WO2023234417A1 - Film de démoulage - Google Patents

Film de démoulage Download PDF

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Publication number
WO2023234417A1
WO2023234417A1 PCT/JP2023/020725 JP2023020725W WO2023234417A1 WO 2023234417 A1 WO2023234417 A1 WO 2023234417A1 JP 2023020725 W JP2023020725 W JP 2023020725W WO 2023234417 A1 WO2023234417 A1 WO 2023234417A1
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WO
WIPO (PCT)
Prior art keywords
film
release
layer
polypropylene
less
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PCT/JP2023/020725
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English (en)
Japanese (ja)
Inventor
健介 種木
徹 今井
一仁 堀之内
Original Assignee
東洋紡株式会社
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Publication of WO2023234417A1 publication Critical patent/WO2023234417A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • 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
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B32B7/028—Heat-shrinkability
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating

Definitions

  • the present invention relates to a polypropylene release film that has excellent rigidity and heat resistance. More specifically, the present invention relates to a polypropylene release film that has good flatness during release processing even when the film thickness is thinner than conventional products, and is suitable for process release films with small unevenness in release properties.
  • Biaxially oriented polypropylene films are moisture-proof and have the necessary rigidity and heat resistance, so they are used for industrial purposes such as packaging, mold release, and adhesive tapes.
  • environmental considerations have required release films to be recyclable and to reduce volume through thinning, so it has become essential to significantly improve the rigidity of polypropylene films.
  • As a means to improve rigidity it is possible to improve the crystallinity and melting point of polypropylene resin by improving the catalyst and process technology during polymerization of polypropylene resin, and to improve the degree of orientation of the film by increasing the stretching ratio during the film forming process.
  • There was a technology to increase However, there is a problem in that the heat resistance decreases while increasing the rigidity, and so far there has been no biaxially oriented polypropylene film with sufficient rigidity and heat resistance.
  • stretched polypropylene films have been proposed that have heat resistance at 150°C comparable to biaxially oriented PET films (see, for example, Patent Documents 3 and 4), but further improvements in lamination strength are expected. .
  • An object of the present invention is to solve the above-mentioned problems. That is, the present invention relates to a polypropylene release film that has both film rigidity and heat resistance at temperatures as high as 150°C.
  • the purpose of the present invention is to solve the above-mentioned conventional problems and to reduce the amount of film waste after use in order to reduce the environmental impact. It is an object of the present invention to provide a release film which is suitable for process release films and the like, which has good flatness without causing any blemishes, and has small irregularities in release properties.
  • the ratio of the thickness of the base material layer A to the thickness of the film is 70% or more and 98% or less.
  • the mesopentad fraction of the polypropylene resin constituting the base layer A is 97.0% or more and 99.9% or less.
  • the mesopentad fraction of the polypropylene resin constituting the surface layer B is 80.0% or more and 96.5% or less.
  • the plane orientation coefficient measured from the surface layer B side of the film is 0.0134 or less.
  • the 150°C heat shrinkage rate in the longitudinal direction of the film is 6.0% or less.
  • the 150°C heat shrinkage rate in the width direction of the film is 5.0% or less.
  • non-silicone resin is at least one selected from fluororesins, alkyd resins, various waxes, and aliphatic olefins.
  • release film of the present invention that does not generate wrinkles or curls during mold release processing, has good flatness, has small irregularities in mold release properties, and is suitable for process release films. I can do it.
  • the release film according to the present invention is a biaxially oriented laminated polypropylene film including at least a base layer A and a surface layer B, and a release coating layer.
  • the biaxially oriented laminated polypropylene film in the present invention is a biaxially oriented laminated polypropylene film that includes at least a base layer A and a surface layer B.
  • the base layer A and the surface layer B are made of a polypropylene resin composition, and the polypropylene resin composition has a polypropylene resin as a main component.
  • main component means that the proportion of the polypropylene resin in the polypropylene resin composition is 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, particularly preferably is 97% by mass or more.
  • the mesopentad fraction ([mmmm]%) which is an index of the stereoregularity of the polypropylene resin constituting the base layer A in the present invention, is 97.0% or more and 99.9% or less, and 97.5% or more. , 99.7% or less, more preferably 98.0% or more and 99.5% or less, and even more preferably 98.5% or more and 99.3% or less.
  • the polypropylene resin used in the base layer A is a mixture of a plurality of polypropylene resins
  • the mesopentad fraction of the mixture is also preferably within the same range as above.
  • the mesopentad fraction of the polypropylene resin constituting the base layer A in the present invention is 97.0% or more, the crystallinity of the polypropylene resin increases, and the melting point, crystallinity, and crystal orientation of the crystals in the film improve. , it is easy to obtain rigidity and heat resistance at high temperatures. If it is 99.9% or less, it is preferable because there will be less breakage during film production and it will be easier to reduce the production cost of polypropylene resin.
  • the mesopentad fraction is measured by nuclear magnetic resonance method (so-called NMR method).
  • Polypropylene resin used for base layer A As the polypropylene resin used for the base layer A in the present invention, a polypropylene homopolymer or a copolymer with ethylene and/or an ⁇ -olefin having 4 or more carbon atoms can be used.
  • a propylene homopolymer that does not substantially contain ethylene and/or an ⁇ -olefin having 4 or more carbon atoms is preferable, and even when it contains ethylene and/or an ⁇ -olefin component having 4 or more carbon atoms, ethylene and/or
  • the amount of the ⁇ -olefin component having 4 or more carbon atoms is preferably 1 mol % or less.
  • the upper limit of the component amount is more preferably 0.5 mol%, still more preferably 0.3 mol%, particularly preferably 0.1 mol%, and most preferably 0%. Within the above range, rigidity and heat resistance tend to improve.
  • the ⁇ -olefin component having 4 or more carbon atoms constituting such a copolymer include 1-butene, 1-pentene, 3-methylpentene-1, 3-methylbutene-1, 1-hexene, and 4-methyl.
  • Examples include pentene-1, 5-ethylhexene-1, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
  • the polypropylene resin two or more different polypropylene homopolymers, a copolymer with ethylene and/or an ⁇ -olefin having 4 or more carbon atoms, or a mixture thereof can be used.
  • the lower limit of the melting temperature (Tm) (hereinafter abbreviated as TmA) measured by DSC of the polypropylene resin used for the base material layer A is preferably 160°C, more preferably 161°C, and even more preferably 162°C. °C, and even more preferably 163°C.
  • TmA melting temperature measured by DSC of the polypropylene resin used for the base material layer A
  • the upper limit of TmA is preferably 180°C, more preferably 178°C. When TmA is 180° C. or less, it is easy to suppress cost increases in terms of manufacturing polypropylene resin.
  • the TmA of the mixture is also preferably within the same range as above.
  • Tm refers to the temperature of approximately 5 mg of sample packed in an aluminum pan, set in a differential scanning calorimeter (DSC), heated to 230°C at a scanning rate of 10°C/min under a nitrogen atmosphere, and melted at 230°C for 5 minutes.
  • DSC differential scanning calorimeter
  • TmA the peak temperature on the lower temperature side is defined as TmA.
  • the lower limit of the crystallization temperature (Tc: hereinafter sometimes abbreviated as Tc) measured by DSC of the polypropylene resin used for the base layer A is 105°C, preferably 108°C, and more preferably 110°C. °C, more preferably 114°C.
  • Tc crystallization temperature measured by DSC of the polypropylene resin used for the base layer A
  • the upper limit of Tc is preferably 135°C, more preferably 133°C, even more preferably 132°C, even more preferably 130°C, particularly preferably 128°C, and most preferably 127°C. It is.
  • Tc is 135° C. or less, it is possible to suppress an increase in cost in terms of polypropylene production, and it is easy to suppress breakage during film formation.
  • the polypropylene resin used in the base layer A is a mixture of a plurality of polypropylene resins
  • the crystallization temperature of the mixture is also preferably within the same range as above.
  • Tc is about 5 mg of sample packed in an aluminum pan, set in DSC, heated to 230 °C at a scanning speed of 10 °C/min under nitrogen atmosphere, melted at 230 °C for 5 minutes, and then heated to 230 °C at a scanning speed of -10 °C.
  • melt flow rate of polypropylene resin used for base material layer A The melt flow rate (MFR: hereinafter sometimes abbreviated as MFR) of the polypropylene resin used for the base material layer A is when measured in accordance with condition M (230 ° C., 2.16 kgf) of JIS K7210 (1995). In, preferably 6.0 g/10 minutes or more and 10 g/10 minutes or less, more preferably 6.2 g/10 minutes or more and 9.0 g/10 minutes or less, 6.3 g/10 minutes or more, It is more preferably 8.5 g/10 minutes or less, particularly preferably 6.4 g/10 minutes or more and 8.0 g/10 minutes or less, and 6.5 g/10 minutes or more and 7.5 g/10 minutes or less.
  • the MFR of the mixture is preferably 6.0 g/10 minutes or more and 10 g/10 minutes or less, and 6.2 g/10 minutes. More preferably, it is 9.0 g/10 minutes or less, more preferably 6.3 g/10 minutes or more and 8.5 g/10 minutes or less, and 6.4 g/10 minutes or more and 8.0 g/10 minutes. It is especially preferable that it is below, and most preferable that it is 6.5 g/10 minutes or more and 7.5 g/10 minutes or less.
  • the MFR of the polypropylene resin is 6.0 g/10 minutes or more, it is easy to obtain a biaxially oriented laminated polypropylene film with low heat shrinkage. Further, when the MFR of the polypropylene resin is 10 g/10 minutes or less, film forming properties can be easily improved.
  • the polypropylene resin used in the base layer A is a mixture of multiple polypropylene resins
  • the MFR of each polypropylene resin is preferably 2.5 g/10 minutes or more and 30 g/10 minutes or less, and 3.5 g/10 It is more preferable that it is 4.5 g/10 minutes or more and 22 g/10 minutes or less, and especially that it is 5.5 g/10 minutes or more and 20 g/10 minutes or less.
  • it is 6.0 g/10 minutes or more and most preferably 20 g/10 minutes or less.
  • a method of controlling the average molecular weight and molecular weight distribution of the polypropylene resin is preferably employed.
  • the propylene resin composition constituting the base layer A can contain an antistatic agent such as a diethanolamine fatty acid ester compound, an amine compound, or a glycerin monofatty acid ester compound.
  • an antistatic agent such as a diethanolamine fatty acid ester compound, an amine compound, or a glycerin monofatty acid ester compound.
  • additives used in base layer A may be added to the polypropylene resin composition constituting the base layer A, as long as they do not impair the effects of the present invention. Therefore, it contains anti-blocking agents such as fine particles, lubricants such as wax and metal soap, plasticizers, processing aids, and well-known heat stabilizers, antioxidants, and ultraviolet absorbers that are usually added to polypropylene films. It is also possible to do so.
  • inorganic fine particles examples include silicon dioxide, calcium carbonate, titanium dioxide, talc, kaolin, mica, and zeolite, and the shapes of these particles are not limited to spherical, elliptical, conical, and irregular shapes.
  • the particle size can also be adjusted as desired depending on the purpose and method of use of the film.
  • organic fine particles crosslinked particles obtained by crosslinking acrylic resin, methyl acrylate resin, styrene-butadiene resin, etc. can be used, and in terms of shape and size, they are similar to inorganic fine particles. It is possible to use a variety of different ones. It is also possible to perform various surface treatments on the surfaces of these inorganic or organic fine particles, and these can be used alone or in combination of two or more.
  • the mesopentad fraction ([mmmm]%) which is an index of the stereoregularity of the polypropylene resin constituting the surface layer B, is 80.0% or more and 96.5% or less, and 85.0% or more and 96.5%. % or less, more preferably 90.0% or more and 96.5% or less.
  • the stereoregularity of the mixture is also preferably within the same range as above.
  • the mesopentad fraction of each polypropylene resin is preferably 80.0% or more and 98.0% or less.
  • the mesopentad fraction of the polypropylene resin constituting the surface layer B is 96.5% or less, it is easy to increase the adhesiveness with the release layer.
  • the mesopentad fraction of the polypropylene resin constituting the surface layer B is 80.0% or more, the rigidity and heat resistance of the film can be easily obtained.
  • the mesopentad fraction is measured by nuclear magnetic resonance method (so-called NMR method).
  • Polypropylene resin used for surface layer B As the polypropylene resin used for the surface layer B, a polypropylene homopolymer or a copolymer with ethylene and/or an ⁇ -olefin having 4 or more carbon atoms can be used.
  • a propylene homopolymer that does not substantially contain ethylene and/or an ⁇ -olefin having 4 or more carbon atoms is preferable, and even when it contains ethylene and/or an ⁇ -olefin component having 4 or more carbon atoms, ethylene and/or
  • the upper limit of the amount of the ⁇ -olefin component having 4 or more carbon atoms is preferably 1 mol% or less, more preferably 0.5 mol%, even more preferably 0.3 mol%, and particularly preferably 0. .1 mol%, most preferably 0%. Within the above range, rigidity and heat resistance tend to improve.
  • Examples of the ⁇ -olefin component having 4 or more carbon atoms constituting such a copolymer include 1-butene, 1-pentene, 3-methylpentene-1, 3-methylbutene-1, 1-hexene, and 4-methyl. Examples include pentene-1, 5-ethylhexene-1, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
  • the polypropylene resin two or more different polypropylene homopolymers, a copolymer with ethylene and/or an ⁇ -olefin having 4 or more carbon atoms, or a mixture thereof can be used.
  • TmB melting temperature measured by DSC of the polypropylene resin used for the surface layer B
  • TmB melting temperature measured by DSC of the polypropylene resin used for the surface layer B
  • the upper limit of TmB is preferably 170°C, more preferably 169°C, still more preferably 168°C, even more preferably 167°C, particularly preferably 166°C.
  • the TmB of the mixture is also preferably within the same range as above.
  • Tm refers to the temperature of approximately 5 mg of sample packed in an aluminum pan, set in a differential scanning calorimeter (DSC), heated to 230°C at a scanning rate of 10°C/min under a nitrogen atmosphere, and melted at 230°C for 5 minutes.
  • DSC differential scanning calorimeter
  • TmB is the main peak temperature of the endothermic peak associated with melting, which is observed when the temperature is lowered to 30°C at a scanning rate of -10°C/min, held for 5 minutes, and then raised at a scanning rate of 10°C/min.
  • TmB the peak temperature on the lower temperature side
  • the lower limit of the crystallization temperature (Tc) measured by DSC of the polypropylene resin used for the surface layer B is 95°C, preferably 100°C, and more preferably 105°C.
  • Tc crystallization temperature measured by DSC of the polypropylene resin used for the surface layer B
  • the upper limit of Tc is preferably 115°C, more preferably 113°C.
  • the Tc of the mixture is also preferably within the same range as above.
  • Tc is about 5 mg of sample packed in an aluminum pan, set in DSC, heated to 230 °C at a scanning speed of 10 °C/min under nitrogen atmosphere, melted at 230 °C for 5 minutes, and then heated to 230 °C at a scanning speed of -10 °C. This is the main peak temperature of the exothermic peak observed when the temperature is lowered to 30° C./min. When multiple peaks are observed, the peak temperature on the low temperature side is defined as Tc.
  • the melt flow rate (MFR) of the polypropylene resin used for the surface layer B is 2.8 g/10 minutes or more, 5 It is preferably .0 g/10 minutes or less, more preferably 3.0 g/10 minutes or more and 5.0 g/10 minutes or less, and 3.0 g/10 minutes or more and 4.5 g/10 minutes or less. More preferably, it is 3.0 g/10 minutes or more and 4.0 g/10 minutes or less.
  • the MFR of the mixture of polypropylene resins is preferably 2.8 g/10 minutes or more and 5.0 g/10 minutes or less; 3. It is more preferably 0 g/10 minutes or more and 5.0 g/10 minutes or less, and even more preferably 3.0 g/10 minutes or more and 4.0 g/10 minutes or less.
  • the MFR of the polypropylene resin is 2.8 g/10 minutes or more, it is easy to obtain a biaxially oriented laminated polypropylene film with low heat shrinkage.
  • the MFR of the polypropylene resin is 5.0 g/10 minutes or less, film forming properties tend to improve and defects are less likely to occur during film forming.
  • the MFR of each polypropylene resin is preferably 2.0 g/10 minutes or more and 5.0 g/10 minutes or less, and 2.2 g/10 minutes or more. It is more preferably 10 minutes or more and 5.0 g/10 minutes or less, and even more preferably 2.3 g/10 minutes or more and 4.5 g/10 minutes or less.
  • the MFR of the polypropylene resin used for the surface layer B is preferably close to the MFR of the polypropylene resin used for the base layer A from the viewpoint of uniformity of the thickness of the laminated film.
  • the polypropylene resin composition constituting the surface layer B may contain various additives to improve quality such as slipperiness and antistatic properties, for example, to improve productivity.
  • Anti-blocking agents such as fine particles, lubricants such as waxes and metal soaps, plasticizers, processing aids, and well-known heat stabilizers, antioxidants, ultraviolet absorbers, and inorganic and organic substances that are usually added to polypropylene films. It is also possible to blend fine particles and the like.
  • inorganic fine particles examples include silicon dioxide, calcium carbonate, titanium dioxide, talc, kaolin, mica, and zeolite, and the shapes of these particles are not limited to spherical, elliptical, conical, and irregular shapes.
  • the particle size can also be adjusted as desired depending on the purpose and method of use of the film.
  • organic fine particles crosslinked particles such as acrylic, methyl acrylate, and styrene-butadiene can be used, and in terms of shape and size, various types can be used like inorganic fine particles. It is possible. It is also possible to perform various surface treatments on the surfaces of these inorganic or organic fine particles, and these can be used alone or in combination of two or more.
  • the total thickness of the biaxially oriented laminated polypropylene film in the present invention varies depending on its purpose and method of use, but from the viewpoint of film strength and resource saving, the lower limit is preferably 5 ⁇ m, more preferably 6 ⁇ m, even more preferably 8 ⁇ m, and 10 ⁇ m. is particularly preferred.
  • the upper limit is preferably 60 ⁇ m, more preferably 40 ⁇ m, even more preferably 35 ⁇ m, particularly preferably 25 ⁇ m, and most preferably 19 ⁇ m. If the total thickness of the film is within this range, it is possible to contribute to resource conservation by making the film thinner while ensuring strength. It may be preferable for the total layer thickness of the film to be larger than 60 ⁇ m depending on the application, and it can generally be used if the total layer thickness of the film is up to 200 ⁇ m.
  • the lower limit of the thickness of the base layer A varies depending on its purpose and method of use, but from the viewpoint of film rigidity and water vapor barrier properties, 5 ⁇ m is preferable.
  • the upper limit of the thickness of the base material layer A is preferably 50 ⁇ m, more preferably 35 ⁇ m, even more preferably 20 ⁇ m or less, and particularly preferably 18 ⁇ m in terms of transparency and environmental impact.
  • the thickness of the base material layer A may be preferably greater than 50 ⁇ m depending on the application, but it can generally be used if it is up to 200 ⁇ m.
  • the lower limit of the thickness of the surface layer B varies depending on its purpose and method of use, but from the viewpoint of adhesiveness with the release layer and antistatic properties, it is preferably 0.3 ⁇ m, more preferably 0.5 ⁇ m, and 0.8 ⁇ m or more. is even more preferable.
  • the upper limit of the thickness of the surface layer B varies depending on its purpose and method of use, but from the viewpoint of film rigidity and heat resistance at high temperatures, it is preferably 4 ⁇ m, and more preferably 2 ⁇ m. Moreover, when the thickness of the surface layer B is large, it is easy to reduce the planar orientation coefficient.
  • the lower limit of the ratio of the thickness of the base layer A to the thickness of the entire film is 70% from the viewpoint of rigidity and heat resistance at high temperatures, more preferably 75%, further preferably 80%, and particularly preferably 85%.
  • the upper limit of the ratio of the thickness of the base layer A to the thickness of the entire film is preferably 98% or less, more preferably 95% or less, and even more preferably 92% or less in order to maintain the function of the surface layer B.
  • the lower limit of the ratio of the thickness of the surface layer B to the thickness of the entire film is preferably 2% from the viewpoint of adhesiveness with the release layer and antistatic property, more preferably 3%, even more preferably 5%, and 8% or more. is more preferable.
  • the upper limit of the ratio of the thickness of the base material layer B to the thickness of the entire film is preferably 30% or less from the viewpoint of rigidity and heat resistance at high temperatures, more preferably 23%, even more preferably 20% or less, and 15% or less. Particularly preferred.
  • the layer structure of the biaxially oriented laminated polyolefin film in the present invention includes surface layer B/base layer A and surface layer B/base layer A/surface layer B.
  • an intermediate layer may be provided between the base material layer A and the surface layer B, and the raw material composition of the intermediate layer is the same as that of the base material layer A.
  • the biaxially oriented laminated polypropylene film in the present invention is obtained by preparing an unstretched sheet made of a polypropylene resin composition containing the above-mentioned polypropylene resin as a main component, and then biaxially stretching the sheet.
  • any of the inflation simultaneous biaxial stretching method, tenter simultaneous biaxial stretching method, and tenter sequential biaxial stretching method may be adopted, but from the viewpoint of film forming stability and thickness uniformity, tenter It is preferable to employ a sequential biaxial stretching method. In particular, it is preferable to stretch in the longitudinal direction and then in the width direction, but a method of stretching in the width direction and then in the longitudinal direction may also be used.
  • a method for producing a biaxially oriented laminated polypropylene film according to the present invention will be described, but the method is not necessarily limited thereto.
  • surface layer B/base layer A/surface layer B will be described in which a tenter sequential biaxial stretching method is adopted.
  • a multilayer sheet of molten polypropylene resin composition having the structure of surface layer B/base layer A/surface layer B is extruded from a T-die.
  • This method is to co-extrude polypropylene resins sent from different flow paths using two or more extruders while laminating them into multiple layers using a multilayer feed block, static mixer, multilayer multi-manifold die, etc. etc. can be used.
  • the sheet is stretched in the longitudinal direction by two pairs of heated stretching rolls by increasing the rotational speed of the rear stretching roll to obtain a uniaxially stretched film.
  • the uniaxially stretched film is stretched in the width direction at a specific temperature while gripping the ends of the film using a tenter-type stretching machine to obtain a biaxially stretched film.
  • the biaxially stretched film is heat treated at a specific temperature. In the heat treatment step, the film may be relaxed in the width direction.
  • the biaxially oriented laminated polypropylene film thus obtained can be subjected to a corona discharge treatment, for example, on at least one side, if necessary, and then wound up with a winder to obtain a film roll.
  • a polypropylene resin composition containing polypropylene resin as a main component is heated and melted in a range of 200°C or higher and 300°C or lower using a single-screw or twin-screw extruder, and a sheet-shaped molten polypropylene resin composition comes out from a T-die. is cooled and solidified by contacting it with a metal cooling roll. It is preferable that the obtained unstretched sheet is further placed in a water tank.
  • the temperature of the cooling roll or the cooling roll and the water tank is preferably a temperature that can suppress crystallization, and if it is desired to increase the transparency of the film, it is preferable to solidify by cooling with a cooling roll at 50° C. or lower.
  • the cooling temperature is 50°C or lower, the transparency of the unstretched sheet tends to increase, and the cooling temperature is preferably 40°C or lower.
  • the cooling temperature is also preferable to set the cooling temperature to 30° C. or higher.
  • the thickness of the unstretched sheet is preferably 3,500 ⁇ m or less in terms of cooling efficiency, more preferably 3,000 ⁇ m or less, and can be adjusted as appropriate depending on the film thickness after successive biaxial stretching.
  • the thickness of the unstretched sheet can be controlled by the extrusion speed of the polypropylene resin composition, the lip width of the T-die, etc.
  • the lower limit of the longitudinal stretching ratio is preferably 3 times, more preferably 3.5 times, particularly preferably 3.8 times. Within the above range, strength can be easily increased and thickness unevenness can be reduced.
  • the upper limit of the longitudinal stretching ratio is preferably 4.3 times, more preferably 4.2 times, particularly preferably 4.1 times. Within the above range, stretchability in the width direction stretching step is good and productivity is improved.
  • the lower limit of the longitudinal stretching temperature is preferably TmA-40°C, more preferably TmA-37°C, and even more preferably TmA- The temperature is 35°C. Within the above range, it is easy to reduce the heat shrinkage rate, facilitate the subsequent stretching in the width direction, and reduce thickness unevenness.
  • the upper limit of the longitudinal stretching temperature is preferably TmA-7°C, more preferably TmA-10°C, and even more preferably TmA-12°C. Within the above range, the resin is less likely to be fused to the stretching roll, making it difficult to stretch, and the quality of the film is less likely to deteriorate due to increased surface roughness. Note that the longitudinal direction stretching may be performed in multiple stages of two or more stages using three or more pairs of stretching rolls.
  • the width direction stretching step Before the width direction stretching step, it is necessary to heat the uniaxially stretched film after longitudinal direction stretching in a range of TmA+5°C or higher and TmA+20°C or lower to soften the polypropylene resin composition.
  • TmA or more By setting it as TmA or more, the softening of the uniaxially stretched film progresses, and stretching in the width direction becomes easy.
  • the temperature By setting the temperature to TmA+20° C. or lower, orientation during width direction stretching progresses, making it easier to develop rigidity. More preferably, the temperature is TmA+8°C or higher and TmA+15°C or lower.
  • the maximum temperature in the preheating step is defined as the preheating temperature.
  • the width direction stretching step it is preferable to stretch at a temperature of TmA -8°C or higher and lower than the preheating temperature. At this time, the width direction stretching may be started at the time when the preheating temperature is reached, or at the time when the temperature is lowered after reaching the preheating temperature to reach a temperature lower than the preheating temperature.
  • the lower limit of the temperature in the width direction stretching step is more preferably TmA-5°C. When the width direction stretching temperature is within this range, the heat shrinkage rate of the obtained biaxially oriented film can be easily reduced.
  • the upper limit of the temperature in the width direction stretching step is preferably TmA+10°C, more preferably TmA+7°C, particularly preferably TmA+5°C.
  • TmA+10°C more preferably TmA+7°C, particularly preferably TmA+5°C.
  • the lower limit of the final widthwise stretching ratio in the widthwise stretching step is preferably 9 times, more preferably 9.5 times, and even more preferably 10 times. If it is 9 times or more, the rigidity can be easily increased and thickness unevenness can be easily reduced.
  • the upper limit of the width direction stretching ratio is preferably 20 times, more preferably 15 times, and even more preferably 11 times. When it is 20 times or less, it is easy to reduce the heat shrinkage rate and it is difficult to break during stretching.
  • the biaxially stretched film is heat treated.
  • the lower limit of the heat treatment temperature is preferably TmA+8°C, particularly preferably TmA+10°C.
  • the upper limit of the heat treatment temperature is preferably TmA+20°C, more preferably TmA+15°C, particularly preferably TmA+12°C.
  • the roughness of the film surface does not become too large, and the film is less likely to whiten.
  • the film in order to further reduce the thermal shrinkage rate, the film can be relaxed (relaxed) in the width direction during heat treatment.
  • the upper limit of the relaxation rate is 15%, more preferably 10%, and still more preferably 8%. If the above is exceeded, thickness unevenness may become large.
  • the lower limit of the relaxation rate is preferably 0%, more preferably 2%, and relaxation in the width direction is easier to reduce the heat shrinkage rate.
  • the watt density at this time is preferably 11 W/m 2 ⁇ min, more preferably 12 W/m 2 ⁇ min, and still more preferably 13 W/m 2 ⁇ min.
  • the biaxially oriented laminated polypropylene film of the present invention is characterized by the following properties.
  • the "longitudinal direction" in the biaxially oriented laminated polypropylene film in the present invention is a direction corresponding to the flow direction in the film manufacturing process, and the "width direction” is perpendicular to the flow direction in the film manufacturing process. It is the direction.
  • the "longitudinal direction” may be abbreviated as "MD direction” and the "width direction” may be abbreviated as "TD direction”.
  • the upper limit of the plane orientation coefficient ( ⁇ P) measured from the surface layer B side of the biaxially oriented laminated polypropylene film in the present invention is preferably 0.0134, more preferably 0.0132. If it is 0.0134 or less, the strength of the release layer interface can be increased. Furthermore, the thermal shrinkage rate at high temperatures can be reduced.
  • the lower limit of the plane orientation coefficient ( ⁇ P) is preferably 0.0112, more preferably 0.0116, still more preferably 0.0120, even more preferably 0.0122, particularly preferably 0. .0124, most preferably 0.0126. If it is 0.0122 or more, the thickness unevenness of the film tends to improve.
  • the plane orientation coefficient ( ⁇ P) can be controlled within the range by adjusting the stretching ratio, relaxation rate, and temperature conditions during film formation.
  • the planar orientation coefficient ( ⁇ P) was calculated using the following formula: [(Nx+Ny)/2]-Nz.
  • the upper limit of the longitudinal heat shrinkage rate at 150°C of the biaxially oriented laminated polypropylene film in the present invention is 6.0%, preferably 5.0%, more preferably 4.8%, and especially Preferably it is 4.6% or less.
  • the upper limit of the heat shrinkage rate in the width direction at 150°C is 5.0%, preferably 4.5%, more preferably 4.0%, still more preferably 3.5%, and more More preferably, it is 3.0%, particularly preferably 2.7%, most preferably 2.1%, and most preferably 1.7%.
  • the heat shrinkage rate at 150°C of the biaxially oriented laminated polypropylene film in the present invention is 6.0% or less in the longitudinal direction and 5.0% or less in the width direction, a release layer is applied and heat-dried. It is possible to suppress the occurrence of wrinkles and curls when the film is rolled up into a roll. Since the heat shrinkage rate of the biaxially oriented polypropylene film in the present invention is preferably low, it is not particularly limited, but the lower limit of the heat shrinkage rate in the longitudinal direction at 150°C is preferably 0.5%, and 1. 0% is more preferred, 2.0% is even more preferred, 3.0% is even more preferred, 3.5% is particularly preferred, and 4.0% is most preferred.
  • the lower limit of the heat shrinkage rate in the width direction at 150° C. is preferably 0.1%, more preferably 0.3%, even more preferably 0.4%, and particularly preferably 0.5%. If it is less than the above, it may become difficult to maintain a balance with the mechanical strength of the film.
  • the lower limit of the stress at 5% elongation (F5, hereinafter the stress at 5% elongation is abbreviated as F5) in the longitudinal direction of the biaxially oriented laminated polypropylene film in the present invention is preferably 35 MPa, more preferably 36 MPa. It is more preferably 38 MPa, even more preferably 40 MPa, particularly preferably 42 MPa. When the pressure is 35 MPa or higher, the rigidity is high, so it is easy to make the film thin.
  • the upper limit of F5 in the longitudinal direction of the film is preferably 70 MPa, more preferably 65 MPa, even more preferably 62 MPa, particularly preferably 61 MPa, and most preferably 60 MPa.
  • the lower limit of F5 in the width direction of the biaxially oriented laminated polypropylene film in the present invention is preferably 95 MPa, more preferably 100 MPa, still more preferably 105 MPa, even more preferably 110 MPa.
  • the upper limit of F5 in the width direction is preferably 200 MPa, more preferably 190 MPa, and even more preferably 180 MPa.
  • F5 can be adjusted within the range by adjusting the stretching ratio, relaxation rate, and temperature conditions during film formation.
  • the lower limit of Young's modulus in the longitudinal direction of the biaxially oriented laminated polypropylene film in the present invention is preferably 1.6 GPa, more preferably 1.7 GPa, still more preferably 1.8 GPa, particularly preferably 1.9 GPa. and most preferably 2.0 GPa.
  • the upper limit of Young's modulus in the longitudinal direction of the film is preferably 3.0 GPa, more preferably 2.9 GPa, even more preferably 2.8 GPa, particularly preferably 2.7 GPa, most preferably 2. .6GPa. Practical manufacturing is easy at 3.0 GPa or less.
  • the lower limit of Young's modulus in the width direction of the biaxially oriented laminated polypropylene film in the present invention is preferably 3.5 GPa, more preferably 3.6 GPa, still more preferably 3.7 GPa, particularly preferably 3.8 GPa. It is. When the pressure is 3.6 GPa or more, the rigidity is high, so it is easy to make the film thin.
  • the upper limit of the Young's modulus in the width direction is preferably 5.0 GPa, more preferably 4.9 GPa, still more preferably 4.8 GPa, even more preferably 4.5 MPa or less. If it is 5.0 GPa or less, practical manufacturing is easy. Further, the balance between the physical properties of the film in the longitudinal direction and the width direction is likely to be improved. Young's modulus can be controlled within the range by adjusting the stretching ratio, relaxation rate, and temperature conditions during film formation.
  • the lower limit of the longitudinal tensile strength of the biaxially oriented laminated polypropylene film in the present invention is preferably 90 MPa, more preferably 95 MPa, still more preferably 100 MPa, even more preferably 110 MPa.
  • the pressure is 90 MPa or more, the film tends to have excellent durability.
  • a higher tensile strength at break in the longitudinal direction is more preferable in terms of durability, but as a practical value for manufacturing, the upper limit is 300 MPa.
  • the lower limit of the tensile strength at break in the width direction of the biaxially oriented laminated polypropylene film in the present invention is preferably 240 MPa, more preferably 260 MPa, still more preferably 280 MPa, even more preferably 300 MPa, and particularly preferably is 340 MPa.
  • the pressure is 240 MPa or more, the film tends to have excellent durability.
  • a higher tensile strength at break in the width direction is more preferable in terms of durability, but as a practical value for manufacturing, the upper limit is 500 MPa.
  • the tensile strength at break can be controlled within the range by adjusting the stretching ratio, relaxation rate, and temperature conditions during film formation.
  • the lower limit of the tensile elongation at break in the longitudinal direction of the biaxially oriented laminated polypropylene film in the present invention is preferably 200%, more preferably 220%, still more preferably 240%, even more preferably 250%. It is particularly preferably 280% or more, and most preferably 300% or more. If it is 200% or more, the film tends to be less likely to break.
  • the upper limit of the tensile elongation at break in the longitudinal direction is preferably 350%, more preferably 340% as a practical value.
  • the lower limit of the tensile elongation at break in the width direction of the biaxially oriented laminated polypropylene film in the present invention is preferably 25%, more preferably 30%, still more preferably 35%, even more preferably 40%. and particularly preferably 50%. If it is 25% or more, the film tends to be less likely to break.
  • the upper limit of the tensile elongation at break in the width direction is preferably 70% as a practical value, more preferably 65%, and even more preferably 60%.
  • the tensile elongation at break can be controlled within the range by adjusting the stretching ratio, relaxation rate, and temperature conditions during film formation.
  • the upper limit of the haze of the biaxially oriented laminated polypropylene film in the present invention is preferably 5.0%, more preferably 4.5%, still more preferably 4.0%, particularly preferably 3.5%. and most preferably 3.0%. When it is 5.0% or less, it is easy to use in applications where transparency is required.
  • the lower limit of haze is preferably 0.1%, more preferably 0.2%, still more preferably 0.3%, and particularly preferably 0.4%. If it is 0.1% or more, it is easy to manufacture.
  • the haze can be kept within a range by adjusting the temperature conditions during film formation, such as the cooling roll (CR) temperature.
  • the surface wetting tension of the surface layer B of the biaxially oriented laminated polypropylene film in the present invention is preferably 38 mN/m or more, more preferably 39 mN/m or more, and even more preferably 40 mN/m or more.
  • the wetting tension is 38 mN/m or more, the adhesiveness with the release layer is improved.
  • it is preferable to perform a physicochemical surface treatment such as corona treatment or flame treatment.
  • corona treatment it is preferable to heat the film using a preheating roll and a treatment roll, and to perform discharge in the air.
  • the wetting tension is related to the strength of the corona treatment, but since the wetting tension is also related to the amount of antistatic agent bleed out, it is effective to set each of them within suitable ranges.
  • the release film of the present invention can be obtained by laminating a release layer on the surface of the biaxially oriented laminated polypropylene film.
  • the surface wetting tension of the biaxially oriented laminated polypropylene film on which the release layer is laminated is preferably 38 mN/m or more. When the wetting tension is 38 mN/m or more, the adhesiveness with the release layer is improved. In order to make the wetting tension 38 mN/m or more, it is preferable to perform a physicochemical surface treatment such as corona treatment, flame treatment, or plasma treatment.
  • the wetting tension is preferably 44 mN/m or less, more preferably 43 mN/m or less, even more preferably 42 mN/m or less.
  • the mold release agent to be laminated on the biaxially oriented polypropylene film for mold release in the present invention is not particularly limited, and may include silicone resins, fluororesins, alkyd resins, amino resins, various waxes, aliphatic olefins, long-chain alkyl group-containing resins, etc. Each resin can be used alone or in combination of two or more. Among these, in applications where it is desired to prevent contamination by silicone, non-silicone mold release agents are preferably used.
  • silicone resins that are generally used as mold release agents can be used.
  • the silicone resin can be selected from among silicone resins commonly used in the field.
  • thermosetting or ionizing radiation curing silicone resins are used.
  • thermosetting silicone resin for example, a condensation reaction type or addition reaction type silicone resin can be used, and as the ionizing radiation curable silicone resin, an ultraviolet ray or electron beam curable silicone resin can be used.
  • a release layer is formed by applying these onto a film, which is a base material, and drying or curing them.
  • the above-mentioned curable silicone resin preferably has a degree of polymerization after curing of about 500,000 to 200,000, particularly about 1000 to 100,000.
  • Specific examples thereof include the following resins: Shin-Etsu Chemical (KS-718, KS-774, KS-775, KS-778, KS-779H, KS-830, KS-835, KS-837, KS-838, KS-839, KS-841, KS- 843, KS-847, KS-847H, X-62-2418, X-62-2422, X-62-2125, X-62-2492, X-62-2494, X-62-5048, 470, X-62-2366, X-62-630, X-92-140, 719; TPR-6701, TPR-6702, TPR-6703, TPR-3704, TPR-6705, TPR-6721, TPR-6722, TPR-6700, XSR-7029, YSR
  • Examples of the addition reaction type silicone resin for the above-mentioned curable silicone resin include those that are cured by reacting polydimethylsiloxane with a vinyl group introduced into the terminal or side chain and hydrogen siloxane using a platinum catalyst. . At this time, it is more preferable to use a resin that can be cured within 30 seconds at 120° C., as this allows processing at low temperatures.
  • Examples include low-temperature addition-curing types manufactured by Dow Corning Toray (LTC1006L, LTC1056L, LTC300B, LTC303E, LTC310, LTC314, LTC350G, LTC450A, LTC371G, LTC750A, LTC755, LTC760A, etc.) and thermal UV-curing types (L TC851, BY24 -510, BY24-561, BY24-562, etc.), Shin-Etsu Chemical's solvent addition + UV curing type (X62-5040, X62-5065, X62-5072T, KS5508, etc.), dual cure curing type (X62-283, X62) -2834, X62-1980, etc.).
  • LTC1006L, LTC1056L, LTC300B, LTC303E, LTC310, LTC314, LTC350G, LTC450A, LTC371G, LTC750A, LTC755, LTC760A, etc. thermal UV
  • silicone resin of the condensation reaction system of the above-mentioned curable silicone resin for example, polydimethylsiloxane having an OH group at the end and polydimethylsiloxane having an H group at the end are subjected to a condensation reaction using an organotin catalyst, and a three-dimensional Examples include those that create a crosslinked structure.
  • curable silicone resins include ultraviolet curable or electron beam curable silicone resins, which are resins that are crosslinked and cured by radical reactions in the same way as normal silicone rubber crosslinking, and resins that are cured by the introduction of acrylic groups.
  • examples include resins that cure with light, resin compositions that crosslink by decomposing onium salts with ultraviolet light to generate strong acids that cleave epoxy rings, and resin compositions that crosslink by addition reaction of thiol to vinylsiloxane.
  • electron beams have more energy than ultraviolet rays, the crosslinking reaction by radicals occurs without the use of an initiator as in the case of ultraviolet curing.
  • fluororesin examples include polymers of olefin compounds containing fluorine atoms, polymers of compounds having perfluoroalkyl groups, and the like.
  • Compounds having a perfluoroalkyl group include perfluoroalkyl (meth)acrylate, perfluoroalkylmethyl (meth)acrylate, 2-perfluoroalkylethyl (meth)acrylate, 3-perfluoroalkylpropyl (meth)acrylate, 3- Perfluoroalkyl group-containing (meth)acrylates such as perfluoroalkyl-1-methylpropyl (meth)acrylate and 3-perfluoroalkyl-2-propenyl (meth)acrylate, and their polymers, perfluoroalkylmethyl vinyl ether, 2- Examples include perfluoroalkyl group-containing vinyl ethers such as perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-perfluoroal
  • Amino resin refers to a resin obtained by an addition condensation reaction between a compound containing an amino group such as urea, melamine, guanamine, or aniline and an aldehyde, and includes aniline aldehyde resin, urea resin, melamine resin, benzoguanamine resin, acetoguanamine resin, etc. can be mentioned.
  • Amino resins may be modified with long chain alkyl groups. Long chain alkyl groups are explained below.
  • Alkyd resin is a resin obtained by a condensation reaction of a polyhydric alcohol and a polybasic acid, and is a condensate of a polyhydric carboxylic acid and a polyhydric alcohol, and fatty acids and the like are added as necessary.
  • polyhydric alcohols examples include dihydric alcohols such as ethylene glycol diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol; trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane; Examples include polyhydric alcohols such as glycerin, triglycerin, pentaerythritol, pentaerythritol, dipentaerythritol, mannitol, and sorbitol.
  • polybasic acids examples include saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid, and sebacic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic anhydride, isophthalic acid, and trimellitic anhydride.
  • saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid, and sebacic acid
  • unsaturated polybasic acids such as cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, rosin-maleic anhydride adduct, and other polybasic acids produced by Diels-Alder reaction.
  • waxes examples include paraffin wax, microcrystalline wax, palm wax, carnauba wax, candelilla wax, rice wax, soy wax, goby wax, beeswax, and lanolin wax.
  • aliphatic olefins examples include polyethylene-based, polypropylene-based, and polymethylpentene-based resins.
  • long-chain alkyl group-containing resins examples include polyvinyl alcohol, ethylene vinyl alcohol copolymer, polyvinyl butyral, polyvinyl acetate, polyethyleneimine, polyethylene amine, reactive group-containing polyester resin, and reactive group-containing poly(meth) resin.
  • Polymers such as acrylic resins are reacted with a compound having a group that can react with the above polymer and a long-chain alkyl group to introduce pendant long-chain alkyl groups into the polymer, long-chain alkyl (meth)acrylates, etc. and a copolymerizable monomer.
  • the long chain alkyl group preferably has 6 to 32 carbon atoms, more preferably 8 to 26 carbon atoms, and even more preferably 10 to 22 carbon atoms.
  • Examples of the group capable of reacting with the above polymer include an isocyanate group, a glycidyl group, a carboxyl group, an acid chloride group, an oxazoline group, and an isocyanate group is particularly preferred. Specific examples include octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate.
  • mold release agents having long-chain alkyl group-containing resins include Rezem (trade name) from Chukyo Yushi Co., Ltd., Pearoyl (registered trademark) from Lion Specialty Chemicals Co., Ltd., and Octadecyl from Nippon Shokubai Co., Ltd. It is commercially available as isocyanate-modified polyethyleneimine (trade name: RP-20).
  • long-chain alkyl (meth)acrylates examples include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, behenyl (meth)acrylate, and the like.
  • Monomers that can be copolymerized with long-chain alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, vinyl acetate, styrene, acrylonitrile, etc.
  • hydroxyl acrylate such as 2-hydroxyethyl acrylate Group-containing (meth)acrylic monomers, carboxyl group-containing (meth)acrylic monomers such as acrylic acid and methacrylic acid, maleic acid, maleic anhydride, fumaric acid, cyano group-containing monomers, amino group-containing monomers, epoxy group-containing monomers , etc. may be copolymerized.
  • the non-silicone release layer may be crosslinked.
  • the crosslinking agent is not particularly limited, and includes isocyanate compounds, glycidyl group-containing compounds, oxazoline group-containing compounds, amino resins, and the like.
  • a double bond may be introduced into a precursor of the resin that will become the release layer, and a crosslinking reaction may be caused by ultraviolet rays, electron beams, or the like.
  • the mold release agent used in the mold release layer in the present invention may be used alone or in a mixture of two or more types. Further, in order to adjust the release force, it is also possible to mix additives such as light release additives and heavy release additives.
  • the release layer in the present invention may contain particles having a particle size of 1 ⁇ m or less, but from the viewpoint of pinhole generation, it is preferable that particles that form protrusions such as particles are not substantially contained.
  • Additives such as adhesion improvers and antistatic agents may be added to the release layer in the present invention.
  • the surface of the biaxially oriented laminated polypropylene film is subjected to pre-treatments such as anchor coating, corona treatment, plasma treatment, atmospheric pressure plasma treatment, etc. before applying the mold release coating layer. It is also preferable to do so.
  • the thickness of the release layer in the present invention may be set depending on the intended use and is not particularly limited, but preferably the thickness of the release layer is in the range of 0.005 to 2 ⁇ m. It is preferable that the thickness of the release layer is 0.005 ⁇ m or more because the release performance is maintained. Further, it is preferable that the thickness of the release layer is 2 ⁇ m or less, since the curing time will not be too long and there will be no risk of uneven thickness due to deterioration of the flatness of the release film.
  • the method of forming the release layer is not particularly limited, and is developed by applying a coating liquid in which a release resin is dissolved or dispersed onto one surface of a biaxially oriented laminated polypropylene film as a base material. After removing the melt etc. by drying, a method of heating drying, thermosetting or ultraviolet curing is used. At this time, the drying temperature during solvent drying and thermosetting is preferably 100 to 170°C. If the drying temperature is higher than 170°C, wrinkles may occur in the film due to heat. On the other hand, if the drying temperature is low, the release coating layer may not be sufficiently thermally cured and release properties may not be obtained.
  • Biaxially oriented laminated polypropylene film has lower thermal dimensional stability at high temperatures than biaxially oriented polyester film, so wrinkles are likely to occur due to heat during drying of the coating film, but the biaxially oriented laminated polypropylene film of the present invention can suppress the appearance of wrinkles.
  • the heat drying time is generally 10 to 60 seconds.
  • any known coating method can be applied to the above mold release agent coating solution, such as roll coating methods such as gravure coating method and reverse coating method, bar coating method such as wire bar coating method, die coating method, and spray coating method. Conventionally known methods such as , air knife coating, etc. can be used.
  • the upper limit of the longitudinal heat shrinkage rate at 150° C. of the release film of the present invention is preferably 5.9%. More preferably, it is 5.5%, still more preferably 5.0%, particularly preferably 4.8%, and most preferably 4.6%.
  • the upper limit of the heat shrinkage rate in the width direction at 150° C. of the release film of the present invention is preferably 5.0%. More preferably, it is 4.5%, still more preferably 4.0%, and particularly preferably 3.5%. Furthermore, the most preferable upper limit values are listed in the order of 3.0%, 2.7, 2.1%, and 1.7%. Since the release film of the present invention has a low heat shrinkage rate at 150°C, it can be used as a release film for processes at higher temperatures.
  • the lower limit of the heat shrinkage rate of the release film of the present invention is preferably small, so there is no restriction on the lower limit. This is the same value as the preferable lower limit of the heat shrinkage rate.
  • the releasability of the release film of the present invention is appropriately designed depending on the intended use. For example, after pasting a double-sided adhesive tape (manufactured by Nitto Denko Corporation, No. 535A) on a stainless steel plate on the surface of the release layer, it is peeled off at a peeling angle of 30 degrees, a peeling temperature of 25°C, and a peeling speed of 10 m/min. It is preferable that the peeling force in this case is 60 mN/mm or less.
  • the release film of the present invention has good thermal dimensional stability of the biaxially oriented laminated polypropylene film as the base material, so wrinkles and curls do not occur when the release layer is applied, heated and dried, and then wound into a roll. Since the amount is small, it is suitable as a process release film that requires precise processing.
  • the thickness of the film was measured using Militron 1202D manufactured by Seiko EM.
  • the thicknesses of the base layer A and the surface layer B were calculated from the total thickness of the laminated polypropylene film measured by the above method, based on the ratio of the discharge amount of the base layer A to the discharge amount of the surface layer B.
  • 150°C heat shrinkage rate Measured according to the following method in accordance with JIS Z1712. A biaxially oriented laminated polypropylene film was cut to a width of 20 mm and a length of 200 mm in the longitudinal direction and width direction of the film, respectively, and was hung in a hot air oven at 150° C. and heated for 5 minutes. The length after heating was measured, and the heat shrinkage rate was calculated as the ratio of the shrunk length to the original length.
  • Refractive index, plane orientation coefficient Measured from the surface layer B side of a biaxially oriented laminated polypropylene film at a wavelength of 589.3 nm and a temperature of 23° C. using an Abbe refractometer manufactured by Atago.
  • the refractive index along the longitudinal direction and the width direction was set as Nx and Ny, respectively, and the refractive index in the thickness direction was set as Nz.
  • the plane orientation coefficient was calculated using the following formula: [(Nx+Ny)/2]-Nz. When the surface layer B was present on both sides, the average value of each plane orientation coefficient was calculated and used as the plane orientation coefficient.
  • the wetting tension is determined by observing the liquid film of the test mixture in a bright place and observing the state of the liquid film after 3 seconds. If the coating maintains its applied state for 3 seconds or more without causing a liquid film break, it is determined to be wet. If wetting is maintained for 3 seconds or more, proceed to the next liquid mixture with higher surface tension, and conversely, if the liquid film breaks in 3 seconds or less, proceed to the next liquid mixture with lower surface tension. Repeat this operation and select a liquid mixture that can accurately wet the surface of the test piece for 3 seconds. 3) Wire bars should be cleaned with methanol and dried after each use. 4) Select a liquid mixture that can wet the surface of the test piece for 3 seconds at least three times. The surface tension of the liquid mixture thus selected is taken as the wetting tension of the film.
  • release film was removed from a roll of biaxially oriented laminated stretched polypropylene film (release film) laminated with the release layer described in the examples so that the width direction was the long side. It was cut to a width of 30 mm and a length of 80 mm to prepare a sample for peel force measurement. After removing the static electricity using a static eliminator (manufactured by Keyence Corporation, SJ-F020), using a peel tester (manufactured by Kyowa Interface Science Co., Ltd., VPA-3), the peeling angle was 30 degrees, the peeling temperature was 25°C, and the peeling speed was 10 m/min. It was peeled off at min.
  • a static eliminator manufactured by Keyence Corporation, SJ-F020
  • a peel tester manufactured by Kyowa Interface Science Co., Ltd., VPA-3
  • a double-sided adhesive tape (manufactured by Nitto Denko Corporation, No. 535A) was pasted on the SUS plate attached to the peel tester, and on top of that, the release layer of the release film and the SUS of the double-sided adhesive tape were pasted.
  • the release film was fixed by gluing the side opposite to the side to which the plate was attached, and the release film was peeled off by pulling the side of the release film.
  • the average value of the peeling force over a peeling distance of 20 mm to 70 mm was calculated, and this value was taken as the peeling force. The measurement was carried out five times in total, and the average value of the peeling force was used for evaluation.
  • the peel angle in this evaluation method refers to the angle in the direction in which the release film is pulled with respect to the evaluation sample axis fixed to the peel tester.
  • Curl of release film Cut the release film into a size of 10 cm x 10 cm from a roll of biaxially oriented laminated stretched polypropylene film (release film) laminated with release layer 1 described in Examples, and The release film sample was placed on a glass plate with the film facing up, and the height of the part floating above the glass plate was measured. Curl generated in the release film was evaluated by the following method. At this time, the height of the part that was the largest floating above the glass plate was taken as the measured value. Curling properties were evaluated based on the following criteria. ⁇ : Curl is 5 mm or less ⁇ : Curl is larger than 5 mm
  • the release film was unwound from a roll of the biaxially oriented laminated stretched polypropylene film (release film) laminated with the release layer 1 described in Examples, and the wrinkles generated on the release film were removed. Evaluation was made by the following method. That is, a 60 cm wide release film was hung in a room at a temperature of 25° C. and a humidity of 65% so that the longitudinal direction of the film was vertical, and a load of 10 N/m was applied to the film for 30 minutes. A fluorescent light is projected onto the film surface from 45 degrees above at a distance of 1 m from the surface where the number of continuous corrugated wrinkles in the longitudinal direction is to be counted. The number was visually counted and evaluated.
  • one wrinkle was defined as a convex wrinkle in the longitudinal direction of the film relative to the surface to be observed, and the number of wrinkles in the width direction of the film was counted.
  • the number of wrinkles is 10 lines/m or less.
  • ⁇ The number of wrinkles is 11 lines/m or more.
  • PP-1 manufactured by Sumitomo Chemical Co., Ltd., FLX80E4
  • MFR 7.5 g / 10 minutes
  • MFR 3.0 g/10 min
  • [mmmm] 98.4%
  • Tc 116 ° C.
  • Tm 163 ° C.
  • stearyl diethanolamine monostearate, stearyl diethanolamine distearate, and stearyl diethanolamine mixture were added to 100 parts by mass of the mixture of these propylene homopolymers, and after mixing.
  • the polypropylene composition was melt-kneaded and granulated using an extruder equipped with a pelletizer to obtain pellets of the polypropylene composition, and a polypropylene resin composition for the base layer A was obtained.
  • the mesopentad fraction of this polypropylene resin composition was 98.8%, the TmA was 163°C, and the MFR was 6.5 g/10 minutes.
  • the mesopentad fraction of this polypropylene resin composition was 95.3%, the TmB was 161°C, and the MFR was 3.5 g/10 minutes.
  • the polypropylene resin compositions constituting the base layer A and the surface layer B are heated and melted at 250°C using two extruders, and using a multilayer feed block, the surface layer B/base material is Layer A/surface layer B was laminated and coextruded into a sheet. The molten sheet was brought into contact with a cooling roll at 37°C, and then put into a water tank at 29°C to obtain an unstretched sheet.
  • the unstretched sheet was stretched 4.0 times in the longitudinal direction with two pairs of rolls at 140°C, then both ends were held with clips, and the sheet was introduced into a hot air oven, preheated at 174°C, and then heated to 160°C in the width direction.
  • the film was stretched 10 times, and then heat-treated in the width direction at 175° C. while being relaxed by 7%.
  • thermosetting silicone compound manufactured by Shin-Etsu Silicone Co., Ltd., KS-774
  • a coating solution containing 1 part by weight of Pt catalyst (manufactured by Shin-Etsu Silicone Co., Ltd., PL-50T) per 100 parts by weight of the solid content of KS-774 was added to the mixture using a coater at a coating amount (WET) of 3 g/ m2.
  • the release layer was dried for 20 seconds at a conveyance tension of 2000 kPa and a drying temperature of 150°C using an air floating conveyance type drying device with a distance of 38 cm between the lower and upper air flow outlets.
  • a release film having a weight after curing of 0.03 g/m 2 was obtained. After drying, the film was cooled at a rate of 20°C/sec using a cooling roll at 50°C, and then wound into a roll to obtain a release film roll.
  • Table 1 shows the properties of the polypropylene resin raw materials used
  • Table 2 shows the raw material composition and film forming conditions for each layer
  • Table 3 shows the film properties.
  • the release layer of the release film coated with a release agent has high rigidity and has excellent adhesion with the film; It was a smooth film with no scratches.
  • Example 2 As shown in Table 2, a film having a thickness of 19 ⁇ m was obtained in the same manner as in Example 1, except that the thickness structure and the relaxation rate during heat treatment were changed.
  • the release film has high rigidity and has excellent adhesion between the film and the release layer coated with a release agent. It was a smooth film with no scratches.
  • Example 3 As shown in Table 2, a film having a thickness of 19 ⁇ m was obtained in the same manner as in Example 2, except that the preheating temperature, width direction stretching temperature, and heat treatment temperature were changed.
  • the release film has high rigidity and has excellent adhesion between the film and the release layer coated with a release agent. It was a smooth film with no scratches.
  • Example 4 As shown in Table 2, a film having a thickness of 16 ⁇ m was obtained in the same manner as in Example 3, except that the thickness structure and preheating temperature were changed.
  • the release film has high rigidity and has excellent adhesion between the film and the release layer coated with a release agent. It was a smooth film with no scratches.
  • Example 5 As shown in Table 2, a film having a thickness of 17 ⁇ m was obtained in the same manner as in Example 4, except that the thickness structure and heat treatment temperature were changed.
  • the release film has high rigidity and has excellent adhesion between the film and the release layer coated with a release agent. It was a smooth film with no scratches.
  • Example 1 a film having a thickness of 19 ⁇ m was obtained in the same manner as in Example 2, except that the same raw material with a high mesopentad fraction as in the base layer A was used as the raw material for the surface layer B.
  • the release film with high rigidity and coated with a release agent had excellent release properties, and the release film was smooth without wrinkles or curls. The adhesion between the layer and the film was poor.
  • Example 2 As shown in Table 2, a film having a thickness of 19 ⁇ m was obtained in the same manner as in Example 2, except that the stretching ratio in the longitudinal direction was changed.
  • the release film with high rigidity and coated with a release agent had excellent release properties, but the release layer of the release film had poor adhesion between the release layer and the film.
  • the release film had wrinkles and curls.
  • Example 3 As shown in Table 2, a film having a thickness of 19 ⁇ m was obtained in the same manner as in Example 2 except that the heat treatment temperature was changed.
  • the release film with high rigidity and coated with a release agent had excellent release properties, but the adhesiveness between the release layer of the release film and the film was poor, resulting in poor release properties.
  • the mold film had wrinkles and curls.
  • Example 4 As shown in Table 2, a film having a thickness of 17 ⁇ m was obtained in the same manner as in Example 1, except that the stretching ratio in the longitudinal direction and the heat treatment temperature were changed.
  • the release film with high rigidity and coated with a release agent had excellent release properties, but the adhesiveness between the release layer of the release film and the film was poor, resulting in poor release properties.
  • the mold film had wrinkles and curls.
  • stearyl diethanolamine monostearate, stearyl diethanolamine distearate, and stearyl diethanolamine mixture (manufactured by Matsumoto Yushi Co., Ltd., KYM-4K) were added to 100 parts by mass of the mixture of these propylene homopolymers, and after mixing.
  • the polypropylene composition was melt-kneaded and granulated using an extruder equipped with a pelletizer to obtain pellets of the polypropylene composition, and a polypropylene resin composition for the base layer A was obtained.
  • the mesopentad fraction of this polypropylene resin composition was 96.4%, the TmA was 161°C, and the MFR was 5.3 g/10 minutes.
  • a film having a thickness of 19 ⁇ m was obtained in the same manner as in Example 2 except that the above polypropylene resin composition was used for the base layer A.
  • the release layer of the release film coated with a release agent had excellent adhesion to the film, and the release film had excellent release properties, but the rigidity was low and the release layer The film showed wrinkles and curls.
  • the release film of the present invention has high rigidity and can be made thin. Even when the film is made thinner, it is easily peeled off, wrinkles are less likely to occur, and curling is less likely to occur, so it can be suitably used as a release film.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film de démoulage qui comprend un film de polypropylène à orientation biaxiale ayant un faible taux de retrait thermique à 150 °C, comparable à celui d'un film de PET à orientation biaxiale, ainsi qu'une adhésivité exceptionnelle d'une couche de démoulage.　Le film de démoulage comporte un film de polypropylène stratifié à orientation biaxiale qui comporte au moins une couche de substrat A et une couche de surface B, et une couche de démoulage, le film de polypropylène stratifié à orientation biaxiale remplissant les conditions suivantes (1) à (6).　(1) La proportion de l'épaisseur de la couche de substrat A par rapport à l'épaisseur de l'ensemble du film est de 70 % à 98 %.　(2) La fraction de mésopentade d'une résine de polypropylène qui forme la couche de substrat A est de 97,0 % à 99,9 %.　(3) La fraction de mésopentade d'une résine de polypropylène qui forme la couche de surface B est de 80,0 % à 96,5 %.　(4) Le facteur d'orientation de surface du film, mesuré à partir du côté couche de surface B, est inférieur ou égal à 0,0134.　(5) Le taux de retrait thermique à 150 °C du film dans une direction longitudinale est de 6,0 % ou moins.　(6) Le taux de retrait thermique à 150 °C du film dans une direction de largeur est de 5,0 % ou moins.
PCT/JP2023/020725 2022-06-02 2023-06-02 Film de démoulage WO2023234417A1 (fr)

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JP2022-090353 2022-06-02
JP2022090353 2022-06-02
JP2023-024346 2023-02-20
JP2023024346 2023-02-20

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05177790A (ja) * 1991-12-26 1993-07-20 Chisso Corp 二軸延伸多層フィルム
JPH10180963A (ja) * 1996-10-29 1998-07-07 Toray Ind Inc 積層フィルムおよびその製造方法
JPH11192680A (ja) * 1998-01-06 1999-07-21 Toray Ind Inc ポリプロピレンフィルムおよびその製造方法
JP2015199228A (ja) * 2014-04-07 2015-11-12 グンゼ株式会社 二軸延伸ポリプロピレン系フィルム及び包装用袋
WO2017169952A1 (fr) * 2016-03-28 2017-10-05 東洋紡株式会社 Film en polypropylène stratifié étiré biaxialement
WO2018142983A1 (fr) * 2017-02-01 2018-08-09 東洋紡株式会社 Film à base de polypropylène orienté de manière biaxiale
JP2018141122A (ja) * 2017-02-28 2018-09-13 東洋紡株式会社 二軸配向ポリプロピレンフィルム
WO2018180164A1 (fr) * 2017-03-28 2018-10-04 東洋紡株式会社 Film de polypropylène biaxialement orienté
WO2019244708A1 (fr) * 2018-06-19 2019-12-26 東洋紡株式会社 Film multicouche à base de polypropylène

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05177790A (ja) * 1991-12-26 1993-07-20 Chisso Corp 二軸延伸多層フィルム
JPH10180963A (ja) * 1996-10-29 1998-07-07 Toray Ind Inc 積層フィルムおよびその製造方法
JPH11192680A (ja) * 1998-01-06 1999-07-21 Toray Ind Inc ポリプロピレンフィルムおよびその製造方法
JP2015199228A (ja) * 2014-04-07 2015-11-12 グンゼ株式会社 二軸延伸ポリプロピレン系フィルム及び包装用袋
WO2017169952A1 (fr) * 2016-03-28 2017-10-05 東洋紡株式会社 Film en polypropylène stratifié étiré biaxialement
WO2018142983A1 (fr) * 2017-02-01 2018-08-09 東洋紡株式会社 Film à base de polypropylène orienté de manière biaxiale
JP2018141122A (ja) * 2017-02-28 2018-09-13 東洋紡株式会社 二軸配向ポリプロピレンフィルム
WO2018180164A1 (fr) * 2017-03-28 2018-10-04 東洋紡株式会社 Film de polypropylène biaxialement orienté
WO2019244708A1 (fr) * 2018-06-19 2019-12-26 東洋紡株式会社 Film multicouche à base de polypropylène

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