US2245429A - Manufacture of photographic film base - Google Patents

Manufacture of photographic film base Download PDF

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Publication number
US2245429A
US2245429A US143302A US14330237A US2245429A US 2245429 A US2245429 A US 2245429A US 143302 A US143302 A US 143302A US 14330237 A US14330237 A US 14330237A US 2245429 A US2245429 A US 2245429A
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United States
Prior art keywords
film
solvent
cellulose nitrate
dope
compositions
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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
Application number
US143302A
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English (en)
Inventor
Emmett K Carver
Clarence L A Wynd
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.)
Eastman Kodak Co
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Eastman Kodak Co
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
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US143302A priority Critical patent/US2245429A/en
Priority to DEK150356D priority patent/DE724836C/de
Priority to GB14429/38A priority patent/GB514715A/en
Priority to FR838071D priority patent/FR838071A/fr
Application granted granted Critical
Publication of US2245429A publication Critical patent/US2245429A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/16—Esters of inorganic acids
    • C08L1/18—Cellulose nitrate, i.e. nitrocellulose
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/16—Esters of inorganic acids
    • C08J2301/18—Cellulose nitrate

Definitions

  • This invention relates to a process of producing cellulose nitrate .sheeting, and more particularlyto a process of producing at hitherto unattainable speeds cellulose nitrate sheeting adapted for use as photographic film base.
  • photographic film base and 7 similar types of sheeting are generally made by depositing a thin layer of a solutionof a cellulose derivative in a volatile solvent or solvent mixture on an appropriate film-forming surface, such as the surface of a slowly rotating wheel, removing solvents therefrom until this layer has set in the form of a, film, removing the film from the surface and curing out residual solvent.
  • an appropriate film-forming surface such as the surface of a slowly rotating wheel
  • solutionsoor dopes of cellulose nitrate of various types One of the most commonly employed dopes is one which may be referred to as non-coagulating, that is, one which gradually dries down into the form of a solid film by evaporation of solvent.
  • This invention has as its principal .object ,to provide a process for producing cellulose nitrate sheeting adapted for use as photographic .film
  • a further object is to 'increasethe speed and efiiciency of manufacture ofcellulose nitrate sheeting by that method which involves coagulation of a coagulable dope in the presence of a humid atmosphere.
  • a specific object is to produce cellulose nitrate film base adapted for use in the manufacture of motion picture :film and other purposes by .the coagulating method more percent greater than the speeds hitherto obtainable in the. production of satisfactory film base.
  • acertain specific type of coagulable dope namely, a dope composed of cellulose nitrate having a nitrogen content of 11.0% to 12.1%, dissolved in methyl alcohol to which a cosolvent such as acetone has been added in an amount sufiicient to give a clear, homogeneous solution, and coagulates this dope by means of steam, film or sheeting of satisfactory qualitycan be produced at greatly increased speeds.
  • arsrnallamount eofacetone for example, we may employ acellulose,nitrate having a nitrogen content as high ,as-,l2.1
  • athatonemust not employ a solvent mixture which too easily dissolves the cellulose nitrate or --one cannot coagulate the composition by means -at speedsup to approximately .rfive hundred or55 -By .theiterm i co solyent .of sufiicientmoisture to attain the desired increase in castingspeedwithout the production of 'undesirablehaze, opacity, or other undesirable effects in the resultingfilm.
  • compositions of this nature we have found that those compositions in which the cellulose nitrate has a nitrogen content of 11.0% to 12.1% and is dissolved in a solvent mixture composed of anywhere from 100% to 86% methyl alcohol and containing from to 14% acetone as co-solvent are peculiar in their ability to be stripped from the film-forming surface while still containing relatively large amounts of solvent.
  • solvent mixture composed of anywhere from 100% to 86% methyl alcohol and containing from to 14% acetone as co-solvent
  • Fig. 1 is a graphical representation of various cellulose nitrate compositions satisfactory for use in our process.
  • Fig. 2 is a diagrammatic sectional elevation of a conventional form of device adapted for the manufacture of film or sheeting from the compositions illustrated in Fig. 1.
  • the area lying underneath curve A designates compositions all of which are coagulable by means of moisture in accordance with our invention to produce clear, transparent film or sheeting satisfactory for photographic and other purposes.
  • the areas lying under curves B and C, respectively, and the area lying between curves C and D, represent preferred film-forming compositions, for use in accordance with our process. It is to be understood from Fig. 1 that not all compositions in which the cellulose nitrate has a nitrogen range from 11.0% to 12.1% dissolved in a solvent mixture containing from 100% to 86% methyl alcohol and from 0% to 14% of acetone are satisfactory for our purpose, but only those compositions which fall Within the area lying underneath curve A.
  • compositions falling within the area underneath curve A may all be coagulated at markedly improved speeds, or to express it in another way, the length of time during which such compositions must remain on the film-forming surface before satisfactory stripping can be attained is reduced from approximately ten minutes (the time required for standard dopes of either the coagulating or noncoagulating types) to as little as 2.4 minutes or less under optimum conditions for a. given dope.
  • compositions of our invention may be satisfactorily stripped while containing anywhere from 50% to 75% solvent. While an almost infinite variety of cellulose nitrate compositions have been known and used for many years in i the film making art and the industry has been This marked decrease in stripping time is diconstantly seeking a method whereby casting speeds could be increased, not until the advent of the present invention has it ever been recognized that the employment of a coagulable dope of the character herein set forth could bring about this highly desirable result. In other words, an increase of anywhere from a few percent to as much as 400% or 500% or more in the speeds hitherto attainable represents a totally inobvious and unexpected result.
  • co-solvent for maintaining the dope in a clear, homogeneous satisfactorily coagulable condition.
  • co-solvent we mean an agent which promotes solution of the cellulose nitrate in the main solvent (methyl alcohol) and renders the dope less subject to incipient coagulation under the conditions of operation when water is unavoidably present therein.
  • acetone While we have found acetone to be the most satisfactory agent for this purpose, it is within the scope of our invention to employ other co-solvents such as methyl ethyl ketone, diethyl ketone, ethyl acetate, butyl acetate, ethyl ether, methyl ethyl ether, isopropyl ether, dioxane, ethyl cellosolve, methyl cellosolve, dimethyl cellosolve and methyl cellosolve acetate.
  • co-solvents such as methyl ethyl ketone, diethyl ketone, ethyl acetate, butyl acetate, ethyl ether, methyl ethyl ether, isopropyl ether, dioxane, ethyl cellosolve, methyl cellosolve, dimethyl cellosolve and methyl cellosolve acetate.
  • a cellulose nitrate solution or dope of a composition falling within the area lying underneath one of curves A, B and C, of Fig. 1, may be coated or cast into the form of a film by means of a device such as that illustrated in Fig. 2.
  • numeral I designates a conventional type of film-forming apparatus comprising the casting or coating wheel 2.
  • the wheel assembly is carried by base 5 and surrounded by wheel casing 6 provided with air inlet conduit 1 and outlet conduit 8.
  • the numeral 9 designates a conventional type of dope hopper provided with adjustable gate member ID for regulating the thickness of the dope stream which flows therefrom, adjustment being by means of thumbscrew ll, attached in known manner to the gate member and threaded through one .wall of, the hopper,
  • Inlet conduit 1 is provided with air filter l2, steam jet I3 for (supplying thefdesired degree of moisture to the wheel casing, and with heater M for heating theair supplied thereto. Circulation of the heated moisture-laden air through conduit 1, wheel casing 8. and conduit 8 is accomplished by means of an appropriate air pumping or circulating device (not shown) connected to conduit 8, the solvent-laden air being passed to a. suitable solvent recovery system (not shown).
  • Numeral l designates a stripping roll to facilitate removal of the coagulated film F from the surface of wheel 2.
  • the film As soon as the film has set sufliciently to be satisfactorily removed from the wheel, it is stripped therefrom at stripping roll 15 and may then, in accordance with standard practice, he passed to an appropriate curing chamber where residual solvent is cured out and the film subjected to any other desired treatment.
  • compositions the use of which we have found result in increased production speeds are those in which the nitrogen content of the cellulose nitrate lies within the ranges indicated in Fig. 1 and in which the solvent has the indicated composition, that is, a solvent composed of at least 86% methyl alcohol and not more than 14% acetone or equivalent co-solvent.
  • the solvent has the indicated composition, that is, a solvent composed of at least 86% methyl alcohol and not more than 14% acetone or equivalent co-solvent.
  • any composition falling within the areas lying under curve A of Fig. 1 of the drawing is satisfactory and the use of such a composition results in an improvement in casting speed.
  • the compositions falling respectively underneath curves B and C, and between curves C and'D constitute preferred species. Examples of the above compositions are as follows:
  • the cellulose nitrate employed in our compositions may be one prepared by any of the standard methods, but we prefer to employ a nitrate having .a nitrogen content ranging from 11.7% to 12.05% and prepared as described in the .sure good solution is in .this case about 1%.
  • a preferred film-forming composition is composed of a nitrate of this nitrogen range prepared in accordance with the procedure of that application, dissolved in methyl alcohol containing as little acetone as is consistent with obtaining a clear, usable solution in view of whatever moisture may be present.
  • the ideal composition from the standpoint of casting speed in accordance with our invention would be one in which the cellulose nitrate has a nitrogen content of about 11.7% .to 12.05% as above indicated, dissolved in anhydrous methyl alcohol and containing no plasticizer. Under the conditions met with in plant practice, however, this ideal of employing an anhydrous solvent is usually unattainable, due to the fact that small amounts of water find their way into the composition, either because of the fact that methyl alcohol is generally contaminated with small amounts of water, or because moisture is introduced into the dope from imperfectly dehydrated cellulose nitrate or even from humid air during the preparation of the solution.
  • the water content of cellulose nitrate solutions prepared in large scale manufacturing equipment rarely exceeds 1%, and the minimum amount of acetone necessary to in- In practice,3-4% of acetone may be employed and the dope may contain up to 14% acetone, depending on the amount of water present and still'be satisfactory for our purpose.
  • the particular amount of acetone will therefore vary, not-only with the water content of the dope, but
  • the specific concentration of Water vapor in the film-forming atmosphere may vary widely, depending upon the composition of the dope, the speed desired, the coagulating temperature and other factors. In general, it may be said that the higher the concentration of moisture, the higher the casting speed.
  • the wheel temperature that is, the temperature at which the film is undergoing coagulation mayvary considerably, depending upon the composition of the dope employed and various other factors, and may range anywhere from room temperature to any temperature below that which would deleteriously affect the film.
  • an air temper- .ature of about 150 F. (whichgives a wheel temperature of about 90 F.) is satisfactory. It will,
  • compositions in which cellulose nitrate of the indicated nitrogen range is dissolved in a solvent mixture the essential solvent portion of which consists of methyl alcohol and one or more co-solvents, the balance comprising butyl alcohol derived from the alcohol-wet cellulose nitrate or elsewhere, plasticizers and/or other appropriate ingredients.
  • a high speed method of making sheeting adapted for use as photographic film base which comprises depositing in the form of a film on a film-forming surface a solution composed of cellulose nitrate having a nitrogen content between 11.0% and 12.1% dissolved in methyl alcohol containing not over about 14%, based on the weight of solvent mixture, of a co-solvent, which solvent mixture will give a clear, homogeneous solution capable of coagulating or setting up by means of water Vapor while containing at least as much solvent as the film is to contain at stripping, to produce a clear, transparent film, said solution having a composition falling within the area underneath curve A of the attached drawing, coagulating said solution by means of water vapor While containing at least as much solvent as the film contains at stripping, removing the film from the film-forming surface while still containing about 50-75% solvent, and then curing out the residual solvent.
  • a high speed method of making sheeting adapted for use as photographic film base which comprises depositing in the form of a film on a film-forming surface a solution composed of cellulose nitrate having a nitrogen content between 11.7% and 12.05% dissolved in methyl alcohol containing not over about 13% based on the weight of solvent mixture, of a co-solvent, which solvent mixture will give a clear, homogeneous solution capable of coagulating or setting up by means of water vapor while containing at least as much solvent as the film is to contain at stripping, to produce a clear, transparent film, said solution having a composition falling within the area underneath curve A of the attached drawing, coagulating said solution by means of water vapor while containing at least as much solvent as the film' contains at stripping, removing the film from the film-forming surface while still containing about 50-75% solvent, and then curing out the residual solvent.
  • a high speed method of making sheeting adapted for use as photographic film base which comprises depositing in the form of a film on a film-forming surface a solution composed of cellulose nitrate having a nitrogen content of 11.6% dissolved in methyl alcohol containing not over about 7%, based on the weight of sollating said solution by means of water vapor while containing at least as much solvent as the film contains at stripping, removing the film from the film-forming surface while still containing about 50-75% solvent, and then curing out the residual solvent.
  • a high speed method of making sheeting adapted for use as photographic film base which comprises depositing in the form of a film on a film-forming surface a solution composed of cellulose nitrate having a nitrogen content of 12.0% dissolved in methyl alcohol containing not over about 12% based on theweight of solvent mixture, of a co-solvent, which solvent mixture will give a clear, homogeneous solution capable of coagulating or setting up by means of water vapor while containing at least as much solvent as the film is to contain at stripping, to produce a clear, transparent film, said solution having a composition falling within the area underneath curve A of the attached drawing, coagulating said solution by means of water vapor while containing at least as much solvent as the film contains at stripping, removing the film from the film-forming surface while still containing about -75% solvent, and then curing out the residual solvent.
  • a high speed method of making sheeting adapted for use as photographic film base which comprises depositing in the form of a film on a film-forming surface a solution composed of cellulose nitrate having a nitrogen content of 11.9% dissolved in methyl alcohol containing not over about 11% based on the weight of solvent mixture, of a co-solvent, which solvent mixture will give a clear, homogeneous solution capable of coagulating or setting up by means of water vapor while containing at least as much solvent as the film is to contain at stripping, to produce a clear, transparent film, said solution having a composition falling within the area underneath curve A of the attached drawing, coagulating said solution by means of water vapor while containing at least as much solvent as the film contains at stripping, removing the film from the filmforming surface while still containing about 50-75% solvent, and then curing out the residual solvent.

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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)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Moulding By Coating Moulds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
US143302A 1937-05-18 1937-05-18 Manufacture of photographic film base Expired - Lifetime US2245429A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US143302A US2245429A (en) 1937-05-18 1937-05-18 Manufacture of photographic film base
DEK150356D DE724836C (de) 1937-05-18 1938-04-15 Verfahren zur Herstellung von Folien
GB14429/38A GB514715A (en) 1937-05-18 1938-05-14 Sheeting adapted for use as photographic film base and solutions for the manufacture thereof
FR838071D FR838071A (fr) 1937-05-18 1938-05-17 Procédé de fabrication de feuilles cellulosiques et en particulier de supports de films photographiques

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Application Number Priority Date Filing Date Title
US143302A US2245429A (en) 1937-05-18 1937-05-18 Manufacture of photographic film base

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US2245429A true US2245429A (en) 1941-06-10

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DE (1) DE724836C (fr)
FR (1) FR838071A (fr)
GB (1) GB514715A (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2926104A (en) * 1955-06-27 1960-02-23 Goetz Alexander Method of making microporous filter film
US3026571A (en) * 1956-07-04 1962-03-27 Membranfiltergesellschaft G M Method of continuous manufacture of membrane filters
US4203848A (en) * 1977-05-25 1980-05-20 Millipore Corporation Processes of making a porous membrane material from polyvinylidene fluoride, and products
US4203847A (en) * 1977-05-25 1980-05-20 Millipore Corporation Making porous membranes and the membrane products
US5314647A (en) * 1992-07-20 1994-05-24 Eastman Kodak Company Method of making cellulose ester photographic film base
US7186923B2 (en) 1993-05-17 2007-03-06 Electrochemicals, Inc. Printed wiring boards and methods for making them

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE818862C (de) * 1949-12-20 1951-10-29 Rudolf Dr Phil Koeppen Verfahren zur Herstellung von Membranen aus Celluloseester
DE3750353T2 (de) * 1986-06-12 1994-12-08 Mitsui Petrochemical Ind Verfahren zur Herstellung von Celluloseesterfolien.

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2926104A (en) * 1955-06-27 1960-02-23 Goetz Alexander Method of making microporous filter film
US3026571A (en) * 1956-07-04 1962-03-27 Membranfiltergesellschaft G M Method of continuous manufacture of membrane filters
US4203848A (en) * 1977-05-25 1980-05-20 Millipore Corporation Processes of making a porous membrane material from polyvinylidene fluoride, and products
US4203847A (en) * 1977-05-25 1980-05-20 Millipore Corporation Making porous membranes and the membrane products
US5314647A (en) * 1992-07-20 1994-05-24 Eastman Kodak Company Method of making cellulose ester photographic film base
US7186923B2 (en) 1993-05-17 2007-03-06 Electrochemicals, Inc. Printed wiring boards and methods for making them

Also Published As

Publication number Publication date
FR838071A (fr) 1939-02-27
GB514715A (en) 1939-11-15
DE724836C (de) 1942-09-08

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