US3211556A - Photographic layers - Google Patents

Photographic layers Download PDF

Info

Publication number
US3211556A
US3211556A US351839A US35183964A US3211556A US 3211556 A US3211556 A US 3211556A US 351839 A US351839 A US 351839A US 35183964 A US35183964 A US 35183964A US 3211556 A US3211556 A US 3211556A
Authority
US
United States
Prior art keywords
group
silver
formula
layer
azoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US351839A
Other languages
English (en)
Inventor
Anderau Walter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CH270060A external-priority patent/CH386247A/de
Application filed by Ciba AG filed Critical Ciba AG
Application granted granted Critical
Publication of US3211556A publication Critical patent/US3211556A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/24—Disazo or polyazo compounds
    • C09B45/28—Disazo or polyazo compounds containing copper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B27/00—Preparations in which the azo group is formed in any way other than by diazotising and coupling, e.g. oxidation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/08—Preparation of azo dyes from other azo compounds by reduction
    • C09B43/085—Preparation of azo dyes from other azo compounds by reduction by reacting nitro azo dyes with amine or amino azo dye with nitro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/08—Preparation of azo dyes from other azo compounds by reduction
    • C09B43/10—Preparation of azo dyes from other azo compounds by reduction with formation of a new azo or an azoxy bridge
    • 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
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
    • G03C7/29—Azo dyes therefor

Definitions

  • the production of a colored photographic image by the silver dyestuff bleaching method is based on the discovery that an azo-dyestuff, one of the wide range of azo-dyestuffs with which the layer-forming substance, especially gelatine, can be colored, is bleached out depending on the quantity of image-forming silver present in the layer.
  • the silver image is usually produced by exposing the light-sensitive, and in some cases sensitized, silver halide present in the colored layer, and developing and fixing the silver image.
  • the method can be applied to a colored layer produced by coloring the layer-forming substance with the azodyestufI before the layer is formed or by coloring the finished layer on its support.
  • the method can also be applied to multilayer photographic materials.
  • three colored layers may be applied to a transparent or white pigmented support or to baryta paper.
  • a selectively red sensitized silver bromide emulsion colored with a green-blue dyestuff then on this layer there is a selectively green sensitized silver bromide emulsion colored purple, and finally a selectively blue sensitive layer colored yellow.
  • an ordinary light source for example, an incadescent tungsten electric lamp or copying color component record with selectively colored light
  • the silver bromide is exposed at the appropriate areas of the layers.
  • each of the colored layers contains a component color record in the form of a negative silver image in a homogeneously colored layer.
  • azo-dyestuff present in each layer is bleached out in accordance with the image, so that, in dependence on the quantity of image silver present (and in the simplest case approximately in proportion to the quantity of such silver), the azo-dyestuifs are reduced to practically colorless decomposition products according to the following equation:
  • R represents the radical of the diazo-compound obtainable from the diazo-component R NH and R represents the radical of the coupling component HR
  • R represents the radical of the coupling component HR
  • Unconsumed image silver is removed in known manner, for example, with farmers reducer, and also the silver bromide formed in the bleaching process. In this manner a positive copy of the originial is obtained.
  • the present invention is based on the observation that it is advantageous to use azoxy-dyestuffs, instead of or in addition to azo-dyestuffs, in photographic layers to be used for the silver dyestu'ff bleaching method.
  • the present invention provides photographic silver halide gelatine layers suitable for the silver dyestufi bleaching method, containing as image dyestuffs dyestuifs that contain at least one azoxy group.
  • the formula which reflects reality better than the formula which contains two trivalent ntirogen atoms.
  • azoxy-dyestuffs yellow, red, purple, blue and green-blue tints are produced .not only on textiles, as is known, but also in photographic layer, especially those of gelatine.
  • the azoxy dyestuffs preferably contain at least one group imparting solubility in water.
  • azoxy-polyazo-dyestufis can also be obtained, that is to say dyestuifs which contain, forexample, one azoxy group and at least two azo groups. These dyestuffs produce blue tints.
  • azoxypolyazo-dyestuifs which contain groups-capable of forming metal complexes and are, therefore, capable of forming complex heavy metal compounds.
  • Such azo-azoxydyestuifs capableof forming metal complexes, andazoxydyestuffs free from azo groups and which are capable of forming metal complexes may contain as the complexforming group, for example, a salicylic acid radical, and may be used in the non-metallized condition to produce the colored layers,.and converted, after the silver dyestuff bleaching operation, into the complex heavy metal compounds, for example, by means of a solution of copper acetate or another agent yielding metal.
  • the complexforming group for example, a salicylic acid radical
  • photographic materials may be colored with the pre-formed complex metal compounds prepared in substance, for example, silver halide emulsions so colored may be used for casting.
  • the complex metal compounds, and especially the complex copper compounds, whether prepared in substance or produced in the colored layer, are distinguished by their very good fastness to light. They can be bleached out completely by the silver dyestufi bleaching method at the areas having the highest density of silver, and this could not be foreseen. It is necessary to take into account the fact that the complex metal compounds of metals having atomic numbers from 22 to 29, and especially the complex copper compounds yield deeper tints thando the 3 i 4 metal-free dyestufis.
  • the azoxy group undergoes reduc- This azoxy-disazo dyestuif yields a blue tint having an abtlon in accordance with the following equation sorption maximum at 620 m
  • This dyestuif itself possesses a remarkably low capacity for diffusion so that it has hardly any tendency to migrate into an adjacent layer.
  • the resistance to diffusion in gelatine can be still further improved by suitable additions, for example, a guanidine base.
  • azoxy dyestufis having a good resistance to diffusion can be produced by incorporating into the molecule of the dyestuif a radical which imparts resistance to diifusion.
  • the primary amino group may be replaced by groups of the so that a larger quantity of image silver is required to bring about the reduction than in the case of the azo group.
  • R4 re presents a hydrogen atom or an alkyl group
  • R4 re presents a hydrogen atom or an alkyl group
  • g f belpw a few dyestuffs Smtable for the and R represents an acyl, sulfacyl or aracyl group or purposes 0 t e mventlon' the chain of an aliphatic or hydro-aromatic radical.
  • the yellow dyestutf of the formula for example, R may represent a'benzyl radical, for ex- 0 o S0311 H038 which is obtainable by condensing 4:4'-dinitro-stilbene ample, a dichlorobenzyl radical, a benzoyl radical, a didisulfonic acid with aniline in the molecular ration 1:2.
  • chlorobenzoyl radical a para-toluene-sulfonyl radical, or No 2
  • This dyestuff dyes gelatine yellowish-red and can be conrupted by hetero atoms, Such as an amyl, n ⁇ mwdecyh verted into its complex copper compound which is very octadecenyl, dodecyl-hydroxypropyl or stearoyl radical.
  • Dyestufl No. 4 corresponds to the formula 4 11,1 OCu )-ou 0 Nrn 1 1103s s03 by reduction with the aid of heat with glucose in a soluits absorption maximum in gelatine is at about 670' mu,
  • tion rendered alkaline with an alkali metal hydroxide. It can also be completely bleached out well by the silver 3,211,556 .5 6 dyestuff bleaching method at the areas having the maxior further sulfonic acid groups.
  • diazo components mum density of silver, and it has an excellent fastness to of the kind defined there may be mentioned, for example, light.
  • the bleaching out of this dyestuif can be still further improved by extracting the dyestuif at the boil Z-amino-1-hyd Y- acid, with hydrochloric acid or a cyanide to remove the copper 2-ami110-1-hYdf0XY-5-chlorobellzene-6-sulf0nic acid bound in complex union, and, after the bleaching oper- Z-amiIIO-1-hYdI0XY5-chlorobenlene-4-sulfonic acid, ation reintroducing the copper into the metal-free dyestuff Z-amino-1-hydroxy-4-methylbenzene-6-sulfonic acid, by treatment with a bath containing a water-soluble -amin y 0 y acid, oopper compound.
  • the azoxy dyestulfs of Formula 6, some of which are known, are obtained by condensing 4:4-dinitrostilbene- B.
  • the aminoazo dyestuffs are obtained by coupling diazo com- RtHN- pounds of orthohydroxyamines of the formula SOQH (8) (PH HO3SR NH in which R has the meaning given above, condensing Wlth ammes of the formula the nitroazo dyestuif with the formation of an azoxy (9) H3O-o group from two nitro groups and then coppering.
  • the I 2 phenylamino-8-hydroxynaphthalene-6-sulfonic acids used as coupling components 1n this process may conwhich couple in paraposition to the amino group, wheretain further substituents in the phenyl radical, for exin R and R have the meanings given above.
  • halogen atoms for example, chlorine, alkyl groups
  • the amines of the Formula 8 may contain additional for example, a methyl group, alkoxy groups, for example, substituents, for example, halogen atoms such as chlorine, a methoxy group, acidic groups imparting solubility in alkyl groups such as ethyl or methyl groups, nitro groups
  • Water for example, carboxylic acid groups, carboxy- 7 methoxy groups HOOCCH 'O-) or especially sulfonic acid groups.
  • substituents for example, halogen atoms such as chlorine, a methoxy group, acidic groups imparting solubility in alkyl groups such as ethyl or methyl groups, nitro groups
  • Water for example, carboxylic acid groups, carboxy- 7 methoxy groups HOOCCH 'O-) or especially sulfonic acid groups.
  • the photographic layers that contain azoxy dyestuffs of the formulae 6 or 11 can be of the usual composition and can be prepared in known manner.
  • the supports for the silver halide layers can be, for example, glass for duplicate positives, or they can be made of cellulose esters, or they can be opaque, white-pigmented films, baryta paper or reflecting supports.
  • a positive copy is obtained by copying a transparent, colored master image on a dyed gelatine layer containing silver halide.
  • a positive (rectified) copies are obtained in a simple manner from a black and white original.
  • a colored positive master image is copied on such a silver halide layer dyed a transparent black that, if necessary, may be sensitized to the color concerned, a positive black and white copy of the colored original is obtained, the grey tones being graduated.
  • the azoxy dyestuffs of Formulae 6 and 11 are specially suitable for the production of such copies.
  • the black dyestuffs used in the silver dyestuffs bleaching process must possess a wide range of properties. A high degree of light fastness is required and the dyestuffs should be capable of being bleached to neutral grey tones. They must be non-diffusing or must be capable of being rendered non-diffusing with precipitating agents, for example, guanidines.
  • the dyestuffs of Formulae 6 and 11 meet these requirements to a large extent.
  • Very strong acid baths are used in the course of the bleaching process which means that the copper-containing dyestuffs are partially demetallized. It is, therefore, of advantage to treat the dyestuffs with a copper-yielding agent in a slightly acid to alkaline medium at the end of the bleaching process in order to convert the demetallized portion back to the complex copper compound.
  • the dyestuffs of Formula 13 may be prepared by treating a nitromonoazo dyestuff of the formula in which R represents a benzene radical bound in the 1-position to the azo group and in the 4-position to the nitro group and containing in the 2-position an alkoxy group or a hydroxyalkoxy group with at most 5 carbon atoms, and R has the meaning given above, with a reducing agent which is capable of reducing a nitro compound to an azoxy compound with the linking of two molecules.
  • Unitary asymmetrical as well as symmetrical dyestuffs of the Formula 13 may be prepared by coupling a tetrazo compound of a diamine of the formula on either side with one of two different aminohydroxynaphthalenedisulfonic acids, or on each side with an identical azo component of this kind.
  • R represents a benzene radical bound in the l-position to the amino group and in the 4-position to the azoxy group and containing in the 2-position an alkoxy group or a hydroxyalkoxy group with at most 5 carbon atoms.
  • the compounds of the Formula 15 may in their turn be prepared by reducing a l-acylamino-Z-alkoxy- 4-nitrobenzene or a 1-acylamino-2-hydroxyalkoxy-4- nitrobenzene to form an azoxy compound of the formula in which R, has the meaning given above, and by subsequent hydrolysis of the acylamino group.
  • the 1-acylamino-2-alkoxy-4-nitrobenzenes or l-acylamino-2-hydroxyalkoxy-4-nitrobenzenes used for the preparation of the diamines of the Formula 15, and the corresponding amino compounds employed for the preparation of the nitromonoazo dyestuffs of Formula 14 contain in the ortho-position to the acylamino group or to the amino group for example a methoxy, n-propoxy, isopropoxy or n-butoxy group. As a rule ethoxy and hydroxyethoxy groups are particularly advantageous. Further substituents, for example a methyl or ethyl group or a chlorine atom, may be present in these compounds but are not necessary.
  • the 8-hydroxynaphthalenedisulfonic acids with a further substituted amino group in the l-position used as azo components for the preparation of the dyestuffs of Formula 13 according to the methods shown, contain the sulfonic acid groups preferably in the 3,6- or 4,6-position.
  • the amino group in the 1-position is further substituted, for example by alkyl groups, such as ethyl or methyl, by benzene radicals which may themselves bear further substituents, by cycloalkyl radicals such as cyclohexyl, or advantageously by acyl radicals.
  • acyl radicals are derived from carboxylic acids or sulfonic acids, especially those of the benzene series, in which latter case the benzene nuclei may bear further substituents, for example chlorine atoms or alkyl radicals, particularly methyl groups.
  • substituents for example chlorine atoms or alkyl radicals, particularly methyl groups.
  • the dyestuffs of Formulae 13, 17, 18 and 19 may be pling 1-amino-Z-ethoxy-S-nitrobenzene with l-toluenesulprepared in a conventional manner known per se, In fonylamino-S-hydroxynaphthalene-3,6-disulfonic acid in order that the coupling may take place in the 7-position, alkaline medium, are reduced in 5 to 10 minutes at a that is to say in vicinal position to the hydroxyl group temperature between 75 and 90 C.
  • the reaction is and 100 parts of an aqueous sodium hydroxide solution of carried out in an alkaline medium.
  • the reduction of by volume with 17 to 18 parts of glucose, dissolved the nitro dyestuffs to form the azoxy dyestuffs is adin 60 parts of water.
  • H0 s so H HOsS- SO3H vantageously performed with glucose in an aqueous is formed in very good yield and can be separated by sodium hydroxide solution. the addition of sodium chloride. It dissolves in water According to the process of the invention these dyestufls with a greenish blue shade.
  • the dyestufi is disare present in photographic layers for the silver dyest f solved in gelatine, the solution shows a green-blue layer bleaching process, These materials may be constituted with an absorption maximum of 640 m,u. and prepared in a manner known per se.
  • the silver The dyestuffs shown under (7) to (9) below may also halide emulsion layers colored with the green-blue dyeb prepared b thi method.
  • stuffs may advantageously be sensitized to red light and form a constituent of a multilayer material, suitable for (7)
  • the dyestuff of the formula HO3S H033- SOzH SO3H the production of multicolored prints, which contains in Absorption maxima in gelatine at 640 and 690 my.
  • the dyestuff of the formula 23 H C-CH2 SOaH HOaS Absorption maximum in gelatine at 620 m (10) l-acetylamino-2-methoxy-4-nitrobenzine is converted at 40 to45 C. with zinc dust in ammoniacal ethanol solution into the azoxy compound of the formula resulting dyestuff of the formula G a a HOaS- SOaH colours gelatine green-blue shades.
  • Example 1 6 grams of dyestuff No. 3 (see above) are dissolved in 550 cc. of Water, the solution is mixed with a red sensitized silver bromide gelatine emulsion, and the homogenized mixture is cast as a layer on a suitable support, for example, an acetyl-cellulose film having a substream layer, so that the dry layer contains 15 milligrams of silver in the form of silver bromide and 7 milligrams of dyestuff per square decimeter.
  • a suitable support for example, an acetyl-cellulose film having a substream layer
  • the resulting blue layer can be used as such or it may be used as part of a three-layer material.
  • the layer is exposed behind a colored diapositive or beneath a positive component color image to red light.
  • the exposed layer is developed with a developer containing 0.75 gram GH -CH; 0-0H HO HN-C (JH,
  • a good resistance to diifusion can be imparted by introducing the substituents mentioned above in connection with dyestufi No. 3 or by converting the too easily diffusible dyestuff acid or akali metal salt into a non-diffusing salt, for example, with an organic base or a biguanide. These expedients may of course be used in combination.
  • azoxy-dyestuifs can also be used for incorporation in so-called droplet-emulsions (packed emulsions) or for mixed grain emulsion systems.
  • the layer is advantageously hardened with formaldehyde solution of 4% strength, and then washed.
  • the silver bleaching bath contains, for example, cc. of hydrochloric acid having a density of 1.19, 12.5 grams of potassium bromide and 10 grams of thiourea dissolved in one liter of water, and if desired, 0.1 gram of dimethylquinoxaline. The bleaching process takes 8 to 15 minutes, and then the layer is washed for five minutes. The layer is then treated in a silver bleaching bath to convert the silver into silver halide.
  • the treatment in this bath lasts 3 to 8 minutes.
  • the layer is then washed for five minutes and fixed for 3 to 5 minutes in a bath containing 200 grams of sodium thiosulfate in one liter of water.
  • the layer is finally washed for 10 minutes.
  • the layer is after- 13 14 treated with a copper acetate solution of 2.5% strength there is obtained a blue-red image having a somewhat for 10 minutes, and is then washed for one minute. purer tint and which is fast to light.
  • the solution is rapidly cooled to 40 C., and 2 parts of one of the salt-free cupriferous dyestuffs of mixed with 1000 grams of a gelatine solution of the formulae (29) (
  • the colored gelatine is then are dissolved in 100 parts of water at 40 C., and the mixed with 1000 grams of a silver bromide gelatine emulsolution is mixed with a preparation obtained by allowing sion, which may be yellow-green sensitized and contains 25 to 30 parts of gelatine to swell in 300 to 600 parts and a quantity of silver bromide such that, after being cast then melting the gelatine at 40 C.
  • the amount of gelaand dried the layer contains 15 milligrams of silver per tine used depends on the support on which the prepared square decimeter.
  • the layer so produced can be used as emulsion is to be cast. 300 to 600 parts of a silver :brosuch or as one of the layers of a three-color material. mide emulsion that can be orthochromatically or pan- After being exposed the layer is treated as follows: 30 chromatically sensitized are added to the colored gelatine.
  • a silver image is developed for 8 minutes at C. Furthermore, water to reduce the viscosity, aqueous soluwith a bath which contains dissolved in 1000 cc. of tions of spreading and dispersing agents, for example, water 0.75 gram of N-Inethyl-para-amino-phenol, 3 saponin, and/or aqueous solutions of hardening agents grams of hydroquinone, grams of sodium sulfite, can be added to the mixture. 40 grams of sodium carbonate and 1 gram of potas- 10 cc. of an emulsion so prepared are cast on a glass sium bromide; plate measuring 13 x 18 cm. and dried.
  • aqueous soluwith a bath which contains dissolved in 1000 cc. of tions of spreading and dispersing agents, for example, water 0.75 gram of N-Inethyl-para-amino-phenol, 3 saponin, and/or aqueous solutions of hardening agents grams of hydroquinone, grams
  • the layer is ex- (2) Washed for three minutes; posed beneath a black and white positive image and the (3) Fixed for 5 minutes in a solution containing 200 silver image developed in a bath which contained in 1000 grams of sodium thiosulfate and 20 grams of potasparts of water, 80 parts of anhydrous sodium sulfite, 55 sium meta-bisulfite per liter of water; parts of anhydrous sodium carbonate, 20 parts of sodium (4) Washed for 5 minutes; borate and 8 parts of N-methyl-para-aminophenol sulfate. (5) Hardened for 5 minutes with an aqueous solu- Development takes 4 to 6 minutes.
  • the layer is given a tion of formaldehyde of 4% strength; short wash with water and then fixed for 5 minutes in a (6) Washed for 5 minutes; bath which contains 200 parts of sodium thiosulfate dis- (7)
  • the dyestuff image is bleached for 10 to 30 minsolved in 1000 parts-of water.
  • the layer is again washed utes with a solution containing, per liter of water, 60 for 5 minutes.
  • a photographic silver halide gelatine layer for the emulsion positive copies in black and white can be obsilver dyestuff bleaching method containing as an image tained from a positive color transparency.
  • a photographic silver halide gelatine layer for the silver dyestuif bleaching method containing as an image dyest-ufi an azoxy dyestuff of the formula (1)
  • a photographic silver halide gelatine layer for the 0 silver dyestutf bleaching method containing as an image @0112 dyestufi an ozoxy dyestutf of the formula Ha (5)
  • the material is exposed, fixed and hardened, then v bleached in a dyestuif bleaching bath containing hydro- 4-position and containing in 2-position a substituent sechloric acid, potassium bromide, thiourea and Z-aminolected from the group consisting of an alkoxy group and 3-hydroxyphenazine, and finally freed.
  • the atoms, and R and R each represent the radical of an dyestuif of Formula 20 is found to be fast to diffusion, 8-hydroxynaphthalene-disulfonic acid bound to the azo bleached pure white at the areas of maximum density group in its 7-position and containing in its l-position a of silver and shows a good fastness to light.
  • a photographic silver halide gelatine layer for the wherein X represents a member selected from the group silver dyestufi bleaching method containing as an image i f oftan grgup i hyd'ofiyalkoxy i con aimng a mos car on a oms' an 9 represen s a dyestuff an azoxy dyestutf of the formula monocyclic benzene radicaL v A OH X X HO A 0 Y- SOaH HOaS- Y i i wherein A and A each represents a member selected 8.
  • a photographic silver halide gelatine layer for the a hydrogen atom and the other Y represents a sulfonic 35 silver dyestufi? bleaching method containing as an image acid group.
  • .Hdyestuff the azoxy dyestuff of the formula HgN OH HgC-O O 'CHQ HO NH,
  • a photographic silver halide gelatine layer for the silver dyestutf bleaching method containing as an image dyestuif an azoxy dyestufi of the formula acyl hll'H (
  • a photographic silver halide gelatine layer for the consisting of an alkoxy group and a hydroxyalkoxy group silver dyestuff bleaching method containing as an image containing at most 5 carbon atoms. dyestufi the azoxy dyestufi of the formula 7.
  • a photographic silver halide gelatine layer for the silver dyestulf bleaching method containing as an image dyestuif an azoxy dyestufif of the formula R9SO2NH OH X X HO HN-SOr-Rn HO S O H O HO S a S a a S 03 3,211,556 19 20 12.
  • a photographic silver halide gelatine layer for the silver dyestufi bleaching method containing as an'image dyestuifthe 'azoxy dyestuff of theformula mN 011 H000 1 00011 HO NH:
  • a photographic silver halide gelatine layer for the silver dyestufl? bleaching method containing as an image dyestufi the azoxy dyestufi of the formula OCu-0 I 0 Cu 0 H035 OCH3 SO3H H038 I H3C--O $0311 14.
  • a photographic silver halide gelatine layer for the silver dyestufi? bleaching method containing as an image 20 dyestuif the azoxy dyestufi' of the formula" 0 HQaS SOaH HOaS- 503E 15.
  • a photographic silver halide gelatine layer for the silver dyestuif bleaching methd containing as an image dyestufi the azoxy dyestuflf of the formula Hic C -so, 1 n on Him-( o-QH, H H1 I-o,sC -0H3 HOaS- 80 11 I O H03s sea 16.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paper (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US351839A 1960-03-09 1964-03-13 Photographic layers Expired - Lifetime US3211556A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH270060A CH386247A (de) 1960-03-09 1960-03-09 Photographische Schicht für das Silberfarbbleichverfahren
CH1442162A CH415296A (de) 1960-03-09 1962-12-07 Photographische Schicht für das Silberfarbbleichverfahren
CH1442062A CH415295A (de) 1960-03-09 1962-12-07 Photographische Schicht für das Silberfarbbleichverfahren

Publications (1)

Publication Number Publication Date
US3211556A true US3211556A (en) 1965-10-12

Family

ID=27173858

Family Applications (1)

Application Number Title Priority Date Filing Date
US351839A Expired - Lifetime US3211556A (en) 1960-03-09 1964-03-13 Photographic layers

Country Status (7)

Country Link
US (1) US3211556A (de)
BE (3) BE640911A (de)
CH (3) CH415296A (de)
DE (3) DE1121469B (de)
FR (3) FR1290363A (de)
GB (3) GB923265A (de)
NL (1) NL262127A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3304181A (en) * 1962-04-10 1967-02-14 Ciba Ltd Photographic materials for the silver dyestuff bleaching process
US3404982A (en) * 1964-06-02 1968-10-08 Ciba Ltd Photographic materials for the silver dyestuff bleaching process
US4235957A (en) * 1979-01-25 1980-11-25 Eastman Kodak Company Thermal silver-dye bleach element and process
EP0029950A1 (de) * 1979-11-29 1981-06-10 Bayer Ag Trisazofarbstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung zum Färben von vegetabilischen Fasermaterialien und Leder
EP2105469A1 (de) 2008-03-28 2009-09-30 Unilever N.V. Partikel mit bipolaren topospezifischen Eigenschaften und Herstellungsverfahren dafür

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3173964D1 (en) * 1980-06-03 1986-04-10 Ciba Geigy Ag Dyeing paper
CH654588A5 (de) * 1981-12-31 1986-02-28 Sandoz Ag Metallisierte stilbenazoverbindungen, verfahren zur herstellung und verwendung.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2987513A (en) * 1958-01-31 1961-06-06 Bayer Ag Azo dyestuffs and process for their manufacture
US3148062A (en) * 1959-04-06 1964-09-08 Eastman Kodak Co Photographic elements and processes using splittable couplers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2987513A (en) * 1958-01-31 1961-06-06 Bayer Ag Azo dyestuffs and process for their manufacture
US3148062A (en) * 1959-04-06 1964-09-08 Eastman Kodak Co Photographic elements and processes using splittable couplers

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3304181A (en) * 1962-04-10 1967-02-14 Ciba Ltd Photographic materials for the silver dyestuff bleaching process
US3404982A (en) * 1964-06-02 1968-10-08 Ciba Ltd Photographic materials for the silver dyestuff bleaching process
US4235957A (en) * 1979-01-25 1980-11-25 Eastman Kodak Company Thermal silver-dye bleach element and process
EP0029950A1 (de) * 1979-11-29 1981-06-10 Bayer Ag Trisazofarbstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung zum Färben von vegetabilischen Fasermaterialien und Leder
US4387050A (en) * 1979-11-29 1983-06-07 Bayer Aktiengesellschaft Polyazo dyestuffs, a process for their preparation and their use for dyeing vegetable fibre materials and leather
EP2105469A1 (de) 2008-03-28 2009-09-30 Unilever N.V. Partikel mit bipolaren topospezifischen Eigenschaften und Herstellungsverfahren dafür

Also Published As

Publication number Publication date
FR1290363A (fr) 1962-04-13
BE640911A (de) 1964-06-08
NL262127A (de)
GB923265A (en) 1963-04-10
CH415296A (de) 1966-06-15
GB1002345A (en) 1965-08-25
CH431272A (de) 1967-02-28
CH415295A (de) 1966-06-15
BE640912A (de) 1964-06-08
DE1173337B (de) 1964-07-02
FR84793E (fr) 1965-04-16
DE1174613B (de) 1964-07-23
BE601095A (de)
GB999996A (en) 1965-07-28
FR84794E (fr) 1965-04-16
DE1121469B (de) 1962-01-04

Similar Documents

Publication Publication Date Title
US3211554A (en) Photographic layers for the silver dyestuff bleaching method
US3211556A (en) Photographic layers
US3053655A (en) Photographic material and process
US3808194A (en) Disazo dyes containing a bis-urea bridging group
US2428130A (en) Tris and polyazo dyes from tetrazotized 0:0' dihydroxybenzidine
US2420631A (en) Dis-azo dyes for color photography
US2384419A (en) Azo dyestuffs
US3318700A (en) Application of dyestuff bleaching catalysts in the silver dyestuff bleaching process
US3278303A (en) Process for the preparation of multicolored images by the silver dyestuff bleaching method
US3223527A (en) Process for the production of photographic images by the silver dyestuff bleaching process and photographic layers therefor
US3404982A (en) Photographic materials for the silver dyestuff bleaching process
US3322543A (en) Photographic layers for the silver dyestuff bleaching process
US3436218A (en) Process for producing color photographs
US3394004A (en) Photographic material for the silver dyestuff bleaching process
US3157508A (en) Photographic material for the silver dye bleaching process
US2192153A (en) Azo dyestuffs
US3178290A (en) Photographic layers suitable for the silver dyestuff bleaching method
US3443953A (en) Photographic materials for the silver dyestuff bleaching process
US4337195A (en) Azo dyestuffs
US3623874A (en) Photographic light-sensitive silver halide material containing disazo dyes
US3038802A (en) Photographic color element with novel cyan dye
US3210190A (en) Photographic layers suitable for the silver dyestuff bleaching process
US3749576A (en) Photographic light-sensitive silver halide material containing azo dyes
US3443952A (en) Photographic materials for the silver dyestuff bleaching process
US3202511A (en) Photographic layers suitable for the silver dyestuff bleaching process