WO2013111779A1 - Film de polypropylène étiré - Google Patents

Film de polypropylène étiré Download PDF

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Publication number
WO2013111779A1
WO2013111779A1 PCT/JP2013/051316 JP2013051316W WO2013111779A1 WO 2013111779 A1 WO2013111779 A1 WO 2013111779A1 JP 2013051316 W JP2013051316 W JP 2013051316W WO 2013111779 A1 WO2013111779 A1 WO 2013111779A1
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Prior art keywords
molecular weight
film
lower limit
stretched
temperature
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PCT/JP2013/051316
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English (en)
Japanese (ja)
Inventor
理 木下
大木　祐和
山田　浩司
多賀　敦
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東洋紡株式会社
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Priority to CN201380006516.0A priority Critical patent/CN104105746B/zh
Priority to KR1020147022521A priority patent/KR101986868B1/ko
Publication of WO2013111779A1 publication Critical patent/WO2013111779A1/fr
Priority to HK14112137.3A priority patent/HK1198701A1/xx

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene

Definitions

  • the present invention relates to a stretched polypropylene film. More specifically, the present invention relates to a stretched polypropylene film excellent in heat resistance and mechanical properties, which can be suitably used in various fields where dimensional stability at high temperature and high rigidity are required.
  • stretched polypropylene films have been widely used for a wide range of applications such as packaging for food and various products, electrical insulation, and surface protection films.
  • the conventional polypropylene film has a shrinkage rate of several tens of percent at 150 ° C., has lower heat resistance and lower rigidity than polyethylene terephthalate (PET) and the like, and thus has limited applications.
  • PET polyethylene terephthalate
  • Patent Documents 1 to 3 have difficulty in stretchability and inferior mechanical properties such as impact resistance.
  • the films described in Patent Documents 4 to 5 still cannot be said to have sufficient heat resistance at high temperatures exceeding 150 ° C., and have high heat resistance close to that of PET films, and productivity.
  • a polypropylene film excellent in impact resistance and uniformity has not been known.
  • the films described in Patent Documents 4 to 5 do not exceed the range of conventional polypropylene films, and their uses are limited. For example, heat resistance at high temperatures exceeding 150 ° C. It was not done.
  • an object of the present invention is to provide a stretched polypropylene film having a low shrinkage comparable to that of a polyethylene terephthalate (PET) film at 150 ° C. and having high rigidity.
  • PET polyethylene terephthalate
  • the present inventor has found that the mesopentad fraction, the amount of copolymerizable monomers other than propylene, the melt flow rate (MFR), the mass average molecular weight (Mw) / number average molecular weight (Mn), And z + 1 average molecular weight (Mz + 1) / number average molecular weight (Mn) are each controlled to a predetermined range, and the plane orientation coefficient of the film is controlled to a predetermined range, the shrinkage rate and rigidity at 150 ° C.
  • PET polyethylene terephthalate
  • the stretched polypropylene film of the present invention is characterized in that the polypropylene resin constituting the film satisfies the following conditions 1) to 5), and the lower limit of the plane orientation coefficient of the film is 0.0125.
  • the lower limit of the mesopentad fraction is 96%.
  • the upper limit of the amount of copolymerization monomers other than propylene is 0.1 mol%.
  • the lower limit of the melt flow rate (MFR) measured at 230 ° C. and 2.16 kgf is 1 g / 10 min. 4)
  • the lower limit of the mass average molecular weight (Mw) / number average molecular weight (Mn) is 5.5. 5)
  • the lower limit of z + 1 average molecular weight (Mz + 1) / number average molecular weight (Mn) is 50.
  • the stretched polypropylene film of the present invention is preferably biaxially stretched.
  • the stretch ratio in the longitudinal direction is 3 to 8 times
  • the stretch ratio in the width direction is 4 to 20 times. Is preferred.
  • the stretched polypropylene film of the present invention According to the stretched polypropylene film of the present invention, a low shrinkage rate and a high rigidity comparable to that of a polyethylene terephthalate (PET) film can be exhibited at 150 ° C., and thus thinning is possible. Furthermore, since the stretched polypropylene film of the present invention can maintain various physical properties even when exposed to an environment of 150 ° C. or higher, it should be used in a high-temperature environment that has not been considered with conventional polypropylene films. Can be applied to a wide range of uses.
  • PET polyethylene terephthalate
  • FIG. 2 is a differential scanning calorimetry (DSC) chart for the stretched polypropylene film obtained in Example 1 and Comparative Example 1.
  • DSC differential scanning calorimetry
  • the present invention relates to a stretched polypropylene film excellent in dimensional stability at high temperatures and mechanical properties.
  • the polypropylene resin constituting the stretched polypropylene film of the present invention has the following characteristics with respect to molecular weight distribution, melt flow rate, regularity, and constituent monomers.
  • the polypropylene resin constituting the stretched polypropylene film of the present invention mainly contains a low molecular weight component and further contains a high molecular weight component having a very high molecular weight. Crystallinity can be greatly increased by mainly using a low molecular weight component, and it is considered that a highly-stretched and heat-resistant stretched polypropylene film that has not been conventionally obtained is obtained.
  • a low molecular weight polypropylene resin has a low melt tension when softened by heating and cannot generally be a stretched film.
  • the presence of several to several tens of percent of the high molecular weight component makes stretching possible, and the high molecular weight component serves as a crystal nucleus, further increasing the crystallinity of the film and improving the effect of the stretched film of the present invention. It is considered to have been achieved.
  • the polypropylene resin constituting the stretched polypropylene film of the present invention is characterized by a wide molecular weight distribution.
  • the breadth of the molecular weight distribution can be expressed as mass average molecular weight (Mw) / number average molecular weight (Mn).
  • Mw mass average molecular weight
  • Mn number average molecular weight
  • the lower limit of Mw / Mn is preferably 6, more preferably 6.5, still more preferably 7, and particularly preferably 7.2. If it is less than the above, the effects of the present application such as a low thermal shrinkage at high temperatures cannot be obtained.
  • the upper limit of Mw / Mn is preferably 30, more preferably 25, still more preferably 20, particularly preferably 15, and most preferably 13. Exceeding the above may make it difficult to produce a realistic resin.
  • the lower limit of Mz + 1 / Mn is 50.
  • the lower limit of Mz + 1 / Mn is preferably 60, more preferably 70, still more preferably 80, and particularly preferably 90. If it is less than the above, the effects of the present application such as a low thermal shrinkage at high temperatures cannot be obtained.
  • the upper limit of Mz + 1 / Mn is preferably 300, more preferably 200. Exceeding the above may make it difficult to produce a realistic resin.
  • the lower limit of Mn of the entire polypropylene resin constituting the stretched polypropylene film of the present invention is preferably 20000, more preferably 22000, still more preferably 24000, particularly preferably 26000, and most preferably 27000. .
  • the upper limit of the total Mn is preferably 65000, more preferably 60000, still more preferably 55000, particularly preferably 53000, and most preferably 52000.
  • the effects of the present application such as a low heat shrinkage rate at a high temperature exhibited by the low molecular weight component can be easily obtained, and stretching can be facilitated.
  • the lower limit of Mw of the entire polypropylene resin constituting the stretched polypropylene film of the present invention is preferably 250,000, more preferably 260000, still more preferably 270000, particularly preferably 280000, and most preferably 290000. .
  • the upper limit of the total Mw is preferably 500,000, more preferably 450,000, still more preferably 400,000, particularly preferably 380000, and most preferably 370000.
  • the mechanical load is small and stretching becomes easy.
  • the lower limit of Mz + 1 of the entire polypropylene resin constituting the stretched polypropylene film of the present invention is preferably 2500,000, more preferably 3000,000, still more preferably 3300000, particularly preferably 3500000, and most preferably 3700000. . Within the above range, the high molecular weight component is sufficient, and the effects of the present invention are easily obtained. On the other hand, the upper limit of the total Mz + 1 is preferably 40000000, more preferably 35000000, and further preferably 30000000. Within the above range, realistic resin production is easy, stretching is easy, and fish eyes in the film are reduced.
  • Mz Z average molecular weight
  • the lower limit of Mz / Mn is preferably 30, more preferably 35, still more preferably 38, and particularly preferably. 40, most preferably 41.
  • the upper limit of Mz / Mn is preferably 100. Within the above range, realistic resin production is facilitated.
  • the lower limit of Mz of the entire polypropylene resin constituting the stretched polypropylene film of the present invention is preferably 1000000, more preferably 1200000, still more preferably 1300000, particularly preferably 1400000, and most preferably 1500000. .
  • the high molecular weight component is sufficient, and the effects of the present invention are easily obtained.
  • the upper limit of the overall Mz is preferably 15000000. Within the above range, realistic resin production is easy, stretching is easy, and fish eyes in the film are reduced.
  • the lower limit of the peak value (Mp) in the molecular weight distribution curve of the polypropylene resin constituting the stretched polypropylene film of the present invention is preferably 50000, more preferably 60000, still more preferably 70000, and particularly preferably 75000. is there. Within the above range, advantages such as easy stretching, reduced thickness unevenness, easy increase in stretching temperature and heat setting temperature, and lower heat shrinkage rate can be obtained.
  • the upper limit of Mp is preferably 150,000, more preferably 130,000, still more preferably 120,000, and particularly preferably 115,000. Within the above range, the effects of the present application such as a low heat shrinkage rate at a high temperature exhibited by the low molecular weight component can be obtained more easily, and stretching can be facilitated.
  • the lower limit of the amount of the component having a molecular weight of 10,000 or less is preferably 2% by mass, more preferably It is 2.5% by mass, more preferably 3% by mass, particularly preferably 3.3% by mass, and most preferably 3.5% by mass.
  • the effects of the present application such as a low thermal shrinkage at a high temperature exhibited by the low molecular weight component can be more easily obtained, and stretching can be facilitated.
  • the upper limit of the amount of the component having a molecular weight of 10,000 or less in the GPC integration curve is preferably 20% by mass, more preferably 17% by mass, still more preferably 15% by mass, and particularly preferably 14% by mass. And most preferably 13% by weight.
  • stretching can be facilitated, thickness spots can be reduced, stretching temperature and heat setting temperature can be easily increased, and the heat shrinkage rate can be further reduced.
  • Molecules with a molecular weight of about 10,000 or less do not contribute to the entanglement between the molecular chains, and have the effect of loosening the entanglement between the molecules as a plasticizer.
  • 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 effects of the present application such as a low heat shrinkage rate at a high temperature exhibited by the low molecular weight component can be easily obtained, and stretching can be facilitated.
  • 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, and particularly preferably 56% by mass. And most preferably 55% by weight.
  • stretching can be facilitated, thickness spots can be reduced, stretching temperature and heat setting temperature can be easily increased, and the heat shrinkage rate can be further reduced.
  • a high molecular weight component and a low molecular weight component suitable for forming a polypropylene resin having such characteristics of molecular weight distribution will be described.
  • the lower limit of the melt flow rate (MFR) measured at 230 ° C. and 2.16 kgf of the high molecular weight component is preferably 0.0001 g / 10 min, more preferably 0.0005 g / 10 min, and further preferably 0.001 g. / 10 min, particularly preferably 0.005 g / 10 min.
  • MFR melt flow rate
  • the MFR at 230 ° C. and 2.16 kgf of the high molecular weight component may be too small to make practical measurement difficult.
  • the high load MFR at 10 times the load (21.6 kgf) may be measured, in which case the preferred lower limit is 0.1 g / 10 min, more preferably 0.5 g / 10 min. More preferably, it is 1 g / 10 min, and particularly preferably 5 g / 10 min.
  • the upper limit of the melt flow rate (MFR) measured at 230 ° C. and 2.16 kgf of the high molecular weight component is preferably 0.5 g / 10 min, more preferably 0.35 g / 10 min, still more preferably 0.3 g. / 10 min, particularly preferably 0.2 g / 10 min, and most preferably 0.1 g / 10 min.
  • the lower limit of Mw of the high molecular weight component is preferably 500,000, more preferably 600,000, still more preferably 700,000, particularly preferably 800000, and most preferably 1000000.
  • the amount is within the above range, the amount of the polymer component necessary for maintaining the overall MFR is small, and the effects of the present application such as a low heat shrinkage rate at a high temperature exhibited by the low molecular weight component are more easily obtained.
  • the upper limit of Mw of the high molecular weight component is preferably 10000000, more preferably 8000000, still more preferably 6000000, and particularly preferably 5000000. Within the above range, it is practically easy to produce the resin, and the fish eyes of the film can be reduced.
  • the lower limit of the intrinsic viscosity ( ⁇ ) of the high molecular weight component is preferably 3 dl / g, more preferably 3.2 dl / g, still more preferably 3.5 dl / g, and particularly preferably 4 dl / g. .
  • the amount is within the above range, the amount of the polymer component necessary for maintaining the overall MFR is small, and the effects of the present application such as a low heat shrinkage rate at a high temperature exhibited by the low molecular weight component are more easily obtained.
  • the upper limit of the intrinsic viscosity ( ⁇ ) of the high molecular weight component is preferably 15 dl / g, more preferably 12 dl / g, still more preferably 10 dl / g, and particularly preferably 9 dl / g.
  • the upper limit of the intrinsic viscosity ( ⁇ ) of the high molecular weight component is preferably 15 dl / g, more preferably 12 dl / g, still more preferably 10 dl / g, and particularly preferably 9 dl / g.
  • the lower limit of the amount of the high molecular weight component is preferably 2% by mass, more preferably 3% by mass, still more preferably 4% by mass, and particularly preferably 5% by mass in 100% by mass of the polypropylene resin. .
  • the upper limit of the amount of the high molecular weight component is 100% by mass of the polypropylene resin, preferably 30% by mass, more preferably 25% by mass, still more preferably 22% by mass, and particularly preferably 20% by mass. It is. Within the above range, the effects of the present application such as a low heat shrinkage at a high temperature exhibited by the low molecular weight component can be obtained more easily.
  • the lower limit of the melt flow rate (MFR) measured at 230 ° C. and 2.16 kgf of the low molecular weight component is preferably 70 g / 10 min, more preferably 80 g / 10 min, still more preferably 100 g / 10 min. Preferably it is 150 g / 10min, Most preferably, it is 200g / 10min.
  • MFR melt flow rate measured at 230 ° C.
  • The16 kgf of the low molecular weight component is preferably 2000 g / 10 min, more preferably 1800 g / 10 min, and further preferably 1600 g / 10 min. Particularly preferred is 1500 g / 10 min, and most preferred is 1400 g / 10 min. Within the above range, the overall MFR is easily maintained, and the film-forming property is excellent.
  • the lower limit of the Mw of the low molecular weight component is preferably 50000, more preferably 53000, still more preferably 55000, particularly preferably 60000, and most preferably 70000. Within the above range, the overall MFR is easily maintained, and the film-forming property is excellent.
  • the upper limit of Mw of the low molecular weight component is preferably 150,000, more preferably 140000, still more preferably 130,000, particularly preferably 120,000, and most preferably 110,000. When the content is in the above range, the crystallinity is improved, and the effects of the present application such as a low heat shrinkage rate at a high temperature are more easily obtained.
  • the lower limit of the intrinsic viscosity ( ⁇ ) of the low molecular weight component is preferably 0.46 dl / g, more preferably 0.48 dl / g, still more preferably 0.50 dl / g, and particularly preferably 0.55 dl. / G, most preferably 0.6 dl / g.
  • the upper limit of the intrinsic viscosity ( ⁇ ) of the low molecular weight component is preferably 1.1 dl / g, more preferably 1.05 dl / g, still more preferably 1 dl / g, and particularly preferably 0.95 dl. / G, most preferably 0.85 dl / g.
  • the lower limit of the amount of the low molecular weight component is preferably 30% by mass, more preferably 40% by mass, still more preferably 50% by mass, and particularly preferably 55% by mass in 100% by mass of the polypropylene resin. .
  • the effects of the present application such as a low heat shrinkage at a high temperature exhibited by the low molecular weight component can be obtained more easily.
  • the upper limit of the amount of the low molecular weight component is preferably 98% by mass, more preferably 97% by mass, still more preferably 96% by mass, and particularly preferably 95% by mass in 100% by mass of the polypropylene resin. It is. Within the above range, it is not necessary to increase the molecular weight of the low molecular weight component in order to maintain the overall MFR, and the effects of the present application such as a low heat shrinkage rate at a high temperature can be more easily obtained.
  • the lower limit of the ratio of low molecular weight component MFR (g / 10 min) / high molecular weight component MFR (g / 10 min) in the polypropylene resin is preferably 500, more preferably 1000, still more preferably 2000, Preferably it is 4000. Within the above range, the effects of the present application such as a low thermal contraction rate at high temperatures are more easily obtained.
  • the upper limit of the low molecular weight component MFR / high molecular weight component MFR ratio is preferably 1,000,000.
  • the high molecular weight component and the low molecular weight component may be a mixture of two or more resins corresponding to each component, and in this case, the preferred range of the amount of each component described above is the total amount of the two or more resins.
  • the polypropylene resin in the present invention may contain a component having a molecular weight other than the above-described high molecular weight component and low molecular weight component in order to adjust the MFR as the entire polypropylene resin.
  • a polypropylene resin having a molecular weight of the low molecular weight component or less, particularly a molecular weight of about 30,000 or less, and further a molecular weight of about 10,000 or less may be contained.
  • a polypropylene resin using a high molecular weight component and a low molecular weight component for example, when the molecular weight of the low molecular weight component is low, the molecular weight of the high molecular weight component is increased, and the amount of the high molecular weight component is increased. It is preferable to adjust the MFR so that it can be easily manufactured as a stretched film.
  • melt flow rate of polypropylene resin It is important that the lower limit of the melt flow rate (MFR) measured at 230 ° C. and 2.16 kgf of the entire polypropylene resin constituting the stretched polypropylene film of the present invention is 1 g / 10 min.
  • the lower limit of the total MFR is preferably 1.2 g / 10 min, more preferably 1.4 g / 10 min, still more preferably 1.5 g / 10 min, and particularly preferably 1.6 g / 10 min. Within the above range, the mechanical load is small and stretching is easy.
  • the upper limit of the total MFR is preferably 11 g / 10 min, more preferably 10 g / 10 min, still more preferably 9 g / 10 min, particularly preferably 8.5 g / 10 min, most preferably 8 g / min. 10 min.
  • stretching becomes easy, thickness unevenness is reduced, and the stretching temperature and heat setting temperature are easily increased, resulting in a lower thermal shrinkage rate.
  • the lower limit of the mesopentad fraction of the polypropylene resin constituting the stretched polypropylene film of the present invention is preferably 96%.
  • the lower limit of the mesopentad fraction is preferably 96.5%, more preferably 97%. Within the above range, the crystallinity is improved, and the thermal shrinkage at high temperatures can be kept low.
  • the upper limit of the mesopentad fraction is preferably 99.5%, more preferably 99.3%, still more preferably 99%. When it is in the above range, realistic production becomes easy.
  • heterogeneous bond of the polypropylene resin which comprises the stretched polypropylene film of this invention is not recognized. “Not recognized here” means that no peak is observed in 500 MHz 13 C-NMR.
  • the lower limit of the xylene soluble content of the polypropylene resin constituting the film is preferably 0.1% by mass from a practical aspect.
  • the upper limit of the xylene-soluble content is preferably 7% by mass, more preferably 6% by mass, and further preferably 5% by mass.
  • the lower limit of the isotactic chain length of the polypropylene resin constituting the stretched polypropylene film of the present invention is preferably 100, more preferably 120, and even more preferably 130. When it is in the above range, the crystallinity is improved and the thermal shrinkage rate at a high temperature is reduced.
  • the upper limit of the isotactic chain length is preferably 5000 from a practical aspect.
  • the polypropylene resin constituting the stretched polypropylene film of the present invention is most preferably a complete homopolypropylene obtained only from a propylene monomer, but may be a copolymer with a copolymer monomer as long as it is in a trace amount.
  • the copolymerization monomer species olefins such as ethylene and butene are preferable.
  • the upper limit of the amount of comonomer other than propylene in the polypropylene resin is 0.1 mol%.
  • the upper limit of the amount of copolymerization monomer is preferably 0.05 mol%, more preferably 0.01 mol%. When it is in the above range, the crystallinity is improved and the thermal shrinkage rate at a high temperature is reduced.
  • a stretched polypropylene film is industrially produced because of the very narrow range of conditions that can be stretched, such as the high crystallinity of perfect homopolypropylene and the rapid drop in melt tension after melt softening.
  • a copolymer component mainly ethylene
  • the polypropylene resin has a molecular weight distribution as described above, even if it contains little or no copolymerization component, the tension drop after melt softening is moderate, and industrial stretching is possible.
  • the present invention by using a polypropylene resin having the characteristic molecular weight distribution as described above, it becomes possible to stretch polypropylene mainly composed of low molecular weight components, which could not be sufficiently stretched conventionally.
  • a high heat setting temperature can be adopted, and the heat shrinkage rate at high temperatures can be lowered by the synergistic effect of high crystallinity and strong heat setting.
  • the polypropylene resin is obtained by polymerizing propylene as a raw material using a Ziegler-Natta catalyst, a metallocene catalyst, or the like.
  • a catalyst capable of highly regular polymerization such as a Ziegler-Natta catalyst.
  • a method of polymerizing in an inert solvent such as hexane, heptane, toluene, xylene a method of polymerizing in liquid propylene or ethylene, a catalyst is added to propylene or ethylene as a gas,
  • polymerizing combining these is mentioned.
  • the high molecular weight component and the low molecular weight component may be polymerized separately and then mixed, or may be polymerized in multiple stages in a single plant having a multistage reactor.
  • a method of using a plant having a multi-stage reactor and polymerizing a low molecular weight component in the presence of the high molecular weight component first is preferable.
  • the molecular weight can be adjusted by the amount of hydrogen mixed in the system during the polymerization.
  • the lower limit of the plane orientation coefficient of the stretched polypropylene film of the present invention is 0.0125.
  • the lower limit of the plane orientation coefficient is preferably 0.0126, more preferably 0.0127, and still more preferably 0.0128.
  • the upper limit of the plane orientation coefficient is preferably 0.0155 as a practical value, more preferably 0.0150, still more preferably 0.0148, and particularly preferably 0.0145.
  • the plane orientation coefficient can be set within the range by adjusting the draw ratio. Within this range, the thickness unevenness of the film is also good.
  • the lower limit of the refractive index (Nx) in the MD direction of the stretched polypropylene film of the present invention is preferably 1.502, more preferably 1.503, and even more preferably 1.504.
  • the upper limit of Nx is preferably 1.52, more preferably 1.517, and even more preferably 1.515.
  • the lower limit of the refractive index (Ny) in the TD direction of the stretched polypropylene film of the present invention is preferably 1.523, and more preferably 1.525.
  • the upper limit of Ny is preferably 1.535, and more preferably 1.532.
  • the lower limit of the refractive index (Nz) in the thickness direction of the stretched polypropylene film of the present invention is preferably 1.480, more preferably 1.490, and even more preferably 1.500.
  • the upper limit of Nz is preferably 1.510, more preferably 1.507, and even more preferably 1.505.
  • the stretched polypropylene film of the present invention is characterized by being highly crystalline. That is, the lower limit of the film crystallinity is preferably 55%, more preferably 56%, still more preferably 57%, particularly preferably 58%, and most preferably 59%. If it is less than the above, the thermal shrinkage at high temperatures may increase. On the other hand, the upper limit of the film crystallinity is preferably 85%, more preferably 80%, still more preferably 79%, particularly preferably 78%, and most preferably 77%. If the above is exceeded, realistic manufacturing may become difficult.
  • the crystallinity of the film is determined by a method such as reducing the amount of copolymerization monomer in the polypropylene resin to 0% by mass, increasing the low molecular weight component, or setting the stretching temperature and heat setting temperature to a high temperature. Can be inside.
  • the lower limit of the melting point of the stretched polypropylene film of the present invention is preferably 168 ° C, more preferably 169 ° C. Within the above range, the thermal shrinkage rate at high temperatures is small.
  • the upper limit of the melting point is preferably 180 ° C, more preferably 177 ° C, and further preferably 175 ° C. When it is in the above range, realistic production becomes easy.
  • Melting point Decrease the amount of copolymerization monomer in polypropylene resin or make it 0% by mass, increase the fraction of mesopentad, decrease the amount of xylene soluble at room temperature, increase the low molecular weight component, stretching temperature, heat setting It can be within the range by a method such as setting the temperature to a high temperature.
  • the conventional polypropylene film has a melting point peak around 170 ° C.
  • a peak rise beginning of melting
  • the heat shrinkage rate increased rapidly at 150 ° C.
  • the polypropylene film of the present invention has no peak rise even at 150 ° C., and low heat shrinkability at 150 ° C. is obtained. This is considered to be achieved by using a polypropylene resin with little or no copolymerization component, promptly generating crystals with a high melting point due to a characteristic molecular weight distribution, and being able to be achieved in combination with a high heat setting temperature. .
  • the polypropylene film of the present invention can maintain various physical properties even when exposed to an environment of 150 ° C. or higher, and can be used in a high-temperature environment that has not been considered with conventional polypropylene films.
  • the melting start can be obtained from the DSC chart.
  • the DSC chart of the stretched polypropylene film obtained in Example 1 and Comparative Example 1 described later is shown in FIG. In Example 1, a peak rise (melting start) is observed between 150 and 160 ° C. (around 155 ° C.), and in Comparative Example 1, a peak rise (melting start) is observed around 140 ° C.
  • the lower limit of the crystallinity at 150 ° C. of the stretched polypropylene film of the present invention is preferably 48%, more preferably 49%, still more preferably 50%, and particularly preferably 51%. Within the above range, the thermal contraction rate at high temperature becomes smaller.
  • the upper limit of the 150 ° C. crystallinity is preferably 85%, more preferably 80%, still more preferably 79%, and particularly preferably 78%, from a practical viewpoint.
  • the crystallinity at 150 ° C. is within the range by reducing the copolymer monomer amount in the polypropylene resin to 0% by mass, increasing the low molecular weight component, or setting the stretching temperature and heat setting temperature to a high temperature. It can be.
  • (Film characteristics) 150 ° C. thermal shrinkage rate in the MD direction of the stretched polypropylene film of the present invention (in the present specification, “MD direction” means the longitudinal direction of the film, and “MD direction” may be referred to as “longitudinal direction”).
  • the lower limit is preferably 0.5%, more preferably 1%, still more preferably 1.5%, particularly preferably 2%, and most preferably 2.5%. If it is in the above range, realistic production may be easy in terms of cost or the like, and thickness unevenness may be reduced.
  • the upper limit of the 150 ° C. heat shrinkage rate in the MD direction is preferably 8%, more preferably 7%, still more preferably 6.5%, particularly preferably 6%, and most preferably 5%. %. When it is in the above range, it is easier to use in applications that may be exposed to a high temperature of about 150 ° C.
  • TD direction means the width direction of the film
  • TD direction may be referred to as “lateral direction”.
  • the lower limit is preferably 0.5%, more preferably 1%, still more preferably 1.5%, particularly preferably 2%, and most preferably 2.5%. If it is in the above range, realistic production may be easy in terms of cost or the like, and thickness unevenness may be reduced.
  • the upper limit of 150 ° C. heat shrinkage in the TD direction is preferably 13%, more preferably 12%, still more preferably 11%, particularly preferably 10%, and most preferably 9%. is there.
  • the heat shrinkage at 150 ° C is up to about 2.5%, it can be achieved by increasing the low molecular weight component, adjusting the stretching conditions and the fixing conditions. It is preferable to process.
  • the lower limit of the impact resistance of the stretched polypropylene film of the present invention at room temperature (23 ° C.) is preferably 0.5 J, more preferably 0.6 J. Within the above range, the film has sufficient toughness and does not break during handling.
  • the upper limit of impact resistance at room temperature (23 ° C.) may be 2J from a practical viewpoint, more preferably 1.5J, and still more preferably 1.2J. Impact resistance tends to decrease when there are many low molecular weight components, when the overall molecular weight is low, when there are few high molecular weight components, and when the molecular weight of high molecular weight components is low. These components can be adjusted to be within the range.
  • the lower limit of the Young's modulus in the MD direction at 23 ° C. is preferably 2 GPa, more preferably 2.1 GPa, still more preferably 2.2 GPa, Particularly preferred is 2.3 GPa, and most preferred is 2.4 GPa.
  • the upper limit of the Young's modulus in the MD direction at 23 ° C. is preferably 4 GPa, more preferably 3.7 GPa, still more preferably 3.5 GPa, particularly preferably 3.4 GPa, and most preferably 3 GPa. .3 GPa. Within the above range, realistic production is easy and the MD-TD balance is improved.
  • the lower limit of the Young's modulus in the TD direction at 23 ° C. is preferably 3.8 GPa, more preferably 4 GPa, even more preferably 4.2 GPa, Particularly preferred is 4.3 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. Within the above range, realistic production is easy and the MD-TD balance is improved.
  • the Young's modulus can be increased by increasing the draw ratio. In the case of MD-TD stretch, the MD stretch ratio should be set low, and the Young's modulus in the TD direction can be increased by increasing the TD stretch ratio. Can do.
  • the lower limit of the thickness uniformity of the stretched polypropylene film of the present invention is preferably 0%, more preferably 0.1%, still more preferably 0.5%, and 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%.
  • defects are unlikely to occur during post-processing such as coating and printing, and it is easy to use in applications that require precision.
  • the thickness uniformity of a film is measured by the method mentioned later in an Example.
  • the haze of the stretched polypropylene film of the present invention is preferably 0.1% as a practical value, more preferably 0.2%, still more preferably 0.3%, and particularly preferably 0.8%. 4%, most preferably 0.5%.
  • the upper limit of haze is preferably 6%, more preferably 5%, still more preferably 4.5%, particularly preferably 4%, and most preferably 3.5%.
  • the lower limit of the density of the stretched polypropylene film of the present invention is preferably 0.91 g / cm 3 , more preferably 0.911 g / cm 3 , still more preferably 0.912 g / cm 3 , and particularly preferably 0. 913 g / cm 3 .
  • the crystallinity is high and the thermal shrinkage rate may be small.
  • the upper limit of the film density is preferably 0.925 g / cm 3, more preferably 0.922 g / cm 3, more preferably from 0.920 g / cm 3, particularly preferably 0.918 g / cm 3 . In the above range, realistic production may be easy.
  • the film density can be increased by increasing the draw ratio and temperature, increasing the heat setting temperature, and further performing offline annealing.
  • the stretched polypropylene film of the present invention can be produced by forming a film-forming resin composition containing a polypropylene resin into a film by a known method and stretching the resulting unstretched film.
  • a stretched film By using a stretched film, a film having a low thermal shrinkage rate can be obtained even at 150 ° C., which could not be expected with a conventional polypropylene film.
  • the resin composition for film molding is mainly composed of the above polypropylene resin, but an additive or other resin may be added as necessary.
  • the additive include an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a nucleating agent, an adhesive, an antifogging agent, a flame retardant, an antiblocking agent, and an inorganic or organic filler.
  • the other resins include polypropylene resins other than the specific polypropylene resin used in the present invention, random copolymers that are copolymers of ethylene and ⁇ -olefin, and various elastomers. It is preferable that the addition amount of an additive and other resin is 50 mass parts or less in total in 100 mass parts of resin compositions for film forming.
  • Stretching may be uniaxial stretching that stretches in either the longitudinal direction or the width direction of the film, or may be biaxial stretching that stretches in both the longitudinal direction or the width direction. In this case, sequential biaxial stretching or simultaneous biaxial stretching may be used.
  • the stretched polypropylene film of the present invention is preferably a biaxially stretched film.
  • a method for producing a film of sequential biaxial stretching of longitudinal stretching and transverse stretching which is a particularly preferable example, will be described.
  • a polypropylene resin is heated and melted with a monoaxial or biaxial extruder and extruded onto a chill roll to obtain an unstretched film.
  • the resin temperature is 200 to 280 ° C.
  • the sheet is extruded from a T-die and cooled and solidified by a cooling roll having a temperature of 10 to 100 ° C.
  • the film is stretched 3 to 8 times in the longitudinal (MD) direction with a stretching roll of 120 to 165 ° C., for example, and subsequently 155 ° C.
  • the film is preferably stretched 4 to 20 times at a temperature. Furthermore, it is preferable to perform heat treatment while allowing relaxation of 1 to 15% at an atmospheric temperature of preferably 165 to 175 ° C. (more preferably 166 to 173 ° C.).
  • the stretched polypropylene film thus obtained can be subjected to a corona discharge treatment on at least one side, and then a roll sample can be obtained by winding with a winder.
  • the lower limit of the draw ratio in the MD direction 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 in the MD direction is preferably 8 times, more preferably 7 times. If the above is exceeded, it may be difficult to continue stretching in the TD direction.
  • the lower limit of the stretching temperature in the MD direction is preferably 120 ° C, more preferably 125 ° C, and further preferably 130 ° C. If it is less than the above, the mechanical load may be increased, the thickness unevenness may be increased, or the film may be roughened.
  • the upper limit of the stretching temperature in the MD direction is preferably higher in terms of heat shrinkage, but it may be difficult to stretch by adhering to the roll, and is preferably 165 ° C, more preferably 160 ° C. More preferably, it is 155 degreeC, Most preferably, it is 150 degreeC.
  • the lower limit of the draw ratio in the TD direction is preferably 4 times, more preferably 5 times, and even more preferably 6 times. If it is less than the above, thickness unevenness may occur.
  • the upper limit of the stretching ratio in the TD direction is preferably 20 times, more preferably 17 times, still more preferably 15 times, and particularly preferably 12 times. If the above is exceeded, the thermal shrinkage rate may be increased or the film may be broken during stretching.
  • the preheating temperature is preferably set to be 10 to 15 ° C. higher than the stretching temperature in order to quickly raise the film temperature near the stretching temperature.
  • the stretching in the TD direction is performed at a higher temperature than the conventional polypropylene film.
  • the lower limit of the stretching temperature in the TD direction is preferably 155 ° C, more preferably 157 ° C, and further preferably 158 ° C. If it is less than the above, it may break without being sufficiently softened, or the thermal shrinkage rate may be increased.
  • the upper limit of the stretching temperature in the TD direction is preferably 175 ° C, more preferably 170 ° C, and even more preferably 168 ° C.
  • the temperature is preferably higher, but if it exceeds the above, the low molecular weight component may melt and recrystallize, and the surface roughness or the film may be whitened.
  • the stretched film is preferably heat-set.
  • the heat setting can be performed at a higher temperature than the conventional polypropylene film.
  • the lower limit of the heat setting temperature is preferably 165 ° C, more preferably 166 ° C. If it is less than the above, the thermal shrinkage rate may increase. In addition, a long heat setting process is required to reduce the heat shrinkage rate, and productivity may be inferior.
  • the upper limit of the heat setting temperature is preferably 175 ° C, more preferably 173 ° C. When the above is exceeded, the low molecular weight component may melt and recrystallize, and the surface roughness and the film may be whitened.
  • the lower limit of relaxation is preferably 1%, more preferably 2%, and even more preferably 3%. If it is less than the above, the thermal shrinkage rate may increase.
  • the upper limit of relaxation is preferably 15%, more preferably 10%, and even more preferably 8%. When the above is exceeded, the thickness unevenness may increase.
  • the film manufactured in the above process can be once wound up in a roll shape and then annealed offline.
  • the lower limit of the offline annealing temperature is preferably 160 ° C., more preferably 162 ° C., and further preferably 163 ° C. If it is less than the above, the effect of annealing may not be obtained.
  • the upper limit of the offline annealing temperature is preferably 175 ° C, more preferably 174 ° C, and further preferably 173 ° C. When the above is exceeded, the transparency may decrease, or the thickness unevenness may increase.
  • the lower limit of the offline annealing time is preferably 0.1 minutes, more preferably 0.5 minutes, and even more preferably 1 minute. If it is less than the above, the effect of annealing may not be obtained.
  • the upper limit of the offline annealing time is preferably 30 minutes, more preferably 25 minutes, and further preferably 20 minutes. When the above is exceeded, productivity may be reduced.
  • 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 further 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 stretched polypropylene film thus obtained is usually formed as a roll having a width of about 2000 to 12000 mm and a length of about 1000 to 50000 m, and is wound into a roll. Furthermore, it is slit according to each application, and is provided as a slit roll having a width of about 300 to 2000 mm and a length of about 500 to 5000 m.
  • the stretched polypropylene film of the present invention has excellent characteristics as described above that are not present in the past. Therefore, when it is used as a packaging film, it is highly rigid, so that it can be thinned, and cost and weight can be reduced. In addition, since it has high heat resistance, it can be dried at a high temperature during drying of a coat or printing, and it is possible to use a coating agent, an ink, a laminating adhesive, or the like, which has been difficult to use conventionally, or has been difficult to use. Furthermore, it can also be used as an insulating film for capacitors and motors, a back sheet for solar cells, a barrier film for inorganic oxides, and a base film for transparent conductive films such as ITO.
  • the present application includes Japanese Patent Application No. 2012-12117 filed on January 24, 2012, Japanese Patent Application No. 2012-146801 filed on June 29, 2012, and August 17, 2012. Claims the benefit of priority based on Japanese Patent Application No. 2012-180971 filed in. Japanese Patent Application No. 2012-12117 filed on January 24, 2012, Japanese Patent Application No. 2012-146801 filed on June 29, 2012, and August 17, 2012 The entire contents of the specification of Japanese Patent Application No. 2012-180971 are incorporated herein by reference.
  • the present invention will be described more specifically with reference to examples and comparative examples.
  • the present invention is not limited by the following examples and the like, and is appropriately within a range that can meet the above and the following purposes.
  • the measuring method of the physical property in a following example and a comparative example is as follows.
  • MFR Melt flow rate
  • the number average molecular weight (Mn), the mass average molecular weight (Mw), the Z average molecular weight (Mz), and the Z + 1 average molecular weight (Mz + 1) are molecular weights (Mi) at the respective elution positions of the GPC curve obtained through the molecular weight calibration curve. It is defined by the following formula by the number of molecules (Ni).
  • the mesopentad fraction (isotactic mesopentad fraction) and meso chain length (meso average chain length) were measured using 13 C-NMR.
  • the isotactic mesopentad fraction was determined according to the method described in “Zambelli et al., Macromolecules, Vol. 6, 925 (1973)”.
  • the isotactic meso average chain length was determined according to “J. C. Randall,“ Polymer Sequence Distribution “Chapter 2 (1977) (Academic Press, New York)”.
  • the 13 C-NMR measurement was performed at 110 ° C. by using “AVANCE 500” manufactured by BRUKER, and dissolving 200 mg of a sample in an 8: 2 (volume ratio) mixture of o-dichlorobenzene and heavy benzene at 135 ° C.
  • Tmp Melting point
  • DSC-60 differential scanning calorimeter
  • the 150 ° C. crystallinity was determined from the heat of fusion of 150 ° C. or higher in the DSC melting profile.
  • CXS Cold xylene soluble part
  • Refractive index (Nx, Ny, Nz) Measurement was performed using an Abbe refractometer (manufactured by Atago Co., Ltd.). The refractive indexes along the MD and TD directions were Nx and Ny, respectively, and the refractive index in the thickness direction was Nz.
  • Plane orientation coefficient It calculated from the Nx, Ny, Nz measured by said (12) using the formula of [(Nx + Ny) / 2] -Nz.
  • Thickness unevenness (thickness uniformity) (%)
  • a square sample having a length of 1 m was cut out from the wound film roll, and divided into 10 parts each in the MD direction and the TD direction, and 100 measurement samples were prepared.
  • the thickness of the substantially central portion of the measurement sample was measured with a contact-type film thickness meter. Then, an average value A of the obtained 100 points of data was obtained, and a difference (absolute value) B between the minimum value and the maximum value was obtained. Thick spots.
  • This polypropylene resin was extruded into a sheet form from a T-die at 250 ° C using a 65 mm extruder, cooled and solidified with a cooling roll at 30 ° C, and then longitudinally (lengthwise) 4.5 times longer at 135 ° C. Stretched, then clipped at both ends, led into a hot air oven, preheated at 170 ° C., then transversely stretched 8.2 times in the width direction (lateral direction) at 160 ° C., then 6.7 in the width direction % Heat treatment at 168 ° C. while relaxing. One side of the film thus obtained was subjected to corona treatment and wound up with a winder to obtain the stretched polypropylene film of the present invention.
  • the thickness of the obtained film was 20 ⁇ m, and the physical properties were as shown in Table 1, Table 2, and Table 3. From the results of the table, it can be seen that this film has a low thermal shrinkage and a high Young's modulus. Moreover, the chart obtained by the differential scanning calorimetry (DSC) of this film is shown in FIG.
  • Example 2 Low molecular weight propylene homopolymer having a narrow molecular weight distribution and a viscosity average molecular weight of 10,000 (90% by weight of the polypropylene homopolymer (PP-1) used in Example 1 (“High Wax NP105” manufactured by Mitsui Chemicals, Inc.): Except that 10 parts by mass of a copolymerization monomer amount (0 mol%) was added and a pellet-like mixture (PP-2) obtained by melt-kneading with a 30 mm twin screw extruder was used as a polypropylene resin.
  • PP-2 pellet-like mixture obtained by melt-kneading with a 30 mm twin screw extruder was used as a polypropylene resin.
  • a stretched polypropylene film of the present invention was obtained. The thickness of the obtained film was 20 ⁇ m, and the physical properties were as shown in Table 1, Table 2, and Table 3. From the results of the table, it can be seen that this film has a low thermal shrinkage and
  • Example 4 In Example 1, the stretched polypropylene film of the present invention was obtained in the same manner as in Example 1 except that the preheating temperature in transverse stretching was 173 ° C., and the stretching temperature and heat treatment temperature were 167 ° C. The thickness of the obtained film was 20 ⁇ m, and the physical properties were as shown in Table 1, Table 2, and Table 3. From the results of the table, it can be seen that this film has a low thermal shrinkage and a high Young's modulus.
  • Example 5 the stretched polypropylene film of the present invention was obtained in the same manner as in Example 2 except that the film was stretched 5.5 times in the longitudinal direction (length direction) and 12 times in the width direction (lateral direction). .
  • the thickness of the obtained film was 20 ⁇ m, and the physical properties were as shown in Table 1, Table 2, and Table 3. From the results of the table, it can be seen that this film has a low thermal shrinkage and a high Young's modulus.
  • Example 6 The stretched polypropylene film obtained in Example 1 was further heat-treated at 170 ° C. for 5 minutes in a tenter hot air oven.
  • the thickness of the obtained film was 20 ⁇ m, and the physical properties were as shown in Table 1, Table 2, and Table 3.
  • the stretched polypropylene film of the present invention was obtained. The thickness of the obtained film was 20 ⁇ m, and the physical properties were as shown in Table 1, Table 2, and Table 3.
  • Comparative Example 2 A comparative stretched polypropylene film was obtained in the same manner as in Comparative Example 1 except that the preheating temperature in the transverse stretching was 171 ° C, the stretching temperature was 160 ° C, and the heat treatment temperature was 165 ° C. The thickness of the obtained film was 20 ⁇ m, and the physical properties were as shown in Table 1, Table 2, and Table 3.
  • the stretched polypropylene film of the present invention can be widely used in packaging applications and industrial applications, but is particularly suitable for applications where cost reduction and weight reduction are required because it is highly rigid and can be thinned.
  • the stretched polypropylene film of the present invention has high heat resistance and can be dried at a high temperature at the time of drying when coating treatment or printing is performed, so that production efficiency can be improved and coating agents and inks that have been difficult to adopt conventionally are used. A treatment using a laminate adhesive or the like can be applied.
  • the stretched polypropylene film of the present invention is also suitable for insulating films such as capacitors and motors, back sheets for solar cells, barrier films for inorganic oxides, base films for transparent conductive films such as ITO, and the like.

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Abstract

L'invention fournit un film de polypropylène étiré d'une rigidité élevée, et possédant un faible indice de retrait comparable à celui d'un polyéthylène téréphtalate (PET) à 150°C. Le film de polypropylène étiré est configuré par une résine polypropylène qui satisfait les conditions 1) à 5), et présente une limite inférieure de coefficient d'orientation planaire de film de 0,0125. 1) La limite inférieure de fraction mésopentade est 96%; 2) la limite supérieure de quantité de monomère de copolymérisation autre qu'un propylène est 0,1% en moles; 3) la limite inférieure de l'indice de fluage (MFR) mesuré à 230°C et 2,16kgf, est 1g/10min; 4) la limite inférieure de masse moléculaire moyenne en poids (Mw) / masse moléculaire moyenne en nombre (Mn), est 5,5; et 5) la limite inférieure de z+1 masse moléculaire moyenne (Mz+1) / masse moléculaire moyenne en nombre (Mn), est 50.
PCT/JP2013/051316 2012-01-24 2013-01-23 Film de polypropylène étiré WO2013111779A1 (fr)

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HK14112137.3A HK1198701A1 (en) 2012-01-24 2014-12-02 Stretched polypropylene film

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11162779A (ja) * 1997-11-27 1999-06-18 Toray Ind Inc コンデンサー用ポリプロピレンフィルム
WO2009060944A1 (fr) * 2007-11-07 2009-05-14 Oji Paper Co., Ltd. Film de polypropylène à orientation biaxiale pour condensateur, film revêtu par dépôt obtenu à partir de celui-ci, et condensateur utilisant celui-ci
JP2010254868A (ja) * 2009-04-28 2010-11-11 Oji Paper Co Ltd コンデンサー用二軸延伸ポリプロピレンフィルムおよびその金属蒸着フィルム

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69508155T2 (de) * 1994-07-08 1999-07-01 Tokuyama Corp Gestreckter Polypropylenfilm
JPH08325327A (ja) 1995-06-02 1996-12-10 Chisso Corp 高立体規則性ポリプロピレン
JP2001146536A (ja) 1999-11-19 2001-05-29 Oji Paper Co Ltd 剥離シート用二軸延伸ポリプロピレンフィルム
JP4145639B2 (ja) 2002-11-27 2008-09-03 株式会社プライムポリマー ポリプロピレン樹脂、該樹脂から得られるシートおよびフィルム
EP1726602A1 (fr) 2005-05-27 2006-11-29 Borealis Technology Oy Polymère de propylene a haute cristallinité
JP4929923B2 (ja) 2005-08-26 2012-05-09 東レ株式会社 ポリプロピレンフィルムおよびその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11162779A (ja) * 1997-11-27 1999-06-18 Toray Ind Inc コンデンサー用ポリプロピレンフィルム
WO2009060944A1 (fr) * 2007-11-07 2009-05-14 Oji Paper Co., Ltd. Film de polypropylène à orientation biaxiale pour condensateur, film revêtu par dépôt obtenu à partir de celui-ci, et condensateur utilisant celui-ci
JP2010254868A (ja) * 2009-04-28 2010-11-11 Oji Paper Co Ltd コンデンサー用二軸延伸ポリプロピレンフィルムおよびその金属蒸着フィルム

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WO2014002934A1 (fr) * 2012-06-29 2014-01-03 東洋紡株式会社 Film de polypropylène étirable
WO2014024968A1 (fr) * 2012-08-09 2014-02-13 東洋紡株式会社 Film de polypropylène pour étiquettes surmoulées
WO2014024969A1 (fr) * 2012-08-09 2014-02-13 東洋紡株式会社 Film de polypropylène
WO2014024970A1 (fr) * 2012-08-09 2014-02-13 東洋紡株式会社 Film de polypropylène
WO2014104089A1 (fr) * 2012-12-25 2014-07-03 東洋紡株式会社 Film de polypropylène biaxialement étiré
JPWO2014104089A1 (ja) * 2012-12-25 2017-01-12 東洋紡株式会社 ２軸延伸ポリプロピレンフィルム
WO2021193509A1 (fr) * 2020-03-24 2021-09-30 東洋紡株式会社 Film de polypropylène à orientation biaxiale
WO2021193508A1 (fr) * 2020-03-24 2021-09-30 東洋紡株式会社 Film de polypropylène à orientation biaxiale
WO2021193510A1 (fr) * 2020-03-24 2021-09-30 東洋紡株式会社 Film de polypropylène à orientation biaxiale
CN115315467A (zh) * 2020-03-24 2022-11-08 东洋纺株式会社 双轴取向聚丙烯薄膜
CN115315467B (zh) * 2020-03-24 2024-06-14 东洋纺株式会社 双轴取向聚丙烯薄膜
WO2023286541A1 (fr) 2021-07-16 2023-01-19 東洋紡株式会社 Film de polypropylène stratifié à orientation biaxiale
KR20240032740A (ko) 2021-07-16 2024-03-12 도요보 가부시키가이샤 2축 배향 적층 폴리프로필렌 필름

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CN104105746A (zh) 2014-10-15
KR101986868B1 (ko) 2019-06-07
TWI631151B (zh) 2018-08-01
JP2014055276A (ja) 2014-03-27
TW201339219A (zh) 2013-10-01
KR20140119117A (ko) 2014-10-08
JP6241039B2 (ja) 2017-12-06
CN104105746B (zh) 2017-09-01

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