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WO2003006548A1 - Composition de particules copolymeres du chlorure de vinylidene - Google Patents

Composition de particules copolymeres du chlorure de vinylidene Download PDF

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Publication number
WO2003006548A1
WO2003006548A1 PCT/JP2002/007063 JP0207063W WO03006548A1 WO 2003006548 A1 WO2003006548 A1 WO 2003006548A1 JP 0207063 W JP0207063 W JP 0207063W WO 03006548 A1 WO03006548 A1 WO 03006548A1
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Prior art keywords
copolymer
vinylidene chloride
composition
mass
parts
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.)
Ceased
Application number
PCT/JP2002/007063
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English (en)
Japanese (ja)
Inventor
Hideaki Kodera
Takao Yashima
Hirokuni Nishida
Keiichi Yoda
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Priority to JP2003512309A priority Critical patent/JP4322667B2/ja
Priority to KR1020047000286A priority patent/KR100591221B1/ko
Publication of WO2003006548A1 publication Critical patent/WO2003006548A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • 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

Definitions

  • the present invention relates to a vinylidene chloride-based copolymer composition, and a film and a sheet using the same. Background technology>
  • Vinylidene chloride-based copolymers have excellent gas barrier properties against water vapor and oxygen and excellent oil resistance, and are therefore particularly suitably used for food packaging films and the like.
  • Methods for producing vinylidene chloride-based copolymers used in food packaging films include suspension polymerization and emulsion polymerization, but the suspension polymerization method is used because there are no problems such as residual emulsifiers. .
  • the suspension polymerization method is a method in which a mixed and dispersed oil droplet of vinylidene chloride and a polymerizable vinyl monomer is formed by mechanical stirring in water containing a dispersant, and then a polymerization initiator is added to carry out polymerization.
  • the vinylidene chloride copolymer obtained by suspension polymerization is stretched by a normal melt molding method, or is stretched into a single-layer or multilayer film. Processed.
  • vinylidene chloride copolymers obtained by suspension polymerization are known to be in the form of particles as disclosed in Japanese Patent Publication No. 55-182242, Japanese Patent Publication No. 57-97575, and the like. A certain force Only a copolymer particle composition having a wide particle size distribution and a large specific gravity can be obtained.
  • USP 3,067,722 discloses a method for obtaining a bi-lidene-based copolymer particle composition by polymerizing biel chloride and vinylidene chloride-based resin by a combination of bulk polymerization and suspension polymerization. Have been. However, in this method, the resin could not be extruded stably, and it was difficult to obtain a film having a uniform thickness.
  • the amount of the copolymer filled from the die into the barrel fluctuates due to the variation in the shape and size of the bilidene chloride-based copolymer, which affects the discharge amount of the extruder.
  • This allows The pressure of the film fluctuates, resulting in uneven film thickness of the extruded film.
  • a high-frequency seal is applied to obtain a film package with a non-uniform film thickness, the sealing strength is not uniform, and the production yield is likely to decrease.
  • no technology specifically addressed this problem no technology specifically addressed this problem.
  • EVA ethylene and vinyl acetate
  • a vinylidene chloride copolymer By blending a copolymer of ethylene and vinyl acetate (hereinafter abbreviated as EVA) with a vinylidene chloride copolymer, the thermal stability during extrusion and the low-temperature properties of the obtained film are improved.
  • EVA ethylene and vinyl acetate
  • Japanese Patent Application Laid-Open No. 55-104442 EVA containing from about 5 to about 18% by weight of vinyl acetate and from about 0.1 to about 1.0 dg Z) About 5 to about 40% by weight
  • Japanese Patent Publication No. 3-503320 (combination of about 0.01 to about 2% by weight of EVA with a vinyl acetate content of about 28%)
  • An object of the present invention is to provide a vinylidene chloride-based copolymer having excellent extrusion stability and, as a result, a film having excellent film thickness uniformity, and a vinylidene chloride-based resin having excellent heat stability and extrusion stability. It is intended to provide a composition.
  • the present inventors have proposed a vinylidene chloride-based copolymer composition having a specific particle size obtained from suspension polymerization and containing a small amount of fine particles of a certain amount or less, or It has been found that a vinylidene chloride-based copolymer particle composition having a bulk specific gravity may be used. Further, a composition obtained by blending the specific particle composition with a copolymer of ethylene monoacetate vinyl chloride and a copolymer obtained from two or more kinds of monomers selected from the group consisting of 3) unsaturated carboxylic acid ester monomers. It has been found that stable extrusion properties can be further improved by using the product, and the present invention has been accomplished.
  • the weight average particle diameter is in the range of 200 to 500 / m and the ratio of particles having a particle diameter of less than 150 ⁇ m is 3 wt% or less.
  • a vinylidene chloride copolymer particle composition characterized by the following, 100 parts by mass of the composition (A), and ethylene-vinyl acetate copolymer (B 1) 0.05 to 2.95.
  • a composition comprising: parts by mass and 0.05 to 2.95 parts by mass of a copolymer (B 2) comprising two or more monomers selected from monomers of a and j3 unsaturated carboxylic acid esters And the sum of the compounding mass of (B 1) and the compounding mass of (B 2) is 3 parts by mass or less. It is a vinylidene copolymer composition.
  • the vinylidene chloride copolymer in the present invention is obtained by copolymerizing a vinylidene chloride monomer and a vinyl monomer copolymerizable with the monomer.
  • vinyl monomer copolymerizable with the biylidene chloride monomer examples include vinyl esters such as vinyl chloride chloride, vinyl acetate, and vinyl propionate; methyl acrylate, ethino acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like.
  • the vinylidene chloride-based copolymer particle composition of the present invention has a weight average particle diameter of 200 to 500 ⁇ . It is preferably from 230 to 400 / xm, and more preferably from 250 to 350 / xm. When the particle diameter is in this range, the extrusion load becomes constant, and stable extrusion can be performed. The resulting film thickness can be uniform.
  • the particle size distribution can be measured with a Coulter Multisizer Single Particle Analyzer TA-II manufactured by Nikkaki Co., Ltd.
  • the mass ratio of particles having a size of less than 150 m needs to be 3% by mass or less. If more fine particles are contained, the melt tension during extrusion processing will not be constant, and the film thickness will be non-uniform. More preferably, the content of particles of 150 / zm or less is 2.5% by mass or less.
  • Is gravity is Shi preferred that made in view of the vinylidene chloride copolymer particle composition can be stably supply a constant amount of 0. 80 gZcm 3 ⁇ l. 0 gZ cm 3,. Preferably, it is 0.90 g / cm 3 to 0.98 gZcm 3 .
  • the bulk specific gravity can be measured based on JIS K-6722.
  • the weight average particle diameter is 230 to 400 ⁇
  • the weight ratio of the fine particles having a particle diameter of less than 150 m is 1.5 wt ° / 0 or less
  • the bulk specific gravity is 0.90 gZcm 3. 00.98 gZc m 3 .
  • the weight average molecular weight of the vinylidene chloride-based copolymer particle composition is preferably about 60,000 to 200,000, and more preferably 70,000 to 150,000. More preferably, it is 80,000 to 130,000. When the content is in the above range, it is preferable from the viewpoints of thermal stability, suitability for a packing and filling machine, and gas barrier property. Two or more kinds of vinylidene chloride-based copolymer particle compositions having different weight average molecular weights may be blended at an arbitrary ratio so that the weight average molecular weight of the composition falls within the above range. The weight average molecular weight was measured using a polystyrene equivalent weight average molecular weight obtained by gel permeation chromatography.
  • the following methods are available for obtaining the vinylidene chloride polymer particle composition of the present invention.
  • the above-mentioned biylidene chloride monomer and a monomer copolymerizable therewith are copolymerized.
  • the polymerization initiator used in the polymerization include, for example, diisopropyl peroxydicarbonate, dioctyl / peroxydicarbonate, dilauryl peroxydicarbonate, dimyristyl peroxydicarbonate, and diacetyl peroxydicarbonate.
  • Perester-based initiators such as tetramethylbutyl peroxyphenoxy acetate; lauroyl peroxide, diisopropyl oxyperoxide, and 2-ethylhexyl peroxy oxy , 3.5.5 Initiators of diasilboxides such as trimethylhexanoyl peroxide, etc .; t-butyl hydroperoxide, tert-butyltinoleperoxide, benzoinoleperoxide, benzoinoleperoxide, di-isopropyl ⁇ Noreoxy dicarbonate, t-butyltinolenooxyisobutyrate, t-hexyloxy Di one t such glycolate - ⁇ Ruki helper O carboxylate diglycolate-based initiators;...
  • An azo initiator such as chloride at the mouth; water-soluble peroxides such as potassium persulfate and ammonium persulfate; or reducing agents such as amine and sodium bisulfite. And the like.
  • polymerization initiators having different half-lives of 10 hours may be used in combination.
  • These polymerization initiators can be used as they are, water emulsion, water suspension, etc. It can be used anyway.
  • the amount of the initiator to be used is preferably from 100 to 7000 ppm, more preferably from 500 to 5000 ppm, based on the mixture of the vinylidene chloride monomer and the vinyl monomer. More preferably, it is 1000 to 3000 ppm.
  • the vinylidene chloride copolymer is polymerized to obtain a particle composition.
  • a suspension polymerization method is preferable.
  • suspending and dispersing agent examples include homopolymers such as polyvinylpyrrolidone, polyacrylic acid, polyvinyl alcohol, polymethinolebininoleatenore, polyacrinoleamide, polyethyleneimine, poly (2-ethyl-2-oxazoline), and maleic anhydride.
  • Synthetic polymers such as butyl monoacetate copolymer, various random copolymers, graft copolymers, block copolymers, macromonomers, etc .; methylcellulose, ethylcellulose, hydroxyshethylcellulose, hydroxypropynolecellulose, carboxymethylcellulose, etc. Water-soluble cellulose derivatives; natural polymer substances such as starch and gelatin.
  • an auxiliary stabilizer may be used in addition to the dispersion stabilizer.
  • co-stabilizers include a-on surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and long-chain alcohols. Among them, methylcellulose, hydroxypropylcellulose and hydroxypropoxymethinoresenolerose are particularly preferred.
  • the surface tension of a 0.2 wt% aqueous solution of these stabilizers at 20 ° C is preferably 5 mN / m or more from the viewpoint of the particle size to be obtained, and 6 OmN / m or less from the viewpoint of polymerization progression. Is preferred.
  • the addition amount of the suspension dispersant is preferably 30 ppr or more with respect to the vinylidene chloride-based monomer from the viewpoint of the stability of suspension polymerization, and 8,000 ppm or less from the viewpoint of the obtained particle size. preferable. It is more preferably from 100 to 5,000 pm, even more preferably from 200 to 3,000 pm. By setting the content in such a range, suspension stability is obtained, and the resin composition has a weight average particle diameter of 200 to 500 ⁇ m and a reduced amount of microparticles having a particle diameter of less than 150 ⁇ m. Can be produced efficiently it can.
  • the suspension and dispersant may be added all at once or in portions, and the timing of their addition is not limited.
  • the slurry pH of the vinylidene chloride copolymer is adjusted so that the slurry pH does not decrease too much during the initial stage or during the polymerization.
  • An alkaline substance may be added to a necessary minimum.
  • the polymerization temperature and polymerization time may be determined as appropriate depending on the type and amount of vinylidene chloride and the polymerizable vinyl monomer, the type and amount of the polymerization initiator, and the type and amount of the chain transfer agent, but generally from 30 ° C to 90 ° C. It is preferably 10 hours to 100 hours at ° C, more preferably 20 hours to 60 hours, and still more preferably 25 hours to 50 hours.
  • the vinylidene chloride copolymer in the present invention includes a lubricant, a gelling improver, a pH adjuster, a chain transfer agent, an antistatic agent, a crosslinking agent, a defoaming agent, a stabilizer, a filler, an antioxidant, An additive such as a scale adhesion inhibitor may be appropriately added. These can be added at the beginning of the polymerization, during the polymerization, or after the polymerization.
  • the stirrer used in the suspension polymerization is not particularly limited, and a baffle can be used if desired.
  • Stirrers include turbine blades, fan turbine blades, faudler blades and blue margin blades, which are usually used for the polymerization of butyl chloride monomers. It is preferable to use Buffers include finger type, cylindrical type, D type and loop type.
  • the bilidene chloride-based copolymer particles having a specific weight average particle size In order to obtain the bilidene chloride-based copolymer particles having a specific weight average particle size according to the present invention, it is necessary to reduce the interfacial tension caused by the suspending agent and to maintain the stirring speed of the stirrer in a well-balanced manner.
  • the polymerization must be completed so that the particles do not settle or stick to the reactor or stirring blades.
  • the stirring speed is set to a high speed so that the polymer particles are sufficiently suspended in order to suspend the polymer particles.
  • the polymer particles are subjected to the shear force of the stirring blade, and the polymer particle diameter is reduced.
  • the stirring speed is reduced to increase the polymer particle diameter, sedimentation of the polymer starts, and further, coagulation and fixation of the polymer occurs, and the entire reactor may be fixed. For this reason, in the past, it was necessary to avoid low-speed rotation and to select high-speed rotation as much as possible in order to promote stable polymerization. As a result, the polymer particles were reduced to 200 zm or less.
  • the stirring speed represented by the following formula (1) is 0.7 sec or more because suspension polymerization is stably performed, and if the stirring speed is 5.5 m / sec or less, the resulting weight is obtained.
  • the particle size of the coalesced is within an appropriate range, which is preferable. Specific conditions need to be changed according to the size of the stirring scale.
  • stirring blade span 40 O mm ⁇ , 1.3 to 4 in 60 to 2001 ”15111 Approximately 2 m / sec, and in the case of 2000 ⁇ , approximately 20-5.3 rpm at 20-50 rpm.
  • the vinylidene chloride-based resin particle composition of the present invention is added to 100 parts by weight of the vinylidene chloride-based resin particle composition (A) and an ethylene-butyl acetate copolymer (100 parts by weight).
  • B 1) and Q; / 3 A vinylidene chloride copolymer composition containing a specific amount of a copolymer (B 2) composed of two or more monomers selected from monomers of unsaturated carboxylic acid esters Good.
  • the ethylene monobutyl acetate copolymer (B1) used in the present invention has an ethylene content in the range of 60 to 90 wt%, more preferably 70 to 90 wt%. In order to maintain the transparency of the formed film, these ethylene contents are 90 w
  • the ethylene content is preferably at least 60 wt% from the viewpoint of the stability of the motor load of the extruder and the barrier property of the molding film.
  • the blending ratio of the copolymer (B 1) is preferably in the range of 0.05 to 2.95 parts by mass with respect to 100 parts by mass of the vinylidene chloride-based copolymer particle composition (A), and is preferably The range is from 0.1 to 2.5 parts by mass, and more preferably from 0.2 to 2.0 parts by mass.
  • the blending ratio of the copolymer (B 1) is 2.95 parts by mass or less, the thermal stability is improved and the barrier property is maintained. Further, when the compounding amount is 0.05 part by mass or more, the effect of suppressing outflow of the degraded product becomes sufficient, and the thermal stability is also improved.
  • the melt index (Ml) of the copolymer (B 1) is preferably from 3 to 180 g / min from the viewpoint of extrusion processability and gas barrier properties. Preferably it is 5 to 160 g / min.
  • the weight average molecular weight is preferably in the range of 30,000 to 150,000.
  • the copolymer (B 2) used in the present invention is a copolymer obtained from two or more monomers selected from monomers of ⁇ and unsaturated carboxylic acid esters.
  • the unsaturated carboxylic acid ester monomer is preferably an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, such as butyl acrylate, propyl acrylate, ethynole acrylate, methyl acrylate, and the like.
  • the alkyl methacrylate monomer is preferably an alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, or hydroxyxyl.
  • alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, or hydroxyxyl.
  • examples include tyl methacrylate, hydroxypropynolemethacrylate, pheninolemethacrylate, cycle hex / remethacrylate, and glycidinolemethacrylate, among which are the balance between extrudability and gas barrier integrity.
  • ⁇ ,] 3 unsaturated carboxylic acid ester monomer copolymer (B 2) can be used as a copolymer obtained by any polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization. . Among these, emulsion polymerization is preferred. Examples of the emulsion polymerization method include seed polymerization, graft polymerization, and multi-stage polymerization, and a copolymer obtained by multi-stage polymerization is particularly preferable.
  • a graft phase and a stepwise polymerization are performed on the core phase, and a polymerization method of sequentially forming a shell phase is performed.
  • a monomer having a glass transition temperature of 0 ° C or lower as a polymer, such as an alkyl acrylate, as the core phase from the viewpoint of film formation.
  • the core phase is obtained by polymerizing an alkyl acrylate monomer or a monomer mixture.
  • an alkyl acrylate monomer or a monomer mixture it is preferable to use butyl acrylate, propyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and the like. . Particularly, butyl acrylate is preferred.
  • the shell phase a monomer or a mixture of alkyl methacrylate and alkyl acrylate is used.
  • methyl methacrylate ethyl methacrylate, butyl methacrylate, butyl acrylate, methinoreal acrylate, and the like.
  • methyl methacrylate is preferred.
  • the mass ratio of the core phase and the shell phase is in the range of 10 to 90 wt%: 90 to 10 wt%, and polymerization is carried out in an optional ratio, preferably 30 to 70 wt%: 70 to 70 wt%. To 30 wt%, more preferably 50 to 70 wt%: 30 to 50 wt%.
  • the ratio of the shell phase is in the above range, the copolymer is uniformly dispersed in the film, and the sealing property is maintained.
  • the proportion of alkyl methacrylate in the shell phase is preferably at least 60 wt%, more preferably at least 80 wt%.
  • the alkyl methacrylate is in the above range, it is compatible with the vinylidene chloride-based copolymer, and a uniform dispersion of the copolymer can be obtained.
  • the weight average molecular weight of these copolymers (B 2) is preferably 10,000 to 500,000, More preferably, it is 30,000 to 300,000, more preferably 50,000 to 250,000.
  • the above range is preferable from the viewpoints of the meltability, heat stability, uniform dispersibility, and seal strength of the vinylidene chloride copolymer composition.
  • the blending ratio of the copolymer (B2) is preferably in the range of 0.05 to 2.95 parts by mass with respect to 100 parts by mass of the vinylidene chloride-based copolymer particle composition (A) in terms of extrudability. Preferably, it is in the range of 0.1 to 2.5 parts by mass, more preferably 0.2 to 2.0 parts by mass.
  • the blending ratio of the copolymer (B 2) is 2.95 parts by mass or less, the barrier property can be maintained while the heat stability is good. Further, when the compounding amount is 0.05 parts by mass or more, the thermal stability is improved, for example, the effect of suppressing outflow of the decomposition product is sufficient.
  • the total of the blending mass of the copolymer (B1) and the blending mass of the copolymer (B2) is preferably 3 parts by mass or less. It is preferably in the range of 0.2 to 2.5 parts by mass, and more preferably in the range of 0.5 to 2.0 parts by mass. When the amount is 3 parts by mass or less, the balance between heat stability and barrier property is particularly good. When the amount is 0.1 parts by mass or more, the effect of suppressing the outflow of decomposition products is high, and the thermal stability is high.
  • the vinylidene chloride-based copolymer particle composition obtained by the present invention may further include a known plasticizer, heat stabilizer, processing aid, light stabilizer, pigment, lubricant, antioxidant, filler, surfactant. And the like may be further contained.
  • a plasticizer such as dioctinolephthalate, acetyltributyl citrate, dibutyl sebacate, dioctyl sebacate and diisobutyl adipate, or a polyester plasticizer comprising a saturated aliphatic dicarboxylic acid and a polyhydric alcohol, or epoxy Epoxy stabilizers such as oxidized soybean oil, epoxidized amayu oil, epoxidized octyl stearate, epoxy group-containing resin, amide derivatives of alkyl esters, oxidized polyethylene, noraffin wax, polyethylene wax, montan ester wax, etc.
  • Lubricants such as waxes, fatty acid esters such as glycerin monoester, etc., and mono- and bisamides of lunar fatty acid: sorbitan fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. O emissions based surfactant plasticizer such like.
  • the mixing ratio of the above additives is 100 mass% of the vinylidene chloride-based copolymer particle composition.
  • the amount is preferably from about 0.01 to about 10 parts by mass, more preferably from 0.05 to 6 parts by mass, per part.
  • Vitamin E cunic acid and its salts, magnesium hydroxide, sodium pyrophosphate, sodium dihydrogen pyrophosphate, tetrasodium pyrophosphate, magnesium oxide and calcium hydroxyphosphate, and salts of ethylenediaminetetraacetic acid , Butylhydroxyanisole, pentaerythritol toletrakis [3- (3,5-di-t-ptinole-1-4-hydroxyphene) propionate], 2,2, methylene-bis- (4-methyl-6-t-ppetitheno) Nore), octadecyl-3— (3,5-di-t-butyl-4-hydroxyphenyl) propionate, ethylenebis (oxyethylene) bis [3- (5-t-butynole-14_hydroxy-1m-tolyl) propionate] , 2-t-butyl-6-(3-t-2-hydroxy-5 Methynolebenzyl) — 4-Methinolephenylis acrylate, 2- [
  • the mixing ratio of the above-mentioned heat stabilizers is 0.0005 to 0.4 part by mass with respect to 100 parts by mass of the vinylidene chloride-based copolymer particle composition in terms of improving thermal stability. Is more preferable, and more preferably 0.01 to 0.1 part by mass.
  • additives (B 1) and (B 2) are usually mixed in powder form before processing the vinylidene chloride-based resin, but when the vinylidene chloride-based monomer is polymerized, the slurry becomes one state. Alternatively, the polymerization may be carried out after adding to the vinylidene chloride monomer before polymerization.
  • Additives are adsorbed or absorbed by the vinylidene chloride copolymer during extrusion and contribute to thermal stability. Additives other than plasticizers and heat stabilizers are preferably used as needed.
  • the mixing method is not particularly limited, and a conventional method can be applied. For example, kneading using a two-roll machine, mixing using a blender such as a blade blender and ribbon blender, mixing using a Henschel high-speed mixer, etc., and a heating mixing method exceeding 60 ° C or a low-temperature mixing method not exceeding 60 ° C And so on.
  • the vinylidene chloride copolymer particle composition (A) and the above-mentioned additives that are added as required are mixed in advance, and the copolymer (B 1) and the copolymer (B 2) are sequentially added. You may mix. At that time, the mixed resin temperature is about 80 ° C. or less, and preferably mixed in a temperature range of 50 ° C. to room temperature, and the homogeneity of the obtained bilidene chloride copolymer-containing resin composition is improved. Preferred from the point.
  • the powdering of the mixed composition powder is performed by a combination of adding the above-mentioned resins. This prevents the powder from digging into the screw during extrusion processing, and can further reduce fluctuations in motor load and extrusion amount.
  • the composition obtained from the vinylidene chloride copolymer composition and the additives (B 1) and (B 2) is supplied to the extruder as a raw material, the composition is continuously fed into the on-machine hopper device. It is preferable to use a feeder that measures and supplies quantitatively.
  • the feeder examples include a screw feeder, a circle feeder, an electromagnetic feeder, a weight feeder, a positive displacement feeder, and the like.
  • a method of mixing using a gravimetric feeder is preferable. Fluctuation of the motor load during extrusion and fluctuation of the extrusion amount can be suppressed, and steady supply to the extruder becomes possible, and stable extrusion becomes possible.
  • the effect of suppressing the adhesion of decomposition products of the resin at the outlet of the die is improved, and coloring of the resin and outflow of decomposition products can be reduced.
  • the vinylidene chloride-based copolymer composition of the present invention is melt-extruded and stretched, or formed into a film, a sheet or the like without stretching.
  • an inflation extrusion molding method using a circular die can be applied.
  • the film obtained by orientation by biaxial stretching has a heat-shrinking property and a heat-resistant film that can be applied to so-called retort conditions of 120 ° C (pressure 0.25 MPa) for 20 minutes. It can be suitably used as a system.
  • the stretching ratio is preferably from 2.0 to 4.5 times in the longitudinal direction and from 3.0 to 5.0 times in the transverse direction.
  • the thickness of the single film is preferably 5 to 30 ⁇ m, more preferably 10 to 25 ⁇ . It is also used as a double film depending on the application.
  • the film obtained under these conditions exhibits the mechanical strength of the film at the time of packaging and filling, and provides sufficient gas barrier properties after packaging and filling, and thus is particularly suitable for use in food preservation.
  • a multilayer film or sheet can be formed by a coextrusion method or a laminating method so that the vinylidene chloride-based copolymer composition is further laminated on one gas barrier.
  • the composition When extruding a vinylidene chloride-based copolymer particle composition or a composition obtained by adding a processing aid to the composition, the composition is supplied to an extruder via a vacuum hopper, whereby stable extrudability and heat stability are achieved. The performance is improved.
  • One 6 degree of vacuum in the vacuum hopper. 6 is preferably not more than 6 X 1 0- 2 MP a, more preferably _ 7. 9 9 X 1 0- 2 from a 1 0. 1 range of X 1 0- 2 MP a It is.
  • the composition is stably supplied to the melt extruder, so that the fluctuation of the load of the extruder motor and the fluctuation of the extrusion amount can be suppressed to a small value.
  • This improves the thermal stability, such as the coloring of the resin, the effect of suppressing the outflow of resin decomposition products, and the effect of suppressing the adhesion of decomposition products at the outlet of the die.
  • bubble rupture during inflation molding is further improved and reduced.
  • the weight average particle size and the ratio of particles having a particle size of less than 150 ⁇ m were measured by a particle size distribution measurement method using a Coulter Multisizer / Particle Measurement System TA-II type (manufactured by Nikkaki Co., Ltd.).
  • the measurement was performed according to JISK—6722.
  • the weight average molecular weight of the polymer particle composition was measured by gel permeation chromatography (GPC) as follows.
  • Measuring device Toso Issei gel permeation chromatograph HLC-820 column: TSKgel SuperHM-H (Toso Isso) 7.8 mmX 30 cmX 2 Eluent: THF, flow rate: 1 ml / min, temperature: 40 ° C, detection: RI
  • Fluctuation rate of feed rate (%) (simple average value of standard deviation) X I 00 (2) From this fluctuation rate, liquidity was determined as follows.
  • Decomposed products with a length of about lmm or more contained in the film were detected by visual observation.
  • An automatic filling and ligating device (Asahi Kasei ADP food packaging and filling machine) that integrates the film supply unit, high-frequency sealing unit, automatic filling unit, and ligating unit is wrapped with a double film slit to a folding width of 4 Omm. Circle sealed with high frequency seal Water was filled as a filler in the cylindrical film, and a package was obtained in which both ends were clipped with metal wires. At that time, the state of the seal and the state of spark generation at the seal electrode were observed.
  • Oxygen gas permeability 100 ° C., 100 ° C. using an oxygen gas permeability measuring device (Oxtran 2/20 manufactured by Moden Control). /. Measured in relative humidity. The unit was cm 3 m 2 day / atm, and the measurement was performed using double film.
  • the separated vinylidene chloride-based copolymer particle composition had a weight average particle diameter of 260 ⁇ m, and the mass ratio of particles having a particle diameter of less than 150 im was 2.2 wt%.
  • the bulk specific gravity was 0.90 gZcm 3 .
  • the copolymer particle composition was dissolved in tetrahydrofuran, and the molecular weight in terms of polystyrene was measured by gel permeation chromatography. The weight average molecular weight was 120,000. (Vinylidene chloride-based copolymer particle composition (A-1))
  • Table 1 shows the evaluation results of the properties of the vinylidene chloride-based copolymer particle composition.
  • the weight average molecular weight was 1 16,000. (Vinylidene chloride copolymer particle composition (A-2))
  • the weight average molecular weight was 120,000. (Vinylidene chloride copolymer particle composition (A-7))
  • Example 2 The same polymerization as in Example 1 was carried out except that the suspending and dispersing agent was (M2), the concentration was 0.1%, and the stirring speed was 0.6 m / sec . The weight average molecular weight was 121,000. (Vinylidene chloride-based copolymer particle composition (A-8))
  • the vacuum pressure in the vacuum hopper about _ 9. to 06 X 10- 2 MP a was extruded in an annular, quenched with a cold bath at 10 ° C, then Pass through a 20 ° C hot tub.
  • air was injected between the films sandwiched between two sets of pinch rolls having different rotational surface speeds 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 obtained film was 10 Om long and had a single thickness of 20 / m.
  • the film thickness and the variation rate ( ⁇ ) of the film thickness were measured. The results are shown in Table 2.
  • Example 2 obtained in chloride Biyuriden copolymer particle composition (alpha-2), one 7. 99 x 10 the vacuum degree - except for using 2 MP a in the same manner as in Example 6 Film was manufactured. The results are shown in Table 2.
  • Example 4 obtained in vinylidene chloride copolymer particle composition (A- 4), except that as one 7. 99 x 10 one 2 MP a the vacuum degree in the same manner as in Example 6 Film To Manufactured. The results are shown in Table 2. [Example 10]
  • Example 5 obtained in vinylidene chloride copolymer particle composition (A- 5), except that as one 6. 66 x 10- 2 MP a the vacuum degree in the same manner as in Example 6 Film was manufactured. The results are shown in Table 2.
  • a film was formed in the same manner as in Example 6, except that no vacuum hopper was used. The results are shown in Table 2.
  • a film was manufactured in the same manner as in Example 6 using the bi-lidene chloride-based copolymer particle composition (A-6) obtained in Comparative Example 1.
  • Table 4 shows the results.
  • Comparative Example 3 obtained in vinylidene chloride copolymer particle composition (A- 8) with the exception of the one 7. 99 x 10 one 2 MP a the vacuum degree in the same manner as in Example 6 Film Was manufactured. Table 4 shows the results.
  • the separated vinylidene chloride-based copolymer particles had a weight average particle diameter of 260 m and a mass ratio of less than 150 / im was 2.3 wt%.
  • the bulk specific gravity was 0.91 g / cm 3 .
  • the copolymer particles were dissolved in tetrahydrofuran, and the molecular weight in terms of polystyrene was measured by gel permeation chromatography. As a result, the weight average molecular weight was 100,000.
  • Vinylidene chloride-based copolymer particle composition (A-9) 100 parts by mass of the vinylidene chloride-based copolymer particle composition (A-9), ethylene-vinyl acetate copolymer (B1- 4) 0.2 part by mass, ⁇ ,) 3 unsaturated carboxylic acid ester copolymer ( ⁇ 2-3) Same as Example 12 except that 0.5 part by mass was used.
  • a film was produced in the same manner as in Example 18 except that the vacuum hopper was not used. The results are shown in Table 6.
  • the separated vinylidene chloride-based copolymer particles had a weight average particle diameter of 260 ⁇ m, and the mass ratio of particles having a particle diameter of less than 150 ⁇ m was 2.0 wt%.
  • the bulk specific gravity was 0.92 gZcm 3 .
  • copolymer particles were dissolved in tetrahydrofuran, and the molecular weight in terms of polystyrene was measured by gel permeation chromatography to find that the weight average molecular weight was 90,000. (Vinylidene chloride-based copolymer particles (A-10)) 10 parts by mass of the obtained vinylidene chloride-based copolymer particle composition (A-10) was added to the vinylidene chloride-based copolymer particle composition.
  • a film was produced in the same manner as in Example 12 except that ⁇ , unsaturated carboxylic acid ester ( ⁇ 2) was not added. The results are shown in Table 7.
  • a film was produced in the same manner as in Example 12, except that the ethylene monoacetate butyl copolymer (B1) was not added. The results are shown in Table 7.
  • Example 17 was repeated except that 1.5 parts by mass of the ethylene-vinyl acetate copolymer (B1-4) and 2.0 parts by mass of ⁇ , unsaturated power rubonic ester ( ⁇ 2-1) were blended. A film was produced in the same manner. The results are shown in Table 7.
  • Example 1 Example 2 Example 3 Example 4 Example 5
  • Example 6 Example 7
  • Example 8 Example 9
  • Example 11 Polymer Type Used (A-1) (A-3) (A-5) (A-1) Rate of change in feed rate (%) 3.1 2.2 1.8 2.4 2.5 3.1
  • Comparative example Comparative car example ⁇ Ratio
  • Example 17 Example 18 Example 19 Example 20 Vinylidene chloride-based copolymer particles ( ⁇ -1) 90
  • the vinylidene chloride-based copolymer particle composition of the present invention can be extruded stably when melt-molded into a film or sheet, a film or sheet having excellent film thickness uniformity can be obtained. Furthermore, a composition comprising a copolymer of two or more monomers selected from monomers of ethylene monovinyl acetate copolymer and [3] unsaturated carboxylic acid ester is added to this copolymer particle composition. Thereby, it is possible to suppress the outflow of the resin decomposition product during the melt molding, suppress the adhesion of the resin decomposition product at the die outlet, and obtain a film or sheet excellent in suitability for a packing and filling machine and gas barrier property. Further, by extruding the above composition through a vacuum hopper, it is possible to improve the extrudability.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

Cette invention concerne une composition de particules copolymères du chlorure de vinylidène qui, lorsqu'elle est extrudée en film ou en feuille, peut être extrudée de manière stable et uniforme, et présente une meilleure stabilité thermique. Ces particules copolymères du chlorure de vinylidène se caractérisent en ce qu'elles présentent un diamètre moyen pondéré compris entre 200 et 500 νm et comportent une teneur égale ou inférieure à 3 % en poids en particules dont le diamètre est inférieur à 150 νm. Cette composition copolymère du chlorure de vinylidène se caractérise en ce qu'elle peut être obtenue par le mélange des particules copolymères avec un copolymère d'acétate d'éthylène/vinylique et un ester d'un acide carboxylique α,β-insaturé.
PCT/JP2002/007063 2001-07-13 2002-07-11 Composition de particules copolymeres du chlorure de vinylidene Ceased WO2003006548A1 (fr)

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JP2018177890A (ja) * 2017-04-06 2018-11-15 旭化成株式会社 塩化ビニリデン系共重合体樹脂組成物
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

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CN103224676B (zh) * 2012-01-30 2016-04-13 旭化成化学株式会社 偏二氯乙烯共聚物组合物、其制造方法及其膜或片材
CN103224580B (zh) * 2012-01-30 2016-03-30 旭化成化学株式会社 偏二氯乙烯类共聚物、其组合物及其膜或片材
CN103224581B (zh) * 2012-01-30 2016-03-02 旭化成化学株式会社 偏二氯乙烯类共聚物、其组合物及其膜或片材
CN103224583B (zh) * 2012-01-30 2015-05-06 旭化成化学株式会社 偏二氯乙烯类共聚物、其组合物及其膜或片材
CN103224582B (zh) * 2012-01-30 2016-03-02 旭化成化学株式会社 偏二氯乙烯类共聚物及其膜或片材

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JPS5991169A (ja) * 1982-11-18 1984-05-25 Asahi Chem Ind Co Ltd 結晶性塩化ビニリデン共重合体高周波接着剤
JPS62280207A (ja) * 1986-05-30 1987-12-05 Asahi Chem Ind Co Ltd 塩化ビニリデン系共重合体粒子とその製法
WO1996034050A1 (fr) * 1995-04-27 1996-10-31 Kureha Chemical Industry Co., Ltd. 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
JPH0959390A (ja) * 1995-08-28 1997-03-04 Japan Synthetic Rubber Co Ltd 球状重合体粒子およびその製造方法
JP2001058807A (ja) * 1999-08-23 2001-03-06 Kureha Chem Ind Co Ltd ポリ塩化ビニリデン系樹脂粉末及び活性炭
JP2002256029A (ja) * 2001-02-27 2002-09-11 Asahi Kasei Corp 塩化ビニリデン系共重合体粒子及び押出加工方法

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JPS5991169A (ja) * 1982-11-18 1984-05-25 Asahi Chem Ind Co Ltd 結晶性塩化ビニリデン共重合体高周波接着剤
JPS62280207A (ja) * 1986-05-30 1987-12-05 Asahi Chem Ind Co Ltd 塩化ビニリデン系共重合体粒子とその製法
WO1996034050A1 (fr) * 1995-04-27 1996-10-31 Kureha Chemical Industry Co., Ltd. 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
JPH0959390A (ja) * 1995-08-28 1997-03-04 Japan Synthetic Rubber Co Ltd 球状重合体粒子およびその製造方法
JP2001058807A (ja) * 1999-08-23 2001-03-06 Kureha Chem Ind Co Ltd ポリ塩化ビニリデン系樹脂粉末及び活性炭
JP2002256029A (ja) * 2001-02-27 2002-09-11 Asahi Kasei Corp 塩化ビニリデン系共重合体粒子及び押出加工方法

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Publication number Priority date Publication date Assignee Title
JP2018177890A (ja) * 2017-04-06 2018-11-15 旭化成株式会社 塩化ビニリデン系共重合体樹脂組成物
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
JP6999384B2 (ja) 2017-11-30 2022-01-18 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

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CN1529736A (zh) 2004-09-15
KR100591221B1 (ko) 2006-06-19

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