US2249541A - Production of natural color photographs by intermediate dye coupling - Google Patents

Production of natural color photographs by intermediate dye coupling Download PDF

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US2249541A
US2249541A US177738A US17773837A US2249541A US 2249541 A US2249541 A US 2249541A US 177738 A US177738 A US 177738A US 17773837 A US17773837 A US 17773837A US 2249541 A US2249541 A US 2249541A
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acid
coupling
dye
amino
derivatives
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Schinzel Karl
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element

Definitions

  • 1,2-dioxy-naphthalene- 4-sulphonic acid may be used for eliminative coupling of amines; in certain cases this may also be done with acid methylene groups attached or with the yellow developer 4-amino-laryl-3-alkyl-5-pyrazolone oxidising its residue to the dye.
  • Primary first development with a neutral or very weakly acid developing solution is, of course, possible as also in all subsequently described modifications.
  • the removal of the residual leuco-derivative after primary coupling can be facilitated by coupling with developing substances or diazo compounds containing a large amount'of hydroxyl. Washing away of the first produced coupling product with sodium carbonate is, however, not absolutely necessary; it may also be done with lye or am- 'ored positive images.
  • the correctly colored positive is formed in the same manner.
  • Gelatine is not affected by washing with sodium carbonate or ammonia and only slightly by alcoholic and acetonlc lye solution, provided it does not contain too much water.
  • agar polyvinyl acetate or other synthetic colloids can replace the gelatine in one, two or all three layers.
  • dextrine, gum arabic, starchsugar, gelatine, etc. which may be washed off, or they are previously softened by alcohol, provided the components'are insoluble in it.
  • vat dyes are employed for the formation of the corresponding leuco-derivatives which are very stable to oxidizing agents, as for example, those of the indanthroneand benzanthrone group, algols, highly-halogenated thioindigo dyes, etc.
  • the leuco-forms of vat dyes are generally prepared with the aid of hydrosulphiteand sodium carbonate or lye, and an addition of alcohol or acetone often favours reduction.
  • Algols and other simple anthraquinone'dyes are also reduced to the anthra-hydroquinone form in this manner.
  • the leuco-derivatives of the vat dyes are not entirely colorless, or at least yellow, but show a color different from the genuine dye and sometimes even complementary to it, as is often the case in anthraquinone dyes, they can still be used in photography in such emulsions as they are transparent to the rays of this color.
  • the coupling speed is increased by the addinamic acid chloride but even more so the o-vinylbenzyl-bromide which can now be prepared fairly easily.
  • Both these halide derivatives can be combined, either before or after polymerization, with amino-phenols, amino-a-naphthols, salicylamide, sodium-u-naphtholsulphamide, etc., or with those leuco-dye derivatives which contain.
  • an amino group in addition to the coupling hydroxyl group primarily reacting with it as for example, the condensation product of substituted anthrone and amino-salicyclic aldehyde or naphthol aldehydes with one amino group in the second nucleus, or with the carbamide acid esters of leuco-vat dyes.
  • the easily prepared o-vinyl-benzylamine can also be allowed to react with mesa-acid chlorides of anthrone or its substitution product, or, of course, with sallcoyl chloride, e-naphthol-2-carboxylic acid chloride, etc.
  • the coupling derivatives with a splitting acid methylene group or a pyrazolone residue are described in the following paragraphs. They can be used for fast coupling and eliminative coupling wtih many leuco-dyes without removing the coupling group, as described in application Serial No. 151,811, because the ketones formed during acid splitting are usually only weakly colored.
  • the leuco-compounds with splitting coupling group which are described later, can be added to the layers also in connection with the other known color-photographic processes. It, is then, of course, unnecessary to introduce a hydroxyl-, arylsulphonylamino group, etc., which is usuallyv necessary for coupling, into the molecule.
  • the sensitizers or any filter dyes are precipitated in the layers as insoluble salts, especially that partwhich is not adsorbed by the silver bromide grain.
  • Precipitants for the sensitizers and filter dyes can also be added to any intermediate or filter layers, or also to all layers to prevent excessive diffusion from layer -to layer with certainty.
  • Thisprinciple is not limited to insoluble or slightly ,difiusing components, but is also gener- "ally applicable to other image producers of this kind and their salts from which the corresponding leuco-dyes are formed by oxidation, reduction or hydrolysis on the image, or generally diffuse before, after or during development, and it especially applies to the leuco-sulphuric acid esters of vat dyes.
  • A. HYDROLYTIC SPLITTING or Tm COUPLING Gnome Ethers of the reduced indigoz'd and lignoz'd vat dyes, Zeuco-, indophenols and Zeuco-indamines
  • the diethers easily prepared with dimethylsulphate,. chlormethylsulphate as well as the monoethers formed under certain conditions, especially I the monobenzylethers with the exception of dinitrobenzyl chloride are so stable to saponifying or oxidising agents that their use with non-hardened gelatine layers appears to be excluded.
  • Aryl ethers especially those formed with chlorodinitrobenzol, of which monoethers may also be prepared, as for example, that of leuco-pyranthrone, are relatively easily split by acid oxidizing agents. Coupling derivatives can be obtained with res orcin, aminoor nitro-phenols with subsequent reduction and arylsulphon'ylation, or by concentrating the diazotized amino-group.
  • Triphenylcarbinol ethers of the leuco-vat dyes hydroxylated in a ring are very easily decomposed by acids or Y oxidising agents, and also the leuco-vat dyes with German Patent 503,812, coupling groups can also be, combined with leuco-vat dyes of which -especially the lactic acidand glycolic acid ester are easily split (1337/3973).
  • the condensation produ ts with acetone, etc. are also pointed out in this connection (German Patents 438,841, 281,998).
  • Synthetic glucosides of leuco vat dyes and their generators thioindoxyl, hydroxy-selenonaphthene, pyrogallol dimethyl ether, etc.,
  • Triphenyl-chlormethane-p carboxylic acid chloride permits etherification of thio-indigo white (344/1627, 1619), whilst the acid chloride groupcan be permitted to act on any amino-a-na-phthol. It is worth mentioning that tribromphenol glucoside can be split much easier than the non-substituted compound; this holds also true for leuco-dye derivatives phenylisocyanite is advisable. Reduction takes (1149/2819) place after esterification of thioindigo white and 3077, 35/4200, 36/236, 39/930, Ann. 427/294, 301,
  • the chlorides of salicylic acid, u-naphthol-2- or -4-carboxylic acid or -6-sulphonic acid, m-hydroxy-benzolsulphochloride or s u l p h i n o a c i d chloride (B.42/3814, 41/4114, 63/2818) dimethylaminobenzoylchloride (350/1045) are allowed to react in the presence of tertiary bases and with the exclusion of oxygen.
  • alkyland aryl-carbonic acid esters of indigo white and of numerous other leuco-vat dyes can easily be saponified by aqueous and especially alcoholic and dilute-alcoholic alkali or ammonia (German Patent 121,866, British Patent 235,247, 334/1858, 54/272, 55/2552, etc.), this is especially true for leuco-esters prepared with carbonic acid benzylester chloride (German Patent 556,798, 13.65/1192, which under certain conditions are split by catalytic neutral reaction.
  • phosgene In the preparation of coupling acylating agents from salicylic alcohol, 1,5-dihydroxy-naphthalene, etc., the action of phosgene can be limited to a single hydroxyl group only when pyrazoloneor antipyrilchlorcarbonyl is used (German Patents 117,624/5, 118,356/7), which act first on the aliphatic hydroxyl group. They can also be allowed to react in excess with thioindigo white, etc., and the chlorformic acid formed with amino-a-naphthol, m-amino-phenol, etc., in the presence of tertiary bases so that the amino-group appears to be connected with the hydroxyl by a carbonyl group.
  • the amino-group is arylsulphonylated.
  • r e-oxidising the leucoform when using these derivatives containing nitro-groups, if the required amount of a suitable reducing agent is not present (359/1817, 1804).
  • the action of phosgene on m-amino-phenol, etc. first forms an addition product which gradually splits off hydrochloric acid (British Patents 372,355, 377,278) forming urea chloride on warming the isocyanate.
  • the isocyanates of naphthols can also be prepared via their carboxylic acid hydroxide (B.58/2850).
  • Ester acids are obtained with sulphochlorides of salicylic acid, a-naphthol-2- or -4-'carboxylic acid, which apparently contain a free sulphonic acid group (German Patent 264,786, British Patents 330,579, 337,846) and on account of their afiinlty to gelatine, cannot always be washed out without difficulty, but more easily so when using other combining agents for the halide.
  • the sulphonic acid group is in the p-position to the hydroxyl, it is split off during coupling; if p-amino-dimethylaniline has been used as developer, then the residual leuco-derivative can be removed with sodium carbonate or alkali and prolonged washing; if 4-amino-resorcin or similar ones have been used as developer, then the indophenol formed can be more easily eliminated than the residual leuco-derivative.
  • Esters with sulphonicor carboxylic acids of quinones are especially easy to split.
  • Thioindigo white, etc. can be esterified with m-naphthol-4- or -2-carboxylicor preferably -sulphbnic acid chloride, also with phenol-por -o-sulphochloride; during the development with p aminodimethylaniline, the corresponding indamines are formed which are split by acid after the unchanged leuco-derivatives have been washed out with alkalies; the quinone residue is then split ofi in the presence of potassium ferricyanide or other oxidising agents or by acid in the presence of aromatic bases with formation of p-hydroxynaphthoquinone imides and liberation of the leuco-vat dye which is immediately oxidised.
  • the mono-chlorsulphuric acid ester of dihydroxybenzols can also be made to act on thioindigo white, etc., or the corresponding sulphurous acid chlorides, especially the hydroxylated benzyl de- Patent 331,842)
  • the dye may be used to advantage for vat dyes, the corresponding o-hydroxybenzylsulphuric acid esters could also be prepared. Analogous to the usual sulphuric acid esters, the
  • esters of thioindigo white and of other leuco-vat dyes can also be prepared in the presence-of tertiary bases, with 'chlormethylsulphuric acid chloride which is rather capable of resisting lye- (360/2292).
  • Energetically acting developers can, however, also couple with the acid methylene
  • the reduced azomethine derivatives of the leuco-vat dyes formed outside the emulsion can be added to the layers as leuco-developers, which yield the corresponding indophenol derivatives even with sodium carbonate.
  • esters and ethers of the anthranol form of acylaminoanthraquinones (British ,Patent 340,983, German Patent 567,845) as well as the mixed esters of the anthrahydroguinone form (German Patent 543,028) which can usually be easily saponified by alkalies, especially in the presence of oxidising agents and also when using u-naphthol-carboxylic acid chloride, .etc., are of special importance.
  • chlormethane sulphonic acid, and the like belong to this group and can be converted into the chloride which is in turn converted with amino-u-naphthol (German Patents 414.426, 499,801, 502,044, British Patent 263,898, BAG/3366).
  • Carbamic acid derivatives The carbamic acid-, allophanic acidand biuret carboxylic acid esters of vat dyes are the most suitable of the compounds concerned, since they are split by dilute alkalies, even when cold, and also slowly by barium hydroxide solution, and are destroyed through oxidation by hypochlorite and acidified nitrite solution.
  • the acyl derivatives obtained couple also in the insoluble or not appreciably difiusing state, or in the sulphonylldes in the form of insoluble salts with or ganic or inorganic bases, preferably in the presence of sodium carbonate or still weaker alkaline reacting substances, since solution often takes place with fixed alkalies (328/2383, 35/781) and the ac'ylated.
  • urethanes are transformed into ureas by dilute ammonia with liberation of the leuco-vat dye.- The same applies to as easily destructible.
  • Hydroxylated derivatives suitable for coupling purposes are not very suitable and are difiicult to prepare, giving only a poor yield, regardless of the positive assertions of British Patents 372,355 and 377,278, since self-esteriflcation takes place very easily, unless the 2-position of the a-naphthol is occupied by the halide or the carboxylic acid aniiide group, or the 6- halide-salicylic acid anilide is used which may also contain the amino-group otherwise provided previously mentioned, by splitting the azo com-- bination after esterification by reduction (German Patent 242,291) and by arylsulphonylation of the diamine formed.
  • the coupling residue can also be combined with hydroxyls of leuco-vat dyes by other dibasic acids instead of by carbonic acid.
  • the chloride of a hydroxylated oxanilic acid can be allowed to act on thioindigo white, or the latter may be allowed to react first on oxalyl-chloride followed by any amino phenol or amino-a-naphthol; the semi-chloride of malonic acid serves similarly for esterification of the leuco-form and the product obtained is converted into the chloride according to British Patent 401,643, or with thionyl chloride.
  • the dichloride of dicarboxylic acids mentioned can also act with ring formation, and the acid methylene group can couple with an energetically acting developer to ammethinzs which are decomposed by acid in the presence of an oxidising agent.
  • chloracetyl chloride or chlormethane sulphochloride can also be esterified with chloracetyl chloride or chlormethane sulphochloride, and the chlorine present in the methyl group can be converted with sodium salicylate acid, phenolsulphonic acid salt, etc.. or preferably with mor p-amino-phenol amino-a-naphthol, also a-naphthol carboxylic acid amide or phenolsulphamide or with their alkali salts in the presence of native copper, or
  • glycocoll oxymethane-sulphonic acid
  • the phenolor naphthol group can generally be combined with reduced vat. dyes by intermediate members containing one or more or some of the .various following groups: ethylene compounds, hydroxyl groups, ketoneor sulphonic groups, carbamide, or urea groups, the acid methylene group or other substituents which are easily attacked by oxidising agents. In addition to this they may contain a terminal sulphonic acidor carboxylic acid group which latter is converted into the acid chloride directly or after preliminary masking of the alcoholic or phenolic hydroxyl'groups with thionyl chloride .or phosgene in the presence of tertiary bases.
  • esters which contain a coupling acid methylene group are noteworthy, since these themselves are not only easily destroyed by oxidation, but also the azomethines formed during coupling developing with p-amino-dimeth-.--
  • the methylene group may-also be brominated and treated with the same precautions for coupling of insoluble components as in application Serial No. 151,811.
  • esters with pyrazolonc carboxylic-or acetic acids or their chlorides are also easily prepared (B.35/1437).
  • Esters obtained with the semi-chloride of malonic acid ethyl ester can be converted by exchanging the alcohol residue for amino-a-naphthol, It is less practical to make malonic acid semi-chloride react first with amino-a-naphthol, to re-convert into the chloride and then allow. it to react with-thioindigo white.
  • -An aminoor halide group can also be introduced into the acid methylene group and this converted with a-naphthol-2-carboxylic acidor sulphonic acid chloride or with aminoa-naphthol or m-amino-phenol, in order to obtain coupling groups more rapidly. It would, however, be a' round about way to esterif thioindigo white with a hydroxylated arylazoacetic acid chloride (German Patent 477,450) and to remove the residual ester after development coupling' by lye, then to split the azo-compound by reduction and to re-convert the amide-acetic ester derivative generated by oxidation-into the vat dye.
  • Phosphoric acid derivatives products obtained can be converted with aminoa-naphthol or m-amino-phenol, etc., also with other hand, esters with aceto-acetic acid can only be indirectly prepared, by first allowing 5- hydroxy- .or p-chlorbutyric acid chloride to acte its 2-halide derivative, and then only allow this dichloride to react with the leuco-vat dye in the presence of tertiary bases.
  • the derivatives-of pentavalent phosphorus mentioned can, however, also be directly reduced to those of phosphoric acid during the preparation or after coupling development.
  • the derivatives which correspond, to phosphoric ester (B.60/295, 59/1120, 58/661, 57/102, 1023) in which, under certain conditions, one-sided saponification can take place with cold lye or the coupling products similarly prepared with phosphorus nitrile chloride, are less suitable (360/160, 57/1343),
  • vat dyes as for example, thioindoxyl, hydroxy-selenonaphthene, pyrogallol dimethyl ether, etc., but it is usually diflicult' to split or reoxydise them to the vat dye.
  • Coupling o-esters of indoxyls and especially of N-methylor N-phenyl indoxyls and of phenyl-oxy-thiophene (345/3393) are not onlycapable of being saponified by themselves with sodium carbonate or acid (3.57/246, 55/1600, 45/2075, 2280, 3393) but like the o-ethers, they are even more readily saponified after previous nitrosation of the imino-group (3.15/781, 16/2190) which may be done on the image individually or collectively.
  • the coupling N-acyl derivatives are not sapo'nified by alkali after the image treatment, but only after oxidation to the indigo dye (German Patent 108,761).'
  • the corresponding acyl derivatives of amido' thionaphthene behave in the same manner (Ann. 351/412) and also those of hydroxy-thi'onaphthene-quinone-a-lmide (CC. 1932, I, 389).
  • indoxyl and the generators of other vat dyes could be combined with salicylic aldehyde, etc., by means of glucose, mannite, etc., to indican-like compounds which are split by acid oxidizing agents similar to the known non-coupling glucoside of indoxyl (B. /4338) (CC. 1923, I. 1628, Chem. Ztg. 1981/7613,
  • Coupling acid chlorides may not only be allowed to react directly on a hydroxyl group, but also on an amino group introduced with alcoholic ammonia or on the arylsulphonyl derivative (13.58/295, 300, 48/268, 52/816) or the suitable use of the acetone derivatives of sugars.
  • the aldehyde group can be combined with the indoxyl residue, and the carboxylic acid group by means of its chloride with amino-@- naphthol or m-amino-phenol.
  • Ethers and esters of the anthrahydroquinone form behave exactly like those of the vat dyes previously described. They difier from those of the vat dyes, however, in that they show a. much stronger individual color. It is obvious that here also, coupling groups can be introduced with salicylic acid chloride, hydroxy-benzyl chloride, etc.
  • analogous derivatives of the mono-valent anthranolor anthranylmercaptan form are more easily prepared on account of their greater stability, but they are more diflicult to re-oxidize, with the exception, perhaps, of carbamic acid esters, etc., as well as their coupling acylation products, both of which are easily oxidized by acidified nitrite.
  • T h e Q-anthrone-actic a c i d (13.56/ 1619) can be transformed into the chloride and converted with m-aminophenol, etc., 9-anthrylamine and 9-anthrylmercaptan alsoreact easily with chloracetic acid, and the corresponding chlorides are converted with amin'o -naphthol, etc., (B.55/3978).
  • the meso-group is removed by oxidation with acidified nitrite or stronger acting oxidizing agents with formation of the dye (318/3170).
  • the meso-methylene group of vat dyes reduced to the anthroneform is relatively easily condensed with coupling aromatic aldehydes, often prepared Without difiiculty, as for example, salicylic aldehyde or a-naphtholaldehyde (B.41/ 1037, 55/228).
  • These compounds are usually reoxidized to the anthraquinone dye even byas mild oxidizing agents as 1% hydrogen peroxide or persulphate in the presence of alkali or sodium carbonate, or by acid oxidizing agents (B.54/2328, 59/767, Ann. 418/30, 420/134, 13.16/703, Ann. 307/213, 0.0.
  • hydroxylated coupling .benzol derivatives of the anthrone form can also be obtained with concentrated sulphuric acid from hydroxy ixanzyl-oxanthrones which, in turn, are readily prepared by benzylation involving reduction with zinc powder and lye, or with the aid of hydroxybenzyl chloride or hydroxylated leucotrope (Bill/2152, 42/1575, 47/1055, 1271) with bridge formation by splitting oil water.
  • the monobrombenzol anthrones prepared from their dibromides by splitting off hydrogen bromide can also be easily reoxidized, as can other compounds 'obtained from it, 'by exchanging the bromine atom for coupling molecules (323/2529, 47/1057,
  • Conversion of meso-carbon atoms leading to coupling derivatives can often be eflected, in the case of finished vat dyes, if they contain stable chromophore groups of which acylamino-, dimethvlarninm, arylaminoor 'nitrogroups are examples. In other cases, they are prepared later by reduction or acylation from the nitro-groups present; or one may start with condensed higher nuclei which themselves have dye characteristics as in the case of naphthanthraquinone.
  • the anthrone form is either partially or entirely prepared with higher anthraquinonazine dyes (indanthrene, flavanthrene, etc.,) or more simply with vat dyes, where one or more anthraquinone nuclei are condensed with indigoid nuclei.
  • indigoid component of the dye is reduced, but it readily reoxidizes itself in air, unless the vat-hydroxyls are converted into leuco-sulphuric acid esters analogous to indigo-sols.
  • the indigoid component is best re-oxidized by very mild oxidizing agents after first general development in the presence of acid, which splits oil sulphuric acid groups, and followed byc'oupling development and combination with the coupling group attached.
  • the indophenols, etc., formed outside the emulsion by condensation of the coupling derivatives with p-NO-dimethyl-aniline or p-NO-phenol can always be reduced and added to the layers.
  • the corresponding m-azo dyes are more suitable than or p-hydroxyand amino azo dyes, since their hydrazo forms are essentially more stable. (8.5/480, 30/2939, 36/4112, 45/596, 1152, 46/824, Ann. 425/141, 427/142-221, 426/76-121, C. C. 1934, I, 755).
  • the coupling group can also be connected by a diazoaminoor are compound with the genuine dye or its leuco-iorm; the former is split by hydrolysis with acids, the latter by reduction (3.25/ 1347, German Patent 410,310, British Patent 377,024, German Patents 268,779, 229,267. 282,890, Ann. 443/216).
  • Dyes with one amino group as for example, aminobenzanthrone, aminoindanthrene and other amino-anthraquinone dyes, also amino-azo dyes or leuco-triphenylmethane dyes with a free amino group, are combined with a-naphthol-4-sulphonic acid containing a diazo group in the second nucleus to form the diazoamino compound, and added to the layers as insoluble salts.
  • a-naphthol-4-sulphonic acid containing a diazo group in the second nucleus to form the diazoamino compound, and added to the layers as insoluble salts.
  • an insoluble indamine derivative is formed by replacement of the 4-sulphonic acid group; the non-coupled diazoamino compound is washed out with sodium carbonate or in and is the genuine image dye liberated by acid from the indamine.
  • diaso-anaphthol could also be used, especially when during development with p-amino-salicylic acid, amino-resorcin, the compound will be washed out at the exposed places and the residual diazoamino compound afterwards decomposed by acid.
  • Any 2,4-dihalogenated amino-a-naphthol can be diazotised and combined with correspondingly substituted amino-thioindigo or its leuco-sulphuric acid ester to form the diam-amino compound oi bisdiazo-amino compound, or coupled with hydroxylated vat dyes or their leuco-esters highly-halogenated compounds, in spite of the data oi German Patent 245,281, Ann.
  • a highly halogenated diazotised aminothioindigo can be combined with resorcin and coupled at the latent image to the indamine, and
  • the dye derivative residue in the image is hydrolyzed by acid in the former procedure. and in the latter the coupling auxiliary group is best split oil by acid reduction of the azo compound. This is especially easy with 539,331, 545,714, 583,315, 540,619) on the other.
  • a resistant yellow dye is added to the upper layer which can be coupled 01! against the reagents otherwise necessary here.
  • 2-anils of isatin, thionaphthenequinone, seleno-naphthenequinone, etc. excel in their ability to split easily (B.47/2300, 43/1371, 77, 42/4278, 45/155, 159, 44/341, German Patents 113,980, 115,465, 241,623, 354,455) and they are also partly soluble in bisulphite.
  • a zomethines of imide are easily decomposed (C. r. 153/531).
  • a molecule of a dye containing a NO-group could be condensed with its derivatives substituted by hydroxyl or with 2-acety1-aceto-6-methylphenol in order to obtain coupling products during development from which the dye can be liberated by acid.
  • These nitroso-derivatives of dyes which are most easily prepared by oxidation of an amino group can also be allowed to react with dehyde dye by dilute acid or in the form of the oxime or phenylhydrazone (3.27/3005, 59/848, 756).
  • Indoxylaldehyde or thioindoxylaldehyde can also be condensed with p-- aminophenol; after coupling, the vat dye is then formed by oxidizing agents, especially acid nitrate from the residue remaining in the image.
  • oxidizing agents especially acid nitrate from the residue remaining in the image.
  • a yellow coupling dye is chosen which is stable to oxidation. and maminophenol are also suitable, especially since homophthalthe latter is nitrosated and oxidized by this and a negative nitrogroup favours splitting of the anil.
  • C-acyl derivatives with salicylic acid esters or other acyls on the two middle carbon atoms which are easily oxidized 017, may be easily split by dilute acids, but they are of little practical importance on account of the difficulty of their (Trans. Ch. Soc. Vol. 125/878,
  • the dye by hydrolysis or oxidation, can also be obtained like the corresponding derivatives of leuco-vat dyes dealt with in previous chapters.
  • the dye may be prepared from dyes with amino-groups, such as aminoanthraquinone, amino-indanthrene, am i no thioindigo, etc.
  • BAG/2201 can be allowed to react with this or with the indol-nitrogen of indigoid mixed dyes, or also cyanide-acetyl chlorid (or chloracetyl chloride followed by phenolsulphamide), since ketonic acid esters formed during hydrolysis of the azomethines produced are especially unstable to saponifying and oxidizing agents.
  • ketonic acid esters formed during hydrolysis of the azomethines produced are especially unstable to saponifying and oxidizing agents.
  • the products obtained with oxalyl chloride and amlno-u-naphthol are also easily destroyed (BAH/1131, 54/1215).
  • Coupling acyl derivatives could also be prepared from indigo-monoand -diimide (346/1694, 2260,57/240) or also from NN'-phenyl-hydrazine-indigo (352/533). With these, however, the vat dye is-regenerated with greater difficulty by hydrolysis or reduction.
  • DialphyZamines.-Two molecules of a dye containing a benzyl-chlorideor alkyl-chloride group can be allowed to react with aniline, a-naphthylamine, etc. This product couples only with diniculty; however, the bis-amino dye can be split from the indamine by the action of strong alkalies.
  • a combination with mor o-aminophenol, 5- or 8-amino-a-naphthol could be effected, then remove the residue with lye after coupling to indamlne, nitrosate and split with lye (3.18/2918, 35/3035, 37/44, 46/953, 960, 48/1080, 83, 90, 1288, Ann. 392/262).
  • melon-ester semi sponding benz-pinacones and -pinacolines of tetra-phenylmethane dyes are better (8.60/1381, 2470). More suitable for photographic purposes are ethers, esters, amines, hydrazones, etc., of carbinols, and also of mixed triphenylmethane azo dyes which, however, are not always colorless or'yellow (3.33/2860-72, 34/880-84, 3384,
  • Coupling derivatives of carbinols are prepared with salicylic acid chloride, hydroxy-benzylbromide', hydroxy-benzylamine, amino-a-naphthol, m-aminophenol, hydroxy-diphenyl-hydrazine and -oxime, etc.
  • salicylic acid chloride hydroxy-benzylbromide', hydroxy-benzylamine, amino-a-naphthol, m-aminophenol, hydroxy-diphenyl-hydrazine and -oxime, etc.
  • C-derivatives are indifferent to silver. bromide gelatine, color fog need hardly be feared.
  • Coupling takes place in the presence of sodium carbonate or even weaker alkalies. but sometimes also in the presence of fixed alkalies or ammonia.
  • the liberation of the basic dye by acids is best done in. the presence of phosphotungsticorsilicotung'stic acid, which forms an insoluble salt and so prevent
  • Carbinol ether are usually colorless oryellow andvery easily saponinedby acids (3.33/3356,
  • Carbine! esters can be prepared observing special precautions, but their stability for photographic purposes is usually too slight.
  • C'arbinol-anilides and -aminobases are prepared by the action of aniline and other organic bases or ammonia-on dyes (3.45/2910, 65/919,
  • Carbinol-phenyl-hydrazones and -o::imes are I stable to bicarbonate, but are saponifled even with cold dilute mineral acids (338/211, 27/1404,
  • Benzoquinone itself is, however, hardly suitableasadye,especiallyasi tisnotinsolublein water.
  • Condensed quinones such as the yellow a-naphthoquinone and the more orange naphthoquinone have a more pronounced indino vidual color; the color of 1,4 and 1,2-anthraquinone and the corresponding naphthanthraquinon'es, as well as their tetraand octo-hydro derivativea'and theusually yellow diaryl-benzoquinones, are still more intense. All these are formed by coupling of the proper phenols, etc., with the developer and splitting of the indophenol, etc., formed-during this process.
  • the coloring power is considerably increased.
  • An example oi the formation of a quinone chromophore in this manner, the coupling development or anthranol and monobromanthrone with p-aminodimethylaniline, is mentioned, where the an may be very easily regenerated by splitting with acid (B. 40/525, 529).
  • Leuco-sulphuric acid esters (German Patent 567,845, British Patent 340,983) can also be obtained from substituted anthranols, or from the I 50 derivatives of meso-anthramines which are more suitable on account of'their stronger acid character similar to meso-bromanthrone. Even if the stability of anthraquinone vat dyes leaves nothing to be desired, quinone dyes prepared with 5 the quicker coupling phenols, anthranols, etc.,
  • the new principle 01 color photography consists, then, in adding to the three layers; phenols, naphtnols, anthrols, arylsulphonylamines, aro- 6o matic amines and diamines, and the like, which i are properly substituted by auxochrome groups or attached hetero-rings, and are insoluble in alkaline developers containing sodium carbonate or which do not appreciably diifuse under these conditions and yet couple quickly during development with p -amino-dimethylaniline or other diamines to insoluble indamines yielding the corresponding quinone with dye character by splitting, the dilute acids.
  • sulphoneor carboxylic acid groups preferably in such a position to hydroxyl that they are split with greater ease during coupling. If quinones of basic character are formed during acid splitting, the presence of phosphotungstic or other inorganic or organic precipitants is desirable in order to prevent difiusion. Quinones are usually formed during acid splitting; under certain conditions, however, or with improper choice of components and developers, the hydroquinone form can also appear (Ann. Bd. 392/17, 418/259), and even addition of the split diamine or aminophenol to the quinone can be brought about.
  • Higher molecular diarylbenzoquinones and -naphtho-quinones, etc. are formed by aggregation of two molecules of benzene, toluene, xylene, phenol, phenol ether, cresols, cresolethers, resorcin mono-ether, naphthols, Michler's hydrol, and the like (55/3105-16, 60/ 1440-51, 66/792, German Patents 459,739, 508,395, 565,423, 566,521, 568,968, British Patent 390,029, German Patent 71,306, 13. 32/2150, 2148, 33/2865, 41/990, Phot. Korr; 1932/4).
  • these quinones contain another free hydroxyl group in the side chain (B. 55/3114, 60/1442, 1444), then they can be al koxylated by alcohols or phenols or acylated by acids, preferably before condensation; high-molecular or colloidal substances, such as polymer-' ized vinylbenzylbromide (B. 50/46) or acrylic acid chloride (German Patent 547,645) and other polymerizing compounds may also serve for this purpose.
  • the color which is usually yellow is not essentially changed by this, unless strongly coloring auxochrome groups are also introduced into the attached aryls.
  • Self-colored condensed quinones are prepared by coupling and acid-splitting from the corresponding phenols, naphthols, anthrols. naphthanthrols, etc.
  • Anthraquinones hydrated in one or both nuclei can be obtained in the same manher from hydrated anthranols or anthrones, meso-brom-anthrones or anthranols (B. 58/2670, 78, 93).
  • These tetraand octo-hydrated anthraquinones and phenanthrene quinones are usually colored rather intense yellow or orange (B.
  • auxochrome groups are most strongly active'in condensed aromatic or heterocyclic systems, as in naphthoqmnones. 1,4-anthraquinone and ordinary anthraquinone, etc.
  • Substituted quinones are obtained from the quinones themselves in the simplest manner by addition or exchange reactions. It may often be advisable to reconvert quinone into the basic phenol or naphthol through the monoxime or phenylhydrazone, as previously described; that is, if they are obtainable at all with the given configuration of the quinone.
  • the auxochrome groups may not only be introduced into the quinone nucleus itself, but also into similar and heterocyciic, rings condensed with it, or alsointo other quinone nuclei connected with the former by saturated or unsaturated intermediate members; such as, the methylene, ethane, ethylene, butadiene group, etc., and their preparation is relatively simple if glutaconic dialdehyde is used (B. 59/2658) which is extensively employed in modern synthesis of This may be used especially for consensitixers. necting two molecules of amino-s-naphthol, because the color of the dianil is not necessarily disturbing, even less so when using maleinic dialdehyde.
  • Ethylene oxide or anthranilic acid chloride, or the like can first be allowed to react and then, in turn, the high-molecular groups or connecting members, if chaining of molecules is desired. 4
  • Components with heterocyclic rings attached are suitable not only or production of yellow and red colors, but for blue quinones of which only few are known, not counting the condensation products oi dialdehyde thym q inone with aromatic amines-(B. /1502); at any rate, the proper derivatives of isopropylphenol are not easily obtainable.
  • Production methods can be usedhere which otherwise are notused in dye technique: for example, condensation of halogenated molecuks among themselves .or with amines, mercaptans, sodium arylsulphamide salts,,etc., in the presence of silver or copper-powder, also with sodium compounds of malonic acid ester, phenyl acetic ester and other acid methylene compounds. (3. /320.
  • l'br o-chlorphenol or 2,5-dichlorphenol can be converted with salts of high-molecular fatty acids, with w boxylic acid amines or sodium salts of sulphonic acid amides.
  • Bensocarbaaolquinone for example, is obtained from the diasotiaation product of l-amino carbaaol and boiling to l-hydroxy-carbasol, similar to S-hydroxy-carbaaol (8. 46/3717, 34/1583, 55/235245) by coupling and splitting with acid.
  • Blah-molecular naphthoquinone-2,3-carbasol gives a pure yellow color, which can also beprepared from the corresponding hydroxy-derivative by oxidation or coupling and splitting with acid (German Patent 454,403)
  • Coupling products which yield usually yellow to orange colored aslneor acridine quinones are obtained from hydroxylat'ed phenaainesand acridin'es during condensation with 2-chloror i-chloror i-brom-s-na mthol or a mixture of the chloro-derivatives (56/2390, German Patents 355,902, 368,188/9, 855,491, 357,286).'
  • the tone of these red dyes can be changed to blueviolet by acylation to a most pronounced degree in the case of the bis-derivatives obtained with Y the aid of dio-anisidine and o-ethoxybenzidine (B. 53/452. 449, J. f. pr. Ch. Bd. 92/370).
  • o-dianisidine and o-ethoxybenzidine their higher analogues, ethers obtained with stearylor ceryl bromide, can also be used as binding members.
  • chlorinated porm-aminodiphenyl can be al- Furthermore, a brominated or lowed to react on the same, and two molecules chained with their external amino groups through phosgene or dibasic acid.
  • Dye derivatives of p-naphthoquinone can be obtained in a similar manner by allowing 3- chlor-p-naphthol to react with the high-molecular auxochromes mentioned, or by forming these auxochromes through connection of several mole. cules of 3-amino-B-n-aphthol or 3-amino-u-naphthols with the polybasic acid chlorides mentioned, also by means of intermediate members acting as enlargers.
  • a chlorine atom is introduced into the 2-position of 3-methylanilino-a-naphthol, and this converted'with one molecule of methylaniline, or the 2,4-diha1ide derivative, is prepared in which only the 2-halide atom reacts with an aromatic amine, whereas, the 4-chlor atom is liberated during indamine coupling, or it may be removed by catalytical reduction with nickel at ordinary temperature.
  • An acetyl group can also be introduced into the 2-position and this replaced by the amino group on the oxime (3.48/1704,
  • a-naphthol analogously substituted is not very apelide, etc.,.or their acyl derivatives, fl-hydroxy- I naphthoquinoneim'lde derivatives or quinone-azo dyes are obtained by coupling and acid splitting (328/546).
  • anisidino derivative are colored green-blue (3.58/1'130, 1137) but the production of 2,3-distable, unless it is added to the layer as completely insoluble phosphotungstate.
  • Blue naphthoquinohe dyes with hetcrocycle These dyes are obtained by linking on a thiodiphenylamine or oxazine ring (346/269, 57/496, Ann, 247/281, 292, 297).
  • 2-chlor-3-anilinoa-naph-thol the chlorine is converted with sodium disulphide and then reduced to 3-mercaptan which is-oxidized to thiazine by atmospheric oxygen.
  • the quinone concerned is colored blue its N-methyl derivative, however, and the product obtained with fl-naphthylamine is greenish-blue.
  • aniline its o-disulphide can also beof 2-chlor--naphthol can also be condensed with the disulphide of o-amino-thiophenol, then reduced andthe ring closed by heating.
  • aniline also its o-disulphide can be allowed to act on 1,3-dioxynaphtha-1ene, or o-chloraniline wit'hchlorination in the 2-position and closure of the hetero-ring.
  • 2,3-a-naphthol which is diflicult to prepare; however, 2,3-dibrom1,4-naphthalene diamine can also be used and one amino group replaced by halide or hydrogen after connecting the heterocyclic ring to the diazo compound; the other one is replaced by a hydroxyl.
  • Similar quinone dyes can also be obtained from 5-brom-3-chlor-pnaphthoquinone or from correspondingly substituted naphthols (3.57/499) This may be done still more easily by reduction or 6-nitro-derivatives of thiazines and oxazines alkylated in the amino group. and arylsulphonylation or replacement by hydroxyl (3.56/2389, 8'1) also by reduction and alkylation or acylation of the corresponding thiazones and oxarones (ass/2390,
  • the dye compounds incorporated in the photographic layers may be dyes themselves or leuco derivatives of dyes, and where reference is made in the claims to coupling derivative-oi a dye compound" it is understood that this reference is to either the dye or the leuco derivative of the dye.
  • These dye compounds are incorporated in the gelatin layer as a non-wandering coupling derivative capable of being split or converted to form the image dye. This splitting or conversion may be brought about by (1) hydrolysis, (2) oxidation, (3) reduction, ,or (4) a combination oi two of these methods, as described in the present specification.
  • Coupledderivative or a dye compound or “coupling derivative oi a dye” mean dyes or dye pling derivatives of dyes or dyeintermediates used in my process must be those which are soluble in strongly alkaline solutions.
  • a dye compound which comprises exposing the of the dye irom the unexposed portions of the layer and developing it in a coupling developer to form a dyeimage soluble in strong alkali. removing the coupling derivative 01 the dye compound i'rom the unexposed portions of the layer in a strong alkaline solution, and regenerating the original dye in the exposed ayer;
  • portions or the a dye compound which comprises exposing the layer and developing it in a primary aromatic amino developing agent to form a dye image insoluble in strong alkali, removing the coupling derivative of the dye compound from the unexposed portions of the layer in an alkaline solution, and regenerating the original dye in the exposed portions of the layer.
  • the method of forming a colored photographic image in a silver halide layer containing a coupling derivative, soluble in strong alkali, of a dye which comprises exposing the layer and developing it in a paraphenylene diamine developing agent to form a dye image insoluble in strong alkali, increasing the solubility of the residual coupling derivative by fogging the layer and coupling the residual coupling derivative with a solubilizing developer, removing said last mentioned coupled derivative from the unexposed portions of the layer in an alkaline solution, and regenerating the original dye in the expom portions of the layer.
  • the method of forming a colored photographic image in a silver halide layer containing a coupling derivative, soluble in strong alkali, of a dye which comprises exposing the layer and developing it in a paraphenylene diamine developlns agent to form a dye image insoluble in strong alkali, removing the coupling derivative of the dye from .the unexposed portions of the layer in a strong alkaline solution, and converting the coupled dye derivative in the exposed portions of the layer. to the original dye by chemical action.
  • a dye which comprises exposing the layer and developing it in a paraphenylene diamine developing agent to form a dye image insoluble in strum alkali, removing the coupling derivative reduction.
  • the method of forrninga colored photographic image in a silver halide layer which comprises condensing a vat dye 'with a phenolic component to form a coupling derivative soluble in strong alkali of the vat dye, incorporating said coupling derivative in the silver halide layer, exposing the'layer and treating it in a silver halide developer whose oxidation product couples with the coupling derivative to form a dye image insoluble in strong alkali, treating the layer in a strongly alkaline solution to remove the undeveloped coupling derivative, and treating the layer in a solution which splits' off the developed phenolic component and regenerates the original KARL SCHINZEL.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2540401A (en) * 1943-09-22 1951-02-06 Gevaert Photo Prod Nv Photographic silver halide emulsion containing color coupler
US2725296A (en) * 1951-09-14 1955-11-29 Eastman Kodak Co Two-layer integral negative positive photographic material
US2865747A (en) * 1955-12-22 1958-12-23 Eastman Kodak Co Photographic color development process

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4152153A (en) 1971-08-31 1979-05-01 Eastman Kodak Company Sulfonamido dye releasing compounds in photographic elements
US4053312A (en) * 1974-09-04 1977-10-11 Eastman Kodak Company O-sulfonamidonaphthol diffusible dye image providing compounds
JPS51113624A (en) 1975-03-28 1976-10-06 Fuji Photo Film Co Ltd Photosensitiver material for color photo

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2540401A (en) * 1943-09-22 1951-02-06 Gevaert Photo Prod Nv Photographic silver halide emulsion containing color coupler
US2725296A (en) * 1951-09-14 1955-11-29 Eastman Kodak Co Two-layer integral negative positive photographic material
US2865747A (en) * 1955-12-22 1958-12-23 Eastman Kodak Co Photographic color development process

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