US3309218A - Flexible cellulosic articles having ultra-violet light shielding properties and method of producing them - Google Patents

Flexible cellulosic articles having ultra-violet light shielding properties and method of producing them Download PDF

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Publication number
US3309218A
US3309218A US247954A US24795462A US3309218A US 3309218 A US3309218 A US 3309218A US 247954 A US247954 A US 247954A US 24795462 A US24795462 A US 24795462A US 3309218 A US3309218 A US 3309218A
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United States
Prior art keywords
film
ultra
ferrie
violet light
light shielding
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Expired - Lifetime
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US247954A
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English (en)
Inventor
Jr Wilbur T Brader
Thomas E Bradley
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FMC Corp
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FMC Corp
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Publication date
Priority to NL300024D priority Critical patent/NL300024A/xx
Application filed by FMC Corp filed Critical FMC Corp
Priority to US247954A priority patent/US3309218A/en
Priority to FR951681A priority patent/FR1386283A/fr
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Publication of US3309218A publication Critical patent/US3309218A/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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least 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
    • C08J2301/00—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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/918—Material abnormally transparent
    • 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]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31884—Regenerated or modified cellulose
    • Y10T428/31891—Where addition polymer is an ester or halide

Definitions

  • This invention relates todliblehhghjop articles which afford improved, ultra-yiolet ⁇ sht pro cction and a method for producing the same, More particularly, it' relates to hydrophilic eellulosic films which may or may not have an appreciable orange color and which demonstrate substantially reduced ⁇ transmission of light rays in the ultra-violet range.n
  • Packaging materials which provide improved shielding of ultra-violet light sensitive materials, particularly fatty or oily foods, are in demand. ln many instances it is preferred or required that the packaging materials be clear and colorless while affording the desired U.V. protection.
  • Transparent non-fibrous cellulosic sheets, Stich as regenerated cellulose films, are extensively used for food wrapping including bakery products and meat products.
  • Fibrous cellulosic casings are used extensively to encase ground meat products. It is essential that any shielding and/'or coloring agent employed for these wrapping materials remain in or on the sheets and not migrate into the food contained therein. While a problem exists in obtaining a shielding and/or coloring agent which has the necessary stability under moist conditions, it is also extremely difficult to obtain such a material which meets the safety standards of state 'and Federal food and drug agencies.
  • Colored pack iging material is often used to provide a d ⁇ stinctivc package for the wrapping of foods and other items. ln addition, the color may act to protect the packaged item from damaging low wave length light 'tlVCS.
  • lt is an object of this invention to provide tlexible ccllulosic material ⁇ containing an ultra-violet light shielding substance which is stable iutlie presence of moisture and ⁇ has either yno appreciable'color or a commercially desirable orangt color.
  • lt is another object of the invention to provide a method of obtaining ultra-violet light shielding, nontibrousfcellulosic sheets.
  • lt is another object of this invention to provide a method for obtaining a clear orange-colored regenerated cellulose film which is stable in the presence of aqueous and olcaginous mediums and has excellent ultra-violet light shielding properties.
  • lt is another object of this invention to provide a package including a wrapping sheet having improved ultra-violet light shielding properties.
  • ferrie oxide or ferrie hydroxide ⁇ and a method of producing a hydrophilic flexible cellulosic article having improved ultra-violet light shielding properties which comprises treating said article with an aqueous solution of an inorganic water-soluble lerric salt and then immersing said article in an aqueous solution maintained at a pH. of at least 5.
  • this invention includes a package comprising ultra-violet light sensitive material and a wrapping sheet at least partially encompassing said material comprising a hydrophilic flexible cellulosic sheet uniformly impregnated with ferrie hydroxide.
  • Flexible cellulosic articles of this invention include, for example, fibrous and non-fibrous sheets, foils, hlms, pelliclesribbons, monof'ilament, multifllamcnt yarn, staple fiber, cord, and similar articles.
  • the hydrophilic cellulosic materials are regenerated cellulose, cellulose ethers including carboxy-methyl cellulose, hydrophilic cellulose esters, cotton, paper, etc.
  • the preferred form of this invention concerns clear, non-fibrous hydrophilic cellulosic sheets and brous base sheets impregnated with hydrophilic ccllulosic film-forming material.
  • Water-soluble inorganic ferrie salts are well known substances and include for example, ferrie chloride, ferrie Of these materials ferrie chloride is preferred since it gives thc best results under varying process conditions.
  • the flexible cellulosic article is introduced into a bath of the aqueous solution of inorganic water-soluble ferrie salt which is maintaiucd'at a salt concentration ranging from about 0.01 to about 15% depending upon the desired U.V. protection and/or shade of color which is to be produced on the finished article.
  • a concentration of about 5% will produce a conventional amber-colored hlm while a concentration of less than about 0.2% will produce a film having UN. light shielding properties without appreciable color.
  • the cellulosic article is first wet prior to treatment with the ferrie salt solution.
  • the ferrie salt solution In the case of regenerated cellulose hlm, for example, it is convenient to run the wet gel film into a ferric Salt bath as it comes from the film spinning machine.
  • the temperature of the ferrie salt bath is not critical and generally is maintained at about room temperature.
  • the immersion time for the eellulesic material in the ferrie salt bath can range from as low as about l second to as high as about 60 seconds in order to produce successful results.
  • the excess solution is removed with rollers, scrapcrs, doctor blades and the like from the cellulosic article and it is then inuncrsed in an aqueous solution which is maintained at a pi-l ol' at least 5 and preferably at least l0.
  • a pl-l of 5 it can be seen that the hydrated ferrie oxide, or ferrie hydroxide begins to precipitate within the ccllulosic material ⁇ lt is necessary, however, for a commercially suitable process that the pl'l of the second bath be maintained at at least l0 or higher. This is accomplished by continually introducing a basic matcrial or solution into the second bath.
  • This basic material preferably includes an alkali or alkaline earth metal basic salt or hydroxide, and most preferably sodium hydroxide.
  • Other basic materials include for example, sodium acctate, sodium carbonate. ammonium hydroxide, potassium hydroxide, calcium hydroxide, ctc. Care must be taken to keep the concentration of the basic material low enough to prevent hydrolysis of the cellulosic material.
  • the temperature of'this second bath is not critical and is generally maintained between room temperature and about 40 C The article is permitted to remain in the second bath for at least seconds up to about 30 seconds to precipitate ferrie oxide within it. After removal from the second bath the excess basic material can be washed olf with rcopious amounts of fresh water.
  • plasticization may be accomplished after removal of excess base therefrom.
  • plasticizcrs including glycerol are useful and are incorporated in an aqueous hath through which the cellulosic sheet is i'un.
  • Anchoring agents which promote adhesion -between the base film and polymeric film-forming coatings which may be applied, are conveniently incorporated in the plasticizing bath.
  • Anchoring agents include, for example, melamine-formaldehyde precondensates, ureatormaldehyde prccondensates, polyalkylenimines, epoxy resins, etc. 1f these materials are not water-soluble they may be applied to the base sheet after drying.
  • the polymeric film-forming coatings which may be used for this invention include, for example, copolymers of at least 50% vinylidene chloride and at least one other monomer copolynierizable therewith, vinylchloride-vinyl acetate copolymers, nitrocellulose, polyalkylcnes such as polyethylene and polypropylene, etc. These coatings may :he applied by melt extrusion or from solutions, including lacquers and latexes, to the colored cellulosic base sheet.
  • Example I A wet gel regenerated cellulose film is first treated in a hath containing an aqueous solution of 5% by weight of ferrie chloride at a bath temperature of 25 C. The film is immersed in the bath for l5 seconds, then removed, and the excess bath solution removed by ruiming the film through a pair of squeeze rollers. The wet film is then treated in a bath containing an aqueous solution of 2% by weight of sodium hydroxide at a bath temperature of 50 C. After 15 seconds immersion the film is removed from the bath. The film is washed many times with copious amounts of fresh water to remove any sodium hydroxide solution. The film has a clear, uniform amber color.
  • This film has a clear, uniform amber color. Films produced substantially as described above show no visible bleeding in water at 50 C. when immersed for one minute.
  • the coating was prepared from a coating lacquer comprising about 20% of a copolymer of by weight of vinylideiie chloride and 10% of aerylonitrile dissolved in a mixture of about 60 parts tetrahydrofuran and 40 parts of toluene. In addition to the copolymer, the coating also contained small proportions of clay, wax and an alkyd resin to promote better surface characteristics.
  • the above coating composition and lacquer coating technique are conventionally used to coat cellophane hlm. Anchorage tests were run on the Saran coated, colored regenerated cellulose film and Saran coated, uncolored film for comparison with the following results.
  • the Tape Pull test is a incasure of adhesion strength and involves impressing a 4 inch by 1 inch cellophane adhesive tape on the coating and then tearing the tape from the coated surface. The amount of coating removed is noted and the adhesion property rated.
  • the Heat Seal test is well known in the coated film art and, in general, involves heat sealing two strips of the same test film together and then measuring the strength necessary to pull them apart on a standard test machine.
  • the Wet Anchorage test is a procedure used to determine how well the coating will remain adhered to the -base film after exposure to excess moisture. ln the test, the sample film is immersed in water at room temperature for 17 hours. The sample is then removed and rubbed vigorously between the fingers in an attempt to remove the coating.
  • Example Il Wet gel regenerated film samples were dipped respectively in aqueous baths of low concentrations of FeCl3 ranging from 0.05 to l.0% of the anhydrous saltl The gel films were dipped in these baths at 25 C. for l5 seconds. Excess solution was removed by blotting between paper towels and running the films through a wriiiger. They were then immersed in a 2% aqueous sodium hydroxide bath at 50 C. for 15 seconds. The lilms were then thoroughly water washed,'plasticized and anchor coated with a second treatment in a 5% glycerol bath containing 0.26% melamine-formatdehyde precondensate. They were then air dried in wooden frames.
  • FIG. 2 of the drawing a comparison of the U.V. protection Obtained from certain wrapping materials is shown.
  • the direct dyed Tango film is a commercially available regenerated cellulose film dyed to an orangetan color with an organic dye.
  • Glassine paper is a commercially available material prepared by the addition of a urea-formaldehyde resin to a thin transparent. paper.
  • the new Tango hlm is an article of this invention comprising regenerated cellulose film impregnated with Fe(OH)3 hy rst treating with a 5% aqueous solution of FeCl3 and then with 2% aqueous solution of sodium hydroxide.
  • the high degree of U.V. protection obtained with the film of this invention is entirely unexpected.
  • Packages of fatty and oily food products prepared with the Fe(OH)3 impregnated tilms of this invention provide appreciable improvement in the protection ofthe wrapped food from the harmful cfTects of alta-violet light radiation when exposed to direct sunlight over packages prepared with untreated films of the sante base material.
  • Fe(OH)3 impregnated sheets may be used to overwrap packages or may he placed in direct. contact with the food product. These films may also be used as the transparent window material in packages or boxes manufactured with opaque packaging materials.
  • A. ⁇ vrappng material for an ultra-violet light sensitive article comprising a clear, non-fibrous regenerated Cil cclltrlose shect uniformly impregnated with ferrie hydroxide in an amount sullicient to improve thc ultraviolet light shielding properties of said sheet.
  • the sheet of claim 1 having a film-forming polymer coating on the surface thereof.
  • the sheet of claim 2 -wherein the film-forming polymer is a copolymer of at least of vinylidcne chloride and at least one other monomer copolymerizable therewith.
  • a method oi preparing a flexible hydrophilic, nonfibrous cellulosic sheet having improved ultra-violet light shielding properties which comprises treating said article with an aqueous solution of an inorganic water-soluble ferrie salt and then immcrsing said article in an inorganic water-soluble ferrie salt and then immcrsing said article in an aqueous solution maintained at a pH of: at least 5 to precipia-te ferrie hydroxide in situ.
  • a method of preparing a flexible hydrophilic, nontibrous cellulosic sheet having improved ultra-violet light shielding properties which comprises treating said sheet with an aqueous solution of an inorganic water-soluble ferrie salt, and then immcrsing said sheet in a bath containing an aqueous solution of a water-soluble compound selected from the group consisting of alkali and alkaline earth metal basic salts and hydroxides, said solution maintained ata pH of at least l0.
  • a continuous method of preparing a flexible, hydrophilic, non-fibrous cellulosic sheet having improved ultraviolet light shiclding properties which comprises treating said sheet with an aqueous solution containing from about i 0.01 to about 10% by weight of ferrie chloride, removing excess ferrie chloride solution from the sheet, and then immcrsing said sheet in an aqueous solution containing about 2% by weight of sodium hydroxide and maintaining the sodium hydroxide solution at a pl-t of at least 10.

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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)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
US247954A 1962-12-28 1962-12-28 Flexible cellulosic articles having ultra-violet light shielding properties and method of producing them Expired - Lifetime US3309218A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
NL300024D NL300024A (enExample) 1962-12-28
US247954A US3309218A (en) 1962-12-28 1962-12-28 Flexible cellulosic articles having ultra-violet light shielding properties and method of producing them
FR951681A FR1386283A (fr) 1962-12-28 1963-10-24 Procédés de préparation de films cellulosiques et nouveaux produits ainsi obtenus

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US247954A US3309218A (en) 1962-12-28 1962-12-28 Flexible cellulosic articles having ultra-violet light shielding properties and method of producing them

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3460960A (en) * 1965-05-03 1969-08-12 Owens Illinois Inc Coated glass and method of making same
US3922420A (en) * 1974-05-31 1975-11-25 Rca Corp Method of making a semi-transparent photomask
US3955017A (en) * 1971-11-26 1976-05-04 Imperial Chemical Industries Limited Method of coating metal phosphates on organic polymeric substrates
US4289171A (en) * 1978-05-26 1981-09-15 Hoechst Aktiengesellschaft Tubular packaging sheath and process for its manufacture

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2380775A (en) * 1942-04-09 1945-07-31 Meyer Hans Compound fabrics and process for producing the same
US2461522A (en) * 1941-08-14 1949-02-15 Rile Coe Filter Process Inc Packaged meat and like products and process thereof
GB730601A (en) * 1952-10-07 1955-05-25 Crosland & Pickstone Ltd Improvements in processes or dyeing materials with inorganic metallic compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2461522A (en) * 1941-08-14 1949-02-15 Rile Coe Filter Process Inc Packaged meat and like products and process thereof
US2380775A (en) * 1942-04-09 1945-07-31 Meyer Hans Compound fabrics and process for producing the same
GB730601A (en) * 1952-10-07 1955-05-25 Crosland & Pickstone Ltd Improvements in processes or dyeing materials with inorganic metallic compounds

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3460960A (en) * 1965-05-03 1969-08-12 Owens Illinois Inc Coated glass and method of making same
US3955017A (en) * 1971-11-26 1976-05-04 Imperial Chemical Industries Limited Method of coating metal phosphates on organic polymeric substrates
US3922420A (en) * 1974-05-31 1975-11-25 Rca Corp Method of making a semi-transparent photomask
US4289171A (en) * 1978-05-26 1981-09-15 Hoechst Aktiengesellschaft Tubular packaging sheath and process for its manufacture

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NL300024A (enExample) 1900-01-01

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