WO2020189180A1 - Resin film and method for manufacturing same - Google Patents

Resin film and method for manufacturing same Download PDF

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Publication number
WO2020189180A1
WO2020189180A1 PCT/JP2020/007088 JP2020007088W WO2020189180A1 WO 2020189180 A1 WO2020189180 A1 WO 2020189180A1 JP 2020007088 W JP2020007088 W JP 2020007088W WO 2020189180 A1 WO2020189180 A1 WO 2020189180A1
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WO
WIPO (PCT)
Prior art keywords
resin film
vinylidene chloride
less
value
resin composition
Prior art date
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PCT/JP2020/007088
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French (fr)
Japanese (ja)
Inventor
壮騎 漆川
細田　友則
整 榎本
太一 清野
孝幸 関
裕子 松浦
Original Assignee
株式会社クレハ
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Application filed by 株式会社クレハ filed Critical 株式会社クレハ
Priority to CN202080015233.2A priority Critical patent/CN113490693B/en
Publication of WO2020189180A1 publication Critical patent/WO2020189180A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and 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
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/08—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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present invention relates to a resin film and a method for producing the same.
  • Vinylidene chloride-based resin film is widely used as a wrap film, etc. because it has characteristics such as difficulty in permeating oxygen and moisture, high adhesion, high heat resistance, and high transparency.
  • the wrap film is usually housed in a storage box as a wound body wound in a roll shape.
  • a storage box having a main body portion for accommodating the wound body and a lid portion rotatably connected to the main body portion is known.
  • the user of the wrap film grips the end portion of the wrap film housed in the main body portion and pulls the end portion while rotating the winding body to use an amount of wrap film between the main body portion and the lid portion.
  • the required length of wrap film can be taken out of the storage box by feeding out from the gap and cutting with a cutting blade installed on the lid. At this time, the end portion of the wound body after cutting is attached to the main body portion and locked in order to facilitate the next feeding.
  • the vinylidene chloride-based resin film is produced by melt-extruding a vinylidene chloride-based resin composition obtained by a method such as suspension polymerization and then stretching it into a film.
  • Patent Document 1 by using a suspension dispersant during suspension polymerization, suspension stability is enhanced and the particle size of the obtained vinylidene chloride resin is controlled to achieve extrusion stability and uniform film thickness. It is stated that it can enhance the sex. Patent Document 1 describes that a film could be satisfactorily produced by using a suspending agent of 500 ppm with respect to a monomer for synthesizing 100 parts by mass of a vinylidene chloride resin.
  • Patent Document 2 describes that by adding liquid paraffin to a polyvinylidene chloride-based film, the film can exhibit appropriate peeling performance.
  • the end portion cut by the reverse rotation of the winding body is rewound into the inside of the main body, and the wrap film is wound.
  • the end portion may be stuck to the surface (hereinafter, the end portion of the wrap film is stuck to the surface of the winding portion due to rewinding). Is also simply referred to as "rewinding state").
  • the wrap film is required to have high adhesion, the adhesion between the wrap films is also very high.
  • the present invention provides a resin film in which the end portion can be easily peeled off from the wound portion in the rewound state without causing tearing of the resin film in the vertical direction, and a method for producing such a resin film.
  • the purpose is to do.
  • the resin film according to one aspect of the present invention for solving the above problems is a resin film made of a vinylidene chloride-based resin composition, and has a surface adhesion value (mN) with respect to a tear strength value (mN) to MD.
  • the ratio of N) value of surface adhesion / value of tear strength to MD is 0.35 or more and less than 0.41.
  • a method for producing a resin film according to another aspect of the present invention for solving the above problems includes a step of stretching a melted and extruded vinylidene chloride-based resin composition, and the stretched vinylidene chloride-based resin. It is a method for producing a resin film having a step of relaxing the composition.
  • the vinylidene chloride-based resin composition contains a monomer for synthesizing a vinylidene chloride-based resin by polymerization in the presence of a water-soluble cellulose derivative in which the content of the monomer with respect to the total mass is 300 ppm or more and 600 ppm or less. It is a resin composition obtained by suspend polymerization in an aqueous medium.
  • the polyvinylidene chloride-based resin composition in the production method, has a stretching ratio of 3.5 times or more and 5.0 times or less for MD and a stretching ratio of 4.0 times or more and 5.5 for TD.
  • the stretched vinylidene chloride resin composition is relaxed so that the relaxation rate to MD is 9.5% or more and 12.5% or less.
  • a resin film in which the end portion can be easily peeled off from the wound portion in the rewound state without causing tearing of the resin film in the vertical direction and a method for producing such a resin film.
  • One embodiment of the present invention relates to a resin film made of a vinylidene chloride-based resin composition.
  • the above resin film has a ratio of the value of surface adhesion (unit: N) to the value of tear strength to MD (unit: mN) (value of surface adhesion (N) / value of tear strength to MD (mN). ).
  • this ratio is also simply referred to as “recovery coefficient”), which is 0.35 or more and less than 0.41.
  • MD means the winding direction of the resin film that is wound in a roll shape.
  • TD means a direction orthogonal to MD in the plane of the resin film.
  • the value of the surface adhesion force is lower. It is desirable that the tear strength to the MD is higher. However, it is not desirable to reduce the surface adhesion force too much in order to sufficiently secure the adhesion of the resin film to the container or the like.
  • the recovery coefficient is set to 0.35 or more and less than 0.41.
  • the recovery coefficient is 0.35 or more, the surface adhesion of the resin film is not excessively reduced, and sufficient adhesion to a container or the like is ensured.
  • the recovery coefficient is less than 0.41, the tear strength of the resin film to the MD is moderately increased and the surface adhesion is moderately reduced, so that the resin film does not tear in the vertical direction. It is easy to restore the resin film in the rewound state.
  • the recovery coefficient is preferably 0.36 or more and 0.40 or less, and more preferably 0.37 or more and 0.40 or less.
  • the value of the tear strength to the MD can be a value measured using a known tear tester. Specifically, a test piece obtained by cutting a resin film into a size of 63.5 mm in the vertical direction (MD) x 50 mm in the width direction (TD) is set in the center of a clamp of a tear tester, and is set in the vertical direction (TD). Make a cut with a knife in the center of the width direction (TD) of the test piece so that the cut length in MD) is 12.7 mm, open the pendulum, and cut the test piece. At this time, the maximum load for tearing the test piece can be a value (unit: mN) of the tear strength of the test piece to the MD.
  • the surface adhesion force can be a value measured using a known tensile tester. Specifically, the resin film is fixed to the bottom surface of two cylindrical aluminum jigs having a bottom area of 25 cm 2 and a mass of 300 g so as not to cause wrinkles, and the two jigs are cured. The resin films fixed to the jig are brought into vertical contact with each other and crimped. Then, using a tensile tester, the above two jigs are pulled in opposite vertical directions. At this time, the maximum load (unit: N) for pulling the jig apart can be set as the value of the surface adhesion force of the test piece.
  • the resin film preferably has a tear strength value of 32.0 mN or more and 34.5 mN or less, and is preferably 32.5 mN or more. It is more preferably 34.5 mN or less, and further preferably 33.0 mN or more and 34.5 mN or less.
  • the resin film is less likely to tear vertically during restoration or other use, so that the ease of use of the resin film can be further improved.
  • the surface adhesion value of the resin film is preferably 12.0 N or more and 13.0 N or less, and 12.0 N or more and 12. It is more preferably 5N or less.
  • the value of the surface adhesion force is 12.0 N or more, the resin film easily adheres to the container or the like during use, so that the ease of use of the resin film can be further improved.
  • the vinylidene chloride-based resin composition containing the vinylidene chloride-based resin polymerized in the presence of a predetermined amount of the water-soluble cellulose derivative is stretched and relaxed at a predetermined ratio.
  • a resin film satisfying the value of the recovery coefficient can be produced.
  • the haze value of the resin film is preferably 1.2% or less, preferably 0.8% or less. More preferably, it is more preferably 0.6% or less.
  • the lower limit of the haze value is not particularly set, it can be 0.05% or more.
  • the haze value can be a value obtained by measuring in accordance with JIS K 7136 (2000).
  • the resin film has an arithmetic surface roughness (Ra) defined in JIS B 0601 (2013) of more than 5.0 nm and less than 20.0 nm. Is more preferable, and it is more preferably larger than 5.0 nm and 7.7 nm or less, and further preferably larger than 6.0 nm and less than 7.5 nm.
  • Ra arithmetic surface roughness
  • the above arithmetic surface roughness (Ra) can be a value obtained by using a known surface roughness measuring instrument.
  • a resin film satisfying the above-mentioned recovery coefficient value can be produced by stretching the vinylidene chloride-based resin composition at a higher magnification than before. Therefore, in the resin film according to the present embodiment, the molecules of the vinylidene chloride resin are oriented in the MD in a more tense state, and it is easier to pierce the cutting blade or the like, and cutting (particularly cutting to TD) is possible. It's easier.
  • the resin film preferably has a piercing strength value of less than 4.0 N, more preferably less than 3.8 N, and even more preferably less than 3.5 N. Although the lower limit of the piercing strength is not particularly determined, it can be 1.5 N or more from the viewpoint of facilitating the maintenance of the shape of the resin film.
  • the piercing strength can be a value obtained by measuring in accordance with JIS Z 1707 (2019).
  • the thickness of the resin film is not particularly limited, but can be 1 ⁇ m or more and 50 ⁇ m or less, preferably 4 ⁇ m or more and 45 ⁇ m or less, and more preferably 7 ⁇ m or more and 40 ⁇ m or less.
  • the thickness is 1 ⁇ m or more, the resin film can be made difficult to tear.
  • the thickness is 50 ⁇ m or less, the cut property of the resin film is good, and the feel of the film is good.
  • the resin film can be a transparent resin film.
  • the resin film has adhesiveness to foods and tableware. Therefore, the resin film can be suitably used as a wrap film.
  • the resin film is stored as a wound body wound in a roll shape.
  • the wound body is housed in a storage box having a main body portion for accommodating the wound body portion and a lid portion rotatably connected to the main body portion, and having a cutting blade on the lid portion.
  • the winding body housed in the storage box pulls the end portion of the resin film while rotating the winding body, and the amount of the resin film to be used is drawn out from the gap between the main body portion and the lid portion to the lid portion. By cutting with the installed cutting blade, it can be taken out of the storage box by the required length.
  • the resin film is a single-layer film formed by molding a vinylidene chloride-based resin composition into a film.
  • the above-mentioned vinylidene chloride-based resin composition is a resin composition containing vinylidene chloride-based resin as a main component.
  • the above-mentioned vinylidene chloride-based resin may be a homopolymer of vinylidene chloride or a copolymer containing a structural unit derived from vinylidene chloride.
  • the above-mentioned copolymer is a copolymer of vinylidene chloride and a monomer copolymerizable with vinylidene chloride.
  • monomers copolymerizable with vinylidene chloride include alkyl groups containing vinyl chloride, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate and the like.
  • Methacrylic acid having 1 or more and 18 or less carbon atoms methacrylic acid having 1 or more and 18 or less carbon atoms in an alkyl group containing methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl tacrylate, etc.
  • Acid alkyl ester vinyl cyanide compound containing acrylic acid nitrile and methacrylic acid, aromatic vinyl compound containing styrene, vinyl ester of aliphatic carboxylic acid having 1 or more and 18 or less carbon atoms including vinyl acetate, carbon number Vinyl polymerizable unsaturated carboxylic acid including alkyl vinyl ether, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid of 1 to 18 or less, vinyl polymerizable unsaturated carboxylic acid such as maleic acid, fumaric acid and itaconic acid.
  • Alkyl esters (which may be partial esters) having an alkyl group having 1 or more and 18 or less carbon atoms, and diene-based monomers are included.
  • vinyl chloride methyl acrylate and butyl acrylate are preferable, and vinyl chloride is more preferable.
  • the ratio of the structural unit derived from vinylidene chloride to the total mass of the copolymer is preferably 60% by mass or more, more preferably 70% by weight or more, and further preferably 80% by weight or more. preferable.
  • the upper limit of the proportion of the constituent units derived from vinylidene chloride is not particularly set, it is preferably 98% by weight or less, more preferably 95% by weight or less, from the viewpoint of improving extrusion processability and the like.
  • the vinylidene chloride-based resin preferably has a reduced viscosity of 0.035 or more and 0.070 or less, and more preferably 0.040 or more and 0.065 or less.
  • the reduced viscosity is 0.035 or more, the extrusion processability of the vinylidene chloride-based resin composition can be further enhanced.
  • the reduced viscosity is 0.070 or less, the coloring of the resin film is suppressed, and the vinylidene chloride-based resin composition can be more easily melted at the time of molding.
  • the vinylidene chloride resin composition includes an ethylene / vinyl acetate copolymer, a copolymer of ethylene and acrylic acid, methacrylic acid or an alkyl ester thereof, and an MBS resin (MBS resin).
  • MBS resin MBS resin
  • Other resins such as methyl methacrylate-butadiene-styrene copolymer
  • the content of the other resin is preferably 0.1 part by mass or more and 20 parts by mass or less, and 1.0 part by mass or more and 15 parts by mass or less, with respect to 100 parts by mass of the vinylidene chloride resin. Is more preferable.
  • the vinylidene chloride-based resin composition may contain a water-soluble cellulose derivative when the vinylidene chloride-based resin is synthesized by suspension polymerization.
  • the water-soluble cellulose derivative not only acts as a suspending agent during suspension polymerization, but also remains on the surface of the resin film to appropriately roughen the surface of the resin film.
  • water-soluble cellulose derivative examples include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropoxymethyl cellulose, carboxymethyl cellulose and the like. Of these, methyl cellulose, hydroxypropyl cellulose, and hydroxypropoxymethyl cellulose are more preferred, and methyl cellulose is even more preferred.
  • the water-soluble cellulose derivative is preferably contained in an amount of 15 ⁇ g or more per 1 m 2 when the resin film is immersed in 100 ml of ethanol, heated to 70 ° C. and extracted for 5 hours.
  • the extraction amount of the water-soluble cellulose derivative under the above conditions is within the above range, the water-soluble cellulose derivative probably remains on the surface of the resin film appropriately, and the surface of the resin film is appropriately roughened to make the resin film surface rough.
  • the surface adhesion force can be appropriately reduced while maintaining the tear strength to the MD. Therefore, it is easy to adjust the recovery coefficient to the above range.
  • the upper limit of the content of the water-soluble cellulose derivative extracted from the resin film is not particularly limited, it can be 100 ⁇ g or less, preferably 50 ⁇ g or less, and more preferably 30 ⁇ g or less per 1 m 2 of the resin film.
  • the vinylidene chloride resin composition may contain additives such as a plasticizer, a stabilizer and a slip agent as long as the recovery coefficient is not significantly affected.
  • plasticizers examples include acetyltributyl phthalate, dioctyl phthalate, dibutyl sebacate, dioctyl sebacate, diacetylated monoglyceride, acetylated diglyceride and acetylated triglyceride.
  • stabilizers include epoxidized soybean oil (ESBO) and epoxidized linseed oil (ELO).
  • the total content of the plasticizer and the stabilizer is preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the vinylidene chloride resin, and 1.0 part by mass or more and 7. It is more preferably 0 parts by mass or less.
  • the slip agent examples include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, and thioether compounds.
  • the content of the slip agent is preferably 0.05 parts by mass or more and 10 parts by mass or less, and 0.1 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the vinylidene chloride resin. More preferably.
  • the vinylidene chloride-based resin composition may contain a tackifier.
  • tackifier examples include sorbitan fatty acid esters such as sorbitan monooleate and sorbitan trioleate, glycerin fatty acid esters such as propylene glycol fatty acid ester, glycerin monooleate and glycerin trioleate, and liquid paraffin. ..
  • the vinylidene chloride-based resin composition does not substantially contain a tackifier.
  • substantially free means that the content of the tackifier is 100 ppm or less (preferably 50 ppm or less, more preferably 20 ppm or less) with respect to 100 parts by mass of the vinylidene chloride resin.
  • the resin film described above can be produced by a method having a step of stretching the melted and extruded vinylidene chloride resin composition and a step of relaxing the stretched vinylidene chloride resin composition. it can.
  • the above-mentioned vinylidene chloride-based resin composition can be prepared by mixing a synthesized vinylidene chloride-based resin and various additives.
  • the vinylidene chloride resin can be synthesized by suspension polymerization of vinylidene chloride and a monomer copolymerizable with vinylidene chloride.
  • vinylidene chloride (a monomer copolymerizable with vinylidene chloride and the vinylidene chloride when synthesizing a copolymer) is used as the water-soluble cellulose.
  • the mixture is stirred and suspended in an aqueous medium and dispersed in oil droplets.
  • a polymerization initiator is added to the suspension, and if necessary, the temperature is raised to polymerize vinylidene chloride (and a monomer copolymerizable with vinylidene chloride).
  • the temperature at this time is usually 25 to 90 ° C., preferably 30 to 85 ° C.
  • the polymerization time is usually 1 to 100 hours, preferably 2 to 60 hours, and more preferably 3 to 50 hours.
  • the amount of the water-soluble cellulose derivative added is 300 ppm or more and 600 ppm or less, preferably 300 ppm or more and 500 ppm or less, based on 100 parts by mass of vinylidene chloride (and a monomer copolymerizable with vinylidene chloride). ..
  • the amount of the water-soluble cellulose derivative in the above range probably by appropriately roughening the surface of the resin film with the water-soluble cellulose derivative remaining on the surface of the resin film, the MD of the produced resin film can be obtained.
  • the surface adhesion force can be appropriately reduced while maintaining the tear strength of the resin. Therefore, it is easy to adjust the recovery coefficient of the produced resin film within the above range.
  • the vinylidene chloride-based resin composition can be prepared by mixing the obtained vinylidene chloride-based resin with additives such as a plasticizer, a stabilizer, and a slip agent contained in the resin film, if necessary. it can.
  • the additive may be mixed at any time, and may be added to the suspension at the time of polymerization, or the vinylidene chloride resin and the additive may be mixed after the polymerization.
  • Henchel mixer is Henchel mixer, cylindrical mixer, screw type mixer, screw type extruder, turbulizer, Nauter type mixer, V type mixer, ribbon type mixer, double arm type kneader, fluid type mixer,
  • a known mixing device such as an air flow type mixer, a rotating disk type mixer, a roll mixer, a rolling type mixer, and a Ladyge mixer.
  • a powdery or pelletized vinylidene chloride-based resin composition can be obtained.
  • the prepared vinylidene chloride resin composition is melted and extruded by a known method, and then stretched and relaxed.
  • the above-mentioned vinylidene chloride resin composition is put into an extruder, melted in a cylinder, and extruded from a die.
  • the die may be a T-die that extrudes the vinylidene chloride-based resin composition in a flat plate shape, or may be an annular die (circular die) that extrudes the vinylidene chloride-based resin composition in a tubular shape.
  • the extruded vinylidene chloride-based resin composition is wound by a take-up roller via a plurality of guide rollers and a plurality of pinch rollers. At this time, the rotation speeds of the continuous pinch rollers among the plurality of pinch rollers may be different, or the amount of air for inflating the vinylidene chloride resin composition extruded into a tubular shape may be adjusted.
  • the extruded vinylidene chloride resin composition can be stretched in the MD (flow direction) at a predetermined ratio. Further, by using a tenter or adjusting the amount of air when inflating the vinylidene chloride resin composition extruded into a tubular shape, the extruded vinylidene chloride resin composition is TD at a predetermined ratio. It can be stretched (in the direction orthogonal to the flow). The vinylidene chloride-based resin composition stretched over the MD and TD is then relaxed by the MD due to a difference in the rotational speeds of the subsequent continuous pinch rollers and the like.
  • the surface adhesion force (recovery coefficient) with respect to the value of the tear strength of the molded resin film to MD can be adjusted by the draw ratio to MD and TD and the relaxation rate to MD at this time. it can.
  • the stretching ratio to MD is 3.5 times or more and 5.0 times or less
  • the stretching ratio to TD is 4.0 times or more and 5.5 times or less
  • the relaxation rate to MD is set. It shall be 9.5% or more and 12.5%.
  • the draw ratio to the MD is more preferably 3.5 times or more and 4.5 times or less, and further preferably 3.8 times or more and 4.5 times or less.
  • the draw ratio to TD is more preferably 4.5 times or more and 5.5 times or less, and further preferably 4.5 times or more and 5.0 times or less.
  • the relaxation rate to MD is more preferably 10.5% or more and 12.0% or less, and further preferably 11.0% or more and 12.0% or less.
  • the vinylidene chloride-based resin composition also contains the water-soluble cellulose derivative, so that the surface of the resin film is appropriately roughened and the surface adhesion is appropriately lowered.
  • the stretched and relaxed vinylidene chloride-based resin composition is then wound up by a winding roller.
  • the vinylidene chloride-based resin composition extruded into a tubular shape by a tubular die may then be incised in the extrusion axis direction to form a single-thickness flat film, or folded to form a double-thickness flat film. ..
  • VD Vinylidene chloride
  • VC vinyl chloride
  • ALG diacetylated monoglyceride
  • epoxidized soybean oil were added to prepare a feedstock.
  • the content of methyl cellulose in the raw material to be charged was adjusted to be 403 ppm with respect to the total mass of VD and VC.
  • the amount of the additive in the raw material to be charged was adjusted so that the total amount of the additive was 8.3 parts by mass with respect to 100 parts by mass of the vinylidene chloride / vinyl chloride copolymer to be synthesized.
  • a vinylidene chloride-based resin composition containing a vinylidene chloride / vinyl chloride copolymer was prepared by a suspension polymerization method.
  • the vinylidene chloride resin composition was melt-extruded from a cyclic die at 185 ° C. using a single-screw extruder, and the obtained tubular parison was rapidly cooled with water and then heated to around room temperature in a hot water bath. After that, inflation biaxial stretching was performed at a stretching ratio of 4.1 times in the longitudinal direction (MD) and 4.7 times in the width direction (TD), and further relaxed to MD at a relaxation rate of 11% in the longitudinal direction (MD). , Winded up with a take-up roller. The wound film was slit and rewound to obtain a resin film-1 having a thickness of 10 ⁇ m, a width of 30 cm, and a length of 50 m, which was a wound body.
  • Resin Film-5 Liquid paraffin as a tackifier was added to the raw material used for the synthesis of vinylidene chloride-based resin composition in an amount of 782 ppm based on the total amount of VD and VC.
  • a resin film-5 as a wound body was obtained in the same manner as in the production of the resin film-4 except for the above.
  • the test piece was immersed in 100 ml of ethanol, heated to 70 ° C., and extracted for 5 hours. Then, the extract was dried to obtain an ethanol extract.
  • the above ethanol extract was dissolved in a 15% aqueous ethanol solution and washed with carbon disulfide. After washing, the aqueous phase was dried to dryness, and iodomethane produced by reacting hydrogen iodide (HI) was dissolved in o-xylene.
  • HI hydrogen iodide
  • the o-xylene layer in which the iodomethane was dissolved was analyzed by gas chromatography (GC), and the obtained amount of iodomethane was converted into the amount of methylcellulose to obtain the amount of methylcellulose eluted from the surface of the resin film.
  • the amount of methylcellulose obtained was divided by the area of the resin film (unit: m 2 ) to obtain the amount of water-soluble cellulose derivative present on the surface of the resin film (unit: ⁇ g / m 2 ).
  • GC was performed with the following equipment and conditions.
  • GC-FID GL sciences GC-4000 Plus Column: Agilent J & W GC Column DB-624 (Length: 30 m, ID: 0.530 mm, Film: 3.00 ⁇ m)
  • Detector temperature 230 ° C
  • Carrier gas N 2 (column flow rate 4.2 ml / min)
  • Injection method split (5: 1) Injection volume: 1 ⁇ l
  • Two aluminum columnar jigs with a bottom area of 25 cm 2 and a mass of 300 g were prepared. Each test piece was fixed to the bottom surface of one of the jigs while being tense so as not to cause wrinkles. A test piece obtained from the same resin film was also fixed to the bottom surface of the other jig while being tense so as not to cause wrinkles. These two jigs were brought into vertical contact with each other so that the bottom surfaces to which the test pieces were fixed completely overlapped with each other, and pressed for 1 minute by the weight of the jig on the vertically upper side to crimp the test pieces to each other.
  • Tensilon RTC-1210A which is a tensile compression tester manufactured by Orientec Co., Ltd.
  • the two jigs are pulled in opposite directions (vertical direction) at a speed of 100 mm / min, and the jig (test) is used.
  • the maximum load (unit: N) for the piece) to be separated was defined as the surface peeling strength of the test piece.
  • the measurement was carried out in an atmosphere of 23 ° C. and 50% RH, and the average value of the surface peeling strength obtained for the five test pieces was taken as the surface adhesion force of the resin film.
  • a light load tear tester manufactured by Toyo Seiki Seisakusho Co., Ltd. 193 Model D was used, the measurement range was 196 mN, and the tear strength of each test piece to MD was determined.
  • After setting the test piece in the center of the clamp make a notch in the center of the width direction (TD) of the test piece with a knife so that the cut length in the vertical direction (MD) is 12.7 mm, and insert the pendulum.
  • the maximum load (unit: mN) for opening and tearing the test piece was measured.
  • the measurement was carried out in an atmosphere of 23 ° C. and 50% RH, and the average value of the tear strength to MD obtained for the five test pieces was taken as the tear strength to MD of the resin film.
  • NDH7000SP a haze meter manufactured by Nippon Denshoku Industries Co., Ltd.
  • the haze value (unit:%) of each test piece was measured in accordance with JIS K 7136 (2000).
  • the average value of the haze values obtained for the five test pieces was taken as the haze value of the resin film.
  • the piercing strength (unit: N) of each test piece was measured in accordance with JIS Z1707 (2019). The measurement was performed in an atmosphere of 23 ° C. and 50% RH, and the average value of the piercing strength obtained for the five test pieces was taken as the piercing strength of the resin film.
  • Table 2 shows the evaluation results of the recovery time. In Table 2, "-" indicates that the evaluation has not been performed.
  • the ratio of the surface adhesion value (N) to the tear strength value (mN) to MD is 0.35 or more and less than 0.41.
  • Resin film-1 and resin film- In No. 2 the recovery time from the rewinding state was significantly shorter than that in Resin Film-3 to Resin Film-5, which were not so.
  • such a resin film-1 and a resin film-2 contain a monomer for synthesizing a vinylidene chloride resin by polymerization with respect to the total mass of the monomer.
  • a resin composition obtained by suspend polymerization in an aqueous medium in the presence of a water-soluble cellulose derivative having a value of 300 ppm or more and 600 ppm or less the resin composition melted and extruded was stretched to MD. Is stretched to 3.5 times or more and 5.0 times or less, and the stretching ratio to TD is 4.0 times or more and 5.5 times or less, and the relaxation rate to MD is 10.0% or more and 12.5%. It was manufactured by a method of relaxation as follows.
  • the resin film of the present invention can easily peel off the end portion from the wound portion in the rewound state without causing tearing of the resin film in the vertical direction. Therefore, the resin film of the present invention can be suitably used in various applications such as home use, experimental use, and industrial use.

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Abstract

An objective of the present invention is to provide a resin film, an end of which can easily be released from a wound section in a wound-back state without tearing the resin film in the longitudinal direction. In order to achieve this objective, a resin film according to the present invention is formed from a vinylidene chloride resin composition in which the ratio (surface adhesive strength value/MD tear strength value) of the value for surface adhesive strength (unit: N) to the value for MD tear strength (unit: mN) is at least 0.35 and less than 0.41.

Description

樹脂フィルムおよびその製造方法Resin film and its manufacturing method
　本発明は、樹脂フィルムおよびその製造方法に関する。 The present invention relates to a resin film and a method for producing the same.
　塩化ビニリデン系樹脂フィルムは、酸素および水分を透過させにくく、密着性が高く、耐熱性が高く、透明性が高いなどの特性を有することから、ラップフィルムなどとして広く用いられている。 Vinylidene chloride-based resin film is widely used as a wrap film, etc. because it has characteristics such as difficulty in permeating oxygen and moisture, high adhesion, high heat resistance, and high transparency.
　ラップフィルムは、通常、ロール状に巻回された巻回体として収容箱に収容される。上記収容箱としては、上記巻回体を収容する本体部と、本体部に対して回動自在に連接された蓋部と、を有する収容箱が知られている。ラップフィルムの使用者は、本体部に収容されたラップフィルムの端部を把持して、巻回体を回転させながら上記端部を引っ張って使用する量のラップフィルムを本体部と蓋部との隙間から繰り出し、蓋部に設置された切断刃によって切断することにより、必要な長さのラップフィルムを収容箱から取り出すことができる。このとき、切断後の巻回体の端部は、次の繰り出しを容易にするため、本体部に付着させて係止させておく。 The wrap film is usually housed in a storage box as a wound body wound in a roll shape. As the storage box, a storage box having a main body portion for accommodating the wound body and a lid portion rotatably connected to the main body portion is known. The user of the wrap film grips the end portion of the wrap film housed in the main body portion and pulls the end portion while rotating the winding body to use an amount of wrap film between the main body portion and the lid portion. The required length of wrap film can be taken out of the storage box by feeding out from the gap and cutting with a cutting blade installed on the lid. At this time, the end portion of the wound body after cutting is attached to the main body portion and locked in order to facilitate the next feeding.
　上記塩化ビニリデン系樹脂フィルムは、懸濁重合などの方法により得られた塩化ビニリデン系樹脂組成物を溶融押し出しし、その後フィルム状に延伸して製造される。 The vinylidene chloride-based resin film is produced by melt-extruding a vinylidene chloride-based resin composition obtained by a method such as suspension polymerization and then stretching it into a film.
　特許文献１には、上記懸濁重合時に懸濁分散剤を用いることにより、懸濁安定性を高めたり、得られる塩化ビニリデン系樹脂の粒子径を制御してフィルムの押出安定性や膜厚均一性を高めたりすることができると記載されている。特許文献１では、１００質量部の塩化ビニリデン系樹脂を合成するための単量体に対して、５００ｐｐｍの懸濁剤を使用することにより、フィルムを良好に製造できたと記載されている。 In Patent Document 1, by using a suspension dispersant during suspension polymerization, suspension stability is enhanced and the particle size of the obtained vinylidene chloride resin is controlled to achieve extrusion stability and uniform film thickness. It is stated that it can enhance the sex. Patent Document 1 describes that a film could be satisfactorily produced by using a suspending agent of 500 ppm with respect to a monomer for synthesizing 100 parts by mass of a vinylidene chloride resin.
　特許文献２には、ポリ塩化ビニリデン系フィルムに流動パラフィンを付与することにより、上記フィルムに適切な剥離性能を発揮させることができると記載されている。 Patent Document 2 describes that by adding liquid paraffin to a polyvinylidene chloride-based film, the film can exhibit appropriate peeling performance.
国際公開第２００３／００６５４８号International Publication No. 2003/006548 特開平１０－０８７８７６号公報Japanese Unexamined Patent Publication No. 10-087876
　ところで、上述した収容箱に巻回体として収容されているラップフィルムには、巻回体の逆回転などにより切断された端部が本体部の内部へ巻き戻って、巻回されているラップフィルム（以下、単に「巻回部」ともいう。）の表面に上記端部が貼り付いてしまうことが生じ得る（以下、巻き戻りによりラップフィルムの端部が巻回部の表面に貼り付いた状態を、単に「巻き戻り状態」ともいう。）。ここで、ラップフィルムには高い密着性が求められるため、ラップフィルム同士の密着性も非常に高くなっている。そのため、上記貼り付いてしまった端部を巻回部から引き剥がして、巻回部から端部が剥離した状態に復旧させようとすると、ラップフィルムの端部をつまんで、外側に大きい力で引っ張る必要があり、このときの端部への力によって縦方向（ＭＤ）へのラップフィルムの引き裂けが生じやすい。上記縦方向への引き裂けが生じないようにラップフィルムを復旧させようとすると、復旧に時間がかかってしまう。 By the way, in the wrap film housed as a winding body in the above-mentioned storage box, the end portion cut by the reverse rotation of the winding body is rewound into the inside of the main body, and the wrap film is wound. (Hereinafter, also simply referred to as “winding portion”), the end portion may be stuck to the surface (hereinafter, the end portion of the wrap film is stuck to the surface of the winding portion due to rewinding). Is also simply referred to as "rewinding state"). Here, since the wrap film is required to have high adhesion, the adhesion between the wrap films is also very high. Therefore, when the end portion that has been stuck is peeled off from the winding portion to restore the state in which the end portion is peeled off from the winding portion, the end portion of the wrap film is pinched and a large force is applied to the outside. It is necessary to pull, and the force on the end portion at this time tends to cause tearing of the wrap film in the vertical direction (MD). If an attempt is made to restore the wrap film so that the tearing in the vertical direction does not occur, the restoration takes time.
　これに対し、特許文献２に記載のように流動パラフィンを付与してラップフィルムとして用いられる樹脂フィルムの剥離性を高めれば、巻き戻り状態からラップフィルムを復旧しやすくできるとも考えられる。しかし、本発明者らの知見によると、近年の規制強化により流動パラフィンの量を低減させようとすると、樹脂フィルムの剥離性を十分に高めることができず、復旧時の、縦方向への樹脂フィルムの引き裂けを十分には抑制できない。 On the other hand, if liquid paraffin is added as described in Patent Document 2 to improve the peelability of the resin film used as the wrap film, it is considered that the wrap film can be easily recovered from the rewound state. However, according to the findings of the present inventors, if the amount of liquid paraffin is reduced by tightening regulations in recent years, the peelability of the resin film cannot be sufficiently improved, and the resin in the vertical direction at the time of restoration cannot be sufficiently improved. The tearing of the film cannot be sufficiently suppressed.
　上記問題に鑑み、本発明は、縦方向への樹脂フィルムの引き裂けを生じずに、巻き戻り状態の巻回部から端部を剥離させやすい樹脂フィルム、およびそのような樹脂フィルムの製造方法を提供することを、その目的とする。 In view of the above problems, the present invention provides a resin film in which the end portion can be easily peeled off from the wound portion in the rewound state without causing tearing of the resin film in the vertical direction, and a method for producing such a resin film. The purpose is to do.
　上記の課題を解決するための本発明の一態様に関する樹脂フィルムは、塩化ビニリデン系樹脂組成物からなる樹脂フィルムであって、ＭＤへの引裂き強度の値（ｍＮ）に対する、面密着力の値（Ｎ）の割合（面密着力の値／ＭＤへの引裂き強度の値）が、０．３５以上０．４１未満である。 The resin film according to one aspect of the present invention for solving the above problems is a resin film made of a vinylidene chloride-based resin composition, and has a surface adhesion value (mN) with respect to a tear strength value (mN) to MD. The ratio of N) (value of surface adhesion / value of tear strength to MD) is 0.35 or more and less than 0.41.
　また、上記の課題を解決するための本発明の別の態様に関する樹脂フィルムの製造方法は、溶融して押出された塩化ビニリデン系樹脂組成物を延伸する工程と、前記延伸された塩化ビニリデン系樹脂組成物を緩和する工程と、を有する樹脂フィルムの製造方法である。前記塩化ビニリデン系樹脂組成物は、重合により塩化ビニリデン系樹脂を合成するための単量体を、前記単量体の全質量に対する含有量が３００ｐｐｍ以上６００ｐｐｍ以下である水溶性セルロース誘導体の存在下、水性媒体中で懸濁重合させて得られる樹脂組成物である。前記製造方法では、前記延伸する工程において、塩化ビニリデン系樹脂組成物を、ＭＤへの延伸倍率が３．５倍以上５．０倍以下、ＴＤへの延伸倍率が４．０倍以上５．５倍以下となるように延伸し、前記緩和する工程において、前記延伸された塩化ビニリデン系樹脂組成物を、ＭＤへの緩和率が９．５％以上１２．５％以下となるように緩和する。 Further, a method for producing a resin film according to another aspect of the present invention for solving the above problems includes a step of stretching a melted and extruded vinylidene chloride-based resin composition, and the stretched vinylidene chloride-based resin. It is a method for producing a resin film having a step of relaxing the composition. The vinylidene chloride-based resin composition contains a monomer for synthesizing a vinylidene chloride-based resin by polymerization in the presence of a water-soluble cellulose derivative in which the content of the monomer with respect to the total mass is 300 ppm or more and 600 ppm or less. It is a resin composition obtained by suspend polymerization in an aqueous medium. In the production method, in the stretching step, the polyvinylidene chloride-based resin composition has a stretching ratio of 3.5 times or more and 5.0 times or less for MD and a stretching ratio of 4.0 times or more and 5.5 for TD. In the step of stretching to a fold or less and relaxing, the stretched vinylidene chloride resin composition is relaxed so that the relaxation rate to MD is 9.5% or more and 12.5% or less.
　本発明によれば、縦方向への樹脂フィルムの引き裂けを生じずに、巻き戻り状態の巻回部から端部を剥離させやすい樹脂フィルム、およびそのような樹脂フィルムの製造方法が提供される。 According to the present invention, there is provided a resin film in which the end portion can be easily peeled off from the wound portion in the rewound state without causing tearing of the resin film in the vertical direction, and a method for producing such a resin film.
　［樹脂フィルム］
　（物性等）
　本発明の一実施形態は、塩化ビニリデン系樹脂組成物からなる樹脂フィルムに関する。上記樹脂フィルムは、ＭＤへの引裂き強度の値（単位：ｍＮ）に対する、面密着力の値（単位：Ｎ）の割合（面密着力の値（Ｎ）／ＭＤへの引裂き強度の値（ｍＮ）。以下、この割合を単に「復旧係数」ともいう。）が、０．３５以上０．４１未満である。 [Resin film]
(Physical properties, etc.)
One embodiment of the present invention relates to a resin film made of a vinylidene chloride-based resin composition. The above resin film has a ratio of the value of surface adhesion (unit: N) to the value of tear strength to MD (unit: mN) (value of surface adhesion (N) / value of tear strength to MD (mN). ). Hereinafter, this ratio is also simply referred to as “recovery coefficient”), which is 0.35 or more and less than 0.41.
　なお、ＭＤとは、ロール状に巻回されている樹脂フィルムの、巻回されている方向を意味する。また、ＴＤとは、樹脂フィルムの平面内のうち、ＭＤとは直交する方向を意味する。 Note that MD means the winding direction of the resin film that is wound in a roll shape. Further, TD means a direction orthogonal to MD in the plane of the resin film.
　塩化ビニリデン系樹脂組成物からなる樹脂フィルムを、縦方向への樹脂フィルムの引き裂けを生じずに、巻き戻り状態の巻回部から復旧させやすくするためには、上記面密着力の値はより低いことが望ましく、上記ＭＤへの引裂き強度はより高いことが望ましい。ただし、樹脂フィルムによる容器などへの密着性を十分に確保するためには、上記面密着力を低下させすぎることは望ましくない。 In order to make it easier for the resin film made of vinylidene chloride-based resin composition to recover from the wound portion in the rewound state without causing tearing of the resin film in the vertical direction, the value of the surface adhesion force is lower. It is desirable that the tear strength to the MD is higher. However, it is not desirable to reduce the surface adhesion force too much in order to sufficiently secure the adhesion of the resin film to the container or the like.
　これらの観点から、本実施形態では、上記復旧係数を０．３５以上０．４１未満とする。上記復旧係数が０．３５以上であると、樹脂フィルムの面密着力が過剰に低下しすぎておらず、容器などへの密着性が十分に確保される。一方で上記復旧係数が０．４１未満であると、樹脂フィルムのＭＤへの引裂き強度がほどよく高まりつつ、面密着力がほどよく低下しているため、縦方向への引き裂けを生じずに、巻き戻り状態の樹脂フィルムを復旧させやすい。上記観点から、上記復旧係数は、０．３６以上０．４０以下であることが好ましく、０．３７以上０．４０以下であることがより好ましい。 From these viewpoints, in the present embodiment, the recovery coefficient is set to 0.35 or more and less than 0.41. When the recovery coefficient is 0.35 or more, the surface adhesion of the resin film is not excessively reduced, and sufficient adhesion to a container or the like is ensured. On the other hand, when the recovery coefficient is less than 0.41, the tear strength of the resin film to the MD is moderately increased and the surface adhesion is moderately reduced, so that the resin film does not tear in the vertical direction. It is easy to restore the resin film in the rewound state. From the above viewpoint, the recovery coefficient is preferably 0.36 or more and 0.40 or less, and more preferably 0.37 or more and 0.40 or less.
　上記ＭＤへの引裂き強度の値は、公知の引裂試験機を用いて測定された値とすることができる。具体的には、樹脂フィルムを縦方向（ＭＤ）６３．５ｍｍ×幅方向（ＴＤ）５０ｍｍの大きさに切断して得た試験片を、引裂試験機のクランプの中央にセットし、縦方向（ＭＤ）への切込み長さが１２．７ｍｍになるように、試験片の幅方向（ＴＤ）の中央にナイフで切込みを入れて、振り子を開放して試験片を切り裂く。このときの、試験片を切り裂くための最大荷重を、当該試験片のＭＤへの引裂き強度の値（単位：ｍＮ）とすることができる。 The value of the tear strength to the MD can be a value measured using a known tear tester. Specifically, a test piece obtained by cutting a resin film into a size of 63.5 mm in the vertical direction (MD) x 50 mm in the width direction (TD) is set in the center of a clamp of a tear tester, and is set in the vertical direction (TD). Make a cut with a knife in the center of the width direction (TD) of the test piece so that the cut length in MD) is 12.7 mm, open the pendulum, and cut the test piece. At this time, the maximum load for tearing the test piece can be a value (unit: mN) of the tear strength of the test piece to the MD.
　上記面密着力は、公知の引っ張り試験器を用いて測定された値とすることができる。具体的には、底面積２５ｃｍ２、質量３００ｇのアルミニウム製の円柱状の２本の治具の、それぞれの底面に皺が入らないように緊張させながら樹脂フィルムを固定させ、当該２本の治具に固定された樹脂フィルム同士を鉛直方向に接触させて圧着させる。その後、引張試験機を用いて上記２本の治具を反対の鉛直方向に引っ張る。このときの、治具を引き離すための最大荷重（単位：Ｎ）を、当該試験片の面密着力の値とすることができる。 The surface adhesion force can be a value measured using a known tensile tester. Specifically, the resin film is fixed to the bottom surface of two cylindrical aluminum jigs having a bottom area of 25 cm 2 and a mass of 300 g so as not to cause wrinkles, and the two jigs are cured. The resin films fixed to the jig are brought into vertical contact with each other and crimped. Then, using a tensile tester, the above two jigs are pulled in opposite vertical directions. At this time, the maximum load (unit: N) for pulling the jig apart can be set as the value of the surface adhesion force of the test piece.
　なお、上記復旧係数を上述した範囲に調整しやすくする観点からは、上記樹脂フィルムは、ＭＤへの引裂き強度の値が、３２．０ｍＮ以上３４．５ｍＮ以下であることが好ましく、３２．５ｍＮ以上３４．５ｍＮ以下であることがより好ましく、３３．０ｍＮ以上３４．５ｍＮ以下であることがさらに好ましい。なお、上記ＭＤへの引裂き強度の値が３２．０ｍＮ以上であると、復旧時やその他の使用時に樹脂フィルムが縦裂けしにくいため、樹脂フィルムの使いやすさをより高めることができる。 From the viewpoint of facilitating the adjustment of the recovery coefficient within the above range, the resin film preferably has a tear strength value of 32.0 mN or more and 34.5 mN or less, and is preferably 32.5 mN or more. It is more preferably 34.5 mN or less, and further preferably 33.0 mN or more and 34.5 mN or less. When the value of the tear strength to the MD is 32.0 mN or more, the resin film is less likely to tear vertically during restoration or other use, so that the ease of use of the resin film can be further improved.
　また、上記復旧係数を上述した範囲に調整しやすくする観点からは、上記樹脂フィルムは、上記面密着力の値が１２．０Ｎ以上１３．０Ｎ以下であることが好ましく、１２．０Ｎ以上１２．５Ｎ以下であることがより好ましい。上記面密着力の値が１２．０Ｎ以上であると、使用時に樹脂フィルムが容器などに密着しやすいため、樹脂フィルムの使いやすさをより高めることができる。 Further, from the viewpoint of facilitating the adjustment of the recovery coefficient within the above range, the surface adhesion value of the resin film is preferably 12.0 N or more and 13.0 N or less, and 12.0 N or more and 12. It is more preferably 5N or less. When the value of the surface adhesion force is 12.0 N or more, the resin film easily adheres to the container or the like during use, so that the ease of use of the resin film can be further improved.
　なお、後述するように、本実施形態では、所定量の水溶性セルロース誘導体の存在下で重合した塩化ビニリデン系樹脂を含有する塩化ビニリデン系樹脂組成物を所定の比率で延伸および緩和することで、上記復旧係数の値を満たす樹脂フィルムを作製することができる。このとき使用する水溶性セルロース誘導体による樹脂フィルムの透明性の低下などを抑制する観点からは、上記樹脂フィルムは、ヘイズ値が１．２％以下であることが好ましく、０．８％以下であることがより好ましく、０．６％以下であることがさらに好ましい。なお、ヘイズ値の下限値は特に定められないものの、０．０５％以上とすることができる。 As will be described later, in the present embodiment, the vinylidene chloride-based resin composition containing the vinylidene chloride-based resin polymerized in the presence of a predetermined amount of the water-soluble cellulose derivative is stretched and relaxed at a predetermined ratio. A resin film satisfying the value of the recovery coefficient can be produced. From the viewpoint of suppressing a decrease in transparency of the resin film due to the water-soluble cellulose derivative used at this time, the haze value of the resin film is preferably 1.2% or less, preferably 0.8% or less. More preferably, it is more preferably 0.6% or less. Although the lower limit of the haze value is not particularly set, it can be 0.05% or more.
　上記ヘイズ値は、ＪＩＳ　Ｋ　７１３６（２０００年）に準拠して測定して得られた値とすることができる。 The haze value can be a value obtained by measuring in accordance with JIS K 7136 (2000).
　また、樹脂フィルムの透明性をより高める観点からは、上記樹脂フィルムは、ＪＩＳ Ｂ ０６０１（２０１３年）に規定される算術表面粗さ（Ｒａ）が５．０ｎｍより大きく２０．０ｎｍ未満であることが好ましく、５．０ｎｍより大きく７．７ｎｍ以下であることがより好ましく、６．０ｎｍより大きく７．５ｎｍ未満であることがさらに好ましい。 From the viewpoint of further enhancing the transparency of the resin film, the resin film has an arithmetic surface roughness (Ra) defined in JIS B 0601 (2013) of more than 5.0 nm and less than 20.0 nm. Is more preferable, and it is more preferably larger than 5.0 nm and 7.7 nm or less, and further preferably larger than 6.0 nm and less than 7.5 nm.
　上記算術表面粗さ（Ｒａ）は、公知の表面粗さ測定器を用いて得られた値とすることができる。 The above arithmetic surface roughness (Ra) can be a value obtained by using a known surface roughness measuring instrument.
　また、後述するように、本実施形態では、塩化ビニリデン系樹脂組成物を従来よりも高い倍率で延伸することで、上記復旧係数の値を満たす樹脂フィルムを作製することができる。そのため、本実施形態に関する樹脂フィルムでは、塩化ビニリデン系樹脂の分子がより緊張した状態でＭＤに配向しており、切断刃などの突き刺しがより容易であり、切断（特にはＴＤへの切断）がより容易である。具体的には、上記樹脂フィルムは、突き刺し強度の値が４．０Ｎ未満であることが好ましく、３．８Ｎ未満であることがより好ましく、３．５Ｎ未満であることがさらに好ましい。なお、突き刺し強度の下限値は特に定められないものの、樹脂フィルムの形状を維持しやすくする観点から、１．５Ｎ以上とすることができる。 Further, as will be described later, in the present embodiment, a resin film satisfying the above-mentioned recovery coefficient value can be produced by stretching the vinylidene chloride-based resin composition at a higher magnification than before. Therefore, in the resin film according to the present embodiment, the molecules of the vinylidene chloride resin are oriented in the MD in a more tense state, and it is easier to pierce the cutting blade or the like, and cutting (particularly cutting to TD) is possible. It's easier. Specifically, the resin film preferably has a piercing strength value of less than 4.0 N, more preferably less than 3.8 N, and even more preferably less than 3.5 N. Although the lower limit of the piercing strength is not particularly determined, it can be 1.5 N or more from the viewpoint of facilitating the maintenance of the shape of the resin film.
　上記突き刺し強度は、ＪＩＳ　Ｚ　１７０７（２０１９年）に準拠して測定して得られた値とすることができる。 The piercing strength can be a value obtained by measuring in accordance with JIS Z 1707 (2019).
　上記樹脂フィルムの厚みは特に限定されないが、１μｍ以上５０μｍ以下とすることができ、４μｍ以上４５μｍ以下であえることが好ましく、７μｍ以上４０μｍ以下であることがより好ましい。上記厚みが１μｍ以上であると、上記樹脂フィルムを破れにくくすることができる。上記厚みが５０μｍ以下であると、上記樹脂フィルムのカット性が良好となり、またフィルムの手触り感が良好なものとなる。 The thickness of the resin film is not particularly limited, but can be 1 μm or more and 50 μm or less, preferably 4 μm or more and 45 μm or less, and more preferably 7 μm or more and 40 μm or less. When the thickness is 1 μm or more, the resin film can be made difficult to tear. When the thickness is 50 μm or less, the cut property of the resin film is good, and the feel of the film is good.
　上記樹脂フィルムは、透明である樹脂フィルムとすることができる。また、上記樹脂フィルムは、食品や食器などへの密着性を有する。そのため、上記樹脂フィルムは、ラップフィルムとして好適に使用することができる。 The resin film can be a transparent resin film. In addition, the resin film has adhesiveness to foods and tableware. Therefore, the resin film can be suitably used as a wrap film.
　また、上記樹脂フィルムは、ロール状に巻回された巻回体として保管されることが好ましい。上記巻回体は、上記巻回体を収容する本体部と、本体部に対して回動自在に連接された蓋部と、を有し、蓋部に切断刃を有する収容箱に収容されることが好ましい。上記収容箱に収容された上記巻回体は、巻回体を回転させながら上記樹脂フィルムの端部を引っ張って使用する量の樹脂フィルムを本体部と蓋部との隙間から繰り出し、蓋部に設置された切断刃によって切断することにより、必要な長さだけ、収容箱から取り出されることができる。 Further, it is preferable that the resin film is stored as a wound body wound in a roll shape. The wound body is housed in a storage box having a main body portion for accommodating the wound body portion and a lid portion rotatably connected to the main body portion, and having a cutting blade on the lid portion. Is preferable. The winding body housed in the storage box pulls the end portion of the resin film while rotating the winding body, and the amount of the resin film to be used is drawn out from the gap between the main body portion and the lid portion to the lid portion. By cutting with the installed cutting blade, it can be taken out of the storage box by the required length.
　（組成等）
　上記樹脂フィルムは、塩化ビニリデン系樹脂組成物をフィルム状に成形してなる単層フィルムである。 (Composition, etc.)
The resin film is a single-layer film formed by molding a vinylidene chloride-based resin composition into a film.
　上記塩化ビニリデン系樹脂組成物は、塩化ビニリデン系樹脂を主成分とする樹脂組成物である。 The above-mentioned vinylidene chloride-based resin composition is a resin composition containing vinylidene chloride-based resin as a main component.
　上記塩化ビニリデン系樹脂は、塩化ビニリデンの単独重合体であってもよいし、塩化ビニリデンに由来する構成単位を含む共重合体であってもよい。 The above-mentioned vinylidene chloride-based resin may be a homopolymer of vinylidene chloride or a copolymer containing a structural unit derived from vinylidene chloride.
　上記共重合体は、塩化ビニリデンと、塩化ビニリデンと共重合可能な単量体と、の共重合体である。上記塩化ビニリデンと共重合可能な単量体の例には、塩化ビニル、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２－エチルヘキシル、アクリル酸ラウリルおよびアクリル酸ステアリルなどを含むアルキル基の炭素数が１以上１８以下であるアクリル酸アルキルエステル、メタクリル酸メチル、メタクリル酸ブチル、メタクリル酸２－エチルヘキシル、メタクリル酸ラウリルおよびタクリル酸ステアリルなどを含むアルキル基の炭素数が１以上１８以下のメタクリル酸アルキルエステル、アクリロニトリルおよびメタクリロニトリルなどを含むシアン化ビニル化合物、スチレンなどを含む芳香族ビニル化合物、酢酸ビニルなどを含む炭素数が１以上１８以下の脂肪族カルボン酸のビニルエステル、炭素数が１以上１８以下のアルキルビニルエーテル、アクリル酸、メタクリル酸、マレイン酸、フマル酸およびイタコン酸などを含むビニル重合性不飽和カルボン酸、マレイン酸、フマル酸およびイタコン酸等のビニル重合性不飽和カルボン酸のアルキル基の炭素数が１以上１８以下であるアルキルエステル（部分エステルであってもよい。）、ならびに、ジエン系単量体などが含まれる。これらのうち、塩化ビニル、アクリル酸メチルおよびアクリル酸ブチルが好ましく、塩化ビニルがより好ましい。 The above-mentioned copolymer is a copolymer of vinylidene chloride and a monomer copolymerizable with vinylidene chloride. Examples of monomers copolymerizable with vinylidene chloride include alkyl groups containing vinyl chloride, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate and the like. Methacrylic acid having 1 or more and 18 or less carbon atoms, methacrylic acid having 1 or more and 18 or less carbon atoms in an alkyl group containing methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl tacrylate, etc. Acid alkyl ester, vinyl cyanide compound containing acrylic acid nitrile and methacrylic acid, aromatic vinyl compound containing styrene, vinyl ester of aliphatic carboxylic acid having 1 or more and 18 or less carbon atoms including vinyl acetate, carbon number Vinyl polymerizable unsaturated carboxylic acid including alkyl vinyl ether, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid of 1 to 18 or less, vinyl polymerizable unsaturated carboxylic acid such as maleic acid, fumaric acid and itaconic acid. Alkyl esters (which may be partial esters) having an alkyl group having 1 or more and 18 or less carbon atoms, and diene-based monomers are included. Of these, vinyl chloride, methyl acrylate and butyl acrylate are preferable, and vinyl chloride is more preferable.
　上記共重合体は、その全質量に対する塩化ビニリデンに由来する構成単位の割合が６０質量％以上であることが好ましく、７０重量％以上であることがより好ましく、８０重量％以上であることがさらに好ましい。上記塩化ビニリデンに由来する構成単位の割合の上限は特に定められないものの、押出加工性などを高める観点から、９８重量％以下であることが好ましく、９５重量％以下であることがより好ましい。 The ratio of the structural unit derived from vinylidene chloride to the total mass of the copolymer is preferably 60% by mass or more, more preferably 70% by weight or more, and further preferably 80% by weight or more. preferable. Although the upper limit of the proportion of the constituent units derived from vinylidene chloride is not particularly set, it is preferably 98% by weight or less, more preferably 95% by weight or less, from the viewpoint of improving extrusion processability and the like.
　上記塩化ビニリデン系樹脂は、還元粘度が０．０３５以上０．０７０以下であることが好ましく、０．０４０以上０．０６５以下であることがより好ましい。上記還元粘度が０．０３５以上であると、塩化ビニリデン系樹脂組成物の押出加工性をより高めることができる。上記還元粘度が０．０７０以下であると、樹脂フィルムの着色が抑制され、かつ、成形時に塩化ビニリデン系樹脂組成物をより容易に溶融させることができる。 The vinylidene chloride-based resin preferably has a reduced viscosity of 0.035 or more and 0.070 or less, and more preferably 0.040 or more and 0.065 or less. When the reduced viscosity is 0.035 or more, the extrusion processability of the vinylidene chloride-based resin composition can be further enhanced. When the reduced viscosity is 0.070 or less, the coloring of the resin film is suppressed, and the vinylidene chloride-based resin composition can be more easily melted at the time of molding.
　上記塩化ビニリデン系樹脂組成物は、押出加工性などをより高める観点から、エチレン・酢酸ビニル共重合体、エチレンとアクリル酸、メタクリル酸またはそれらのアルキルエステルとの共重合体、ならびに、ＭＢＳ樹脂（メタクリル酸メチル－ブタジエン－スチレン共重合体）などの他の樹脂をさらに含有してもよい。上記他の樹脂の含有量は、１００質量部の上記塩化ビニリデン系樹脂に対して、０．１質量部以上２０質量部以下であることが好ましく、１．０質量部以上１５質量部以下であることがより好ましい。 From the viewpoint of further enhancing the extrusion processability, the vinylidene chloride resin composition includes an ethylene / vinyl acetate copolymer, a copolymer of ethylene and acrylic acid, methacrylic acid or an alkyl ester thereof, and an MBS resin (MBS resin). Other resins such as methyl methacrylate-butadiene-styrene copolymer) may be further contained. The content of the other resin is preferably 0.1 part by mass or more and 20 parts by mass or less, and 1.0 part by mass or more and 15 parts by mass or less, with respect to 100 parts by mass of the vinylidene chloride resin. Is more preferable.
　上記塩化ビニリデン系樹脂組成物は、懸濁重合により上記塩化ビニリデン系樹脂を合成する際に水溶性セルロース誘導体を含有していてもよい。上記水溶性セルロース誘導体は、懸濁重合時の懸濁剤として作用するほか、樹脂フィルムの表面に残存して樹脂フィルムの表面を適度に粗面化する。 The vinylidene chloride-based resin composition may contain a water-soluble cellulose derivative when the vinylidene chloride-based resin is synthesized by suspension polymerization. The water-soluble cellulose derivative not only acts as a suspending agent during suspension polymerization, but also remains on the surface of the resin film to appropriately roughen the surface of the resin film.
　上記水溶性セルロース誘導体の例には、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロポキシメチルセルロース、およびカルボキシメチルセルロースなどが含まれる。これらのうち、メチルセルロース、ヒドロキシプロピルセルロース、およびヒドロキシプロポキシメチルセルロースがより好ましく、メチルセルロースがさらに好ましい。 Examples of the water-soluble cellulose derivative include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropoxymethyl cellulose, carboxymethyl cellulose and the like. Of these, methyl cellulose, hydroxypropyl cellulose, and hydroxypropoxymethyl cellulose are more preferred, and methyl cellulose is even more preferred.
　上記水溶性セルロース誘導体は、樹脂フィルムを１００ｍｌのエタノールに浸漬させ、７０℃に加熱して５時間抽出した際に、１ｍ２あたり１５μｇ以上が抽出される量で含まれることが好ましい。上記条件における水溶性セルロース誘導体の抽出量が上記範囲であると、おそらくは上記水溶性セルロース誘導体が樹脂フィルムの表面に適度に残存し、樹脂フィルムの表面を適度に粗面化することにより、樹脂フィルムのＭＤへの引裂き強度はほぼ維持しつつ、面密着力を適度に低下させることができる。そのため、上記復旧係数を上述した範囲に調整しやすい。樹脂フィルムから抽出される上記水溶性セルロース誘導体の含有量の上限は特に限定されないものの、樹脂フィルム１ｍ２あたり１００μｇ以下、好ましくは５０μｇ以下、さらに好ましくは３０μｇ以下とすることができる。 The water-soluble cellulose derivative is preferably contained in an amount of 15 μg or more per 1 m 2 when the resin film is immersed in 100 ml of ethanol, heated to 70 ° C. and extracted for 5 hours. When the extraction amount of the water-soluble cellulose derivative under the above conditions is within the above range, the water-soluble cellulose derivative probably remains on the surface of the resin film appropriately, and the surface of the resin film is appropriately roughened to make the resin film surface rough. The surface adhesion force can be appropriately reduced while maintaining the tear strength to the MD. Therefore, it is easy to adjust the recovery coefficient to the above range. Although the upper limit of the content of the water-soluble cellulose derivative extracted from the resin film is not particularly limited, it can be 100 μg or less, preferably 50 μg or less, and more preferably 30 μg or less per 1 m 2 of the resin film.
　上記塩化ビニリデン系樹脂組成物は、上記復旧係数に顕著な影響がない限りにおいて、可塑剤、安定剤およびスリップ剤などの添加剤を含有していてもよい。 The vinylidene chloride resin composition may contain additives such as a plasticizer, a stabilizer and a slip agent as long as the recovery coefficient is not significantly affected.
　上記可塑剤の例には、アセチルトリブチルサイトレート、ジオクチルフタレート、ジブチルセバケート、ジオクチルセバケート、ジアセチル化モノグリセライド、アセチル化ジグリセライドおよびアセチル化トリグリセライドなどが含まれる。上記安定剤の例には、エポキシ化大豆油（ＥＳＢＯ）およびエポキシ化亜麻仁油（ＥＬＯ）などが含まれる。上記可塑剤および安定剤の合計の含有量は、１００質量部の上記塩化ビニリデン系樹脂に対して、０．５質量部以上１０質量部以下であることが好ましく、１．０質量部以上７．０重量部以下であることがより好ましい。 Examples of the above plasticizers include acetyltributyl phthalate, dioctyl phthalate, dibutyl sebacate, dioctyl sebacate, diacetylated monoglyceride, acetylated diglyceride and acetylated triglyceride. Examples of the stabilizers include epoxidized soybean oil (ESBO) and epoxidized linseed oil (ELO). The total content of the plasticizer and the stabilizer is preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the vinylidene chloride resin, and 1.0 part by mass or more and 7. It is more preferably 0 parts by mass or less.
　上記スリップ剤の例には、飽和脂肪酸アミド、不飽和脂肪酸アミド、置換アミドおよびチオエーテル系化合物などが含まれる。上記スリップ剤の含有量は、１００質量部の上記塩化ビニリデン系樹脂に対して、０．０５質量部以上１０質量部以下であることが好ましく、０．１質量部以上６．０重量部以下であることがより好ましい。 Examples of the slip agent include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, and thioether compounds. The content of the slip agent is preferably 0.05 parts by mass or more and 10 parts by mass or less, and 0.1 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the vinylidene chloride resin. More preferably.
　また、上記塩化ビニリデン系樹脂組成物は、粘着付与剤を含有してもよい。 Further, the vinylidene chloride-based resin composition may contain a tackifier.
　上記粘着付与剤の例には、ソルビタンモノオレエートおよびソルビタントリオレエートなどのソルビタン脂肪酸エステル、プロピレングリコール脂肪酸エステル、グリセリンモノオレエートおよびグリセリントリオレエートなどのグリセリン脂肪酸エステル、ならびに、流動パラフィンなどが含まれる。 Examples of the tackifier include sorbitan fatty acid esters such as sorbitan monooleate and sorbitan trioleate, glycerin fatty acid esters such as propylene glycol fatty acid ester, glycerin monooleate and glycerin trioleate, and liquid paraffin. ..
　ただし、上記塩化ビニリデン系樹脂組成物は、粘着付与剤を実質的に含有しないことが好ましい。実質的に含有しないとは、粘着付与剤の含有量が、１００質量部の上記塩化ビニリデン系樹脂に対して１００ｐｐｍ以下（好ましくは５０ｐｐｍ以下、より好ましくは２０ｐｐｍ以下）であることを意味する。 However, it is preferable that the vinylidene chloride-based resin composition does not substantially contain a tackifier. The term "substantially free" means that the content of the tackifier is 100 ppm or less (preferably 50 ppm or less, more preferably 20 ppm or less) with respect to 100 parts by mass of the vinylidene chloride resin.
　［樹脂フィルムの製造方法］
　上述した樹脂フィルムは、溶融して押出された上記塩化ビニリデン系樹脂組成物を延伸する工程と、前記延伸された塩化ビニリデン系樹脂組成物を緩和する工程と、を有する方法によって、製造することができる。 [Manufacturing method of resin film]
The resin film described above can be produced by a method having a step of stretching the melted and extruded vinylidene chloride resin composition and a step of relaxing the stretched vinylidene chloride resin composition. it can.
　（塩化ビニリデン系樹脂組成物の調製）
　上記塩化ビニリデン系樹脂組成物は、合成された塩化ビニリデン系樹脂と、各種添加剤と、を混合して調製することができる。 (Preparation of vinylidene chloride resin composition)
The above-mentioned vinylidene chloride-based resin composition can be prepared by mixing a synthesized vinylidene chloride-based resin and various additives.
　上記塩化ビニリデン系樹脂は、塩化ビニリデンと、上記塩化ビニリデンと共重合可能な単量体と、を懸濁重合して、合成することができる。 The vinylidene chloride resin can be synthesized by suspension polymerization of vinylidene chloride and a monomer copolymerizable with vinylidene chloride.
　具体的には、ステンレス製などの反応機（重合機）内において、塩化ビニリデン（共重合体を合成するときは塩化ビニリデンおよび上記塩化ビニリデンと共重合可能な単量体）を、上記水溶性セルロース誘導体の存在下、水性媒体中で撹拌して懸濁させ、油滴に分散させる。その後、重合開始剤を上記懸濁液に添加し、必要に応じて昇温して、塩化ビニリデン（および上記塩化ビニリデンと共重合可能な単量体）を重合させる。このときの温度は、通常は２５～９０℃、好ましくは３０～８５℃であり、重合時間は、通常は１～１００時間、好ましくは２～６０時間、より好ましくは３～５０時間である。 Specifically, in a reactor (polymerizer) made of stainless steel or the like, vinylidene chloride (a monomer copolymerizable with vinylidene chloride and the vinylidene chloride when synthesizing a copolymer) is used as the water-soluble cellulose. In the presence of the derivative, the mixture is stirred and suspended in an aqueous medium and dispersed in oil droplets. Then, a polymerization initiator is added to the suspension, and if necessary, the temperature is raised to polymerize vinylidene chloride (and a monomer copolymerizable with vinylidene chloride). The temperature at this time is usually 25 to 90 ° C., preferably 30 to 85 ° C., and the polymerization time is usually 1 to 100 hours, preferably 2 to 60 hours, and more preferably 3 to 50 hours.
　このとき、上記水溶性セルロース誘導体の添加量を、１００質量部の塩化ビニリデン（および上記塩化ビニリデンと共重合可能な単量体）に対して、３００ｐｐｍ以上６００ｐｐｍ以下、好ましくは３００ｐｐｍ以上５００ｐｐｍ以下とする。水溶性セルロース誘導体の量を上記範囲にすることによって、おそらくは樹脂フィルムの表面に残存した上記水溶性セルロース誘導体が樹脂フィルムの表面を適度に粗面化することにより、製造される樹脂フィルムのＭＤへの引裂き強度はほぼ維持しつつ、面密着力を適度に低下させることができる。そのため、製造される樹脂フィルムの上記復旧係数を上述した範囲に調整しやすい。 At this time, the amount of the water-soluble cellulose derivative added is 300 ppm or more and 600 ppm or less, preferably 300 ppm or more and 500 ppm or less, based on 100 parts by mass of vinylidene chloride (and a monomer copolymerizable with vinylidene chloride). .. By setting the amount of the water-soluble cellulose derivative in the above range, probably by appropriately roughening the surface of the resin film with the water-soluble cellulose derivative remaining on the surface of the resin film, the MD of the produced resin film can be obtained. The surface adhesion force can be appropriately reduced while maintaining the tear strength of the resin. Therefore, it is easy to adjust the recovery coefficient of the produced resin film within the above range.
　得られた塩化ビニリデン系樹脂と、必要に応じて樹脂フィルムに含有される可塑剤、安定剤およびスリップ剤などの添加剤と、を混合して、上記塩化ビニリデン系樹脂組成物を調製することができる。なお、上記添加剤はどの時点で混合もよく、重合時に懸濁液に添加してもよいし、重合後に塩化ビニリデン系樹脂と上記添加剤とを混合してもよい。混合は、ヘンシェルミキサー、円筒型混合機、スクリュー型混合機、スクリュー型押出機、タービュライザー、ナウター型混合機、Ｖ型混合機、リボン型混合機、双腕型ニーダー、流動式混合機、気流型混合機、回転円盤型混合機、ロールミキサー、転動式混合機およびレディゲミキサーなどの公知の混合装置により行うことができる。これにより、粉体状またはペレット状の塩化ビニリデン系樹脂組成物を得ることができる。 The vinylidene chloride-based resin composition can be prepared by mixing the obtained vinylidene chloride-based resin with additives such as a plasticizer, a stabilizer, and a slip agent contained in the resin film, if necessary. it can. The additive may be mixed at any time, and may be added to the suspension at the time of polymerization, or the vinylidene chloride resin and the additive may be mixed after the polymerization. Mixing is Henchel mixer, cylindrical mixer, screw type mixer, screw type extruder, turbulizer, Nauter type mixer, V type mixer, ribbon type mixer, double arm type kneader, fluid type mixer, This can be performed by a known mixing device such as an air flow type mixer, a rotating disk type mixer, a roll mixer, a rolling type mixer, and a Ladyge mixer. Thereby, a powdery or pelletized vinylidene chloride-based resin composition can be obtained.
　（樹脂フィルムの成形）
　上記調製された塩化ビニリデン系樹脂組成物は、公知の方法で溶融および押出した後、延伸および緩和される。 (Molding of resin film)
The prepared vinylidene chloride resin composition is melted and extruded by a known method, and then stretched and relaxed.
　まず、上記塩化ビニリデン系樹脂組成物を押出機に投入し、シリンダー内で溶融させてダイから押出す。ダイは、上記塩化ビニリデン系樹脂組成物を平板状に押し出すＴダイであってもよいし、上記塩化ビニリデン系樹脂組成物を管状に押し出す環状ダイ（サーキュラーダイ）であってもよい。 First, the above-mentioned vinylidene chloride resin composition is put into an extruder, melted in a cylinder, and extruded from a die. The die may be a T-die that extrudes the vinylidene chloride-based resin composition in a flat plate shape, or may be an annular die (circular die) that extrudes the vinylidene chloride-based resin composition in a tubular shape.
　上記押し出された塩化ビニリデン系樹脂組成物は、複数のガイドローラおよび複数のピンチローラを経て、巻き取りローラによって巻き取られる。このとき、上記複数のピンチローラのうち連続するピンチローラの回転速度を異なるものとしたり、管状に押し出された上記塩化ビニリデン系樹脂組成物のインフレーションさせるときの空気量を調製したりすることで、上記押し出された塩化ビニリデン系樹脂組成物を所定の割合でＭＤ（流れ方向）に延伸させることができる。また、テンターを用いたり、管状に押し出された上記塩化ビニリデン系樹脂組成物のインフレーションさせるときの空気量を調製したりすることで、上記押し出された塩化ビニリデン系樹脂組成物を所定の割合でＴＤ（流れに直交する方向）に延伸させることができる。上記ＭＤおよびＴＤに延伸された上記塩化ビニリデン系樹脂組成物は、その後、後続の連続するピンチローラの回転速度差などにより、ＭＤに緩和される。 The extruded vinylidene chloride-based resin composition is wound by a take-up roller via a plurality of guide rollers and a plurality of pinch rollers. At this time, the rotation speeds of the continuous pinch rollers among the plurality of pinch rollers may be different, or the amount of air for inflating the vinylidene chloride resin composition extruded into a tubular shape may be adjusted. The extruded vinylidene chloride resin composition can be stretched in the MD (flow direction) at a predetermined ratio. Further, by using a tenter or adjusting the amount of air when inflating the vinylidene chloride resin composition extruded into a tubular shape, the extruded vinylidene chloride resin composition is TD at a predetermined ratio. It can be stretched (in the direction orthogonal to the flow). The vinylidene chloride-based resin composition stretched over the MD and TD is then relaxed by the MD due to a difference in the rotational speeds of the subsequent continuous pinch rollers and the like.
　本実施形態では、このときのＭＤおよびＴＤへの延伸倍率、およびＭＤへの緩和率によって、成形される樹脂フィルムのＭＤへの引裂き強度の値に対する面密着力（復旧係数）を調整することができる。 In the present embodiment, the surface adhesion force (recovery coefficient) with respect to the value of the tear strength of the molded resin film to MD can be adjusted by the draw ratio to MD and TD and the relaxation rate to MD at this time. it can.
　具体的には、このとき、ＭＤへの延伸倍率を３．５倍以上５．０倍以下とし、ＴＤへの延伸倍率を４．０倍以上５．５倍以下とし、ＭＤへの緩和率を９．５％以上１２．５％とする。 Specifically, at this time, the stretching ratio to MD is 3.5 times or more and 5.0 times or less, the stretching ratio to TD is 4.0 times or more and 5.5 times or less, and the relaxation rate to MD is set. It shall be 9.5% or more and 12.5%.
　上記ＭＤへの延伸倍率は、３．５倍以上４．５倍以下であることがより好ましく、３．８倍以上４．５倍以下であることがさらに好ましい。上記ＴＤへの延伸倍率は、４．５倍以上５．５倍以下であることがより好ましく、４．５倍以上５．０倍以下であることがさらに好ましい。上記ＭＤへの緩和率は、１０．５％以上１２．０％以下であることがより好ましく、１１．０％以上１２．０％以下であることがさらに好ましい。 The draw ratio to the MD is more preferably 3.5 times or more and 4.5 times or less, and further preferably 3.8 times or more and 4.5 times or less. The draw ratio to TD is more preferably 4.5 times or more and 5.5 times or less, and further preferably 4.5 times or more and 5.0 times or less. The relaxation rate to MD is more preferably 10.5% or more and 12.0% or less, and further preferably 11.0% or more and 12.0% or less.
　このように延伸倍率を高くして、その後の緩和率も高くすることで、塩化ビニリデン系樹脂の分子をより緊張した状態でＭＤに配向させやすくして樹脂フィルムのＭＤへの引裂き強度を適度に高め、かつ、緩和により樹脂フィルムの表面を適度に粗面化して面密着力を適度に低くすることができる。さらに、本実施形態では、上記塩化ビニリデン系樹脂組成物が水溶性セルロース誘導体を含有することによっても、樹脂フィルムの表面が適度に粗面化されて面密着力が適度に低くなる。これらの作用によって、復旧係数が０．３５以上０．４１未満であり、縦方向への樹脂フィルムの引き裂けを生じずに、巻き戻り状態の巻回部から端部を剥離させやすい樹脂フィルムが得られるものと、考えられる。 By increasing the draw ratio and the subsequent relaxation rate in this way, it becomes easier to orient the molecules of the vinylidene chloride resin in the MD in a more tense state, and the tear strength of the resin film to the MD is appropriately increased. By increasing and relaxing, the surface of the resin film can be appropriately roughened and the surface adhesion can be appropriately lowered. Further, in the present embodiment, the vinylidene chloride-based resin composition also contains the water-soluble cellulose derivative, so that the surface of the resin film is appropriately roughened and the surface adhesion is appropriately lowered. Due to these actions, a resin film having a recovery coefficient of 0.35 or more and less than 0.41 and easily peeling off the end portion from the wound portion in the rewound state without causing tearing of the resin film in the vertical direction is obtained. It is thought that it will be done.
　延伸および緩和された上記塩化ビニリデン系樹脂組成物は、その後、巻き取りローラによって巻き取られる。 The stretched and relaxed vinylidene chloride-based resin composition is then wound up by a winding roller.
　なお、管状ダイにより管状に押し出された上記塩化ビニリデン系樹脂組成物は、その後、押出軸方向に切開してシングル厚みの平板状フィルムとしてもよいし、折り畳んでダブル厚みの平板状フィルムとしてもよい。 The vinylidene chloride-based resin composition extruded into a tubular shape by a tubular die may then be incised in the extrusion axis direction to form a single-thickness flat film, or folded to form a double-thickness flat film. ..
　以下、実施例を参照して本発明を更に具体的に説明するが、本発明の範囲は実施例の記載に限定されない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the description of Examples.
　１．樹脂フィルムの作製
　１－１．樹脂フィルム－１の作製
　塩化ビニリデン（ＶＤ）と塩化ビニル（ＶＣ）とを、ＶＤ：ＶＣ＝８２：１８（質量比）で混合し、さらにメチルセルロースを溶解した水と、添加剤としてのアセチルトリブチルサイトレート（ＡＴＢＣ）、ジアセチル化モノグリセライド（ＤＡＬＧ）、およびエポキシ化大豆油と、を添加して、仕込み原料を調製した。仕込み原料中のメチルセルロースの含有量は、ＶＤの質量とＶＣの質量との合計量に対し４０３ｐｐｍとなる量に調整した。仕込み原料中の上記添加剤の量は、１００質量部の合成される塩化ビニリデン・塩化ビニル共重合体に対して、添加剤の合計量が８．３質量部となる量に調整した。この仕込み原料を用い、懸濁重合法により塩化ビニリデン・塩化ビニル共重合体を含む塩化ビニリデン系樹脂組成物を調製した。 1. 1. Preparation of resin film 1-1. Preparation of Resin Film-1 Vinylidene chloride (VD) and vinyl chloride (VC) were mixed at a ratio of VD: VC = 82: 18 (mass ratio), and water in which methyl cellulose was further dissolved and acetyltributylsite as an additive were added. Rate (ATBC), diacetylated monoglyceride (DALG), and epoxidized soybean oil were added to prepare a feedstock. The content of methyl cellulose in the raw material to be charged was adjusted to be 403 ppm with respect to the total mass of VD and VC. The amount of the additive in the raw material to be charged was adjusted so that the total amount of the additive was 8.3 parts by mass with respect to 100 parts by mass of the vinylidene chloride / vinyl chloride copolymer to be synthesized. Using this raw material, a vinylidene chloride-based resin composition containing a vinylidene chloride / vinyl chloride copolymer was prepared by a suspension polymerization method.
　塩化ビニリデン系樹脂組成物を、単軸押出機を用いて１８５℃で環状ダイから溶融押出し、得られた管状パリソンを水で急冷し、次いで、室温付近まで温水バスで加熱した。その後、縦方向（ＭＤ）４．１倍、幅方向（ＴＤ）４．７倍の延伸倍率でインフレーション二軸延伸を行い、さらに、縦方向（ＭＤ）１１％の緩和率でＭＤに緩和した後、巻取りローラで巻き取った。巻き取ったフィルムのスリットと巻き返しを行い、厚み１０μｍ、幅３０ｃｍ、長さ５０ｍの、巻回体となっている樹脂フィルム－１を得た。 The vinylidene chloride resin composition was melt-extruded from a cyclic die at 185 ° C. using a single-screw extruder, and the obtained tubular parison was rapidly cooled with water and then heated to around room temperature in a hot water bath. After that, inflation biaxial stretching was performed at a stretching ratio of 4.1 times in the longitudinal direction (MD) and 4.7 times in the width direction (TD), and further relaxed to MD at a relaxation rate of 11% in the longitudinal direction (MD). , Winded up with a take-up roller. The wound film was slit and rewound to obtain a resin film-1 having a thickness of 10 μm, a width of 30 cm, and a length of 50 m, which was a wound body.
　１－２．樹脂フィルム－２の作製
　塩化ビニリデン系樹脂組成物をフィルム化する際の縦方向（ＭＤ）の緩和率を１２％とした以外は、樹脂フィルム－１の作製と同様にして、巻回体となっている樹脂フィルム－２を得た。 1-2. Preparation of Resin Film-2 A wound body is formed in the same manner as in the preparation of Resin Film-1, except that the relaxation rate in the vertical direction (MD) when the vinylidene chloride-based resin composition is formed into a film is 12%. A resin film-2 was obtained.
　１－３．樹脂フィルム－３の作製
　塩化ビニリデン系樹脂組成物をフィルム化する際の縦方向（ＭＤ）の緩和率を９％とした以外は、樹脂フィルム－１の作製と同様にして、巻回体となっている樹脂フィルム－３を得た。 1-3. Preparation of Resin Film-3 A wound body is formed in the same manner as in the preparation of Resin Film-1, except that the relaxation rate in the vertical direction (MD) when the vinylidene chloride-based resin composition is formed into a film is 9%. A resin film-3 was obtained.
　１－４．樹脂フィルム－４の作製
　塩化ビニリデン系樹脂組成物の合成に使用する仕込み原料へのメチルセルロースの添加料を、ＶＤの質量とＶＣの質量との合計量に対し２５０ｐｐｍとし、得られた塩化ビニリデン系樹脂組成物をフィルム化する際の縦方向（ＭＤ）の緩和率を９％とした以外は、樹脂フィルム－１の作製と同様にして、巻回体となっている樹脂フィルム－４を得た。 1-4. Preparation of Resin Film-4 The additive of methyl cellulose to the raw material used for the synthesis of the vinylidene chloride resin composition was 250 ppm with respect to the total amount of the mass of VD and the mass of VC, and the obtained vinylidene chloride resin was obtained. A resin film-4 as a wound body was obtained in the same manner as in the production of the resin film-1 except that the relaxation rate in the vertical direction (MD) when the composition was formed into a film was set to 9%.
　１－５．樹脂フィルム－５の作製
　塩化ビニリデン系樹脂組成物の合成に使用する仕込み原料に、ＶＤの質量とＶＣの質量との合計量に対し７８２ｐｐｍとなる量の、粘着付与剤としての流動パラフィンを添加した以外は樹脂フィルム－４の作製と同様にして、巻回体となっている樹脂フィルム－５を得た。 1-5. Preparation of Resin Film-5 Liquid paraffin as a tackifier was added to the raw material used for the synthesis of vinylidene chloride-based resin composition in an amount of 782 ppm based on the total amount of VD and VC. A resin film-5 as a wound body was obtained in the same manner as in the production of the resin film-4 except for the above.
　１－６．樹脂フィルム－６の作製
　塩化ビニリデン系樹脂組成物の合成に使用する仕込み原料に、ＶＤの質量とＶＣの質量との合計量に対し７８２ｐｐｍとなる量の流動パラフィンを添加し、得られた塩化ビニリデン系樹脂組成物をフィルム化する際の縦方向（ＭＤ）の延伸倍率を３．２倍、幅方向（ＴＤ）の延伸倍率を５．４倍、縦方向（ＭＤ）の緩和率を１０％とした以外は、樹脂フィルム－１の作製と同様にして、巻回体となっている樹脂フィルム－６を得た。 1-6. Preparation of Resin Film-6 Vinylidene Chloride obtained by adding liquid paraffin in an amount of 782 ppm based on the total amount of VD and VC to the raw material used for synthesizing the vinylidene chloride resin composition. When the based resin composition is made into a film, the stretching ratio in the vertical direction (MD) is 3.2 times, the stretching ratio in the width direction (TD) is 5.4 times, and the relaxation rate in the vertical direction (MD) is 10%. A resin film-6 as a wound body was obtained in the same manner as in the production of the resin film-1 except for the above.
　１－７．樹脂フィルム－７の作製
　塩化ビニリデン系樹脂組成物の合成に使用する仕込み原料へのメチルセルロースの添加料を、ＶＤの質量とＶＣの質量との合計量に対し７５５ｐｐｍとし、得られた塩化ビニリデン系樹脂組成物をフィルム化する際の縦方向（ＭＤ）の緩和率を９％とした以外は、樹脂フィルム－１の作製と同様にして、巻回体となっている樹脂フィルム－７を得た。 1-7. Preparation of Resin Film-7 The additive of methyl cellulose to the raw material used for the synthesis of the vinylidene chloride resin composition was set to 755 ppm with respect to the total amount of the mass of VD and the mass of VC, and the obtained vinylidene chloride resin was obtained. A resin film-7 as a wound body was obtained in the same manner as in the production of the resin film-1 except that the relaxation rate in the vertical direction (MD) when the composition was formed into a film was set to 9%.
　樹脂フィルム－１～樹脂フィルム－７の作製に用いた添加剤（水溶性セルロース誘導体および粘着付与剤）の量、ならびに製造条件（縦方向（ＭＤ）の延伸倍率、幅方向（ＴＤ）の延伸倍率、および縦方向（ＭＤ）の緩和率）を、表１に示す。 The amount of additives (water-soluble cellulose derivative and tackifier) used to prepare the resin film-1 to the resin film-7, and the production conditions (longitudinal (MD) stretching ratio, width direction (TD) stretching ratio). , And the relaxation rate in the vertical direction (MD)) are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　２．評価
　２－１．水溶性セルロース誘導体の抽出量
　十分な長さの樹脂フィルム－１～樹脂フィルム－７のそれぞれを巻回体から引き出して切断し、試験片とした。 2. 2. Evaluation 2-1. Extraction amount of water-soluble cellulose derivative Each of the resin film-1 to the resin film-7 having a sufficient length was pulled out from the winding body and cut to obtain a test piece.
　試験片を１００ｍｌのエタノールに浸漬させ、７０℃に加熱して５時間の抽出を行った。その後、抽出液を乾固して、エタノール抽出物を得た。上記エタノール抽出物を１５％エタノール水溶液に転溶し、二硫化炭素で洗浄した。洗浄後、水相を乾固して、ヨウ化水素（ＨＩ）を反応させて生成したヨードメタンをｏ－キシレンに溶解した。 The test piece was immersed in 100 ml of ethanol, heated to 70 ° C., and extracted for 5 hours. Then, the extract was dried to obtain an ethanol extract. The above ethanol extract was dissolved in a 15% aqueous ethanol solution and washed with carbon disulfide. After washing, the aqueous phase was dried to dryness, and iodomethane produced by reacting hydrogen iodide (HI) was dissolved in o-xylene.
　上記ヨードメタンが溶解したｏ－キシレン層をガスクロマトグラフィー（ＧＣ）で分析し、得られたヨードメタン量をメチルセルロース量に換算して、樹脂フィルムの表面から溶出したメチルセルロース量を得た。得られたメチルセルロース量を、樹脂フィルムの面積（単位：ｍ２）で除算して、樹脂フィルムの表面に存在する水溶性セルロース誘導体の量（単位：μｇ／ｍ２）とした。 The o-xylene layer in which the iodomethane was dissolved was analyzed by gas chromatography (GC), and the obtained amount of iodomethane was converted into the amount of methylcellulose to obtain the amount of methylcellulose eluted from the surface of the resin film. The amount of methylcellulose obtained was divided by the area of the resin film (unit: m 2 ) to obtain the amount of water-soluble cellulose derivative present on the surface of the resin film (unit: μg / m 2 ).
　ＧＣは、以下の機器および条件で行った。
　（測定機器・カラム）
　ＧＣ－ＦＩＤ：　ＧＬ　ｓｃｉｅｎｃｅｓ　ＧＣ－４０００　Ｐｌｕｓ
　カラム：　　　　Ａｇｉｌｅｎｔ　Ｊ＆Ｗ　ＧＣ　カラム　ＤＢ－６２４
　　　　　　　　（Ｌｅｎｇｔｈ：３０ｍ、Ｉ．Ｄ．：０．５３０ｍｍ、Ｆｉｌｍ：３．００μｍ）
　（ＧＣ条件）
　カラム温度：　　６０℃（５分間保持）→昇温２０℃／ｍｉｎ→２１０℃（５分間保持）
　注入口温度：　　２３０℃
　検出器温度：　　２３０℃
　キャリアガス：　Ｎ２（カラム流量　４．２ｍｌ／ｍｉｎ）
　注入法：　　　　スプリット（５：１）
　注入量：　　　　１μｌ GC was performed with the following equipment and conditions.
(Measuring equipment / column)
GC-FID: GL sciences GC-4000 Plus
Column: Agilent J & W GC Column DB-624
(Length: 30 m, ID: 0.530 mm, Film: 3.00 μm)
(GC condition)
Column temperature: 60 ° C (hold for 5 minutes) → temperature rise 20 ° C / min → 210 ° C (hold for 5 minutes)
Injection port temperature: 230 ° C
Detector temperature: 230 ° C
Carrier gas: N 2 (column flow rate 4.2 ml / min)
Injection method: split (5: 1)
Injection volume: 1 μl
　２－２．面密着力
　樹脂フィルム－１～樹脂フィルム－７のそれぞれを巻回体から引き出し、縦方向（ＭＤ）２００～３００ｍｍ×幅方向（ＴＤ）３００ｍｍの大きさに切断して、試験片とした。 2-2. Surface Adhesion Strength Each of the resin film-1 to the resin film-7 was pulled out from the winding body and cut into a size of 200 to 300 mm in the vertical direction (MD) x 300 mm in the width direction (TD) to prepare a test piece.
　底面積２５ｃｍ２、質量３００ｇのアルミニウム製の円柱状の治具を２つ用意した。一方の治具の底面に、それぞれの試験片を、皺が入らないように緊張させながら固定した。他方の治具の底面にも、同じ樹脂フィルムから得られた試験片を、皺が入らないように緊張させながら固定した。これら２つの治具を、試験片が固定された底面同士が完全に重なり合うように鉛直方向に接触させ、鉛直上方側の治具の自重により１分間押圧して、試験片同士を圧着させた。続いて、株式会社オリエンテック製の引張圧縮試験機であるテンシロンＲＴＣ－１２１０Ａを使用して、１００ｍｍ／分の速度で２つの治具を互いに反対の方向（鉛直方向）に引っ張り、治具（試験片）が引き離すための最大荷重（単位：Ｎ）を、当該試験片の面剥離強度とした。測定は２３℃、５０％ＲＨの雰囲気中で行い、５枚の試験片について得られた面剥離強度の平均値を、当該樹脂フィルムの面密着力とした。 Two aluminum columnar jigs with a bottom area of 25 cm 2 and a mass of 300 g were prepared. Each test piece was fixed to the bottom surface of one of the jigs while being tense so as not to cause wrinkles. A test piece obtained from the same resin film was also fixed to the bottom surface of the other jig while being tense so as not to cause wrinkles. These two jigs were brought into vertical contact with each other so that the bottom surfaces to which the test pieces were fixed completely overlapped with each other, and pressed for 1 minute by the weight of the jig on the vertically upper side to crimp the test pieces to each other. Subsequently, using Tensilon RTC-1210A, which is a tensile compression tester manufactured by Orientec Co., Ltd., the two jigs are pulled in opposite directions (vertical direction) at a speed of 100 mm / min, and the jig (test) is used. The maximum load (unit: N) for the piece) to be separated was defined as the surface peeling strength of the test piece. The measurement was carried out in an atmosphere of 23 ° C. and 50% RH, and the average value of the surface peeling strength obtained for the five test pieces was taken as the surface adhesion force of the resin film.
　２－３．ＭＤへの引裂き強度
　樹脂フィルム－１～樹脂フィルム－７のそれぞれを巻回体から引き出し、縦方向（ＭＤ）６３．５ｍｍ×幅方向（ＴＤ）５０ｍｍの大きさに切断して、試験片とした。 2-3. Tear strength to MD Each of the resin film-1 to the resin film-7 was pulled out from the winding body and cut into a size of 63.5 mm in the vertical direction (MD) x 50 mm in the width direction (TD) to obtain a test piece. ..
　株式会社東洋精機製作所製の軽荷重引裂試験機であるＮｏ．１９３　型式Ｄを用いて、測定レンジを１９６ｍＮとして、それぞれの試験片のＭＤへの引裂き強度を求めた。クランプの中央に試験片をセットした後、縦方向（ＭＤ）への切込み長さが１２．７ｍｍになるように、試験片の幅方向（ＴＤ）の中央にナイフで切込みを入れて、振り子を開放して試験片を切り裂くための最大荷重（単位：ｍＮ）を測定した。測定は２３℃、５０％ＲＨの雰囲気中で行い、５枚の試験片について得られたＭＤへの引裂き強度の平均値を、当該樹脂フィルムのＭＤへの引裂き強度とした。 No., a light load tear tester manufactured by Toyo Seiki Seisakusho Co., Ltd. 193 Model D was used, the measurement range was 196 mN, and the tear strength of each test piece to MD was determined. After setting the test piece in the center of the clamp, make a notch in the center of the width direction (TD) of the test piece with a knife so that the cut length in the vertical direction (MD) is 12.7 mm, and insert the pendulum. The maximum load (unit: mN) for opening and tearing the test piece was measured. The measurement was carried out in an atmosphere of 23 ° C. and 50% RH, and the average value of the tear strength to MD obtained for the five test pieces was taken as the tear strength to MD of the resin film.
　２－４．ヘイズ値
　十分な長さの樹脂フィルム－１～樹脂フィルム－７のそれぞれを巻回体から引き出して切断し、試験片とした。 2-4. Haze value Each of the resin film-1 to the resin film-7 having a sufficient length was pulled out from the winding body and cut to obtain a test piece.
　日本電色工業株式会社製のヘーズメーターであるＮＤＨ７０００ＳＰを用いて、ＪＩＳ　Ｋ　７１３６（２０００年）に準拠し、それぞれの試験片のヘイズ値（単位：％）を測定した。５枚の試験片について得られたヘイズ値の平均値を、当該樹脂フィルムのヘイズ値とした。 Using NDH7000SP, a haze meter manufactured by Nippon Denshoku Industries Co., Ltd., the haze value (unit:%) of each test piece was measured in accordance with JIS K 7136 (2000). The average value of the haze values obtained for the five test pieces was taken as the haze value of the resin film.
　２－５．突き刺し強度
　十分な長さの樹脂フィルム－１～樹脂フィルム－７のそれぞれを巻回体から引き出して切断し、試験片とした。 2-5. Puncture strength Each of the resin film-1 to the resin film-7 having a sufficient length was pulled out from the winding body and cut to obtain a test piece.
　株式会社エー・アンド・デイ 製の引張試験機であるＴＥＮＳＩＬＯＮ　ＲＴＧ－１２１０を用いて、ＪＩＳ　Ｚ　１７０７（２０１９年）に準拠し、それぞれの試験片の突き刺し強さ（単位：Ｎ）を測定した。測定は２３℃、５０％ＲＨの雰囲気中で行い、５枚の試験片について得られた突き刺し強さの平均値を、当該樹脂フィルムの突き刺し強度とした。 Using a tensile tester manufactured by A & D Co., Ltd., TENSILON RTG-1210, the piercing strength (unit: N) of each test piece was measured in accordance with JIS Z1707 (2019). The measurement was performed in an atmosphere of 23 ° C. and 50% RH, and the average value of the piercing strength obtained for the five test pieces was taken as the piercing strength of the resin film.
　２－６．復旧時間
　樹脂フィルム－１～樹脂フィルム－７のそれぞれを、収容箱（株式会社クレハ製、クレラップ用収容箱）に収容し、収容箱から３０ｃｍ繰り出して、蓋部をしっかりと閉めた状態で、刃型が樹脂フィルムに残るようにそれぞれの樹脂フィルムを切断した。その後、残された樹脂フィルムを、皺ができるだけ入らないようにして収容体の内部に巻き戻し、樹脂フィルムの端部を巻回されている樹脂フィルムに密着させた。 2-6. Restoration time Each of the resin film-1 to resin film-7 is housed in a storage box (Kureha Co., Ltd., storage box for clerap), extended 30 cm from the storage box, and with the lid tightly closed, the blade. Each resin film was cut so that the mold remained on the resin film. Then, the remaining resin film was rewound into the inside of the container with as few wrinkles as possible, and the end portion of the resin film was brought into close contact with the wound resin film.
　この状態から、男女を含む評価者４０名に、テープなどの道具は使用しないで、縦方向（ＭＤ）への引き裂けが生じないように、樹脂フィルムの全幅を収容箱の外部に引き出させた。評価者が巻回されている樹脂フィルムに密着している樹脂フィルムの端部を発見してから、樹脂フィルムの全幅を収容箱の外部に引き出すまでの時間を計測して、復旧時間とした。測定は２３℃、５０％ＲＨの雰囲気中で行い、５回の試験で得られた復旧時間の平均値を、当該樹脂フィルムの復旧時間とした。 From this state, 40 evaluators, including men and women, were made to pull out the entire width of the resin film to the outside of the storage box so that it would not tear in the vertical direction (MD) without using tools such as tape. The time from when the evaluator found the end of the resin film which was in close contact with the wound resin film until the entire width of the resin film was pulled out of the storage box was measured and used as the recovery time. The measurement was performed in an atmosphere of 23 ° C. and 50% RH, and the average value of the recovery times obtained in the five tests was taken as the recovery time of the resin film.
　樹脂フィルム－１～樹脂フィルム－７の、上記面密着力、ＭＤへの引裂き強度、ＭＤへの引裂き強度に対する面密着力の値の割合（面密着力／ＭＤへの引裂き強度）、突き刺し強度、および復旧時間の評価結果を、表２に示す。なお、表２中、「－」は、評価を行っていないことを示す。 The ratio of the value of the surface adhesion force, the tear strength to the MD, the surface adhesion force to the tear strength to the MD (surface adhesion force / tear strength to the MD), the piercing strength, of the resin film-1 to the resin film-7. Table 2 shows the evaluation results of the recovery time. In Table 2, "-" indicates that the evaluation has not been performed.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２から明らかなように、ＭＤへの引裂き強度の値（ｍＮ）に対する、面密着力の値（Ｎ）の割合が、０．３５以上０．４１未満である樹脂フィルム－１および樹脂フィルム－２は、そうではない樹脂フィルム－３～樹脂フィルム－５と比較して、巻き戻り状態からの復旧時間が顕著に短くなっていた。 As is clear from Table 2, the ratio of the surface adhesion value (N) to the tear strength value (mN) to MD is 0.35 or more and less than 0.41. Resin film-1 and resin film- In No. 2, the recovery time from the rewinding state was significantly shorter than that in Resin Film-3 to Resin Film-5, which were not so.
　また、表１から明らかなように、このような樹脂フィルム－１および樹脂フィルム－２は、重合により塩化ビニリデン系樹脂を合成するための単量体を、前記単量体の全質量に対する含有量が３００ｐｐｍ以上６００ｐｐｍ以下である水溶性セルロース誘導体の存在下、水性媒体中で懸濁重合させて得られる樹脂組成物を用いて、溶融して押出された上記樹脂組成物を、ＭＤへの延伸倍率が３．５倍以上５．０倍以下、ＴＤへの延伸倍率が４．０倍以上５．５倍以下となるように延伸し、ＭＤへの緩和率が１０．０％以上１２．５％以下となるように緩和する方法で、製造されたものであった。 Further, as is clear from Table 1, such a resin film-1 and a resin film-2 contain a monomer for synthesizing a vinylidene chloride resin by polymerization with respect to the total mass of the monomer. Using a resin composition obtained by suspend polymerization in an aqueous medium in the presence of a water-soluble cellulose derivative having a value of 300 ppm or more and 600 ppm or less, the resin composition melted and extruded was stretched to MD. Is stretched to 3.5 times or more and 5.0 times or less, and the stretching ratio to TD is 4.0 times or more and 5.5 times or less, and the relaxation rate to MD is 10.0% or more and 12.5%. It was manufactured by a method of relaxation as follows.
　本出願は、２０１９年３月１８日出願の日本国出願番号２０１９－０４９６１４号に基づく優先権を主張する出願であり、当該出願の特許請求の範囲および明細書に記載された内容は本出願に援用される。 This application is an application claiming priority based on Japanese Application No. 2019-049614 filed on March 18, 2019, and the scope of claims of the application and the contents described in the specification are included in this application. It will be used.
　本発明の樹脂フィルムは、縦方向への樹脂フィルムの引き裂けを生じずに、巻き戻り状態の巻回部から端部を剥離させやすい。そのため、本発明の樹脂フィルムは、家庭用、実験用および工業用などの多様な用途において、好適に使用することができる。 The resin film of the present invention can easily peel off the end portion from the wound portion in the rewound state without causing tearing of the resin film in the vertical direction. Therefore, the resin film of the present invention can be suitably used in various applications such as home use, experimental use, and industrial use.

Claims (5)

  1. 　塩化ビニリデン系樹脂組成物からなる樹脂フィルムであって、
    　ＭＤへの引裂き強度の値（単位：ｍＮ）に対する、面密着力の値（単位：Ｎ）の割合（面密着力の値／ＭＤへの引裂き強度の値）が、０．３５以上０．４１未満である、
    　樹脂フィルム。     A resin film made of a vinylidene chloride-based resin composition.
    The ratio of the surface adhesion value (unit: N) to the tear strength value (unit: mN) to MD (surface adhesion value / tear strength value to MD) is 0.35 or more and 0.41. Is less than
    Resin film.
  2. 　前記ＭＤへの引裂き強度の値は、３２．０ｍＮ以上３４．５ｍＮ以下であり、
    　前記面密着力の値は、１２．０Ｎ以上１３．０Ｎ以下である、
    　請求項１に記載の樹脂フィルム。     The value of the tear strength to the MD is 32.0 mN or more and 34.5 mN or less.
    The value of the surface adhesion force is 12.0 N or more and 13.0 N or less.
    The resin film according to claim 1.
  3. 　ヘイズ値が１．２％以下である、請求項１または２に記載の樹脂フィルム。 The resin film according to claim 1 or 2, wherein the haze value is 1.2% or less.
  4. 　突き刺し強度の値が４．０Ｎ未満である、請求項１～３のいずれか１項に記載の樹脂フィルム。 The resin film according to any one of claims 1 to 3, wherein the value of the piercing strength is less than 4.0 N.
  5. 　溶融して押出された塩化ビニリデン系樹脂組成物を延伸する工程と、前記延伸された塩化ビニリデン系樹脂組成物を緩和する工程と、を有する樹脂フィルムの製造方法であって、
    　前記塩化ビニリデン系樹脂組成物は、重合により塩化ビニリデン系樹脂を合成するための単量体を、前記単量体の全質量に対する含有量が３００ｐｐｍ以上６００ｐｐｍ以下である水溶性セルロース誘導体の存在下、水性媒体中で懸濁重合させて得られる樹脂組成物であり、
    　前記延伸する工程において、塩化ビニリデン系樹脂組成物を、ＭＤへの延伸倍率が３．５倍以上５．０倍以下、ＴＤへの延伸倍率が４．０倍以上５．５倍以下となるように延伸し、
    　前記緩和する工程において、前記延伸された塩化ビニリデン系樹脂組成物を、ＭＤへの緩和率が９．５％以上１２．５％以下となるように緩和する、
    　樹脂フィルムの製造方法。     A method for producing a resin film, which comprises a step of stretching a melted and extruded vinylidene chloride-based resin composition and a step of relaxing the stretched vinylidene chloride-based resin composition.
    The vinylidene chloride-based resin composition contains a monomer for synthesizing a vinylidene chloride-based resin by polymerization in the presence of a water-soluble cellulose derivative in which the content of the monomer with respect to the total mass is 300 ppm or more and 600 ppm or less. A resin composition obtained by suspension polymerization in an aqueous medium.
    In the stretching step, the polyvinylidene chloride-based resin composition has a draw ratio of 3.5 times or more and 5.0 times or less to MD and a draw ratio of 4.0 times or more and 5.5 times or less to TD. Stretched to
    In the relaxation step, the stretched vinylidene chloride-based resin composition is relaxed so that the relaxation rate to MD is 9.5% or more and 12.5% or less.
    A method for manufacturing a resin film.
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JP2002256029A (en) * 2001-02-27 2002-09-11 Asahi Kasei Corp Vinylidene chloride-based copolymer particle and extrusion method
JP2003137911A (en) * 2001-11-05 2003-05-14 Kureha Chem Ind Co Ltd Method for producing vinylidene chloride-based resin
JP2014172312A (en) * 2013-03-11 2014-09-22 Asahi Kasei Chemicals Corp Vinylidene chloride resin wrap film and production method thereof
JP2014234271A (en) * 2013-06-03 2014-12-15 旭化成ケミカルズ株式会社 Wrap film wound body and wound body housing
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JP2016023272A (en) * 2014-07-23 2016-02-08 旭化成ケミカルズ株式会社 Vinylidene chloride resin wrap film
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Publication number Priority date Publication date Assignee Title
JPH1025387A (en) * 1996-07-10 1998-01-27 Asahi Chem Ind Co Ltd Vinylidene chloride-based resin composition and wrap film
JP2002256029A (en) * 2001-02-27 2002-09-11 Asahi Kasei Corp Vinylidene chloride-based copolymer particle and extrusion method
JP2003137911A (en) * 2001-11-05 2003-05-14 Kureha Chem Ind Co Ltd Method for producing vinylidene chloride-based resin
JP2014172312A (en) * 2013-03-11 2014-09-22 Asahi Kasei Chemicals Corp Vinylidene chloride resin wrap film and production method thereof
JP2014234271A (en) * 2013-06-03 2014-12-15 旭化成ケミカルズ株式会社 Wrap film wound body and wound body housing
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