US3130052A - Method of manufacturing, by photographic agency, internal and/or external images on and/or in macromolecular supports with mercury and silver salts germ introduction baths - Google Patents

Method of manufacturing, by photographic agency, internal and/or external images on and/or in macromolecular supports with mercury and silver salts germ introduction baths Download PDF

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US3130052A
US3130052A US41920A US4192060A US3130052A US 3130052 A US3130052 A US 3130052A US 41920 A US41920 A US 41920A US 4192060 A US4192060 A US 4192060A US 3130052 A US3130052 A US 3130052A
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mercurous
mol
germ
litre
sensitivity
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Dippel Cornelis Johannes
Jonker Hendrik
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US Philips Corp
North American Philips Co Inc
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/185—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method by making a catalytic pattern by photo-imaging
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/62—Metal compounds reducible to metal
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
    • H05K3/106—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam by photographic methods
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/137—Cobalt complex containing

Definitions

  • a mercurous salt may be caused to react either in the layer containing the lightsensitive compound prior to exposure or a solution of mercurous salt may be caused to react with the exposed layer.
  • the preservability of the light-sensitive layer is, as a rule, very restricted; moreover, the results are, in general, insufiiciently reproducible.
  • the second variant the so-called germ introduction method would be preferable.
  • the mechanism of the present image formation is based of the fact that the aforesaid light-reaction product is capable of producing, in the presence of moisture, a so-called disproportioning of mercurous salts. This disproportioning is performed in accordance with the reaction equation:
  • the mercury atoms thus set free unite to form mercury drops, which together, form the mercury germ image. Otherwise it is immaterial for the result of the image formation whether the mercury is obtained only by disproportioning or partly by reduction.
  • a frequently used physical developer is, for example, a solution of silver nitrate in water, to which is added hydroquinone, metol or p-phenylene-diamine.
  • Such a developer contains furthermore, as a rule, in order to improve its preservab'dity or to control the speed of development, further substances, for example, organic acids, buffer mixtures or substances reacting with the noble metal compound whilst forming complex compounds.
  • the mercury drops forming the mercury germ image operate as germs, on which free noble metal formed from the noble-metal salt by reduction is deposited.
  • this involves a material intensification of the image, since the quantity of noble metal deposited on the mercury germs is, as a rule, many times larger than the quantity of mercury of the mercury germs together.
  • the latter images may be distinguished by so-called grown external metal images, which are obtained by development with the aid of a non-stabilized physical developer, of an at least partly external metal germ image, which is produced in itself by employing special exposure energies, i.e., the so-called mirror exposures, and the so-called outgrown external noble-metal images, obtained by developing for such a long time the internal part of the metal germ image obtained by using a so-called outgrowth exposure, with the aid of a stabilized, if necessary activated, purely physical developer, which may be refreshed or regenerated, that this metal germ image grows out into an external noble-metal layer.
  • the lastmentioned class of external images exhibits, as a rule, a materially improved adhesion to the support as compared with the first-mentioned images.
  • mirror exposure is to be understood to mean that exposure energy per surface unit of the lightsensitive layer which, with the chosen concentration of metal ions in the germ introduction bath, provides an at least partly external metal germ image, which after intensification by means of the selected, non stabilized, purely physical developer, under chosen conditions of temperature and developing time, yields an external noble-metal layer which, subsequent to washing in water and to heating at 150 C. for one hour, has an electric resistance not exceeding ohms per square surface.
  • outgrowth exposure is to be understood to mean herein that exposure energy per surface unit of the light-sensitive layer which, with the chosen concentration of metal ions in the germ introduction bath, provides a metal germ image which, subsequent to intensification by means of a stabilized, purely physical developer obtained by dissolving, in distilled water,
  • photographic noblemetal layers use will therefore be made, preferably, of exposure energies which are weaker than a mirror exposure.
  • the growth of a metal germ image which may still be partly external but which is insufiicient to form a grown external image with reproducible properties, may then be prevented by using stabilizers in the physical developer with the aid of which the limit of the mirror exposure has been assessed. In this case the developing time must not be prolonged to an extent such that the development image grows out of the support.
  • the light-sensitivity of the described variants of the mercurous system can be increased by enhancing the number of developable mercury germs. Such an increase may be achieved by providing in the layer, prior to the pure physical development, a compound which contains an anion which is capable of reducing the concentration of the free mercurous ions, and which does not form a permanent precipitate with the mercurous ions under the prevailing conditions.
  • Anions of the said kind are, for example, the lactate ion, the citrate ion and the acetate ron.
  • the invention has for its object to enhance the lightsensitivity of the photographic material processed by the germ introduction method of the mercurous system by a further increase in the number of developable germs, whilst it is at the same time intended to act upon the characteristic curve of this material. It is based on the known method in which a support containing at least one light-sensitive compound of which the light-reaction product is capable of producing metallic mercury from mercurous ions in the presence of moisture, is exposed and then treated with a Water-containing solution of one or .more mercurous salts (which solution will be termed herein the germ introduction bath), followed by stabilized or non-stabilized purely physical development of the mercury germ image thus formed.
  • the total concentration of the mercurous salts in the germ introduction bath is chosen to be not lower than 1 mol/ litre and preferably between 0.5 and 10 mmol/litre.
  • the concentration of the silver salts in the germ introduction bath As far as the concentration of the silver salts in the germ introduction bath is concerned, the following should be noted. It has been found that, when a given total concentration of the silver salts in the germ introduction bath, which concentration will be termed herein the activating concentration, is exceeded, a gain in sensitivity and/ or an increase in the steepness of the characteristic curve are introduced. At a further increase in the concentnation of the silver salt the sensitivity and the steepness increase further until a maximum is attained, after which these effects diminish, often even to an extent such that they vanish completely and even become negative. The maximum of the sensitivity and of the steepness do not appear to occur always with the same silver salt concentration. The total concentration of the silver salts at which the two effects are lost will be termed herein the de-activating concentration.
  • both the activating concentration and the de-activating concentration vary in accordance with the concentration of the mercurous salt, the nature of the support layer, the acidity of the germ introduction bath, the kind of lightsensitive compound, the manner of purely physical development, the absence or presence of an anti-regression agent and, in the latter case, the nature thereof.
  • the increase in sensitivity and the gradation control may be utilized to advantage.
  • I.B.-uses are aimed at, to which end the method according to the invention is to be employed to control 7 ments of the steepness of the density characteristic curve.
  • this field will be determined with the aid of sensitivity measurements, i.e., the quantity of exposure energy per surface unit of the light-sensitive layer (if desired in a relative measure) is determined, which is required to produce, in a test strip of the layer, a density D of 0.10 in excess of the basic density of the strip (i.e., the density of the non-exposed portions of the strip).
  • U.B. uses the determination of the sensitivity effect is linked to the criteria of the minimum mirror exposure (A.U.B. uses) or the minimum outgrowth exposure (U.U.B. uses), i.e., the quantities of exposure energy just producing external noble-metal layers in accordance with the definition referred to above, which images, after washing and heating at 150 C. for one hour, exhibit an electric resistance not exceeding 100 ohms per square surface or, without this thermal aftertreatment, a resistance not exceeding ohms per square surface.
  • A.U.B. uses the minimum mirror exposure
  • U.U.B. uses the minimum outgrowth exposure
  • a series of test strips is manufactured on the basis of the light-sensitive material concerned with, with the aid of a series of sensitometer exposures, for example with the aid of a densitometric wedge.
  • the standard test may be repeated for a more accurate determination of the limits of activity with the aid of a sequence of germ introduction baths, of which the concentration is varied by a lower factor.
  • the results of this standard test may be illustrated by plotting graphically on the ordinate the negative logarithms of the quantities of exposure energy corresponding to the LB. or the U.B., sensitivity concerned and on the abscissa the logarithms of the silver salt concentrations, after which two further horizontal straight lines are drawn on the level of the negative logarithms of the exposure energies corresponding to the LB. or the UB. sensitivity concerned of the lank test strip.
  • the same result may be obtained in a simpler man ner by counting for each test strip, in one case, the steps which exhibit a visually distinguishable difference in density with respect to, for example, the basic density of the strip, or, in the other case, the steps which exhibit, after being subjected or not to a thermal after-treatment in the manner described, an electric resistance not exceeding 100 or 18 ohms per square surface respectively, whilst these two numbers of steps are plotted on the ordinate, the logarithms of the silver salt concentrations being plotted on the abscissa.
  • the coiresponding numbers of steps of the blank test strip are indicated in the figure in the form of horizontal straight lines. Also in this way the limitation of the regions of the active silver salt concentrations are found.
  • a method in which test strips of the type (1) are obtained is extremely suitable for the manufacture of internal photographic images and the standard test described indicates the compositions of the germ introduction baths with the increased sensitivities.
  • a method yielding the results in accordance with (3) is particularly suitable for the manufacture of external electrically conductive images.
  • the standard test indicates the compositions of germ introduction baths with an increased U.B. sensitivity. The latter applies, in particular, to a U.U.B. If the conditions are favourable to the formation of an external image, strips according to (2) are obtained, however, for which case both for the internal image and for the external image the silver salt curves can be drawn, so that it is easy to read the advantageous compositions of the germ intro duction baths.
  • a sequence or sensitometer exposures is employed to determine, by varying the concentration of the mercurous salt in the germ introduction bath the concentration w ch provides the maximum light-sensitivity. Then, on the basis of the most active germ introduction bath found, with the aid of a new sequence of sensitometer exposures, by varying the concentration of the silver salt in this special germ introduction bath, the most active silver concentration is determined. Both below and above this most active silver salt concentration there is a region of useful concentrations, confined by an activating concentration and a deactivating concentration, in which region the use of the method according to the invention produces a gain in sensitivity.
  • the germ introduction bath and the stabilized or non-stabilized purely physical developer are combined into a single bath (so-called disproportioning developer), so that the number of processes to manufacture the final internal and/or external noble-metal image is reduced by one and the method is simplified.
  • the disproportioning developer concerned contains, consequently, on the one hand, one or more mercurous salts ais 0,05
  • the total concentration of the mercurous salts in the disproportioning developer is not more than mmol/ litre, whilst the total concentration of the silver salts in the said bath must then be at least twice the total concentration of the mercurous salts therein.
  • mercurous salt concentrations 0.5 to 10 'mmol/h'tre.
  • the measure according to the invention if combined with the aforesaid, known measure, in which prior to the purely physical development, a compound is provided in the layer with an anion capable of reducing the concentration of free mercurous ions and not forming a subsisting precipitate with the mercurous ions under the prevailing conditions, can produce a combination effect.
  • the said compound may be provided in the layer prior to exposure, but it may be added, as an alternative, to the germ introduction bath, in which case it is advisable to choose the total concentration of the mercurous salts in this bath to be not lower than 0.1 mmol/litre.
  • the most active silver salt concentration is determined.
  • the germ introduction bath in which the total concentration of the mercurous salts is at least 0.1 mmol/ litre, one or more organic hydroxy acids, chosen from the group of citric acid, tartaric acid, glycolic acid, malic acid and glycerol acid. Such a quantity thereof is to be added that the deposit initially formed with the mercurous salt is again dissolved. External noble-metal images obtained with the aid of such germ introduction baths have a beautiful gloss and are excellently reproducible.
  • the germ introduction baths contain always a quantity of strong acid which serves to dissolve completely the whole quantity of mercurous salt.
  • mercurous salts tend to hydrolyze. It has been found that the gain in sensitivity attainable at a maximum in accordance with the invention decreases with an increasing concentration of the strong acid in the germ introduction bath. On the contrary, however, the density homo geneity of the developed images deteriorates below a given acid concentration. In View of these two conditions, it is advisable to adjust the concentration of the free, strong acid in the germ introduction bath to a normality lying between 5X 10- and 2.l0
  • the use of the method according to the invention yields, apart from a gain in sensitivity which is important for all uses, a possibility of gradation control; The last-mentioned effect is particularly important for I.B.-uses.
  • FIG. 2 illustrates this.
  • I.B.-uses the density homogeneity and the depth of the density of the images obtained are, moreover, often materially improved.
  • themethod according to the invention yields not only an increase in sensitivity but also an improvement in the adhesion of the external noble-metal images to the support, which is frequently desired with certain A.U.B. uses.
  • noble-metal layers is to be understood to mean herein not only layers having an uninterrupted surface but also those having patterns of which the portions are coherent or not coherent, for example, station-name dials for radio apparatus, ornamental objects, printed wirings, printed circuits, flat electric component parts, and so forth.
  • station-name dials for radio apparatus ornamental objects, printed wirings, printed circuits, flat electric component parts, and so forth.
  • such a layer will be or must be subjected, subsequent to its formation, in order to modify the physical or chemical properties of the layer or of its surface, to .a physical and/or chemical after-treatment,
  • the external noble-metal layers obtained by purely physical development often have electric resistance values exceeding many times (to 10 times) the value calculated from the resistivity of the metal concerned. By a thermal or chemical after-treatment or by mechanical polishing this high resistance value may be materially reduced, which is important for various electrical uses.
  • the thermal after-treatment is carried out by heating the noble-metal layer to a temperature of at least C.
  • the chemical aftentreatment to reduce the electric resistance of silver layers consists in that these layers are brought into contact with an aqueous solution contining one or more compounds separating off, therein, a potential-anion determining with respect to the silver metal, for example Cir, Br, I, CNS: CN", S 80 S 0 or OH: or a hydrogen ion.
  • a mechanical polishing treatment can provide the said reduction of the resistance.
  • an electrochemical after-treatment necessary followed by a superficial chemical conversion or coloration.
  • electrochemical after-treatment necessary followed by a superficial chemical conversion or coloration.
  • electrolytical polishing electrolytical deposition of metals
  • electrolytical coloration of the deposited metal or electrophoretical coating with a protective or insulating, or photoand/or semiconductive surface layer.
  • electrolytical polishing electrolytical deposition of metals
  • electrolytical coloration of the deposited metal or electrophoretical coating with a protective or insulating, or photoand/or semiconductive surface layer.
  • a combination of different electro-chemical and/ or chemical after-treatments may be employed.
  • a choice may be made from a great number of mechanical after-treatments, which may be combined with the aforesaid aftertreatments.
  • a few important suitable after-treatments of the said kind are, inter alia polishing of the surface, application of a lacquer or varnish layer to the layer surface, embedding of the layer together with the support in an insulating envelope of thermo-nardening or thermoplastic material, transfer of the layer, if desired together with the support, to a further support of high electrical qualities, also of thermo-hardening or thermo-plastic material, application of electrical connections by soldering (for example, dip soldering).
  • Suitable materials to be used as supports in carrying out the present method for the manufacture of internal or external photographic images are, in general, all filmforming high-polymer products which, if not yet so, are rendered superficially accessible to the various baths, for example, regenerated cellulose, wholly or partly saponified cellulose esters, paper, cotton, polyvinyl alcohol and the like.
  • Examples 1 A surface of about 7 of a cellulose acetate foil with a thickness of 120 and an acetyl content of 38.2% was hydrophilized by saponification. This layer was sensitized b-y impregnation, for two minutes, in an aqueous solution containing (A) 1.5 l mol of o-methoxybenzene-diazosulphonic acid sodium per litre.
  • Such a saponified foil was sensitized in a similar manner with the aid of a solution (B) containing, in addition: 10- mol of cadmium lactate per litre.
  • the LB. sensitivity was graphically determined for each strip.
  • the results of these measurements are illustrated in the form of the four sensitivity curves in FIG. 1 (LB. sensitivity plotted against the silver salt concentration on a logarithmic scale).
  • the group of silver-salt curves may provide graphically, in a simple manner shown in the figure, a survey of the total of sensitivity variations of the material concerned as a function of the mercurous saltand of the silver-salt concentrations in the germ introduction bath. This results in three point-assemblies, which may be connected per assembly by a flowing curve.
  • the vertical distance between the curves b and a provides directly the optimum LB. sensitivity increase which can be attained for the material A by the addition of silver nitrate to the germ introduction bath. This distance varies in this example with the concentration of the mercurous nitrate in the bath. If the sensitivity with the corresponding germ introduction bath with at silver nitrate (curve a is taken as a reference point (i.e., if this sensitivity is assumed to be equal to l), the relative LB. sensitivity with the bath of optimum activity, containing a quantity of mercurous nitrate corresponding to a concentration of:
  • FIG. 1 shows furthermore the curve 12 for the material B From the test material it may be concluded that the anti-regression effect of the cadmium lactate in the layer and of the silver nitrate in the germ introduction bath are additive, so that in the method according to the invention the presence of the anti-regression agent in the light-sensitive layer can be utilized to full advantage.
  • the I.B.-sensitivity increase attainable owing to the presence of the cadmium lactate in the light-sensitive layer amounts, in the present example, if the sensitivity values of the curve b are taken as reference points (:1), for a germ introduction bath containing a quantity of mercurous nitrate corresponding to a concentration of 5 l0- mol/litre, to a factor of 13.8, for a bath with a concentration of 5 X 10- mol/ litre, to a factor of 4.7 and for a bath with a concentration of 5 X 10* mol/litre, to a factor of 1.7.
  • colouring physical development may be carried out, for example, in blue-green with the aid of a developer containing 0.08% of dimethyl-amino-4-phenylamine-nitrate, 5% of tartaric acid and 0.4% of silver nitrate in water, to which is added, per 25 cm. 2 cm. of a 10% solution of a-naphthol in ethanol.
  • the silver image may be removed by means of a liquid containing potassium ferric cyanide and sodium thiosulphate.
  • Example II A cellulose tri-acetate foil saponified to a depth of 6a was sensitized by means of the solution B of Example I. In the manner described in Example I the silver salt curve was determined for strips of'this material, in this AgNOa, mols/litre relative A.U.B.- sensitivity 1 1X10- 2 3X10 1. 5 5X10- 0. 7
  • the strips were developed in a stabilized, physical developer obtained by dissolving Metol (0.025 mol/litre) Citric acid (0.1 mol/ litre) 'Silver nitrate (0.01 mol/litre) Lissapol N (0.02% by weight), and Armac 12 D. (0.02% by weight),
  • Lissapol N is a condensation product AgNO moIs/litre Developing time in min.
  • a cellulose acetobutyrate foil was sapom'fied superficially to a depth of about 6 impregnated for two minutes in a. solution containing, per litre of water, 2X mol of p-methoxy-benzene-diazosulphonic acid sodium and 10 mol of cadmium lactate, after which it is wiped OE and dried in air in darkness.
  • the exposed strips were dipped for 2 sec. in germ introduction baths containing 5 10- mol of mercurous nitrate, 4X10" mol of nitric acid per litre and a varying concentration of silver nitrate, as is indicated in the joined table.
  • germ introduction baths containing 5 10- mol of mercurous nitrate, 4X10" mol of nitric acid per litre and a varying concentration of silver nitrate, as is indicated in the joined table.
  • After washing in distilled water purely physical development was carried out with the developer of Example I, at a temperature of about C. for 10 min. for the sensitivity tests and for 7 min. for the gradation tests. The results of the tests are indicated in the following table:
  • 1 E is the exposure energy in ergs/cmfl of film surface.
  • 2 Gamma is the slope of the straight portion of the density curve.
  • Example IX The superficially saponified foil of Example IX was impregnated for 2 min. in a 0.1 molar solution of o-nitromandelic acid nitril in 40% of alcohol and then wiped off and dried. Strips of this material were, subsequent to exposure with the aid of a sensitometer, treated with germ introduction baths having compositions as indicated in the following table. Physical development: as in Example I.
  • the germ introduction baths contained invariably per litre 5X l0 mol of mercurous nitrate and 5X l0 mol of nitric acid. The development was carried out as stated above in this example.
  • MATERIAL (A) XII An acetyl-cellulose foil having an acetyl content of 42% was rendered superficially hydrophilic by saponification and then sensitized by impregnation in the solution B of Example I.
  • The. LB. sensitivities were measured at a number of exposed strips of this material, whilst using germ introduction baths containing or not containing silver nitrate, which baths had the properties of purely physical devel- 7 opers by adding metol and citric acid.
  • the compositions of these disproportioning developers were as follows:
  • Tartaric acid 3.3x l0- mol/ litre
  • Mercurous nitrate 5 10 mol/ litre
  • Silver nitrate from 10* to 10- mol/litre.
  • the bath may obtain, moreover, the properties of a colouring physical developer.
  • Acetic acid 2.5 mol/litre
  • Mercurous nitrate 5 X 10- mol/ litre
  • Silver nitrate from 10 to 10 mol/litre solution.
  • Citric acid 101 mol/ litre
  • Mercurous nitrate 10- mol/ litre
  • Silver nitrate 10 mol/ litre.
  • the latent metal images were formed, after the exposure of strips of these materials, with the aid of a sensitometer, by using aqueous germ introduction baths containing 5 10- mol of mercurous nitrate and 10- mol of nitric acid per litre, to which quantities of silver nitrate were added, corresponding to the maxima of the silver salt curves; for comparison the bath without silver nitrate was included in the experiment.
  • aqueous germ introduction baths containing 5 10- mol of mercurous nitrate and 10- mol of nitric acid per litre, to which quantities of silver nitrate were added, corresponding to the maxima of the silver salt curves; for comparison the bath without silver nitrate was included in the experiment.
  • the germ images were developed in the purely physical developer of Example 1. The results of the determination of the sensitivity are indicated in the following table.
  • Example XV The superficially saponified cellulose triacetate foil referred to in Example XIV was sensitized by impregnation in an aqueous solution containing 7 10- mol of p-methoxy-benzene-diazosulphonic acid-sodium and 7 lO mol of cadmium lactate per litre.
  • Germ introduction baths with Na-lactate, mols/litre As sensitivity reference point (sensitivity 1) is chosen the sensitivity of a strip treated with the corresponding germ introduction bath not containing either silver nitrate or sodium lactate.
  • Example 11 Sensitized foil of Example 11 was exposed, after drying, behind a line negative with a quantity of energy equal to the minimum mirror exposure. Then it was treated with an aqueous solution containing 5X 10 mol of mercurous nitrate, 10- mol of silver nitrate and 10 mol of citric acid per litre and then developed as described in Example I. The resistance of the resultant grown external image was 2.7 l0 ohms per square sufrace, which value dropped to 3.2 ohms per square surface after a thermal after-treatment for one hour at 150 C.
  • the resistances (in ohms per square surface) of the resultant grown, external metal images and of those attained subsequently by heating for one hour at 150 C. in a drying cabinet are indicated in the following table.
  • the exposure energies are indicated with respect to the minimum mirror exposure as a unit: the relative mirror exposure energy.
  • a film strip was sensitized as described in Example II and then exposed behind a line negative to a high-pressure mercury-vapour lamp with an exposure energy of about 10 times the minimum mirror exposure. Subsequently to this exposure, the foil was treated with an aqueous solution of 5 10 molar mercurous nitrate, 5 10 molar silver nitrate and 5x10 molar nitric acidI and then developed purely physically as in Example The resistance of the metal image thus obtained amounted to 4 10 ohms per square surface.
  • Example II A foil sensitized as described in Example II was exposed in a vacuum pressure frame behind a cross grid negative with the aid of a high-pressure mercury-vapour lamp with an exposure energy of about 5 times the minimum mirror exposure. Subsequently to the exposure the foil was treated with a solution of 5X 10 mol of mercurous nitrate, 2X10 mol of silver nitrate, 5X10" mol of rliitric acid and then developed as described in Examp e Then the image was intensified electrolytically in an acidic copper-deposition bath containing 20% by weight of copper sulphate (SH O) and 6% by weight of sulphuric acid for 10 to 15 min. with a current density of 200 to 500 ma./dm. of grid surface. The width of the E9 grid lines thus obtainable amounted to l0/,u, whereas the distance between the lines was '25-30/,LL.
  • SH O copper sulphate
  • a method of producing noble-metal images on nonmetallic supports whiohmethod comprises sensitizing a non-metallic support by treating said support with a lightsensitive compound selected from the group consisting of hydroxy-benzene diazonium compounds, hydroXy-naphthalene diazonium compounds, aromatic diazo sulfonates, sulfito-diethylene-diamine cobaltic chloride and o-nitromandelic acid nitrile, exposing said sensitized support to light, treating said exposed support with an aqueous nu cleus introduction solution containing a mercurous salt in a concentration of more than 1 ,umol/liter and a silver salt in a concentration of at least twice that of the mercurous salt to thereby produce a latent metallic image on said support and then developing said latent metallic image by applying to said latent metallic image an aqueous solution of a reducible compound of a metal selected from the group consisting of gold, silver, platinum and mercury and an organic reducing agent capable
  • sensitized sup port contains at least one anti-regression agent.
  • nucleus intro duction solution and the physical developer are a single solution and contain mercurous salts in the concentration of 0.1 to mmol/litre, silver ions in a concentration at least twice that of the mercurous ions, a reducing agent for said silver ions, and an organic buiIer acid.
  • the intensity of exposure is suflicient at least so that upon completion of the physicaldevelopment step the resultant noble metal image has a resistance not exceeding 10 ohms per square surface.
  • I e I 6.
  • the aqueous nucleus introduction solution contains dissolved mercurous salts in the concentration of at least 0.1 mol per litre and an organic hydroxy acid selected fiom the group consisting of citric acid, tartaric acid, glycolic acid, malic acid and glyceric acid, said hydroxy acid being employed in a quantity suflicient to dissolve any precipitate initially formed.

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  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Laminated Bodies (AREA)
US41920A 1959-07-27 1960-07-11 Method of manufacturing, by photographic agency, internal and/or external images on and/or in macromolecular supports with mercury and silver salts germ introduction baths Expired - Lifetime US3130052A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385705A (en) * 1963-10-09 1968-05-28 Philips Corp Photo-sensitive material having a shallow layer containing a benzenediazo sulfonic acid compound or salts thereof
US4144062A (en) * 1976-07-08 1979-03-13 Eastman Kodak Company Organotellurium (II) and (IV) compounds in heat-developable photographic materials and process
US4188218A (en) * 1976-07-08 1980-02-12 Eastman Kodak Company Images formed by decomposition of Te (II) coordination complexes
US4251623A (en) * 1979-06-21 1981-02-17 Eastman Kodak Company Imaging process involving thermal decomposition of Te(II) coordination complexes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE29015E (en) * 1968-04-09 1976-10-26 Western Electric Company, Inc. Method of generating precious metal-reducing patterns
US4005229A (en) * 1975-06-23 1977-01-25 Ppg Industries, Inc. Novel method for the rapid deposition of gold films onto non-metallic substrates at ambient temperatures

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US2067690A (en) * 1930-02-05 1937-01-12 Philips Nv Method and material for obtaining photographic contrasts
US2317591A (en) * 1939-05-27 1943-04-27 Hartford Nat Bank & Trust Co Method of treating photographic material
US2575002A (en) * 1948-07-21 1951-11-13 Eastman Kodak Co Latent image intensification
US2735773A (en) * 1951-03-27 1956-02-21 Method of producing a photographic
US2750292A (en) * 1950-05-26 1956-06-12 Hartford Nat Bank & Trust Co Process for producing colored photographic contrasts

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US641709A (en) * 1899-03-10 1900-01-23 William H Legate Process of plating aluminium.
US1497265A (en) * 1922-09-16 1924-06-10 Roessler And Hasslacher Chemic Zinc-electroplated articles
US1720216A (en) * 1923-11-05 1929-07-09 Oneida Community Ltd Tarnish-resisting silver plate and process for producing same
GB339339A (en) * 1929-09-03 1930-12-03 Martin Kristensen De Trairu A process for applying a metal coating to aluminium by galvanic means
US2195231A (en) * 1937-09-22 1940-03-26 Gen Electric Art of coating metals
US2940018A (en) * 1955-04-11 1960-06-07 Gen Am Transport Printed electric circuits
US2906582A (en) * 1955-09-16 1959-09-29 Jr Franklin Page Printer bar and magnet structure

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Publication number Priority date Publication date Assignee Title
US2067690A (en) * 1930-02-05 1937-01-12 Philips Nv Method and material for obtaining photographic contrasts
US2317591A (en) * 1939-05-27 1943-04-27 Hartford Nat Bank & Trust Co Method of treating photographic material
US2575002A (en) * 1948-07-21 1951-11-13 Eastman Kodak Co Latent image intensification
US2750292A (en) * 1950-05-26 1956-06-12 Hartford Nat Bank & Trust Co Process for producing colored photographic contrasts
US2735773A (en) * 1951-03-27 1956-02-21 Method of producing a photographic

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385705A (en) * 1963-10-09 1968-05-28 Philips Corp Photo-sensitive material having a shallow layer containing a benzenediazo sulfonic acid compound or salts thereof
US4144062A (en) * 1976-07-08 1979-03-13 Eastman Kodak Company Organotellurium (II) and (IV) compounds in heat-developable photographic materials and process
US4152155A (en) * 1976-07-08 1979-05-01 Eastman Kodak Company Organotellurium (II) and (IV) compounds in heat-developable imaging materials and process with physically developable nuclei
US4188218A (en) * 1976-07-08 1980-02-12 Eastman Kodak Company Images formed by decomposition of Te (II) coordination complexes
US4251623A (en) * 1979-06-21 1981-02-17 Eastman Kodak Company Imaging process involving thermal decomposition of Te(II) coordination complexes

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BE593390A (de)
NL114011C (de)
CH435973A (de) 1967-05-15
US3192137A (en) 1965-06-29
NL241689A (de)
NL241688A (de)
DE1422933A1 (de) 1969-08-07
GB960695A (en) 1964-06-17
SE307292B (de) 1968-12-23

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