US2584337A - Antistatic treating composition for photographic film supports - Google Patents

Antistatic treating composition for photographic film supports Download PDF

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Publication number
US2584337A
US2584337A US10104649A US2584337A US 2584337 A US2584337 A US 2584337A US 10104649 A US10104649 A US 10104649A US 2584337 A US2584337 A US 2584337A
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US
United States
Prior art keywords
film
cellulose
static
calcium silicate
cellulose acetate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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English (en)
Inventor
Famulener Keith
Hoerlin Herman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GAF Chemicals Corp
Original Assignee
General Aniline and Film Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE495251D priority Critical patent/BE495251A/xx
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US10104649 priority patent/US2584337A/en
Priority to GB1510150A priority patent/GB705159A/en
Application granted granted Critical
Publication of US2584337A publication Critical patent/US2584337A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • 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
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • 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
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05F—STATIC ELECTRICITY; NATURALLY-OCCURRING ELECTRICITY
    • H05F3/00—Carrying-off electrostatic charges
    • H05F3/02—Carrying-off electrostatic charges by means of earthing connections
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • 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
    • Y10S260/00—Chemistry of carbon compounds
    • Y10S260/15—Antistatic agents not otherwise provided for
    • Y10S260/16—Antistatic agents containing a metal, silicon, boron or phosphorus
    • 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]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31975—Of cellulosic next to another carbohydrate
    • Y10T428/31978—Cellulosic next to another cellulosic
    • Y10T428/31986—Regenerated or modified

Definitions

  • This invention relates to photographic film an particularly to a film treating composition havin anti-static properties.
  • a film base is coated on one or both sides with a subbing composition which usually consists of a dispersion of gelatin in a suitable solvent or solvent mixture, so as to facilitate the adherence, or anchorage, of one or more of the photo-sensitive, non-curling or anti-halation layers.
  • a subbing composition which usually consists of a dispersion of gelatin in a suitable solvent or solvent mixture, so as to facilitate the adherence, or anchorage, of one or more of the photo-sensitive, non-curling or anti-halation layers.
  • the roughening material must be deposited. on the surface in extremely minute quantities in order to beeffective.
  • Such materials as barium sulfate, calcium silicate, finely divided chalk, and numerous clays, for example, bentonite 'areused as suspensoids in suitable media to roughen the surface slightly. All of these materials have the common disadvantage that they must be-used in colloidal suspensions suitable for slightly coating the plastic sheet. Such suspensionsare very;dif-s; ficult to prepare and are unstable, especially when the colloid is gelatin.
  • Aqueous dispersions of such materials in gelatin solutions,-which are em loyed as subbing layers or carriers for antihalation dyes, are extremelyunstable and cannot be applied to the film support without the application of constant agitation. This agitation, though troublesome and time consuming, .is necessary to prevent the deposit ,of any minute quantities of roughening material tending to precipitate from the dispersion.
  • the principal object of the present invention is to provide photographic film supports which will possess improved anti-static properties.
  • Another object is to provide an improved film surface treating composition ha "ng anti-static properties.
  • a further object is to provide a, surface'treating' composition for photographic film supports which will readily permit the treated film to slip over other film and highly polished metal surf faces without creating static electrical charges.
  • CaSiOs calcium silicate
  • the calcium silicate as above, has the purpose of reducing the area of surface contact.
  • the reduction of contact area alone, though reducing the electrostatic charge density, is, however, not the only factor determiningthe static-susceptibility of cellulosic photographic film-support or sheeting.
  • Treating cellulose nitrate film Base witli a suspension of calcium silicate in alcoh'oFreduces'the' relative static susceptibility to a similar'extentl V Before-proceeding with the practical aspects ofth'e'presentinvention; it will'be desirable and helpful” to brieflydescribe the apparatus employed in evaluating" the"static' susceptibility of a treated'film,
  • V By reference to'the drawing, which is' selfexplanatory, it will be observed that it consists essentially of 5 afilm rewinding machine.
  • This machine is operated as follows: The test film, after leaving unwind A is first discharged completelyjby means of tinsel bars B to prevent disturbing efie cts'by residual charges. When going over roller: C, the film acquires a certain amount ofi'ch'arge and the-corresponding charge of oppo- "site polarityis permitted to'fiow from the roller surfacethrough galvanometer G to ground.
  • the electric charges generated are measured and the relative static susceptibility determined.
  • l"he galvanometer and electrometer data singly, or average after: proper weighting, permit the evaluation of the static susceptibility of a film sample in arbitrary units.
  • the charge density per unit surface area quantitatively in absolute units. The latter conversion is'not, however, required for most practical applications and only relative values of static susceptibility will be given in the following examples.
  • An arbitrary value of -100 is usually assigned to the untreated sample or type.
  • a dispersion of calcium silicate in an aralkyl alcohol such as benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, cinnamic alcohol, saligenin and the like is first prepared by grinding a mixture of calcium silicate and alcohol in a labora-' tory ball mill for a period of 8: hours.
  • the amount of calcium silicate tobeemployed may range from 5 to 30% by weight of. the alcohol.
  • the quantity of calcium silicate is not critical, it has been found that a 20% alcohol dispersion of calcium silicate is satisfactory for most practical purposes.
  • the dope consists essentially of a 5-15% solution of cellulose acetate, ranging from to 56% of combined acetic acid, in the usual organic solvents, or mixtures thereof, such as, for ex ample, methanol, ethanol, benzyl alcohol, acetone, ethylene dichloride, and the like.
  • the solvent or solvent mixture actually employed must be such that it will have a solvent or at least a' softening or swelling action on the cellulose derivamagnitude. of.
  • the film After passing idle rollers D, the film is wound on windup. ro1l ..E.' Halfway between roll -ers '13,. there is a fiat-condenser plate H'mounted parallel to the filmsurface at a distance of approximately 1.25 cm, The'condenser plate is tivefilm base so as" to stick or anchor the antistatic coating composition upon'thei area of the base which has been softened onswollen.
  • eachdifierent type of cellulose ester requires aislightly different solvent or solvent combination.
  • a ketone such as acetone, or a mixture of a low molecularweight alcohol, e; g., methanol, ethanol, and the like
  • acetone' may be employed.
  • the ratio of alcohol to: acetone ranges from about 30-60% to -25%, respectively.
  • an alkyl ester such as, for example, methyl acetate, ethyl acetate, butyl acetate, and the like, either. alone or with methanol, may beefiectively employed.
  • Theprepared' solution may be filtered if. desired. to remove'small agglomeratesof calcium silicate.
  • the poly-(methylene salicylic acid) is prepared by. placing a mixture of 1000 grams of salicylic acid, 1715 ml. of formaldehyde (40%) and 377 ml. of hydrochloric acid (conc.) in a liter round-bottom two-neck flask (or a 5-liter single-neck flask with two-way adapter) equipped with stirrer and condenser. The flask is heated on a steam bath, in which it should be at least halfway submerged, or proper insulation should be provided to insure eflicient heating.
  • the white plastic mass is washed once with water, and then dissolved in come. NI-hOI-I (28%)
  • the solution is diluted in a large crock to 4-5 times the volume with water. Conc. HCl is added with stirring, until the solution is strongly acidic. At this point, a colloidal mass of resin may be formed. Steam is passed through the mass to flocculate the resin and facilitate filtration. The resin is chilled with ice until the mixture is, at least, at room temperature. It is then filtered, washed with water and again dissolved-now in 2-3 1. of 6 N NaOH.
  • the solution is diluted as before and the resin is precipitated with conc. HCl. On appearance of a colloidal mass, steam is passed through.
  • the resin is chilled with ice, filtered, washed with water (until only slightly acidic of a pH of 3-4) and dried in air for approximately 3 days, or until no moisture appears to be present. It is then placed in the oven at 80-90 C. for approximately 3 days. When no odor of formaldehyde is evident, the resin is removed -from the oven and ground to a fine yellow powder.
  • Example I A strip of 35 mm. cellulose nitrate film support was coated with the following composition:
  • Example I Relative Static Susceptibility Untreated Strip l00 Treated Strip 1 Example]! Example I was repeated with the exception that the following composition was employed:
  • benzyl alcohol has been specifically disclosed as the dispersing medium for the calcium silicate in the above examples, any of the other aralkyl alcohols mentioned previously may be utilized with equal effect.
  • the reason that benzyl alcohol has been specifically utilized is because of its relative cheapness and commercial availability.
  • the treated photographic film bases produced according to the present invention in addition. to preventing the accumulation of static charges when unwound during a coating operation were found to be very satisfactory from the standpoint of physical requirements, such as high strength, flexibility, slippage, and good water resistance.
  • the invention is not limited to the treatment of finished photographic motion picture film nor the base utilized in the manufacture of such film, but is also useful in treating the back surface of any photographic roll or sheet film having a basis of a cellulose derivative. Its particular advantage, however, is in the treatment of finished motion picture negative film so as to protect the exposed and processed film against the accumulation of dust and dirt particles which occur when the film is moved through a printer or projector.
  • An anti-static cellulose acetate composition suitable for treating a film of a cellulose ester which comprises --15% solution-of cellulose acetate in a solvent for said. film and containing poly-(methylene salicylic acid) and calcium silicate dispersed in an aralkyl alcohol of the benzene series.
  • An anti-static cellulose acetate composition suitable for the treating of a film of a cellulose ester which consists of the following constituents:
  • a process of improving the anti-static and slippage characteristics of a film of a cellulose ester which comprises treating one surface of said film with a composition consisting of the following constituents:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
US10104649 1949-06-24 1949-06-24 Antistatic treating composition for photographic film supports Expired - Lifetime US2584337A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BE495251D BE495251A (da) 1949-06-24
US10104649 US2584337A (en) 1949-06-24 1949-06-24 Antistatic treating composition for photographic film supports
GB1510150A GB705159A (en) 1949-06-24 1950-06-16 Anti-static treating composition for photographic film supports and finished films

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Application Number Priority Date Filing Date Title
US10104649 US2584337A (en) 1949-06-24 1949-06-24 Antistatic treating composition for photographic film supports

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2996646A (en) * 1957-01-09 1961-08-15 Eastman Kodak Co Antistatic device
US3033699A (en) * 1959-05-08 1962-05-08 Du Pont Antistatic composition
US3223554A (en) * 1962-10-22 1965-12-14 Columbia Ribbon & Carbon Process of preparing transfer media
US3359126A (en) * 1966-01-12 1967-12-19 Celanese Corp Alkylolamine anti-static surface treatment of plastic films
US3401047A (en) * 1963-11-22 1968-09-10 Ici Ltd Anti-static nitrocellulose lacquers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1930134A (en) * 1932-02-02 1933-10-10 Eastman Kodak Co Cellulose organic ester composition containing propylene chloride
US1950907A (en) * 1932-07-29 1934-03-13 Eastman Kodak Co Cellulose organic ester composition comprising a phthalic acid ester of a monoether of hydroquinone
US2181609A (en) * 1937-05-15 1939-11-28 Standard Oil Dev Co Cellulose compound compositions
US2371990A (en) * 1942-02-18 1945-03-20 Du Pont Polymeric esters
US2382938A (en) * 1941-05-06 1945-08-14 Du Pont Oxygenated organic polymers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1930134A (en) * 1932-02-02 1933-10-10 Eastman Kodak Co Cellulose organic ester composition containing propylene chloride
US1950907A (en) * 1932-07-29 1934-03-13 Eastman Kodak Co Cellulose organic ester composition comprising a phthalic acid ester of a monoether of hydroquinone
US2181609A (en) * 1937-05-15 1939-11-28 Standard Oil Dev Co Cellulose compound compositions
US2382938A (en) * 1941-05-06 1945-08-14 Du Pont Oxygenated organic polymers
US2371990A (en) * 1942-02-18 1945-03-20 Du Pont Polymeric esters

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2996646A (en) * 1957-01-09 1961-08-15 Eastman Kodak Co Antistatic device
US3033699A (en) * 1959-05-08 1962-05-08 Du Pont Antistatic composition
US3223554A (en) * 1962-10-22 1965-12-14 Columbia Ribbon & Carbon Process of preparing transfer media
US3401047A (en) * 1963-11-22 1968-09-10 Ici Ltd Anti-static nitrocellulose lacquers
US3359126A (en) * 1966-01-12 1967-12-19 Celanese Corp Alkylolamine anti-static surface treatment of plastic films

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Publication number Publication date
GB705159A (en) 1954-03-10
BE495251A (da) 1900-01-01

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