US3318700A - Application of dyestuff bleaching catalysts in the silver dyestuff bleaching process - Google Patents

Application of dyestuff bleaching catalysts in the silver dyestuff bleaching process Download PDF

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Publication number
US3318700A
US3318700A US306690A US30669063A US3318700A US 3318700 A US3318700 A US 3318700A US 306690 A US306690 A US 306690A US 30669063 A US30669063 A US 30669063A US 3318700 A US3318700 A US 3318700A
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Prior art keywords
silver
bleaching
formula
azine
catalyst
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US306690A
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English (en)
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Anderau Walter
Mory Rudolf
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BASF Schweiz AG
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Ciba AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • 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
    • C09B17/00—Azine dyes
    • 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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/021—Disazo dyes characterised by two coupling components of the same type
    • C09B35/023—Disazo dyes characterised by two coupling components of the same type in which the coupling component is a hydroxy or polyhydroxy compound
    • 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
    • C09B39/00—Other azo dyes prepared by diazotising and coupling
    • 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
    • C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
    • 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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/08—Azo dyes
    • C09B62/09—Disazo or polyazo dyes
    • 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

Definitions

  • alkali-metal halides and other substances such as urea, thiosemicarbazide or especially thiourea or derivatives thereof generally must be present in the dyestulf bleaching bath in addition to acids such as hydrochloric acid, sulfuric acid or citric acid, examples of such alkalimetal halides being potassium bromide, potassium chloride and sodium chloride.
  • a common silver dyestulf bleaching bath thus contains 30 to 80 parts of potassium bromide, 20 to 70 parts of thiourea and 35 to 70 parts of 30% sulfuric acid or hydrochloric acid in 1000 parts of Water.
  • the bleaching time for dif ferent types of azo dyestuffs varies, for example, between 1 minute and 60 minutes.
  • the gradation of the color image depends not only on that of the silver image but also on the bleaching time. If the silver dyestuif bleaching bath is allowed to act on the material for only a short period, the color image shows a flat gradation curve. The gradation curve becomes steeper the longer the dyestuff bleaching bath is allowed to act on the material.
  • This invention is based on the observation that certain naphthazine compounds are specially suitable as dyestuif bleaching catalysts in the silver dyestulf bleaching process.
  • the present invention provides a process for the production of color photographic images by the silver dyestutt bleaching process wherein there is used an azine compound having at least one acidic group imparting solubility in water and corresponding to the formula in which R represents a naphthalene radical condensed with the azine ring in the manner indicated by the valence lines, which naphthalene radical carries a hydroxyl group, an amino group and/ or an azo group attached to the sixmembered ring not directly bound to the azine ring, and R represents a benzene or naphthalene radical condensed with the azine ring in the manner indicated by the valence lines, as a dyestulf bleaching catalyst.
  • the compounds of the Formula 3 contain at least one acidic group imparting solubility in water, for example, a sulfonic acid or a carboxylic acid group.
  • a sulfonic acid or a carboxylic acid group Such groups can be bound directly to the carbon atoms which are ring members of the azine compounds, but carboxylic acid groups, in particular, can also be joined to the carbon atoms of the ring systems R and/ or R through a bridge member, for example, through a CH or an --OCH group.
  • the naphthalene radical R is condensed with the azine ring in such a manner that two adjacent carbon atoms of the naphthalene ring, advantageously in cup-position, are shared with the azine ring.
  • the naphthalene radical R contains a hydroxyl group or an amino group or an azo group attached to the siX-membered ring not directly bound to the azine ring; it can also contain more than one of these groups, for example, a hydroxyl group and an amino group or a hydroxyl group and an azo group.
  • a sulfonic acid group can also be present in this ring.
  • the azo group which is bounud on one side to the naphthalene radical R is bound on the other side, for example, to a benzene radical or to another naphthalene radical.
  • R can be a benzene radical or a naphthalene radical, which can also correspond to the definition of R thus forming, for example, azine compounds having a centrosymmetric constitution of the kind. exemplified by Formula 6a.
  • radicals R and R and more especially the radicals bound to the naphthalene radicals through an azo group can contain further substituents of the kind defined or other substituents, for example, halogen atoms such as chlorine, alkyl groups such as methyl and ethyl groups and alkoxy groups such as methoxy and ethoxy groups.
  • azine compounds of the Formula Even larger molecules of azine compounds of the Formula Specially important are the azine compounds containing at least one sulfonic acid group that correspond to the formula R4 H t in which R has the meaning given above and R represents an amino group or an azo group bound to a further aromatic radical. Also worthy of special mention are the azine compounds of the formula (5) SOaH (in which R and R have the meanings given above), and also those of the formula in which R, and R, may be identical or different and represent an amino group or an azo group bound to a further aromatic radical.
  • azine compounds to be used in the process of the invention are known; the azine compounds can be prepared by known methods.
  • the said catalysts may be added to the dyestuff bleaching bath in a solution containing one gram of catalyst per liter of water in an amount of 1 to 50 cc. per liter of bleaching bath.
  • a bath that contains for example, 30 parts of potassium bromide, 30 parts of thiourea and 35 parts of 30% hydrochloric acid in 1000 parts of water, a blue azo dyestutf of the formula HOsS- for example, is bleached very slowly, and even after 30 minutes the'layer is not quite colorless at the places where the silver was at maximum density, but if a solution of 1 g./ liter of the catalyst of the formula (8) SOaH 803K 10 H0% $011 is added to such a bleaching bath in an amout of 1 to 4 cc.
  • the places where the silver was at maximum density are completely colorless after 3 to 6 minutes.
  • the catalysts herein described can be used singly, in pairs or in mixtures comprising more than two such catalysts and, if desired or required, they can also be used in admixture with other catalysts, for example, pyridine, aminohydroxyphenazine or quinoxaline. It is also possible to allow the catalysts to act on the material for some minutes in a separate bath prior to the treatment in the bleaching bath.
  • the material can be treated in the subsequent silver dyestutf bleaching bath without a catalyst of the invention or in the presence of other catalysts.
  • the catalysts can be added to the emulsion prior to casting, thus incorporating them in the layer along with the silver halide and the dyestuff.
  • Compounds also suitable for use as catalysts in the process of the present invention are those of the formulae ⁇ N Hots N-N N Boss- BIO: H0 7' IR r O CHIP-CH! /n-l jm H6 HOaS- HaN- (18) SOaH 0.5 mol of 1-aminobenzene-4-sulfonic acid is diazotized in the usual manner, and the diazo suspension is mixed with 0.5 mol of Z-phenylamino-S-hydroxynaphthalene-7- sulfonic acid and 500 cc. of water, while cooling with ice. The pH value of the coupling mixture is then adjusted to 2.5 to 3.0 by the addition of sodium acetate.
  • the mixture is stirred for 3 hours at to 5 C. and then for 16 hours at room temperature. Concentrated hydrochloric acid is then added until the pH value is 0.8 to 1.0 and the mixture is heated for 1 hour at 80 to 90 C. The temperature is allowed to drop to about 50 C., whereupon the mixture is filtered and the filter radical is Washed with 5% hydrochloric acid.
  • the product so obtained of the Formula 16 is then pasted in /2 liter of water, and the pH of the mixture adjusted to 7 by the addition of sodium hydroxide solution and sodium acetate. The mixture is quickly suction-filtered, and the filter radical recrystallized from water. The yield is about 75% of the theoretical yield.
  • the product is a green-yellow powder when dry.
  • 0.1 mol of 4 hydroxybenzo[aJ-phenazine 2 sulfonic acid of the Formula 16 are introduced into 500 cc. of water.
  • a diazo suspension prepared in the usual manner from 0.1 mol of 1-aminobenzene-4-sulf0nic acid is added thereto.
  • the pH value is adjusted to 9.8 to 10.0 by the subsequent addition of sodium carbonate, and the coupling mixture is stirred for 16 hours at room temperature.
  • the dyestutf is then precipitated with sodium acetate and filtered. It is then dissolved in 1200 cc. of water, the solution is adjusted to pH 7.5 with a small amount of acetic acid, and the dyestuff is again preciptated with sodium acetate.
  • the dyestufi is again isolated by filtration, washed free from acetate with ethyl alcohol and dried in vacuo at C. The yield is about of the theoretical yield.
  • the azine compound of the Formula 18 so obtained is a dark brown powder.
  • the aminoazine compound of the Formula 17 can be obtained from this azine compound containing an azo group by reduction with sodium hydrosulfite.
  • Example 1 The following layers are applied successively to a cellulose acetate film provided with an adhesive layer:
  • the time of treatment in the dyestufit bleaching bath should be just suflicient to bring about complete bleach- 7 ing of the dyestufis in all layers at the places most highly E l 3 exposed, the said time of treatment having been determined by tests. It is much shorter than when the opera- A colored gelatin silver bromide layer is prepared by tion is carried out without the phenazine compound in mixing 5 grams of 5% aqueous solution of a cyan dyethe dyestuff bleaching bath. stuff of the formula with 3.3 grams of' a silver bromide gelatine, casting 10 cc. of this mixture on to a glass plate measuring 13 cm. x 18 cm. and then drying it.
  • the layer so prepared is exposed under a master image and the silver image is developed in a developer that contains 6 grams of l-methylamino-4-hydroxybenzene, 6 parts of anhydrous sodium carbonate, 20 parts of sodium borate and 80 parts of crystalline sodium sulfite per liter of Water. After a short rinse, the layer is fixed for to 7 minutes and bleached in a silver dyestuff bleaching bath that contains 30 to 70 cc. of 37% hydrochloric acid, 20 grams of potassium bromide, 20 to 50 grams of thiourea and 4 cc. of an 0.1 aqueous solution of the catalyst of the Formula 8 per liter of water.
  • the dyestutf is bleached at the areas containing silver to a degree proportional to the amount of silver present. After removal of the excess silver in a bleach fixing bath, a color image is obtained the dark and light areas of which exhibit the same blue tint.
  • 2-hydroxy-3-aminophenazine of the Formula 1 as catalystor dimcthyl-quinoxaline, the tint of the areas of the image that are only partly bleached is changed to red-violet and the image is therefore unusable.
  • the silver halide layer described herein can form a part of three-color material.
  • Example 4 A solution of 5 mg. of the dyestufi of the Formula 29, 20 mg. of 2-phenylamino-4:6-dichloro-l:3:5-triazine-4- sulfonic acid and 0.1 mg. of the catalyst of the Formula 12 in 3.5 cc. of water is mixed with 3.3 cc. of 6% gelati-ne solution and 3.3 cc. of silver bromide gelatine. The mixture is cast on a glass plate measuring 13 cm. x 18 cm. provided with an adhesive layer. When the layer is dry it is exposed in the usual manner behind stepped wedges and the silver image developed and fixed in the usual manner.
  • a process for the production of a color photographic image by the silver dyestuff bleaching process which comprises carrying out the bleaching operation in the presence of an azine catalyst that contains at least one acidic group imparting solubility in water and that corresponds to the formula I R: N in which R represents a naphthalene radical condensed with the azine ring in the manner indicated by the valence lines which naphthalene radical contains at least one substituent selected from the groups consisting of a hydroxyl group, an amino group and an azo group, said substituent being attached to the six-membered ring not directly bound to the azine ring, and R represents a member selected from the group consisting of a benzene radical and a naphthalene radical condensed with the azine ring in the manner indicated by the valence lines.
  • a process for the production of a color photographic image by the silver dyestuff bleaching process which comprises carrying out the bleaching operation in the presence of an azine catalyst that contains at least one sulfonic acid group and that corresponds to the formula in which R represents a member selected from the group consisting of a benzene radical and a naphthalene radical condensed with the azine ring in the manner indicated by the valence lines, and R represents a member selected from the group consisting of an amino group and an azo group bound to a further aromatic radical.
  • a process for the production of a color photographic image by the silver dyestuif bleaching process which comprises carrying out the bleaching operation in the presence of an azine catalyst of the formula SOaH in which R represents a benzene radical condensed with the azine ring in the manner indicated by the valence lines, and R represents an amino group.
  • a process for the production of a color photographic image by the silver dyestufi bleaching process which comprises carrying out the bleaching operation in the presence of an azine catalyst of the formula SOsH in which R represents a naphthaline radical condensed with the azine ring in the manner indicated by the valence lines, and R represents an amino group.
  • a process for the production of a color photographic image by the silver dyestuff bleaching comprises carrying out the bleaching operation in the presence of an azine catalyst of the formula SOaH 10 N l H0 in which R represents a benzene radical condensed with the azine ring in the manner mdlcated by the va ence 10'
  • a process for the production of a color photographic HO image by the silver dyestufi bleaching process which comprises carrying out the bleaching operation in the pres- 11.
  • a process for the production of a color photo which comprises carrying out the bleaching operation in graphic image by the silver dyestuff bleaching process, the presence of the azine catalyst of the formula which comprises carrying out the bleaching operation in the presence of the azine catalyst of the formula N N l N SIOaH nos s Hots Hols at; Ht)
  • a process for the production of a color photographic image by the silver dyestuff bleaching process, graphic image by the silver dyestulf bleaching process, which comprises carrying out the bleaching operation in which comprises carrying out the bleaching operation in ,the presence of the azine catalyst of the formula V 7 the presence of the azine catalyst of the formula N 5 i N l TH HOaS- NA "N N 10 L H0 13.
  • a process for the production of a color photographic image by the silver dyestufr' bleaching process, 15 which comprises carrying out the bleaching operation in the presence of the azine catalyst of the formula HaO-O 0-4311;
  • a process for the production of a color photographic image by the silver dyestufi bleaching process which comprises carrying out the bleaching operation in the presence of the azine catalyst of the formula HO S0311 H038 OH N N y 1 N N HOaS- H SOsH H018 H0 3,318,700 1.
  • a process for the production of a color photo which comprises carrying out the bleaching operation in graphic image by the silver dyestulf bleaching process, the presence of the azine catalyst of the formula 110- $0311 HOaS- 0H OH N N N i N SOaH HN([1 i l-NH HOaS- 5H HOaS SIOQH H(

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
US306690A 1962-09-14 1963-09-05 Application of dyestuff bleaching catalysts in the silver dyestuff bleaching process Expired - Lifetime US3318700A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1092862A CH424475A (de) 1962-09-14 1962-09-14 Verwendung von Azinverbindungen als Farbbleichkatalysatoren für das Silberfarbbleichverfahren

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US (1) US3318700A (en, 2012)
AT (1) AT243081B (en, 2012)
BE (1) BE637277A (en, 2012)
CH (1) CH424475A (en, 2012)
DE (1) DE1167652B (en, 2012)
ES (1) ES291630A1 (en, 2012)
GB (1) GB1026779A (en, 2012)
NL (2) NL140346B (en, 2012)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3443947A (en) * 1964-11-20 1969-05-13 Ciba Ltd Colour bleaching catalysts for the silver dyestuff bleaching process
US3533799A (en) * 1965-10-15 1970-10-13 Agfa Gevaert Ag Color photographic material for the silver dye bleach process

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH433980A (de) * 1964-07-07 1967-04-15 Ciba Geigy Verwendung von Acylaminoverbindungen als Farbbleichkatalysatoren für das Silberfarbbleichverfahren
US3414411A (en) * 1965-12-10 1968-12-03 Eastman Kodak Co Dye bleach process
DE1270949B (de) * 1966-09-21 1968-06-20 Agfa Gevaert Ag Waessriges Farbbleichbad fuer das Silberfarbbleichverfahren

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2410025A (en) * 1936-12-14 1946-10-29 Chromogen Inc Production of colored photographic pictures
US2627461A (en) * 1950-07-22 1953-02-03 Gen Aniline & Film Corp Indophenazines as catalysts in dye bleach baths for color photography

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2410025A (en) * 1936-12-14 1946-10-29 Chromogen Inc Production of colored photographic pictures
US2627461A (en) * 1950-07-22 1953-02-03 Gen Aniline & Film Corp Indophenazines as catalysts in dye bleach baths for color photography

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3443947A (en) * 1964-11-20 1969-05-13 Ciba Ltd Colour bleaching catalysts for the silver dyestuff bleaching process
US3533799A (en) * 1965-10-15 1970-10-13 Agfa Gevaert Ag Color photographic material for the silver dye bleach process

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Publication number Publication date
AT243081B (de) 1965-10-25
GB1026779A (en) 1966-04-20
CH424475A (de) 1966-11-15
DE1167652B (de) 1964-04-09
ES291630A1 (es) 1964-02-16
NL140346B (nl) 1973-11-15
BE637277A (en, 2012)
NL297895A (en, 2012)

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