WO2019065306A1 - Film stratifié à base de polypropylène - Google Patents

Film stratifié à base de polypropylène Download PDF

Info

Publication number
WO2019065306A1
WO2019065306A1 PCT/JP2018/034179 JP2018034179W WO2019065306A1 WO 2019065306 A1 WO2019065306 A1 WO 2019065306A1 JP 2018034179 W JP2018034179 W JP 2018034179W WO 2019065306 A1 WO2019065306 A1 WO 2019065306A1
Authority
WO
WIPO (PCT)
Prior art keywords
polypropylene
molecular weight
film
heat seal
laminate film
Prior art date
Application number
PCT/JP2018/034179
Other languages
English (en)
Japanese (ja)
Inventor
理 木下
山田　浩司
Original Assignee
東洋紡株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to KR1020207011453A priority Critical patent/KR102593205B1/ko
Priority to CN201880061951.6A priority patent/CN111132831A/zh
Priority to JP2019544588A priority patent/JP7238779B2/ja
Publication of WO2019065306A1 publication Critical patent/WO2019065306A1/fr
Priority to JP2022166463A priority patent/JP7409459B2/ja

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene

Definitions

  • the present invention relates to a polypropylene-based laminate film having heat sealability. More particularly, it relates to a polypropylene-based laminate film having excellent heat seal strength for use as a packaging application.
  • the present invention relates to a polypropylene-based laminate film which can be suitably used in various fields where dimensional stability at high temperature and high rigidity are required, and which is excellent in heat resistance and mechanical properties and which is excellent in heat sealability.
  • polypropylene-based oriented films have been used for a wide range of applications such as packaging for food and various products, electrical insulation, surface protection films, etc., but applications that require heat sealability in one of them There is.
  • a polypropylene-based laminated film having heat sealability a co-extrusion laminated polypropylene-based resin film in which a low melting point polyolefin-based resin is laminated on a polypropylene-based resin has been widely used.
  • a stretched polypropylene laminated film which has a low shrinkage comparable to PET at 150 ° C. and can be heat-sealed at a high temperature has been proposed (see, for example, Patent Document 1). .
  • this film also has room for improvement in mechanical properties.
  • an object of the present invention is to provide a polypropylene-based laminate film having excellent heat seal strength for use as a packaging application.
  • a heat composed of a base material layer (A) in which the polypropylene resin constituting the layer satisfies the following conditions 1) to 4) and a polyolefin resin laminated on one side or both sides of this base layer It is a polypropylene-type laminated film which consists of a sealing layer (B) and the lower limit of the plane orientation coefficient of a film is 0.0125.
  • the lower limit of the mesopentad fraction is 96%.
  • the upper limit of the amount of copolymerized monomers other than propylene is 0.1 mol%.
  • Mass average molecular weight (Mw) / number average molecular weight (Mn) is 3.0 or more and 5.4 or less.
  • the melt flow rate (MFR) measured at 230 ° C. and 2.16 kgf is 6.2 g / 10 min or more and 9.0 g / 10 min or less.
  • the thermal shrinkage at 150 ° C. in the longitudinal direction and the transverse direction of the film is 8% or less.
  • the Young's modulus in the MD direction is 2.1 GPa or more, and the Young's modulus in the TD direction is 3.7 GPa or more.
  • the 180 ° peel strength of a 10 mm wide test piece obtained by overlapping the heat seal layer (B) surfaces and performing hot plate sealing at 140 ° C. for 1 second is 8.0 N / 15 mm or more Is preferred.
  • the polyolefin resin constituting the heat seal resin (B) is a propylene random copolymer and / or a propylene block copolymer.
  • the present invention it was excellent for use as a packaging application and very suitable for heat seal processing. Furthermore, for example, by setting the heat seal temperature high, it is possible to increase the line speed in bag-making processing and the like, and the productivity is improved. In addition, the heat seal strength can also be improved by increasing the heat seal temperature. Furthermore, it can be suitably used in various fields where dimensional stability at high temperatures and high rigidity are required, and for example, when performing high temperature treatment such as retort, the amount of deformation of the bag can be suppressed. As a result, thinning can be achieved.
  • the present invention relates to a polypropylene-based laminate film having heat sealability. More particularly, it relates to a polypropylene-based laminate film having sufficient heat seal strength which is excellent for use as a packaging application.
  • the feature of the polypropylene-based laminate film of the present invention lies in the molecular weight distribution of the polypropylene resin used for the substrate layer (A).
  • the polypropylene-based laminate film of the present invention comprises a substrate layer (A) in which the polypropylene resin constituting the layer satisfies the following conditions 1) to 4), and a polyolefin-based resin laminated on one side or both sides of this substrate layer. It is a polypropylene-based laminated film comprising the heat seal layer (B) and the lower limit of the plane orientation coefficient of the film being 0.0125. 1) The lower limit of the mesopentad fraction is 96%. 2) The upper limit of the amount of copolymerized monomers other than propylene is 0.1 mol%. 3) Mass average molecular weight (Mw) / number average molecular weight (Mn) is 3.0 or more and 5.4 or less. 4) The melt flow rate (MFR) measured at 230 ° C. and 2.16 kgf is 6.2 g / 10 min or more and 9.0 g / 10 min or less. Further details are described below.
  • the polypropylene resin used for the base material layer (A) of the present invention may be a polypropylene resin copolymerized with ethylene and / or an ⁇ -olefin having 4 or more carbon atoms at 0.5 mol% or less.
  • Such copolymerized polypropylene resin is also included in the polypropylene resin of the present invention (hereinafter, polypropylene resin).
  • polypropylene resin 0.3 mol% or less is preferable, 0.1 mol% or less is more preferable, and the completely homopolypropylene resin which does not contain a copolymerization component is the most preferable.
  • the mesopentad fraction ([mm mm]%) measured by 13 C-NMR, which is an index of stereoregularity of a polypropylene resin, is preferably 96 to 99.5%. More preferably, it is 97% or more, and more preferably 98% or more.
  • the mesopentad ratio of the polypropylene of the base material layer (A) is small, the melting point of the crystals is lowered, and the elastic modulus and the heat resistance at high temperature may be insufficient. 99.5% is a realistic upper limit.
  • Mw / Mn which is an index of molecular weight distribution, is preferably 3.0 to 5.4 in the polypropylene resin. More preferably, it is 3.0 to 5.0, still more preferably 3.2 to 4.5, and particularly preferably 3.3 to 4.0.
  • Mw / Mn of the entire polypropylene resin constituting the base material layer (A) is 5.4 or less, although the high molecular weight component is present, the amount thereof tends to be small, and the heat shrinkage tends to be small.
  • Mw means mass average molecular weight
  • Mn means number average molecular weight
  • the mass average molecular weight (Mw) of the polypropylene resin is preferably 180,000 to 500,000.
  • the lower limit of Mw is more preferably 190,000, further preferably 200,000, and the upper limit of Mw is more preferably 320,000, further preferably 300,000, particularly preferably 250,000.
  • the number average molecular weight (Mn) of the polypropylene resin is preferably 20,000 to 200,000.
  • the lower limit of Mn is more preferably 30,000, more preferably 40,000, particularly preferably 50,000, and the upper limit of Mn is more preferably 80,000, still more preferably 70,000, particularly preferably 60,000. is there.
  • the lower limit of the amount of the component having a molecular weight of 100,000 or less is preferably 35% by mass, more preferably It is 38% by mass, more preferably 40% by mass, particularly preferably 41% by mass, and most preferably 42% by mass.
  • the upper limit of the amount of the component having a molecular weight of 100,000 or less in the GPC integration curve is preferably 65% by mass, more preferably 60% by mass, still more preferably 58% by mass, particularly preferably 56% by mass Most preferably 55% by weight.
  • the lower limit of the amount of the component having a molecular weight of 10,000 or less is preferably 1% by mass, more preferably It is 1.5% by mass.
  • the upper limit of the amount of components having a molecular weight of 10,000 or less in the GPC integration curve is preferably 5% by mass, more preferably 4% by mass, still more preferably 3.5% by mass, particularly preferably 3 It is weight%.
  • the melt flow rate (MFR; 230 ° C., 2.16 kgf) of the polypropylene resin at this time is preferably 6.2 g / 10 minutes to 10.0 g / 10 minutes.
  • the lower limit of the MFR of the polypropylene resin is more preferably 6.5 g / 10 min, still more preferably 7 g / 10 min, and particularly preferably 7.5 g / 10 min.
  • the upper limit of the MFR of the polypropylene resin is more preferably 9 g / 10 min, still more preferably 8.5 g / 10 min, and particularly preferably 8.2 g / 10 min.
  • melt flow rate MFR; 230 ° C., 2.16 kgf
  • the heat shrinkage at high temperatures can also be made smaller.
  • the degree of crystallization of the film generated by stretching becomes strong, the rigidity of the film, in particular, the tensile elastic modulus (Young's modulus) in the width (TD) direction becomes high.
  • melt flow rate MFR; 230 ° C., 2.16 kgf
  • melt flow rate MFR; 230 ° C., 2.16 kgf
  • the molecular weight distribution of the polypropylene resin can be obtained by polymerizing components of different molecular weights in multiple stages in a series of plants, blending components of different molecular weights offline with a kneader, or blending catalysts having different performances for polymerization. It is possible to adjust by using a catalyst that can realize a desired molecular weight distribution.
  • the polypropylene resin used in the present invention can be obtained by polymerizing propylene as a raw material using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Among them, it is preferable to use a Ziegler-Natta catalyst and to use a catalyst capable of highly stereoregular polymerization in order to eliminate foreign bonds.
  • a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.
  • a Ziegler-Natta catalyst it is preferable to use a Ziegler-Natta catalyst and to use a catalyst capable of highly stereoregular polymerization in order to eliminate foreign bonds.
  • a known method may be adopted, for example, a method of polymerizing in an inert solvent such as hexane, heptane, toluene, xylene or the like, a method of polymerizing in a liquid monomer, a catalyst to a gas monomer And polymerizing in the gas phase, or a method of polymerizing these in combination, and the like.
  • an inert solvent such as hexane, heptane, toluene, xylene or the like
  • a method of polymerizing in a liquid monomer such as hexane, heptane, toluene, xylene or the like
  • a method of polymerizing in a liquid monomer such as hexane, heptane, toluene, xylene or the like
  • a method of polymerizing in a liquid monomer such as hexane, heptane, toluene,
  • the polypropylene resin may contain additives and other resins.
  • the additive include an antioxidant, an ultraviolet light absorber, a nucleating agent, an adhesive, an antifogging agent, a flame retardant, an inorganic or organic filler, and the like.
  • Other resins include polypropylene resins other than polypropylene resins used in the present invention, random copolymers which are copolymers of propylene and ethylene and / or ⁇ -olefins having 4 or more carbon atoms, and various elastomers.
  • the resin used for the heat seal layer (B) is preferably a low melting point propylene random copolymer having a melting point of 150 ° C. or less, or a propylene block copolymer in which an elastomer component containing a comonomer is dispersed, Moreover, these can be used individually or in mixture.
  • the comonomer it is preferable to use ethylene or at least one selected from ⁇ -olefins having 3 to 10 carbon atoms such as butene, pentene, hexene, octene and decene.
  • the melting point of the propylene random copolymer forming the heat seal layer (B) is preferably 60 to 150 ° C. Thereby, sufficient heat seal strength can be given to an oriented polypropylene resin laminated film.
  • the melting point of the elastomer component contained in the propylene block copolymer is also preferably 150 ° C. or less.
  • the MFR may be in the range of 0.1 to 100 g / 10 min, preferably 0.5 to 20 g / 10 min, more preferably 1.0 to 10 g / 10 min.
  • the polypropylene resin used in the heat seal layer (B) is obtained by polymerizing propylene as a raw material using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Among them, in order to eliminate foreign bonds, it is preferable to use a Ziegler-Natta catalyst and to use a catalyst capable of highly regular polymerization.
  • a polymerization method of propylene a known method may be used, a method of polymerizing in an inert solvent such as hexane, heptane, toluene, xylene or the like, a method of polymerizing in liquid propylene or ethylene, propylene in gas or propylene.
  • the method of adding a catalyst and polymerizing in a gas phase state, or the method of combining and polymerizing these, etc. are mentioned.
  • the high molecular weight component and the low molecular weight component may be separately polymerized and then mixed, or may be produced in a series of plants in a multistage reactor.
  • a method is preferable in which a high molecular weight component is first polymerized and then the low molecular weight component is polymerized in the presence thereof using a plant having a multistage reactor.
  • the polypropylene-based laminate film of the present invention may be a uniaxially stretched film in the longitudinal direction (MD direction) or the transverse direction (TD direction), but is preferably a biaxially stretched film.
  • biaxial stretching it may be sequential biaxial stretching or simultaneous biaxial stretching.
  • the base material layer (A) is melt-extruded from one extruder
  • the heat seal layer (B) is melt-extruded using the other extruder
  • heat is applied to the polypropylene resin layer (A) in the T die. It laminates
  • the resin temperature is set to 200 to 280 ° C.
  • the sheet is extruded from a T-die, and it is cooled and solidified by a cooling roll at a temperature of 10 to 100 ° C.
  • the film is stretched 3 to 7 times in the length (MD) direction with a stretching roll at 120 to 165 ° C., and subsequently at a temperature of 155 ° C. to 175 ° C., preferably 158 ° C. to 170 ° C. in the width (TD) direction.
  • heat treatment is performed while allowing 1 to 15% relaxation at an ambient temperature of 165 to 175 ° C., preferably 166 to 173 ° C.
  • a roll sample can be obtained by applying corona discharge treatment to at least one side and winding with a winder.
  • the lower limit of the draw ratio of MD is preferably 3 times, more preferably 3.5 times. If it is less than the above, film thickness unevenness may occur.
  • the upper limit of the draw ratio of MD is preferably 8 times, more preferably 7 times. If the above is exceeded, it may be difficult to carry out the subsequent TD stretching.
  • the lower limit of the stretching temperature of MD is preferably 120 ° C., more preferably 122 ° C. If it is less than the above, mechanical load may increase, thickness unevenness may increase, or surface roughness of the film may occur.
  • the upper limit of the MD stretching temperature is preferably 150 ° C., more preferably 145 ° C., still more preferably 135 ° C., particularly preferably 130 ° C. A higher temperature is preferable for lowering the heat shrinkage, but it may stick to the roll and not be able to be stretched.
  • the lower limit of the draw ratio of TD is preferably 4 times, more preferably 5 times, and still more preferably 6 times. If it is less than the above, thickness unevenness may occur.
  • the upper limit of the TD stretch ratio is preferably 20 times, more preferably 17 times, and still more preferably 15 times. If the above is exceeded, the thermal contraction rate may be high, or the film may break during stretching.
  • the preheating temperature in TD stretching is preferably set 10 to 15 ° C. higher than the stretching temperature in order to rapidly raise the film temperature to around the stretching temperature.
  • TD stretching is performed at a higher temperature than conventional heat sealable polypropylene laminated stretched films.
  • the lower limit of the stretching temperature of TD is preferably 157 ° C., more preferably 158 ° C. If the amount is less than the above, breakage may occur without sufficient softening, or the heat shrinkage may increase.
  • the upper limit of the TD stretching temperature is preferably 170 ° C., more preferably 168 ° C. In order to lower the heat shrinkage rate, it is preferable that the temperature be higher, but if the temperature is higher than the above, the low molecular weight component may be melted and recrystallized to cause surface roughness and whitening of the film.
  • the stretched film is heat set. Heat setting can be done at higher temperatures than conventional polypropylene films.
  • the lower limit of the heat setting temperature is preferably 165 ° C, more preferably 166 ° C. When it is less than the above, the heat shrinkage may be high. In addition, a long time may be required to lower the thermal contraction rate, and the productivity may be poor.
  • the upper limit of the heat setting temperature is preferably 175 ° C, more preferably 173 ° C. If the above is exceeded, low molecular weight components may melt and recrystallize to cause surface roughness and whitening of the film.
  • the lower limit of relaxation is preferably 2%, more preferably 3%. When it is less than the above, the heat shrinkage may be high.
  • the upper limit of relaxation is preferably 10%, more preferably 8%. When the above is exceeded, thickness unevenness may become large.
  • the film produced in the above process may be once wound into a roll and then annealed off-line.
  • the lower limit of the off-line annealing temperature is preferably 160 ° C., more preferably 162 ° C., and still more preferably 163 ° C. If it is less than the above, the effect of annealing may not be obtained.
  • the upper limit of the off-line annealing temperature is preferably 175 ° C., more preferably 174 ° C., and still more preferably 173 ° C. If the above is exceeded, the transparency may be reduced, or the thickness unevenness may be significant.
  • the lower limit of the off-line annealing time is preferably 0.1 minutes, more preferably 0.5 minutes, and still more preferably 1 minute. If it is less than the above, the effect of annealing may not be obtained.
  • the upper limit of the off-line annealing time is preferably 30 minutes, more preferably 25 minutes, and still more preferably 20 minutes. If the above is exceeded, productivity may fall.
  • the thickness of the film is set according to each application, but the lower limit of the film thickness is preferably 2 ⁇ m, more preferably 3 ⁇ m, and still more preferably 4 ⁇ m.
  • the upper limit of the film thickness is preferably 300 ⁇ m, more preferably 250 ⁇ m, still more preferably 200 ⁇ m, particularly preferably 100 ⁇ m, and most preferably 50 ⁇ m.
  • the polypropylene-based laminate film thus obtained is usually formed as a roll having a width of 2000 to 12000 mm and a length of about 1000 to 50000 m, and is wound into a roll. Furthermore, it is slitted according to each use and provided as a slit roll having a width of about 300 to 2000 mm and a length of about 500 to 5000 m.
  • the polypropylene-based laminate film of the present invention has the above-mentioned excellent properties not heretofore available.
  • it When it is used as a packaging film, it can be made thin because it has high rigidity, and cost and weight can be reduced.
  • the heat resistance is high, high-temperature drying can be performed at the time of drying of the coating or printing, and it is possible to use a coating agent, an ink, a laminating adhesive, etc. Since there is no need for a lamination process using an organic solvent or the like, it is preferable from the viewpoints of both economic and global impact.
  • the lower limit of the thermal shrinkage at 150 ° C. in the MD and TD directions of the polypropylene-based laminate film of the present invention is preferably 0.5%, more preferably 1%, still more preferably 1.5%, Preferably it is 2%, most preferably 2.5%. If it is in the above-mentioned range, realistic production may be facilitated in terms of cost and the like, or thickness unevenness may be reduced.
  • the upper limit of the heat shrinkage at 150 ° C. in the MD direction is preferably 7%, more preferably 6%, and still more preferably 5%. If it is in the above range, it becomes easier to use in applications that may be exposed to high temperatures of about 150 ° C. In addition, if the thermal contraction rate at 150 ° C. is up to about 2.5%, for example, it is possible by increasing the low molecular weight component, adjusting the stretching conditions and fixing conditions, but annealing below that may be performed offline. preferable. In the conventional stretched polypropylene laminated film, the thermal contraction rate at 150 ° C. in the MD direction is 15% or more, and the thermal contraction rate at 120 ° C. is about 3%. By making heat contraction rate into said range, the polypropylene-type laminated film excellent in heat resistance can be obtained.
  • the upper limit of the heat shrinkage at 150 ° C. in the TD direction is preferably 8%, more preferably 7%, and still more preferably 7%. If it is in the above range, it becomes easier to use in applications that may be exposed to high temperatures of about 150 ° C. In addition, if the thermal contraction rate at 150 ° C. is up to about 2.5%, for example, it is possible by increasing the low molecular weight component, adjusting the stretching conditions and fixing conditions, but annealing below that may be performed offline. preferable. In the conventional stretched polypropylene laminated film, the thermal contraction rate at 150 ° C. in the TD direction is 15% or more, and the thermal contraction rate at 120 ° C. is about 3%. By making heat contraction rate into said range, the polypropylene-type laminated film excellent in heat resistance can be obtained.
  • the lower limit of Young's modulus (23 ° C.) in the MD direction is preferably 1.8 GPa, more preferably 1.9 GPa, and still more preferably 2. 0 GPa, particularly preferably 2.1 GPa, most preferably 2.2 GPa.
  • the upper limit of Young's modulus in the MD direction is preferably 3.7 GPa, more preferably 3.6 GPa, still more preferably 3.5 GPa, particularly preferably 3.4 GPa, and most preferably 3.3 GPa. is there. Within the above range, practical manufacture may be easy, or MD-TD balance may be improved.
  • the lower limit of Young's modulus (23 ° C.) in the TD direction is preferably 4.4 GPa, more preferably 4.5 GPa, and still more preferably 4. 6 GPa, particularly preferably 4.7 GPa.
  • the upper limit of the Young's modulus in the TD direction is preferably 8 GPa, more preferably 7.5 GPa, still more preferably 7 GPa, and particularly preferably 6.5 GPa.
  • practical manufacture may be facilitated, or MD-TD balance may be improved.
  • the Young's modulus can be increased by increasing the draw ratio, and in the case of MD-TD stretching, the MD draw ratio is set to a lower value, and the TD draw ratio is increased to increase the Young's modulus in the TD direction. Can.
  • the lower limit of the plane orientation coefficient of the polypropylene film of the present invention is preferably 0.0125, more preferably 0.0126, still more preferably 0.0127, particularly preferably 0.0128. .
  • the upper limit of the plane orientation coefficient is preferably 0.0155, more preferably 0.0150, still more preferably 0.0148, particularly preferably 0.0145, as a practical value. Preferably it is 0.0140.
  • the plane orientation coefficient can be in the range by adjusting the draw ratio. When the plane orientation coefficient is in this range, the thickness unevenness of the film is also good.
  • the heat seal strength of the polypropylene-based laminate film of the present invention at 140 ° C. is preferably 8.0 N / 15 mm or more, more preferably 9.0 N / 15 mm or more, and further preferably 10 N / 15 mm or more preferable.
  • the heat seal strength of the polypropylene-based laminate film of the present invention is preferably 1.5 N / 15 mm or more at 110 ° C., more preferably 2.0 N / 15 mm or more, and 2.2 N / 15 mm or more. It is further preferred that
  • the lower limit of the impact resistance (23 ° C.) of the stretched polypropylene film of the present invention is preferably 0.6 J, more preferably 0.7 J. If it is in the above range, it has sufficient toughness as a film and does not break during handling.
  • the upper limit of the impact resistance is preferably 3 J, more preferably 2.5 J, still more preferably 2.2 J, and particularly preferably 2 J from the practical viewpoint. For example, when the low molecular weight component is large, the impact resistance tends to decrease when the total molecular weight is low, or when the high molecular weight component is low or when the molecular weight of the high molecular weight component is low. These components can be adjusted to be in the range.
  • the lower limit of the haze of the polypropylene-based laminate film of the present invention is preferably 0.1%, more preferably 0.2%, still more preferably 0.3%, particularly preferably 0. It is 4%, most preferably 0.5%.
  • the upper limit of the haze is preferably 6%, more preferably 5%, still more preferably 4.5%, particularly preferably 4%, most preferably 3.5%.
  • the haze tends to be worse, for example, when the stretching temperature and the heat setting temperature are too high, when the cooling roll (CR) temperature is high and the cooling rate is slow, and when the low molecular weight is too high. You can do it.
  • the lower limit of the thickness uniformity of the polypropylene-based laminate film of the present invention is preferably 0%, more preferably 0.1%, still more preferably 0.5%, particularly preferably 1%.
  • the upper limit of thickness uniformity is preferably 20%, more preferably 17%, still more preferably 15%, particularly preferably 12%, and most preferably 10%. Within the above range, defects are less likely to occur during post-processing such as coating and printing, and it is easy to use for applications requiring precision.
  • the baseline is set in the range up to the lowest position on the high molecular weight side of the elution peak on the high molecular weight side closest to the elution peak of the standard substance.
  • peak separation was performed on two or more components having different molecular weights from the obtained GPC curve.
  • CXS Cold xylene soluble part
  • Heat shrinkage rate (%) It measured based on JIS Z 1712. (The stretched film was cut in the MD and TD directions with a width of 20 mm and a length of 200 mm, respectively, suspended in a hot air oven at 150 ° C. and heated for 5 minutes. The length after heating was measured and the shrinkage relative to the original length The heat shrinkage rate was determined by the ratio of
  • Plane orientation coefficient ( ⁇ P) It was measured according to JIS K7142-1996 5.1 (Method A) using an Atago Abbe refractometer. The refractive indices along the MD and TD directions are Nx and Ny, respectively, and the refractive index in the thickness direction is Nz. The plane orientation coefficient ( ⁇ P) was determined by (Nx + Ny) / 2-Nz.
  • the surface opposite to the sealing layer was measured three times, and the average value thereof was taken. In the case where the sealing layer is on both sides: the surface of the sealing layer was measured three times on both sides and the average value thereof was taken.
  • Heat seal strength is 140 ° C. and 110 ° C., pressure is 1 kg / cm 2 , heat seal time is 1 second, heat seal layer (B) faces of laminated stretched films are superposed and heat plate seal is formed. It carried out and produced the test piece of 10 mm width. The 180 degree peel strength of this test piece was measured to obtain the heat seal strength (N / 15 mm).
  • Thickness spots A square sample having a length of 1 m was cut out from the wound film roll, and divided into 10 equal parts in the MD direction and the TD direction to prepare 100 measurement samples. The thickness of the substantially central portion of the measurement sample was measured with a contact-type film thickness meter. The average value of the obtained data of 100 points is determined, and the difference between the minimum value and the maximum value (absolute value) is determined, and the absolute value of the difference between the minimum value and the maximum value is divided by the average value And
  • Example 1 Using two melt extruders and using the first extruder as the polypropylene resin, the polypropylene homopolymer PP-1 shown in Table 1 is used as the substrate layer (A), and using the second extruder as propylene. 85% by weight of ethylene-butene random copolymer (PP-7: Pr-Et-Bu, density 0.89 g / cm 3 , MFR 4.6 g / 10 min, melting point 128 ° C.), propylene-butene random copolymer A mixed resin of 15 wt% (PP-8: Pr-Bu, density 0.89 g / cm 3 , MFR 9.0 g / 10 min, melting point 130 ° C.) is used as a heat seal layer (B) in a die.
  • PP-7 ethylene-butene random copolymer
  • PP-7 Pr-Et-Bu, density 0.89 g / cm 3 , MFR 4.6 g / 10 min, melting point 128 ° C.
  • the thickness of the film thus obtained was 20 ⁇ m, and a laminated stretched film in which the thicknesses of the base material layer and the heat seal layer were 18 ⁇ m and 2 ⁇ m in this order, respectively, was obtained.
  • the resulting laminated stretched film satisfies the requirements of the present invention, has a low thermal shrinkage, high rigidity, and has heat seal strength, stiffness and curling properties. Was also excellent.
  • Example 2 A polypropylene-based laminate film was obtained in the same manner as Example 1, except that the raw material used for the base material layer (A) was changed to the polypropylene homopolymer PP-2 shown in Table 1. As shown in Tables 1, 2 and 3, the resulting laminated stretched film satisfies the requirements of the present invention, has a low thermal shrinkage, high rigidity, and has heat seal strength, stiffness and curling properties. Was also excellent.
  • Example 1 A polypropylene-based laminate film was obtained in the same manner as Example 1, except that the raw material used for the base material layer (A) was changed to the polypropylene homopolymer PP-3 shown in Table 1. As shown in Table 1, Table 2 and Table 3, the resulting laminated stretched film was excellent in heat seal strength, waist feel and curlability, but had a large heat shrinkage.
  • Example 3 A polypropylene-based laminate film was obtained in the same manner as in Example 1, except that the raw material used for the base material layer (A) was changed to the polypropylene homopolymer PP-5 shown in Table 1. As shown in Table 1, Table 2 and Table 3, the resulting laminated stretched film was excellent in heat seal strength, waist feel and curlability, but had a large heat shrinkage.
  • the raw material used for the base material layer (A) is changed to polypropylene homopolymer PP-6 shown in Table 1, and the width direction stretch preheating temperature is 170 ° C., the width direction stretch temperature is 158 ° C., and the heat setting temperature is 165.
  • a polypropylene-based laminate film was obtained in the same manner as in Example 1 except that the temperature was changed to ° C. As shown in Table 1, Table 2 and Table 3, the resulting laminated stretched film was excellent in heat seal strength, waist feel and curlability, but the heat shrinkage rate was very large.
  • the polypropylene-based laminate film of the present invention was excellent for use as a packaging application, and was very suitable for heat sealing. Furthermore, for example, by setting the heat seal temperature high, it is possible to increase the line speed in bag-making processing and the like, and the productivity is improved. In addition, the heat seal strength can also be improved by increasing the heat seal temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Wrappers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention fournit un film stratifié de polypropylène étiré thermosoudable hautement rigide qui présente un coefficient de retrait faible comparable à celui du PET à 150°C. Plus précisément, l'invention concerne un film stratifié à base de polypropylène qui est constitué d'une couche de matériau de base (A) telle qu'une résine polypropylène la configurant satisfait les conditions 1) à 4), et d'une couche de thermosoudage (B) configurée à partir d'une résine à base de polyoléfine et stratifiée sur une face ou sur les deux faces de cette couche de matériau de base, et qui présente une limite inférieure de coefficient d'orientation planaire de film de 0,0125. 1) La limite inférieure de sa fraction mésopentade est de 96%. 2) La limite supérieure de quantité de monomère de copolymérisation autre qu'un propylène, est de ０,１% en moles. 3) Sa masse moléculaire moyenne en poids (Mw) / sa masse moléculaire moyenne en nombre (Mn) est supérieure ou égale à 3,0 et inférieure ou égale à 5,4. 4) Son indice de fluidité (MFR) mesuré à 230°C et ２,１６ｋｇｆ est supérieur ou égal à ６,２ｇ／１０ｍｉｎ et inférieur ou égal à ９,０ｇ／１０ｍｉｎ.
PCT/JP2018/034179 2017-09-26 2018-09-14 Film stratifié à base de polypropylène WO2019065306A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020207011453A KR102593205B1 (ko) 2017-09-26 2018-09-14 폴리프로필렌계 적층 필름
CN201880061951.6A CN111132831A (zh) 2017-09-26 2018-09-14 聚丙烯系层叠薄膜
JP2019544588A JP7238779B2 (ja) 2017-09-26 2018-09-14 ポリプロピレン系積層フィルム
JP2022166463A JP7409459B2 (ja) 2017-09-26 2022-10-17 ポリプロピレン系積層フィルム

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2017184990 2017-09-26
JP2017-184990 2017-09-26
JP2017-193574 2017-10-03
JP2017193574 2017-10-03
JP2018-116034 2018-06-19
JP2018116034 2018-06-19

Publications (1)

Publication Number Publication Date
WO2019065306A1 true WO2019065306A1 (fr) 2019-04-04

Family

ID=65902380

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/034179 WO2019065306A1 (fr) 2017-09-26 2018-09-14 Film stratifié à base de polypropylène

Country Status (5)

Country Link
JP (2) JP7238779B2 (fr)
KR (1) KR102593205B1 (fr)
CN (1) CN111132831A (fr)
TW (1) TWI835744B (fr)
WO (1) WO2019065306A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020255642A1 (fr) * 2019-06-20 2020-12-24 東洋紡株式会社 Film de résine à base de polyoléfine, et stratifié mettant en œuvre celui-ci
WO2020255643A1 (fr) * 2019-06-20 2020-12-24 東洋紡株式会社 Film de résine à base de polyoléfine, et stratifié mettant en œuvre celui-ci
WO2023112995A1 (fr) 2021-12-16 2023-06-22 三井化学株式会社 Non-tissé, matériau sanitaire, et procédé de fabrication de non-tissé
WO2023181852A1 (fr) * 2022-03-25 2023-09-28 凸版印刷株式会社 Stratifié d'emballage et sac d'emballage
WO2023238825A1 (fr) * 2022-06-09 2023-12-14 Ｔｏｐｐａｎホールディングス株式会社 Stratifié d'emballage et sac d'emballage
WO2024019049A1 (fr) * 2022-07-21 2024-01-25 Ｔｏｐｐａｎホールディングス株式会社 Stratifié pour emballage, procédé de sélection associé, procédé d'évaluation associé, sac d'emballage et procédé de production associé
US12098269B2 (en) 2019-06-20 2024-09-24 Toyobo Co., Ltd. Polyolefin-based resin film and laminate including the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003205584A (ja) * 2002-01-15 2003-07-22 Toyobo Co Ltd ヒートシール性積層フィルム
JP2007508423A (ja) * 2003-10-07 2007-04-05 ダウ グローバル テクノロジーズ インコーポレイティド 空気急冷ブロンフィルム用のポリプロピレン組成物
WO2014002934A1 (fr) * 2012-06-29 2014-01-03 東洋紡株式会社 Film de polypropylène étirable
WO2015012165A1 (fr) * 2013-07-23 2015-01-29 東洋紡株式会社 Film stratifié et étiré de polypropylène thermosoudable
WO2015012324A1 (fr) * 2013-07-23 2015-01-29 東洋紡株式会社 Film de polypropylène étiré
WO2017170244A1 (fr) * 2016-03-28 2017-10-05 東洋紡株式会社 Film de polypropylène à orientation biaxiale

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63149149A (ja) * 1986-12-15 1988-06-21 東レ株式会社 熱接着性２軸配向ポリプロピレンフイルム
JP6241039B2 (ja) * 2012-01-24 2017-12-06 東洋紡株式会社 延伸ポリプロピレンフィルム
KR101396828B1 (ko) 2014-02-19 2014-05-20 (주)아셈스 접착성 원단을 이용한 입체 문양 형성방법
JP2018141122A (ja) 2017-02-28 2018-09-13 東洋紡株式会社 二軸配向ポリプロピレンフィルム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003205584A (ja) * 2002-01-15 2003-07-22 Toyobo Co Ltd ヒートシール性積層フィルム
JP2007508423A (ja) * 2003-10-07 2007-04-05 ダウ グローバル テクノロジーズ インコーポレイティド 空気急冷ブロンフィルム用のポリプロピレン組成物
WO2014002934A1 (fr) * 2012-06-29 2014-01-03 東洋紡株式会社 Film de polypropylène étirable
WO2015012165A1 (fr) * 2013-07-23 2015-01-29 東洋紡株式会社 Film stratifié et étiré de polypropylène thermosoudable
WO2015012324A1 (fr) * 2013-07-23 2015-01-29 東洋紡株式会社 Film de polypropylène étiré
WO2017170244A1 (fr) * 2016-03-28 2017-10-05 東洋紡株式会社 Film de polypropylène à orientation biaxiale

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3988280A4 (fr) * 2019-06-20 2023-10-25 Toyobo Co., Ltd. Film de résine à base de polyoléfine, et stratifié mettant en oeuvre celui-ci
US12098269B2 (en) 2019-06-20 2024-09-24 Toyobo Co., Ltd. Polyolefin-based resin film and laminate including the same
WO2020255642A1 (fr) * 2019-06-20 2020-12-24 東洋紡株式会社 Film de résine à base de polyoléfine, et stratifié mettant en œuvre celui-ci
JPWO2020255642A1 (fr) * 2019-06-20 2020-12-24
CN113993685A (zh) * 2019-06-20 2022-01-28 东洋纺株式会社 聚烯烃系树脂薄膜及使用其的层叠体
CN114007844A (zh) * 2019-06-20 2022-02-01 东洋纺株式会社 聚烯烃系树脂薄膜和使用其的层叠体
EP3988279A4 (fr) * 2019-06-20 2023-10-25 Toyobo Co., Ltd. Film de résine à base de polyoléfine, et stratifié mettant en oeuvre celui-ci
JP7484908B2 (ja) 2019-06-20 2024-05-16 東洋紡株式会社 ポリオレフィン系樹脂フィルム、及びそれを用いた積層体
JPWO2020255643A1 (fr) * 2019-06-20 2020-12-24
WO2020255643A1 (fr) * 2019-06-20 2020-12-24 東洋紡株式会社 Film de résine à base de polyoléfine, et stratifié mettant en œuvre celui-ci
JP7392718B2 (ja) 2019-06-20 2023-12-06 東洋紡株式会社 ポリオレフィン系樹脂フィルム、及びそれを用いた積層体
CN114007844B (zh) * 2019-06-20 2023-11-24 东洋纺株式会社 聚烯烃系树脂薄膜和使用其的层叠体
CN113993685B (zh) * 2019-06-20 2024-03-08 东洋纺株式会社 聚烯烃系树脂薄膜及使用其的层叠体
US11866572B2 (en) 2019-06-20 2024-01-09 Toyobo Co., Ltd. Polyolefin-based resin film and laminate including the same
WO2023112995A1 (fr) 2021-12-16 2023-06-22 三井化学株式会社 Non-tissé, matériau sanitaire, et procédé de fabrication de non-tissé
WO2023181852A1 (fr) * 2022-03-25 2023-09-28 凸版印刷株式会社 Stratifié d'emballage et sac d'emballage
WO2023238825A1 (fr) * 2022-06-09 2023-12-14 Ｔｏｐｐａｎホールディングス株式会社 Stratifié d'emballage et sac d'emballage
JP7487851B2 (ja) 2022-06-09 2024-05-21 Ｔｏｐｐａｎホールディングス株式会社 包装用の積層体及び包装袋
WO2024019049A1 (fr) * 2022-07-21 2024-01-25 Ｔｏｐｐａｎホールディングス株式会社 Stratifié pour emballage, procédé de sélection associé, procédé d'évaluation associé, sac d'emballage et procédé de production associé

Also Published As

Publication number Publication date
KR102593205B1 (ko) 2023-10-24
JPWO2019065306A1 (ja) 2020-11-19
KR20200047733A (ko) 2020-05-07
JP7238779B2 (ja) 2023-03-14
JP2023001143A (ja) 2023-01-04
TW201919900A (zh) 2019-06-01
JP7409459B2 (ja) 2024-01-09
CN111132831A (zh) 2020-05-08
TWI835744B (zh) 2024-03-21

Similar Documents

Publication Publication Date Title
JP6443334B2 (ja) ヒートシール性ポリプロピレン積層延伸フィルム
TWI711539B (zh) 雙軸延伸積層聚丙烯膜
TWI631151B (zh) 拉伸聚丙烯薄膜
JP7409459B2 (ja) ポリプロピレン系積層フィルム
TWI597309B (zh) 拉伸聚丙烯薄膜
JP6554765B2 (ja) ポリプロピレン積層延伸フィルム
JP7298751B2 (ja) 二軸配向ポリプロピレンフィルム
WO2019244708A1 (fr) Film multicouche à base de polypropylène
TW201418288A (zh) 聚丙烯薄膜
JP6409773B2 (ja) 積層フィルム
TW201412778A (zh) 聚丙烯薄膜
JP6414378B2 (ja) インモールドラベル用ポリプロピレンフィルム
KR20160034906A (ko) 공동 함유 폴리프로필렌 필름

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18861979

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019544588

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207011453

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 18861979

Country of ref document: EP

Kind code of ref document: A1