WO2020196602A1 - Film de polypropylène - Google Patents

Film de polypropylène Download PDF

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Publication number
WO2020196602A1
WO2020196602A1 PCT/JP2020/013262 JP2020013262W WO2020196602A1 WO 2020196602 A1 WO2020196602 A1 WO 2020196602A1 JP 2020013262 W JP2020013262 W JP 2020013262W WO 2020196602 A1 WO2020196602 A1 WO 2020196602A1
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WO
WIPO (PCT)
Prior art keywords
film
polypropylene
mass
polypropylene film
orientation axis
Prior art date
Application number
PCT/JP2020/013262
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English (en)
Japanese (ja)
Inventor
岡田一馬
大倉正寿
山中康平
Original Assignee
東レ株式会社
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.)
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Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to KR1020217028005A priority Critical patent/KR20210148096A/ko
Priority to CN202080016897.0A priority patent/CN113490704B/zh
Priority to JP2020539114A priority patent/JPWO2020196602A1/ja
Publication of WO2020196602A1 publication Critical patent/WO2020196602A1/fr

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Classifications

    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners

Definitions

  • the present invention relates to a polypropylene film having excellent shrinkage characteristics at high temperatures, mechanical strength at high temperatures, heat resistance, productivity, and quality.
  • Polypropylene film has excellent transparency, mechanical properties, electrical properties, etc., so it is used in various applications such as packaging, mold release, tape, cable wrapping, and electrical applications such as capacitors.
  • it since it has excellent surface releasability and mechanical properties, it is suitably used as a releasable film or process film for various members such as plastic products, building materials, and optical members.
  • the required characteristics of the release film are appropriately set depending on the intended use, but one of the ways to use it is to attach it to an adherend and then heat it to a high temperature of 140 to 150 ° C, such as an oven or an oven. May go through the process. In such cases, PET films with excellent heat resistance have often been used, but PET films have poor mold releasability and may not satisfy the required characteristics, and have excellent heat resistance and releasability. Film may be required.
  • shrinkage force at high temperature is large, it may peel off from the adherend or curl when it is attached to the adherend and passes through the heating process.
  • polypropylene has a low melting point of about 160 ° C., and it is very difficult to suppress a shrinkage force of about 140 to 150 ° C.
  • Patent Document 1 describes an example in which the heat treatment temperature is extremely high and the orientation is relaxed to reduce the shrinkage force at 120 ° C.
  • Patent Documents 3 and 4 describe an example in which the heat shrinkage rate is lowered by raising the heat treatment temperature in the relaxation treatment and relaxing the orientation.
  • Patent Document 2 describes an example in which the heat shrinkage rate is lowered by lowering the molecular weight of the polypropylene raw material.
  • Patent Document 5 describes an example in which the contraction force at 140 ° C. is lowered by making the relaxation rate after lateral stretching extremely large.
  • Patent Document 5 describes an example in which the contraction force at 140 ° C. is lowered by making the relaxation rate after lateral stretching extremely large.
  • Patent Documents 1 and 3 have a problem that the mechanical strength is low and wrinkles are formed when the polypropylene film and the adhesive film are transported at a high temperature.
  • the methods described in Patent Documents 2 and 4 have problems such as high heat shrinkage at high temperature, peeling from the adherend, and curling.
  • the method described in Patent Document 5 has a problem that the rigidity of the film at a high temperature is low, the film stretches in the flow direction when the adhesive film is conveyed at a high temperature, and the width shrinkage becomes large.
  • the subject of the present invention is to solve the above-mentioned problems. That is, it is an object of the present invention to provide a polypropylene film which is excellent in mechanical strength at room temperature and high temperature despite its low heat shrinkage force and can be suitably used as a release film in a high temperature environment.
  • the polypropylene film of the present invention has a heat shrinkage force at 140 ° C. in both the main orientation axis direction and the direction orthogonal to the main orientation axis direction of 400 mN or less, and the main orientation axis.
  • the Young's modulus in both the direction and the direction orthogonal to the direction is 1.8 GPa or more.
  • the polypropylene film of the present invention has excellent mechanical strength at room temperature and high temperature, and can be suitably used as a release film in a high temperature environment.
  • the polypropylene film of the present invention has a heat shrinkage force of 400 mN or less at 140 ° C. in both the main orientation axis direction and the direction orthogonal to the main orientation axis direction, and the Young's modulus in both the main orientation axis direction and the direction orthogonal to the main orientation axis direction is 1. It is 8 GPa or more.
  • the heat shrinkage force at 140 ° C. in the direction of the main orientation axis and in the direction orthogonal to the main orientation axis is more preferably 350 mN or less, further preferably 100 mN or less, still more preferably 95 mN or less, and most preferably 30 mN or less. is there.
  • the heat shrinkage force at 140 ° C. in the main orientation axis direction and the direction orthogonal to it exceeds 400 mN in at least one of them, it may be peeled off from the adherend due to shrinkage when it is bonded to the adherend and passed through the heating step. , Curls may occur.
  • the heat shrinkage force means a heat shrinkage force in a width of 4 mm, and the measurement thereof can be performed by the method shown in the examples.
  • the main orientation axis direction in the present invention is 15 °, 30 °, 45 °, 60 °, 75 °, 90 ° with respect to the longitudinal direction when the longitudinal direction is 0 ° in the film plane. , 105 °, 120 °, 135 °, 150 °, 165 °, the direction showing the highest value when Young's modulus is measured in each direction.
  • the "longitudinal direction” is the direction corresponding to the flow direction in the film manufacturing process (hereinafter, may be referred to as "MD")
  • the "width direction” is the above-mentioned film.
  • TD a direction orthogonal to the flow direction in the manufacturing process
  • the film winding direction can be said to be the longitudinal direction.
  • a line is drawn in 15 ° increments with reference to an arbitrary straight line on the film plane.
  • a slit-shaped film piece is sampled in parallel with each line, the Young ratio is obtained with a tensile tester, and the direction in which the maximum Young ratio is given is regarded as the main orientation axis direction.
  • the crystal orientation of the ⁇ crystal (110) plane of the polypropylene film by wide-angle X-ray is measured as follows.
  • the highest direction is the main orientation axis direction.
  • the Young's modulus in the main orientation axis direction and the direction orthogonal to the main orientation axis direction is more preferably 2.0 GPa or more, and further preferably 2.3 GPa or more.
  • the Young's modulus in the main orientation axis direction and the direction orthogonal to the main orientation axis is less than 1.8 GPa in at least one of them, the polypropylene film is adhesively coated and the adhesive layer is dried in a high temperature oven when wrinkles are formed.
  • the upper limit of Young's modulus in the direction of the main orientation axis and the direction orthogonal to the main orientation axis direction is not particularly limited, but is substantially about 10 GPa.
  • the raw material composition of the film should be in the range described later, and the film forming conditions should be in the range described later.
  • a raw material having high crystallinity, a low cold xylene-soluble portion, and a high melting point was used, and the preheating roll temperature during longitudinal stretching was set within the range described later to make the crystalline state before stretching uniform.
  • highly oriented stretching is effective.
  • the polypropylene film of the present invention preferably has a temperature of 116 ° C. or higher, more preferably 124 ° C. or higher, and even more preferably 124 ° C. or higher when the heat shrinkage force is 20 mN or higher in the main orientation axis direction and the direction orthogonal to the main orientation axis direction. Both are 132 ° C. or higher, most preferably 142 ° C. or higher.
  • the temperature at which the heat shrinkage force is 20 mN or more is less than 116 ° C. in at least one of the main orientation axis direction and the direction orthogonal to the main orientation axis direction, due to shrinkage when the material is bonded to the adherend and passes through the heating step.
  • the upper limit of the temperature when the heat shrinkage force becomes 20 mN or more is not particularly limited, but is substantially about 160 ° C.
  • the raw material composition of the film is set in the range described later, and the film forming conditions are set in the range described later, and in particular, it is highly crystalline and cold.
  • Use a raw material with a low xylene-soluble part and a high melting point set the preheating roll temperature during longitudinal stretching to the range described later, homogenize the crystal state before stretching, and perform the heat treatment step after transverse stretching. It is effective to moderately promote the relaxation of the film.
  • the maximum point stress at 120 ° C. in both the main orientation axis direction and the direction orthogonal to the main orientation axis direction is preferably 80 MPa or more, more preferably both 100 MPa ° C. or higher, and further preferably 120 MPa or higher. ..
  • the polypropylene film is adhesively coated and the adhesive layer is dried in a high temperature oven. Wrinkles may occur.
  • the upper limit of the maximum point stress is not particularly limited, but is substantially about 300 MPa.
  • the raw material composition of the film is set in the range described later, and the film forming conditions are set in the range described later.
  • it is highly crystalline, has a low cold xylene-soluble portion, and has a high melting point.
  • it is preferable to use a raw material set the preheating roll temperature at the time of longitudinal stretching within the range described later, homogenize the crystal state before stretching, and then perform highly oriented stretching. Further, it is preferable that the heat treatment temperature after lateral stretching and the relaxation rate are set in the ranges described later, and the orientation of the film is not relaxed more than necessary.
  • the polypropylene film of the present invention preferably has a maximum protrusion roughness St on at least one side of 2000 nm or more, more preferably 4000 nm or more, and further preferably 6000 nm or more. If the St on both sides of the film is less than 2000 nm, the releasability when peeling from the adherend is insufficient, and the adherend may be deformed or ruptured.
  • the upper limit of St is not particularly limited, but is substantially about 30,000 nm.
  • the raw material composition of the film is set to the range described later, and the film forming conditions are set to the range described later.
  • the casting temperature is raised and ⁇ crystals are formed in the unstretched film in the casting step. It is effective to do.
  • the polypropylene film of the present invention preferably has a thickness unevenness in the main orientation axis direction of less than 6.0%, more preferably less than 4.0%, and further preferably less than 2.0%. If the thickness unevenness in the main orientation axis direction is 6.0% or more, it becomes difficult to attach the adherend to the adherend neatly, and the adherend may be peeled off or air biting may be mixed. ..
  • the lower limit of the thickness unevenness in the main orientation axis direction is not particularly limited, but is substantially about 0.1%.
  • the raw material composition of the film is set to the range described later
  • the film forming conditions are set to the range described later
  • the preheating and stretching temperature during transverse stretching are set to the range described later. It is effective to adjust to and increase the lateral stretching ratio.
  • the polypropylene film of the present invention preferably has a heat shrinkage force of 95 mN or less at 140 ° C. in the direction orthogonal to the main orientation axis direction, more preferably 60 mN or less, still more preferably 30 mN or less, and most preferably 10 mN or less.
  • a heat shrinkage force at 140 ° C. in the direction orthogonal to the main orientation axis direction exceeds 95 mN, the shrinkage causes peeling or curling from the adherend when it is attached to the adherend and passes through the heating step. It may happen.
  • the lower limit of the heat shrinkage force at 140 ° C. in the direction orthogonal to the main orientation axis direction is not particularly limited, but is substantially ⁇ 100 mN.
  • the raw material composition of the film is set to the range described later, and the film forming conditions are set to the range described later, particularly longitudinal stretching. It is effective to set the preheating roll temperature at that time in the range described later, make the crystal state before stretching uniform, and then perform highly oriented stretching. In addition, it is more effective to set the preheating temperature and stretching temperature at the time of lateral stretching within the range described later, raise the preheating temperature to a high temperature, preheat the polypropylene film uniformly, and perform high stress stretching at a temperature lower than the preheating temperature. Is.
  • the polypropylene film of the present invention has a value obtained by multiplying the Young's ratio (GPa) at 120 ° C. in the direction orthogonal to the main orientation axis direction by the film thickness ( ⁇ m) at 1.5 (GPa ⁇ ⁇ m) or more. It is preferably 3.0 (GPa ⁇ ⁇ m) or more, more preferably 4.0 (GPa ⁇ ⁇ m) or more, and most preferably 5.5 or more.
  • the value obtained by multiplying the Young's modulus at 120 ° C. in the direction orthogonal to the main orientation axis direction by the film thickness has a high correlation with the rigidity of the film in a high temperature environment, and the value is less than 1.5.
  • the film being conveyed may stretch in the flow direction and the width of the film may shrink significantly when the film is bonded to the adherend and passed through the heating step.
  • the upper limit of the value obtained by multiplying the Young's modulus at 120 ° C. in the direction orthogonal to the main orientation axis direction by the thickness of the film is not particularly limited, but is substantially about 30.
  • the raw material composition of the film should be in the range described later, and the film forming conditions should be set.
  • the preheating roll temperature at the time of longitudinal stretching is the range to be described later, and after homogenizing the crystal state before stretching, highly oriented stretching, the preheating at the time of transverse stretching, and the stretching temperature are the ranges to be described later. It is effective that the film is uniformly preheated at a high temperature, highly oriented and stretched at a low temperature, the relaxation rate is not too large, and the orientation is not relaxed too much.
  • the polypropylene film of the present invention has a laminated structure of two or more layers, and at least one layer contains 50 polypropylene having a cold xylene-soluble portion (CXS) of 3.5% or less based on 100% by mass of the whole layer. It is preferable that the layer contains by mass% or more and 100% by mass or less, a more preferable content is 70% by mass or more and 100% by mass or less, a further preferable content is 90% by mass or more and 100% by mass or less, and the most preferable content is 95. It is 100% by mass or more and 100% by mass or less.
  • CXS cold xylene-soluble portion
  • CXS refers to a polyolefin component dissolved in xylene when the sample is completely dissolved in xylene and then precipitated at room temperature, for reasons such as low stereoregularity and low molecular weight. It is considered that it corresponds to a component that is difficult to crystallize. If a large amount of such a component is contained in the resin, the thermal dimensional stability of the film may be inferior. Therefore, the CXS of polypropylene contained in the polypropylene film of the present invention is more preferably 2.0% or less, further preferably 1.5% or less.
  • the polypropylene film has a laminated structure of two or more layers and the content of polypropylene having a CXS of 3.5% or less in at least one layer is less than 50% by mass, the mechanical strength of the polypropylene film at a high temperature is insufficient.
  • wrinkles may occur.
  • polypropylene having a CXS of more than 3.5% is contained in 50% by mass or more and 100% by mass or less in at least one layer, the heat shrinkage force becomes large and the polypropylene is bonded to the adherend.
  • the lower limit of CXS of at least one layer is not particularly limited, but is substantially about 0.1%. In order to set CXS in the above range, it is effective to set the raw material composition of the film in the range described later, and in particular, to use a polypropylene raw material having a low CXS.
  • the polypropylene film of the present invention is not particularly limited in whether it has a single-layer structure or a laminated structure as long as it contains polypropylene, but as described above, the polypropylene film of the present invention has a laminated structure of two or more layers. Therefore, at least one layer is preferably a layer containing 50% by mass or more and 100% by mass or less of polypropylene having a CXS of 3.5% or less.
  • the layer containing 50% by mass or more and 100% by mass or less of polypropylene having a CXS of 3.5% or less is preferably the thickest layer among the layers having a laminated structure.
  • the inner layer having a three-layer structure is a layer containing 50% by mass or more and 100% by mass or less of polypropylene having a CXS of 3.5% or less.
  • the polypropylene film of the present invention has a laminated structure of two or more layers, and at least one layer is heated from 25 ° C. to 250 ° C. at 20 ° C./min by a differential scanning calorimeter DSC, and then from 250 ° C. to 25 ° C.
  • the crystallization peak temperature (Tc) when the temperature is lowered at 20 ° C./min is preferably 110 ° C. or higher, more preferably 112 ° C. or higher, and further preferably 114 ° C. or higher.
  • Tc has a correlation with the ease of crystallization, and the higher the Tc, the easier it is to crystallize.
  • the polypropylene film crystallizes to form spherulites when solidified on a cooling drum after melt extrusion.
  • the higher the Tc the more dense spherulites are generated on the unstretched sheet, and the protrusions on the surface shape of the film after biaxial stretching become finer accordingly.
  • the higher the Tc the more preferable, from the viewpoint of obtaining a surface in which the protrusions having good releasability are obtained without dent transfer to the adherend.
  • the upper limit of Tc is not particularly limited, but is substantially about 125 ° C.
  • the raw material composition of the film is set in the range described later, and it is particularly effective to use branched-chain polypropylene or a polypropylene raw material having a high molecular weight.
  • Tc branched-chain polypropylene or a polypropylene raw material having a high molecular weight.
  • the polypropylene film is evaluated as a whole and the value is regarded as a representative value.
  • the thickness of the polypropylene film of the present invention is appropriately adjusted depending on the intended use and is not particularly limited, but it is preferably 0.5 ⁇ m or more and 100 ⁇ m or less from the viewpoint of handleability. In order to take advantage of such characteristics, the thickness is more preferably 1 ⁇ m or more and 40 ⁇ m or less, further preferably 1 ⁇ m or more and 30 ⁇ m or less, and most preferably 6 ⁇ m or more and 30 ⁇ m or less.
  • the thickness can be adjusted by adjusting the screw rotation speed of the extruder, the width of the unstretched sheet, the film forming speed, the stretching ratio, and the like within a range that does not deteriorate other physical properties.
  • the polypropylene film of the present invention is not particularly limited in whether it has a single-layer structure or a laminated structure as long as it contains polypropylene, but as described above, the polypropylene film of the present invention has a laminated structure of two or more layers. Therefore, at least one layer is preferably a layer containing 50% by mass or more and 100% by mass or less of polypropylene having a CXS of 3.5% or less.
  • a raw material having a CXS of 3.5% or less (hereinafter, As a raw material, polypropylene having a CXS of 3.5% or less is preferably used as the polypropylene raw material A).
  • the CXS of the polypolopylene raw material A is more preferably 2.0% or less, still more preferably 1.5% or less.
  • the content of the polypropylene raw material A is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more, when the layer containing the polypropylene raw material A is 100% by mass.
  • homopolypropylene is preferably used from the viewpoint of strength and heat resistance.
  • the polypropylene raw material A preferably has a melting point of 155 ° C. or higher, more preferably 160 ° C. or higher, and even more preferably 165 ° C. or higher.
  • the melting point is less than 155 ° C., the heat resistance is poor, and when the product is bonded to the adherend and passed through the heating step, it may be peeled off from the adherend or curled due to shrinkage.
  • the polypropylene raw material A preferably has a mesopentad fraction of 0.94 or more, and more preferably 0.97 or more.
  • the mesopentad fraction is an index showing the stereoregularity of the polypropylene crystal phase measured by nuclear magnetic resonance spectroscopy (NMR method), and the higher the value, the higher the crystallinity, the higher the melting point, and the higher the temperature. This is preferable because it increases dimensional stability.
  • the upper limit of the mesopentad fraction is not specified.
  • a method of washing the resin powder obtained with a solvent such as n-heptane, a method of appropriately selecting a catalyst and / or a cocatalyst, a method of appropriately selecting a composition, and the like are used. It is preferably adopted.
  • the melt flow rate (MFR) is more preferably 1 to 10 g / 10 minutes (230 ° C., 21.18 N load), and more preferably 1 to 8 g / 10 minutes (230 ° C., 21. 18N load), and particularly preferably in the range of 4 to 8g / 10 minutes (230 ° C., 21.18N load) from the viewpoint of film forming property and film strength.
  • a method of controlling the average molecular weight or the molecular weight distribution is adopted.
  • the polypropylene raw material A may contain a copolymerization component of other unsaturated hydrocarbons or the like as long as the object of the present invention is not impaired, or may be blended with a polymer.
  • the monomer components constituting such copolymerization components and blends include ethylene, propylene (in the case of a copolymerized blend), 1-butene, 1-pentene, 3-methylpentene-1,3-methylbutene.
  • the copolymerization amount or the blend amount is preferably less than 1 mol% in the copolymerization amount and less than 10% by mass in the blend amount.
  • the content of the ethylene component contained in the polypropylene raw material A is preferably 10% by mass or less. It is more preferably 5% by mass or less, still more preferably 3% by mass or less.
  • the content of the ethylene component exceeds 10% by mass, the strength is lowered or the heat resistance is lowered to heat. The shrinkage rate may worsen.
  • the resin may easily deteriorate during the extrusion process, and fish eyes may easily occur in the film.
  • the polyolefin raw material used for the polypropylene film of the present invention contains various additives as long as the object of the present invention is not impaired. For example, a crystal nucleating agent, an antioxidant, a heat stabilizer, a slip agent, an antistatic agent, an antiblocking agent, a filler, a viscosity modifier, an antioxidant and the like can be contained.
  • the antioxidant is preferably a phenolic agent having steric hindrance, and at least one of them is a high molecular weight type having a molecular weight of 500 or more. Specific examples thereof include various examples. For example, 1,3,5-trimethyl-2,4,6-with 2,6-di-t-butyl-p-cresol (BHT: molecular weight 220.4).
  • Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene eg, BASF's "Irganox”® 1330: molecular weight 775.2
  • t-butyl-4-hydroxyphenyl) propionate] methane for example, "Irganox” (registered trademark) 1010 manufactured by BASF, Inc., molecular weight 1177.7 or the like.
  • the total content of these antioxidants is preferably in the range of 0.03 to 1.0% by mass with respect to the total amount of the polyolefin raw material.
  • a more preferable content is 0.05 to 0.9% by mass, and particularly preferably 0.1 to 0.8% by mass.
  • the polypropylene film of the present invention has at least one layer containing branched chain polypropylene.
  • the content of the branched-chain polypropylene in the layer containing the branched-chain polypropylene resin is preferably 0.05 to 10% by mass when the entire layer is 100% by mass.
  • the crystallization peak temperature (Tc) of the polypropylene film is raised, the spherulite size generated in the cooling process of the melt-extruded resin sheet is controlled to be small, and the sharp height difference of the film surface unevenness after biaxial stretching is reduced.
  • the lower limit of the content of the branched polypropylene resin is more preferably 0.5% by mass or more, still more preferably 1% by mass or more.
  • the upper limit of the content of the branched chain polypropylene resin is more preferably 8% by mass or less, still more preferably 5% by mass or less.
  • a crystal nucleating agent can be added to the polypropylene raw material used for the polypropylene film of the present invention within a range not contrary to the object of the present invention.
  • ⁇ -crystal nucleating agents dibenzylideneacetone sorbitols, sodium benzoate, etc.
  • ⁇ -crystal nucleating agents potassium 1,2-hydroxystearate, magnesium benzoate, N, N'-dicyclohexyl-2,6-naphthalenecarboxamide, etc. Amide compounds, quinacridone compounds, etc.) are exemplified.
  • the addition amount is usually 0.5% by mass or less, preferably 0.1. It is preferably mass% or less, more preferably 0.05 mass% or less.
  • the polypropylene film of the present invention is preferably biaxially stretched using the above-mentioned raw materials.
  • the biaxial stretching method can be obtained by any of the simultaneous inflation biaxial stretching method, the simultaneous biaxial stretching method of the stenter, and the sequential biaxial stretching method of the stenter. Among them, the film forming stability, the thickness uniformity, and the film It is preferable to adopt the stenter sequential biaxial stretching method in terms of controlling high rigidity and dimensional stability.
  • 80 parts by mass of the polypropylene raw material A and 20 parts by mass of the branched polypropylene raw material are dry-blended and supplied to a single-screw extruder for the B layer (base layer (II)), and the polypropylene raw material A is supplied to the A layer (surface layer (surface layer (II)). It is supplied to the single-screw extruder for I)), and melt extrusion is performed at 200 to 280 ° C., more preferably 220 to 280 ° C., and even more preferably 240 to 270 ° C.
  • the laminated thickness ratio is preferably in the range of 1/8/1 to 1/60/1. Within the above range, at least one layer having a CXS of 3.5% or less and a layer having a Tc of 112 ° C. or higher is formed, and the film is excellent in heat resistance and mechanical strength at high temperature. Can be obtained.
  • the surface temperature of the casting drum is preferably 40 to 120 ° C., preferably 60 to 120 ° C., and more preferably 80 to 110 ° C.
  • a two-layer laminated structure of A layer / B layer may be used. Any of the electrostatic application method, the adhesion method using the surface tension of water, the air knife method, the press roll method, the underwater casting method, etc. may be used as the adhesion method to the casting drum, but the flatness is good.
  • the air knife method which is capable of controlling the surface roughness, is preferable.
  • the air temperature of the air knife is preferably 40 to 100 ° C., and the blown air speed is preferably 130 to 150 m / s. Further, it is preferable to appropriately adjust the position of the air knife so that air flows to the downstream side of the film formation so as not to cause vibration of the film.
  • the obtained unstretched sheet is introduced into the longitudinal stretching step.
  • the longitudinal stretching step first, the unstretched sheet is brought into contact with a plurality of metal rolls kept at 10 ° C. or higher and 160 ° C. or lower, preferably 140 ° C. or higher and 158 ° C. or lower, and more preferably 145 ° C. or higher and 155 ° C. or lower to preheat them.
  • the mixture is cooled to room temperature.
  • the stretching temperature is 100 ° C. or higher and 150 ° C. or lower, preferably 100 ° C. or higher and 140 ° C. or lower, and more preferably 110 ° C. or higher and 130 ° C. or lower.
  • ⁇ crystals in the unstretched film are transferred to ⁇ crystals, and the crystal state in the polypropylene film can be made uniform. Further, by lowering the stretching temperature to a lower temperature than the preheating temperature, stretching can be performed with high stress. In this way, by making the crystal state in the polypropylene film uniform and stretching with high stress in the longitudinal stretching step, it is possible to obtain a polypropylene film having excellent mechanical strength at high temperature and low heat shrinkage. ..
  • the draw ratio is preferably 3 times or more and 6 times or less, and more preferably 4 times or more and 5.5 times or less.
  • the preheating temperature is raised, the polypropylene film is uniformly preheated, and the polypropylene film is stretched under high stress at a temperature lower than the preheating temperature to obtain a polypropylene film having excellent mechanical strength at high temperatures and low heat shrinkage.
  • the preheating temperature is 165 to 180 ° C, more preferably 170 to 180 ° C, and even more preferably 173 to 180 ° C.
  • the transverse stretching temperature is 155 to 170 ° C, more preferably 155 to 165 ° C, and even more preferably 155 to 160 ° C.
  • relaxation is applied at a relaxation rate of 2 to 20%, more preferably 8 to 18%, still more preferably 10 to 15% in the width direction, and 140 ° C.
  • Heat-fixed at a temperature of 140 ° C. or higher and lower than 160 ° C., and guided to the outside of the tenter through a cooling step at 80 to 100 ° C. while tension-grasping in the width direction with a clip. Release the clip, slit the film edge in the winder process, and wind up the film product roll.
  • the heat treatment is performed at a high temperature of 170 ° C. or higher, the orientation of the polypropylene film is relaxed, which may lead to a decrease in mechanical strength.
  • the decrease in mechanical strength in the high temperature range becomes remarkable. Further, if the relaxation treatment is performed at a relaxation rate of 20% or more, the orientation of the polypropylene film is relaxed, which may lead to a decrease in mechanical strength. In particular, the decrease in mechanical strength in the high temperature range becomes remarkable.
  • the polypropylene film obtained as described above can be used for various purposes such as packaging films, surface protective films, process films, sanitary products, agricultural products, construction products, medical products, etc., but especially for surface smoothness. Since it is excellent, it can be preferably used as a surface protective film, a process film, and a release film, and particularly preferably as a release film.
  • the polypropylene film of the present invention can be an adhesive film having an adhesive layer on at least one side thereof.
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer in the pressure-sensitive adhesive film of the present invention is not particularly limited, and rubber-based, vinyl polymerization-based, condensation polymerization-based, thermosetting resin-based, silicone-based, and the like can be used.
  • examples of the rubber-based pressure-sensitive adhesive include a butadiene-styrene copolymer system, a butadiene-acrylonitrile copolymer system, and an isobutylene-isoprene copolymer system.
  • Examples of the vinyl polymerization type pressure-sensitive adhesive include an acrylic type, a styrene type, a vinyl acetate-ethylene copolymer system, and a vinyl chloride-vinyl acetate copolymer system. Further, as the condensation polymerization type pressure-sensitive adhesive, a polyester type can be mentioned. Further, examples of the thermosetting resin-based adhesive include an epoxy resin-based adhesive and a urethane resin-based adhesive.
  • an acrylic adhesive is preferably used in consideration of excellent transparency, weather resistance, heat resistance, moisture heat resistance, substrate adhesion, and the like.
  • acrylic pressure-sensitive adhesives include "SK Dyne” (registered trademark) 1310, 1435, SK Dyne 1811L, SK Dyne 1888, SK Dyne 2094, SK Dyne 2096, SK Dyne 2137, SK manufactured by Soken Kagaku Co., Ltd.
  • Preferable examples include Dyne 3096 and SK Dyne 1852.
  • a curing agent together with the acrylic pressure-sensitive adhesive.
  • the curing agent include toluene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylene diisocyanate, and diphenylmethane-4 in the case of isocyanate.
  • the mixing ratio of the curing agent is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer is not sufficiently cured in the drying furnace, and lining may occur. If it exceeds 10 parts by mass, the excess curing agent may be transferred to the substrate or gasified at a high temperature to cause contamination.
  • the acrylic pressure-sensitive adhesive may be appropriately added with an antioxidant, an ultraviolet absorber, a silane coupling agent, a metal deactivator, etc., depending on the material of the adherend (glass or functional film). ..
  • the pressure-sensitive adhesive film using the polypropylene film of the present invention preferably has a pressure-sensitive adhesive layer thickness d of 2.0 ⁇ m or less. It is more preferably 1.5 ⁇ m or less, still more preferably 1.0 ⁇ m or less. If the thickness d of the adhesive layer exceeds 2.0 ⁇ m, the slipperiness between the back surface of the base film and the surface of the adhesive layer may deteriorate and winding may become difficult. In addition, the adhesive layer may not be sufficiently dried in the drying oven, resulting in lining. “Bleed” means that after applying a solution of an adhesive layer on one side of a base film, it is dried and cured in a drying furnace, and the adhesive film of the present invention is wound into a roll without passing through a release film.
  • the adhesive film is unwound during use, a part of the adhesive layer is transferred to the back surface of the base film.
  • a known technique can be used for the method of setting the thickness of the adhesive layer in the above range, and it can be controlled by adjusting the solid content concentration of the solution of the adhesive layer and the coating thickness in various coating methods. If the thickness of the adhesive layer is too thin, stable coating may be difficult, or the adhesive strength may be too low to adhere to the adherend. Therefore, the lower limit is about 0.1 ⁇ m.
  • the adhesive film using the polypropylene film of the present invention preferably has a 180 ° peeling force of 200 mN / 25 mm or less after being attached to an acrylic plate.
  • the peeling force is more preferably 100 mN / 25 mm or less, still more preferably 80 mN / 25 mm or less. If the peeling force exceeds 200 mN / 25 mm, the slipperiness between the back surface of the base film and the surface of the adhesive layer deteriorates, which may make winding difficult or line-off may occur.
  • the composition and thickness of the adhesive layer are set in the range described later, and the raw material composition and film forming conditions of the film are set in the range described later, and the surface roughness of the base film is controlled. Is effective. If the peeling force is less than 10 mN / 25 mm, the adhesive film may peel off during transportation after bonding with the adherend, so the lower limit is about 10 mN / 25 mm.
  • the coating agent can be used by dissolving the above-mentioned additives such as a pressure-sensitive adhesive and a curing agent in a solvent.
  • the solvent can be appropriately adjusted depending on the drying temperature of the coater, the viscosity of the coating material, and the like.
  • At least one solvent selected from -methoxy-2-propanol, propylene glycol monomethyl ether, cyclohexanone, toluene, ethyl acetate, butyl acetate, isopropyl acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetyl acetone and acetyl acetone can be used.
  • the solid content concentration in the coating material is appropriately selected depending on the viscosity of the coating material and the thickness of the adhesive layer, but is preferably 5 to 20% by mass.
  • the above-mentioned base film is conveyed to the coater, and the coating agent for the adhesive layer is applied.
  • the surface to be coated with the adhesive layer may be either surface of the base film, but the coated surface may be pretreated with a corona treatment or the like in advance to improve the wettability with the coating agent. preferable.
  • the coating method (coating method) is not particularly limited, and existing coating methods such as a metabar method, a doctor blade method, a gravure method, a die method, a knife method, a reverse method, and a dip method can be adopted.
  • the thickness of the adhesive layer is as thin as 2.0 ⁇ m or less, and the gravure method or the reverse method is preferable from the viewpoint of stably obtaining the thin coating layer.
  • the drying temperature is appropriately set depending on the heat resistance of the base film and the boiling point of the solvent, but is preferably 60 to 170 ° C. If the temperature is lower than 60 ° C., the adhesive layer may not be sufficiently cured and betrayed may occur. If it exceeds 170 ° C., the base film may be deformed and the flatness may be deteriorated.
  • the drying time is preferably 15 to 60 seconds. If it is less than 15 seconds, the adhesive layer may not be sufficiently cured and betrayed may occur. If it exceeds 60 seconds, the productivity will decrease, which is not preferable.
  • the dried adhesive film is wound with a winder without attaching a release film or the like to the adhesive surface to obtain an adhesive film roll.
  • the pressure-sensitive adhesive film of the present invention has the above-mentioned structure, so that the pressure-sensitive adhesive layer is sufficiently cured and the slipperiness between the back surface of the base film and the surface of the pressure-sensitive adhesive layer is good. Therefore, the pressure-sensitive adhesive film is wound without a release film. Even if it is taken, there is no problem such as line-up or wrinkles during winding, and a high-quality adhesive film roll can be obtained.
  • the adhesive film of the present invention obtained as described above can be used for various purposes such as packaging film, surface protective film, process film, sanitary product, agricultural product, building product, medical product, etc., but particularly on the surface. Since it is excellent in smoothness, it can be preferably used as a surface protective film or a process film.
  • the polypropylene film of the present invention is excellent in heat resistance and quality, it can be preferably used as a release film that requires extremely high quality in optical members and semiconductor manufacturing processes.
  • the Young's modulus was measured at 23 ° C. and 65% RH using a film strength elongation measuring device (AMF / RTA-100) manufactured by Orientec Co., Ltd.
  • the sample was cut into a size of measurement direction (main orientation axis direction and direction orthogonal to it): 25 cm, direction perpendicular to the measurement direction: 1 cm, stretched at an original length of 100 mm and a tensile speed of 300 mm / min, and the Young ratio was JIS. -Measured according to the method specified in Z1702 (1994).
  • Young's modulus at 120 ° C. Young's modulus at 120 ° C. is chucked into an oven heated to 120 ° C. using a film strength elongation measuring device (AMF / RTA-100) manufactured by Orientec Co., Ltd. After charging for 1 minute, the film was subjected to a tensile test at a tensile speed of 300 mm / min. The sample is cut into a size of 25 cm in the measurement direction (orthogonal direction of the main orientation axis) and 1 cm in the direction perpendicular to the measurement direction, stretched at an original length of 100 mm and a tensile speed of 300 mm / min, and specified in JIS-Z1702 (1994). It was measured according to the above method.
  • Thickness unevenness A polypropylene film was prepared, the film was cut into a width of 10 mm, and 20 points were measured at intervals of 50 mm in the main orientation axis direction. The average value of the obtained 20 points of data is calculated, the difference between the maximum value and the minimum value (absolute value) is calculated, and the value obtained by dividing the absolute value of the difference between the minimum value and the maximum value by the average value is the main component of the film. The thickness was uneven in the axis of orientation. The measurement was carried out in an atmosphere of 23 ° C. and 65% RH using a contact-type electronic micrometer manufactured by Anritsu Co., Ltd. (K-312A type).
  • Crystallization peak temperature (Tc) Using a differential scanning calorimeter (EXSTAR DSC6220 manufactured by Seiko Instruments Inc.), each layer of 3 mg polypropylene film was heated from 25 ° C. to 250 ° C. at 20 ° C./min and held for 5 minutes in a nitrogen atmosphere. Then, the temperature is lowered from 250 ° C. to 25 ° C. at 20 ° C./min. The peak temperature of the heat generation curve obtained at the time of this temperature decrease was defined as the crystallization temperature (Tc) of the polypropylene film. When a plurality of peak temperatures could be observed, the highest temperature in the region of 80 ° C. to 130 ° C. was defined as the crystallization temperature (Tc) of the polypropylene film.
  • the height of the curled bonded sample is less than 5 mm.
  • A The height of the curled bonded sample is 5 mm or more and less than 10 mm.
  • B The height of the curled bonded sample is 10 mm or more and less than 15 mm.
  • C The height of the curled bonded sample is 15 mm or more.
  • Width shrinkage rate (%) (500-adhesive film width) / 500 x 100 Based on the calculated width shrinkage rate, evaluation was made according to the following criteria.
  • the width shrinkage rate is less than 0.5%.
  • Example 1 As a raw material for the surface layer (I), 98.5 parts by mass of a homopolypropylene raw material A (MFR: 7.5 g / 10 minutes, melting point: 163 ° C., CXS: 1.0%) manufactured by Sumitomo Chemical Co., Ltd. 1.5 parts by mass of the nutter-catalyzed branched-chain polypropylene raw material B (Profax PF-814) is dry-blended and supplied to a single-screw extruder for the surface layer (I) as a raw material for the inner layer (II).
  • the end was gripped by a clip and introduced into a tenter type stretching machine, preheated at 180 ° C. for 5 seconds, stretched 9.6 times at 170 ° C., and at 167 ° C. while giving 14% relaxation in the width direction.
  • a heat treatment was performed, and then the film was guided to the outside of the tenter through a cooling step of 100 ° C., the clip at the end of the film was released, and the film was wound around a core to obtain a polypropylene film having a thickness of 25 ⁇ m.
  • Table 1 shows the physical properties of the obtained film and the evaluation results.
  • Example 2 Homopolypropylene raw material D (MFR: 3.0 g / 10 minutes, melting point: 164 ° C, CXS: 3.3%) manufactured by Prime Polymer Co., Ltd. 90 parts by mass, 4-Methyl-1-manufactured by Mitsui Chemicals, Inc. Raw materials are supplied from the measuring hopper to the twin-screw extruder so that 10 parts by mass of the penten-based polymer "MX004" (melting point: 230 ° C.) is mixed at this ratio, melt-kneaded at 260 ° C., and from the die in a strand shape.
  • MFR 3.0 g / 10 minutes, melting point: 164 ° C, CXS: 3.3%) manufactured by Prime Polymer Co., Ltd. 90 parts by mass, 4-Methyl-1-manufactured by Mitsui Chemicals, Inc.
  • Raw materials are supplied from the measuring hopper to the twin-screw extruder so that 10 parts by mass of
  • a polypropylene raw material (1) As a raw material for the surface layer (I), 98 parts by mass of the homopolypropylene raw material C and 2 parts by mass of the polypropylene raw material (1) are dry-blended and supplied to a single-screw extruder for the surface layer (I). As a raw material for the inner layer (II), 98.5 parts by mass of the homopolypropylene raw material C and 1.5 parts by mass of the branched polypropylene raw material B are dry-blended to form a single shaft for the inner layer (II).
  • the end was gripped by a clip and introduced into a tenter type stretching machine, preheated at 179 ° C. for 5 seconds, stretched 9.5 times at 173 ° C., and at 148 ° C. while giving 11% relaxation in the width direction.
  • a heat treatment was performed, and then the film was guided to the outside of the tenter through a cooling step of 100 ° C., the clip at the end of the film was released, and the film was wound around a core to obtain a polypropylene film having a thickness of 25 ⁇ m.
  • Table 1 shows the physical properties of the obtained film and the evaluation results.
  • Example 3 As a raw material for the surface layer (I), 98 parts by mass of the homopolypropylene raw material A and 2 parts by mass of the polypropylene raw material (1) are dry-blended and supplied to a single-screw extruder for the surface layer (I). As a raw material for the inner layer (II), 70 parts by mass of the homopolypropylene raw material C and 30 parts by mass of the homopolypropylene raw material A are dry-blended and supplied to a single-screw extruder for the inner layer (II) layer.
  • Melt extrusion is performed at 250 ° C., foreign matter is removed with a 20 ⁇ m cut sintered filter, and then laminated with a feed block type A / B / A composite T-die at a thickness ratio of 1/8/1, and the surface is heated to 58 ° C.
  • the material was discharged to a temperature-controlled casting drum and brought into close contact with the casting drum with an air knife to obtain an unstretched sheet. Subsequently, the sheet was preheated to 144 ° C. using a ceramic roll, and stretched 4.4 times in the longitudinal direction of the film between rolls at 138 ° C. provided with a peripheral speed difference.
  • the end was gripped with a clip and introduced into a tenter type stretching machine, preheated at 176 ° C for 5 seconds, stretched 8.8 times at 167 ° C, and at 163 ° C while giving 9% relaxation in the width direction.
  • a heat treatment was performed, and then the film was guided to the outside of the tenter through a cooling step of 100 ° C., the clip at the end of the film was released, and the film was wound around a core to obtain a polypropylene film having a thickness of 25 ⁇ m.
  • Table 1 shows the physical properties of the obtained film and the evaluation results.
  • Example 4 As a raw material for the surface layer (I), 95.7 parts by mass of the homopolypropylene raw material D, 2.3 parts by mass of the branched polypropylene raw material B, and 2 parts by mass of the polypropylene raw material (1) are dry-blended. It is supplied to a single-screw extruder for the surface layer (I), and 97.7 parts by mass of the homopolypropylene raw material D and 2.3 parts by mass of the branched polypropylene raw material B as raw materials for the inner layer (II).
  • the parts are dry-blended and supplied to a single-screw extruder for the inner layer (II) layer, melt-extruded at 250 ° C., and after removing foreign matter with a 20 ⁇ m-cut sintering filter, feed block type A / It was laminated with a B / A composite T-die at a thickness ratio of 1/10/1, discharged to a casting drum whose surface temperature was controlled at 110 ° C., and brought into close contact with the casting drum with an air knife to obtain an unstretched sheet. Subsequently, the sheet was preheated to 159 ° C. using a ceramic roll, and stretched 4.1 times in the longitudinal direction of the film between rolls at 125 ° C. provided with a peripheral speed difference.
  • the end was gripped by a clip and introduced into a tenter type stretching machine, preheated at 180 ° C. for 5 seconds, stretched 10.2 times at 175 ° C., and at 140 ° C. while giving 14% relaxation in the width direction.
  • a heat treatment was performed, and then the film was guided to the outside of the tenter through a cooling step of 100 ° C., the clip at the end of the film was released, and the film was wound around a core to obtain a polypropylene film having a thickness of 25 ⁇ m.
  • Table 1 shows the physical properties of the obtained film and the evaluation results.
  • Example 5 As a raw material for the surface layer (I), 98.5 parts by mass of the homopolypropylene raw material C and 1.5 parts by mass of the branched polypropylene raw material B are dry-blended to form a single shaft for the surface layer (I). Supply to a uniaxial extruder, 100 parts by mass of the homopolypropylene raw material C as a raw material for the inner layer (II) is supplied to a uniaxial uniaxial extruder for the inner layer (II) layer, and melt extrusion is performed at 250 ° C.
  • the end was gripped by a clip and introduced into a tenter type stretching machine, preheated at 177 ° C for 5 seconds, stretched 6.8 times at 169 ° C, and at 170 ° C while giving 16% relaxation in the width direction.
  • a heat treatment was performed, and then the film was guided to the outside of the tenter through a cooling step of 100 ° C., the clip at the end of the film was released, and the film was wound around a core to obtain a polypropylene film having a thickness of 25 ⁇ m.
  • Table 1 shows the physical properties of the obtained film and the evaluation results.
  • Example 6 As a raw material for the surface layer (I), 95 parts by mass of the homopolypropylene raw material D and 5 parts by mass of a metallocene catalytically branched branched polypropylene raw material (WAYMAX MFX3 manufactured by Japan Polypropylene Corporation) are dry-blended to form the surface layer (I). 100 parts by mass of the homopolypropylene raw material D as a raw material for the inner layer (II) is supplied to the single-screw extruder for the inner layer (II), and the temperature is 250 ° C.
  • WAYMAX MFX3 metallocene catalytically branched branched polypropylene raw material
  • the end was gripped by a clip and introduced into a tenter type stretching machine, preheated at 176 ° C for 5 seconds, stretched 7.8 times at 166 ° C, and at 153 ° C while giving 11% relaxation in the width direction.
  • a heat treatment was performed, and then the film was guided to the outside of the tenter through a cooling step of 100 ° C., the clip at the end of the film was released, and the film was wound around a core to obtain a polypropylene film having a thickness of 7 ⁇ m.
  • Table 1 shows the physical properties of the obtained film and the evaluation results.
  • a polypropylene resin (MFR: 2.0 g / 10 minutes) having a copolymerization composition of 98.4 parts by mass of a propylene component and 1.6 parts by mass of an ethylene component is supplied to a uniaxial extruder and sheeted from a T die at 280 ° C. After being extruded into a shape and cooled and solidified on a cooling roll at 60 ° C., it was longitudinally stretched 4.4 times by a heating roll stretching machine set at 141 ° C., and then 9.2 times laterally stretched by a tenter stretching machine set at 162 ° C. The film was stretched, transversely stretched, and then heat-treated at 170 ° C. to obtain a 30 ⁇ m polypropylene-based film. Table 1 shows the physical properties of the obtained film and the evaluation results.
  • the homopolypropylene raw material D is supplied to a single-screw melt extruder for the surface layer (I), melt-extruded at 240 ° C., and after removing foreign substances with an 80 ⁇ m-cut sintering filter, a feed block type
  • the particles were laminated with a B / A / B composite T-die at a thickness ratio of 1/50/1, and discharged to a cast drum whose surface temperature was controlled at 30 ° C. to obtain a cast sheet.
  • the film was preheated to 140 ° C. using a plurality of ceramic rolls and stretched 4.6 times in the longitudinal direction of the film.
  • the end portion was gripped by a clip and introduced into a tenter type stretching machine, preheated at 165 ° C. for 3 seconds, and then stretched 8.0 times at 160 ° C.
  • heat treatment is performed at 160 ° C while giving 10% relaxation in the width direction, and then the film is guided to the outside of the tenter through a cooling step at 130 ° C, the clip at the end of the film is released, and the film is wound around the core.
  • a polypropylene film having a thickness of 25 ⁇ m was obtained. Table 1 shows the physical properties of the obtained film and the evaluation results.
  • the raw material was supplied to an extruder, melt-kneaded at 300 ° C., discharged from a die in a strand shape, cooled and solidified in a water tank at 25 ° C., and cut into chips to obtain a polypropylene raw material (2).
  • the homopolypropylene raw material D is supplied to a single-screw melt extruder for the inner layer (II) layer, and the polypropylene raw material (2) is supplied to a single-screw melt extruder for the surface layer (I) layer at 240 ° C.
  • the cast drum is laminated with a feed block type A / B composite T-die at a thickness ratio of 8/1, and the surface temperature is controlled at 90 ° C.
  • a cast sheet was obtained by ejection. Then, the film was preheated to 125 ° C. using a plurality of ceramic rolls and stretched 4.6 times in the longitudinal direction of the film.
  • the end portion was gripped by a clip and introduced into a tenter type stretching machine, preheated at 165 ° C. for 3 seconds, and then stretched 8.0 times at 160 ° C.
  • heat treatment is performed at 160 ° C while giving 10% relaxation in the width direction, and then the film is guided to the outside of the tenter through a cooling step at 130 ° C, the clip at the end of the film is released, and the film is wound around the core.
  • a polypropylene film having a thickness of 15 ⁇ m was obtained. Table 1 shows the physical properties of the obtained film and the evaluation results.
  • the polypropylene was laminated at a thickness ratio of 1/10/1, discharged to a casting drum whose surface temperature was controlled at 35 ° C., and brought into close contact with the casting drum with an air knife to obtain an unstretched sheet. Subsequently, the sheet was preheated to 153 ° C. using a ceramic roll, and stretched 3.7 times in the longitudinal direction of the film between rolls at 148 ° C. provided with a peripheral speed difference. Next, the end was gripped with a clip and introduced into a tenter type stretching machine, preheated at 180 ° C. for 5 seconds, stretched 7.2 times at 178 ° C., and at 170 ° C. while giving 16% relaxation in the width direction.
  • the molten sheet was melt-extruded and solidified by cooling on a casting drum having a diameter of 1 m held at 90 ° C. at an air knife temperature of 90 ° C. and an air speed of 140 m / s.
  • the sheet was gradually preheated to 140 ° C., continuously maintained at a temperature of 145 ° C., passed between rolls provided with a peripheral speed difference, and stretched 4.8 times in the longitudinal direction.
  • a radiation heater output 3.5 kW was used in the stretched portion to supplement the amount of heat and stretch.
  • the film was led to a tenter, stretched 10 times in the width direction at a stretching temperature of 160 ° C., and then relaxed in three stages with a total relaxation rate of 23% in the width direction. (The first stage is 12.0%, the second stage is 9.0%, and the third stage is 3.9%.)
  • the heat treatment is performed at a heat fixing temperature of 150 ° C. and a cooling temperature of 140 ° C., and then at room temperature.
  • the mixture was rapidly cooled for 5 seconds to obtain a biaxially oriented polypropylene film having a film thickness of 3.0 ⁇ m. Table 1 shows the physical properties of the obtained film and the evaluation results.
  • the "direction orthogonal to the main orientation axis" in the table means a direction orthogonal to the direction of the main orientation axis.
  • the polypropylene film of the present invention can be used for various purposes such as packaging films, release films, process films, sanitary products, agricultural products, building products, and medical products.
  • it since it is excellent in heat resistance, mechanical strength, releasability, and quality, it can be preferably used as a releasable film or process film that passes through a high temperature process after being bonded to an adherend.

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Abstract

Un film de polypropylène selon la présente invention a une force de retrait thermique à 140°C inférieure ou égale à 400 mN à la fois dans une direction d'axe d'orientation principale et dans une direction perpendiculaire à celle-ci, et un module de Young supérieur ou égal à 1,8 GP à la fois dans la direction d'axe d'orientation principale et dans la direction perpendiculaire à celle-ci.　L'invention concerne un film de polypropylène ayant une résistance thermique et une qualité excellentes.
PCT/JP2020/013262 2019-03-28 2020-03-25 Film de polypropylène WO2020196602A1 (fr)

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WO2022210688A1 (fr) 2021-03-31 2022-10-06 東レ株式会社 Film de polypropylène
KR20230164012A (ko) 2021-03-31 2023-12-01 도레이 카부시키가이샤 폴리프로필렌 필름

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KR20230164014A (ko) 2021-03-31 2023-12-01 도레이 카부시키가이샤 폴리프로필렌 필름

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