US3595660A - Method of producing photographic images by physical developing utilizing diazosulfonates - Google Patents

Method of producing photographic images by physical developing utilizing diazosulfonates Download PDF

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US3595660A
US3595660A US708593A US3595660DA US3595660A US 3595660 A US3595660 A US 3595660A US 708593 A US708593 A US 708593A US 3595660D A US3595660D A US 3595660DA US 3595660 A US3595660 A US 3595660A
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acid
mol
strips
light
mercurous
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US708593A
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Leendert Klaas Hellinga V Beek
Johannes Helfeerich
Hendrik Jonker
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US Philips Corp
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US Philips Corp
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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
    • G03C1/00—Photosensitive materials
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/62—Metal compounds reducible to metal

Definitions

  • the invention relates to a method of producing photographic images With the aid of a light-sensitive material consisting of a basic layer which at the surface at least is not electrically conductive and on or in which surface where the light-sensitive layer proper is provided, contains an aromatic diazosulphonate.
  • the light-sensitive layer may be obtained by saponifying a surface layer of a cellulose-ester foil or by anodic oxidation of an aluminum foil and subsequent impregnation of the hydrophilic layer with a solution containing a diazosulphonate.
  • the layer may also contain a hydrophilic base, for example, paper or cellophane.
  • the material may furthermore consist of a basic layer of a material which cannot be impregnated with water and on which a vitreous, light-sensitive layer is provided by means of a predominantly aqueous solution containing the aromatic diazosulphonate and, if necessary, a wetting agent and/or one or more further compounds for preventing crystalline drying of the layer.
  • Such light-sensitive material is employed in a known method producing photographic pictures, in which the diazosulphonate dissociates by the effect of the light at least partly via a labile isomeric form into a light-reaction product consisting of a diazoniumdon and a sulphite ion.
  • a latent image is formed which consists of physically developable metal nuclei, the formation of which is due to the sulphite ions. By physical development this latent image is intensified into a visible metal picture.
  • a disadvantage of the known compounds suitable for the aforesaid photographic purposes for example the sodium salt of 0- or p-methoxy benzene diazosulphonic acid, resides in that the spectral absorption only very slightly extends into the visible Wave range (about 400 nm.). For this reason, when using the known physical method of development for example for magnification, for instance of microfilm pictures, it is necessary to employ special light sources (mercury vapor discharge lamps) and to use optical systems which have a good transmittance for radiation of the wave-range between 300 and 400 nm. and which permit a reasonable correction for said radiation. Such optical systems are very difiicult to obtain commercially.
  • a class of diazosulphonates suitable for the instant photographic system which have dissociation constants in the dark reaction of less than 5 X10 and molecular extinction coefiicients at 435 nm. of at least 1000.
  • n has avalue of l or 2
  • Y Y Z and Z at the most three are hydrogen and, if Y and/or Y is not hydrogen, Z and/or Z may be an alkyl-group.
  • the substituent R in X and/or in Y and Y designates an alkyl-group having more than 8 carbon atoms.
  • the use of such long chain groups diminishes the diffusion of the light-sensitive compound. When the sensitized layer is dried, substance transfer may occur, so that an unhomogeneous light-sensitive material is obtained. By introducing these long chains as substituents this risk is considerably reduced.
  • a preferred class of the benzenediazosulfonates that may be employed in our invention are those of the above formula wherein X is a moiety selected from the group consisting of diethylamino, dimethylamino, methylamino and morpholino, Y is selected from the group consisting of hydrogen and chlorine, Y is selected from the group consisting of hydrogen, chlorine, bromine, nitro and carboxy, Z is selected from the group consisting of hydrogen, chlorine and methoxy and Z is selected from the group consisting of hydrogen, fluorine, chlorine and methyl.
  • the diazosulphonate tends to regress, as is known, from the light reaction product to the diazosulfonate molecule so that the physical developability of the layer will disappear gradually and tends to become more prevalent as the period of time between the termination of the exposure and the contact with the solution containing mercurous ions increases.
  • This phenomenon is known as the regression of the result of exposure and it is combatted effectively by providing in the light-sensitive layer, in addition, a compound, called an anti-regression agent, which prevents diazosulphonate from being reformed from its lightreaction product, by binding either the sulphite ion or the diazonium ion or both so that the sulphite remains capable of reacting with the mercurous salt While forming mercury nuclei.
  • the most elfective anti-regression agents are the Water-soluble salts having cations which form with sulphite ions poorly soluble or slightly dissociated sulphites, such as Zn++, Cd++, Pb++, Cu++ and Na These cations may also be employed in the form of salts of the light-sensitive diazosulphonic acids.
  • the known anti-regression agents are also employed.
  • the effect of the sensitivity to visible radiation may in some cases be surprisingly intensified by adding an anti-regression agent. Examples of such anti-regression agents are disclosed in US. Pat. 2,838,398.
  • the light-sensitive layer contains, apart from a suitable diszosulphonate, a soluble silver salt as an anti-regression agent in conjunction with a soluble mercurous salt.
  • a soluble silver salt as an anti-regression agent in conjunction with a soluble mercurous salt.
  • partial formation of the image consisting of nuclei may take place directly during the exposure.
  • the presence of the mercurous compound is, moreover, conducive to the preservability of the light-sensitive material, also owing to the mercuric ions in the equilibrium; the use of a silver compound alone would be harmful to said preservability.
  • the presence of the silver compounds furthers the stability of the formed image consisting of nuclei.
  • diazosulphonates containing a group X consisting of morpholino or piperidino are used in the layer together with a mercurousand a silver-salt, the advantages of this method: a very slight regression of the result of exposure and an excellent resolving power may be obtained.
  • a base layer which is hydrophilic at least at the surface can be sensitized in a simple manner by impregnating it with an aqueous solution containing the diazosulphonate and, if necessary, auxiliary substances. If, however, one or more of these compounds are not adequately soluble in water, they may be introduced into the layer by indirect means by impregnating them with water and subsequently replacing the water by dissolving the diazosulphonate and auxiliary substances, if any, in a solvent which is miscible with water.
  • EXAMPLE 1 Strips of cellulose triacetate foil saponified to a depth of 2 m. were sensitized on one surface by impregnating them for 2 minutes and 24 C. in aqueous solutions containing, apart from 10 drops of 50% by weight of Lissapol N as a wetting agent, per litre:
  • the film strips were dried in a fiow of hot air and then kept for about 12 hours in a space through which there was passed air of 50% of relative humidity.
  • Lengths of the strips (21) and (b) were exposed by means of a sensitometer to light of a longer wavelength than 420 nm., obtained from a combination of a highpressure mercury-vapor discharge lamp (250 w.) and a G.G.3-filter (Jenaer Glaswerk Schoot and Gen.).
  • the exposed strips were treated immediately after exposure for 4 seconds with a solution of 0.005 mol mercurous nitrate and 0.01 mol of silver nitrate and 0.01 mol of nitric acid in distilled water in order to form an image.
  • the strips were rinsed in distilled water for 10 seconds and then physically developed at 25 for 4 minutes by means of a solution containing per litre:
  • Lissapol N is a non-ionic surface-active substance consisting of a condensation product of ethylene oxide with alkyl phenols.
  • EXAMPLE 2 Strips of a cellulose triacetate foil, saponified to a depth of 2 m., were sensitized on one side by impregnating them for 2 minutes at 25 C. in aqueous solutions, containing per litre:
  • the film strips were dried in a flow of hot air and then kept overnight in a space conditioned at 50% of relative humidity. Lengths of these strips were exposed by means of a sensitometer to light of longer wavelengths than 420 nm., obtained from the combination of a high-pressure mercury vapor discharge lamp (250 w.) and a G.G.3-filter (Jenaer Glaswerk Schott and Gen).
  • the exposed strips were treated directly after exposure for 4 seconds with the mercurous ions containing solution of Example 1.
  • the strips were then rinsed for 10 seconds in distilled water and then physically developed for 4 minutes at 25 C. in the developer of Example 1.
  • EXAMPLE 3 Strips of a cellulose triacetate foil, saponified to a depth of 2 m., were unilaterally sensitized by impregnating them on one side for 2 minutes at 25 C. in aqueous solutions containing, apart from 0.10 mol of cadmium lactate and 10 drops of 50% by weight of Lissapol N, per litre:
  • Lengths of these strips were exposed for 2 minutes to light of a wavelength of 435 nm. (band width 10 nm.), obtained from a combination of a Bausch and Lomb monochromator (light source high-pressure mercuryvapor discharge lamp HP and a G.G.-3-filter (Jenaer Glaswerk Schott and Gen).
  • the distance between the film strip and the outlet gap of the monochromator was 7.5 ems.
  • the exposed strips were treated immediately after the exposure for 4 seconds with the solution of mercurous ions of Example 1. Then the strips were rinsed in distilled water for 10 econds and then physically developed at 25 C. for 4 minutes in the developer of Example 1. After rinsing and drying the density of the exposed areas was measured the results being as follows:
  • Film strip 0 has no density at all.
  • EXAMPLE 4 Strips of a cellulose triacetate foil, aponified to a depth of 2 m, were unilaterally sensitized on one side by impregnating them for 2 minutes at 25 C. in aqueous solutions containing, apart from 10 drops of 50% by weight of Lissapol N, per litre:
  • the film strips were dried in a flow of hot air and then kept for about 12 hours in a space having a relative humidity of 50%. Lengths of these strips were exposed by means of a sensitometer to light of a longer wavelength than 420 nm., obtained from the combination of a high-pressure mercury-vapor discharge lamp (250 w.) and a G.G.-3- filter (Jenaer Glaswerk Schott and Gen). Immediately after exposure the strips were treated for 4 seconds with the solution containing mercurous ions of Example 1. Then they were rinsed in distilled water for 10 seconds and then physically developed for 4 minutes at 25 C. in the developer of Example 1.
  • the threshold Sensitivity of the strips (a), (b), (c) and (d) is a factor, 2, 3, 2 and 3 respectively higher than that of the strip (e).
  • each of these sheets was provided with an 8-fold magnification of a micro-negative with the aid of a commercially available slide projector.
  • the sheets were treated for 4 seconds with a solution containing 0.005 mol of mercurous nitrate and 0.001 mol of silver nitrate and 0.01 mol of nitric acid in distilled Water.
  • the sheets were then rinsed for 10 seconds in distilled Water and subsequently physically developed for 2.5 minutes at room temperature in the developer of Example 1.
  • the magnifications were rinsed again and fixed in 0.10 mol of sodium thiosulphate for at least 1 minute, after which the sheets were again rinsed in water.
  • the exposure time in the case (a) could be chosen a factor 2 shorter than in the case (b).
  • the film strips were dried in a flow of hot air and then kept overnight in a space having a relative humidity of 50%. Lengths of these strips were exposed by means of a sensitometer to light of a longer wavelength than 400 nm., produced by the combination of a high-pressure mercury-vapor discharge lamp (250 w.) and a G.G.4-filter (Jenaer Glaswerk Schott and Gen.). The exposed strips were treated with the mercurous solution of Example 1. Then the strips were rinsed in distilled water for 10 seconds and subsequently physically developed for 4 minutes at C.
  • EXAMPLE 7 Strips of a cellulose-triacetate foil, saponified to a depth of 2 ,um. were sensitized on one side by impregnating them for 2 minutes in distilled water and then for 3 minutes, immediately after the removal of the adhering liquid by wiping it off between two rubber strips, in alcoholic solutions at room temperature, containing per litre:
  • the film strips were dried in a flow of hot air and then kept overnight in a space having a relative humidity of 50%. Lengths of these strips were exposed by means of a sensitometer to light of a longer wavelength than 400 nm. produced by the combination of a high-pressure mercury vapor discharge lamp (250 w.) and a G.G.4-filter (Jenaer Glaswerk Schott and Gen.). After the exposure the film strips were treated for 4 seconds with the mercurous solution of Example 1. Then the strips were rinsed in distilled water for 10 seconds and then physically developed for 4 min utes at 25 C. in the developer of Example 1. After rinsing and drying the completely fog-free density wedges on the film strips were measured by a densitometer.
  • the threshold sensitivity of the strip (a) is a factor 6 higher than that of the strip (b).
  • EXAMPLE 8 Strips of a cellulose-triacetate foil, saponified to a depth of 2 ,um. were sensitized on one side by impregnating them at 25 C. for 2 minutes in aqueous solutions containing, apart from 10 drops of by weight of Lissapol N as a wetting agent, per litre:
  • the film strips were dried in a 'flow of hot air and then kept for about 12 hours in a space traversed by air of 50% of relative humidity.
  • Lengths of the strips (a) and (b) were exposed by means of a sensitometer to light of a longer wavelength than 400 nm., produced by the combination of a highpressure mercury vapor discharge lamp (250 v.) and a G.G.4-filter (Jenaer Glaswerk Schott and Gen.). The exposed strips were treated for 4 seconds with a mercurous solution of Example 1.
  • the strips were rinsed for 10 seconds in distilled water and then physically developed for 4 minutes at 25 C. in the developer of Example 1. After rinsing and drying the completely fog-free density wedges 0n the film strips were measured by means of a densitometer.
  • the threshold sensitivity of the strip (a) is at least a factor 3 higher than that of the strip (b).
  • R is a member selected from the group consisting of alkyl, phenyl and cyclohexyl, Z and Z are each moieties selected from the group consisting of hydrogen, halogen and alkyl of 1 to 6 carbon atoms, Me is a metal cation, selected from the group consisting of Na+, Zn++, Cd++, Pb++ and Cu++, n is a whole number from 1 to 2 inclusive,
  • said light sensitive diazosulfonate being further characterized in having a molecular extinction coeiiicient at 435 mm. of at least 1000 and a dissociation constant in the dark reaction of less than 5 1()- when determined in an aqueous solution of pH 7.8.
  • the light-sensitive layer contains in addition an anti-regression agent capable of reacting with one or more of the light decomposition products of the diazosulfonate formed upon exposure to light and prevents formation of the diazosulfonate from these light decomposition products.
  • the light sensitive layer contains a Water soluble mercurous compound and a water-soluble silver salt of the diazosulfonate and the electrophobic moiety X is selected from the group consisting of morpholino and piperidino.
  • a light sensitive material comprising a support the surface at least of which is electrically non-conductive said material having a light-sensitive layer thereon, said layer containing a water soluble mercurous salt and as a light-sensitive diazosulfonate a compound of the formula wherein X is an electrophobic moiety selected from the group consisting of morpholino, piperidino and wherein R and R are each selected from the group consisting of phenyl, cyclohexyl, hydrogen and alkyl, Y and Y are each moieties selected from the group consisting of hydrogen, halogen, NO CN, CF;,,,
  • R H and OR wherein R is a member selected from the group consisting of alkyl, phenyl and cyclohexyl, Z and Z are each moieties selected from the group consisting of hydrogen, halogen and alkyl of 1 to 6 carbon atoms, Me is a metal cation, selected from the group consisting of Na+, Zn++, Cd++, Pb++ and Cu++, n is a whole number from 1 to 2 inclusive, with the proviso that at least one of the moieties Y and Z is alkyl only when one of the moieties Y and Y is other than hydrogen, said light sensitive diazosulfonate being further characterized in having a molecular extinction coefficient at 435 nm. of at 1 1 least 1000 and a dissociation constant in the dark reaction of less than 5 x10 when determined in an aqueous solution of pH 7.8.
US708593A 1967-02-28 1968-02-27 Method of producing photographic images by physical developing utilizing diazosulfonates Expired - Lifetime US3595660A (en)

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NL6703133.A NL157434B (nl) 1967-02-28 1967-02-28 Werkwijze voor de vervaardiging van fotografische beelden.

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US (1) US3595660A (zh)
BE (1) BE711300A (zh)
DE (1) DE1622295C3 (zh)
FR (1) FR1556586A (zh)
GB (1) GB1201668A (zh)
NL (1) NL157434B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3719491A (en) * 1968-06-18 1973-03-06 Gaf Corp Diazo-type reproduction process
US4230788A (en) * 1973-11-26 1980-10-28 U.S. Philips Corporation Method of manufacturing an external electrically conducting metal pattern

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3719491A (en) * 1968-06-18 1973-03-06 Gaf Corp Diazo-type reproduction process
US4230788A (en) * 1973-11-26 1980-10-28 U.S. Philips Corporation Method of manufacturing an external electrically conducting metal pattern

Also Published As

Publication number Publication date
NL157434B (nl) 1978-07-17
GB1201668A (en) 1970-08-12
DE1622295A1 (de) 1970-10-29
NL6703133A (zh) 1968-08-29
DE1622295B2 (de) 1977-07-21
FR1556586A (zh) 1969-02-07
DE1622295C3 (de) 1978-03-16
BE711300A (zh) 1968-08-26

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