US3252798A - Stabilized physical developments - Google Patents

Stabilized physical developments Download PDF

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Publication number
US3252798A
US3252798A US405644A US40564464A US3252798A US 3252798 A US3252798 A US 3252798A US 405644 A US405644 A US 405644A US 40564464 A US40564464 A US 40564464A US 3252798 A US3252798 A US 3252798A
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United States
Prior art keywords
developer
photographic
metal
development
compounds
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
US405644A
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English (en)
Inventor
Jonker Hendrik
Dippel Cornelis Johannes
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US Philips Corp
North American Philips Co Inc
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US Philips Corp
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 to NL232192D priority Critical patent/NL232192A/xx
Priority to NL113525D priority patent/NL113525C/xx
Priority to CH7919659A priority patent/CH421704A/de
Priority to GB34155/59A priority patent/GB936609A/en
Priority to US845098A priority patent/US3157502A/en
Priority claimed from US845098A external-priority patent/US3157502A/en
Priority to DEN17365A priority patent/DE1106601B/de
Priority to FR807407A priority patent/FR1241905A/fr
Application filed by US Philips Corp filed Critical US Philips Corp
Priority to US405644A priority patent/US3252798A/en
Priority to US445760A priority patent/US3251692A/en
Application granted granted Critical
Publication of US3252798A publication Critical patent/US3252798A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/58—Processes for obtaining metallic images by vapour deposition or physical development

Definitions

  • This invention relates to developers used in the purely physical developments of photographic images and to processes employing such developers.
  • the metal in the visual photographic image is obtained by the reduction of metal ions of the water insoluble metal compound present in the latent image in the exposed light sensitive layer.
  • the developing solution employed in chemical development initially does not contain any dissolved compounds of the visual image metal. However, after the chemical developer is used for a while it may contain in solution ions of the visual image metal.
  • the intensification or development of the latent image is carried out by treating the latent image with a developing solution which contains a water soluble reducible metal compound and a photographic reducing agent.
  • photographic reducing agent is to be understood herein to mean a compound which, in the dissolved state, is capable of reducing the said metal ions or complex metal anions into free metal andthe activity of which in the physical developer under the conditions otherwise prevailing therein is accelerated by the presence of a photographic latent image so as to obtain a sufficiently selective deposition of metal on this latent image.
  • the photographic reducers which may be used in physical development are frequently similar to those which are also used in chemical development.
  • C represents a carbon atom
  • a and b each represent hydroxyl (OH) groups, amino groups or substituted amino groups (NH ,NHR,NRR' wherein R and R are alkyl or aryl radicals groups)
  • n is zero or an integer.
  • hydroquinone type a and 15 both are OH groups.
  • This class includes, in addition to hydroquinone itself, inter alia: pyrocatechol, pyrogallol, gallic acid and ascorbic acid.
  • That of the aminophenol type a is an OH- group and b is an amino group which is substituted or not substituted.
  • This class includes inter alia: oand p-aminophenol, p-methylami-nophenolsulphate (metol), p-hydroxyphenylglycine (Kodurol).
  • That of the phenylenediamine type a is an amino group or a mono-substituted amino group, b is an amino group which is substituted or non-substituted.
  • This class includes inter alia: oand p-phenylenediamine and N,N- diethyl-p-phenylenediamine.
  • precious metals In purely physical developers, only metal ions and complex metal anions of metals which are more precious than copper i.e. mercury, silver, platinum, gold or paladium may be used in combination with photographic reducing agents. These metals in the instant application will be hereinafter designated as precious metals.
  • a physical developer frequently used is, for example, a solution of silver nitrate in water to which hydroquinone, metol or p-phenylenediamine has been added.
  • some furthersubstances are usually added to such a developer, which substances serve to increase the length of life or to control the velocity of development. These are, for example, organic acids, buffer mixtures or substances which enter into reaction with the precious metal salt to form thereby complex metal anions.
  • the spontaneous formation of the metal germs and resultant formation of precipitates in the photographic material outside the latent image obtained by illumination may give rise to unwanted fogging of the ultimate photographic image.
  • the spontaneous dissociation reaction in physical developers is usually accomplished in a period of time which is not very much longer than the time required for the development of the metal latent image into a photographic visual metal image of desired optical density.
  • Another object of this invention is to provide purely physical developers which do not cause fogging.
  • ionic surfactants are based on the different behaviours of the ionic surfactants in physical development, so far as the metal precipitates spontaneously formed in the developer and the visual metal image in the photographic material are concerned. Such a selectively is, of course, essential to proper action of the development stabilizers. It is extremely surprising that the said ionic surfactants considerably delay the growth of the metal precipitates spontaneously formed, Without nevertheless affecting the growth of the photographic metal visual image in the exposed layer in a manner which is of practical importance.
  • the process of the invention may be carried out 'with all those photographic materials in which a physically developable metal latent image may be obtained directly or indirectly by the action of light.
  • These photographic materials include first of all those materials which contain a photo-sensitive compound, the light reaction product of which as such already behaves as a physically developable photographic metal latent image, for example materials containing silver halide as the photo-sensitive compound.
  • they include all those photographic materials which contain a photosensitive compound the light reaction product of which as such is not physically developable, but by a secondary reaction may be converted or react into a physically developable photographic metal latent image.
  • this secondary reaction consists in isolating metal particles from the metal compound, as is the case, for example, in the photographic process in which use is made of the photo-sensitivity of the so-called Eder solution and in which the light reaction product is mercurous chloride.
  • Numerous photo-sensitive compounds are also known, the light reaction product of which in a secondary reaction may react in the presence of moisture with mercurous-ions or 'With silver-ions while forming physically developable latent mercury images and latent silver images respectively.
  • Such photo-sensitive compounds such as aromatic diazonium compounds, diazosulphonates and diazoeyanide and inorganic complex compounds, are used in a large number of processes for the manufacture of photographic images.
  • Surfactants or surface-active substances that is to say, substances which are adsorbed at the boundary surface of two phases, are usually organic compounds having amphipathic properties.
  • Their molecule or ion contains one or more hydrophobic and one or more hydrophilic groups, which are bonded together either directly or via, for example, an ester, ether or amide bond.
  • the hydrophobic groups are, for example, aliphatic carbon chains having from 8 to 18 carbon atoms with a very small atfinity to the medium (water), in contradistinction to the hydrophilic groups which have a great affinity to water.
  • the latter are therefor sometimes referred to as solubilising or polar groups.
  • These may be, for example, sulphonate or pyridinium groups.
  • the surfactants may chemically be divided into two classes:
  • the non-ionic surfactants are thus unserviceable as development stabilizers.
  • the serviceable surfactants chiefly belong to the classes of the cation-active, anion-active and amphoteric micell-producing surfactants and to the class of the cation-active macromolecular surfactants.
  • new latent image foils-identical with the first-mentioned are introduced some more times into the two developers at given intervals, the period of which may naturally be varied as a function of the length of the developers.
  • the lengths of life of the two developers are thus approximately determined, that is to say, the times which elapse between the moment when the two developers were prepared and the moments when their developing power has disappeared almost completely. This test has at the most a semi-quantitative character, since the spontaneous formation of the precipitate in non-stabilized developers is naturally not reproducible with great accuracy.
  • the stabilization effect of the surfactants may be related to micelle formation by the hydrophilic ions of the surfactants at or about the small spontaneous precious metal germs from the precious rnetal compound thus preventing the germs from growing large enough to precipitate out of the developer solution.
  • the surfactants act to increase the existing charge of the precious metal germs or to provide a new strong charge of opposite polarity on the precious metal germ depending on whether cationor anion-active surfactants are employed and Whether the charge on the precious metal germ is the same or opposite to that of the hydrophilic ion released by the surfactant.
  • hydrophilic ions on the charge of spontaneous precious metal germs involves probably the formation of micelles which as stated before prevents the growth 'of these germs.
  • a strong positive charge of the germs will prevent the approach of positive metal ions, whereas a strong negative charge may prevent transmission of electrons to the germs and approach of negative complex metal ions. Consequently, in certain cases, a hydrophilic ion of one type of charge and, in other cases, one of the other type of charge, but frequently hydrophilic ions of both types of charge result in a stabilizing effect in a physical developer.
  • the photographic test above described always gives an answer to the question whether a given stabilizer is effective in certain kinds of developer.
  • alkylarylsulphonates derivatives of diphenyl also have admirable stabilizing properties.
  • anion-active stabilizers In physical developers containing a soluble mercury compound, the use of anion-active stabilizers usually yields optimum results. However, if these developers react alkaline it is also possible to obtain a favorable stabilizing effect with cation-active compounds and more particularly with surfactants having a basic, hydrophilic, nitrogencontaining group which forms part of a pyridine ring system.
  • a very good stabilizing effect may be obtained in physical development by means of acid reacting developers containing soluble silver compounds or mercury compounds if the reducing agent employed is a compound of the hydroquinone type and the stabilizer is an alkylaryl sulphonate derived from diphenyl.
  • a given surfactant may sometimes show a considerably smaller stabilizing effect than could be expected due to its being flocculated under the conditions which prevail in the physical developer or due to its having itself unduly low solubility.
  • a given surfactant may sometimes show a considerably smaller stabilizing effect than could be expected due to its being flocculated under the conditions which prevail in the physical developer or due to its having itself unduly low solubility.
  • the activity of the surfactant may be considerably increased by solubilization. This may be effected by means of another ionic surfactant of the same charge type or by means of a non-ionic surfactant.
  • a process is also known for obtaining metallic images in photographic material by purely physical development of photographic metal latent images, the photographic material being developed in the form of a stack of sheets in a physical developer which may be inactivated, if desired, and which contains an amount of metal salt not more than about three times as much as suffices for building up the visual images.
  • surfactants in the developers, much more beautiful results, less fogging and less contamination of the sheet due to finely-divided metal loosely deposited on them is obtained.
  • the invention In combination with known steps by which the purely physical development is used in a continuous process, the invention imparts to the developer properties rendering it even much more attractive for practical use.
  • the present invention also permits of regenerating this developing liquid at will by adding metal salt or an aqueous solution thereof which may be provided with a stabilizer.
  • the process of regenerating the developer may, of course, also be carried out continuously.
  • the known continuous process in which the photographic material is caused to absorb an amount of inactivated developer at least sufficient for building up the images and in which the development is accomplished substantially outside this supply may be considerably improved by the use of the invention, since by means of stabilizers it is possible to prepare developer solutions which are durable for a much longer time than are the corresponding non-stabilized solutions and which nevertheless exhibit a reasonable developing activity.
  • a superficially saponified film of cellulose acetate was sensitized by impregnating for 2 minutes with an aqueous solution containing 0.15 gram mole of the sodium salt of o-methoxy-benzenediazosulphonic acid and 0.1 gram mode of cadmium lactate per liter, followed by wiping off and drying.
  • a piece of this film was exposed to the light of a mercury lamp behind a sensitometer wedge and subsequently treated with an aqueous solution containing 0.005 gram mole of mercurous nitrate and 0.01 mol of nitric acid per liter, resulting in a mercury germ image being formed (the so-called germ image foil). After the formation of the germ image, the foil was rinsed in distilled water.
  • a strip of the germ image foil was physically developed for 10 minutes in a fresh solution of 0.5 g. of metol, 2 g. of citric acid and 0.2 g. of silver nitrate in g. of distilled water.
  • the silver germs spontaneously formed in this solution were found to have a negative electrophoretic charge.
  • Another strip of the same germ image foil was developed for the same period in a fresh solution which, in addition to the said constituents, also contained 0.02 g. of the cation-active surfactant Sapamine KW.
  • Example II A portion of a germ image foil obtained in the manner described in Example I was physically developed for 5 minutes in a fresh aqueous solution containing 0.036 gram mole of hydroquinone, 0.1 mol of nitric acid and 0.005 gram mole of mercurous nitrate per liter. It was determined by electrophoretic means that the mercury germs spontaneously forming in this solution had a positive charge. Another piece of the same foil was developed during the same time in a similar fresh solution containing, in addition, 0.2% by weight of the anion-active surfactant Areseklene 400 (Formula II), the dibutyl- O'phenylphenolsodium disulphonate. The spontaneous germs in this solution had a distinct negative charge.
  • Areseklene 400 Forma II
  • strips of identical germ image foils could be intensified into neutral-black images in developer solutions 50 hours old when using a time of development of 5 minutes.
  • compositions of the developers without stabilizers are provided.
  • Acid metol developer Molar p-Methylaminophenolsulphate (metol) 0.012 Nitric acid 0.1
  • N,N-dimethyl-p-phenylene diamine-nitrate 0.01 Lactic acid 0.02 Mercurous nitrate 0.001
  • photo-sensitive material manufactured by impregnating a superficially-saponified foil of cellulose acetate for 2 minutes in a solution containing 5 gms. of mercuric chloride, 5 gms. of ferric ammonium oxalate and 2.5 gms. of ammonium oxalate per gms. of distilled water.
  • anionic surfactant for reducing said mercury salt to mercury and as a development stabilizer at least one anionic surfactant, said anionic surfactant being selected from the group consist ing of alkylarylsulfonates and sulfonated alkyl alcohols,
  • a stabilized photographic physical developer comsaid stabilized developer having a life useful for physical prising an aqueous alkaline solution of a water solublemercury salt reducible to mercury, a photographic reducing agent for reducing said mercury salt to mercury and as a development stabilizer at least one cationic surfactant, said cationic surfactant being selected from the group consisting of water soluble salts of primary alkylamines wherein the alkyl moiety is hydrophobic and contains at least 8 carbon atoms, cetyl pyridinium halides, the methyl sulphate of monostearylamidoethylene-trimethyl-amine, imidazolidine derivatives containing an alkyl of 16 carbons atoms attached to a carbon atom of the heterocyclic nucleus and a lower a-lkyl attached to a nitrogen of the heterocyclic nucleus, tolyundecyla-mmonium compounds, benzyldimethyl ⁇ 2- ⁇ 2-[4-(1,1,3,3-te

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US405644A 1958-10-11 1964-10-02 Stabilized physical developments Expired - Lifetime US3252798A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
NL232192D NL232192A (cs) 1958-10-11
NL113525D NL113525C (cs) 1958-10-11
GB34155/59A GB936609A (en) 1958-10-11 1959-10-08 Improvements in or relating to stabilized photographic physical developers
US845098A US3157502A (en) 1958-10-11 1959-10-08 Stabilized physical developers containing ionogenic surfactants
CH7919659A CH421704A (de) 1958-10-11 1959-10-08 Verfahren zur Herstellung photographischer Bilder und physikalische Entwicklungslösung zur Durchführung dieses Verfahrens
DEN17365A DE1106601B (de) 1958-10-11 1959-10-09 Verfahren und Mittel zur physikalischen Entwicklung photographischer Bilder
FR807407A FR1241905A (fr) 1958-10-11 1959-10-12 Réalisation d'images photographiques par un développement physique stabilisé
US405644A US3252798A (en) 1958-10-11 1964-10-02 Stabilized physical developments
US445760A US3251692A (en) 1958-10-11 1965-04-05 Stabilized physical developments

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL232192 1958-10-11
US845098A US3157502A (en) 1958-10-11 1959-10-08 Stabilized physical developers containing ionogenic surfactants
US405644A US3252798A (en) 1958-10-11 1964-10-02 Stabilized physical developments

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US3252798A true US3252798A (en) 1966-05-24

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US405644A Expired - Lifetime US3252798A (en) 1958-10-11 1964-10-02 Stabilized physical developments

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US (1) US3252798A (cs)
CH (1) CH421704A (cs)
DE (1) DE1106601B (cs)
FR (1) FR1241905A (cs)
GB (1) GB936609A (cs)
NL (2) NL232192A (cs)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3512973A (en) * 1965-12-16 1970-05-19 Itek Corp Data storage systems
US3650748A (en) * 1968-11-22 1972-03-21 Eastman Kodak Co Photographic reproduction using novel physical developers
US3775114A (en) * 1968-07-15 1973-11-27 Itek Corp Photosensitive silver halide layers and process
DE2363654A1 (de) * 1972-12-26 1974-06-27 Itek Corp Verbesserte physikalisshe photographische entwickler, enthaltend ein wasserloesliches salz einer alkenylaminverbindung als ionisches oberflaechenaktives mittel, und verwendung dieser entwickler
US3835780A (en) * 1968-07-15 1974-09-17 Itek Corp Process of printing by driography
US3839038A (en) * 1970-06-12 1974-10-01 Itek Corp Photosensitive silver halide layers and process
US3885966A (en) * 1970-06-12 1975-05-27 Itek Corp Photosensitive silver halide layers and process
US6218093B1 (en) * 1997-08-04 2001-04-17 Eastman Kodak Company Photographic solution for developing a silver halide photographic product

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647439A (en) * 1968-10-01 1972-03-07 Eastman Kodak Co Photographic element, composition and process

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157502A (en) * 1958-10-11 1964-11-17 Philips Corp Stabilized physical developers containing ionogenic surfactants

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE552434C (de) * 1930-01-14 1932-06-13 Ig Farbenindustrie Ag Verfahren zum Vermeiden von Luftflecken in den Bildschichten photographischer Materialien beim Behandeln in Baedern aller Art

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157502A (en) * 1958-10-11 1964-11-17 Philips Corp Stabilized physical developers containing ionogenic surfactants

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3512973A (en) * 1965-12-16 1970-05-19 Itek Corp Data storage systems
US3512974A (en) * 1965-12-16 1970-05-19 Itek Corp Data storage systems
US3775114A (en) * 1968-07-15 1973-11-27 Itek Corp Photosensitive silver halide layers and process
US3835780A (en) * 1968-07-15 1974-09-17 Itek Corp Process of printing by driography
US3650748A (en) * 1968-11-22 1972-03-21 Eastman Kodak Co Photographic reproduction using novel physical developers
US3839038A (en) * 1970-06-12 1974-10-01 Itek Corp Photosensitive silver halide layers and process
US3885966A (en) * 1970-06-12 1975-05-27 Itek Corp Photosensitive silver halide layers and process
DE2363654A1 (de) * 1972-12-26 1974-06-27 Itek Corp Verbesserte physikalisshe photographische entwickler, enthaltend ein wasserloesliches salz einer alkenylaminverbindung als ionisches oberflaechenaktives mittel, und verwendung dieser entwickler
US6218093B1 (en) * 1997-08-04 2001-04-17 Eastman Kodak Company Photographic solution for developing a silver halide photographic product

Also Published As

Publication number Publication date
NL232192A (cs)
DE1106601B (de) 1961-05-10
NL113525C (cs)
FR1241905A (fr) 1960-09-23
GB936609A (en) 1963-09-11
CH421704A (de) 1966-09-30

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