Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
• • 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
  • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
• • 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
  • G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • 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
  • Y10S430/131—Anticurl layer
• • 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
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

• ABSTRACT A concave curvature is imparted to the backing surface of a polyester photographic film support (prior to coating the other surface) by a process which comprises applying to said backing surface a solution of treating composition comprising a volatile phenolic compound and a surfactant in a volatile solvent and drying and heating the film above the second order transition temperature of the polymer for a time sufficient to volatilize the solvent and phenolic compound from the surface.
• a flat photographic film product having no anti-curl backing layer is produced from the concavely curved film upon coating the other surface of the film with one or more layers of the usual coatings used in the structure on the photosensitive side of the film, at least one of said layers being such that it shrinks when drying and imparts a compensating countercurvature force to the film, thereby flattening the film.
• This invention relates to the manufacture of film supports used in the production of flat photographic films. Particularly, it relates to a process for treatment of thermoplastic film supports which renders the latter suitable for the preparation of flat photographic film products, especially film for moving picture camera use, without it being necessary to apply to the nonsensitized surface of a support film an anticurl backing layer to compensate the undesirable incurvature of the sensitized surface produced by the coating on the latter surface of a photosensitive layer the binder of which is a hydrophilic colloid.
• an anti-curl backing layer generally a gelatin layer
• the fragility of such a backing layer is a cause for local defects that can form in the course of manufacture of the photographic product, of picture taking, of chemical treatment of the exposed film during developing, or of use of the finished photographic document.
• This difficulty is one of the reasons why no backing layer is applied to cinematographic films, the emulsified surfaces of which are usually very concave in the absence of external pressure, as they must move at a great speed on rollers.
• the heating is done at to C.
• the treated film is dried by means of heating at such temperature above the second order transition point of the polymer of the film that is treated, so as to remove the solvent first, and then to volatilize the attacking agent, substantially completely.
• backing surface is meant the surface intended to be reverse to that surface which ordinarily would become concave by the application thereon of a layer or several layers of photosensitive materials at least one of which being such that it tends to shrink when drying.
• this layer contains a hydrophilic colloid, such as gelatin.
• the attacking agent is a volatile hydroxy aromatic compound, preferably a phenolic compound, such as resorcinol.
• the treatment preferably, is effected on photographic film supports intended for coating with preselected photosensitive materials, so that the final photographic products predictably will be flat.
• the incurvature can be controlled by varying the concentration of the surface-attacking agent and the maximum temperature of volatilization. It appears that the surface attack on the film at the specified temperature range creates internal tensions in the attacked surface area of the latter and in this way produces the incurvature, the concavity being on the attacked surface.
• the invention thus makes it possible to obtain substantially flat photographic film products, as well as other one-side-coated film products, having film supports free of a special anti-curl backing layer, the disadvantages of which backing layers are indicated above.
• the invention therefore, is a substantial advance in the art of manufacture of thermoplastic photographic and other film supports and products.
• the invention concerns more particularly photographic film products having film supports consisting of polyester or polycarbonate resin films of photographic quality, particularly poly( l ,4- cyclohexylenedimethylene terephthalate) films, and,
• poly(ethylene terephthalate) films More particularly, poly(ethylene terephthalate) films.
• the surface treatments of such films with compositions producing a surface attack for the purpose of increasing adherence of one layer, or numerous sub-layers, to the polyester or polycarbonate film is known.
• dihydroxy aromatic compounds are taught to be included in polymeric subbing compositions as anchoring compositions.
• Specific adhesion-improving dihydroxy aromatic compounds disclosed in said patent are exemplified by resorcinol, and include, in addition, orcinol, 4-chloro-resorcinol, 1,3-naphthalene diol, 1,6-naphthalene diol, catechol, and 2,4-dihydroxy toluene.
• resorcinol include, in addition, orcinol, 4-chloro-resorcinol, 1,3-naphthalene diol, 1,6-naphthalene diol, catechol, and 2,4-dihydroxy toluene.
• 3,271,190 teaches an anti-blocking composition for polyester sheeting which is comprised of l an anionic surface-active agent and (2) an adhesion promoter.
• the adhesion promoter is selected from a group including hydroxy, dihydroxy and trihydroxy aromatic compounds, specifically, resorcinol, orcinol, catechol, pyrogallol, l-naphthol, 2,4-dinitrophenol, 2,4,6-trinitrophenol, 4-chlororesorcino1, 2,4- dihydroxytoluene, 1,3-naphthalenediol, 1,6- naphthalenediol and o-cresol.
• An aqueous solution of the anti-blocking composition is applied to at least one surface of a polyester sheet and dried with sufficient heat to remove only the water, leaving the anti blocking composition as a residue on the sheet.
• the anti-blocking composition serves to keep polyester sheets from adhering to each other.
• the process of the invention uses substantially the same hydroxy aromatic compounds in a different manner to achieve a different result.
• one of the same hydroxy aromatic compounds as described above, for example, resorcinol is applied in a treating composition to only one surface of the polyester or polycarbonate photographic film support and then the film is heated to a temperature above the second order transition point of the polymer to volatilize the resorcinol substantially completely away from the film.
• the result obtained is that the treated film surface is made concave.
• the selection of the volatile attacking agent to be used depends on the chemical nature of the photographic film to be used as a support film.
• a solution of a hydroxy aromatic compound is used advantageously, which compound can be any of the hydroxy, dihydroxy or trihydroxy aromatic compounds listed in the patents discussed above, provided only that the compound is volatile at a temperature above about the second order transition point of the polymer forming the film.
• the compound is, for example, phenol itself, resorcinol, pyrogallol, or 4-hexylresorcinol.
• These preferred phenols are volatile; and the first three listed are water-soluble, and are used advantageously in the form of aqueous solutions. It is also possible to use these phenolic compounds in solution in an organic solvent, such as dichloromethane or methylisobutylketone.
• auxiliary product facilitating its coating Le
• auxiliary product facilitating its coating
• Le a product having a surface active action
• surface active agents of the anionic type disclosed in US. Pat. No. 3,271,190 for example, the sodium salts of fatty alcohol sulfates or of alkyl aryl sulfonates, may be used.
• US. Pat. No. 3,271,190 is incorporated herein by reference.
• Nonionic surface active agents may also be used to practice the invention.
• Especially preferred is the use of the Antarox CO 436 agent, sold by the General Aniline and Film Corporation.
• the means for coating the treating composition on the surface of the film are well known in the art and any of such coating or applicator means may be used. It is preferred, however, to apply the composition by means of a wick and then to smooth the coated layer with an air knife in a known way.
• the treating composition whether containing an aqueous or an organic solvent is used in concentrations which can be readily determined by one skilled in the art.
• the amount of solvent should be sufficient to form a solution which easily can be applied by a particular applicator means to the surface to be treated.
• the treating composition will contain by weight from about 1 to about 50 parts of hydroxy aromatic compound dissolved in from 99 to 50 parts of solvent per 100 parts of composition.
• the amount of hydroxy aromatic compound present in the composition will be from about 15 to about 20 parts.
• the composition also may, and preferably will, contain by weight from about 0.05 to about 2 parts, preferably about 0.1 part, of a surface active agent, in place of an equivalent amount of solvent.
• preferred treating compositions according to the invention will consist essentially of from about 15 to 20 parts of hydroxy aromatic compound, about 0.1 part of surface active agent and about 79.9 to 84.9 parts of solvent, all parts being by weight.
• the drying temperature used to remove the treating composition from the treated surface is higher than that of the second order transition temperature point of the polymer forming the film.
• a temperature above approximately C. e.g. between 120 and 6 130 C. is very suitable.
• the period of heating is generresorcinol and 0.1% of Antarox CO 436 surface acally between about 10 and seconds, these limits not tive agent.
• a cotton wick was used to spread the combeing absolutely required. position, then the layer was smoothened by means of an air knife, under a pressure of 0.014 psi.
• the layer was dried at 130 C., in one set of samples, and at 85 C. in a second set of samples. The results are shown in Table 1.
• Tg Second order transition temperature or glass transi- 5 tion temperature
• transition temperature varies d i d treating temperature f 130 C b none i somewhat with the nature of the glycol and the dibasic i d at a d i d treating temperature f 85 C field reacted togethel' to form the p y For P y- If to the untreated surface of the thusly treated photo- (ethylene terephthalate) of a p g p q y, graphic support, a high-contrast photographic emulwhich is biaxially oriented and highly crystalline, the ign, f h type d i h h h i l processes,
• Second Order transition temperature g) is about 1200 is applied, a substantially flat photographic product is Because of its high Crystalline melting P (about obtained by compensation of the incurvature itself of 265 C.) and second order transition temperature, such h Support d f h incurvature i h opposite dip y( y terephthalate) retains g mechanical rection produced by the drying of the photographic properties at temperatures up to about 150-l75 C. emulsion Accordingly, in heating the treated photographic film support to remove the composition the heating should EXAMPLE 2 not be carried above said temperature range One operates in a manner similar to Example 1, by
• Example 2 shows the effects of different tempera- 55 tures of heating of the film to remove the treating com- EXAMPLE 3 position.
• Examples 1 and 2 are repeated by using as processing
• the incurvature depth of solution a solution containing 50% Of phenol in dichlothe concavity is expressed by the sagitta in 1/32s of an romethane.
• the following results are obtained, the dryinch for an arc of 35mm, on a 35mm-wide film strip, 0 g mperature being 130 C.
• the relative humidity is expressed in percent at the indicated drying M" temperature.
• composition was applied containing, by weight, 15% of Measurements of products TABLE Ill-Continued Measurements of recently Percent Example 3 shows that upon increasing the concentration of the processing solution and using a different phenolic compound, phenol, in place of the resorcinol used in Examples 1 and 2 the amount of incurvature of the film was substantially increased to a high degree.
• the incurvature forces on the other surface accordingly can be made correspondingly great and a flat film product will be obtained by applying sufficient layers and thicknesses of coating materials, including a hydrophilic binder material.
• an incurvature in the order of 2 yields a more or less flat final product with a poly(ethylene terephthalate) support, 100a thick, coated with a negative photographic emulsion layer, of the usual type and of average thickness.
• a method for making a substantially flat photographic film product having a polyester or polycarbonate support coated on one surface with at least one layer including photosensitive material and a hydrophilic binder for said material consisting essentially of a. first treating one surface of said support before applying said layer by (i) applying to said surface a treating composition consisting essentially of a solution of a volatile hydroxy aromatic compound in an organic or aqueous solvent for said compound, said compound having a volatilization point above that of the solvent and being volatile at a temperature above about the second order transition temperature (Tg) of said polymer and below about 175 C., and (ii) subjecting the treated support from (i) to a temperature in the temperature range of from said second order transition temperature (Tg) to below about 175 C. for a period of time sufficient to evaporate substantially all of said solvent and said compound and to impart internal tensions and incurvature to the treated surface,
• a coating comprising at least one layer of coating composition including photographic material and a hydrophilic binder for said material, said coating being of sufficient thickness to provide, when dry, compensating incurvature forces on the coated surface sufficient to counteract the internal tensions of incurvature of said first treated surface, and
• the layer of coating composition comprises photographic silver halide.
• the treating composition by weight, consists essentially of from about 1 to about 50 parts of said volatile hydroxy aromatic compound and from about 99 to 50 parts of said solvent.
• said treating composition contains from about 0.05 to about 2 parts of surfactant agent.
• said volatile hydroxy aromatic compound is phenol, resorcinol, pyrogallol or 4-hexylresorcinol.

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• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Health & Medical Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)
• Laminated Bodies (AREA)

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Cited By (9)

Citations (11)

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• 0
  • BE BE790087D patent/BE790087A/xx unknown
• 1971
  • 1971-10-13 FR FR7136705A patent/FR2155881B1/fr not_active Expired
• 1972
  • 1972-09-07 US US287131A patent/US3861942A/en not_active Expired - Lifetime
  • 1972-10-11 DE DE2249869A patent/DE2249869A1/de active Pending
  • 1972-10-12 GB GB4718972A patent/GB1413678A/en not_active Expired
  • 1972-10-13 JP JP47101987A patent/JPS4847559A/ja active Pending

Patent Citations (11)

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