EP0859811A1 - Compositions de polymere de chlorure de vinylidene et articles irradies prepares a partir desdites compositions - Google Patents

Compositions de polymere de chlorure de vinylidene et articles irradies prepares a partir desdites compositions

Info

Publication number
EP0859811A1
EP0859811A1 EP96941964A EP96941964A EP0859811A1 EP 0859811 A1 EP0859811 A1 EP 0859811A1 EP 96941964 A EP96941964 A EP 96941964A EP 96941964 A EP96941964 A EP 96941964A EP 0859811 A1 EP0859811 A1 EP 0859811A1
Authority
EP
European Patent Office
Prior art keywords
composition
pvdc
multilayer film
aliphatic ester
unsaturated monomer
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.)
Withdrawn
Application number
EP96941964A
Other languages
German (de)
English (en)
Inventor
Douglas E. Beyer
Martin F. Debney
Levi Kishbaugh
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.)
Dow Chemical Co
Original Assignee
Dow Chemical 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 Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0859811A1 publication Critical patent/EP0859811A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2327/00—Polyvinylhalogenides

Definitions

  • VINYLIDENE CHLORIDE POLYMER COMPOSITIONS AND IRRADIATED ARTICLES PREPARED THEREFROM
  • This invention relates to vinylidene chloride polymer (PVDC) compositions and films comprising said compositions. More particularly, this invention relates to vinylidene chloride compositions having improved resistance to color degradation induced by irradiation.
  • PVDC vinylidene chloride polymer
  • Irradiation of PVDC films often improves film properties such as puncture resistance, tensile strength and toughness. However, under most circumstances, irradiation results in substantial discoloration, such as yellowing, of the films.
  • this invention is a composition
  • a composition comprising a mixture of (1) a vinylidene chloride polymer (PVDC) formed from a monomer mixture wherein the major component is vinylidene chloride and the remainder is at least one monoethylenically unsaturated monomer copolymerizable therewith, and (2) an amount of an aliphatic ester compound sufficient to minimize color degradation (formation of color bodies) of the PVDC during and after irradiation of the composition.
  • PVDC vinylidene chloride polymer
  • this invention is a composition
  • a composition comprising a mixture of (1) a vinylidene chloride polymer (PVDC) formed from a monomer mixture wherein the major component is vinylidene chloride and the remainder is at least one monoethylenically unsaturated monomer copolymerizable therewith, an amount of an aliphatic ester compound sufficient to minimize color degradation (formation of color bodies) of the PVDC, and an amount of a color stable violet or blue dye sufficient to mask color bodies formed, during and after irradiation of the composition.
  • PVDC vinylidene chloride polymer
  • this invention is a heat-shrinkable multilayer film comprising a layer of a vinylidene chloride polymer formed from a monomer mixture wherein the major component is vinylidene chloride and the remainder is at least one monoethylenically unsaturated monomer copolymerizable therewith, and containing an amount of an aliphatic ester compound sufficient to minimize color degradation (formation of color bodies) of the PVDC, and or an amount of a color stable violet or blue dye sufficient to mask color bodies formed, during and after irradiation of the composition.
  • the aliphatic ester compounds have been found to minimize color degradation in PVDC films during and after irradiation of the PVDC films while imparting the desirable effects as a processing aid during film extrusion.
  • Vinylidene chloride polymers suitable for use in the present invention are well-known in the art. See, for example, U.S. Patents 3,642,743; and 3,879,359
  • the term "vinylidene chloride polymer” encompasses homopolymers of vinylidene chloride, and also copolymers, te ⁇ olymers. thereof, wherein the major component is vinylidene chloride and the remainder is one or more ethylenically unsaturated monomer copolymerizable with the vinylidene chloride monomer.
  • Monoethylenically unsaturated monomers suitable for use in the present invention are those which can be polymerized with the vinylidene chloride monomers, to form the vinylidene chloride polymers.
  • Examples of monoethylenically unsaturated monomers include alkyl acrylates, alkyl methacrylates, acrylic acid, methacrylic acid, itaconic acid, vinyl chloride, acrylonitrile and methacrylonitrile.
  • the monoethylenically unsaturated monomers are desirably selected from alkyl acrylates and alkyl methacrylates having from 1 to 8 carbon atoms per alkyl group.
  • the alkyl acrylates and alkyi methacrylates preferably have from 1 to 4 carbon atoms per alkyl group.
  • the alkyl acrylates and alkyl methacrylates are most preferably selected from methylacrylates, ethylacrylates, and methyl methacrylates.
  • Most preferred vinylidene chloride polymers include polymers formed from 91 to 96 weight percent vinylidene chloride and from 4 to 9 weight percent of methyl acrylate.
  • the vinylidene chloride polymers are generally formed through an emulsion or suspension polymerization process. Exemplary of such processes are described in U.S. Patents 2,558,728; 3,007,903; 3,642,743; and 3,879,359; and the methods described by R. A. Wessling, in Polyvinylidene Chloride. Gordon and Breach Science Publishers, New York, 1977, Chapter 3.
  • the monomeric materials are emulsified or suspended in an aqueous phase.
  • the aqueous phase contains a surface active agent capable of emulsifying or suspending the monomeric materials in the aqueous phase.
  • the polymerization of the monomeric materials is usually carried out with heating and agitation in the presence of a polymerization initiator. After polymerization is complete, the resultant polymeric material is vacuum stripped. Thereafter, the slurry is cooled down, unloaded and dewatered, and the resin is collected and further dried.
  • the aliphatic ester compounds suitable for use in the present invention for minimizing color degradation in irradiated PVDC films include linear and branched aliphatic ester compounds, polymeric aliphatic esters and mixtures thereof, which are essentially free of epoxy or aromatic functionality and have a molecular weight of from 300 to 8000.
  • Preferred aliphatic ester compounds include acetyl tributyl citrate, acetylated monoglycerides, diesters of adipic, azelaic, sebacic and glutaric acids; polyesters of glycerol and pentaerythritol and polymeric adipates, azelates, sebacates and glutarates.
  • More preferred aliphatic ester compounds are acetyl tributyl citrate, acetylated monoglycerides, dibutyl sebacate and polymeric adipates.
  • the most preferred aliphatic ester compounds are acetylated monoglycerides. These aliphatic ester compounds are well known in the art and are commercially available.
  • the amount of aliphatic ester compound most advantageously employed depends on a variety of factors, such as the specific monomers, in general, the aliphatic ester compound is used in an amount of from 0.2 to 15 weight percent, preferably from 0.5 to 10 weight percent and most preferably from 1 to 4 weight percent, based on the weight of the PVDC.
  • Violet or blue dyes suitable for use in the present invention are the organic dyestuffs which are sufficiently color stable to withstand the acidic processing environment of PVDC extrusion at about 160°C and include the 1-hydroxy-4-aryl-aminoanthraquinones which are color stable.
  • the 1-hydroxy-4-aryl-aminoanthraquinones are known and are described, for example in U.S. Patent 2,419,405.
  • the most preferred violet pigment is commercially known as C.l. Solvent Violet 13, available as MacrolexTM Violet B, a product of Bayer AG and represented by the formula:
  • the amount of violet or blue dye used must be sufficient to mask at least a portion of color bodies developed in the vinylidene chloride polymer composition during irradiation of the composition.
  • the violet or blue dye can be present in an amount of from 0.0005 to 0.05 weight percent, preferably, from 0.0007 to 0.01 weight percent and most preferably, from 0.001 to 0.005 weight percent, based on the weight of the PVDC.
  • the vinylidene chloride polymer composition of the present invention may also contain various additives to impart desirable properties such as, for example, heat stabilizers, light stabilizers, processing aids, and lubricants, but substantially excluding the aromatic or epoxidized processing aids, such as dioctyl phthalate or epoxidized soybean oil, which may not be effective to minimize the color degradation (formation of color bodies) of the PVDC.
  • additives to impart desirable properties such as, for example, heat stabilizers, light stabilizers, processing aids, and lubricants, but substantially excluding the aromatic or epoxidized processing aids, such as dioctyl phthalate or epoxidized soybean oil, which may not be effective to minimize the color degradation (formation of color bodies) of the PVDC.
  • additives is known and several types of each are commercially available.
  • the vinylidene chloride polymer composition of the present invention can be prepared by adding the aliphatic ester compound and/or violet or blue dye to the monomer mix before or during polymerization or to the dry vinylidene chloride polymer by dry blending.
  • the composition is prepared by adding the aliphatic ester compound and/or violet or blue dye to the monomer mix to ensure a more uniform distribution of the aliphatic ester compound and/or violet or blue dye in the resulting polymer.
  • the violet or blue dye can also be added in the form of a concentrate by melt blending the concentrate with the vinylidene chloride composition using typical melt processing equipment such as, for example, two-roll compounding mills, Brabender mixers, Banbury mixers, single screw extruders, twin screw extruders and the like.
  • the concentrate can be prepared by mixing the violet or blue dye with a carrier resin which, preferably, is vinylidene chloride polymer. Methods for preparing the concentrate are well-known in the art.
  • the carrier resin and the violet or blue dye are blended in the melt using conventional melt processing techniques, using typical melt processing equipment such as those mentioned previously.
  • composition is prepared by dry blending
  • the components should be mixed to form a visually uniform admixture.
  • Suitable dry blending equipment includes tumble blenders, Hobart mixers, Welex mixers, and Henschel high intensity mixers.
  • the vinylidene chloride polymer composition of the present invention can be coextruded into a multilayer film with conventional coextrusion machines.
  • Heat-shrinkable multilayer films employed in packaging meats can be produced by coextruding the multiple layers into a primary tube, and then biaxially stretching the tube by known techniques, such as that described in U.S. Patent 3,555,604, to form a heat-shrinkable film.
  • the biaxially-stretched film is then irradiated to a dosage level of up to about 5 megarads by passing it, for example, through an electron beam irradiation unit or Co-60 gamma radiation source.
  • the multilayer film can have one or more layers comprising the vinylidene chloride polymer composition of the present invention and one or more layers comprising a polyolefin, such as polyethylene.
  • the vinylidene chloride polymer layer can be sandwiched between two or more layers of a polyolefin.
  • the multilayer film can also have a glue layer disposed between a vinylidene chloride polymer layer and an adjacent polyolefin layer.
  • the glue layer typically comprises ethylene vinyl acetate or any polymer or copolymer having good adhesive properties.
  • the PVDC compositions of the present invention can also be fabricated into articles using conventional fabrication techniques such as injection molding, extrusion molding, calendering, thermoforming, and lamination techniques.
  • Articles formed therefrom include blown and cast monolayer and multilayer films, foam sheets, tubes, pipes, fibers and the like. Examples of such articles include flexible and rigid containers used for the preservation of food, drink, medicine and other perishables.
  • Fabricated articles from the present invention may be irradiated for purposes of sterilization, improving toughness, improving solvent resistance and the like. Irradiation with about 1 to 20 Mrad is accomplished, for example, by passing the articles through an electron beam irradiation unit or Co-60 irradiation source. Irradiation may be done during or after fabrication of the article.
  • a multilayer film sample (Sample 1) composed of outer layers of polypropylene and a core layer of 92.25 weight percent vinylidene chloride/7.75 weight percent methyl acrylate, which contained 4.0 weight percent dibutyl sebacate and 0.2 weight percent epoxidized soybean oil, was produced by conventional coextrusion technique. Prior to irradiation, the film was annealed at 120°F for 3 hours to ensure full crystallization of the vinylidene chloride copolymer. The coextruded film was irradiated with 4 Mrad Co-60 gamma radiation at ambient temperature.
  • Example 2 Two multilayer film samples (Samples 2 and 3) composed of outer layers of polypropylene and a core layer of 92.25 weight percent vinylidene chloride/ .75 weight percent methyl acrylate were prepared and tested (irradiated and color measurement taken) as in Example 1, except that 4 percent acetyl tributyl citrate (ATBC) is added in Sample 2 and 4 percent Eastman EPZ, an acetylated monoglyceride commercially available from Eastman Chemical, was added in Sample 3, instead of the 4 percent dibutyl sebacate. Color measurements of the irradiated films were taken as in Example 1 and the results are shown in Table I.
  • ATBC acetyl tributyl citrate
  • Eastman EPZ an acetylated monoglyceride commercially available from Eastman Chemical
  • Example A A multilayer film sample (Sample A) comprising a 92.25 vinylidene chioride 7.75 methyl acrylate copolymer core layer containing 1.2 weight percent epoxidized soybean oil was prepared and tested as in Example I. The results are shown in Table I.
  • Multilayer film samples comprising a 92.25 vinylidene chloride/7.75 methyl acrylate copolymer core layer were prepared and tested as in Comparative Example A except that Samples B and C contained 2.2 weight percent and 4.2 weight percent epoxidized soybean oil, respectively. The results are shown in Table I.
  • the multilayer film of this comparative example was the same as that of Comparative
  • Water, suspending agent (MethocelTM K4M, a product of The Dow Chemical Company) and buffer at a ratio of approximately 1.00/.0009/0.0093 were charged into a reactor.
  • an organic phase consisting of methyl acrylate, vinylidene chloride, t-butyl per-2-ethylhexanoate, and violet pigment at a ratio of 7.72/92.280.369/0.0005.
  • the ratio of water phase to organic phase was 1.25/1.00
  • the violet pigment was an anthraquinone dyestuff, MacrolexTM Violet B (C.l. Solvent Violet 13), a product of Bayer AG and described in U.S. Patent 2,419,405.
  • the reaction vessel was sealed and placed in a water bath at 25°C and mixing is begun. The temperature was then raised to a maximum of 84°C over the course of 630 minutes to allow polymerization. The resulting polymer slurry was then cooled, dewatered and dried at 80°C to remove residual water and monomers. The product was then flash molded at a temperature of 165°C for 1 minute at 1000 psi followed by 2 minutes at 20,000 psi. The yellowness of the flash molding as determined according to ASTM method D 1925-70 is shown in Table II.
  • a polymer sample was prepared in the same manner as shown in Example 4 except the Macrolex Violet B dye is omitted.
  • the sample was flash molded and tested in the manner shown in Example 4. The yellowness results are shown in Table II.
  • Macrolex Violet B dye was substituted with an equal amount of Macrolex Violet 3R (Comparative Example F) or Macrolex Blue RR (Comparative Example G) dyes.
  • Macrolex Violet 3R and Macrolex Blue RR were examples of dyes which are not sufficiently color stable to withstand the acidic processing environment of PVDC extrusion at about 160°C.
  • Macrolex Violet 3R a product of Bayer AG, was commercially known as C. I. Solvent Violet 36 and represented by the formula:
  • Macrolex Blue RR also a product of Bayer Ag, is commercially known as C. I. Solvent Blue 97 and represented by the formula:
  • Example 5 A multilayer film sample composed of outer layers of polypropylene and a core layer of
  • 92.25 weight percent vinylidene chloride/7.75 weight percent methyl acrylate which contained 1.4% Eastman EPZ plasticizer, an acetylated monoglyceride commercially available form Eastman Chemical, was produced by conventional coextrusion technique. Prior to irradiation, the film was annealed at 120°F for 3 hours to ensure full crystallization of the vinylidene chloride copolymer. The coextruded film was irradiated with 4 Mrad Co-60 gamma radiation at ambient temperature. The PVDC film layer was then separated from the polypropylene layers.
  • Example 5 2000 grams of the vinylidene chloride copolymer described in Example 5 was added to a Prodex high-intensity mixer. Then 1.00 gram Macrolex B dye was added with mixing over approximately 1 1/2 minutes, resulting in a uniform color concentrate. This color concentrate was then mixed in a tumble blender with an additional quantity of the vinylidene chloride copolymer described in Example 5 at a ratio of 2/98.

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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)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Composition comprenant un mélange (1) d'un polymère de chlorure de vinylidène obtenu à partir d'un mélange de monomères, dans lequel le constituant principal est chlorure de vinylidène et le reste est au moins un monomère éthylèniquement insaturé copolymérisable avec ledit polymère et (2) une quantité d'un composé d'ester aliphatique suffisante pour diminuer au maximum la dégradation de la couleur (formation de masses colorées) du polymère de chlorure de vinylidène pendant et après l'irradiation de la composition, qu'on utilise pour préparer un film thermorétractable à couches multiples. Cette composition peut également contenir une quantité d'un colorant stable violet ou bleu, afin de masquer les masses colorées générées pendant et après l'irradiation de ladite composition.
EP96941964A 1995-11-09 1996-11-05 Compositions de polymere de chlorure de vinylidene et articles irradies prepares a partir desdites compositions Withdrawn EP0859811A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US55543995A 1995-11-09 1995-11-09
US555439 1995-11-09
PCT/US1996/017733 WO1997017399A1 (fr) 1995-11-09 1996-11-05 Compositions de polymere de chlorure de vinylidene et articles irradies prepares a partir desdites compositions

Publications (1)

Publication Number Publication Date
EP0859811A1 true EP0859811A1 (fr) 1998-08-26

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP96941964A Withdrawn EP0859811A1 (fr) 1995-11-09 1996-11-05 Compositions de polymere de chlorure de vinylidene et articles irradies prepares a partir desdites compositions

Country Status (7)

Country Link
EP (1) EP0859811A1 (fr)
JP (1) JP2000500511A (fr)
KR (1) KR19990067401A (fr)
CN (1) CN1202189A (fr)
AU (1) AU1116697A (fr)
CA (1) CA2236147A1 (fr)
WO (1) WO1997017399A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7371804B2 (en) 2004-09-07 2008-05-13 Ophthonix, Inc. Monomers and polymers for optical elements
US8000013B2 (en) * 2004-09-07 2011-08-16 Ophthonix, Inc. Tinted lenses that correct for high order aberrations
US7701641B2 (en) * 2006-03-20 2010-04-20 Ophthonix, Inc. Materials and methods for producing lenses
WO2015069418A1 (fr) * 2013-11-11 2015-05-14 Dow Global Technologies Llc Procédé de production d'un hétéropolymère à base de chlorure de vinylidène
JP6191809B1 (ja) * 2015-11-30 2017-09-06 日立化成株式会社 食品包装用フィルム

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2429165A (en) * 1945-05-04 1947-10-14 Dow Chemical Co Vinylidene chloride polymer compositions stable to light
JPS4987765A (fr) * 1972-12-26 1974-08-22
JPS5333250A (en) * 1976-09-08 1978-03-29 Kureha Chem Ind Co Ltd Vinylidene chloride resin film
US6291565B1 (en) * 1994-05-19 2001-09-18 The Dow Chemical Company Food packaging film
JP3523340B2 (ja) * 1994-08-30 2004-04-26 呉羽化学工業株式会社 塩化ビニリデン系重合体成形物
US5538770A (en) * 1994-11-18 1996-07-23 W. R. Grace & Co. -Conn. Vinylidene chloride film with controlled gas permeability

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9717399A1 *

Also Published As

Publication number Publication date
CN1202189A (zh) 1998-12-16
AU1116697A (en) 1997-05-29
CA2236147A1 (fr) 1997-05-15
WO1997017399A1 (fr) 1997-05-15
JP2000500511A (ja) 2000-01-18
KR19990067401A (ko) 1999-08-16

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