[1]3 @ 7 6 1 , 2 6 3 'United S'tates Patetit Office l,t,,Id Sept. 25, 1973 3,761,263 DIAZOTYPE COMPOSITTONS AND PHOTOGRAPMC PROCESSES James C. Fleming and AUchael D. Shea, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y. 5 No Drawing. Ffled Nov. 3, 1971, Ser. No. 195,466 Int. Cl. G03c 1158 U.S. Cl. 96-49 9 Claims 10 ABSTRACT OF THE DISCLOSURE Diazotype compositions including a light-sensitive diazonium salt and a coupler compound that can react with the diazonium salt to form an azo dye, wherein the coupler is a 3'-hydroxy-2'-naphthoylurea, such as those 15 wherein the terminal urea nitrogen atom (i.e., the nitrogen not bonded to the naphthoyl group) is substituted with members like hydrogen atoms, aryl groups, alkyl groups, or atoms which, in combination with the nitrogen atom, forfn 5 to 6-membered heterocyclic groups like 20 morpholino, piperidino or pyrroliding, produce blue dyes of increased red light opacity on development with base. OptiGnally, a yellow dye-forming coupler can be included in the composition to promote the formation of neutral hue (black line) images. The diazotype compositions Of 25 this type can be carried on a support to prepare composite diazotype photographic elements. This invention pertains to photography, to new azo3 0 d ye-forming couplers and to Eght-sensitive diazotype c ompositions and photographic elements containing such c ouplers. Two-component, light-sensitive diazotype compositi.ons g enerally include at least one light-sensitive, diazomum 3 ,3 s alt, preferably acid-stabilized to reduce premature c oupling of the salt and coupler, and at least one c oupler compound which can react with the diazon ium salt, typically in the presence of a base to form a n azo dye. In addition, there can be present various other 4 0 a dditives, such as image enhancers, ultraviolet absorbers a s weR as additional known addenda. These diazotype c ompositions or azo-dye forming systems have been emp loyed as duplicating media. Their use typically involves a n imagewise exposure to activating radiation, e.g. actinic 4 5 li ght, through an original, whereby the transmitted light d ecomposes the diazonium salt. After exposure, the film is usuauy treated with a base such as aqueous ammonia v apor to promote coupling of the undecomposed diazon ium salt and coupler compound and develop an azo dye 5 0 i n the unexposed areas. This provides a positive photog raphic image corresponding to that of the original. It is desirable, for many purposes, to have an azo dye o f neutral hue produced in image areas. This is generally o btained by including one or more blue dyefomiing 5 5 c ouplers and one or more yellow dye-forming couplers in t he diazotype composition. Ideally, when treated with a b asic developer, e.g. aqueous ammonia vapors, ammonia g as, aqueous nitrogen bases, etc., the couplers form optic ally balancing amounts of blue and yellow dyes such 6 0 t hat the image appears black or grey in color. P reviously, however, it has been difficult to obtain the desired optical neutrality due to a limiting property of 2 existing blue couplers. Blue dye-forming couplers desirably yield dyes which absorb light in the upper portion of the visible spectrum, but the blue dyes derived frgm known couplers have been characterized by inadequate absorption in the longest visible wavelengths, the red light region of the spectrum. It is noted that this shortcoming is particularly prominent when the images are viewed under red-rich tungsten illumination. This problem is further complicated in that certain diazonium salts are less able to form red absorbing azo dyes when reacted with conventional blue dye-formiing couplers. Generally, the diazonium salts that present the greatest problem are those of high light-sensitivity. It is this very type of diazonium salt which is most advantageous for use in the high speed diazotype compositions that are extremely useful for rapid duplicating operations. As an example of this difference in dye-forming ability, when reacted with 3-hydroxy-2-naphthaniUde, the lower speed diazonium salt 4-diethylaminobenzenediazonium fluoroborate produces a blue dye having an absorption maximum 19 nm. higher than that of the dye produced when the higher speed diazonium salt, 2,5-diethoxy-4morpholinobenzenediazonium fluoroborate, is reacted with the same coupler. As well as producing dyes of low red opacity, many naphthoic acid amide couplers absorb light in the ultraviolet portion of the spectrum. When these couplers are in the presence of a diazonium salt, such as in a diazotype composition, they compete with the light-sensitive diazonium salt for absorption of exposing actinic rays and thereby cause an undesirable reduction in the photographic speed of the diazotype composition. Accordingly, it is an object of this invention to produce new diazotype compositions and elements. It is another object of this invention to provide new naphthoic and amide blue azo dye-forming couplers of decreased ultraviolet opacity that produce dyes of increased red light opacity. It is still another object of the present invention to provide new two-component diazotype compositions and elements that produce neutral hue azo dye images. Still another object of this invention is to provide new photogtaphic processes for the preparation of azo dye images. The objects of this invention are accomplished, in one aspect, with improved two-component diazotype compositions and elements that include a diazonium salt and a 3'-hydroxy-2'- naphthoylurea blue dye-forming coupler. Optionally, a yellow dye-forming coupler can be included where black line images are desired. The diazotype compositions and elements of this invention can also be used in new photographic processes. In a preferred embodiment, the present invention relates to twocomponent diazotype compositions that contain a light-sensitive diazonium salt, preferably a p-aminobenzenediazonium salt, and a 3-hydroxy-2-naphthoylurea coupler having the following formula: (1) OH 0 n CN]lg 8 wherein each of R and RI, when taken alone, represents
[2]3,761,263 3 4 either a hydrogen atom, an alkyl group (preferably a @@s mentioned herein, the couplers are advantageously lower alkyl group having from I to 4 carbon atoms) or combined with a light-sensitive diazonium salt to prepare an aryl group (preferably phenyl) and R and R', when a diazo-type composition. Generally, diazonium salts are taken together, represent the atoms necessary to complete sensitive to actinic rays including ultraviolet light, etc. a divalent group having the formula: 5 Useful diazonium salts include benzenediazonium salts such as those having the formula: @CH2+,,Ob-@CH,@-, M-C--,,@-N20 Ze wherein b represents an integer having a value of 0 or 1, each of a and c represents a positive integer and the sum I 0 wherein of a, b and c is 5 when b is 1 and 4 or 5 when h is 0. As used herein, the term alkyl group refers to straight and branched chain alkyl groups having from 1 to about 18 carbon atoms in the chain used as a basis for the nomenclature for the alkyl group. Included within such 15 alkyl groups are substituted and unsubstituted groups such as methyl, halomethyl, ethyl, hydroxyethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like. Aryl groups, 20 as presently defined, include unsaturated carbocyclic groups having from 6 to 14 carbon atoms in a mono or polycyclic fused ring nucleus and preferably phenyl and naphthyl. Couplers of this type can be prepared by convenient 25 techniques such as those described in Abrahart, J. Chem. Society, (1938), pp. 424-426, especially Equation 1 as described therein. Another useful technique is described in Clanson-Kaas and G. Jansen, Acta, Chem. Scaiid., 20 (1966), p. 2010. Still another preparation is demonstrated 30 by the following equation. 0\ C=O 35 I + CBIIsNH2 NH C/ OH 40 0 CNH8NHCoH5 Particularly useful such couplers of the present type in- 45 clude those of Formula I above wherein, in that formula, the group R 50 -N RI represents either H 11 55 -N2; -N -NI -N=S -Nl--'\O; \(4HO 60 c2H5 65 -NC]; -N c2H5 or -N M is either: (I) 'an aryl group, (2) an amino group including substituted amino group such as those having the formula R2 -N Rs, wherein R2 and R3 are the same or different and can be a hydrogen atom, an alkyl group or an aryl group such as phenyl or naphthyi, or (3) an alkyl or aryl thioether group, and Z(D is an acid anion. These compounds can also be substituted on one or more of the nuclear benzene carbons with, for example, at least one of either a halogen atom, an alkyl group, an alkoxy group, an acyl group, a carbamyl group, a carboxyl group or a nitro group. Particularly useful diazonium salts include p-aminobenzene diazonium salts having the above formula wherein M is either an amino group including substituted amino groups and diazonium salts wherein M is a thioether group a s described above, and wherein the benzene nucleus is unsubstituted or substituted in at least one of the 2-position and the 5- position with either an alkyl group, an alkoxy group or a halogen atom. This class of useful diazonium salts can be represented by the formula: R4 ZI(9 Rb wherein: (1) D is either a sulfur atom or a radical having the formula NR7 ' (2) R6, when taken alone, is either a hydrogen atom when D is NR7, or a lower alkyl group having from I to 4 carbon atoms, a lower alkoxy group having from 1 to 4 carbon atoms, an acyl group having the formula -8-T wherein T is either an aryl group or an alkyl group as described elsewhere herein, or a phenyl group when D is either a sulfur atom or NR7, (3) R7 . when taken alone, is either a hydrogen atom, a lower alkyl group or a lower alkoxy group, (4) R6 and R7, when taken together, complete a divalent group having the formula: -ECH2+.Ob-(CH2)@c wherein b is an integer having a value of 0 or 1, each of a and c is a positive integer, and the sum of a, b and Ul 70 c is 5, (5) R4 and R5 are each either a hydrogen atom, a halogen atom, a lower alkyl group (preferably methyl or as well as similar chemical groups wherein the alkyl or ethyl) or a lower alkoxy group (preferably methoxy aryl groups can be additionally substituted with alkyl or ethoxy), and groups, halogen atoms, hydroxyl groups, etc. 75 (6) Zle is an acid anion.
[3]3)761,263 5 Preferred p-aminobenzene diazonium salts include substituted aminobenzene diazonium salts having the formula: Rio I 5 N-@p-N,(DZE) wherein: I 0 (1) each of R8 and R9, when taken alone, is a lower alkyl group, (2) R8 and Rg, when taken together, are the number of carbon and hetero oxygen atoms necessary to complete a morpholino group, 1 5 (3) each of RIO and RI' is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, and (4) Z2E) is either a chlorozincate anion, a fluoroborate (tetrafluoroborate) anion, a sulfate anion, a phosphate anion, or a chlorostannate anion. 20 The most preferred benzene diazonium salts are the fluoroborate salts wherein: (1) R'O and R" are alkoxy groups when R8 and R9 complete a morpholino group, and (2) RIO and R" are each a hydrogen atom when R8 and 25 R9 are each a lower alkyl group. ]Rlustrative diazonium salts include such compounds as the salts of 4-diazo-2,5-dimethoxybiphenyl; 30 4-diazo-2,5,4'-triethoxybiphenyl; 1-diazo-4-dimethylanii,nobenzene; 1-diazo-4-(diethylamino)benzene; 1-diazo-4- [bis (hydroxypropyl) amino] benzene; 35 1-diazo-4- (N-methyl-N-allylantino) benzene; 1-diazo-4-(diamylamino)benzene; 1-diazo-4-(oxazolidino)benzene; 1-diazo-4-(cyclohexylamino)benzene; 1-diazo-4-(9-carbazolyl)benzene; 40 1-diazo-4-(dihydroxyethylamino)-3-methyl@benzene; 1-diazo-4-dimethylamino-3-methylbenzene; 1-diazo-2-methyl-4-(N-methyl-N-hydroxypropylamino)benzene; 1-diazo-4-dimethylamino-3-ethoxybenzene; 1-diazo-4-diethylamino-3-chlorobenzene; 45 1-diazo-2-carboxy-4-dimethylaminobenzene; 1-diazo-3-(2-hydroxyethoxy)4-pyrrolidinobenzene; 1-diazo-2,5-diethoxy-4-acetoxyaminobenzene; 1-diazo-4-methylamino-3-ethoxy-6-chlorobenzene; 50 1-diazo-2,5-dichloro-4-benzylaminobenzene; 1-diazo-4-phenylaminobenzene; 1-diazo-4-morpholinobenzene; 1-diazo-4-morpholino-3-metlioxybenzene; 1-diazo-4-morpholino-2,5-dimethoxybenzene; 1-diazo-4-morpholino-2-ethoxy-5-methoxybenzene; 55 1-diazo-4-morpholino-2,5-dibutoxybenzene; 1-diazo-2,5-diethoxy-4-benzoylaminobenzene; 1-diazo-2,5-dibutoxy-4-benzoylaminobenzene; 1-diazo-4-ethylmercapto-2,5-diethoxybenzene; 1-diazo-4-tolylmercapto-2,5-diethoxybenzene r)O and the like, as well as mixtures thereof. As previously mentioned, the blue dye-forming couplers are desirably used in combination with yellow dyeforming couplers such as the types described in Kosar, 6,5 Light-Sensitive Systems, John Wiley and Sons, Inc., New York (1965), pp. 220-248. Especially desirable yellow dye-forming couplers include 2,5-disubstituted phenois such as those having the formula: 70 OH NRCORIS 75 6 wherein R12 represents either an alkyl group, preferably having from 1 to 8 carbon atoms, an alkoxy group, preferably having from I to 8 carbon atoms, or a phenyl group, and R13 represents either an alkyl group, or an aryl group like phenyl or naphthyl. Preferred 2,5-disubstituted phenols include such compounds as 2-acetamido-5-methylphenol 2- ( 1', 1', I'-trffluoroacetamido) -5-methylphenol 2-acetamido-5-ethylphenol 2-propionoylamido-5-methylphenol 2-hexanoylamido-5-propylphenol 2-octanoylamido-5-phenylphenol 2- (2'-phenylacetamido) -5-methylphenol 2- (2'-phenylacetamido) -5-n-hexylphenol 2- (6'-phenylhexanoylamido) -5-ethylphenol 2-acetamido-5-ethoxyphe-nol 2-benxoylamido-5-ethylphenol 2-benzoylamido-5-amyloxyphenol 2-acetamido-5-hexyloxyphenol. Other advantageous yeflow couplers include the 1-hy droxy-2-naphthamides such as those having the formula: OEE / Rll CN \RIB wherein each of R'4 and R15, when taken alone, represents either a hydrogen atom, an alkyl group, a cycloalkyl group having from 4 to 6 carbon atoms, or an aryl group and wherein R'4 and R'5, when taken together, represent the carbon and oxygen atoms necessary to complete a piperidino group or morpholino group. Particularly useful compounds of this type include 1-hydroxy-2-naphthamide, N-methyl-l-hydroxy-2-naphthamide, N-butyl-l-hydroxy-2-naphthamide, N-octadecyl-l-hydroxy-2-naphthamide, N-phenyl-l-hydroxy-2-naphthamide, N-methyl-N-phenyl-t-hydroxy-2-naphthamide, N-(2'-tetradecyloxyphenyl)-l-hydroxy-2-naphthamide, N-[4-(2,4-di-tert-amylphenoxy)buty11-1-hydroxy-2- naphthamide, 1-hydroxy-2-naphthopiperidide, N-(3',5'-dicarboxyphenyl)-N-ethyl-l-hydroxy-2- naphthamide, N,N-dibenzyl-l-hydroxy-2-naphtharnide, N- (2'-chlorophenyl)-l-hydroxy-2-naphthamide, N-(4'-methoxyphenyl)-l-hydroxy-2-naphthamide, 1-hydroxy-2-naphthopiperizide, 1',3'-bis(I-hydroxy-2-naphthamidobenzene). Between the constituent coupler compounds in a diazotype composition of the present type, the blue dye-forming coupler compounds are generally admixed with the yellow dye-forming coupler compounds in a molar ratio between total blue coupler and total yehow coupler of from 3:1 to 1:3 respectively, with a molar ratio of from 1.8:1 to 1: 1.8 being preferred in most formulations. Most preferred is a ratio of about 1: 1.5, e.g., 1: 1.4 to 1.6, between blue dye-forming coupler or couplers and yellow dye-forming coupler or couplers, but wider variations than those described herein can be advantageous for particular formulations. To prepare a light-sensitive diazotype composition, the diazonium salt is generally admixed with a stoichiometric excess amount of the coupler compounds. TypicaRy a slight molar excess of coupler (e.g., from about 10%
[4]3)761,263 7 excess up to about 2: 1) is used with the diazonium salt to insure maximum dye formation in the final image. For ease of coating and stability of the coated layer, the diazotype composition is generally dispersed in a polymeric matrix such as those described hereinbelow, conventionally in an amount of from about 2 to about 40 parts by weight per 100 parts of matrix polymer. In addition to the dye-forming components, the diazotype composition can contain and usually does contain other additives such as ultraviolet absorbers, stabilizers and the like to advantageously modify its photographic and chemical properties. Acid stabilized diazonium salts can be preferred in certain situations and accordingly, a preferred class of additives includes the known acid stabilizers which operate to prevent premature coupling of the diazonium salt and coupler compound. These acid stabilizers include organic acids such as 5-sulfosalicyclic acid and the like. In general, an organic acid stabilizer is preferably present in all of the diazotype compositions and elements of this invention, with the amount normally varying from about I part to about 6, and preferably from about 2 to about 5 parts by weight per 100 parts of polymeric matrix. Additionally, metal salts like zinc chloride can also be present as a development accelerator or a dye brightener, generally in an amount of from about 0.@ to about 1.5 parts by weight per 100 parts of matrix polymer. Another, and especially desirable, class of additives for diazotype compositions are hindered phenols containing in the 2-position either an alkyl or a cycloalkyl radical and in the 4-position either an alkyl radical, an alkoxy radical, a hydroxyl radical or a thioether radical, which with the bindered phenolic moiety completes a bindered bisthiophenol and more generally a symmetrical bistbiophenol. Such advantageous hindered phenols, which operate to stabilize azo dyes such as those formed by the elements of this invention upon suitable development, are described in detail in U.S. Pat. 3,591,381. T'he diazotype compositions, including all supplemental addenda, are typically dispersed in a polymeric matrix or binder when preparing photographic elements, both for ease of coating and physical stability of the resultant lightsensitive layer. Advantageous matrix polymers include a wide variety of hydrophobic film-forming polymeric substances such as, for example, cellulosic compounds like ethyl cellulose, butyl cellulose, as well as cellulose esters like cellulose acetate, cellulose triacetate, cellulose butyrate and cellulose acetate butyrate; vinyl polymers such as poly(vinyl acetate), poly(vinylidene chloride), poly (vinyl butyral), copolymers of vinyl cbloride and vinyl acetate, polystyrenes, poly(methyl methaerylate), copolymers of alkylacrylates and acrylic acid, etc.; as well as additional polymers such as polyphenylene oxides, terpolymers of ethylene glycol, isophthalic acid and terephthalic acid, terpolymers of p-cyclohexane dicarboxylic acid, isophthalic acid and cyclobexylenebismethanol, copolymers of pcyclohexanedicarboxylic acid and 2,2,4,4tetramethyl cyclobutane-1,3-diol, and additional polymers such as, for example, 4,4'-isop ropylidenediphenyl-2-hydroxy-1,3- propylene ether. Photographic elements utilizing the light-sensitive- diazotype compositions of this invention are conveniently prepared by coating such a composition onto a support material by means such as immersion, flow coating, whirler coating, brushing, doctor blade coating, hopper coating and the like to prepare alight-sensitive layer. Advantageous support materials include conventional photographic film base materials like cellulose esters such as cellulose acetate, cellulose triacetate, cellulose acetate butyrate, etc.; poly-ci-olefins like polyethylene, polypropylene and polystyrene; polyesters such as poly(ethylene terephthalate); polycarbonates as well as metals such as zinc and aluminum and paper inciuding polyethylene and 8 polypropylene coated papers. Other support materials that are suitably used herein are known in the art. Coating is typically by solvent coating means, since it offers the potential for rapid, convenient, continuous ooeration. Coating is effected by first dissolving thephotographic image-forming composition in a suitable solvent, along with a matrix polymer if desired. Exemplary matrix polymers are described hereinabove. The coating solution conventionally contains from about 5 to about 20 weight lo percent solids, and preferably from about 8 to about 15 percent solids. Wider variations are possible where desired, but the above-mentioned ratios are typical for most conventional preparations. After coating by such means as whirler coat15 ing, brushing, doctor blade coating, hopper coating or the like, typically at a wet thickness of from about .001 in. to about .005 in., the coated material is dried to prepare a composite photographic element of this invention. The present photographic elements can be imagewise 20 exposed and developed to prepare a positive, substantially neutral hue azo dye image corresponding to the original. Exposure is typically to a light source rich in actinic light including ultraviolet rays, such as a mercury arc lamp, a photoflood lamp or the like. Image development is con25 veniently accomplished by contacting the exposed element with an alkaline medium such as moist ammonia vapors at ambient pressure or high pressure anhydrous ammonia gas, which promotes the reaction of diazonium salt and coupler compound to form an azo dye image. 30 No further image stabilization is necessary. The following example is included for a further understanding of the invention. 35 EXAMPLE Each of seven azo dye-forming couplers, three non-urea types (No. 1-3) and four 2'-hydroxy-3'-naphthoylurea couplers (No. 4-7) is used in combination with each of two diazonium salts, lower speed Diazo H (p-diethyl40 aminobenzenediazonium tetrafluoroborate), and bigher speed Diazo III (2,5-diethoxy-4-morpholinobenzenediazonium tetrafluoroborate) to prepare diazotype compositions and photographic elements. Diazotype compositions are prepared as coating solutions containing 45 Wt. (gms.) p-Diethylaminobenzenediazonium tetrafluoroborate (Diazo Il)-- 0.0263 (0.10 mmole). or tio 2,5-diethoxy - 4 - morpholinobenzenediazonium tetrafluoroborate (Diazo III) ------------ 0.0361 (0.10mmole). Coupler --------------------- - (0.12 mmole). 5-sulfosalicyclic acid ---------- 0.040. 55 Cellulose acetate butyrate ------ 0.91. 212-dichloroethane ------------ 5.0. Methanol ------------------- 3.0. Each diazotype comopsition is doctor blade coated at 60 a wet thickness of .003 inch on a poly(ethylene terephthalate) support and dried to prepare a composite photographic element. Each element is then treated with aqueous ammonia vapors to produce an azo dye. Since no imagewise exposure is used to decompose the diazonium 65 salts, an overall dye image is produced in each case. Using a standard optical densitometer, appropriate absorption data obtained relative to each image dye is summarized in Table 1, with maximum absorption wavelength (N) in nanometers (nm.) and red light optical density at 675 nm. 70 (D-675) being indicated. The optical density at 675 nm. is a normalized density, that being the density at 675 nm. which corresponds to a density of 1.5 for the dye at 550 nm. This normalized density correlates well with visual observations. The extinction coefficient at 365 nm. indi75 cates U.V. opacity of the coupler.
[5]3,761,263 10 TABLE I Dye characteristics Diazo II Diazo HI Coupler, - Number Structure eao5 nm. X..X. 0'075 D'eis ------------ OH 0 525,587 0.57 559 0.19 OH OH 2,600 542,688 0.60 569 0.37 ONHCEIsCH20H 11 0 OH 2,800 594 0.84 675 0.52 ONHC5Ha 11 v 4 OH 1,500 602 1.20 578 0.70 0 CNHbl NIE[2 0 5 -------- OH 1,900 612 1.53 587 1..01 0 CNHCNHCOHB 0 6 ------------- OH 2,000 604 1.17 581 0.72 0 CNHCNHnC4Ho 0 7 ----------- OH 1,650 595 1.00 580 0.72 0 - - - > C NH Icl NI 11 "_ 0 From the table, it is demonstrated that the dyes from coupler No. I exhibit extremely low optical density at 675 45 nm. relative to dyes from the urea couplers of the present type (Nos. 4-7). Couplers No. 2 and No. 3 which are @aphthoic acid amide derivatives, also yield dyes exhibiting low relative red light opacity. Additionally, couplers No. 2 and No. 3 exhibit high U.V. opacity which inhibits 50 photographic speed of the diazotype composition. The naphthoylurea couplers of the subject type, couplers No. 4, No. 5, No. 6 and No. 7, which are also naphthoic acid amide derivatives, yield dye of increased red light opacity and themselves exhibit a decreased ultraviolet opacity rela55 tive to known couplers such as No. 2 and No. 3 in the table. As well as using the ammonia development process indicated in the above example, a wide range of other processing techniques such as are described in Zollinger, 60 Azo and Diazo Chemistry, Interscience Publishers, New York, 1961; Dinaburg, Photosensitive Diazo Compounds, Focal Press, London, 1964 and Kosar, Light-Sensitive Systems, John Wiley and Sons, New York, 1965, can be used to advantage. 65 The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 70 What is
