Classifications

• • 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
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
• • 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
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings

Definitions

• This invention relates to photosensitive elements containing a permanent antistatic layer. More particularly, this invention relates to photosensitive elements containing auxiliary layers which exhibit improved adhesion to permanent antistatic layers.
• Static charge is a particular problem when the film is a support for a machine processable photosensitive element. Static charges caused when the film slides in and out of these machines can be discharged causing unwanted exposure of the photosensitive layer.
• an antistatic layer that is, a layer which prevents the build-up of static charge
• the antistatic layer reduces the propensity of the film to build-up static charge.
• the photosensitive element can be wound, unwound, processed, and otherwise used successfully without problems caused by static build-up.
• auxiliary layers it is also conventional to apply auxiliary layers to these supports for a myriad of reasons. For example, it may be necessary to have an antiblocking layer to prevent the support from sticking while wound up or while stacked in layers. It may be necessary to have a gelatin-containing backing layer for a photosensitive element. This backing layer may be useful as an anticurl or antihalation layer, for example.
• auxiliary layers When auxiliary layers are used over antistatic layers, they must conduct the antistatic qualities from that layer to the surface. It is also necessary that these auxiliary layers have excellent adhesion to the antistatic layer. This is especially necessary when the antistatic layer is applied at a high coating weights, e.g., 4 mg/dm2 to about 15 mg/dm2, for example. Good adherence means that there is essentially no separation between the auxiliary layer and the antistatic layer during normal handling and processing of the photosensitive element.
• Antistatic layers are well known in the art.
• Schadt, U.S. Patent 4,225,665 and Miller, U.S. Patents 4,701,403 and 4,859,570 disclose particularly effective antistatic layers for photosensitive elements.
• Schadt, U.S. Patent 4,225,665 describes the art in this area.
• Cho U.S. Patent 4,585,730, describes an auxiliary layer containing a conductive polymer. This layer is coated above the antistatic layer and maintains the antistatic properties of the element. Additionally, in Gundlach, U.S. Patent 4,940,555, another auxiliary layer with excellent qualities is described. This layer, which comprises gelatin and an aqueous dispersion of a polymerized vinyl compound, is applied over the antistatic layer after the pH is adjusted to 5 to 7. However, in both the photosensitive element disclosed by Cho and that disclosed by Gundlach there are occasional problems caused by poor adhesion between the antistatic layer and the auxiliary layer.
• a photographic element comprising:
• Preferred classes of adhesion agents are amides containing at least one -NH2 group, amides containing at least two -NH groups, urea, substituted ureas containing containing at least one -NH2 group, substituted ureas containing at least two -NH groups, guanidine hydrochloride, and thiourea.
• the preferred adhesion agents are urea, thiourea and 2-imidazolidone (ethyleneurea).
• this invention is a photographic film element comprising dimensionally stable polyethylene terephthalate film suitably subbed on both sides with a thin, anchoring substratum of a conventional resin sub over which is applied a gelatin sublayer on one side only.
• a standard, gelatino, silver halide emulsion layer is applied and this layer overcoated with a conventional gelatin abrasion layer.
• a permanent antistatic layer disclosed in Miller, U.S. Patent 4,859,570 is applied, directly over the resin sub, preferably at a coating weight of about 4 mg/dm2 to about 15 mg/dm2.
• the novel auxiliary layer herein described is coated on top of the antistatic layer at a coating weight of about 20 mg/dm2 to about 100 mg/dm2.
• the invention is a versatile photosensitive element comprising: a support, a photosensitive layer, at least one permanent antistatic layer present on the support, and an auxiliary layer on the antistatic layer.
• the novel auxiliary layer of this invention consists essentially of an aqueous gelatin dispersion of at least one crosslinking agent, optionally, but preferably, at least one dispersing agent, and an adhesion promoting amount of adhesion agent more fully described below. It is coated over the antistatic layer at a coating weight of about 20 mg/dm2 to about 100 mg/dm2, preferably about 35 mg/dm2 to about 65 mg/dm2, expressed as the weight of gel coated, using conventional coating techniques.
• the auxiliary layer is preferably coated at a pH in the range of about 4.5 to 6, more preferably about 4.8 to about 5.4.
• the adhesion agent is a compound possessing in its structure at least one -NH2 group, at least two -NH groups, or mixtures thereof and which is sufficiently soluble in water that said adhesion promoting amount of adhesion agent may be dissolved in the dispersion used to coat said auxiliary layer.
• the adhesion agent should be sufficiently high boiling or be sufficiently soluble in water that it is not lost from the auxiliary layer during the coating operations. Compounds with a boiling point greater than 65°C may be used to advantage.
• the adhesion agent should not have an adverse effect on the photographic properties of the photosensitive layer.
• Compounds which have been shown to be effective in promoting adhesion include: primary amines, such as iso-butyl amine, ethylenediamine, diethylenetriamine, triethylenetetraamine, etc.; secondary amines which contain two secondary amine groups, such as piperazine, etc.; amides containing at least one -NH2 group, such as acetamide, etc.; amides containing at least two -NH groups, such as 2,5-piperazinedione (glycine anhydride), etc.; urea; thiourea; substituted ureas containing at least one -NH2 group, such as methylurea, N,N-dimethylurea, ethylenebisurea, hydroxymethylurea, biuret, etc.; substituted ureas containing least two -NH groups, such as 1,3-dimethylurea, 1,3-diethylurea, dihydroxymethylurea, 2-imidazolidone (ethyleneurea), etc.;
• adhesion agents are primary amides, compounds containing at least two secondary amide groups, urea, substituted ureas containing containing at least one -NH2 group or at least two -NH groups, and guanidine hydrochloride.
• Preferred adhesion agents are urea, thiourea and 2-imidazolidone.
• Adhesion promoting amount of adhesion agent means sufficient adhesion agent to enhance the adhesion without causing any deleterious side effects. While this amount may vary depending on the adhesion agent chosen, the adhesion agent is normally present in the auxiliary layer in the broad range of 10-150 mmol per 200 gm of gelatin present, and more preferably in the range of 30-110 mmol per 200 gm of gelatin.
• Gelatin dispersion denotes a binder wherein the major component is gelatin.
• Gelatin substitutes e.g., polyvinyl alcohol, dextran, cellulose derivatives, modified gelatins, a water-soluble latex, etc.
• minor amounts e.g., less than 17% by weight.
• Addition of the adhesion promoting amount of adhesion agent to form the novel auxiliary layer represents a simple and easy manner in which both antistatic properties and improved adhesion can be achieved.
• this layer will provide excellent antistatic properties on the surface of the film.
• this layer is stable and will survive the rigors of processing the photosensitive layer without any visible delamination of any of the aforementioned layers, one from the other. Additionally, this element will have good visible properties.
• a mixture of the gelatin binder in water, the gelatin crosslinking agent, the adhesion promoting amount of adhesion agent, and preferably the dispersing agent, are made up prior to coating.
• An optional conductive polymer may also be added.
• Other conventional additives, e.g., antihalation dyes, etc. may also be present.
• Adhesion agent may be added to the aqueous dispersion used to make the auxiliary layer of this invention at any time.
• a convenient way to add the adhesion agent is to add 20% by weight aqueous adhesion agent to the aqueous dispersion just prior to coating the auxiliary layer.
• Gelatin crosslinking agents common in the field of photographic elements used in the auxiliary layer of this invention include: formaldehyde, chrome alum, etc.
• Formaldehyde is a particularly preferred agent and is present in the range of 0.5% to 3.0% by weight, and preferable, in a range of 0.75% to 2.5% by weight of the gelatin binder.
• At least one dispersing agent or coating aid such as an anionic surfactant, is added to improve the ability of the dispersion to be applied on the antistatic layer.
• a dispersing agent or coating aid such as an anionic surfactant
• Low levels e.g., 10 to 100 gm per 200 gm of gelatin present, of a 14.9% aqueous solution of sodium lauryl ether sulfate, e.g. Polystep® B-27, Stephan Chem. Co., Northfield, IL, can be used, for example.
• Mixtures of two or more coating aids may also be present. Most conventional coating aids are suitable within the metes and bounds of this invention.
• a conductive polymer or polymers may be added to the auxiliary layer.
• a useful conductive polymer is the 3:1 copolymer of the sodium salt of styrene sulfonic acid and maleic acid. If present, these polymers may be added to the auxiliary layer in a range of 1 to 10% by weight of the gelatin dispersion/binder, preferably at 4 to 6% by weight.
• the preferred coating weight is 4 mg/dm2 to 15 mg/dm2; the more preferred coating weight is 8 mg/dm2 to 10 mg/dm2.
• the element is then heat relaxed and the auxiliary layer of this invention coated on top of antistatic layer.
• an aqueous solution of a water-soluble, electrically conductive polymer and a polyfunctional substituted aziridine is prepared, and a small amount of a suitable wetting agent or coating agent added thereto.
• the aqueous solution is coated onto the support having carboxyl groups attached to the surface.
• the aziridine interlinks the water-soluble, electrically conductive polymer and the carboxyl groups of the support to form a permanent antistatic layer.
• ranges of from 100:4 to 100:30 (weight to weight) may be used to advantage, a conductive polymer/aziridine ratio of 100:10 is preferred.
• a preferred electrically conductive polymer is the 3:1 copolymer of the sodium salt of styrene sulfonic acid and maleic acid (disodium salt).
• polyfunctional aziridine at least one hydrogen atom on a carbon atom of the aziridine ring is substituted with an alkyl substituent of 1 to 6 carbon atoms.
• Preferred polyfunctional aziridines are pentaerythritol-tri-[beta-(N-alkyl or dialkyl-substituted aziridinyl) propionate]s, represented by the formula: where R is alkyl or dialkyl of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
• R is methyl.
• the film support may be any of the conventional polymeric films used in the manufacture of photosensitive elements, provided it either contains surface carbonyl groups or can be treated to produce carboxyl groups at the surface by, for example, flame treatment.
• the preferred support is polyethylene terephthalate film.
• Conventional photographic grade polyethylene terephthalate film made according to the well-known teachings of the art, is the most preferred film support.
• the film is cast and then stretched in both dimensions and heat relaxed to attain dimensional stability.
• a standard resin sub layer is applied on at least one side of the film support.
• the resin sub is applied to both sides of the film support.
• the film support is a photographic film element comprising dimensionally stable polyethylene terephthalate film, suitably subbed on each side with a thin, anchoring substratum of a conventional resin sublayer, over which may be applied a gelatin sublayer.
• a preferred polyethylene terephthalate support is taught by Alles, U.S. Patent 2,779,684, and a preferred resin subbing layer such as the mixed polymer subbing compositions of vinylidene chloride-itaconic acid is taught by Rawlins, U.S. Patent 3,567,452, the specific disclosures of which are incorporated hereby reference.
• the photosensitive layer is preferably a standard, gelatino silver halide emulsion layer which is applied on one side of the element.
• Conventional photographic silver halide emulsions employing any of the commonly known halides may be used. These may be of varied content and may be negative and/or positive working. Conventional additives may also be present for specific purposes, such as, for example, to enhance and stabilize the response of the emulsion.
• the emulsion layer is then overcoated with a conventional gelatin abrasion layer.
• photosensitive layers may also be substituted for the silver halide emulsion.
• Conventional photosensitive materials include: photopolymerizable compositions, diazo, vesicular image-forming materials, and the like.
• the films described may be used in any of the conventional imaging fields, such as, graphic arts, printing, medical and information systems, among others.
• the film element of this invention is particularly useful in processes where rapid transport and machine handling of photographic film is practiced, such as, phototypesetting applications.
• the following solution was prepared by mixing 20,000 gm of gelatin (Kind and Knox Low Viscosity Blend #5734), added in two, substantially equal portions, to 181,000 gm of distilled water. This mixture of gelatin and water was stirred at room temperature in a conventional stirred, jacketed stainless steel reaction kettle for about 20 min and then heated to 130°F (54°C). When 95°F (35°C) was achieved, 80 gm of a 16.8% solution of synthetic silica (#72, Davison Chemical Co., Cincinnati, OH) dispersed in a 6.7% aqueous solution of gelatin, was added. An additional 1,000 gm of deionized water was used to rinse the silica dispersion into the vessel.
• This dispersion was held for at 130°F (54°C) for 30 min. Then cooling to 115°F (46°C) was started. At 128°F (53°C), 5,000 gm of a 14.9% aqueous solution of sodium lauryl ether sulfate (Polystep® B-27, Stephan Chemical Co., Northfield, IL) was added. At 121°F (49°C), 1,720 gm of an 18.5% aqueous solution of Dye S-1240 was added. At 119°F (48°C), 750 gm of a 10% aqueous solution of Acid Violet 520-T Dye and 850 gm of a 4.0% aqueous solution of light green SF Yellowish Dye were then added.
• a 0.004 inch (about 100 ⁇ m) dimensionally stable polyethylene terephthalate film having a conventional resin sublayer coated on both sides thereof was prepared.
• Film made according to Cho, U.S. Patent 4,891,308, Examples 1 to 5, and film similar to that disclosed by Cho, U.S. Patent 4,585,730 were used as controls.
• Each sample was tested with a device which simulates the rollers of a Type 44C Du Pont Automatic Processor.
• the film passes through opposed rollers as it moves from the developer to the fixer. Since considerable strain is applied to the developer soaked film during this process, delamination may occur.
• a pair of stainless steel rollers with a drive mechanism were set up with a device which can assert a measured amount of pressure thereon. This device can exert uneven pressure to simulate that caused in the processor.
• Example 1 was repeated except that the pH was adjusted to 6.05 prior to coating. Adhesion was similar to that of the control elements of Example 1.
• Example 1 was repeated except that Rousselot standard viscosity lime bone gelatin was substituted for kind and Knox #5374 low viscosity gelatin.
• the urea solution was added just prior to coating as described in Example 1. Samples of the film were dried and tested for anchorage and propensity to develop static. In all cases, the film made according to the teachings of this invention had excellent adhesion to the antistatic layer. Static protection was also excellent. The base roll of polyester film coated in this manner did not telescope during handling.
• Example 1 was repeated except that Nitta P-3130 low viscosity lime bone gelatin was substituted for kind and Knox #5374 low viscosity gelatin.
• the urea solution was added just prior to coating as described in Example 1. Samples of the film were dried and tested for anchorage and propensity to develop static. In all cases, the film made according to the teachings of this invention had excellent adhesion to the antistatic layer. Static protection was also excellent. The base roll of polyester film coated in this manner did not telescope during handling.
• This example shows that improved anchorage is obtained with urea derivatives.
• Example 11 shows the effect of various amides on anchorage.
• the general procedure of Example 11 was repeated with the indicated compounds. Results are given in Table 4.
• Example 11 shows the effect of 2-imidazolidone and thiourea on adhesion.
• Example 11 shows the effect of various amines on adhesion.
• the following solution was prepared by mixing 200 gm of gelatin (PB Gelatins UK Ltd, Type 5003), 1881 gm of distilled water, and 0.8 gm of a 17% dispersion of synthetic silica (Syloid® 378, Grace GmbH, Worms, Germany) in gelatin. This mixture was stirred at room temperature in a conventional stainless steel reaction kettle for about 40 min and then heated to 130°F (54°C)
• the dispersion was held at 130°F (54°C) for 25 min. Then cooling to 100°F (38°C) was started.
• 100°F (38°C) 140 gm of 1:1 ethanol/water, 29.9 gm of a 10% aqueous solution of Acid Violet 520, 111.7 gm of a 10% aqueous solution of Oxonol Yellow (S-1240 Gaspar Yellow), 105 gm of a 14.9% aqueous solution of sodium lauryl ether sulfate (Triton® X-200, Rohm and Haas, Philadelphia, PA), 24 gm of a 5% aqueous solution of fluorocarbon anionic surfactant (Fluorad® FC-127, 3M Co., St.
• a 0.004 inch (about 100 ⁇ m) dimensionally stable polyethylene terephthalate film having a conventional resin sublayer coated on both sides thereof was prepared.
• the gelatin solutions were coated on a laboratory bar coater and dried in a spiral drier. Anchorage was measured as described in Example 1. Results are given in Table 9.

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• 1991
  • 1991-01-23 CA CA 2034788 patent/CA2034788A1/en not_active Abandoned
  • 1991-01-25 AU AU69999/91A patent/AU628250B2/en not_active Ceased
  • 1991-01-25 JP JP2380691A patent/JPH04298738A/ja active Pending
  • 1991-01-25 EP EP19910100935 patent/EP0439181A3/en not_active Withdrawn

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