insert tetrahydroxy- Column 7, line 70, delete "5.55" and insert therefor Column 12, line 39, insert -4.23% in the column under "Found"; and delete the number or numbers which appear in the column under "Theoretical" and insert therefor --4.l0%-.

Column 12, line 73, "n" should read m-.

Column 12, line 74, "trifluoromethyl) should read (trifluoromethyl)-.

Column 14, line 21, "ro" should read -or--.

Column 14, line 24, after "to" (first occurrence) and before "five", insert ---about-.

'- Cont.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,619,191 Dated November 9, 1971 Inventor) Robert C. Desjarlais P 4 of '9 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 16, line 58, "as" should read -was.

Column 16, line 66, insert ll.63-- in the column under "Found"; and delete the number or numbers which appear in the column under "Theoretical" and insert therefor --ll.66--.

Column 17, line 26, "N,N" should read -N,N'.

Column 17, line 53, "Triphenylimidazolidene" should read Triphenylimidazolidine.

Column 18, line 29, "illustrated" should read --illustrat e.

Column 18, line '39, delete "g." which appears under the column entitled "AMOUNT".

Column 18, line 46, "2Hydroxy" should read --2Hydroxy.

Column 18, line 63, delete the word "imidazolidine".

Column 19, line 1, "5" should read -4-.

Column 19, line 4, "dimethylethylene" should read --diphenylethylene-.

Column 19, line 28, "0.6g." should read -0.6 cc.-.

Column 19, line 32, "(3' [N" should read (3'[N Cont J UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 36l9 Dated November 1971 Inventor) Robert C. Desjarlais p 5 f 9 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 19, line 34, "2,2"" should read -2,2' ,4,4'

Column 19, line 36, "hexfluorophosphate" should read -hexafluorophosphate-.

Column 19, line 55, "0.6g." should read -0.3gm..

Column 19, line 58, "0.759" should be relocated so that it appears under the column entitled "AMOUNT" Column 19, line 70, "2,2',4,4"' should read 2,2',4,4'

tetrahydroxy- Column 19, line 71, "2,2',4,4'3,3'-dimethyl 5,5'dichlorodiphenyl" should read 2,2',4,4'tetrahydroxy3,3'dimethyl 5,5'-' dichlorodiphenyl In the Claims:

Claim 1, lines 3 and 4 (Column 20, lines 19 and 20) [derived from a dialkoxy subsitituted p-phenylene diamine] should be deleted.

L Cont. J

Fo-w UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,619,191 Dated November 9, 1971 Inventor) Robert C. Desjarlais Page 6 of 9 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 1, on the line on which the fourth structural formula begins (Column 20, line 54), insert (3)- on the left-hand edge of the column. I

Claim 1, on the line on which the fifth structural formula begins (Column 20, line 59), insert -(4) on the left-hand edge of the column. I 2

Claim 1, last line (Column 20, line 68), after "atoms" and before insert the following: or a group represented by Ar; and R is a methylene group or an aryl-substituted methylene group; and

D. an acidic stabilizer.

Claim 2, lines 2 to 6 (Column 20, lines 70 to 74) [derived from 4-morpholino2,5-diisopropoxyaniline, 4-morpholino2,5

di (tertiary butoxy) aniline; 4-morpholino-2,5di (secondary butoxy) aniline; or 4-morpholino-2,5-dicyclo-pentoxyaniline]" should be deleted.

Claim 3, line 8 (Column 21, line 11), "1,2,3 triphenylimidazolidene" should read -l,2,3-triphenylimidazolidine.

Cont.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,619 Dated November 9, 1971 Inventor) Robert C. Desjarlai's p 7 f 9 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 3, line 9 (Column 21, line 12) ylimidazolidene" should read ylimidazolidine, and "1,3-di (p-tolyl)" should read l,3-di(p-tolyl)--.

Claim 3, line 10 (Column 21, line 13) "methylimidazolidene" should read --methylimidazolidine, and "1,2,3 triphenyl 4" should read --l,2,3triphenyl4.

Claim 4, line 2 (Column 21, line 17) after "the" and before "compound" insert --coupling components for the diazonium.

Claim 8, line 3 (Column 22, line 37) "2.5" should read Claim 9, line 6 (Column 22, line 48), "tetrohydroxy" should read --tetrahydroxy.

Claim 13, line 3 (Column 23, line 4) "4 morpholino" should read -4-morpholino.

Claim 13, line 5 (Column 23, line 6) "2,2"" should read Cont

Claims

2. A light-sensitive diazo composition as claimed in claim 1 wherein the light-sensitive diazonium compound is (derived from 4-morpholino-2,5-diisopropoxyaniline, 4-morpholino-2,5-di(tertiary butoxy) aniline; 4-morpholino-2,5-di(secondary butoxy) aniline; or 4-morpholino-2,5-dicyclopentoxyaniline) a 4-morpholino-2,5-di(isopropoxy) benzene diazonium salt, a 4-morpholino-2,5-di(tertiary butoxy) benzene diazonium salt, a 4-morpholino-2,5-di(secondary butoxy) benzene diazonium salt or a 4-morpholino-2,5-di(cyclopentoxy) benzene diazonium salt.
3. A light-sensitive diazo composition as claimed in claim 2 which comprises as a background discoloration inhibitor at least one compound selected from the class consisting of N,N''-diphenylethylenediamine, N,N''di(m-tolyl) ethylene diamine, N, N''di(p-tolyl) ethylenediamine, N,N''diphenylpropylenediamine, N, N''diphenyl-2,3-butylenediamine, N,N''-diphenyl-1,2-butylenediamine, N,N''-diphenylstyrenediamine, 1,2, 3triphenylimidazolidene, 1,3-di-(m-tolyl)-2-phenylimidazolidene, and 1,3-di(p-tolyl)-2-phenylimidazolidene, 1,2,3-triphenyl-4-methylimidazolidene, 1,2,3triphenyl4,5-dimethylimidazolidine, 1, 2,3-triphenyl-4-ethylimidazolidine, and 1,2,3,4-tetraphenylimidazolidine.
4. A light-sensitive diazo composition as claimed in claim 3, wherein at least one of the compound is a compound having the general formula selected from the class consisting of:
5. A light-sensitive diazo composition as claimed in claim 4 wherein R4 is methyl.
6. A light-sensitive diazo composition as claimed in claim 3 wherein at least one of the coupling components for the diazonium compound is a compound having the general formula:
7. A Light-sensitive diazo composition as claimed in claim 3 wherein the coupling component for the diazonium compound is a mixture of A) a compound having the general formula selected from the class consisting of:
8. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholino-2.5-diisopropoxybenzenediazonium hexafluorophosphate; the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide, 2,2'',4,4''-tetrahydroxy-5,5''-dichlorodiphenyl sulfide, and 2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide; and the background discoloration inhibitor is 1, 2,3-triphenylimidazolidine.
9. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholino-2, 5-diisopropoxybenezenediazonium hexafluorophosphate; the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide, 2,2'',4,4''-tetrohydroxy-5,5''-dichlorodiphenyl sulfide, and 2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide; and the background discoloration inhibitor is N,N''-diphenylethylene diamine.
10. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholino-2, 5-diisopropoxybenzenediazonium hexafluorophosphate; the coupling compounds are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide, 2,2'',4,4''-tetrahydroxy-5,5''-dichlorodiphenyl sulfide, and 2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide, and the background discoloration inhibitor is N,N''-di(p-tolyl)ethylene diamine.
11. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholino-2, 5-diisopropoxybenzenediazonium hexafluorophosphate; the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide, 2,2'',4,4''-tetrahydroxy-5,5''-dichlorodiphenyl sulfide, and 2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide; and the background discoloration inhibitor is N,N''-di(m-tolyl)ethylene diamine.
12. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholino-2, 5-diisopropoxybenezenediazonium hexafluorophosphate; the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide, 2,2'',4,4''-tetrahydroxy-5,5''-dichlorodiphenyl sulfide, and 2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide; and the background discoloration inhibitor is 1,3-di(p-tolyl)-2-phEnylimidazolidine.
13. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4morpholino-2, 5-diisopropoxybenzendiazonium hexafluorophosphate; the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide, 2,2-tetrahydroxy-5,5'' -dichlorodiphenyl sulfide, and 2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide; and the background discoloration inhibitor is 1,3-di(m-tolyl)-2-phenylimidizolidine.
14. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholino-2, 5-diisopropoxybenzenediazonium hexafluorophosphate; the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide; 2,2'',4,4''-tetrahydroxy-5,5''-dichlorodiphenyl sulfide, 2-hydroxy-3-naphthoic acid (3''-sulfonamide) anilide; and 2-hydroxy 3-naphthoic acid (3''(N-methyl)sulfonamido)anilide; and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.
15. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compounds is 4-morpholino-2,5-diisopropoxybenzenediazonium hexafluorophosphate, the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide and 2-hydroxy-3-naphthoic acid (3''-acetyl)anilide, and the background discoloration inhibitor is 1, 2,3-triphenylimidazolidine.
16. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholino-2, 5-diisopropoxybenezenediazonium hexafluorophosphate, the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyl sulfoxide and 2-hydroxy-3-naphthoic acid (3''-acetyl)anilide, and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.
17. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholino-2, 5-diisopropoxybenzene diazonium hexafluorophosphate, the coupling components are 2,2'',4,''-tetrahydroxy-3,3''-dimethyl-5,5''-dichlorodiphenyl sulfide and 2-hydroxy-3naphthoic acid (3''-acetyl)anilde and the background discoloration inhibitor is 1,2, 3-triphenylimidazoliclne.
18. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholino-2, 5-disopropoxybenaenediazonium hexafluorophosphate, the coupling components are diresorcyl sulfide and 2-hydroxy-3 naphthoic acid (3''-acetyl)anilide, and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.
19. A light-sensitive diazo composition as claimed in claim 7, wherein the light sensitive diazonium compound is 4-morpholineo-2,5-diisopropoxybenzenediazonium hexafluorophosphate, the coupling components are diresorcyl sulfoxide and 2-hydroxy-3-naphthoic acid (3''-acetyl)anilide, and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.
20. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholino-2, 5-diisopropoxybenzenediazpmoi, hexafluorophosphate, the coupling components are diresorcinol and 2-hydroxy-3-naphthoic acid(3''-acetyl) anilide, and the background discoloration inhibitor is 1, 2,3-triphenylimidazolidine.
21. A light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholineo-2,5dicyclopentyloxybenzene diazonium hexafluorophosphate, the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyl-5, 5''-dichlorodiphenyl sulFide and 2-hydroxy-3-naphthoic acid(3''-acetyl)lide, and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.
22. -tetrahydroxy-light-sensitive diazo composition as claimed in claim 7, wherein the light-sensitive diazonium compound is 4-morpholineo-2,5-di(secondary-butoxy)benzene diazonium hexafluorophosphate, the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-diemthyl 5,5''-dichlorodiphenyl sulfide and 2-hydroxy-3-naphthoic acid (3''-acetyl)anilide, and the background discoloration inhibitor is 1,2,3-triphenylimidazolidine.
23. A diaztotype material comprising a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 1.
24. A diazotype material as claimed in claim 23, wherein the support is selected from the class consisting of paper, cloth, transparentized paper, a cellulose ether film a cellulose ester film and a polyester film having a subcoat thereon of cellulose acetate butyrate.
25. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 8.
26. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 9.
27. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 10.
28. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 11.
29. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 12.
30. A diazotype material comprising a cellulose diacetate film as a support and diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 13.
31. A diazotype material comprising a cellulose diacetate film as a support and a daizo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 14.
32. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 15.
33. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 16.
34. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 17.
35. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 18.
36. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 19.
37. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 20.
38. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said layer comprising the light-sensitive diazo composition claimed in claim 21.
39. A diazotype material comprising a cellulose diacetate film as a support and a diazo layer coated on said support, said lAyer comprising the light-sensitive diazo composition claimed in claim 21.