WO2015033468A1 - Polyvinyl chloride resin composition film - Google Patents

Polyvinyl chloride resin composition film Download PDF

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Publication number
WO2015033468A1
WO2015033468A1 PCT/JP2013/074242 JP2013074242W WO2015033468A1 WO 2015033468 A1 WO2015033468 A1 WO 2015033468A1 JP 2013074242 W JP2013074242 W JP 2013074242W WO 2015033468 A1 WO2015033468 A1 WO 2015033468A1
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Prior art keywords
molecular weight
component
polyvinyl chloride
chloride resin
film
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PCT/JP2013/074242
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French (fr)
Japanese (ja)
Inventor
和彦 岩倉
佐藤　真澄
貴央 堀井
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リケンテクノス株式会社
リケンファブロ株式会社
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Application filed by リケンテクノス株式会社, リケンファブロ株式会社 filed Critical リケンテクノス株式会社
Priority to MYPI2016700767A priority Critical patent/MY175488A/en
Priority to JP2015535261A priority patent/JP6093022B2/en
Priority to CN201380079458.4A priority patent/CN105518061B/en
Priority to PCT/JP2013/074242 priority patent/WO2015033468A1/en
Publication of WO2015033468A1 publication Critical patent/WO2015033468A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a polyvinyl chloride resin composition film. More specifically, the present invention relates to a polyvinyl chloride resin composition film having excellent low temperature impact resistance and suitable for food packaging.
  • the polyvinyl chloride resin composition film is excellent in self-adhesiveness, stretchability, and transparency, and is widely used for food packaging in general households, food sales, food and beverage provision services, and the like.
  • the polyvinyl chloride resin composition film has the disadvantage of insufficient impact resistance at low temperatures. Therefore, low temperature impact resistance has been improved by the kind and blending amount of the plasticizer contained in the polyvinyl chloride resin composition (see, for example, paragraph 0015 of Patent Document 1).
  • the temperature of the freezer its low temperature impact resistance is quite insufficient, and further improvement is desired.
  • One object of the present invention is to provide a polyvinyl chloride resin composition film suitable for food packaging, which is excellent in low temperature impact resistance in addition to self-adhesiveness, stretchability and transparency, and has a good appearance. is there.
  • Another object of the present invention is a polyvinyl chloride resin composition film that is excellent in self-adhesiveness, stretchability, transparency, low-temperature impact resistance and appearance, and can be produced efficiently, and a method for producing the same. Is to provide.
  • the inventor of the present invention has a polyvinyl chloride resin composition film having a polystyrene equivalent molecular weight of 10 ⁇ 6.0 or more and 10 ⁇ 7.0 or less in a differential molecular weight distribution curve measured by gel permeation chromatography. It has been found that by including an ultra-high molecular weight polyvinyl chloride resin component having a peak top, in addition to excellent self-adhesiveness, stretchability and transparency, excellent low temperature impact resistance and good appearance can be obtained. Based on this discovery, the present invention has been completed.
  • a film comprising a polyvinyl chloride resin composition It contains a polyvinyl chloride resin component (A) having a peak top in a region where the polystyrene equivalent molecular weight of the differential molecular weight distribution curve measured by gel permeation chromatography is 10 ⁇ 6.0 to 10 ⁇ 7.0. the film.
  • the polystyrene equivalent molecular weight of the polyvinyl chloride resin is a scale that relatively indicates the molecular weight of the polyvinyl chloride resin in the molecular weight measurement by gel permeation chromatography.
  • Polystyrene equivalent molecular weight is a calibration that shows the relationship between retention capacity and polystyrene molecular weight obtained from monodisperse linear polystyrene of various molecular weights with known molecular weights measured using the same gel permeation chromatography measurement conditions as polyvinyl chloride resin. The curve is calculated by applying it to a polyvinyl chloride resin.
  • the molecular weight in terms of polystyrene is also equivalent to the molecular weight equivalent to polystyrene.
  • the polyvinyl chloride resin and polystyrene both have the same polystyrene equivalent molecular weight) eluted in the same holding capacity have the same radius of inertia. Therefore, the polystyrene-equivalent molecular weight of the polyvinyl chloride resin does not depend on the branched structure such that the resin is linear or has long chain branches, short chain branches, or both branches.
  • the polyvinyl chloride resin composition film of the present invention is excellent in low-temperature impact resistance, self-adhesiveness, stretchability, transparency, and good appearance. Therefore, it can be suitably used as a food packaging film.
  • the film comprising the polyvinyl chloride resin composition of the present invention has a differential molecular weight distribution curve (hereinafter abbreviated as GPC curve) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of this film.
  • GPC curve differential molecular weight distribution curve measured by gel permeation chromatography
  • Component (A) is an ultra-high molecular weight polyvinyl chloride resin component having a peak top in the region where the polystyrene equivalent molecular weight of the GPC curve is 10 ⁇ 6.0 to 10 ⁇ 7.0, and the low-temperature impact resistance of the film It plays an important role in improving.
  • the polystyrene-equivalent molecular weight at the peak top of the GPC curve is 10 ⁇ 6.0 or more, a sufficient effect of improving low-temperature impact resistance can be obtained.
  • the polystyrene equivalent molecular weight of the peak top of the GPC curve is 10 ⁇ 7.0 or less, a good film appearance can be obtained.
  • the lower limit of the polystyrene equivalent molecular weight at the peak top of the GPC curve of the component (A) is preferably 10 ⁇ 6.2 or more.
  • the upper limit of the polystyrene conversion molecular weight of the peak top of the GPC curve of a component (A) becomes like this.
  • it is 10 ⁇ 6.8 or less.
  • the polystyrene conversion molecular weight of the peak top of the GPC curve of a component (A) is 10 ⁇ 6.2 or more and 10 ⁇ 6.8 or less.
  • the ultra high molecular weight polyvinyl chloride resin component of component (A) is not particularly limited except that the polystyrene equivalent molecular weight at the peak top of the GPC curve is in the above range, and one obtained by any method is used. Can do.
  • a high-polymerization degree polyvinyl chloride-based resin in which the polymerization degree of the polyvinyl chloride-based resin is increased so that the molecular weight in terms of polystyrene falls within the above range can be exemplified.
  • the ultra-high molecular weight polyvinyl chloride resin component as the component (A) is that a polyvinyl chloride resin having a normal polymerization degree, for example, a polyvinyl chloride resin having a polymerization degree of 700 to 2000 has a molecular weight in terms of polystyrene.
  • a cross-linked product that has undergone a cross-linking reaction within the above range can be exemplified.
  • the production method of the component (A) using a normal molecular weight polyvinyl chloride resin, which is also referred to as the component (B), will be specifically described later as an embodiment, but the production method of the component (A) is there. It is not limited to.
  • polyvinyl chloride resin having a normal polymerization degree examples include, for example, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, vinyl chloride / (meth) acrylic acid copolymer, vinyl chloride / methyl (meth) acrylate.
  • Copolymer vinyl chloride / ethyl (meth) acrylate copolymer, vinyl chloride / maleic acid ester copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride / styrene copolymer , Vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride terpolymer, vinyl chloride / styrene / acrylonitrile terpolymer, vinyl chloride / butadiene copolymer Polymer, vinyl chloride / isoprene copolymer, vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinyl chloride 1 type such as vinyl chloride terpolymer, vinyl chloride / acrylonitrile copolymer, vinyl chloride / various vinyl ether
  • the measurement of gel permeation chromatography can typically be performed as follows.
  • a high performance liquid chromatography system “LC-2000Plus (trade name)” of JASCO Corporation (Degasser, liquid pump “PU-2080 (trade name)”, autosampler “AS-2055 (trade name)”, column A system including an oven and a RI (differential refractive index) detector.);
  • LC-2000Plus trade name
  • PU-2080 liquid pump
  • AS-2055 trade name
  • RI differential refractive index
  • two styrene divinylbenzene copolymer columns “GPC KF-806L (trade name)” of Showa Denko Co., Ltd. are connected and used; Wako Pure Chemical Industries, Ltd.
  • the film comprising the polyvinyl chloride resin composition of the present invention contains the component (A), and further has a polystyrene-equivalent molecular weight of GPC curve in the region of 10 ⁇ 3.5 or more and less than 10 ⁇ 6.0.
  • a polyvinyl chloride resin component (B) having a peak top is included.
  • the film which consists of a polyvinyl chloride-type resin composition of this invention does not contain the component which has a peak top in the area
  • the film which consists of a polyvinyl chloride-type resin composition of this invention contains the component (A) in further another embodiment, and also the polystyrene conversion molecular weight of GPC curve is 10 ⁇ 3.5 or more and 10 ⁇ 6.0.
  • the polyvinyl chloride resin component (B) having a peak top is included in a region less than that, and the component having a peak top is not included in a region where the polystyrene equivalent molecular weight of the GPC curve exceeds 10 ⁇ 7.0.
  • Component (B) is a normal molecular weight polyvinyl chloride resin component. Considering only the low-temperature impact resistance of the film made of the polyvinyl chloride resin composition, all the polyvinyl chloride resins in the composition may be the ultrahigh molecular weight component (A). However, industrially, it is advantageous to use a component (B) because it is advantageous to obtain a film product with a smaller motor load and a higher film forming speed.
  • the polystyrene equivalent molecular weight of the peak top of the component (B) in the GPC curve is 10 ⁇ 3.5 or more, the tensile strength of the film made of the polyvinyl chloride resin composition can be kept good.
  • the polystyrene equivalent molecular weight of the peak top of the component (B) in the GPC curve is less than 10 ⁇ 6.0, the effect of reducing the motor load during production can be obtained.
  • the lower limit of the molecular weight in terms of polystyrene at the peak top of component (B) in the GPC curve is more preferably 10 ⁇ 4.0 or more.
  • the upper limit of the molecular weight in terms of polystyrene at the peak top of the component (B) in the GPC curve is more preferably 10 ⁇ 5.5 or less.
  • the polystyrene conversion molecular weight of the peak top of the component (B) in the GPC curve may be preferably 10 ⁇ 4.0 or more and 10 ⁇ 5.5 or less.
  • component (B) polyvinyl chloride resin examples include polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, vinyl chloride / (meth) acrylic acid copolymer, vinyl chloride / methyl (meth) acrylate copolymer.
  • the film made of the polyvinyl chloride resin composition of the present invention does not contain a component having a peak top in a region where the molecular weight in terms of polystyrene of the GPC curve exceeds 10 ⁇ 7.0, thereby further maintaining the appearance of the film. be able to.
  • the content of component (A) calculated in this way is preferably 0.5% by mass or more, more preferably 1% by mass or more with respect to the lower limit, from the viewpoint of improving the low-temperature impact resistance. It's okay. Further, the content of the component (A) is preferably 10% by mass or less, more preferably 6% by mass or less with respect to the upper limit from the viewpoint of the production efficiency of the resin composition. Furthermore, the content of the component (A) calculated as described above may be preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 6% by mass or less. Good. Further, the lower limit of the content of the component (B) calculated as described above may be 90% by mass or more from the viewpoint of expressing a motor load reduction effect during film production.
  • the upper limit of the content of the component (B) may be 99.5% by mass or less from the viewpoint of the effect of improving the low temperature impact resistance by the component (A).
  • the content of component (A) calculated as described above is 0.5 to 10% by mass, and the content of component (B) is 99.5 to 90% by mass. %. More preferably, the content of the component (A) may be 1 to 6% by mass, and the content of the component (B) may be 99 to 94% by mass.
  • the polyvinyl chloride resin contains a component having a peak top in a region where the molecular weight in terms of polystyrene exceeds 10 ⁇ 7.0
  • the value that can be regarded as the content of the components (A) and (B) in the vinyl resin is calculated according to the following equation.
  • a preferable method for producing a polyvinyl chloride resin composition containing a mixture of the component (A) and the component (B) includes a method of producing the component (A) by crosslinking a part of the component (B). be able to.
  • the method for producing a film from a polyvinyl chloride resin composition containing a mixture of component (A) and component (B) is not particularly limited, and known means can be used.
  • the composition is used as a T die or an inflation die.
  • a method for forming a film by feeding to a known extrusion die can be mentioned.
  • the method includes: 100 parts by weight of polyvinyl chloride resin used as component (B); 10-60 parts by weight of at least one plasticizer selected from the group consisting of adipic acid plasticizers, sebacic acid plasticizers, acetylated monofatty acid glycerides, acetylated difatty acid glycerides, and epoxidized soybean oil; and calcium Zinc stabilizer 0.1-5.0 parts by mass; A raw material mixture containing is preferably used.
  • the plasticizer When the plasticizer is 10 parts by mass or more, appropriate shearing is performed, and formation of a crosslinked gel and accompanying film appearance deterioration can be prevented. When the plasticizer is 60 parts by mass or less, the fluidity of the raw material mixture is moderately suppressed and shearing can be performed satisfactorily, so that it becomes easier to obtain the component (A).
  • the plasticizer is more preferably used in an amount in the range of 15 to 50 parts by mass.
  • the crosslinking reaction of the polyvinyl chloride resin is controlled, and the target component ( A) can be obtained efficiently.
  • the said calcium zinc type stabilizer is 5.0 mass parts or less, the crosslinking reaction of a polyvinyl chloride-type resin can advance suitably, and a desired quantity of a component (A) can be obtained.
  • the calcium zinc stabilizer is more preferably used in an amount in the range of 0.3 to 2.0 parts by mass.
  • the calcium zinc stabilizer is preferably used by dissolving or dispersing in advance in an alcohol solvent or a mixed solvent of an alcohol solvent and a hydrocarbon solvent.
  • the stabilizer is uniformly dispersed in the raw material mixture, a crosslinking reaction controlled at a high shear rate occurs, and the ultrahigh molecular weight component (A) is added. It can be generated more easily.
  • Examples of the alcohol solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, hexamethylene glycol, methoxybutanol, isopropanol.
  • Examples include octanol, 2-ethylhexanol, and benzyl alcohol.
  • hydrocarbon solvent examples include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and mixtures thereof.
  • these hydrocarbon solvents may have a functional group.
  • liquid paraffin is particularly preferable.
  • the preferred shear rate depends on the molecular weight of component (B) used and the blending amount of plasticizer and stabilizer. It may be about 1000 (1 / s). When the shear rate is 120 (1 / s) or more, the component (A) is sufficiently generated, and the low-temperature impact resistance can be improved well. Whether or not the shear rate is appropriate can be determined by whether or not the maximum shear rate applied during film formation is within the above range. When the shear rate is 1000 (1 / s) or less, it is possible to suppress the occurrence of burning and cross-linked gel. The shear rate is more preferably about 130 to 800 (1 / s). The shear rate is more preferably about 150 to 500 (1 / s).
  • the shear rate in the die is generally defined as follows in the lip portion where the largest shear rate is applied.
  • ⁇ V / St ⁇ : Shear rate (1 / s)
  • S Surface area of die slip part (mm ⁇ 2)
  • t Die slip opening (mm)
  • V discharge volume in terms of volume (mm ⁇ 3 / s)
  • the film made of the polyvinyl chloride resin composition of the present invention can further contain a commonly used plasticizer.
  • a plasticizer for example, Phthalate plasticizers such as di-2-ethylhexyl phthalate, dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate; Adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyldiglycol) adipate; Phosphate plasticizer systems such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphen
  • tetrahydrophthalic acid plasticizer azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid plasticizer, biphenyltetra Examples thereof include carboxylic acid ester plasticizers and chlorine plasticizers.
  • the film made of the polyvinyl chloride resin composition of the present invention can further contain commonly used additives.
  • an additive for example, Chlorine scavengers such as hydrotalcite compounds, zeolite compounds, metal soaps; Phosphorous, phenolic and sulfur antioxidants; Light stabilizers such as hindered amines; Epoxy compounds such as epoxidized soybean oil; UV absorbers such as benzotriazole and benzophenone; ⁇ -diketone compounds; perchlorates; polyhydric alcohols; pigments; lubricants; cross-linking agents; antistatic agents; antifogging agents; plate-out preventing agents; surface treatment agents; A bactericidal agent, a metal deactivator, a mold release agent, a processing aid, and the like.
  • (B) Self-adhesive A small piece of film was torn with a blade, and a test piece having a length of 100 mm and a width of 50 mm was cut out so that the machine direction of the film was the length direction while the two films were in close contact with each other. . After peeling 50 mm from one end in the length direction of the test piece, a T-shaped peel test was performed under the condition of 200 mm / min. The peel strength was the mean square value of the portion where the stress takes a substantially constant value in the obtained stress-strain curve. A conceptual diagram for calculating peel strength from the stress-strain curve of the film is shown in FIG. In addition, the judgment scale of the peeling strength concerning self-adhesiveness is as follows.
  • Peel strength is less than 15 N / cm: poor Peel strength is 15 N / cm or more and less than 50 N / cm: Somewhat poor Peel strength is 50 N / cm or more and less than 250 N / cm: Good Peel strength is 250 N / cm or more: Good enough
  • Polyvinyl chloride resin (1-1) Polyvinyl chloride resin from Kaneka Corporation: Polymerization degree 800, polystyrene conversion molecular weight 10 ⁇ 4.9 measured by GPC (1-2) Kaneka Corporation's polyvinyl chloride resin: Polymerization degree 1300, polystyrene conversion molecular weight 10 ⁇ 5.1 measured by GPC (1-3) Polyvinyl chloride resin from Kaneka Corporation: Polymerization degree 1500, polystyrene conversion molecular weight 10 ⁇ 5.2 measured by GPC
  • Plasticizer (2-1) Adipate plasticizer “DINA (trade name)” by Taoka Chemical Co., Ltd. (2-2) Epoxidized soybean oil “ADEKA SIZER O-130P (trade name)” by ADEKA Corporation
  • Example 1 (1-1) 100 parts by mass of the above; (2-1) 35 parts by mass; (2-2) 10 parts by mass of the above; (3-1) 0.8 parts by mass above; (4-1) 2.0 parts by mass; Using a composition consisting of Using a device equipped with a single screw extruder and a T die, a film having a thickness of 10 ⁇ m was formed under the condition of the largest shear rate of 200 (1 / s) applied during film formation.
  • component (A) When GPC measurement of the film thus obtained was performed, component (A) was produced.
  • the polystyrene equivalent molecular weight of the peak top of the component (A) in the GPC curve was 10 ⁇ 6.5.
  • the value regarded as the content of the component (A) calculated from the GPC curve according to the formula described in the above paragraph 0028 was 2.8% by mass.
  • region where the molecular weight of polystyrene conversion exceeds 10 ⁇ 7.0 was not recognized.
  • the physical properties of (i) to (e) above were evaluated for this film. The results are shown in Table 1.
  • Examples 7-12 Film production was performed in the same manner as in Example 1 except that the composition of the vinyl chloride resin composition used was changed as shown in Table 1. In any case, a component having a peak top in the region where the molecular weight in terms of polystyrene exceeds 10 ⁇ 7.0 was not observed. The results are shown in Table 1.

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Abstract

The present invention relates to a polyvinyl chloride resin composition film which has excellent self-adhesion, stretchability, transparency, and low-temperature impact resistance, has good appearance and is suitable for food packaging. A film is provided which comprises a polyvinyl chloride resin composition which includes a polyvinyl chloride resin component (A) in which polystyrene equivalent molecular weight of a differential molecular weight distribution curve measured by gel permeation chromatography has a peak top in a range of 10^6.0 to 10^7.0. This film may further include a polyvinyl chloride resin component (B) in which polystyrene equivalent molecular weight of a differential molecular weight distribution curve measured by gel permeation chromatography has a peak top in a range of 10^3.5 or more to less than 10^6.0. Furthermore, this film preferably does not include a component in which polystyrene equivalent molecular weight of a differential molecular weight distribution curve measured by gel permeation chromatography has a peak top in a range of over 10^7.0.

Description

ポリ塩化ビニル系樹脂組成物フィルムPolyvinyl chloride resin composition film
　本発明は、ポリ塩化ビニル系樹脂組成物フィルムに関する。更に詳しくは、耐低温衝撃性に優れ、食品包装に好適なポリ塩化ビニル系樹脂組成物フィルムに関する。 The present invention relates to a polyvinyl chloride resin composition film. More specifically, the present invention relates to a polyvinyl chloride resin composition film having excellent low temperature impact resistance and suitable for food packaging.
　ポリ塩化ビニル系樹脂組成物フィルムは、自己粘着性、ストレッチ性、透明性に優れており、一般家庭、食料品販売業、飲食物提供役務等において食品包装に汎用されている。その一方、ポリ塩化ビニル系樹脂組成物フィルムは、低温における耐衝撃性が不十分であるという短所があった。そこでポリ塩化ビニル系樹脂組成物に含ませる可塑剤の種類と配合量により、耐低温衝撃性の改良が行われてきた（例えば、特許文献１の段落００１５参照）。しかし、冷凍庫の温度を考慮すれば、その耐低温衝撃性は全く不十分なものであり、更なる改良が望まれている。 The polyvinyl chloride resin composition film is excellent in self-adhesiveness, stretchability, and transparency, and is widely used for food packaging in general households, food sales, food and beverage provision services, and the like. On the other hand, the polyvinyl chloride resin composition film has the disadvantage of insufficient impact resistance at low temperatures. Therefore, low temperature impact resistance has been improved by the kind and blending amount of the plasticizer contained in the polyvinyl chloride resin composition (see, for example, paragraph 0015 of Patent Document 1). However, considering the temperature of the freezer, its low temperature impact resistance is quite insufficient, and further improvement is desired.
特開平９－１０９２３５号公報JP-A-9-109235
　本発明の一つの目的は、自己粘着性、ストレッチ性、透明性に加えて耐低温衝撃性に優れ、外観も良好な、食品包装に好適なポリ塩化ビニル系樹脂組成物フィルムを提供することである。 One object of the present invention is to provide a polyvinyl chloride resin composition film suitable for food packaging, which is excellent in low temperature impact resistance in addition to self-adhesiveness, stretchability and transparency, and has a good appearance. is there.
　本発明の他の目的は、自己粘着性、ストレッチ性、透明性、耐低温衝撃性及び外観に優れ、かつ効率的に製造することが可能なポリ塩化ビニル系樹脂組成物フィルム、並びにその製造方法を提供することである。 Another object of the present invention is a polyvinyl chloride resin composition film that is excellent in self-adhesiveness, stretchability, transparency, low-temperature impact resistance and appearance, and can be produced efficiently, and a method for producing the same. Is to provide.
　本発明者は、驚くべきことに、ポリ塩化ビニル系樹脂組成物フィルムに、ゲル浸透クロマトグラフィにより測定した微分分子量分布曲線のポリスチレン換算分子量が１０＾６．０以上１０＾７．０以下の領域にピークトップを有する超高分子量ポリ塩化ビニル系樹脂成分を含ませることにより、優れた自己粘着性、ストレッチ性、透明性に加えて、優れた耐低温衝撃性及び良好な外観が得られることを見出し、この発見に基づいて本発明を完成させた。 Surprisingly, the inventor of the present invention has a polyvinyl chloride resin composition film having a polystyrene equivalent molecular weight of 10 ^ 6.0 or more and 10 ^ 7.0 or less in a differential molecular weight distribution curve measured by gel permeation chromatography. It has been found that by including an ultra-high molecular weight polyvinyl chloride resin component having a peak top, in addition to excellent self-adhesiveness, stretchability and transparency, excellent low temperature impact resistance and good appearance can be obtained. Based on this discovery, the present invention has been completed.
　すなわち、本発明の構成は以下のとおりである。
　ポリ塩化ビニル系樹脂組成物からなるフィルムであって、
　ゲル浸透クロマトグラフィにより測定した微分分子量分布曲線のポリスチレン換算分子量が１０＾６．０以上１０＾７．０以下の領域にピークトップを有するポリ塩化ビニル系樹脂成分（Ａ）を含むことを特徴とするフィルム。 That is, the configuration of the present invention is as follows.
A film comprising a polyvinyl chloride resin composition,
It contains a polyvinyl chloride resin component (A) having a peak top in a region where the polystyrene equivalent molecular weight of the differential molecular weight distribution curve measured by gel permeation chromatography is 10 ^ 6.0 to 10 ^ 7.0. the film.
　本明細書でいうポリ塩化ビニル系樹脂のポリスチレン換算分子量は、ゲル浸透クロマトグラフィによる分子量測定において、ポリ塩化ビニル系樹脂の分子量を相対的に示す尺度である。ポリスチレン換算分子量は、ポリ塩化ビニル系樹脂と同一ゲル浸透クロマトグラフィ測定条件を用いて測定した分子量が既知の種々の分子量の単分散直鎖ポリスチレンから得られた保持容量とポリスチレン分子量との関係を示す較正曲線を、ポリ塩化ビニル系樹脂に適用することによって算出される。この点、ポリスチレン換算分子量は、ポリスチレン相当分子量であるとも換言される。同一の保持容量に溶出したポリ塩化ビニル系樹脂とポリスチレン（両者は同じポリスチレン換算分子量である）とは同一慣性半径を持つ。それゆえ、ポリ塩化ビニル系樹脂のポリスチレン換算分子量は、当該樹脂が直鎖状であるか、長鎖分岐、短鎖分岐、あるいは両分岐を持つ等の分岐構造に依らない。 In the present specification, the polystyrene equivalent molecular weight of the polyvinyl chloride resin is a scale that relatively indicates the molecular weight of the polyvinyl chloride resin in the molecular weight measurement by gel permeation chromatography. Polystyrene equivalent molecular weight is a calibration that shows the relationship between retention capacity and polystyrene molecular weight obtained from monodisperse linear polystyrene of various molecular weights with known molecular weights measured using the same gel permeation chromatography measurement conditions as polyvinyl chloride resin. The curve is calculated by applying it to a polyvinyl chloride resin. In other words, the molecular weight in terms of polystyrene is also equivalent to the molecular weight equivalent to polystyrene. The polyvinyl chloride resin and polystyrene (both have the same polystyrene equivalent molecular weight) eluted in the same holding capacity have the same radius of inertia. Therefore, the polystyrene-equivalent molecular weight of the polyvinyl chloride resin does not depend on the branched structure such that the resin is linear or has long chain branches, short chain branches, or both branches.
　本発明のポリ塩化ビニル系樹脂組成物フィルムは、耐低温衝撃性、自己粘着性、ストレッチ性、透明性に優れ、外観も良好である。そのため食品包装用フィルムとして好適に用いることができる。 The polyvinyl chloride resin composition film of the present invention is excellent in low-temperature impact resistance, self-adhesiveness, stretchability, transparency, and good appearance. Therefore, it can be suitably used as a food packaging film.
本発明のフィルムのゲル浸透クロマトグラフィにより測定した微分分子量分布曲線の概念図である。It is a conceptual diagram of the differential molecular weight distribution curve measured by the gel permeation chromatography of the film of this invention. 本発明のフィルムの応力－歪曲線からの剥離強度算出についての概念図である。It is a conceptual diagram about calculation of peel strength from the stress-strain curve of the film of the present invention.
成分（Ａ）
　本発明のポリ塩化ビニル系樹脂組成物からなるフィルムは、このフィルムのゲル浸透クロマトグラフィ（以下ＧＰＣと略すことがある。）により測定した微分分子量分布曲線（以下ＧＰＣ曲線と略すことがある。）のポリスチレン換算分子量が１０＾６．０以上１０＾７．０以下の領域にピークトップを有するポリ塩化ビニル系樹脂成分（Ａ）を含む。 Ingredient (A)
The film comprising the polyvinyl chloride resin composition of the present invention has a differential molecular weight distribution curve (hereinafter abbreviated as GPC curve) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of this film. A polyvinyl chloride resin component (A) having a peak top in a region where the molecular weight in terms of polystyrene is from 10 ^ 6.0 to 10 ^ 7.0 is included.
　成分（Ａ）は、ＧＰＣ曲線のポリスチレン換算分子量が１０＾６．０以上１０＾７．０以下の領域にピークトップを有する超高分子量ポリ塩化ビニル系樹脂成分であり、フィルムの耐低温衝撃性の改良に重要な働きをする。ＧＰＣ曲線のピークトップのポリスチレン換算分子量が１０＾６．０以上であることによって、十分な耐低温衝撃性の改良効果を得ることができる。ＧＰＣ曲線のピークトップのポリスチレン換算分子量が１０＾７．０以下であることによって、良好なフィルムの外観を得ることができる。成分（Ａ）のＧＰＣ曲線のピークトップのポリスチレン換算分子量の下限は、好ましくは、１０＾６．２以上である。また、成分（Ａ）のＧＰＣ曲線のピークトップのポリスチレン換算分子量の上限は、好ましくは１０＾６．８以下である。さらに、成分（Ａ）のＧＰＣ曲線のピークトップのポリスチレン換算分子量は、１０＾６．２以上１０＾６．８以下であることが、好ましい。 Component (A) is an ultra-high molecular weight polyvinyl chloride resin component having a peak top in the region where the polystyrene equivalent molecular weight of the GPC curve is 10 ^ 6.0 to 10 ^ 7.0, and the low-temperature impact resistance of the film It plays an important role in improving. When the polystyrene-equivalent molecular weight at the peak top of the GPC curve is 10 ^ 6.0 or more, a sufficient effect of improving low-temperature impact resistance can be obtained. When the polystyrene equivalent molecular weight of the peak top of the GPC curve is 10 ^ 7.0 or less, a good film appearance can be obtained. The lower limit of the polystyrene equivalent molecular weight at the peak top of the GPC curve of the component (A) is preferably 10 ^ 6.2 or more. Moreover, the upper limit of the polystyrene conversion molecular weight of the peak top of the GPC curve of a component (A) becomes like this. Preferably it is 10 ^ 6.8 or less. Furthermore, it is preferable that the polystyrene conversion molecular weight of the peak top of the GPC curve of a component (A) is 10 ^ 6.2 or more and 10 ^ 6.8 or less.
　成分（Ａ）の超高分子量ポリ塩化ビニル系樹脂成分としては、ＧＰＣ曲線のピークトップのポリスチレン換算分子量が上記範囲であること以外は、特に限定されず、任意の方法で得たものを用いることができる。 The ultra high molecular weight polyvinyl chloride resin component of component (A) is not particularly limited except that the polystyrene equivalent molecular weight at the peak top of the GPC curve is in the above range, and one obtained by any method is used. Can do.
　例えば、成分（Ａ）として、ポリ塩化ビニル系樹脂の重合度をポリスチレン換算分子量が上記範囲になるように高めた、高重合度ポリ塩化ビニル系樹脂を挙げることができる。 For example, as the component (A), a high-polymerization degree polyvinyl chloride-based resin in which the polymerization degree of the polyvinyl chloride-based resin is increased so that the molecular weight in terms of polystyrene falls within the above range can be exemplified.
　上記、高重合度ポリ塩化ビニル系樹脂は、ポリスチレン換算分子量が上記範囲であること以外は、当業界にて公知のポリ塩化ビニル系樹脂と同様の化学組成の樹脂である。このようなポリ塩化ビニル系樹脂としては、例えば、ポリ塩化ビニル、塩化ビニル・酢酸ビニル共重合体、塩化ビニル・（メタ）アクリル酸共重合体、塩化ビニル・（メタ）アクリル酸メチル共重合体、塩化ビニル・（メタ）アクリル酸エチル共重合体、塩化ビニル・マレイン酸エステル共重合体、塩化ビニル・エチレン共重合体、塩化ビニル・プロピレン共重合体、塩化ビニル・スチレン共重合体、塩化ビニル・イソブチレン共重合体、塩化ビニル・塩化ビニリデン共重合体、塩化ビニル・スチレン・無水マレイン酸三元共重合体、塩化ビニル・スチレン・アクリロニトリル三元共重合体、塩化ビニル・ブタジエン共重合体、塩化ビニル・イソプレン共重合体、塩化ビニル・塩素化プロピレン共重合体、塩化ビニル・塩化ビニリデン・酢酸ビニル三元共重合体、塩化ビニル・アクリロニトリル共重合体、塩化ビニル・各種ビニルエーテル共重合体等の塩化ビニル及び塩化ビニルと共重合可能な他のモノマーの共重合体；などの１種又は２種以上の混合物を用いることができる。 The above high-polymerization degree polyvinyl chloride resin is a resin having the same chemical composition as a polyvinyl chloride resin known in the art, except that the molecular weight in terms of polystyrene is in the above range. Examples of such polyvinyl chloride resins include polyvinyl chloride, vinyl chloride / vinyl acetate copolymers, vinyl chloride / (meth) acrylic acid copolymers, and vinyl chloride / methyl (meth) acrylate copolymers. , Vinyl chloride / ethyl (meth) acrylate copolymer, vinyl chloride / maleic acid ester copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride / styrene copolymer, vinyl chloride・ Isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride terpolymer, vinyl chloride / styrene / acrylonitrile terpolymer, vinyl chloride / butadiene copolymer, chloride Vinyl / isoprene copolymer, vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinylidene chloride / acetic acid 1 type or 2 types of copolymer of other monomers copolymerizable with vinyl chloride and vinyl chloride, such as Nyl terpolymer, vinyl chloride / acrylonitrile copolymer, vinyl chloride / various vinyl ether copolymers, etc. A mixture of the above can be used.
　成分（Ａ）としての超高分子量ポリ塩化ビニル系樹脂成分の他の一例としては、通常の重合度のポリ塩化ビニル系樹脂、例えば重合度７００～２０００のポリ塩化ビニル系樹脂をポリスチレン換算分子量が上記範囲になるように架橋反応させた架橋体を挙げることができる。成分（Ｂ）としても言及される通常の分子量のポリ塩化ビニル系樹脂を用いた成分（Ａ）の製造方法は、一実施形態として具体的に後述するが、成分（Ａ）の製造方法はそこに限定されるわけではない。 Another example of the ultra-high molecular weight polyvinyl chloride resin component as the component (A) is that a polyvinyl chloride resin having a normal polymerization degree, for example, a polyvinyl chloride resin having a polymerization degree of 700 to 2000 has a molecular weight in terms of polystyrene. A cross-linked product that has undergone a cross-linking reaction within the above range can be exemplified. The production method of the component (A) using a normal molecular weight polyvinyl chloride resin, which is also referred to as the component (B), will be specifically described later as an embodiment, but the production method of the component (A) is there. It is not limited to.
　この通常の重合度のポリ塩化ビニル系樹脂としては、例えば、ポリ塩化ビニル、塩化ビニル・酢酸ビニル共重合体、塩化ビニル・（メタ）アクリル酸共重合体、塩化ビニル・（メタ）アクリル酸メチル共重合体、塩化ビニル・（メタ）アクリル酸エチル共重合体、塩化ビニル・マレイン酸エステル共重合体、塩化ビニル・エチレン共重合体、塩化ビニル・プロピレン共重合体、塩化ビニル・スチレン共重合体、塩化ビニル・イソブチレン共重合体、塩化ビニル・塩化ビニリデン共重合体、塩化ビニル・スチレン・無水マレイン酸三元共重合体、塩化ビニル・スチレン・アクリロニトリル三元共重合体、塩化ビニル・ブタジエン共重合体、塩化ビニル・イソプレン共重合体、塩化ビニル・塩素化プロピレン共重合体、塩化ビニル・塩化ビニリデン・酢酸ビニル三元共重合体、塩化ビニル・アクリロニトリル共重合体、塩化ビニル・各種ビニルエーテル共重合体等の塩化ビニル及び塩化ビニルと共重合可能な他のモノマーの共重合体；などの１種又は２種以上の混合物を用いることができる。 Examples of the polyvinyl chloride resin having a normal polymerization degree include, for example, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, vinyl chloride / (meth) acrylic acid copolymer, vinyl chloride / methyl (meth) acrylate. Copolymer, vinyl chloride / ethyl (meth) acrylate copolymer, vinyl chloride / maleic acid ester copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride / styrene copolymer , Vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride terpolymer, vinyl chloride / styrene / acrylonitrile terpolymer, vinyl chloride / butadiene copolymer Polymer, vinyl chloride / isoprene copolymer, vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinyl chloride 1 type such as vinyl chloride terpolymer, vinyl chloride / acrylonitrile copolymer, vinyl chloride / various vinyl ether copolymer, etc. Alternatively, a mixture of two or more kinds can be used.
　本明細書において、ゲル浸透クロマトグラフィ（ＧＰＣ）の測定は、典型的には以下のように行うことができる。
　システムとして、日本分光株式会社の高速液体クロマトグラフィシステム「ＬＣ－２０００Ｐｌｕｓ（商品名）」（デガッサー、送液ポンプ「ＰＵ－２０８０（商品名）」、オートサンプラー「ＡＳ－２０５５（商品名）」、カラムオーブン及びＲＩ（示差屈折率）検出器を含むシステム。）を用い；
　カラムとして、昭和電工株式会社のスチレンジビニルベンゼン共重合体カラム「ＧＰＣ　ＫＦ－８０６Ｌ（商品名）」２本を連結して用い；
　和光純薬工業株式会社の特級テトラヒドロフラン（安定剤不含）を移動相として；
　流速１．０ミリリットル／分、カラム温度４０℃、試料濃度１．５ミリグラム／ミリリットル、試料注入量１００マイクロリットルの条件で測定する。なお、各保持容量における溶出量は、ポリ塩化ビニル系樹脂の屈折率の分子量依存性が無いと見なしてＲＩ検出器の検出量から求める。 In this specification, the measurement of gel permeation chromatography (GPC) can typically be performed as follows.
As a system, a high performance liquid chromatography system “LC-2000Plus (trade name)” of JASCO Corporation (Degasser, liquid pump “PU-2080 (trade name)”, autosampler “AS-2055 (trade name)”, column A system including an oven and a RI (differential refractive index) detector.);
As a column, two styrene divinylbenzene copolymer columns “GPC KF-806L (trade name)” of Showa Denko Co., Ltd. are connected and used;
Wako Pure Chemical Industries, Ltd. special grade tetrahydrofuran (without stabilizer) as mobile phase;
The measurement is performed under the conditions of a flow rate of 1.0 ml / min, a column temperature of 40 ° C., a sample concentration of 1.5 mg / ml, and a sample injection amount of 100 microliters. Note that the elution amount in each holding volume is determined from the detection amount of the RI detector on the assumption that the refractive index of the polyvinyl chloride resin does not depend on the molecular weight.
　上記移動相に使用したテトラヒドロフラン１０ミリリットルに、試料として裁断フィルム１５ミリグラムを投入し、室温で静置して溶解後、トムシック（ＴＯＭＩＳＩＣ）株式会社のシリンジフィルター「ＴＩＴＡＮ３－ＰＴＦＥ（商品名）」のポアサイズ０．４５μｍのものを使用して濾過し、調製する。また、保持容量からポリスチレン換算分子量への較正曲線は、アジレントテクノロジー（Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｙ）株式会社の標準ポリスチレン「ＥａｓｉＣａｌ　ＰＳ－１（商品名）」（Ｐｌａｉｎ　Ａの分子量６８７００００、８４１７００、１５２８００、２８７７０、２９３０；Ｐｌａｉｎ　Ｂの分子量２３４８０００、３２７３００、７４８００、１０１１０、５８０）を使用して作成する。解析プログラムは、日本分光株式会社の「ＣｈｒｏｍＮＡＶ　ＧＰＣ（商品名）」を使用する。なお、カラムとしては、「ＧＰＣ　ＫＦ－８０６Ｌ（商品名）」２本を連結して用いる以外に、「ＧＰＣ　ＫＦ－８０２（商品名）」１本および「ＧＰＣ　ＫＦ－８０１（商品名）」１本を連結して用いることもでき、また、「ＧＰＣ　ＫＦ８００Ｄ（商品名）」等１本を「ＧＰＣ　ＫＦ－８０６Ｌ（商品名）」２本に連結して用いることもできる。 Into 10 ml of tetrahydrofuran used in the above mobile phase, 15 mg of a cut film is put as a sample, and left standing at room temperature for dissolution. Then, the pore size of a syringe filter “TITAN3-PTFE (trade name)” by TOMICIC Co., Ltd. Filter and prepare using 0.45 μm. The calibration curve from the retention capacity to the molecular weight in terms of polystyrene is the standard polystyrene “EasiCal PS-1 (trade name)” of Agilent Technology, Inc. (Plain A molecular weight 6870000, 841700, 152800, 28770, 2930; The molecular weight of Plain B is 2348000, 327300, 74800, 10110, 580). The analysis program uses “ChromNAV GPC (trade name)” of JASCO Corporation. As the column, in addition to using two “GPC KF-806L (product name)” in combination, one “GPC KF-802 (product name)” and “GPC KF-801 (product name)” 1 One book such as “GPC KF800D (trade name)” or the like can be used in conjunction with two “GPC KF-806L (trade name)”.
　ＧＰＣの理論及び測定の実際については、共立出版株式会社の「サイズ排除クロマトグラフィー　高分子の高速液体クロマトグラフィー、著者：森定雄、初版第１刷１９９１年１２月１０日」などの参考書を参照することができる。 For details on the theory and measurement of GPC, refer to reference books such as "Size Exclusion Chromatography, High Performance Liquid Chromatography of Polymers, Author: Sadao Mori, First Edition, First Edition, December 10, 1991" by Kyoritsu Publishing Co., Ltd. can do.
成分（Ｂ）
　本発明のポリ塩化ビニル系樹脂組成物からなるフィルムは、一実施態様において、成分（Ａ）を含み、更にＧＰＣ曲線のポリスチレン換算分子量が１０＾３．５以上１０＾６．０未満の領域にピークトップを有するポリ塩化ビニル系樹脂成分（Ｂ）を含む。また、本発明のポリ塩化ビニル系樹脂組成物からなるフィルムは、他の実施態様において、ＧＰＣ曲線のポリスチレン換算分子量が１０＾７．０を超える領域にピークトップを有する成分を含まない。また、本発明のポリ塩化ビニル系樹脂組成物からなるフィルムは、さらなる他の実施態様において、成分（Ａ）を含み、更にＧＰＣ曲線のポリスチレン換算分子量が１０＾３．５以上１０＾６．０未満の領域にピークトップを有するポリ塩化ビニル系樹脂成分（Ｂ）を含み、かつ、ＧＰＣ曲線のポリスチレン換算分子量が１０＾７．０を超える領域にピークトップを有する成分を含まない。 Ingredient (B)
In one embodiment, the film comprising the polyvinyl chloride resin composition of the present invention contains the component (A), and further has a polystyrene-equivalent molecular weight of GPC curve in the region of 10 ^ 3.5 or more and less than 10 ^ 6.0. A polyvinyl chloride resin component (B) having a peak top is included. Moreover, the film which consists of a polyvinyl chloride-type resin composition of this invention does not contain the component which has a peak top in the area | region where the polystyrene conversion molecular weight of a GPC curve exceeds 10 ^ 7.0 in other embodiment. Moreover, the film which consists of a polyvinyl chloride-type resin composition of this invention contains the component (A) in further another embodiment, and also the polystyrene conversion molecular weight of GPC curve is 10 ^ 3.5 or more and 10 ^ 6.0. The polyvinyl chloride resin component (B) having a peak top is included in a region less than that, and the component having a peak top is not included in a region where the polystyrene equivalent molecular weight of the GPC curve exceeds 10 ^ 7.0.
　成分（Ｂ）は、通常の分子量のポリ塩化ビニル系樹脂成分である。ポリ塩化ビニル系樹脂組成物からなるフィルムの低温耐衝撃性のみを考慮すれば、この組成物中の全てのポリ塩化ビニル系樹脂が超高分子量の成分（Ａ）であっても良い。しかし、工業的には、より小さいモーター負荷で、より速い製膜速度でフィルム製品を得ることが有利であるため、成分（Ｂ）を用いることが好ましい。 Component (B) is a normal molecular weight polyvinyl chloride resin component. Considering only the low-temperature impact resistance of the film made of the polyvinyl chloride resin composition, all the polyvinyl chloride resins in the composition may be the ultrahigh molecular weight component (A). However, industrially, it is advantageous to use a component (B) because it is advantageous to obtain a film product with a smaller motor load and a higher film forming speed.
　ＧＰＣ曲線における成分（Ｂ）のピークトップのポリスチレン換算分子量が１０＾３．５以上であることによって、ポリ塩化ビニル系樹脂組成物からなるフィルムの引張強度を良好に保つことができる。ＧＰＣ曲線における成分（Ｂ）のピークトップのポリスチレン換算分子量が１０＾６．０未満であることによって、製造時のモーター負荷低減効果を得ることができる。ＧＰＣ曲線における成分（Ｂ）のピークトップのポリスチレン換算分子量の下限は、さらに好ましくは１０＾４．０以上である。また、ＧＰＣ曲線における成分（Ｂ）のピークトップのポリスチレン換算分子量の上限は、さらに好ましくは１０＾５．５以下である。また、ＧＰＣ曲線における成分（Ｂ）のピークトップのポリスチレン換算分子量は、好ましくは１０＾４．０以上１０＾５．５以下であってよい。 When the polystyrene equivalent molecular weight of the peak top of the component (B) in the GPC curve is 10 ^ 3.5 or more, the tensile strength of the film made of the polyvinyl chloride resin composition can be kept good. When the polystyrene equivalent molecular weight of the peak top of the component (B) in the GPC curve is less than 10 ^ 6.0, the effect of reducing the motor load during production can be obtained. The lower limit of the molecular weight in terms of polystyrene at the peak top of component (B) in the GPC curve is more preferably 10 ^ 4.0 or more. Moreover, the upper limit of the molecular weight in terms of polystyrene at the peak top of the component (B) in the GPC curve is more preferably 10 ^ 5.5 or less. Moreover, the polystyrene conversion molecular weight of the peak top of the component (B) in the GPC curve may be preferably 10 ^ 4.0 or more and 10 ^ 5.5 or less.
　成分（Ｂ）のポリ塩化ビニル系樹脂としては、例えば、ポリ塩化ビニル、塩化ビニル・酢酸ビニル共重合体、塩化ビニル・（メタ）アクリル酸共重合体、塩化ビニル・（メタ）アクリル酸メチル共重合体、塩化ビニル・（メタ）アクリル酸エチル共重合体、塩化ビニル・マレイン酸エステル共重合体、塩化ビニル・エチレン共重合体、塩化ビニル・プロピレン共重合体、塩化ビニル・スチレン共重合体、塩化ビニル・イソブチレン共重合体、塩化ビニル・塩化ビニリデン共重合体、塩化ビニル・スチレン・無水マレイン酸三元共重合体、塩化ビニル・スチレン・アクリロニトリル三元共重合体、塩化ビニル・ブタジエン共重合体、塩化ビニル・イソプレン共重合体、塩化ビニル・塩素化プロピレン共重合体、塩化ビニル・塩化ビニリデン・酢酸ビニル三元共重合体、塩化ビニル・アクリロニトリル共重合体、塩化ビニル・各種ビニルエーテル共重合体等の塩化ビニル及び塩化ビニルと共重合可能な他のモノマーの共重合体；などの１種又は２種以上の混合物を用いることができる。 Examples of the component (B) polyvinyl chloride resin include polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, vinyl chloride / (meth) acrylic acid copolymer, vinyl chloride / methyl (meth) acrylate copolymer. Polymer, vinyl chloride / (meth) acrylate copolymer, vinyl chloride / maleic ester copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride / styrene copolymer, Vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride terpolymer, vinyl chloride / styrene / acrylonitrile terpolymer, vinyl chloride / butadiene copolymer , Vinyl chloride / isoprene copolymer, vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinylidene chloride, 1 type or 2 types, such as a vinyl acid terpolymer, a vinyl chloride and acrylonitrile copolymer, vinyl chloride and other vinyl ether copolymers, etc., and other monomers copolymerizable with vinyl chloride; Mixtures of more than one species can be used.
　成分（Ｂ）のポリ塩化ビニル系樹脂の重合度は、ポリスチレン換算分子量が上記範囲である限り特に限定されるものではないが、通常７００～２０００であってよい。 The degree of polymerization of the component (B) polyvinyl chloride resin is not particularly limited as long as the molecular weight in terms of polystyrene is in the above range, but it may usually be 700 to 2,000.
　本発明のポリ塩化ビニル系樹脂組成物からなるフィルムは、ＧＰＣ曲線のポリスチレン換算分子量が１０＾７．０を超える領域にピークトップを有する成分を含まないことによって、フィルムの外観をさらに良好に保つことができる。 The film made of the polyvinyl chloride resin composition of the present invention does not contain a component having a peak top in a region where the molecular weight in terms of polystyrene of the GPC curve exceeds 10 ^ 7.0, thereby further maintaining the appearance of the film. be able to.
　次に、本発明のポリ塩化ビニル系樹脂組成物からなるフィルムが成分（Ａ）及び（Ｂ）を含む態様におけるこれらの成分の含量の計算について説明する。
　ここでは、ポリ塩化ビニル系樹脂が成分（Ａ）及び（Ｂ）以外の成分を含まない（当該樹脂が成分（Ａ）及び（Ｂ）のみからなる）場合の各成分の含量計算について例示する。すなわち、ここでの成分（Ａ）及び（Ｂ）の含量は、それらの和が１００質量％であることを前提として算出された値である。 Next, calculation of the content of these components in an embodiment in which the film made of the polyvinyl chloride resin composition of the present invention contains components (A) and (B) will be described.
Here, the content calculation of each component when the polyvinyl chloride resin does not contain components other than the components (A) and (B) (the resin consists only of the components (A) and (B)) will be exemplified. That is, the contents of the components (A) and (B) here are values calculated on the assumption that the sum of them is 100% by mass.
　上記方法で得られたＧＰＣ曲線において、近似的に、ポリ塩化ビニル系樹脂中の成分（Ａ）及び（Ｂ）の含量とみなすことができる値は、以下の式に従って計算される。
　成分（Ａ）の含量　＝　以下の（ｉ）の値／以下の（ｉｉｉ）の値
　成分（Ｂ）の含量　＝　以下の（ｉｉ）の値／以下の（ｉｉｉ）の値
　（ｉ）：極小値をとる位置から、ポリスチレン換算分子量１０＾７．０以上であってＧＰＣ曲線の傾きが安定的にゼロになる位置までの部分の面積
　（ｉｉ）：ポリスチレン換算分子量１０＾３．５近傍であってＧＰＣ曲線の傾きが安定的にゼロになる位置から、極小値をとる位置までの部分の面積
　（ｉｉｉ）：ポリスチレン換算分子量１０＾３．５近傍であってＧＰＣ曲線の傾きが安定的にゼロになる位置から、ポリスチレン換算分子量１０＾７．０以上であってＧＰＣ曲線の傾きが安定的にゼロになる位置までの部分の面積
　ＧＰＣ曲線からの面積比の計算と成分（Ａ）及び（Ｂ）の含量との関係についての概念図を、図１に示す。図中において、「１」は成分（Ａ）のピーク、「２」は成分（Ａ）の含量とみなされる面積、「３」は成分（Ｂ）のピーク、「４」は成分（Ｂ）の含量とみなされる面積、「５」はポリスチレン換算分子量１０＾３．５近傍であってＧＰＣ曲線の傾きが安定的にゼロになる位置、「６」はＧＰＣ曲線が極小値をとる位置、「７」はポリスチレン換算分子量１０＾７．０以上であってＧＰＣ曲線の傾きが安定的にゼロになる位置を示す。 In the GPC curve obtained by the above method, a value that can be approximately regarded as the contents of the components (A) and (B) in the polyvinyl chloride resin is calculated according to the following equation.
Content of Component (A) = Value of the following (i) / Value of the following (iii) Content of Component (B) = Value of the following (ii) / Value of the following (iii) (i): Minimal value The area from the position where the molecular weight of polystyrene conversion is 10 ^ 7.0 or more to the position where the gradient of the GPC curve is stably zero (ii): near the polystyrene conversion molecular weight of 10 ^ 3.5 Area of the portion from the position where the slope of the GPC curve is stably zero to the position where the minimum value is obtained (iii): The polystyrene equivalent molecular weight is around 10 ^ 3.5 and the slope of the GPC curve is stably zero The area of the part from the position to the position where the polystyrene equivalent molecular weight is 10 ^ 7.0 or more and the slope of the GPC curve is stably zero. Calculation of the area ratio from the GPC curve and components (A) and (B) About the relationship with the content of The conceptual diagram is shown in Figure 1. In the figure, “1” is the peak of component (A), “2” is the area regarded as the content of component (A), “3” is the peak of component (B), and “4” is the component (B). “5” is a position where the molecular weight of polystyrene is about 10 ^ 3.5 and the gradient of the GPC curve is stably zero, “6” is a position where the GPC curve takes a minimum value, “7” "Indicates a position where the molecular weight of polystyrene equivalent is 10 ^ 7.0 or more and the slope of the GPC curve is stably zero.
　このように算出される成分（Ａ）の含量は、低温耐衝撃性の改良効果発現の観点から、下限について好ましくは０．５質量％以上であってよく、より好ましくは１質量％以上であってよい。また、成分（Ａ）の含量は、樹脂組成物の製造効率の観点から、上限について好ましくは１０質量％以下であってよく、より好ましくは６質量％以下であってよい。さらに、上述のように算出される成分（Ａ）の含量は、好ましくは、０．５質量％以上１０質量％以下であってよく、より好ましくは、１質量％以上６質量％以下であってよい。また、上記のように算出される成分（Ｂ）の含量の下限は、フィルム製造時のモーター負荷低減効果発現の観点から、９０質量％以上であってよい。また、成分（Ｂ）の含量の上限は、成分（Ａ）による低温耐衝撃性の改良効果発現の観点から、９９．５質量％以下であってよい。これらの量的関係をまとめると、好ましくは、上記のように算出される成分（Ａ）の含量は０．５～１０質量％であり、かつ成分（Ｂ）の含量は９９．５～９０質量％であってよい。より好ましくは、成分（Ａ）の含量が１～６質量％であり、かつ成分（Ｂ）の含量が９９～９４質量％であってよい。 The content of component (A) calculated in this way is preferably 0.5% by mass or more, more preferably 1% by mass or more with respect to the lower limit, from the viewpoint of improving the low-temperature impact resistance. It's okay. Further, the content of the component (A) is preferably 10% by mass or less, more preferably 6% by mass or less with respect to the upper limit from the viewpoint of the production efficiency of the resin composition. Furthermore, the content of the component (A) calculated as described above may be preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 6% by mass or less. Good. Further, the lower limit of the content of the component (B) calculated as described above may be 90% by mass or more from the viewpoint of expressing a motor load reduction effect during film production. Moreover, the upper limit of the content of the component (B) may be 99.5% by mass or less from the viewpoint of the effect of improving the low temperature impact resistance by the component (A). Summarizing these quantitative relationships, preferably, the content of component (A) calculated as described above is 0.5 to 10% by mass, and the content of component (B) is 99.5 to 90% by mass. %. More preferably, the content of the component (A) may be 1 to 6% by mass, and the content of the component (B) may be 99 to 94% by mass.
　なお、ポリ塩化ビニル系樹脂が、成分（Ａ）及び（Ｂ）以外に、ポリスチレン換算分子量が１０＾７．０を超える領域にピークトップを有する成分を含む場合には、近似的に、ポリ塩化ビニル系樹脂中の成分（Ａ）及び（Ｂ）の含量とみなすことができる値は、以下の式に従って計算される。
　成分（Ａ）の含量　＝　以下の（ｉ’）の値／以下の（ｉｉｉ’）の値
　成分（Ｂ）の含量　＝　以下の（ｉｉ）の値／以下の（ｉｉｉ’）の値
　（ｉ’）：ポリスチレン換算分子量１０＾７．０以下の極小値（第一の極小値）をとる位置から、ポリスチレン換算分子量１０＾７．０以上であって、かつ直近のピークとの間でＧＰＣ曲線の傾きが安定的にゼロになる位置又は直近のピークとの間の極小値（第二の極小値）をとる位置までの部分の面積
　（ｉｉ）：ポリスチレン換算分子量１０＾３．５近傍であってＧＰＣ曲線の傾きが安定的にゼロになる位置から、極小値（第一の極小値）をとる位置までの部分の面積
　（ｉｉｉ’）：ポリスチレン換算分子量１０＾３．５近傍であってＧＰＣ曲線の傾きが安定的にゼロになる位置から、ポリスチレン換算分子量１０＾７．０以上であって、かつ、最も高分子量側のピークよりも高分子量側の領域でＧＰＣ曲線の傾きが安定的にゼロになる位置までの部分の面積
　この態様における成分（Ａ）及び（Ｂ）の含量の好ましい比率は、ポリ塩化ビニル系樹脂が成分（Ａ）及び（Ｂ）のみからなる上記態様におけるこれらの成分の好ましい量に関する上記説明に準じる。 In addition, when the polyvinyl chloride resin contains a component having a peak top in a region where the molecular weight in terms of polystyrene exceeds 10 ^ 7.0, in addition to the components (A) and (B), The value that can be regarded as the content of the components (A) and (B) in the vinyl resin is calculated according to the following equation.
Component (A) content = value of the following (i ′) / value of the following (iii ′) Content of the component (B) = value of the following (ii) / value of the following (iii ′) (i ′ ): Polystyrene conversion molecular weight of 10 ^ 7.0 or less from the position where the molecular weight is 10 ^ 7.0 or less (first minimum value), polystyrene conversion molecular weight of 10 ^ 7.0 or more and the GPC curve of the nearest peak Area of the portion up to the position where the slope is stably zero or the position where the minimum value (second minimum value) between the nearest peak is taken (ii): near the polystyrene equivalent molecular weight of 10 ^ 3.5 The area of the portion from the position where the slope of the GPC curve is stably zero to the position where the minimum value (first minimum value) is taken (iii ′): near the polystyrene equivalent molecular weight of 10 ^ 3.5 and the GPC curve From the position where the slope of the stable is zero The area of the portion up to a position where the amount of the GPC curve is stably zero in the region having the amount of 10 ^ 7.0 or more and the highest molecular weight side with respect to the highest molecular weight side component (A The preferred ratio of the content of (B) and (B) is in accordance with the above description regarding the preferred amount of these components in the above embodiment in which the polyvinyl chloride resin consists solely of components (A) and (B).
ポリ塩化ビニル系樹脂組成物からなるフィルムの製造方法
　本発明に係るポリ塩化ビニル系樹脂組成物からなるフィルムは、所定成分を含む（場合によっては別の所定成分を含まない）ものである限り、特に限定されるものではないが、通常１～１００μｍ程度の厚みを有していてよい。また、このポリ塩化ビニル系樹脂組成物からなるフィルムは、公知のいかなる方法によっても製造されうる。以下では、典型例として、成分（Ａ）と成分（Ｂ）との混合物を含むポリ塩化ビニル系樹脂組成物からなるフィルムの製造方法を説明する。 Method for Producing Film Consisting of Polyvinyl Chloride Resin Composition As long as the film comprising the polyvinyl chloride resin composition according to the present invention includes a predetermined component (sometimes not including another predetermined component), Although it is not particularly limited, it may usually have a thickness of about 1 to 100 μm. Moreover, the film consisting of this polyvinyl chloride resin composition can be produced by any known method. Below, the manufacturing method of the film which consists of a polyvinyl chloride-type resin composition containing the mixture of a component (A) and a component (B) is demonstrated as a typical example.
　成分（Ａ）と成分（Ｂ）との混合物を含むポリ塩化ビニル系樹脂組成物の好ましい製造方法としては、成分（Ｂ）の一部を架橋させることにより成分（Ａ）を生成する方法を挙げることができる。 A preferable method for producing a polyvinyl chloride resin composition containing a mixture of the component (A) and the component (B) includes a method of producing the component (A) by crosslinking a part of the component (B). be able to.
　成分（Ａ）と成分（Ｂ）との混合物を含むポリ塩化ビニル系樹脂組成物からフィルムを製造する方法は、特に限定されず、公知の手段を用いることができる。好ましくは、成分（Ｂ）の一部を架橋させることにより成分（Ａ）を生成することによってポリ塩化ビニル系樹脂組成物を得るのに連続して、この組成物をＴダイやインフレーションダイなどの公知の押出ダイへ送り、製膜する方法を挙げることができる。 The method for producing a film from a polyvinyl chloride resin composition containing a mixture of component (A) and component (B) is not particularly limited, and known means can be used. Preferably, in order to obtain a polyvinyl chloride resin composition by producing the component (A) by crosslinking a part of the component (B), the composition is used as a T die or an inflation die. A method for forming a film by feeding to a known extrusion die can be mentioned.
　成分（Ｂ）の一部を架橋させることにより成分（Ａ）を生成する方法の好ましい一態様を、以下にて具体的に説明する。
　該方法には、
　成分（Ｂ）として用いるポリ塩化ビニル系樹脂１００質量部；
　アジピン酸系可塑剤、セバシン酸系可塑剤、アセチル化モノ脂肪酸グリセライド、アセチル化ジ脂肪酸グリセライド、及びエポキシ化大豆油からなる群から選択される少なくとも１種の可塑剤１０～６０質量部；並びに
　カルシウム亜鉛系安定剤　０．１～５．０質量部；
を含む原料混合物が好ましく用いられる。 One preferred embodiment of the method for producing the component (A) by crosslinking a part of the component (B) will be specifically described below.
The method includes:
100 parts by weight of polyvinyl chloride resin used as component (B);
10-60 parts by weight of at least one plasticizer selected from the group consisting of adipic acid plasticizers, sebacic acid plasticizers, acetylated monofatty acid glycerides, acetylated difatty acid glycerides, and epoxidized soybean oil; and calcium Zinc stabilizer 0.1-5.0 parts by mass;
A raw material mixture containing is preferably used.
　上記可塑剤が１０質量部以上であることによって、適切なせん断が行われ、架橋ゲルの生成及びそれに伴うフィルム外観の低下を防止することができる。上記可塑剤が６０質量部以下であることによって、原料混合物の流動性が適度に抑制され、せん断を良好に行うことができるため、成分（Ａ）を得るのがより容易になる。上記可塑剤は、より好ましくは１５～５０質量部の範囲の量で用いられる。 When the plasticizer is 10 parts by mass or more, appropriate shearing is performed, and formation of a crosslinked gel and accompanying film appearance deterioration can be prevented. When the plasticizer is 60 parts by mass or less, the fluidity of the raw material mixture is moderately suppressed and shearing can be performed satisfactorily, so that it becomes easier to obtain the component (A). The plasticizer is more preferably used in an amount in the range of 15 to 50 parts by mass.
　上記カルシウム亜鉛系安定剤が０．１質量部以上であることによって、ポリ塩化ビニル系樹脂の架橋反応が制御され、架橋ゲルの生成及びそれに伴うフィルム外観の低下を防止しつつ、目的の成分（Ａ）を効率的に得ることが可能になる。上記カルシウム亜鉛系安定剤が５．０質量部以下であることによって、ポリ塩化ビニル系樹脂の架橋反応が適切に進行し、所望量の成分（Ａ）を得ることができる。上記カルシウム亜鉛系安定剤は、より好ましくは０．３～２．０質量部の範囲の量で用いられる。 When the calcium zinc-based stabilizer is 0.1 part by mass or more, the crosslinking reaction of the polyvinyl chloride resin is controlled, and the target component ( A) can be obtained efficiently. When the said calcium zinc type stabilizer is 5.0 mass parts or less, the crosslinking reaction of a polyvinyl chloride-type resin can advance suitably, and a desired quantity of a component (A) can be obtained. The calcium zinc stabilizer is more preferably used in an amount in the range of 0.3 to 2.0 parts by mass.
　また上記カルシウム亜鉛系安定剤は、予め、アルコール系溶剤又はアルコール系溶剤と炭化水素系溶剤との混合溶剤に溶解又は分散させて使用するのが好ましい。上記カルシウム亜鉛系安定剤を予め溶剤に溶解又は分散させることにより、安定剤が原料混合物中に均一に分散し、高いせん断速度で制御された架橋反応が起こり、超高分子量の成分（Ａ）を生成させることがより容易に可能になる。 The calcium zinc stabilizer is preferably used by dissolving or dispersing in advance in an alcohol solvent or a mixed solvent of an alcohol solvent and a hydrocarbon solvent. By dissolving or dispersing the calcium zinc stabilizer in a solvent in advance, the stabilizer is uniformly dispersed in the raw material mixture, a crosslinking reaction controlled at a high shear rate occurs, and the ultrahigh molecular weight component (A) is added. It can be generated more easily.
　上記アルコール溶剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，４－ブチレングリコール、１，３－ブチレングリコール、ヘキサメチレングリコール、メトキシブタノール、イソオクタノール、２－エチルヘキサノール、ベンジルアルコールなどを挙げることができる。 Examples of the alcohol solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, hexamethylene glycol, methoxybutanol, isopropanol. Examples include octanol, 2-ethylhexanol, and benzyl alcohol.
　上記炭化水素系溶剤としては、脂肪族炭化水素系溶剤、芳香族炭化水素系溶剤、及びこれらの混合物を挙げることができる。またこれらの炭化水素系溶剤は、官能基を有するものであってもよい。これらの中で流動パラフィンが特に好ましい。 Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and mixtures thereof. In addition, these hydrocarbon solvents may have a functional group. Among these, liquid paraffin is particularly preferable.
　従来、ポリ塩化ビニル系樹脂を原料として用いるフィルム製膜では、焼けや架橋ゲルが発生し易いことから、反応中にかかるせん断速度を、通常、２０～１００（１／ｓ）程度と非常に小さくするようにされてきた。しかし、せん断速度を焼けや架橋ゲルの発生するぎりぎりまで上げたところ、制御された架橋反応が起きて、超高分子量の成分（Ａ）が十分に生成し、フィルムの耐低温衝撃性を高めることができることが分かった。 Conventionally, in film formation using a polyvinyl chloride resin as a raw material, burning and cross-linking gel are likely to occur, so the shear rate applied during the reaction is usually very low, about 20 to 100 (1 / s). Have been to. However, when the shear rate is increased to the point where burning or crosslinking gel is generated, a controlled crosslinking reaction occurs, and the ultra-high molecular weight component (A) is sufficiently generated to improve the low-temperature impact resistance of the film. I found out that
　成分（Ｂ）の一部を架橋させることにより成分（Ａ）を生成する方法において、好ましいせん断速度は、用いる成分（Ｂ）の分子量、並びに可塑剤及び安定剤の配合量にもよるが、１２０～１０００（１／ｓ）程度であってよい。せん断速度が１２０（１／ｓ）以上であることによって、成分（Ａ）が十分に生成し、耐低温衝撃性を良く改善することができる。せん断速度が適切か否かは、製膜時にかかる最も大きなせん断速度が、上記範囲にあるか否かによって判断することができる。せん断速度が１０００（１／ｓ）以下であることによって、焼けや架橋ゲルの発生を抑制することができる。せん断速度は、より好ましくは１３０～８００（１／ｓ）程度である。せん断速度は、更に好ましくは１５０～５００（１／ｓ）程度である。 In the method of producing component (A) by crosslinking a part of component (B), the preferred shear rate depends on the molecular weight of component (B) used and the blending amount of plasticizer and stabilizer. It may be about 1000 (1 / s). When the shear rate is 120 (1 / s) or more, the component (A) is sufficiently generated, and the low-temperature impact resistance can be improved well. Whether or not the shear rate is appropriate can be determined by whether or not the maximum shear rate applied during film formation is within the above range. When the shear rate is 1000 (1 / s) or less, it is possible to suppress the occurrence of burning and cross-linked gel. The shear rate is more preferably about 130 to 800 (1 / s). The shear rate is more preferably about 150 to 500 (1 / s).
　例えば、せん断速度は、単軸押出機を用いる場合において、一般に以下のとおり定義される。
　γ＝πＤＮ／６０ｈ
γ：せん断速度（１／ｓ）
π：円周率
Ｄ：単軸押出機のシリンダ内径（ｍｍ）
Ｎ：スクリュウ回転数（ｒｐｍ）
ｈ：シリンダ内面とスクリュウ外周との距離（ｍｍ） For example, the shear rate is generally defined as follows when a single screw extruder is used.
γ = πDN / 60h
γ: Shear rate (1 / s)
π: Circumference ratio D: Cylinder inner diameter of single screw extruder (mm)
N: Screw rotation speed (rpm)
h: Distance between cylinder inner surface and screw outer circumference (mm)
　また、二軸押出機を用いる場合において、以下の式で近似的にせん断速度を見積もることができる。
　γ＝πＤＮ／６０ｈ
γ：せん断速度（１／ｓ）
π：円周率
Ｄ：二軸押出機のシリンダ内径（ｍｍ）
Ｎ：スクリュウ回転数（ｒｐｍ）
ｈ：シリンダ内面とスクリュウ外周との距離（ｍｍ） Moreover, when using a twin-screw extruder, a shear rate can be estimated approximately by the following formula.
γ = πDN / 60h
γ: Shear rate (1 / s)
π: Circumference ratio D: Cylinder inner diameter (mm) of twin-screw extruder
N: Screw rotation speed (rpm)
h: Distance between cylinder inner surface and screw outer circumference (mm)
　また、ダイスにおけるせん断速度は、最も大きなせん断速度がかかるリップ部において一般に以下のとおり定義される。
　γ＝Ｖ／Ｓｔ
γ：せん断速度（１／ｓ）
Ｓ：ダイスリップ部の表面積（ｍｍ＾２）
ｔ：ダイスリップの開度（ｍｍ）
Ｖ：体積換算の吐出量（ｍｍ＾３／ｓ） The shear rate in the die is generally defined as follows in the lip portion where the largest shear rate is applied.
γ = V / St
γ: Shear rate (1 / s)
S: Surface area of die slip part (mm ^ 2)
t: Die slip opening (mm)
V: discharge volume in terms of volume (mm ^ 3 / s)
　本発明のポリ塩化ビニル系樹脂組成物からなるフィルムには、通常使用される可塑剤を更に含ませることができる。
　このような可塑剤としては、例えば、
　ジ－２－エチルヘキシルフタレート、ジブチルフタレート、ブチルヘキシルフタレート、ジヘプチルフタレート、ジオクチルフタレート、ジイソノニルフタレート、ジイソデシルフタレート、ジラウリルフタレート、ジシクロヘキシルフタレート、ジオクチルテレフタレートなどのフタレート系可塑剤；
　ジオクチルアジペート、ジイソノニルアジペート、ジイソデシルアジペート、ジ（ブチルジグリコール）アジペートなどのアジペート系可塑剤；
　トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリ（イソプロピルフェニル）ホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリ（ブトキシエチル）ホスフェート、オクチルジフェニルホスフェートなどのホスフェート可塑剤系；
　多価アルコールとしてエチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ヘキサンジオール、１，６－ヘキサンジオール、ネオペンチルグリコールなどを用い、二塩基酸としてシュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバチン酸、フタール酸、イソフタル酸、テレフタル酸などを用い、必要により一価アルコール、モノカルボン酸をストッパーに使用したポリエステル系可塑剤；
　その他、テトラヒドロフタール酸系可塑剤、アゼライン酸系可塑剤、セバチン酸系可塑剤、ステアリン酸系可塑剤、クエン酸系可塑剤、トリメリット酸系可塑剤、ピロメリット酸系可塑剤、ビフェニルテトラカルボン酸エステル系可塑剤、塩素系可塑剤などを挙げることができる。 The film made of the polyvinyl chloride resin composition of the present invention can further contain a commonly used plasticizer.
As such a plasticizer, for example,
Phthalate plasticizers such as di-2-ethylhexyl phthalate, dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate;
Adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyldiglycol) adipate;
Phosphate plasticizer systems such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate;
As polyhydric alcohols, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1, Using 6-hexanediol, neopentyl glycol, etc., oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid as dibasic acids Polyester plasticizer using acid etc. and using monohydric alcohol or monocarboxylic acid as a stopper if necessary;
In addition, tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid plasticizer, biphenyltetra Examples thereof include carboxylic acid ester plasticizers and chlorine plasticizers.
　また、本発明のポリ塩化ビニル系樹脂組成物からなるフィルムには、通常使用される添加剤を更に含ませることができる。
　このような添加剤としては、例えば、
　ハイドロタルサイト化合物、ゼオライト化合物、金属石鹸などの塩素捕捉剤；
　リン系、フェノール系、硫黄系などの酸化防止剤；
　ヒンダードアミン系などの光安定剤；
　エポキシ化大豆油などのエポキシ化合物；
　ベンゾトリアゾール系、ベンゾフェノン系などの紫外線吸収剤；
　β－ジケトン化合物；過塩素酸塩類；多価アルコール；顔料；滑剤；架橋剤；帯電防止剤；防曇剤；プレートアウト防止剤；表面処理剤；難燃剤；充填剤；蛍光剤；防黴剤；殺菌剤；金属不活性剤；離型剤；加工助剤等を挙げることができる。 In addition, the film made of the polyvinyl chloride resin composition of the present invention can further contain commonly used additives.
As such an additive, for example,
Chlorine scavengers such as hydrotalcite compounds, zeolite compounds, metal soaps;
Phosphorous, phenolic and sulfur antioxidants;
Light stabilizers such as hindered amines;
Epoxy compounds such as epoxidized soybean oil;
UV absorbers such as benzotriazole and benzophenone;
β-diketone compounds; perchlorates; polyhydric alcohols; pigments; lubricants; cross-linking agents; antistatic agents; antifogging agents; plate-out preventing agents; surface treatment agents; A bactericidal agent, a metal deactivator, a mold release agent, a processing aid, and the like.
　以下、本発明を実施例により説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.
フィルム物性の測定方法
（イ）耐低温衝撃性
　内径７６ｍｍ、外径８３ｍｍの鉄製円筒枠に、フィルムを略緊張状態で枠口全体を覆うように張り、低温庫で３０分間状態調節した後、外径３７．５ｍｍ、質量４３ｇの半球形落錘具を、円筒枠口に張ったフィルムの上４０ｃｍの高さから、その中心に落とした。試験片５枚を１セットし、５枚全てが割れなかった最低温度を測定した。 Method of measuring film properties (a) Low temperature impact resistance The film is stretched over an iron cylindrical frame with an inner diameter of 76 mm and an outer diameter of 83 mm so as to cover the entire frame mouth in a substantially tension state, and after conditioning for 30 minutes in a low temperature chamber A hemispherical falling weight tool having a diameter of 37.5 mm and a mass of 43 g was dropped from the height of 40 cm above the film stretched on the cylindrical frame mouth to the center thereof. One set of five test pieces was measured, and the minimum temperature at which all five pieces did not break was measured.
（ロ）自己粘着性
　フィルムの小巻を刃物で裂き、フィルム２枚が密着した状態のまま、長さ１００ｍｍ×幅５０ｍｍの試験片を、フィルムのマシン方向が長さ方向となるように切出した。試験片の長さ方向の片方の端部から５０ｍｍを剥離した後、Ｔ字剥離試験を、２００ｍｍ／分の条件で行った。剥離強度は、得られた応力－歪曲線における、応力が略一定値をとる部分の二乗平均値とした。フィルムの応力－歪曲線からの剥離強度算出についての概念図を、図２に示す。
　なお、自己粘着性に係る剥離強度の判断尺度は、以下のとおりである。
　・剥離強度が１５Ｎ／ｃｍ未満：不良
　・剥離強度が１５Ｎ／ｃｍ以上、５０Ｎ／ｃｍ未満：やや不良
　・剥離強度が５０Ｎ／ｃｍ以上、２５０Ｎ／ｃｍ未満：良好
　・剥離強度が２５０Ｎ／ｃｍ以上：十分に良好 (B) Self-adhesive A small piece of film was torn with a blade, and a test piece having a length of 100 mm and a width of 50 mm was cut out so that the machine direction of the film was the length direction while the two films were in close contact with each other. . After peeling 50 mm from one end in the length direction of the test piece, a T-shaped peel test was performed under the condition of 200 mm / min. The peel strength was the mean square value of the portion where the stress takes a substantially constant value in the obtained stress-strain curve. A conceptual diagram for calculating peel strength from the stress-strain curve of the film is shown in FIG.
In addition, the judgment scale of the peeling strength concerning self-adhesiveness is as follows.
Peel strength is less than 15 N / cm: poor Peel strength is 15 N / cm or more and less than 50 N / cm: Somewhat poor Peel strength is 50 N / cm or more and less than 250 N / cm: Good Peel strength is 250 N / cm or more: Good enough
（ハ）ストレッチ性
　ＪＩＳ　Ｋ７１２７－１９９９に従い、試験片タイプ５、試験速度２００ｍｍ／分の条件で引張試験を行い、破断時の伸び率を測定した。
　なお、ストレッチ性に係る破断時の伸び率の判断尺度は、以下のとおりである。
　・破断時の伸び率が２００％未満：不良
　・破断時の伸び率が２００％以上、２５０％未満：やや不良
　・破断時の伸び率が２５０％以上、３００％未満：良好
　・破断時の伸び率が３００％以上：十分に良好 (C) Stretchability According to JIS K7127-1999, a tensile test was performed under the conditions of test piece type 5 and a test speed of 200 mm / min, and the elongation at break was measured.
In addition, the judgment scale of the elongation rate at the time of the fracture | rupture concerning stretch property is as follows.
・ Elongation at break is less than 200%: Defective ・ Elongation at break is 200% or more and less than 250%: Slightly bad ・ Elongation at break is 250% or more and less than 300%: Good ・ Elongation at break Rate is over 300%: good enough
（ニ）透明性（ヘイズ）
　ＪＩＳ　Ｋ７１０５－１９８１に従い、ヘイズ値を測定した。
　なお、透明性に係るヘイズ値の判断尺度は、以下のとおりである。
　・ヘイズ値が３.５％超過：不良
　・ヘイズ値が２.５％超過、３.５％以下：やや不良
　・ヘイズ値が１.５％超過、２.５％以下：良好
　・ヘイズ値が１.５％以下：十分に良好 (D) Transparency (haze)
The haze value was measured according to JIS K7105-1981.
In addition, the judgment scale of the haze value concerning transparency is as follows.
-Haze value is over 3.5%: poor-Haze value is over 2.5%, 3.5% or less: Slightly bad-Haze value is over 1.5%, 2.5% or less: Good-Haze value is 1.5% or less: sufficiently good
（ホ）フィルム外観
　フィルムの表面に、入射角をいろいろと変えつつ蛍光灯の光を当てながら、これを目視観察し、以下の基準で評価した。
　◎（十分に良好）：直径０．１ｍｍ以上の大きさの異物やフィッシュアイは観察されない。
　○（良好）：直径０．１ｍｍ以上の大きさの異物やフィッシュアイが観察されるが、直径０．３ｍｍ以上の大きさの異物やフィッシュアイは観察されない。
　△（やや不良）：直径０．３ｍｍ以上の大きさの異物やフィッシュアイが１個／Ａ４サイズ未満の頻度で存在する。
　×（不良）：直径０．３ｍｍ以上の大きさの異物やフィッシュアイが１個／Ａ４サイズ以上の頻度で存在する。 (E) Appearance of film The surface of the film was visually observed while applying light from a fluorescent lamp while changing the incident angle in various ways, and evaluated according to the following criteria.
A (sufficiently good): Foreign matters and fish eyes having a diameter of 0.1 mm or more are not observed.
○ (Good): Foreign matters and fish eyes having a diameter of 0.1 mm or more are observed, but foreign matters and fish eyes having a diameter of 0.3 mm or more are not observed.
Δ (slightly defective): Foreign matter or fish eye with a diameter of 0.3 mm or more is present at a frequency of less than 1 / A4 size.
X (defect): Foreign matter or fish eye having a diameter of 0.3 mm or more is present at a frequency of 1 / A4 size or more.
使用した原材料
（１）ポリ塩化ビニル系樹脂
（１－１）株式会社カネカのポリ塩化ビニル樹脂：
重合度８００、ＧＰＣにより測定したポリスチレン換算分子量１０＾４．９
（１－２）株式会社カネカのポリ塩化ビニル樹脂：
重合度１３００、ＧＰＣにより測定したポリスチレン換算分子量１０＾５．１
（１－３）株式会社カネカのポリ塩化ビニル樹脂：
重合度１５００、ＧＰＣにより測定したポリスチレン換算分子量１０＾５．２ Raw materials used (1) Polyvinyl chloride resin (1-1) Polyvinyl chloride resin from Kaneka Corporation:
Polymerization degree 800, polystyrene conversion molecular weight 10 ^ 4.9 measured by GPC
(1-2) Kaneka Corporation's polyvinyl chloride resin:
Polymerization degree 1300, polystyrene conversion molecular weight 10 ^ 5.1 measured by GPC
(1-3) Polyvinyl chloride resin from Kaneka Corporation:
Polymerization degree 1500, polystyrene conversion molecular weight 10 ^ 5.2 measured by GPC
（２）可塑剤
（２－１）田岡化学工業株式会社のアジピン酸系可塑剤「ＤＩＮＡ（商品名）」
（２－２）株式会社ＡＤＥＫＡのエポキシ化大豆油「アデカサイザーＯ－１３０Ｐ（商品名）」 (2) Plasticizer (2-1) Adipate plasticizer “DINA (trade name)” by Taoka Chemical Co., Ltd.
(2-2) Epoxidized soybean oil "ADEKA SIZER O-130P (trade name)" by ADEKA Corporation
（３）カルシウム亜鉛系安定剤
（３－１）勝田化工株式会社の「ＣＺ－４４０（商品名）」 (3) Calcium zinc stabilizer (3-1) “CZ-440 (trade name)” by Katsuta Chemical Co., Ltd.
（４）その他成分
（４－１）理研ビタミン株式会社の防曇剤「ＲＶＭ－０６（商品名）」 (4) Other components (4-1) Anti-fogging agent “RVM-06 (trade name)” of Riken Vitamin Co., Ltd.
実施例１
　上記（１－１）１００質量部；　
　上記（２－１）３５質量部；
　上記（２－２）１０質量部；
　上記（３－１）０．８質量部；
　上記（４－１）２．０質量部；
からなる配合物を用い、
単軸押出機とＴダイを備えた装置を使用し、製膜時にかかる最も大きなせん断速度２００（１／ｓ）の条件で、厚み１０μｍのフィルムを製膜した。 Example 1
(1-1) 100 parts by mass of the above;
(2-1) 35 parts by mass;
(2-2) 10 parts by mass of the above;
(3-1) 0.8 parts by mass above;
(4-1) 2.0 parts by mass;
Using a composition consisting of
Using a device equipped with a single screw extruder and a T die, a film having a thickness of 10 μm was formed under the condition of the largest shear rate of 200 (1 / s) applied during film formation.
　このようにして得られたフィルムのＧＰＣ測定を行ったところ、成分（Ａ）が生成していた。ＧＰＣ曲線における成分（Ａ）のピークトップのポリスチレン換算分子量は１０＾６．５であった。ＧＰＣ曲線から、上記段落００２８記載の式により算出された成分（Ａ）の含量とみなされる値は、２．８質量％であった。またポリスチレン換算分子量が１０＾７．０を超える領域にピークトップを有する成分は認められなかった。
　さらに、このフィルムについて、上記（イ）～（ホ）の物性評価を行った。結果を表１に示す。 When GPC measurement of the film thus obtained was performed, component (A) was produced. The polystyrene equivalent molecular weight of the peak top of the component (A) in the GPC curve was 10 ^ 6.5. The value regarded as the content of the component (A) calculated from the GPC curve according to the formula described in the above paragraph 0028 was 2.8% by mass. Moreover, the component which has a peak top in the area | region where the molecular weight of polystyrene conversion exceeds 10 ^ 7.0 was not recognized.
Further, the physical properties of (i) to (e) above were evaluated for this film. The results are shown in Table 1.
比較例、実施例２～６、参考例
　製膜時にかかる最も大きなせん断速度を表２に示す値に変更したこと以外は、全て実施例１と同様にフィルム製造を行った。いずれもポリスチレン換算分子量が１０＾７．０を超える領域にピークトップを有する成分は認められなかった。結果を表２に示す。 Comparative Examples, Examples 2 to 6, and Reference Examples Film production was carried out in the same manner as in Example 1 except that the maximum shear rate applied during film formation was changed to the values shown in Table 2. In any case, a component having a peak top in the region where the molecular weight in terms of polystyrene exceeds 10 ^ 7.0 was not observed. The results are shown in Table 2.
実施例７～１２
　用いる塩化ビニル系樹脂組成物の配合を、表１に示すように変更したこと以外は、全て実施例１と同様にフィルム製造を行った。いずれもポリスチレン換算分子量が１０＾７．０を超える領域にピークトップを有する成分は認められなかった。結果を表１に示す。 Examples 7-12
Film production was performed in the same manner as in Example 1 except that the composition of the vinyl chloride resin composition used was changed as shown in Table 1. In any case, a component having a peak top in the region where the molecular weight in terms of polystyrene exceeds 10 ^ 7.0 was not observed. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
１：成分（Ａ）のピーク
２：成分（Ａ）の含量とみなされる面積
３：成分（Ｂ）のピーク
４：成分（Ｂ）の含量とみなされる面積
５：ポリスチレン換算分子量１０＾３．５近傍であってＧＰＣ曲線の傾きが安定的にゼロになる位置
６：微分分子量分布曲線（ＧＰＣ曲線）が極小値をとる位置
７：ポリスチレン換算分子量１０＾７．０以上であってＧＰＣ曲線の傾きが安定的にゼロになる位置 1: Component (A) peak 2: Area regarded as content of component (A) 3: Component (B) peak 4: Area regarded as content of component (B) 5: Polystyrene equivalent molecular weight 10 ^ 3.5 Position 6 where the slope of the GPC curve is stably zero in the vicinity 6: Position where the differential molecular weight distribution curve (GPC curve) takes the minimum value 7: Position of the polystyrene equivalent molecular weight 10 ^ 7.0 or more and the slope of the GPC curve Where is stable to zero

Claims (8)

  1. 　ポリ塩化ビニル系樹脂組成物からなるフィルムであって、
    　ゲル浸透クロマトグラフィにより測定した微分分子量分布曲線のポリスチレン換算分子量が１０＾６．０以上１０＾７．０以下の領域にピークトップを有するポリ塩化ビニル系樹脂成分（Ａ）を含むことを特徴とするフィルム。     A film comprising a polyvinyl chloride resin composition,
    It contains a polyvinyl chloride resin component (A) having a peak top in a region where the polystyrene equivalent molecular weight of the differential molecular weight distribution curve measured by gel permeation chromatography is 10 ^ 6.0 to 10 ^ 7.0. the film.
  2. 　更に、ゲル浸透クロマトグラフィにより測定した微分分子量分布曲線のポリスチレン換算分子量が１０＾３．５以上１０＾６．０未満の領域にピークトップを有するポリ塩化ビニル系樹脂成分（Ｂ）を含むことを特徴とする請求項１に記載のフィルム。 Furthermore, it contains a polyvinyl chloride resin component (B) having a peak top in a region where the polystyrene equivalent molecular weight of the differential molecular weight distribution curve measured by gel permeation chromatography is 10 ^ 3.5 or more and less than 10 ^ 6.0. The film according to claim 1.
  3. 　ゲル浸透クロマトグラフィにより測定した微分分子量分布曲線のポリスチレン換算分子量が１０＾７．０を超える領域にピークトップを有する成分を含まないことを特徴とする請求項１に記載のフィルム。 2. The film according to claim 1, which does not contain a component having a peak top in a region where the polystyrene equivalent molecular weight of the differential molecular weight distribution curve measured by gel permeation chromatography exceeds 10 ^ 7.0.
  4. 　更に、ゲル浸透クロマトグラフィにより測定した微分分子量分布曲線のポリスチレン換算分子量が１０＾３．５以上１０＾６．０未満の領域にピークトップを有するポリ塩化ビニル系樹脂成分（Ｂ）を含み、かつ、ゲル浸透クロマトグラフィにより測定した微分分子量分布曲線のポリスチレン換算分子量が１０＾７．０を超える領域にピークトップを有する成分を含まないことを特徴とする請求項１に記載のフィルム。 And a polyvinyl chloride resin component (B) having a peak top in a region where the polystyrene equivalent molecular weight of the differential molecular weight distribution curve measured by gel permeation chromatography is 10 ^ 3.5 or more and less than 10 ^ 6.0, and 2. The film according to claim 1, wherein a component having a peak top is not included in a region where the polystyrene-equivalent molecular weight of the differential molecular weight distribution curve measured by gel permeation chromatography exceeds 10 ^ 7.0.
  5. 　上記成分（Ａ）が、上記成分（Ｂ）の架橋反応により形成されたものであることを特徴とする請求項２又は４に記載のフィルム。 The film according to claim 2 or 4, wherein the component (A) is formed by a crosslinking reaction of the component (B).
  6. 　請求項５に記載のフィルムの製造方法であって、
    　上記成分（Ｂ）としてのポリ塩化ビニル系樹脂１００質量部；
    　アジピン酸系可塑剤、セバシン酸系可塑剤、アセチル化モノ脂肪酸グリセライド、アセチル化ジ脂肪酸グリセライド、及びエポキシ化大豆油からなる群から選択される少なくとも１種の可塑剤１０～６０質量部；並びに
    　カルシウム亜鉛系安定剤０．１～５．０質量部；
    を含む原料混合物を用い、
    　上記成分（Ｂ）の一部を架橋させることにより上記成分（Ａ）を生成させることを含む方法。     It is a manufacturing method of the film of Claim 5, Comprising:
    100 parts by mass of a polyvinyl chloride resin as the component (B);
    10-60 parts by weight of at least one plasticizer selected from the group consisting of adipic acid plasticizers, sebacic acid plasticizers, acetylated monofatty acid glycerides, acetylated difatty acid glycerides, and epoxidized soybean oil; and calcium Zinc stabilizer 0.1-5.0 parts by mass;
    Using a raw material mixture containing
    The method including producing | generating the said component (A) by bridge | crosslinking a part of said component (B).
  7. 　請求項１～５のいずれか１項に記載のフィルムの食品包装への使用。 Use of the film according to any one of claims 1 to 5 for food packaging.
  8. 　請求項６に記載の方法で得られたフィルムの食品包装への使用。 Use of the film obtained by the method according to claim 6 for food packaging.
PCT/JP2013/074242 2013-09-09 2013-09-09 Polyvinyl chloride resin composition film WO2015033468A1 (en)

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