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WO1996034050A1 - Composition de resine copolymere de chlorure de vinylidene, film obtenu a partir de cette composition, procede d'extrusion destine a cette composition et procede d'elaboration du film - Google Patents

Composition de resine copolymere de chlorure de vinylidene, film obtenu a partir de cette composition, procede d'extrusion destine a cette composition et procede d'elaboration du film Download PDF

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Publication number
WO1996034050A1
WO1996034050A1 PCT/JP1996/001118 JP9601118W WO9634050A1 WO 1996034050 A1 WO1996034050 A1 WO 1996034050A1 JP 9601118 W JP9601118 W JP 9601118W WO 9634050 A1 WO9634050 A1 WO 9634050A1
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WO
WIPO (PCT)
Prior art keywords
vinylidene chloride
copolymer
chloride copolymer
mass
resin composition
Prior art date
Application number
PCT/JP1996/001118
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English (en)
Japanese (ja)
Inventor
Katsuhiko Sugeno
Yoshiharu Nishimoto
Original Assignee
Kureha Chemical Industry Co., Ltd.
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 Kureha Chemical Industry Co., Ltd. filed Critical Kureha Chemical Industry Co., Ltd.
Priority to JP53235596A priority Critical patent/JP3931994B2/ja
Publication of WO1996034050A1 publication Critical patent/WO1996034050A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/08—Homopolymers or copolymers of vinylidene chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/08—Homopolymers or copolymers of vinylidene chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene

Definitions

  • the present invention relates to a resin composition containing a vinylidene chloride copolymer, a method for extruding the same, a film formed therefrom, and a method for producing the film. More specifically, a resin composition containing a vinylidene chloride copolymer comprising a mixed vinylidene chloride resin (A) and a specific copolymer (B), a mixed vinylidene chloride resin (A) or a vinylidene chloride copolymer Extrusion processing method of vinylidene chloride copolymer-containing resin composition consisting of unified ( ⁇ ') and specific copolymer ( ⁇ ), extrudability formed therefrom, and suitability for packaging machine, cold resistance, gas barrier A film with excellent properties.
  • Background art
  • vinylidene chloride copolymers have excellent properties of shielding gas such as water vapor and oxygen, and are therefore extruded and used for food packaging films.
  • shielding gas such as water vapor and oxygen
  • ordinary vinylidene chloride-based copolymers themselves have poor thermal stability and are liable to be thermally decomposed, so that extrusion processing is unstable, and it is difficult to obtain a uniform packaging film utilizing the characteristics. Therefore, the following various improvements have been conventionally proposed.
  • Japanese Patent Publication No. 40-16141 discloses a molding containing an elastic substance such as a vinylidene chloride polymer and a copolymer of ethylene and vinyl alcohol or a rubbery substance in an amount of 2 to 20% by weight. Compositions are described.
  • Japanese Unexamined Patent Publication (Kokai) No. 55-108442 discloses a polyvinylidene chloride copolymer of 60 to 95% by weight, a vinyl acetate content of 5 to 18% by weight and a melt flow of about 0.1 to : A copolymer of ethylene and vinyl acetate for 1.0 dg Z Films comprising from about 5 to about 40% by weight are described.
  • Japanese Patent Application Laid-Open No. 62-72732 describes a melt-processable blend comprising a vinylidene chloride terpolymer, an olefin polymer and a compatibilizing polymer.
  • Japanese Unexamined Patent Publication (Kokai) No. 11131628 discloses an olefin copolymer comprising about 70 to about 97% by weight of vinylidene chloride copolymer and about 15 to about 3% by weight of acrylic acid or methacrylic acid.
  • An inflated film comprising a blended polymer comprising from about 0 to about 15% by weight of an olefin copolymer which is 30 to about 3% by weight and about 30 to about 3% by weight of vinyl acetate is described.
  • Japanese Patent Publication No. 3-5303290 discloses vinylidene chloride interpolymer and about 0.01 to about 0.5% by weight of oxidized polyethylene, oxidized polypropylene or a mixture thereof.
  • JP-A-3-35043 proposes a composition comprising a low weight average molecular weight vinylidene chloride copolymer and about 0.01 to 6% by weight of a processing aid.
  • U.S. Pat. Nos. 4,798,751 propose a mixture of vinylidene chloride copolymers having different copolymer compositions.
  • Japanese Patent Application Laid-Open No. Sho 61-2012 discloses the content of the methyl acrylate component of the vinylidene chloride-methyl acrylate copolymer and the weight average molecular weight of the copolymer (70,000 to 250,000). Improvements in a molding method using a melt extrusion method characterized by using a vinylidene chloride-methyl acrylate copolymer having a content of a copolymer having a molecular weight of 20,000 or less have been proposed.
  • a vinylidene chloride resin As described above, when various resins and additives are mixed to improve the extrudability of vinylidene chloride copolymer, it is required for films such as suitability for packaging machine, cold resistance, and gas barrier property. Often degrade other film properties, There is a need for a vinylidene chloride resin provided.
  • a method of suppressing heat generation of the resin is employed. For this purpose, for example, it is conceivable to reduce the degree of polymerization of the resin or to use a large amount of additives. If the degree of polymerization of the resin is reduced, PVDC (abbreviation for vinylidene chloride copolymer) itself becomes brittle and the cold resistance is reduced. Also, the use of a large amount of additives lowers gas barrier uniformity.
  • the extrudability of the vinylidene chloride copolymer resin is closely related to the suitability for packaging machines.
  • the fluctuation of the extrusion motor load is large, and the amount of extrusion is uneven, and the thickness of the film in the flow direction is uneven.
  • the film is melted too much when sealing in areas where the film is too thin, resulting in pinhole breakage, and trouble where the film is not sealed is generated in areas where the film is too thick.
  • decomposed substances flow out of the die outlet during extrusion, and these decomposed substances dispersed in the film induce conduction of the seal electrode of the packaging machine capable of high-frequency welding, and the film is finely broken by sparks to form pinholes.
  • the amount of extrusion changes partially due to the decomposition products adhering to the die outlet, causing partial thickness unevenness in the width direction of the film, preventing the seal portion from welding or the film from running evenly. May not be possible.
  • the present invention is directed to a resin composition containing a vinylidene chloride copolymer, which solves the above problems, excels in extrudability, and provides a film that is well balanced with respect to suitability for packaging machinery, cold resistance, and gas barrier properties.
  • An object of the present invention is to provide an extrusion method using a resin composition containing a vinylidene copolymer, a film obtained therefrom, and a method for producing the film.
  • the present inventors have developed a vinylidene chloride copolymer-containing resin composition
  • a vinylidene chloride copolymer-containing resin composition comprising a mixed vinylidene chloride resin (A) in which specific vinylidene chloride copolymers having different reduced viscosities are mixed at a specific ratio and a specific copolymer (B).
  • the product has excellent extrusion processability, and the film formed therefrom has an excellent balance in terms of suitability for packaging machinery, cold resistance, and gas barrier properties, and forms a film from the vinylidene chloride copolymer-containing resin composition.
  • the present inventors have found that the above characteristics can be further improved by using a vacuum hopper when performing the present invention.
  • a first aspect of the present invention is that a mixed vinylidene chloride resin (A) composed of at least two kinds of vinylidene chloride copolymers (A) (100 parts by mass) and ethylene and vinyl acetate copolymer ( ⁇ ,). Ethylene and acrylic acid, methacrylic acid Or at least one copolymer (B) selected from a copolymer ( ⁇ 2 ) and an MBS resin (B 3 ) with an alkyl ester thereof; a vinylidene chloride copolymer comprising: 0 to 20 parts by mass
  • An object of the present invention is to provide a resin composition and a film formed therefrom.
  • the second vinylidene chloride copolymer of the present invention and (Alpha '), ethylene and vinyl acetate copolymer polymer (beta,), ethylene and acrylic acid, methacrylic acid or copolymers thereof with Arukirue ester (beta 2) and at least one copolymer (B) because comprising vinylidene chloride copolymer-containing resin composition consists of supplying to the extruder via a vacuum e wrapper extruded selected from MBS resin (B 3) It provides a way.
  • the third aspect of the present invention is a method for producing a film comprising the following steps.
  • A et chosen vinylidene chloride copolymerization
  • B ethylene and vinyl acetate copolymer
  • B 2 copolymer of ethylene
  • the vinylidene chloride copolymer (A and the vinylidene chloride copolymer (A 2 )) used in the present invention are copolymers of vinylidene chloride and at least one monoethylenically unsaturated monomer copolymerizable with vinylidene chloride.
  • the content of the monoethylenically unsaturated monomer in the copolymer is about 40 to about 2% by mass, and preferably about 35 to about 4% by mass in terms of balance between extrudability and gas barrier property.
  • Monoethylenically unsaturated monomers include vinyl chloride, vinyl acetate, vinyl propionate, alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, acrylonitrile, methacrylonitrile, and acrylamide. , Vinyl alkyl ether, vinyl alkyl ketone, acrolein, aryl ester and ether, butadiene, The vinylidene chloride copolymers (A and (A 2 ) may be terpolymers obtained by copolymerizing two or more of these monoethylenically unsaturated monomers.
  • vinyl chloride alkyl acrylate having 1 to 8 carbon atoms in the alkyl group and alkyl methacrylate, for example, methyl acrylate, ethyl acrylate, methyl methacrylate Vinyl chloride is more preferable because it is easy to balance the extrudability with the gas barrier property.
  • the vinylidene chloride copolymer (A and vinylidene chloride copolymer (A 2 ) are easily melted uniformly in the extruder, and undesired fish eyes are formed due to decomposition or unmelting of the resin, which is not desirable in the quality of the molded film. (A and
  • the vinylidene chloride copolymer is a copolymer of vinylidene chloride and vinyl chloride
  • the vinylidene chloride copolymer (A 2 ) is also preferably a copolymer of vinylidene chloride and vinyl chloride.
  • the vinylidene chloride copolymer (Alpha,) and preferably to be a vinylidene copolymer Polymer chloride (Alpha 2) is a binary copolymer of respective vinylidene chloride and vinyl chloride is uniform melting of the resin .
  • the composition ratio of vinylidene chloride in the vinylidene chloride copolymer (A) is larger than the composition ratio of vinylidene chloride in the vinylidene chloride copolymer (A 2 ) in terms of extrusion processability and film cold resistance.
  • the vinylidene chloride copolymer ( ⁇ ,) preferably has a reduced viscosity of 0.048 or more, and is preferably used in the range of 0.048 to 0.080.
  • the reduced viscosity of the vinylidene chloride copolymer ( ⁇ ,) is preferably in the range of 0.05 to 0.080, more preferably 0.055 to 0.075, in view of suitability for packaging machine, cold resistance, and stretchability.
  • the vinylidene chloride copolymer (A 2 ) preferably has a reduced viscosity of less than 0.048, more preferably 0.025 to less than 0.048, and particularly preferably less than 0.035 to 0.045.
  • the film has cold resistance, and the vinylidene chloride copolymer-containing resin composition
  • Vinylidene chloride copolymer (A is an extruder that suppresses heat generation in the extruder, reduces resin adhesion and decomposition at the die outlet, and reduces fluctuations in the motor load of the extruder.
  • the mixing ratio of the copolymer (A 2 ) is preferably less than 50% by mass, more preferably 3 to 25% by mass, and most preferably 5 to 25% by mass based on 100% by mass of the vinylidene chloride copolymer in total. Range.
  • the copolymer (B) is a copolymer of ethylene and vinyl acetate copolymer ( ⁇ ,), ethylene and acrylic acid, methacrylic acid or their alkyl esters (especially alkyl esters having 1 to 4 carbon atoms). It is at least one member selected from the group consisting of coalesced ( ⁇ 2 ) and MBS resin (B 3 ).
  • the copolymers ( ⁇ ,) and ( ⁇ 2 ) have an ethylene content of 65 to 85% by mass, more preferably 75 to 80% by mass. In order to maintain the transparency of the formed film, the ethylene content is preferably 85% by mass or less. In view of the stability of the motor load of the extruder and the gas barrier property of the formed film, the ethylene content is 65% by mass. The above is preferred.
  • the copolymer (beta) is of the mixture, in order to increase the compatibility with the mixed vinylidene chloride resin (Alpha), adding a small amount of ethylene content 65 mass% less than the copolymer (beta or (beta 2) can do.
  • the MBS resin is mainly a butadiene homopolymer or butadiene described in JP-B-46-19550, and any one of styrene, methacrylic acid ester, acrylyltritriol, and vinylidene chloride alone or optionally.
  • the mixing ratio of the two is in the range of 0.1 to 20 parts by mass, preferably 0.5 to 5 parts by mass, more preferably 100 to 100 parts by mass of the copolymerized vinylidene chloride resin (A). Is in the range of 0.7 to 1.5 parts by mass.
  • the mixing ratio of the copolymer ( ⁇ ) is more than 20 parts by mass, the motor load of the extruder fluctuates and becomes unstable, and the extrusion processability such as an increase in the adhered decomposition products at the die outlet decreases. Conversely, if the mixing amount is less than 0.1 part by mass, the outflow of the decomposition product increases, and it is difficult to maintain the cold resistance of the obtained film.
  • Vinylidene chloride copolymer (The mixing ratio of A is preferably at least 50% by mass, more preferably 75 to 97% by mass, most preferably 75 to 95% by mass with respect to 100% by mass of the total vinylidene chloride copolymer.) The remainder is the vinylidene chloride copolymer (A 2 )
  • the mixing ratio of the copolymer (B) is preferably smaller than the vinylidene chloride copolymer (A.
  • the melt index (Ml) of the copolymer ( ⁇ ) according to ASTM D-1238 is preferably about 3 or more from the viewpoint of extrudability and gas barrier property, usually 5 to 40 g / min, preferably 10 to 30 g / min.
  • the vinylidene chloride copolymer-containing resin composition of the present invention contains additives such as known plasticizers, heat stabilizers, processing aids, light stabilizers, pigments, lubricants, antioxidants, filters, and surfactants. Can be blended.
  • oils and resins such as dioctyl phthalate, acetyl tributyl citrate, dibutyl sebaguet, dioctyl sebaguet and diisobutyl adipate, epoxidized soybean oil, epoxidized linseed oil, and resin of alkyl ester Derivatives, magnesium hydroxide, tetrasodium pyrophosphate, magnesium oxide and calcium hydroxyphosphate, polyethylene oxide, Plasticizers such as waxes such as raffin wax, polyethylene wax, and montan ester wax, heat stabilizers, processing aids, those that act as lubricants, and fillers such as gay oxide and calcium carbonate, and sorbitan Various additives such as surfactants such as fatty acid esters and polyoxyethylene sorbitan fatty acid esters are included.
  • Titanium oxide pigments are effective in preventing discoloration of food contents such as sausage due to ultraviolet rays, but increase the adhesion and decomposition of the die outlet. Since the adhesive decomposition is effectively reduced by extrusion using a vacuum hopper, it is possible to add a large amount of 0.10 to 10 parts by mass.
  • the plasticizer and the stabilizer are added in an amount of about 1 to about 10 parts by mass, preferably 2 to 6 parts by mass, based on 100 parts by mass of the mixed vinylidene chloride resin (A). Some of these additives may be added during the polymerization of the vinylidene chloride copolymer (A or (A 2 ).
  • the additives are adsorbed or absorbed by the vinylidene chloride copolymer during extrusion and are extruded. After the film is formed, it transfers to the copolymer (B) and improves the gas barrier properties of the film, so that a film balanced with the extrudability can be obtained. Additives are used as needed Is preferred. Vinylidene chloride copolymers (A!), Vinylidene chloride copolymer (A 2), the method of mixing the copolymer (B) and the additives are not particularly limited, conventional methods can be applied.
  • the mixing device examples include known dry mixing devices such as a Hensile high-speed mixer, a blade blender, and a ribbon blender. There is also a method in which these raw materials are mixed by using a screw feeder or the like in an on-machine hopper device of the extruder immediately before extruding the vinylidene chloride copolymer-containing resin composition. Mixing at this temperature can reduce the generation of decomposed products due to resin adhesion at the die outlet, resin coloration, and outflow of decomposed products. In addition, mixing of the mixed resin powder at a temperature of 60 ° C.
  • the vinylidene chloride copolymer-containing resin composition obtained by mixing is extruded in the form of a powder or in the form of a pellet, and is used for forming a film. --Yes.
  • the plasticizer, heat stabilizer, processing aid, light stabilizer, pigment, lubricant, antioxidant, filler, and surfactant are added as necessary to homogenize the resin composition containing vinylidene chloride copolymer.
  • the additive selected from such agents the copolymer (B) before addition of the pre-salt fluoride copolymer (a vinylidene chloride copolymer (a 2) and the mixed chloride-bi two isopropylidene resin (a) It is preferable to add and mix, so that the additive is suppressed from being locally absorbed or adsorbed to the copolymer (B), and the amount of the adhering material at the die outlet can be reduced.
  • the recovered pulverized copolymer (recycle resin) can be mixed with the mixed vinylidene chloride resin (A) for recycling, and the mixing ratio of the pulverized product at this time is based on the mixed vinylidene chloride resin (A).
  • the vinylidene chloride copolymer-containing resin composition of the present invention is melt-extruded and molded into a stretched or unstretched film, sheet, etc.
  • a molding method those skilled in the art
  • an inflation extrusion molding method using a circuit die can be applied, etc.
  • a film obtained by stretching by stretching, particularly preferably biaxial stretching has heat shrinkability or heat resistance capable of retorting.
  • the stretching ratio is preferably 2.0 to 4.5 times in the longitudinal direction and 3.0 to 5.0 times in the transverse direction, and the film thickness is 5 to 30 as a single film.
  • the film is also used as a double film depending on the application Usually, the heat shrinkage is about 30 to about 60% in both length and width (at 120 ° C glycerin bath, 3 minutes)
  • the main method of use for packaging is that after inflation, the two ears are stacked on top of each other, the ears at both ends of the film are slit, sealed in a cylindrical shape by a packaging machine, and the contents are filled. Used to get a package with both ends gripped.
  • the retort conditions are 120 ° C (pressurization: 0.245 MPa) for 20 minutes.
  • the film of the present invention may be laminated with a film made of another resin or resin composition that can be co-extruded with the same kind of resin or vinylidene chloride copolymer.
  • the second aspect of the present invention relates to a method for extruding a resin composition containing a vinylidene chloride copolymer ( ⁇ ′).
  • ⁇ ′ a vinylidene chloride copolymer
  • the resin composition is supplied to an extruder via a vacuum hopper, thereby improving extrudability. .
  • the use of a vacuum hopper is effective in reducing the adhesion and decomposition of the resin at the die outlet, reducing the coloration of the resin and outflow of decomposed products, and reducing the burst of bubbles during inflation molding.
  • the degree of vacuum of the vacuum hopper is less than 500 mm of mercury, preferably in the range of 1 600 to 1 755 mm.
  • the vinylidene chloride copolymer ( ⁇ ') is not particularly limited, but is preferably a vinylidene chloride copolymer having a reduced viscosity of 0.048 or more (a vinylidene chloride copolymer having an A content of 50% by mass or more and a reduced viscosity of less than 0.048).
  • (A 2 ) Vinylidene chloride resin mixed with less than 50% by mass (A) (However, the total of both is 100% by mass) or vinylidene chloride copolymer (A 3 ) having a reduced viscosity of 0.045 or more
  • the vinylidene chloride copolymer (A 3 ) having a reduced viscosity of 0.045 or more is preferably used having a reduced viscosity in the range of 0.045 to 0.080. It is advisable to add at least one kind of copolymer ( ⁇ ) to 100 parts by mass of the dencopolymer (A ') in an amount of from 0 to 20 parts by mass. Adhesion decomposition is reduced, and the use of titanium oxide pigments is effective. .
  • the third present invention to prepare a resin composition comprising a vinylidene chloride copolymer and (Alpha ") And a method of extruding a resin composition containing the vinylidene chloride copolymer ( ⁇ ′), which is the second aspect of the present invention.
  • vinylidene chloride copolymer reduced viscosity of 0.045 or more (Alpha 3) or other chloride under reduced viscosity 0.048 or more vinylidene chloride copolymers (Alpha 50 mass% or more and reduced viscosity 0.048 vinylidene copolymer (Alpha 2) mixed-vinylidene chloride resin of less than 50 wt% (Alpha 4) (eight, and eight 2 total 100 mass%) from the chosen salt fluoride copolymer (Alpha ") 100 parts by mass, at least one selected from ethylene and vinyl acetate copolymer ( ⁇ ), ethylene and acrylic acid, methacrylic acid or a copolymer thereof ( ⁇ 2 ) and MBS resin (B 3 ) Mixing 0.1 to 20 parts by mass of the seed copolymer (B) with a temperature of the raw resin of 60 ° C.
  • a film is produced by a known method through a melt extruder connected to a lower part of a vacuum hopper, or formed into a film or a sheet without being stretched.
  • the degree of vacuum of the hopper is as described in the invention of the second extrusion method of the present invention
  • the known method as described above can be applied to the method of forming a film, for example, inflation extrusion molding using a sacrificial die.
  • a film obtained by stretching and orientation, particularly a biaxially stretched film, has good heat shrinkability, or is suitably used as a retortable heat-resistant film.
  • the heat shrinkage of the film is about 30 to about 60% in both length and width (120 ° C glycerin bath, 3 minutes) as measured on the test piece Retort condition is 120 ° C (pressurized 0.245 MP) a) 20
  • the film thickness of a single film is 5 to 3 °, preferably 10 to 25 / m, and the film obtained by the present invention can be laminated with a film made of the same resin or another resin.
  • the vinylidene chloride copolymer-containing resin composition according to the first aspect of the present invention is relatively homogeneous. And maintain stretchability and stretchability stably.
  • the supply of the vinylidene chloride copolymer-containing resin composition to the melt extruder is performed stably, so that the fluctuation of the load of the motor of the extruder, Fluctuations in extrusion rate are kept small.
  • This further improves the extrudability, such as reducing the adhesion and decomposition of the resin at the die outlet, the coloring of the resin and the outflow of decomposed products, and the reduction of bubble burst during inflation molding.
  • these vinylidene chloride copolymer-containing resin compositions can be arranged in a gas barrier layer and formed into a multilayer film or sheet by a coextrusion method or a laminating method.
  • Reduced viscosity Add 1 g of vinylidene chloride copolymer to 50 cc of tetrahydrofuran, dissolve at 40 ° C, filter, precipitate a polymer with methanol, wash and dry. 8 Omg of the dried polymer is precisely weighed, 20 cc of cyclohexanone at 30 ° C is added, and the mixture is dissolved by heating at 70 ° C for 60 minutes. After cooling at room temperature, the solution is filtered with filter paper to obtain a solution viscosity measurement sample.
  • the cyclohexanone solution (5 cc) was placed in an Ubbelohde viscometer, allowed to stand in a thermostat at 30 ° C for 5 minutes, and the flow-down seconds were measured by a normal operation method, and the reduced viscosity was determined by the following equation.
  • T 2 Seconds of flow of cyclohexanone sample solution at 30 ° C --Oxygen gas permeability: Measured at 30 ° C and 100% relative humidity using an oxygen gas permeability measuring device (Ox-tran 2Z20 manufactured by Moden Control). The unit is cm3 m2Zd ayZa tm, and was measured with a double film.
  • Cold resistance test Tested using a film embrittlement temperature tester (Kureha Ichinogami). One end of a double film cut to a width of 30 mm and a length of about 500 mm, held at the measurement temperature for 23 seconds, is passed between two upper and lower film holding plates adjusted to the measurement temperature by flowing a heat transfer medium through one end. Pinch.
  • the push-up moves once every 23 seconds to supply a new side of the film.
  • the number of thrusts shall be 5 times at each measurement temperature. All samples are not destroyed at the measurement temperature (destruction rate 0%) Measured at two intervals from the temperature, and measured until the temperature at which all samples are destroyed (destruction rate 100%).
  • the 50% breaking temperature (T b) of the film is determined by the following.
  • T b T, oo + B ⁇ (A / 1 0 0)-0.5 ⁇
  • Discoloration test The test was performed using a dye friction fastness tester (Toyo Seiki Seisakusho). A gauze with lard is pressed against one surface of the double film with a load of 35 N, and performs a reciprocating frictional motion at a speed of 30 cm / min and 100 times. The degree of coloration of the gauze by R-200) was compared with that of plain gauze, and represented by a color difference ⁇ E.
  • Decomposed product outflow Decomposed products having a length of about 1 mm or more in the film were detected by visual observation. "Small” means less than 10 pieces per 1500 m of raw material, “Slightly noticeable” means 10 to less than 15 pieces per 150 Om of raw material, and “Conspicuous” means 15 or more pieces per 150 Om of raw material. Represents
  • Suitable for packaging machine Automatic filling and ligating device (Kureha type KAP500, Kureha Chemical Industry Co., Ltd.) with integrated film supply part, high-frequency seal part, automatic filling part and ligating part, with a folding width of 4 Omm A double film was slit so as to form a package, and a cylindrical film center-sealed with a high-frequency seal was filled with water as a filler, and a package having both ends clipped with a metal wire was obtained. At that time, the state of the seal and the state of spark generation at the seal electrode were observed.
  • Kureha type KAP500 Kureha Chemical Industry Co., Ltd.
  • “Stable” means that the packaging machine is operating at a sealing speed of 3 Om / min and no trouble or spark caused by the sealing is observed for 50 minutes of operation time, and "Slightly unstable” means that the film is partially The thinner part where the seal wire was melted too often occurred once or twice every 50 minutes, and ⁇ Slight spark '' means that the spark occurred once or twice every 50 minutes. “Spark” indicates that the spark occurred more than 3 times in 50 minutes.
  • Conspicuous means that the film has a strong yellow tinge and has a decomposition odor.
  • Low means that the film coloring is inconspicuous.
  • Small refers to the degree of coloring between “conspicuous” and “low”.
  • the mixture was mixed at a temperature of 30 ° C to prepare a compound (a resin composition containing a vinylidene chloride copolymer). Then, using a 90 mm diameter extruder, extrude into a ring with a vacuum pressure of about 680 mm of mercury in a vacuum hopper, quenching it in a usual way using 10 cooling tanks, passing it through 20 hot water baths, and rotating it in two sets. Air was injected between pinch rolls having different surface velocities to expand the film, and the film was oriented 2.8 times in the longitudinal direction and 3.7 times in the width direction. The thickness of the obtained film was 20 for a single film.
  • Example 3 The procedure was the same as in Example 1, except that the vacuum hose was not used. (Example 3)
  • Example 5 BTA—IVSS (MBS manufactured by Kureha Chemical Industry Co., Ltd.) in place of EVA 1 in Example 1. Resin) The same procedure as in Example 1 was performed except that 1.5 parts by mass was used. (Example 5)
  • EVA 2 was performed in the same manner as in Example 1 except that 3 parts by mass of was used.
  • VDZVC mass ratio of vinyl chloride
  • Example 5 was repeated except that no vacuum hopper was used. (Comparative Example 2)
  • Example 5 was carried out in the same manner as in Example 5 except that 3 parts by mass of EVA 2 was heated and mixed with 70 parts without using a vacuum hopper. (Comparative Example 3)
  • EVA 3 a 10% ethylene-vinyl acetate copolymer
  • the heat shrinkage measured by the following method was 40-50% in both the vertical and horizontal directions, and no difference was observed between the example and the comparative example.
  • the heat shrinkage was determined by cutting the double films obtained in each of the examples and comparative examples to a length of 10 cm in both the vertical and horizontal directions, taking out 120 test specimens, holding them in a glycerin bath for 3 minutes, and removing them. Was measured, and the rate of change with respect to the original length was shown in%.
  • ⁇ indicates “implement” or “use”.
  • the extrudability is excellent (for example, the variation of the extrusion amount is reduced, the adhesion of the decomposition product of the resin at the outlet of the die is reduced, and the bubble breakage during the blow molding is reduced).
  • a resin composition containing a vinylidene chloride copolymer can be obtained.
  • the method comprises an extrusion method of supplying the vinylidene chloride copolymer-containing resin composition to an extruder via a vacuum hopper, a step of preparing the vinylidene chloride copolymer-containing resin composition, and an extrusion processing method.
  • the effect of improving the extrudability can be further improved by the film manufacturing method.

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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)
  • Materials Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Composition de résine copolymère de chlorure de vinylidène présentant d'excellentes qualités d'aptitude à l'extrusion et donnant un film bien équilibré du point de vue de l'aptitude au traitement, de la résistance au gel et de l'étanchéité aux gaz. L'invention porte en outre sur un procédé d'extrusion destiné à cette composition et sur un film élaborés à partir de cette composition ainsi que sur un procédé d'élaboration de ce film. La composition précitée renferme 100 parties en poids d'une résine mélangée de chlorure de vinylidène (A) comprenant au moins deux copolymères de chlorure de vinylidène et 0,1 à 20 parties en poids d'au moins un copolymère (B) choisi entre (B1) les copolymères d'acétate d'éthylène/vinyle, (B2) les copolymères d'éthylène et d'acide (méth)acrylique ou de ses esters alkyles, et (B3) des résines MBS.
PCT/JP1996/001118 1995-04-27 1996-04-25 Composition de resine copolymere de chlorure de vinylidene, film obtenu a partir de cette composition, procede d'extrusion destine a cette composition et procede d'elaboration du film WO1996034050A1 (fr)

Priority Applications (1)

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JP53235596A JP3931994B2 (ja) 1995-04-27 1996-04-25 塩化ビニリデン共重合体含有樹脂組成物、そのフィルム、その押出加工方法、及びそのフィルムの製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP12703095 1995-04-27
JP7/127029 1995-04-27
JP12702995 1995-04-27
JP7/127030 1995-04-27

Publications (1)

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WO1996034050A1 true WO1996034050A1 (fr) 1996-10-31

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Country Link
JP (1) JP3931994B2 (fr)
KR (1) KR100427629B1 (fr)
CN (4) CN1126789C (fr)
WO (1) WO1996034050A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1171492A (ja) * 1997-06-20 1999-03-16 Kureha Chem Ind Co Ltd 塩化ビニリデン共重合体樹脂組成物、そのフィルム、その押出加工方法
WO2003006548A1 (fr) * 2001-07-13 2003-01-23 Asahi Kasei Kabushiki Kaisha Composition de particules copolymeres du chlorure de vinylidene
JP2007169665A (ja) * 2001-05-09 2007-07-05 Kureha Corp ポリ塩化ビニリデン系樹脂組成物の製造に適した着色用樹脂組成物
JP2008063418A (ja) * 2006-09-06 2008-03-21 Asahi Kasei Chemicals Corp 塩化ビニリデン系樹脂着色用組成物及びその製造方法
US8324298B2 (en) 2006-09-05 2012-12-04 Solvay (Societe Anonyme) Composition of at least one vinylidene chloride polymer
JP2019099663A (ja) * 2017-11-30 2019-06-24 株式会社クレハ 塩化ビニリデン系樹脂フィルム、それを用いた充填包装体、及びその製造方法
CN111542433A (zh) * 2018-01-30 2020-08-14 大赛璐优越涂层株式会社 阻气性膜及其制造方法
CN114044995A (zh) * 2021-12-01 2022-02-15 郑州新生印务有限公司 一种pvdc高阻隔基材膜及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102443231B (zh) * 2011-11-07 2014-07-02 中国科学院宁波材料技术与工程研究所 一种消除晶点、提高阻隔的pvdc薄膜的制造方法
WO2013125699A1 (fr) * 2012-02-23 2013-08-29 旭化成ケミカルズ株式会社 Latex de copolymère de chlorure de vinylidène et film pour emballage-coque

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55108442A (en) * 1979-01-03 1980-08-20 Union Carbide Corp Film of polyvinylidene chloride and ethylene vinyl acetate copolymer and its manufacture
JPH0532834A (ja) * 1991-07-26 1993-02-09 Kureha Chem Ind Co Ltd ヒートシール性に優れた樹脂フイルムまたはシート

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55108492A (en) * 1979-02-14 1980-08-20 Yasutake Kamiezu Liquid fuel
CN1042440C (zh) * 1993-03-05 1999-03-10 旭化成工业株式会社 偏氯乙烯共聚物组合物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55108442A (en) * 1979-01-03 1980-08-20 Union Carbide Corp Film of polyvinylidene chloride and ethylene vinyl acetate copolymer and its manufacture
JPH0532834A (ja) * 1991-07-26 1993-02-09 Kureha Chem Ind Co Ltd ヒートシール性に優れた樹脂フイルムまたはシート

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1171492A (ja) * 1997-06-20 1999-03-16 Kureha Chem Ind Co Ltd 塩化ビニリデン共重合体樹脂組成物、そのフィルム、その押出加工方法
JP2007169665A (ja) * 2001-05-09 2007-07-05 Kureha Corp ポリ塩化ビニリデン系樹脂組成物の製造に適した着色用樹脂組成物
WO2003006548A1 (fr) * 2001-07-13 2003-01-23 Asahi Kasei Kabushiki Kaisha Composition de particules copolymeres du chlorure de vinylidene
US8324298B2 (en) 2006-09-05 2012-12-04 Solvay (Societe Anonyme) Composition of at least one vinylidene chloride polymer
JP2008063418A (ja) * 2006-09-06 2008-03-21 Asahi Kasei Chemicals Corp 塩化ビニリデン系樹脂着色用組成物及びその製造方法
JP2019099663A (ja) * 2017-11-30 2019-06-24 株式会社クレハ 塩化ビニリデン系樹脂フィルム、それを用いた充填包装体、及びその製造方法
CN111542433A (zh) * 2018-01-30 2020-08-14 大赛璐优越涂层株式会社 阻气性膜及其制造方法
CN111542433B (zh) * 2018-01-30 2022-05-03 大赛璐优越涂层株式会社 阻气性膜及其制造方法
CN114044995A (zh) * 2021-12-01 2022-02-15 郑州新生印务有限公司 一种pvdc高阻隔基材膜及其制备方法

Also Published As

Publication number Publication date
CN1183111A (zh) 1998-05-27
CN1126789C (zh) 2003-11-05
CN1172783C (zh) 2004-10-27
CN1375389A (zh) 2002-10-23
CN1172784C (zh) 2004-10-27
KR100427629B1 (ko) 2004-07-19
CN1375388A (zh) 2002-10-23
CN100410317C (zh) 2008-08-13
CN1375518A (zh) 2002-10-23
JP3931994B2 (ja) 2007-06-20

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