WO2025164065A1 - Biaxially oriented polypropylene film - Google Patents
Biaxially oriented polypropylene filmInfo
- Publication number
- WO2025164065A1 WO2025164065A1 PCT/JP2024/042143 JP2024042143W WO2025164065A1 WO 2025164065 A1 WO2025164065 A1 WO 2025164065A1 JP 2024042143 W JP2024042143 W JP 2024042143W WO 2025164065 A1 WO2025164065 A1 WO 2025164065A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- less
- film
- layer
- polypropylene
- biaxially oriented
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
Definitions
- the present invention relates to a biaxially oriented polypropylene film.
- polypropylene-based resin films have been widely used as heat-sealable films for packaging.
- a polypropylene-based resin film with heat-sealability is a laminated polypropylene-based resin film made by laminating an unstretched polyethylene-based resin film or an unstretched polypropylene-based resin film with an oriented polypropylene-based resin film.
- the above-mentioned laminated polypropylene-based resin film has sufficient sealing strength, it requires a lamination process that uses organic solvents, making it undesirable from both a cost perspective and an environmental impact perspective.
- Patent Documents 1 and 2 disclose biaxially oriented polypropylene resin films that have excellent rigidity, transparency, and heat sealability.
- Patent Documents 1 and 2 had the problem of poor processability. There was also a demand for improved transparency.
- the object of the present invention is to provide a biaxially oriented polypropylene film that has high clarity, a high storage modulus at high temperatures, and a low heat shrinkage rate at high temperatures.
- the present invention includes the following inventions.
- a biaxially oriented polypropylene film having a base layer A made of a polypropylene-based resin composition and a seal layer B made of a polypropylene-based resin composition, and satisfying the following (1) to (4): (1) The seal layer B is provided on at least one outermost surface. (2) Clarity is between 90% and 100%. (3) The storage modulus in the width direction at 140° C. is 0.7 GPa or more and 5.0 GPa or less.
- the thermal shrinkage rate at 150°C in the width direction is 10% or less.
- [2] The biaxially oriented polypropylene film according to [1 ] , wherein, in a thermomechanical analysis, when heated from 30°C to 160°C at a heating rate of 10°C/min, the temperature at which the widthwise length is 0.9950 x X0 or less relative to the widthwise length X0 at 30°C is 129°C or higher, and the storage modulus in the longitudinal direction at 23°C is 2.0 GPa or higher and the storage modulus in the widthwise direction at 23°C is 7.0 GPa or higher.
- the biaxially oriented polypropylene film according to any one of [1] to [10] having a thickness of 10 ⁇ m or more and 100 ⁇ m or less.
- the polypropylene film of the present invention is a heat-sealable film with excellent rigidity and heat resistance, so it easily maintains its bag shape when made into a packaging bag. It can also be used suitably in applications requiring high rigidity without laminating a sealant film, and can maintain its strength even when the film is thin. Furthermore, because it has excellent heat resistance, there are fewer wrinkles in the sealed area when heat-sealed, resulting in an excellent appearance when made into a bag.
- FIG. 1 is a diagram showing the relationship between temperature and the length in the width direction of the film in Example 1 according to the present invention, Comparative Example 1, and Comparative Example 4.
- FIG. 2 is a diagram showing the relationship between temperature and loss modulus in Example 1 according to the present invention and Comparative Example 1.
- FIG. 3 is a diagram showing the relationship between temperature and storage modulus in Example 1 according to the present invention and Comparative Example 1.
- the biaxially oriented polypropylene film of the present invention has a base layer A made of a polypropylene-based resin composition and a seal layer B made of a polypropylene-based resin composition.
- the biaxially oriented polypropylene film of the present invention may have an intermediate layer C made of a polypropylene-based resin composition between the base layer A and the seal layer B.
- the biaxially oriented polypropylene film of the present invention may have a functional layer D.
- the substrate layer A, the seal layer B, the intermediate layer C, and the functional layer D will be described in detail below.
- the base layer A made of a polypropylene-based resin composition is preferably made of a polypropylene-based resin composition containing a polypropylene homopolymer as a main component.
- the term "main component" means that 80% by mass or more of the entire base layer A is polypropylene homopolymer, more preferably 90% by mass or more of the entire base layer A is polypropylene homopolymer, even more preferably 95% by mass or more of the entire base layer A is polypropylene homopolymer, particularly preferably 97% by mass or more of the entire base layer A is polypropylene homopolymer, and most preferably 99% by mass or more of the entire base layer A is polypropylene homopolymer.
- the upper limit of this ratio is not particularly limited, but 100% by mass or less of the entire base layer A may be polypropylene homopolymer.
- the polypropylene homopolymer used in the base layer A is a polypropylene polymer that is substantially free of ⁇ -olefin components other than propylene. Specifically, it is a 100 mol% propylene homopolymer or a polypropylene copolymer having structural units of more than 0 mol% and 1 mol% or less of ⁇ -olefin components other than propylene and 99 mol% or more but less than 100 mol% of propylene (total 100 mol%).
- ⁇ -olefin components other than propylene refer to ethylene and ⁇ -olefins having 4 or more carbon atoms.
- the content of ⁇ -olefin components other than propylene is 1 mol% or less, as described above, preferably 0.3 mol% or less, more preferably 0.2 mol% or less, and even more preferably 0.1 mol% or less. Within the above range, crystallinity is likely to be improved.
- Examples of ⁇ -olefin components having 4 or more carbon atoms include 1-butene, 1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 5-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
- the polypropylene homopolymer used in base layer A includes not only polypropylene homopolymers containing no ⁇ -olefin components other than propylene, but also polypropylene copolymers whose constituent units are more than 0 mol% and not more than 1 mol% ⁇ -olefin components other than propylene and 99 mol% or more but less than 100 mol% propylene.
- the physical property values are the mass average values of the physical properties of each polypropylene homopolymer.
- the melting point Tm a of the polypropylene homopolymer used in the base layer A is preferably 160°C or higher and 170°C or lower. If Tm a is 160°C or higher, rigidity and heat resistance at high temperatures are likely to be obtained. If Tm a is 170°C or lower, it is easy to suppress an increase in the cost of polypropylene production and the film is less likely to break during film formation. Tm a is more preferably 161°C or higher, even more preferably 162°C or higher, more preferably 169°C or lower, even more preferably 168°C or lower, particularly preferably 167°C or lower, and most preferably 166°C or lower.
- Tm a can also be further increased by blending a crystal nucleating agent with the above-mentioned polypropylene resin.
- the melting point of the resin is the main peak temperature of the endothermic peak accompanying melting, which is observed when 5 mg of polypropylene homopolymer is packed into an aluminum pan, set in a differential scanning calorimeter (DSC), heated from 30°C to 230°C at a heating rate of 20°C/min in a nitrogen atmosphere, and held at 230°C for 5 minutes to melt the polypropylene homopolymer, then cooled to 30°C at a heating rate of -10°C/min, held at 30°C for 5 minutes, and then heated at a heating rate of 10°C/min.
- DSC differential scanning calorimeter
- the polypropylene homopolymer used in the base layer A preferably has a mesopentad fraction ([mmmm]%), which is an index of stereoregularity, of 97.0% or more and 99.9% or less.
- a mesopentad fraction of 97.0% or more enhances the crystallinity of the polypropylene resin, improving the melting point Tm a of the crystals in the base layer A, the degree of crystallinity, and the degree of crystal orientation, making it easier to obtain rigidity and heat resistance at high temperatures.
- a mesopentad fraction of 99.9% or less makes it easier to reduce the cost of polypropylene production and makes the film less susceptible to breakage during film formation.
- the mesopentad fraction is more preferably 97.5% or more, even more preferably 98.0% or more, and more preferably 99.7% or less, and even more preferably 99.5% or less.
- the mesopentad fraction is measured by nuclear magnetic resonance (NMR) spectroscopy.
- NMR nuclear magnetic resonance
- a method of washing the obtained polypropylene polymer powder with a solvent such as n-heptane, a method of appropriately selecting a catalyst and/or a co-catalyst, and a method of appropriately selecting components of the polypropylene resin composition are preferably employed.
- the melt flow rate (MFR) of the polypropylene homopolymer used in the base layer A is preferably 5.0 g/10 min or more and 30 g/10 min or less when measured at a temperature of 230°C and a load of 2.16 kgf in accordance with condition M of JIS K 7210 (1995).
- the polypropylene resin constituting the base layer A contains a large amount of low-molecular-weight components, and therefore, by employing a width direction stretching step in the film formation process described below, oriented crystallization of the polypropylene resin is further promoted, the crystallinity of the base layer A is more likely to be increased, and entanglement of polypropylene molecular chains in the amorphous portion is reduced, making it easier to improve heat resistance. Furthermore, when the polypropylene resin has an MFR of 30 g/10 min or less, the film formability of the film is easily maintained.
- the MFR is more preferably 5.5 g/10 min or more, even more preferably 6.0 g/10 min or more, particularly preferably 6.3 g/10 min or more, and most preferably 6.5 g/10 min or more. It is more preferably 25 g/10 min or less, even more preferably 22 g/10 min or less, particularly preferably 20 g/10 min or less, and most preferably 10 g/10 min or less.
- the polypropylene homopolymer used in the base layer A has a lower limit of Mw / Mn , which is an index of molecular weight distribution, of preferably 3.5, more preferably 4.0, even more preferably 4.5, and particularly preferably 5.0.
- the upper limit of Mw / Mn is preferably 30, more preferably 25, even more preferably 23, particularly preferably 21, and most preferably 20.
- Mw / Mn can be obtained using gel permeation chromatography (GPC).
- the molecular weight distribution of polypropylene polymers can be adjusted by polymerizing components of different molecular weights in multiple stages in a series of plants, blending components of different molecular weights offline in a kneader, polymerizing by blending catalysts with different performance, or using a catalyst that can achieve the desired molecular weight distribution.
- the shape of the molecular weight distribution obtained by GPC may be a gentle molecular weight distribution with a single peak on a GPC chart with the logarithm (logM) of molecular weight (M) on the horizontal axis and the differential distribution value (mass fraction per logM) on the vertical axis, or a molecular weight distribution with multiple peaks or shoulders.
- the amount of components with a molecular weight of 100,000 or less in the GPC cumulative curve of the propylene-based resin composition constituting the base layer A is preferably 38% by mass or more, and more preferably 38% by mass or more and 65% by mass or less. By ensuring that the amount of components with a molecular weight of 100,000 or less is 38% by mass or more, heat resistance is easily improved. If the amount of components with a molecular weight of 100,000 or less is 65% by mass or less, film strength is less likely to decrease.
- the amount of components with a molecular weight of 100,000 or less contained in the polypropylene resin without significantly changing the overall viscosity, making it easier to improve film formability without significantly affecting rigidity or heat resistance.
- the above amount is even more preferably 40% by mass or more, particularly preferably 41% by mass or more, most preferably 42% by mass or more, even more preferably 60% by mass or less, particularly preferably 55% by mass or less, and most preferably 50% by mass or less.
- the biaxially oriented polypropylene film of the present invention can be processed into packaging bags, and when fruits and vegetables are placed in the packaging bags, the addition of an anti-fogging agent can prevent fogging of the packaging bags, since the physiological functions of the fruits and vegetables continue even after harvest.
- antifogging agent examples include known antifogging agents such as ethylene oxide adducts of aliphatic amines, ethylene oxide adducts of aliphatic amides, esters of ethylene oxide adducts of aliphatic amines and fatty acids, fatty acid esters of polyhydric alcohols, fatty acid amines, fatty acid amides, etc.
- ethylene oxide adducts of aliphatic amines and esters of ethylene oxide adducts of aliphatic amines and fatty acids it is more preferable to include ethylene oxide adducts of aliphatic amines and esters of ethylene oxide adducts of aliphatic amines and fatty acids.
- the ester of an ethylene oxide adduct of an aliphatic amine and a fatty acid preferably comprises at least one selected from the group consisting of stearyl diethanolamine monoester and stearyl diethanolamine diester.
- Packaging bags are often stored at room temperature rather than frozen, and in order to maintain excellent anti-fogging properties over the long term during distribution, it is preferable to use an anti-fogging agent that continuously exhibits anti-fogging properties over repeated temperature changes between 5°C and 30°C, taking into account temperature changes during storage or distribution.
- the anti-fogging agent is not limited to the above preferred embodiment and may be selected appropriately depending on the application.
- One type of anti-fogging agent may be used alone, or two or more types may be used in combination.
- Examples of stearyl diethanolamine monoesters include stearyl diethanolamine monolaurate, stearyl diethanolamine monomyristate, stearyl diethanolamine monopalmitate, stearyl diethanolamine monostearate, and stearyl diethanolamine monooleate, with stearyl diethanolamine monostearate being preferred.
- Examples of stearyl diethanolamine diesters include stearyl diethanolamine dilaurate, stearyl diethanolamine dimyristate, stearyl diethanolamine dipalmitate, stearyl diethanolamine distearate, and stearyl diethanolamine dioleate, with stearyl diethanolamine distearate being preferred.
- Examples of the ethylene oxide adducts of aliphatic amines include lauryldiethanolamine, myristyldiethanolamine, palmityldiethanolamine, and stearyldiethanolamine, with stearyldiethanolamine being preferred.
- the ethylene oxide adducts of aliphatic amines may be used alone or in combination of two or more.
- the amount of antifogging agent in the propylene-based resin composition constituting base layer A is preferably 0.2% by mass or more and 2.0% by mass or less. This amount is more preferably 0.3% by mass or more, even more preferably 0.35% by mass or more, more preferably 1.8% by mass or less, and even more preferably 1.6% by mass or less.
- the antifogging agent may migrate from base layer A to other layers such as intermediate layer C during the film-forming process.
- the polypropylene resin composition constituting the base layer A may contain resins other than polypropylene homopolymers, as well as known additives such as heat stabilizers, antioxidants, ultraviolet absorbers, nucleating agents, adhesives, flame retardants, and inorganic or organic fillers, as long as the effects of the present invention are not impaired. However, it is preferable that these be added in small amounts, and in the polypropylene resin composition constituting the base layer A, the amount of resins other than polypropylene homopolymers is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 2% by mass or less, and most preferably 1% by mass or less.
- the amount of additives other than resins is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less.
- These resins other than polypropylene homopolymers and/or additives other than resins do not need to be blended into the base layer A. That is, the amount of resins other than polypropylene homopolymers and/or additives other than resins in the base layer A is 0% by mass or more.
- resins other than polypropylene homopolymers include polyolefin resins other than the polypropylene homopolymer used in the base layer A, various elastomers, etc.
- the seal layer B made of a polypropylene resin composition preferably contains a polypropylene copolymer containing an ⁇ -olefin other than propylene. That is, the polypropylene resin composition constituting the seal layer B preferably contains a polypropylene copolymer containing an ⁇ -olefin other than propylene.
- the term "polypropylene copolymer (contained in seal layer B)" is simply used, it refers to a polypropylene copolymer containing propylene and an ⁇ -olefin other than propylene.
- the seal layer B preferably contains 70% by mass or more of the polypropylene copolymer.
- 70% by mass or more of the polypropylene copolymer it is easy to improve the interlayer adhesion between the seal layer B and the intermediate layer C, thereby further increasing the heat seal strength of the biaxially oriented polypropylene film.
- the proportion is more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
- the polypropylene copolymer contained in the seal layer B can also be two or more different polypropylene copolymers, and the total content is preferably within the above range.
- the polypropylene copolymer may account for up to 100% by mass of the entire seal layer B.
- the content of ⁇ -olefin components other than propylene in the polypropylene copolymer contained in the seal layer B is preferably 4.0 mol% or more.
- the propylene content in the polypropylene copolymer is 96 mol% or less, and the sum of the propylene content and the content of ⁇ -olefin components other than propylene is 100 mol%.
- the content of ⁇ -olefin components is the total amount of ethylene and ⁇ -olefins having 4 or more carbon atoms.
- the content of ⁇ -olefin components other than propylene is more preferably 5.0 mol% or more, even more preferably 6.0 mol% or more, particularly preferably 7.0 mol% or more, and more preferably 15 mol% or less, even more preferably 12 mol% or less, and particularly preferably 10 mol% or less.
- Examples of the ⁇ -olefin component having 4 or more carbon atoms include 1-butene, 1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 5-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
- the ⁇ -olefin component other than propylene is preferably an ⁇ -olefin component other than propylene having 2 or more and 20 or less carbon atoms, more preferably an ⁇ -olefin component other than propylene having 2 or more and 10 or less carbon atoms, even more preferably an ⁇ -olefin component other than propylene having 2 or more and 6 or less carbon atoms, and particularly preferably an ⁇ -olefin component other than propylene having 2 or more and 4 or less carbon atoms.
- the melting point Tmb of the polypropylene resin composition constituting the seal layer B is preferably 150°C or lower, more preferably 145°C or lower, even more preferably 140°C or lower, particularly preferably 135°C or lower, and most preferably 130°C or lower.
- Tmb melting point
- the melting point Tmb of the polypropylene resin composition constituting the seal layer B is lower than the melting point Tmc of the polypropylene resin composition constituting the intermediate layer C.
- the melt flow rate (MFR) of the polypropylene resin composition constituting seal layer B is preferably 5.0 g/10 min or more and 8.0 g/10 min or less.
- the MFR is more preferably 5.5 g/10 min or more, even more preferably 6.0 g/10 min or more, and particularly preferably 6.3 g/10 min or more, and more preferably 7.5 g/10 min or less, even more preferably 7.0 g/10 min or less, and particularly preferably 6.8 g/10 min or less.
- the melt flow rate of the polypropylene resin composition constituting seal layer B is preferably higher than the melt flow rate of the polypropylene resin composition constituting intermediate layer C.
- the polypropylene copolymer contained in sealing layer B preferably includes at least one selected from the group consisting of propylene-butene copolymer, propylene-ethylene-butene copolymer, and propylene-ethylene copolymer, and more preferably includes propylene-butene copolymer.
- the content of ⁇ -olefin components other than propylene in the propylene-ethylene-butene copolymer is preferably 4 mol% or more.
- the content of ⁇ -olefin components other than propylene is more preferably 5 mol% or more, and even more preferably 6 mol% or more.
- the content of ⁇ -olefin components other than propylene is, for example, 25 mol% or less.
- the ethylene content is preferably 1 mol% or more, more preferably 2 mol% or more.
- the butene content is preferably 1 mol% or more, more preferably 2 mol% or more.
- the upper limit is, for example, 16 mol% or less.
- a commercially available product may be used, for example, FSX66E8 manufactured by Sumitomo Chemical Co., Ltd.
- the butene content in the propylene-butene copolymer is preferably 4 mol% or more.
- a butene content of 4 mol% or more tends to improve the interlayer adhesion between the intermediate layer C and the seal layer B, and as a result, tends to improve heat seal strength and hermetic sealability.
- the butene content is more preferably 5 mol% or more, and even more preferably 6 mol% or more.
- There is no particular upper limit for the butene content but if the butene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may decrease, so for example, it is 16 mol% or less, preferably 12 mol% or less.
- propylene-butene copolymer having a butene content of 4 mol% or more commercially available products may be used, such as SP7843 manufactured by Sumitomo Chemical Co., Ltd., SPX78J1 manufactured by Sumitomo Chemical Co., Ltd., and XR110H manufactured by Mitsui Chemicals, Inc.
- the ethylene content of the propylene-ethylene copolymer is preferably 4 mol% or more.
- the ethylene content is more preferably 5 mol% or more, and even more preferably 6 mol% or more.
- There is no particular upper limit for the ethylene content but if the ethylene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may be reduced, so for example, it is 12 mol% or less.
- propylene-ethylene copolymer having an ethylene content of 4 mol% or more commercially available products may be used, such as PC540R manufactured by SunAllomer Co., Ltd. and VM3588FL manufactured by Mitsui Chemicals, Inc.
- the polypropylene resin composition constituting the seal layer B may or may not contain an anti-fogging agent.
- the anti-fogging agents described in the description of the substrate layer A can be used as the anti-fogging agent. Even if the polypropylene resin composition constituting the seal layer B does not contain an anti-fogging agent, the anti-fogging agent may migrate from the substrate layer A to the seal layer B during the film formation process, and the obtained biaxially oriented polypropylene film may contain the anti-fogging agent in the seal layer B.
- the polypropylene-based resin composition constituting the sealing layer B may contain additives such as resins other than polypropylene copolymers, the above-mentioned antifogging agents, known heat stabilizers, antioxidants, UV absorbers, nucleating agents, adhesives, flame retardants, inorganic or organic fillers, etc.
- resins other than polypropylene copolymers include polyolefin resins other than the polypropylene copolymers used in the sealing layer B, and various elastomers.
- the amount of resins other than polypropylene copolymers in the polypropylene-based resin composition constituting the sealing layer B is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 2% by mass or less, and may even be 0% by mass or more.
- the amount of additives other than resins in the polypropylene-based resin composition constituting the sealing layer B is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, particularly preferably 1% by mass or less, and may even be 0% by mass or more.
- middle class C 3-1 Polypropylene Resin Composition
- the intermediate layer C made of a polypropylene resin composition preferably contains a polypropylene copolymer containing an ⁇ -olefin other than propylene. That is, the polypropylene resin composition constituting the intermediate layer C preferably contains a polypropylene copolymer containing an ⁇ -olefin other than propylene.
- the provision of the intermediate layer C can improve heat seal strength.
- the term "polypropylene copolymer" refers to a polypropylene copolymer containing an ⁇ -olefin other than propylene.
- the intermediate layer C preferably contains 70% by mass or more of the polypropylene copolymer.
- 70% by mass or more of the polypropylene copolymer it is easy to improve the interlayer adhesion between the intermediate layer C and the seal layer B and between the base layer A and the intermediate layer C, thereby further increasing the heat seal strength of the biaxially oriented polypropylene film.
- the proportion of the polypropylene copolymer in the intermediate layer C is more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may even be 100% by mass or more.
- polypropylene copolymers can be used as the polypropylene copolymer contained in the intermediate layer C, and it is preferable that the total content is within the above range.
- the content of ⁇ -olefin components other than propylene in the polypropylene copolymer contained in the intermediate layer C i.e., the total amount of ethylene and ⁇ -olefins having 4 or more carbon atoms, is preferably 4.0 mol% or more.
- the propylene content in the polypropylene copolymer is 96 mol% or less, and the sum of the propylene content and the content of ⁇ -olefin components other than propylene is 100 mol%.
- the amount is more preferably 4.0 mol% or more, even more preferably 5.0 mol% or more, particularly preferably 6.0 mol% or more, more preferably 12 mol% or less, even more preferably 11 mol% or less, and particularly preferably 10 mol% or less.
- Examples of the ⁇ -olefin component having 4 or more carbon atoms include 1-butene, 1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 5-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
- the ⁇ -olefin component other than propylene is preferably an ⁇ -olefin component other than propylene having 2 or more and 20 or less carbon atoms, more preferably an ⁇ -olefin component other than propylene having 2 or more and 10 or less carbon atoms, even more preferably an ⁇ -olefin component other than propylene having 2 or more and 6 or less carbon atoms, and particularly preferably an ⁇ -olefin component other than propylene having 2 or more and 4 or less carbon atoms.
- the physical property values are the mass average values of the physical properties of each polypropylene copolymer.
- the melting point Tmc of the polypropylene resin composition constituting the intermediate layer C is preferably 150°C or lower, more preferably 145°C or lower, and even more preferably 140°C or lower. By setting Tmc within the above range, the heat seal strength can be increased.
- the lower limit of the melting point Tmc of the polypropylene resin composition constituting the intermediate layer C is not particularly limited, and is, for example, 120°C or higher. Furthermore, from the viewpoint of increasing the heat seal strength, it is preferable that the melting point Tmc of the polypropylene resin composition constituting the intermediate layer C is higher than the melting point Tmb of the polypropylene resin composition constituting the seal layer B.
- the melt flow rate (MFR) of the polypropylene resin composition constituting intermediate layer C is preferably 3.0 g/10 min or more and 6.0 g/10 min or less.
- the melt flow rate value is more preferably 3.5 g/10 min or more, even more preferably 4.0 g/10 min or more, particularly preferably 4.3 g/10 min or more, more preferably 5.5 g/10 min or less, even more preferably 5.0 g/10 min or less, and particularly preferably 4.8 g/10 min or less.
- the melt flow rate of the polypropylene resin composition constituting intermediate layer C is preferably lower than the melt flow rate of the polypropylene resin composition constituting seal layer B.
- the polypropylene copolymer contained in the intermediate layer C is preferably at least one selected from the group consisting of propylene-butene copolymer, propylene-ethylene-butene copolymer, and propylene-ethylene copolymer, with propylene-ethylene-butene copolymer being more preferred.
- the content of the ⁇ -olefin component other than propylene in the propylene-ethylene-butene copolymer in the intermediate layer C is preferably 4 mol% or more.
- the content of the ⁇ -olefin component other than propylene is 4 mol% or more, the interlayer adhesion between the intermediate layer C and the seal layer B is likely to be improved, and as a result, the heat seal strength and hermetic sealability are likely to be improved.
- the content of the ⁇ -olefin component other than propylene is more preferably 5 mol% or more, and even more preferably 6 mol% or more.
- the content of the ⁇ -olefin component other than propylene there is no particular upper limit for the content of the ⁇ -olefin component other than propylene, and it is, for example, 25 mol% or less.
- the total amount is taken as the content of the ⁇ -olefin components other than propylene.
- the ethylene content is preferably 1 mol% or more, more preferably 2 mol% or more.
- the upper limit is 10 mol% or less.
- the butene content is preferably 1 mol% or more, more preferably 2 mol% or more.
- the upper limit is 16 mol% or less.
- a commercially available product may be used, for example, FSX66E8 manufactured by Sumitomo Chemical Co., Ltd.
- the butene content in the propylene-butene copolymer is preferably 4 mol% or more.
- a butene content of 4 mol% or more tends to improve the interlayer adhesion between the intermediate layer C and the seal layer B, and as a result, the heat seal strength and hermetic sealability are likely to be improved.
- the butene content is preferably 5 mol% or more, and even more preferably 6 mol% or more. There is no particular upper limit for the butene content, but if the butene content is too high, crystallization is too suppressed, resulting in lower crystallinity compared to propylene homopolymer, which may result in a decrease in the stiffness of the film.
- the upper limit is 16 mol% or less, and preferably 12 mol% or less.
- a propylene-butene copolymer having a butene content of 4 mol% or more commercially available products may be used, such as SP7843 manufactured by Sumitomo Chemical Co., Ltd., SPX78J1 manufactured by Sumitomo Chemical Co., Ltd., and XR110H manufactured by Mitsui Chemicals, Inc.
- the ethylene content of the propylene-ethylene copolymer is preferably 4 mol% or more.
- An ethylene content of 4 mol% or more tends to improve the interlayer adhesion between the intermediate layer C and the seal layer B, and as a result, tends to improve heat seal strength and hermetic sealability.
- the ethylene content is more preferably 5 mol% or more, and even more preferably 6 mol% or more.
- There is no particular upper limit for the ethylene content but if the ethylene content is too high, crystallization is too suppressed, resulting in lower crystallinity compared to propylene homopolymer, which may result in a decrease in the stiffness of the film.
- the upper limit is 12 mol% or less.
- a propylene-ethylene copolymer having an ethylene content of 4 mol% or more commercially available products may be used, such as PC540R manufactured by SunAllomer Co., Ltd. and VM3588FL manufactured by Mitsui Chemicals, Inc.
- the polypropylene resin composition constituting the intermediate layer C may or may not contain an anti-fogging agent.
- the anti-fogging agent the anti-fogging agents described in the description of the base layer A can be used. Even if the polypropylene resin composition constituting the intermediate layer C does not contain an anti-fogging agent, the anti-fogging agent may migrate from the base layer A to the intermediate layer C during the film formation process, and the obtained biaxially oriented polypropylene film may contain the anti-fogging agent in the intermediate layer C.
- the polypropylene-based resin composition constituting the intermediate layer C may contain additives such as resins other than polypropylene copolymers, the above-mentioned antifogging agents, known heat stabilizers, antioxidants, UV absorbers, nucleating agents, adhesives, flame retardants, inorganic or organic fillers, etc.
- resins other than polypropylene copolymers include polyolefin resins other than the polypropylene copolymers used in the intermediate layer B, and various elastomers.
- the amount of these additives is preferably small, and the amount of resins other than polypropylene copolymers in the polypropylene-based resin composition constituting the intermediate layer C is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 2% by mass or less, and may even be 0% by mass or more. Furthermore, the amount of additives other than resins in the polypropylene-based resin composition constituting the intermediate layer C is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, particularly preferably 1% by mass or less, and may even be 0% by mass or more.
- the functional layer D is preferably provided on the surface of the base layer A on which the seal layer B is not provided.
- the functional layer D is not particularly limited and may be a layer of the same composition as the intermediate layer C.
- an antiblocking agent, a lubricant such as wax or metal soap, a plasticizer, a processing aid, an antistatic agent, etc. may be blended into the polypropylene resin composition constituting the functional layer D.
- the functional layer D is preferably a layer made of a polypropylene resin composition, and more preferably contains a polypropylene copolymer containing an ⁇ -olefin other than propylene. That is, the polypropylene resin composition constituting the functional layer D more preferably contains a polypropylene copolymer containing an ⁇ -olefin other than propylene.
- the term "polypropylene copolymer” refers to a polypropylene copolymer containing an ⁇ -olefin other than propylene.
- the functional layer D preferably contains 70% by mass or more of the polypropylene copolymer, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. This proportion may be 100% by mass or less.
- the polypropylene copolymer contained in the functional layer D can also be two or more different polypropylene copolymers, with the total content preferably being within the above range. By containing the polypropylene copolymer in an amount of 70% by mass or more and 100% by mass or less, it is easy to improve the interlayer adhesion between the functional layer D and the layer adjacent to the functional layer D, thereby further increasing the heat seal strength of the biaxially oriented polypropylene film.
- the content of ⁇ -olefin components other than propylene in the polypropylene copolymer contained in the functional layer D i.e., the total amount of ethylene and ⁇ -olefins having 4 or more carbon atoms, is preferably 4.0 mol% or more.
- the propylene content in the polypropylene copolymer is 96 mol% or less, and the sum of the propylene content and the content of ⁇ -olefin components other than propylene is 100 mol%.
- the amount is more preferably 4.0 mol% or more, even more preferably 5.0 mol% or more, particularly preferably 6.0 mol% or more, more preferably 12 mol% or less, even more preferably 11 mol% or less, and particularly preferably 10 mol% or less.
- Examples of the ⁇ -olefin component having 4 or more carbon atoms include 1-butene, 1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 5-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
- the ⁇ -olefin component other than propylene is preferably an ⁇ -olefin component other than propylene having 2 or more and 20 or less carbon atoms, more preferably an ⁇ -olefin component other than propylene having 2 or more and 10 or less carbon atoms, even more preferably an ⁇ -olefin component other than propylene having 2 or more and 6 or less carbon atoms, and particularly preferably an ⁇ -olefin component other than propylene having 2 or more and 4 or less carbon atoms.
- the melting point Tmd of the polypropylene resin composition constituting the functional layer D is preferably 150°C or lower, more preferably 145°C or lower, and even more preferably 140°C or lower. By setting Tmd within the above range, the heat seal strength can be increased.
- the lower limit of the melting point Tmd of the polypropylene resin composition constituting the functional layer D is not particularly limited, and is, for example, 120°C or higher.
- the melt flow rate (MFR) of the polypropylene resin composition constituting functional layer D, measured at a temperature of 230°C and a load of 2.16 kgf, is preferably 3.0 g/10 min or more and 6.0 g/10 min or less.
- the melt flow rate is more preferably 3.5 g/10 min or more, even more preferably 4.0 g/10 min or more, and particularly preferably 4.3 g/10 min or more. It is more preferably 5.5 g/10 min or less, even more preferably 5.0 g/10 min or less, and particularly preferably 4.8 g/10 min or less.
- the polypropylene copolymer contained in functional layer D preferably contains at least one selected from the group consisting of propylene-butene copolymer, propylene-ethylene-butene copolymer, and propylene-ethylene copolymer, and more preferably contains propylene-ethylene-butene copolymer.
- the content of ⁇ -olefin components other than propylene in the propylene-ethylene-butene copolymer is preferably 4 mol% or more.
- the content of ⁇ -olefin components other than propylene is more preferably 5 mol% or more, and even more preferably 6 mol% or more.
- the content of ⁇ -olefin components other than propylene is, for example, 25 mol% or less.
- the ethylene content is preferably 1 mol% or more, more preferably 2 mol% or more.
- the butene content is preferably 1 mol% or more, more preferably 2 mol% or more.
- the upper limit is, for example, 16 mol% or less.
- a commercially available product may be used, for example, FSX66E8 manufactured by Sumitomo Chemical Co., Ltd.
- the butene content in the propylene-butene copolymer is preferably 4 mol% or more.
- a butene content of 4 mol% or more tends to improve the interlayer adhesion between the functional layer D and the layer adjacent to the functional layer D, and as a result, tends to improve heat seal strength and hermetic sealability.
- the butene content is more preferably 5 mol% or more, and even more preferably 6 mol% or more.
- There is no particular upper limit for the butene content but if the butene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may decrease. Therefore, for example, it is 16 mol% or less, preferably 12 mol% or less.
- propylene-butene copolymer having a butene content of 4 mol% or more commercially available products may be used, such as SP7843 manufactured by Sumitomo Chemical Co., Ltd., SPX78J1 manufactured by Sumitomo Chemical Co., Ltd., and XR110H manufactured by Mitsui Chemicals, Inc.
- the ethylene content of the propylene-ethylene copolymer is preferably 4 mol% or more.
- the ethylene content is more preferably 5 mol% or more, and even more preferably 6 mol% or more.
- There is no particular upper limit for the ethylene content but if the ethylene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may be reduced, so for example, it is 12 mol% or less.
- propylene-ethylene copolymer having an ethylene content of 4 mol% or more commercially available products may be used, such as PC540R manufactured by SunAllomer Co., Ltd. and VM3588FL manufactured by Mitsui Chemicals, Inc.
- the polypropylene resin composition constituting the functional layer D may or may not contain an anti-fogging agent.
- the anti-fogging agent the anti-fogging agents described in the description of the base layer A can be used. Even if the polypropylene resin composition constituting the functional layer D does not contain an anti-fogging agent, the anti-fogging agent may migrate from the base layer A to the functional layer D during the film formation process, and the functional layer D may contain the anti-fogging agent in the obtained biaxially oriented polypropylene film.
- the polypropylene-based resin composition constituting the functional layer D may contain additives such as resins other than polypropylene copolymers, the above-mentioned anti-fogging agents, known heat stabilizers, antioxidants, ultraviolet absorbers, nucleating agents, adhesives, flame retardants, inorganic or organic fillers, etc.
- resins other than polypropylene copolymers include polyolefin resins other than the polypropylene copolymers used in the functional layer D, various elastomers, and the like.
- the amount of resins other than polypropylene copolymers in the polypropylene-based resin composition constituting the functional layer D is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 2% by mass or less, and can be 0% by mass or more.
- the amount of additives other than resins in the polypropylene-based resin composition constituting the functional layer D is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, particularly preferably 1% by mass or less, and can be 0% by mass or more.
- the content of the anti-fogging agent in the biaxially oriented polypropylene film of the present invention is preferably 0.1% by mass or more and 10% by mass or less.
- the content is more preferably 0.15% by mass or more, even more preferably 0.2% by mass or more, particularly preferably 0.25% by mass or more, most preferably 0.3% by mass or more, more preferably 5.0% by mass or less, even more preferably 3.0% by mass or less, particularly preferably 2.0% by mass or less, and most preferably 1.5% by mass or less.
- the anti-fogging agent may migrate from the base layer A to other layers during film formation and storage after film formation, and the anti-fogging agent may migrate to the outermost seal layer B, causing the anti-fogging agent to be present on the surface of the seal layer B, thereby providing anti-fogging properties.
- the biaxially oriented polypropylene film of the present invention has a base layer A and a seal layer B.
- An intermediate layer C may be present between the base layer A and the seal layer B.
- the layer structure of the biaxially oriented polypropylene film of the present invention has the base layer A and the seal layer B, and as long as the seal layer B is present on at least one outermost surface, the intermediate layer C may be present between the base layer A and the seal layer B, or another layer may be present between the base layer A and the intermediate layer C, or the intermediate layer C may be laminated directly on the base layer A.
- the seal layer B may be laminated directly on the intermediate layer C.
- the biaxially oriented polypropylene film of the present invention include a two-layer structure of base layer A/seal layer B, a three-layer structure of base layer A/intermediate layer C/seal layer B, a three-layer structure of seal layer B1/base layer A/seal layer B2, a four-layer structure of seal layer B1/base layer A/intermediate layer C/seal layer B2, a five-layer structure of seal layer B1/intermediate layer C1/base layer A/intermediate layer C2/seal layer B2, and a six-layer structure of seal layer B1/base layer A1/intermediate layer C1/base layer A2/intermediate layer C2/seal layer B2.
- the base layer A1 and the base layer A2 may be made of different polypropylene-based resin compositions or may be the same
- the intermediate layers C1 and C2 may be made of different polypropylene-based resin compositions or may be the same
- the seal layer B1 and the seal layer B2 may be made of different polypropylene-based resin compositions or may be the same.
- the functional layer D may be laminated directly on the surface of the substrate layer A, or an intermediate layer C may be interposed between the substrate layer A and the functional layer D.
- the functional layer D may also be located between the substrate layer A and the intermediate layer C, or between the intermediate layer C and the sealing layer B.
- the functional layer D is present, there are no particular limitations as long as the substrate layer A, intermediate layer C, and sealing layer B are present in this order, with sealing layer B on at least one outermost surface.
- Examples of such a structure include a four-layer structure of functional layer D/substrate layer A/intermediate layer C/sealing layer B, in which the substrate layer A/intermediate layer C/sealing layer B structure further has a functional layer D, and a five-layer structure of functional layer D/intermediate layer C/substrate layer A/intermediate layer C/sealing layer B, in which the intermediate layer C/substrate layer A/intermediate layer C/sealing layer B structure further has a functional layer D.
- the overall thickness of the biaxially oriented polypropylene film of the present invention will vary depending on the application and method of use, but from the viewpoints of film strength, airtightness, and water vapor barrier properties, it is preferably 5 ⁇ m or more and 100 ⁇ m or less.
- the thickness is more preferably 10 ⁇ m or more, even more preferably 18 ⁇ m or more, more preferably 80 ⁇ m or less, and even more preferably 50 ⁇ m or less.
- the thickness is preferably 33 ⁇ m or less, more preferably 28 ⁇ m or less, even more preferably 23 ⁇ m or less, and particularly preferably 18 ⁇ m or less.
- the thickness of the base layer A varies depending on the application and method of use, but is preferably 5 ⁇ m or more and 90 ⁇ m or less. A thickness of 5 ⁇ m or more can improve film strength, sealing properties, and water vapor barrier properties. Furthermore, a thickness of 90 ⁇ m or less can reduce the environmental impact by reducing the volume.
- the thickness of the base layer A is more preferably 10 ⁇ m or more, even more preferably 15 ⁇ m or more, more preferably 50 ⁇ m or less, and even more preferably 30 ⁇ m or less.
- the thickness of intermediate layer C varies depending on its application and method of use, but is preferably 0.5 ⁇ m or more and 4 ⁇ m or less.
- a thickness of 0.5 ⁇ m or more can improve adhesion between base layer A and seal layer B, thereby increasing seal strength.
- a thickness of 4 ⁇ m or less can reduce the environmental impact by reducing volume.
- the thickness of intermediate layer C is more preferably 1 ⁇ m or more and 3 ⁇ m or less.
- the thickness of sealing layer B varies depending on its application and method of use, but is preferably 0.3 ⁇ m or more and 2 ⁇ m or less. A thickness of 0.3 ⁇ m or more can increase heat seal strength. Furthermore, a thickness of 2 ⁇ m or less can reduce the environmental impact by reducing the volume. The thickness of sealing layer B is more preferably 0.5 ⁇ m or more and 1.5 ⁇ m or less.
- the thickness of functional layer D varies depending on its application and method of use, but is preferably 0.3 ⁇ m or more and 2 ⁇ m or less. A thickness of 0.3 ⁇ m or more can increase heat seal strength. Furthermore, a thickness of 2 ⁇ m or less can reduce the environmental impact by reducing the volume. The thickness of functional layer D is more preferably 0.5 ⁇ m or more and 1.5 ⁇ m or less.
- the method for producing the biaxially oriented polypropylene film of the present invention is not particularly limited, but examples thereof include a method in which melt lamination is performed by a T-die method, inflation method, or the like using an extruder suitable for the number of layers, followed by cooling by a cooling roll method, water cooling method, or air cooling method to obtain an unstretched laminated film, and then stretching the obtained film by a sequential biaxial stretching method, simultaneous biaxial stretching method, tube stretching method, or the like.
- the polypropylene resin composition constituting each of the functional layer D, substrate layer A, intermediate layer C, and seal layer B is melt-extruded using one or more extruders, and the extruded multilayer sheet is cooled on a cooling roll to form an unstretched sheet.
- the resulting unstretched sheet is then stretched in the longitudinal direction (MD).
- the stretched sheet is then preheated, stretched in the transverse direction (TD), and finally heat-set to obtain the biaxially oriented polypropylene film of the present invention.
- at least one side of the biaxially oriented polypropylene film can be surface-treated, and then wound up on a winder to obtain a film roll.
- the polypropylene resin compositions constituting the functional layer D, base layer A, intermediate layer C, and seal layer B are each melted at, for example, 200°C or higher and 260°C or lower, and the molten polypropylene resin compositions are delivered from different flow paths using four extruders.
- the delivered polypropylene resin compositions are laminated in multiple layers using a multi-layer feed block, static mixer, multi-layer multi-manifold die, or the like, and a multi-layer sheet laminated in the order of functional layer D/base layer A/intermediate layer C/seal layer B is extruded from a T-die.
- the thickness of the unstretched multilayer sheet is preferably 3500 ⁇ m or less from the perspective of improving cooling efficiency, and more preferably 3000 ⁇ m or less, but this can be adjusted appropriately depending on the film thickness after sequential biaxial stretching.
- the thickness of the unstretched multilayer sheet can be adjusted by the extrusion speed of the polypropylene resin composition and the lip width of the T-die, etc. There is no particular lower limit to the thickness of the unstretched multilayer sheet, but it can be set to 500 ⁇ m, for example.
- Cooling step The unstretched multilayer sheet co-extruded from the T-die into a sheet form is brought into contact with a metal cooling roll and cooled and solidified. At this time, it is preferable that the seal layer B side is grounded on the cooling roll. In order to promote solidification, it is also preferable to further cool the unstretched multilayer sheet cooled by the cooling roll by, for example, immersing it in a water bath.
- the temperature of the chill roll is preferably 10°C or higher and lower than the crystallization temperature of the polypropylene resin composition. When increasing the transparency of the film, it is preferable to cool and solidify using a chill roll at 10°C or higher and 50°C or lower.
- the chill roll temperature tends to increase the transparency of the unstretched multilayer sheet, and it is more preferably 40°C or lower, and even more preferably 30°C or lower.
- a cooling temperature of 40°C or higher may be preferable.
- the chill roll temperature is preferably 40°C or lower, more preferably 30°C or lower, from the viewpoint of facilitating the subsequent stretching step and reducing thickness unevenness.
- the temperature of the water bath is also preferably 10°C or higher and 50°C or lower, more preferably 40°C or lower, and even more preferably 30°C or lower, for the same reasons as above.
- the longitudinal stretching temperature is preferably Tm-30°C or higher and Tm-7°C or lower. If the temperature is Tm-30°C or higher, the subsequent widthwise stretching becomes easier and film thickness unevenness tends to be reduced. If the temperature is Tm-7°C or lower, the thermal shrinkage rate is easily reduced, and there is little risk of the film becoming difficult to stretch when applied to the stretching rolls or of the film becoming rough on the surface, resulting in a decrease in quality.
- the temperature is more preferably Tm-27°C or higher, even more preferably Tm-25°C or higher, more preferably Tm-12°C or lower, and even more preferably Tm-10°C or lower.
- Tm refers to the Tm of the resin forming the thickest layer.
- the stretching ratio in the longitudinal direction is preferably 3.5 times or more and 8.0 times or less. When the stretching ratio is 3.5 times or more, it is easy to increase the strength and reduce thickness unevenness. Furthermore, when the stretching ratio is 8.0 times or less, it is easy to perform width direction stretching in the width direction stretching step, and it is easy to improve productivity.
- the stretching ratio is more preferably 3.8 times or more, even more preferably 4.2 times or more, and more preferably 7.0 times or less, and even more preferably 6.0 times or less.
- the longitudinal stretching may be performed in two or more stages using three or more pairs of stretching rolls, but it is preferable to perform stretching in one stage using two pairs of stretching rolls. When performing stretching in multiple stages, it is preferable that the highest stretching temperature is within the above range.
- Preheating Step It is preferable to heat the uniaxially stretched film after longitudinal stretching in a preheating step to sufficiently soften the polypropylene resin composition before the widthwise stretching step.
- the heating temperature in the preheating step is preferably Tm or higher and Tm + 25°C or lower. By setting the heating temperature in the preheating step to the melting point or higher, softening proceeds, facilitating widthwise stretching. Furthermore, by setting the heating temperature in the preheating step to Tm + 25°C or lower, orientation proceeds during widthwise stretching, making it easier to develop rigidity.
- the heating temperature is more preferably Tm + 2°C or higher, even more preferably Tm + 3°C or higher, more preferably Tm + 20°C or lower, and even more preferably Tm + 15°C or lower. Note that if the preheating step consists of multiple zones, the temperature of the hottest zone among them is taken as the preheating temperature. Note that Tm here refers to the Tm of the resin forming the thickest layer.
- the width direction stretching temperature is preferably Tm-10°C or higher and the heating temperature in the preheating process or lower. If the temperature is Tm-10°C or higher, the rigidity of the resulting film is easily improved, and if the temperature is lower than the heating temperature in the preheating process, stretching unevenness is less likely to occur.
- the temperature is more preferably Tm-9°C or higher, even more preferably Tm-7°C or higher, particularly preferably Tm-5°C or higher, and more preferably Tm+10°C or lower, even more preferably Tm+7°C or lower, and particularly preferably Tm+5°C or lower. Note that Tm here refers to the Tm of the resin forming the thickest layer.
- the width direction stretching step it is preferable to add a later stretching step in which the film is stretched at a lower temperature following the width direction stretching step in the above temperature range (hereinafter sometimes referred to as the "early stretching step").
- the later stretching step By providing the later stretching step, the rigidity of the film can be easily increased.
- the stretching ratio in the width direction is preferably 10 times or more and 20 times or less. When the stretching ratio is 10 times or more, rigidity is easily increased and thickness unevenness is easily reduced. Furthermore, when the stretching ratio is 20 times or less, the heat shrinkage rate is easily reduced and the film is less likely to break during stretching.
- the stretching ratio is more preferably 11 times or more, even more preferably 12 times or more, particularly preferably 12.5 times or more, and more preferably 17 times or less, and even more preferably 15 times or less.
- the total stretching ratio is set within the above range.
- Heat Treatment Step It is preferable to perform heat treatment after the width direction stretching step.
- Specific means for heat treatment include providing a zone with a higher temperature than the stretching zone after the width direction stretching is completed, or increasing the zone temperature in the latter half of stretching and passing the film through a zone at the same temperature after the stretching is completed to increase the film temperature.
- heating methods include blowing hot air or heating with an infrared heater, but there are no particular limitations as long as the method increases the film temperature from the temperature at the end of the width direction stretching step.
- the heat treatment step is preferably carried out immediately after the widthwise stretching step is completed, i.e., immediately after the widthwise stretching has reached the final stretch ratio.
- the temperature in the heat treatment step is preferably higher than that at the end of the widthwise stretching step, and specifically, is preferably at least 1°C higher than the widthwise stretching temperature. It is also preferable to carry out the heat treatment step in two stages, with the early heat treatment step being performed at a temperature higher than that at the end of the widthwise stretching step, and the later heat treatment step being performed at a temperature lower than that in the early heat treatment step.
- the early and later heat treatment steps are explained below.
- the heating temperature in the preliminary heat treatment step is preferably Tm or higher and Tm + 20°C or lower. Heating at a temperature above Tm promotes relaxation, reducing tension in the molecular chains and allowing crystallization to proceed more reliably. On the other hand, heating at a temperature below Tm + 20°C suppresses melting while suppressing relaxation of the oriented molecular chains, thereby more reliably preventing a decrease in rigidity.
- the heating temperature is more preferably Tm + 3°C or higher, even more preferably Tm + 4°C or higher, particularly preferably Tm + 5°C or higher, more preferably Tm + 18°C or lower, even more preferably Tm + 14°C or lower, and particularly preferably Tm + 10°C or lower.
- Heating in the heat treatment step after the stretching step relaxes the molecular chain orientation formed during stretching, making crystallization more likely to occur in the final heat treatment step.
- the temperature can be gradually increased from the temperature at the end of width direction stretching to the temperature during heating, or it can be increased in stages or in a single step. It is preferable to raise the temperature stepwise or in one step, since this makes it easier to control the orientation of molecular chains in the film.
- the film may or may not be relaxed in the width direction.
- the relaxation rate is preferably 0% or more and 3% or less. If the relaxation rate is within this range, the rigidity is less likely to decrease and the film thickness fluctuation is likely to be small.
- the relaxation rate is more preferably 0% or more and 1% or less, and even more preferably 0%, i.e., no relaxation. If it is desired to further increase the rigidity, relaxation is not necessary.
- the film may be slightly expanded to suppress sagging, etc., as long as it does not impair the effects of the present invention.
- the heating temperature in the later heat treatment step is preferably Tm-70°C or higher and Tm or lower. If the heating temperature is Tm-70°C or higher, lamellar thickening proceeds and the melting point of the film is likely to increase. In other words, heat resistance at high temperatures can be obtained. On the other hand, if the heating temperature is Tm or lower, crystallization proceeds and the heat shrinkage rate is likely to decrease.
- the heating temperature is more preferably Tm-50°C or higher, even more preferably Tm-40°C or higher, particularly preferably Tm-30°C or higher, more preferably Tm-1°C or lower, even more preferably Tm-2°C or lower, and particularly preferably Tm-3°C or lower.
- Tm here refers to the Tm of the resin forming the thickest layer.
- the film may be relaxed in the width direction in order to adjust the thermal shrinkage rate.
- the relaxation rate is preferably 1% or more and 8% or less.
- the relaxation rate is more preferably 2% or more, even more preferably 3% or more, and more preferably 6% or less, and even more preferably 5% or less.
- relaxation is not necessary.
- increasing the amount of low-molecular-weight polypropylene components in the polypropylene resin composition that makes up the biaxially oriented polypropylene film can reduce entanglement of molecular chains, thereby weakening the heat shrinkage stress in areas other than the lamellae of the crystalline portion and further reducing the heat shrinkage rate, which is preferable.
- Cooling Step It is preferable to cool the film immediately after the heat treatment step.
- the cooling temperature is preferably 10°C or higher and 140°C or lower.
- the cooling temperature is more preferably 15°C or higher, even more preferably 20°C or higher, more preferably 135°C or lower, even more preferably 130°C or lower, particularly preferably 80°C or lower, and most preferably 50°C or lower.
- the biaxially oriented polypropylene film of the present invention is preferably surface-treated on at least one of the seal layer B and the surface layer opposite to the seal layer B, and it is more preferable to surface-treat the seal layer B from the viewpoint of increasing the surface tension of the seal layer B.
- the surface treatment method include corona discharge treatment, plasma treatment, flame treatment, and acid treatment, and there are no particular restrictions on the method.
- corona discharge treatment plasma treatment, or flame treatment
- corona discharge treatment plasma treatment, or flame treatment
- the biaxially oriented polypropylene film of the present invention preferably has the following properties.
- the "longitudinal direction (MD direction)" of the biaxially oriented polypropylene film of the present invention refers to the direction corresponding to the flow direction in the film production process
- the "transverse direction (TD direction)” refers to the direction perpendicular to the flow direction in the film production process, and the same applies hereinafter.
- Width Direction Length In thermomechanical analysis, when the temperature of the biaxially oriented polypropylene film of the present invention is increased from 30°C to 130°C at a rate of 10°C/min, where X0 is the width direction length at 30°C, X1 is the maximum width direction length during the temperature increase, and X2 is the minimum width direction length during the temperature increase, the percentage of ( X1 - X0 )/ X0 is preferably 0.50% or less. When this percentage is 0.50% or less, film deformation can be suppressed even after heating at high temperatures, such as during heat processing with a roll, printing, or heat sealing. This reduces the deterioration of film flatness and improves film processability.
- the percentage is more preferably 0.45% or less, even more preferably 0.40% or less, particularly preferably 0.35% or less, and most preferably 0.30% or less.
- the percentage of (X 1 -X 0 )/X 0 is preferably small, and although there is no particular lower limit, it is, for example, 0.01% or more, preferably 0.02% or more, in view of technical difficulties.
- the percentage of (X 2 -X 0 )/X 0 of the biaxially oriented polypropylene film of the present invention is preferably -0.50% or more.
- this percentage is -0.50% or more, deformation of the film can be suppressed even after heating at high temperatures, such as during heat processing with a roll, printing, or heat sealing. This prevents deterioration of the film's flatness and improves the film's processability.
- the percentage is more preferably -0.45% or more, even more preferably -0.40% or more, particularly preferably -0.35% or more, and most preferably -0.30% or more.
- a larger percentage of (X 2 -X 0 )/X 0 is preferable. While there is no particular upper limit, it is, for example, 0.01% or less, preferably 0.00% or less, due to technical difficulties.
- the temperature at which the width direction length of the film is 0.9950 x X0 or less is preferably 129°C or higher, more preferably 130°C or higher, even more preferably 131°C or higher, particularly preferably 132°C or higher, and most preferably 133°C or higher.
- the "temperature at which the width direction length is 0.9950 x X0 or less” refers to the lowest temperature at which the width direction length is 0.9950 x X0 or less when the film is heated from 30°C to 160°C at a heating rate of 10°C/min.
- the temperature at which the width direction length is 0.9950 x X0 or less is 129°C or higher, deformation of the film can be suppressed even after heating at high temperatures, such as during heat processing with a roll, printing, or heat sealing. This makes it less likely that the flatness of the film will deteriorate and improves the processability of the film.
- the loss modulus is determined by dynamic viscoelasticity measurement. Specifically, the temperature is raised from -60°C to 160°C at a rate of 5°C/min under a nitrogen atmosphere with a measurement load of 10 g and a frequency of 10 Hz, and the loss modulus is measured at each temperature during the temperature rise.
- the inventors have found that while increasing the rigidity and heat resistance alone may not be enough to maintain the flatness of the film after heating, controlling the loss modulus in a predetermined temperature range to fall within a predetermined range makes it possible to maintain the flatness of the film even after heating.
- E"(A) the maximum value of the loss modulus between -25°C and 25°C
- E"(B) the minimum value of the loss modulus between 25°C and 75°C
- E"(C) the maximum value of the loss modulus between 100°C and 160°C
- E"(C)/E"(A) the maximum value of the loss modulus between 100°C and 160°C
- E"(C)/E"(A) the maximum value of the loss modulus between 100°C and 160°C
- E"(B)/E”(C the loss modulus in the width direction.
- the present inventors have found that by using highly stereoregular polypropylene and employing the above-mentioned width direction stretching process, it is possible to increase the orientation in the film, i.e., to increase the value of the loss modulus between -25°C and 25°C.
- E"(A) of the biaxially oriented polypropylene film of the present invention is preferably 0.40 GPa or more.
- E"(A) is 0.40 GPa or more, rigidity tends to be high.
- E"(A) is more preferably 0.42 GPa or more, even more preferably 0.44 GPa or more, particularly preferably 0.46 GPa or more, and most preferably 0.48 GPa or more.
- E"(A) There is no particular upper limit for E"(A), but a realistic value is, for example, 0.70 GPa or less, and preferably 0.60 GPa or less.
- Minimum loss modulus E (B) from 25°C to 75°C Takayanagi Motoo, "Temperature Dispersion of Crystalline Polymers," Polymer, Society of Polymer Science, 1961, Vol. 10, No. 3, pp. 289-295, describes that increasing the crystallinity in a film, which contributes greatly to heat resistance, and reducing the amount of crystals that melt in a relatively low temperature range above the glass transition temperature of the polypropylene resin (hereinafter referred to as the low temperature range) makes it difficult for relaxation to occur due to melting, which in turn suppresses relaxation of the amorphous portion, i.e., even when treated at high temperatures, the mobility of the amorphous portion is reduced, resulting in good heat resistance.
- the present inventors have found that by using a highly stereoregular polypropylene and employing the width direction stretching process described above, it is possible to reduce the amount of crystals that melt in the low temperature range, thereby reducing the change in loss modulus from the glass transition temperature to 75°C.
- E"(B) of the biaxially oriented polypropylene film of the present invention is preferably 0.16 GPa or more. If E"(B) is 0.16 GPa or more, the heat shrinkage rate is likely to decrease. Furthermore, if E"(B) is 0.16 GPa or more, fewer crystals will melt in the above-mentioned low temperature range, thereby improving flatness. E"(B) is more preferably 0.17 GPa or more, even more preferably 0.18 GPa or more, particularly preferably 0.19 GPa or more, and most preferably 0.20 GPa or more. There is no particular upper limit for E"(B), but a realistic value is, for example, 0.60 GPa or less, and preferably 0.50 GPa or less.
- the E"(C) of the biaxially oriented polypropylene film of the present invention is preferably 0.28 GPa or more and 0.80 GPa or less.
- E"(C) is 0.28 GPa or more, the high rigidity makes it easier to maintain the shape of the bag when made into a packaging bag, and the film is less likely to deform during processing such as printing.
- E"(C) is 0.80 GPa or less, practical manufacturing is easier and the film is less likely to tear in the width direction.
- E"(C) is more preferably 0.29 GPa or more, even more preferably 0.30 GPa or more, particularly preferably 0.31 GPa or more, and most preferably 0.32 GPa or more. It is more preferably 0.75 GPa or less, even more preferably 0.70 GPa or less, particularly preferably 0.65 GPa or less, and most preferably 0.60 GPa or less.
- the E"(C)/E"(A) ratio of the biaxially oriented polypropylene film of the present invention is preferably 0.55 or greater, and more preferably 0.55 or greater and 1.30 or less.
- E"(C)/E"(A) is 0.55 or greater, the film has high rigidity, making it easier to maintain the shape of the packaging bag when made into it, and the film is less likely to deform during processing such as printing.
- E"(C)/E"(A) is 1.30 or less, practical manufacturing is easier and the film is less likely to tear in the width direction.
- E"(C)/E"(A) is more preferably 0.60 or greater or 0.62 or greater, particularly preferably 0.64 or greater, and most preferably 0.66 or greater. It is even more preferably 1.20 or less or 1.10 or less, particularly preferably 1.00 or less, and most preferably 0.90 or less.
- the E"(B)/E"(C) ratio of the biaxially oriented polypropylene film of the present invention is preferably 0.55 or greater, and more preferably 0.55 or greater and 1.30 or less.
- E"(B)/E"(C) is 0.55 or greater, fewer crystals melt in the low-temperature range, making relaxation associated with melting less likely to occur. This in turn suppresses relaxation of the amorphous portion. As a result, the mobility of the amorphous portion is reduced even when processed at high temperatures, improving flatness and heat resistance.
- E"(B)/E"(C) is 1.30 or less, rigidity is less likely to decrease and film thickness fluctuations tend to be small.
- E"(B)/E"(C) is more preferably 0.60 or greater or 0.61 or greater, particularly preferably 0.62 or greater, and most preferably 0.63 or greater. It is even more preferably 1.25 or less or 1.20 or less, particularly preferably 1.15 or less, and most preferably 1.10 or less.
- the storage modulus is determined by dynamic viscoelasticity measurement. Specifically, the temperature is increased from -60°C to 160°C at a rate of 5°C/min under a nitrogen atmosphere with a measurement load of 10 g and a frequency of 10 Hz, and the storage modulus is measured at each temperature during the temperature increase.
- the storage modulus in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 23° C. is preferably 2.0 GPa or more and 5.0 GPa or less.
- the storage modulus is more preferably 2.3 GPa or more, even more preferably 2.5 GPa or more, particularly preferably 2.9 GPa or more, most preferably 3.0 GPa or more, and more preferably 4.5 GPa or less, even more preferably 4.3 GPa or less, particularly preferably 4.2 GPa or less, and most preferably 4.0 GPa or less.
- the storage modulus in the width direction of the biaxially oriented polypropylene film of the present invention at 23° C. is preferably 7.0 GPa or more and 15.0 GPa or less.
- the storage modulus is more preferably 7.3 GPa or more, even more preferably 7.6 GPa or more, and particularly preferably 8.0 GPa or more, and more preferably 14.0 GPa or less, even more preferably 13.5 GPa or less, and particularly preferably 13.0 GPa or less.
- the strength of the biaxially oriented polypropylene film is significantly increased, and even if the film is thin, it can maintain its stiffness and strength, which greatly contributes to reducing the volume of the film.
- the storage modulus in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 120°C is preferably 0.5 GPa or more and 2.5 GPa or less.
- the storage modulus is more preferably 0.6 GPa or more, even more preferably 0.7 GPa or more, and particularly preferably 0.8 GPa or more, and is more preferably 2.3 GPa or less, even more preferably 2.1 GPa or less, and particularly preferably 2.0 GPa or less.
- the storage modulus in the width direction of the biaxially oriented polypropylene film of the present invention at 120°C is preferably 1.5 GPa or more and 8.0 GPa or less.
- the storage modulus is more preferably 1.8 GPa or more, even more preferably 2.0 GPa or more, and particularly preferably 2.1 GPa or more, and is more preferably 7.8 GPa or less, even more preferably 7.6 GPa or less, and particularly preferably 7.4 GPa or less.
- the storage modulus in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 140° C. is preferably 0.3 GPa or more and 1.5 GPa or less, more preferably 0.35 GPa or more, even more preferably 0.4 GPa or more, particularly preferably 0.45 GPa or more, and more preferably 1.45 GPa or less, even more preferably 1.4 GPa or less, particularly preferably 1.35 GPa or less.
- the storage modulus at 140°C in the longitudinal and transverse directions is within the above range, the strength at high temperatures tends to be high, and printing pitch deviation is less likely to occur when transferring high-temperature printing ink during printing. In addition, the flatness of the film is less likely to deteriorate and the processability of the film can be improved.
- the storage modulus in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 150° C. is preferably 0.1 GPa or more and 1.0 GPa or less, more preferably 0.15 GPa or more, even more preferably 0.2 GPa or more, particularly preferably 0.25 GPa or more, and more preferably 0.9 GPa or less, even more preferably 0.8 GPa or less, particularly preferably 0.7 GPa or less.
- the storage modulus at 150°C in the longitudinal and transverse directions is within the above range, the strength at high temperatures tends to be high, and printing pitch deviation is less likely to occur when transferring high-temperature printing ink during printing. In addition, the flatness of the film is less likely to deteriorate and the processability of the film can be improved.
- the sum of the longitudinal storage modulus at 23° C. and the longitudinal storage modulus at 140° C. of the biaxially oriented polypropylene film of the present invention is preferably 2.8 GPa or more and 8.0 GPa or less.
- the sum of these storage moduli is more preferably 3.0 GPa or more, even more preferably 3.1 GPa or more, and particularly preferably 3.2 GPa or more, and more preferably 7.5 GPa or less, even more preferably 7.0 GPa or less, and particularly preferably 6.5 GPa or less.
- the biaxially oriented polypropylene film of the present invention is preferably 8.5 GPa or more and 19.0 GPa or less.
- the sum of these storage moduli is more preferably 8.8 GPa or more, even more preferably 9.1 GPa or more, and particularly preferably 9.5 GPa or more, and is more preferably 18.0 GPa or less, even more preferably 17.0 GPa or less, and particularly preferably 16.0 GPa or less.
- the strength at high temperatures is likely to be high, and printing pitch deviation is unlikely to occur when transferring high-temperature printing ink during printing.
- the flatness of the film is unlikely to be deteriorated and the processability of the film can be improved.
- the stress at 5% elongation in the longitudinal direction (F5) of the biaxially oriented polypropylene film of the present invention at 23°C is preferably 40 MPa or more and 70 MPa or less. If the F5 is 40 MPa or more, the film has high rigidity, making it easier to maintain the shape of the bag when made into a packaging bag, and the film is less likely to deform during processing such as printing. If the F5 is 70 MPa or less, practical production becomes easier and the balance between the longitudinal direction and the width direction tends to be improved.
- the F5 is more preferably 42 MPa or more, even more preferably 46 MPa or more, particularly preferably 48 MPa or more, and more preferably 65 MPa or less, even more preferably 62 MPa or less, and particularly preferably 60 MPa or less.
- the F5 in the longitudinal direction can be adjusted within the above range by adjusting the stretch ratio or relaxation rate or adjusting the temperature during film formation.
- the stress at 5% elongation in the width direction (F5) of the biaxially oriented polypropylene film of the present invention at 23°C is preferably 90 MPa or more and 280 MPa or less. If the F5 is 90 MPa or more, the film has high rigidity, making it easier to maintain the shape of the bag when made into a packaging bag, and the film is less likely to deform during processing such as printing. Furthermore, if the F5 is 90 MPa or more, flatness can be improved. If the F5 is 280 MPa or less, practical manufacturing is easier and the film is less likely to tear in the width direction.
- the F5 is preferably 110 MPa or more or 120 MPa or more, more preferably 130 MPa or more, particularly preferably 150 MPa or more, most preferably 156 MPa or more, more preferably 250 MPa or less, even more preferably 230 MPa or less, particularly preferably 210 MPa or less, and most preferably 200 MPa or less.
- the F5 in the width direction can be adjusted within the above range by adjusting the stretch ratio and relaxation rate, or by adjusting the temperature during film formation.
- the heat shrinkage in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 120°C is preferably 2.5% or less. If the heat shrinkage is 2.5% or less, printing pitch deviation is less likely to occur when transferring printing ink.
- the heat shrinkage is more preferably 2.0% or less, even more preferably 1.7% or less, and particularly preferably 1.5% or less.
- the heat shrinkage in the longitudinal direction at 120°C can be adjusted to fall within the above range by adjusting the stretch ratio, stretching temperature, and heat treatment temperature.
- the heat shrinkage rate in the width direction of the biaxially oriented polypropylene film of the present invention at 120°C is preferably 1.1% or less. If the heat shrinkage rate is 1.1% or less, wrinkles are less likely to occur during heat sealing.
- the heat shrinkage rate is more preferably 1.0% or less, even more preferably 0.7% or less, particularly preferably 0.5% or less, and most preferably 0.3% or less.
- the heat shrinkage rate in the width direction at 120°C can be kept within the above range by adjusting the stretch ratio, stretching temperature, and heat treatment temperature.
- the sum of the thermal shrinkage rates in the longitudinal and transverse directions of the biaxially oriented polypropylene film of the present invention at 120°C is preferably 3.5% or less. When this sum is 3.5% or less, flatness is easily improved and printing pitch deviation when transferring printing ink is less likely to occur. This sum is more preferably 3.0% or less, even more preferably 2.5% or less, particularly preferably 2.0% or less, and most preferably 1.7% or less. A lower sum is preferable, and although there is no particular lower limit, considering technical difficulties, it is, for example, 1.0% or more, preferably 1.3% or more.
- the sum of the thermal shrinkage rates in the longitudinal and transverse directions at 120°C can be kept within the above range by adjusting the stretch ratio, stretching temperature, and heat treatment temperature.
- the heat shrinkage in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 150°C is preferably 10% or less. If the heat shrinkage is 10% or less, printing pitch deviation is less likely to occur when transferring printing ink.
- the heat shrinkage is more preferably 7.0% or less, even more preferably 6.0% or less, particularly preferably 5.0% or less, and most preferably 4.0% or less.
- the heat shrinkage in the longitudinal direction at 150°C can be adjusted to fall within the above range by adjusting the stretch ratio, stretching temperature, and heat treatment temperature.
- the heat shrinkage rate in the width direction of the biaxially oriented polypropylene film of the present invention at 150°C is preferably 20% or less. If the heat shrinkage rate is 20% or less, wrinkles are less likely to occur during heat sealing.
- the heat shrinkage rate is more preferably 15% or less, even more preferably 12% or less, and particularly preferably 10% or less.
- the heat shrinkage rate in the width direction at 150°C can be kept within the above range by adjusting the stretch ratio, stretching temperature, and heat treatment temperature.
- the heat shrinkage rate in the longitudinal direction at 150°C is 10% or less and the heat shrinkage rate in the width direction is 20% or less, wrinkles are less likely to occur during heat sealing.
- the heat shrinkage rate in the longitudinal direction at 150°C is 8.0% or less and the heat shrinkage rate in the width direction at 150°C is 15% or less, distortion when the zipper part is fused to the opening is small, which is preferable.
- GPC gel permeation chromatography
- the lower limit of the thickness uniformity of the biaxially oriented polypropylene film of the present invention is preferably 0%, more preferably 0.1%, even more preferably 0.5%, and particularly preferably 1%.
- the upper limit of the thickness uniformity is preferably 20%, more preferably 17%, even more preferably 15%, particularly preferably 12%, and most preferably 10%. Within the above range, defects are unlikely to occur during post-processing such as coating or printing, making the film suitable for use in applications requiring precision.
- the upper limit of the haze of the biaxially oriented polypropylene film of the present invention is preferably 7.0%.
- a haze of 7.0% or less makes it easy to use in applications requiring transparency.
- the haze is more preferably 5.0% or less, even more preferably 4.0% or less, particularly preferably 3.5% or less, and most preferably 3.0% or less.
- the lower limit of the haze is preferably 0%, with 0.1% being a practical value.
- the haze can be adjusted within the above range by adjusting the cooling roll temperature, the longitudinal stretching temperature, the tenter preheating temperature before widthwise stretching, the widthwise stretching temperature, the heat setting temperature, or the amount of polypropylene polymer components with a molecular weight of 100,000 or less.
- the haze may increase depending on the addition of an antiblocking agent or the composition of the sealing layer B.
- the lower limit of the image clarity of the biaxially oriented polypropylene film of the present invention is preferably 55%.
- An image clarity of 55% or higher is easy to use in applications requiring transparency.
- the image clarity is more preferably 57% or higher, even more preferably 59% or higher, particularly preferably 61% or higher, and most preferably 65% or higher.
- the upper limit of the image clarity is preferably 100%, with 95% being a realistic value.
- the image clarity can be kept within the range by adjusting the chill roll temperature, longitudinal stretching temperature, tenter preheating temperature before widthwise stretching, widthwise stretching temperature, heat setting temperature, or the amount of polypropylene polymer components with a molecular weight of 100,000 or less.
- the image clarity may be increased by adding an antiblocking agent or by adjusting the composition of the sealing layer B.
- the lower limit of the clarity of the biaxially oriented polypropylene film of the present invention is preferably 90%.
- a clarity of 90% or higher makes it easy to use in applications requiring transparency.
- the clarity is more preferably 92% or higher, even more preferably 93% or higher, particularly preferably 94% or higher, and most preferably 95% or higher.
- the upper limit of the clarity is preferably 100%, with 99% being a realistic value.
- the clarity can be adjusted within the above range by adjusting the cooling roll temperature, longitudinal stretching temperature, tenter preheating temperature before widthwise stretching, widthwise stretching temperature, heat setting temperature, or the amount of polypropylene polymer components with a molecular weight of 100,000 or less.
- the clarity may be increased by adding an antiblocking agent or by adjusting the composition of the sealing layer B.
- the biaxially oriented polypropylene film of the present invention exhibits little dimensional change over the entire temperature range from room temperature to 130°C. Therefore, deformation of the film can be suppressed even after heating at high temperatures, such as during heat processing with a roll, printing, or heat sealing. This makes it difficult for the film's flatness to deteriorate and improves its processability. Furthermore, it allows for thinner films, which contributes to reducing the volume of packaging materials. From the above, when the biaxially oriented polypropylene film of the present invention is used to make a packaging bag, the bag shape is easily maintained, the film is less likely to deform during processing such as heat sealing at high temperatures, and printing pitch deviation is less likely to occur during printing, making it suitable for packaging. In addition, the film is less likely to lose flatness even after being coated with a silicone release agent and heated and dried, making it suitable as a release film for optical applications and other applications where a high degree of flatness is required.
- a sealant film made of polyethylene resin, polypropylene resin, or the like is laminated onto the biaxially oriented polypropylene film of the present invention as the base film, and the sealant film surfaces are fused together.
- the heating method involves applying pressure from a heating plate from the base film side to hold down the film and seal it, with a seal width of approximately 10 mm being common.
- the base film is also heated during this process, and the resulting expansion and contraction causes wrinkles. Fewer wrinkles are preferable for bag durability and to increase consumer appetite.
- the sealing temperature can be around 120°C, higher temperatures are required to increase the bag-making processing speed, and even in this case, small expansion and contraction are preferable. If a zipper is to be fused to the opening of the bag, sealing at even higher temperatures is required.
- the biaxially oriented polypropylene film of the present invention preferably has a heat seal strength at 130°C on the seal layer B side, measured by the measurement method described below, of 4.8 N/15 mm or more, more preferably 5.0 N/15 mm or more, even more preferably 5.5 N/15 mm or more, and particularly preferably 6.0 N/15 mm or more.
- the upper limit is about 8.0 N/15 mm.
- one surface of the biaxially oriented polypropylene film of the present invention is a sealing layer B and the other surface is a functional layer D
- the heat-sealed portion after bag-making processing is folded to bond the functional layers D together.
- the heat seal strength at 130°C on the functional layer D side is lower than the heat seal strength at 130°C on the sealing layer B side, for example, 3.5 N/15 mm or less, preferably 2.0 N/15 mm or less, and more preferably 1.0 N/15 mm or less.
- Heat-sealing start temperature of the seal layer B of the biaxially oriented polypropylene film of the present invention is preferably 90°C or higher and 130°C or lower.
- the heat-sealing start temperature of the seal layer B is 130°C or lower, high heat-sealing strength can be achieved at a relatively low temperature of around 130°C, allowing the temperature of the processing equipment during heat-sealing to be relatively low, enabling high-speed operation during automatic packaging.
- heat-sealing processing can be performed at a relatively low temperature, the entire film is less likely to shrink and wrinkles are less likely to form in the sealed area.
- the film By setting the heat-sealing start temperature of the seal layer B to 90°C or higher, the film can be made less likely to fuse to the film-forming equipment.
- the above temperature is more preferably 100°C or higher, even more preferably 110°C or higher, and more preferably 125°C or lower, and even more preferably 120°C or lower.
- the heat seal rise temperature can be set within the above range by adjusting the raw material composition of each layer, particularly the raw material composition of the base layer A, the stretching ratio during film formation, the relaxation rate, the temperature of each film formation step, etc.
- the coefficient of dynamic friction of the biaxially oriented polypropylene film of the present invention is preferably 0.50 or less on both sides, i.e., on both the seal layer B and the surface layer opposite to the seal layer B. If the coefficient of dynamic friction is 0.50 or less on both sides, the film can be smoothly unwound from the roll film, facilitating printing processing.
- the coefficient of dynamic friction is more preferably 0.48 or less, and even more preferably 0.45 or less. There is no particular restriction on the lower limit of the coefficient of dynamic friction, but it is, for example, 0.10 or more.
- the wet tension of the surface of the seal layer B of the biaxially oriented polypropylene film of the present invention is preferably 35 mN/m or more.
- a wet tension of 35 mN/m or more can improve adhesion to the surface layer opposite the seal layer B.
- a wet tension of 35 mN/m or more can improve the anti-fogging properties of the film.
- it is preferable to perform a physicochemical surface treatment such as corona treatment or flame treatment. In corona treatment, it is preferable to use a preheating roll and a treatment roll and perform discharge in the air.
- the wet tension is more preferably 37 mN/m or more. If the wet tension is too high, the effect will saturate, so it is preferably 43 mN/m or less.
- the anti-fogging property of the surface of the seal layer B of the biaxially oriented polypropylene film of the present invention is preferably grade 1 to 3, more preferably grade 1 or 2, and even more preferably grade 1, as determined by the evaluation method described below.
- the biaxially oriented polypropylene film of the present invention When used as a packaging material, it may be used alone or with a printed layer provided thereon.
- the biaxially oriented polypropylene film of the present invention can be used as a packaging material to produce three-side seal type, pillow type and gusset type packaging bags having good seal strength and good appearance of the sealed portion.
- the biaxially oriented polypropylene film of the present invention can be subjected to relief printing, lithographic printing, intaglio printing, stencil printing and transfer printing depending on the application.
- melt flow rate (MFR) was measured in accordance with JIS K7210 at a temperature of 230°C and a load of 2.16 kgf.
- TMA Thermomechanical analysis
- the maximum value of the length between the chucks during the temperature increase was defined as X1 (mm), and the minimum value of the length between the chucks during the temperature increase was defined as X2 (mm), and the percentages of (X1 - 10 )/10 and (X2 - 10)/10 were calculated.
- Thermomechanical analysis (TMA) measurement (temperature measurement at 0.5% shrinkage) A film was cut out so that the width direction of the film was 40 mm and the length direction of the film was 4 mm, and the film was set in a thermomechanical analyzer ("TMA-60", manufactured by Shimadzu Corporation) so that the chuck width was 10 mm. The temperature was raised from 30°C to 160°C at a heating rate of 10°C/min with a measurement load of 0.5 g, and the width direction length of the sample was continuously measured during the temperature rise. From the measurement results, the lowest temperature at which the width direction length of the sample was 9.95 mm or less was determined to be the temperature at which 0.5% shrinkage occurred.
- TMA thermomechanical analyzer
- Loss modulus by dynamic mechanical analysis A film was cut to a width of 40 mm and a length of 4 mm, and set in a solid viscoelastic analyzer (RSA-G2, manufactured by TA Instruments Japan) with a chuck width of 10 mm. The film was heated from -60°C to 160°C at a heating rate of 5°C/min under a nitrogen atmosphere with a measuring load of 10 g and a frequency of 10 Hz, and the loss modulus of the film was measured during the heating in the width direction.
- DMA dynamic mechanical analysis
- a graph was drawn with temperature on the horizontal axis and loss modulus on the vertical axis, and the maximum loss modulus E"(A) from -25°C to 25°C, the minimum loss modulus E"(B) from 25°C to 75°C, and the maximum loss modulus E"(C) at 100°C or higher were calculated.
- the values of E"(C)/E"(A) and E"(B)/E"(C) were also calculated.
- Image clarity Using an image clarity measuring instrument ("ICM-1T" manufactured by Suga Test Instruments Co., Ltd.), image clarity was measured in accordance with the transmission method of JIS K7374: 2007, with the slit width of the optical comb set to 0.5 mm. During measurement, the sample was set so that the width direction was perpendicular to the optical comb of the measuring instrument.
- ICM-1T image clarity measuring instrument
- Clarity Clarity was measured using a transparency measuring device ("Hazeguard i" manufactured by BYK).
- the light transmitted through the film during measurement includes straight light that travels straight along the optical axis of the incident parallel light and narrow-angle scattered light that has an angle of ⁇ 2.5° or less with respect to the optical axis of the parallel light.
- Clarity (%) (I c - I s ) / (I c + I s ) ⁇ 100
- the tensile modulus was calculated from the slope of the linear portion at the beginning of elongation, and the stress at 5% elongation was designated as F5.
- the tensile breaking strength and tensile breaking elongation were defined as the strength and elongation, respectively, at the time the sample broke.
- Dynamic friction coefficient A sample measuring 400 mm in length and 100 mm in width was cut out from the film. This was aged for 12 hours in an atmosphere of 23°C and 65% RH, and then divided into a sample for a test table measuring 300 mm in length and 100 mm in width and a sample for a sliding piece measuring 100 mm in length and 100 mm in width. The test table sample was set on the test table, and the slider sample was attached to the bottom surface (square with an area of 39.7 mm 2 ) of a metal slider with a load of 1.5 kg so that the sealing layers B were in contact with each other.
- a tensile tester (“Tensilon RTG-1210" manufactured by A&D Co., Ltd.) was used to measure the dynamic friction coefficient of the seal layer surface B under conditions of a sliding speed of the test piece of 200 mm/min, 23°C, and 65% RH, and the average of three measurements was used.
- the coefficient of dynamic friction of the surface opposite to the sealing layer B was also determined in the same manner as above, except that the surfaces opposite to the sealing layer B were attached so as to be in contact with each other.
- wetting tension (mN/m) The film was cut into a size of 297 mm in the longitudinal direction and 210 mm in the width direction, and after aging for 24 hours at a temperature of 23°C and a relative humidity of 50%, the wet tension of the surface on the seal layer B side of the sample was measured by the following procedure in accordance with JIS K 6768. The wet tension was measured in a laboratory atmosphere at a temperature of 23°C and a relative humidity of 50%, in accordance with JIS K7100. The sample was placed on a flat substrate, and several drops of a wetting tension standard solution (a test mixture according to JIS K 6768) were placed on the sealing layer B of the sample.
- a wetting tension standard solution a test mixture according to JIS K 6768
- the wetting tension standard solution was then spread over the surface of the sealing layer B with a cotton swab to an area of 6 cm2 or more.
- the state of the liquid film was visually observed in a bright place 3 seconds after application. If the liquid film did not break 3 seconds after formation and remained in the same state as when it was applied, this meant that the liquid film was wet. Therefore, a liquid film was formed using a wetting tension standard solution with a surface tension one level higher than the wetting tension standard solution used to form the liquid film. On the other hand, if the liquid film broke within 3 seconds, a liquid film was formed using a wetting tension standard solution with a surface tension one level lower than the wetting tension standard solution used to form the liquid film.
- a new cotton swab was used for each liquid film formation.
- the above liquid film formation was repeated, and the value of the maximum wetting tension standard solution among the wetting tension standard solutions that could wet the surface of the sealing layer B in 3 seconds was taken as the wetting tension. Note that a liquid film was formed three times using the wetting tension standard solution with the maximum value, and it was confirmed that the state at the time of application was maintained after 3 seconds had elapsed.
- the wetting tension of the surface layer on the opposite side to the sealing layer B was also measured using the same measuring and calculation methods as above.
- Grade 1 No dew on the entire surface (0 adhesion area)
- Grade 2 Dew adheres to a small area of the surface (adhesion area is greater than 0 and less than 1/4)
- Grade 3 Dew on just under half of the surface (adhesion area: over 1/4 and less than 2/4)
- Grade 4 Dew on most of the surface (adhesion area: over 2/4 and less than 3/4)
- Grade 5 Dew on almost the entire surface (more than 3/4 of the surface area)
- the heat-sealing temperatures were different for each heat-sealed surface, and were 80°C, 85°C, 90°C, 95°C, and 100°C.
- the heat-sealing pressure was 1 kg/ cm2 , and the heat-sealing time was 1 second.
- the sample was then cut to a length of 19 cm in the longitudinal direction and a central 1.5 cm in the width direction so that five heat-sealed surfaces were included.
- the sample was cut in the longitudinal direction so that the longitudinal direction of the sample and the longitudinal direction of the cut sample were parallel, and the heat-sealed surface heat-sealed at 90°C was located in the longitudinal center.
- the cut sample was attached to the upper and lower chucks of a tensile tester ("5965 Dual Column Tabletop Tester” manufactured by Instron), and the heat-seal strength was measured for each heat-sealed surface when pulled at a pulling speed of 200 mm/min (unit: N/15 mm).
- a tensile tester (5965 Dual Column Tabletop Tester” manufactured by Instron)
- two new cut-out samples were prepared and heat-sealed at 105°C, 110°C, 115°C, 120°C, and 125°C in the same manner as above, except that five measurement samples were prepared and the heat-seal strength was measured.
- a linear graph was drawn with the horizontal axis representing temperature and the vertical axis representing heat seal strength, and the temperature at which the heat seal strength reached 1 N/15 mm was taken as the heat seal initiation temperature.
- Another sample was prepared and the heat seal strength was measured two more times at 80 to 125°C to determine the heat seal initiation temperature, and the average of the three calculated values was taken as the heat seal initiation temperature of the film.
- the heat seal rise temperature of the film was determined using the same measurement and calculation methods as above, except that the surface layers on the opposite side to seal layer B were stacked facing each other.
- the sample was cut so that the longitudinal direction of the sample and the longitudinal direction of the cut sample were parallel, and the heat seal surface was located in the center of the longitudinal direction.
- the cut sample was attached to the upper and lower chucks of a tensile tester (Instron's "5965 Dual Column Tabletop Tester") and pulled at a pulling speed of 200 mm/min to measure the heat seal strength (unit: N/15 mm).
- Two other samples were prepared and their heat seal strengths were measured, and the average of the three calculated values was used as the heat seal strength of the film.
- the heat seal strength of the film was determined using the same measuring and calculating methods as above, except that the surface layers of the two cut-out samples on the side opposite to the seal layer B were placed face to face.
- the heat seal strength of the seal layer B and the heat seal strength of the surface layer opposite to the seal layer B were determined using the same measuring and calculation methods as above, except that the heat seal temperature was set to 140°C.
- PP-1 Propylene homopolymer ("FLX80H5" manufactured by Sumitomo Chemical Co., Ltd., mesopentad fraction: 98.9%, melting point: 163°C, MFR: 7.5g/10min, amount of components with molecular weight of 10,000 or less: 4.0% by mass, amount of components with molecular weight of 100,000 or less: 40.5% by mass)
- PP-2 Propylene homopolymer ("EL80F5" manufactured by Sumitomo Chemical Co., Ltd., mesopentad fraction: 98.8%, melting point: 162°C, MFR: 11 g/10 min, amount of components with a molecular weight of 10,000 or less: 6.9% by mass, amount of components with a molecular weight of 100,000 or less: 53.1% by mass)
- PP-3 A composition containing PP-1 and, as an anti-fogging agent, stearyl
- PP-4 Propylene homopolymer ("FY6H", manufactured by Japan Polypropylene Corporation, MFR: 1.9 g/10 min, melting point: 163°C, mesopentad fraction: 98.9%)
- PP-5 A composition containing propylene homopolymer ("FL203D” manufactured by Japan Polypropylene Corporation, mesopentad fraction: 94.8%, melting point: 161°C, MFR: 3g/10 min, amount of components with a molecular weight of 10,000 or less: 3.0% by mass, amount of components with a molecular weight of 100,000 or less: 37.1% by mass), 1.7% by mass of stearyl diethanolamine monostearate as an anti-fogging agent, and 0.25% by mass of glycerin monostearate.
- PP-6 A composition containing propylene-ethylene-butene copolymer ("FSX66M4" manufactured by Sumitomo Chemical Co., Ltd., melting point: 138°C, MFR: 4.5g/10 min, ethylene content: 3.3 mol%, butene content: 2.9 mol%, glycerin monostearate content: 0.45% by mass).
- PP-7 Propylene-butene copolymer ("SP7843" manufactured by Sumitomo Chemical Co., Ltd., melting point: 128°C, MFR: 6.5 g/10 min, butene content: 8.2 mol%)
- Example 1 (1) Preparation of raw materials for base layer A A polypropylene-based resin composition containing 20% by mass of propylene homopolymer PP-1, 20% by mass of propylene homopolymer PP-2, and 60% by mass of propylene homopolymer PP-3 was used as the raw material.
- the polypropylene-based resin composition constituting base layer A had a mesopentad fraction of 98.88%, a melting point of 162.8°C, an MFR of 8.2 g/10 min, a content of components with a molecular weight of 10,000 or less of 4.58% by mass, and a content of components with a molecular weight of 100,000 or less of 43.02% by mass.
- (2) Raw Materials for Sealing Layer B Propylene-butene copolymer PP-7 was used as the raw material.
- (3) Raw Materials for Functional Layer D Propylene-ethylene-butene copolymer PP-6 was used as the raw material.
- the polypropylene resin compositions constituting each of the functional layer D, base layer A, and seal layer B were heated and melted in an extruder using a multi-layer feed block at 250°C, 250°C, and 210°C, respectively, and the molten polypropylene resin compositions were then laminated from a T-die at 250°C to produce a 1.8 mm thick laminated molten sheet, with the thickness ratio of the functional layer D, base layer A, and seal layer B being 1/14/1.
- the functional layer D side of the molten sheet was brought into contact with a cooling roll at 20 ° C. and then placed in a water bath at 20 ° C.
- the sheet was then stretched 4.5 times in the longitudinal direction using two pairs of rolls at 142 ° C., then clamped at both ends with clips and introduced into a hot air oven, preheated to 172 ° C., and then stretched 12.7 times in the width direction at 162 ° C.
- the sheet was heat-treated at 170 ° C. while still held by the clips without relaxation, and then heat-treated at 140 ° C. to achieve a relaxation rate of 3% in the width direction. Finally, the sheet was cooled to room temperature.
- the surface of the seal layer B side of the obtained biaxially oriented polypropylene film was subjected to corona treatment using a corona treatment machine (manufactured by Softal Corona & Plasma GmbH) at an applied current of 0.75 A and an applied voltage of 1.8 kW, and then wound up on a winder to obtain the biaxially oriented polypropylene film of the present invention.
- the thickness of the obtained film was 16 ⁇ m.
- the thicknesses of the functional layer D, the base layer A and the seal layer B were 1 ⁇ m, 14 ⁇ m and 1 ⁇ m, respectively.
- Table 1 The raw material composition of each layer and the film-forming conditions are shown in Table 1, and various physical properties of the film are shown in Table 2.
- the biaxially oriented polypropylene film had low heat shrinkage at high temperatures, high seal strength, and excellent anti-fogging properties. It also had excellent flatness after treatment at 130°C.
- the three-side sealed bag produced using the film of Example 1 had a good heat-sealed appearance and excellent handleability due to the excellent stiffness of the bag.
- Examples 2 to 4 films were produced using the same production method as in Example 1, except that the film production conditions were changed to those shown in Table 1. Various physical properties of the films are shown in Table 2.
- the biaxially oriented polypropylene films of Examples 2 to 4 had high rigidity like that of Example 1, but also had low heat shrinkage at high temperatures, high seal strength, and excellent anti-fogging properties.
- Examples 5 and 6 The same materials as those used in Examples 1 to 4 were used as the raw materials for the base layer A and the seal layer B, and the propylene-ethylene-butene copolymer PP-6 was used as the raw material for the intermediate layer C.
- the polypropylene resin compositions constituting each of the base layer A, intermediate layer C, and seal layer B were heated and melted in an extruder using a multi-layer feed block at 250°C, 250°C, and 210°C, respectively, and the molten polypropylene resin compositions were laminated from a T-die at 250°C to produce a 1.8 mm thick laminated molten sheet, with the thickness ratio of the base layer A, intermediate layer C, and seal layer B being 13/2/1.
- a molten sheet was obtained in the same manner as in Example 1 and stretched in the longitudinal and width directions. Immediately after stretching in the width direction, the sheet was heat-treated at 170°C while held by the clips without relaxation, then heat-treated at 140°C to relax the sheet in the width direction by 3%, and finally cooled to room temperature.
- the surface of the resulting biaxially oriented polypropylene film on the side of the seal layer B was corona-treated, and the resulting film was wound up on a winder to form a biaxially oriented polypropylene film of the present invention.
- the thickness of the resulting film was 16 ⁇ m.
- the thicknesses of the base layer A, intermediate layer C, and seal layer B were 13 ⁇ m, 2 ⁇ m, and 1 ⁇ m.
- the raw material composition of each layer and the film-forming conditions are shown in Table 1, and various physical properties of the film are shown in Table 2.
- the biaxially oriented polypropylene films of Examples 5 and 6 had high rigidity, but also had low heat shrinkage at high temperatures, high seal strength, and excellent anti-fogging properties.
- Example 7 The same materials as those used in Examples 1 to 4 were used as the raw materials for the base layer A, the sealing layer B, and the functional layer D, and the propylene-ethylene-butene copolymer PP-6 was used as the raw material for the intermediate layer C.
- the polypropylene resin compositions constituting each of the functional layer D, base layer A, intermediate layer C, and seal layer B were heated and melted in an extruder using a multi-layer feed block at 250°C, 250°C, 250°C, and 210°C, respectively, and the molten polypropylene resin compositions were laminated from a T-die at 250°C to produce a 1.8 mm thick laminated molten sheet, with the thickness ratio of the functional layer D, base layer A, intermediate layer C, and seal layer B being 1/16/2/1.
- a molten sheet was obtained in the same manner as in Example 1 and stretched in the longitudinal and width directions.
- the sheet was heat-treated at 170°C while held by the clips without relaxation, then heat-treated at 140°C to relax the sheet in the width direction by 3%, and finally cooled to room temperature.
- the surface of the resulting biaxially oriented polypropylene film on the side of the seal layer B was corona-treated, and the resulting film was wound up on a winder to form a biaxially oriented polypropylene film of the present invention.
- the thickness of the resulting film was 20 ⁇ m.
- the thicknesses of the functional layer D, base layer A, intermediate layer C, and seal layer B were 1 ⁇ m, 16 ⁇ m, 2 ⁇ m, and 1 ⁇ m.
- the raw material composition of each layer and the film-forming conditions are shown in Table 1, and various physical properties of the film are shown in Table 2.
- the biaxially oriented polypropylene film of Example 7 had high rigidity, but also had low heat shrinkage at high temperatures, high seal strength, and excellent anti-fogging properties.
- Comparative Examples 1 to 6 In Comparative Examples 1 to 6, the same raw materials as in Example 7 were used to form a layer structure of functional layer D/substrate layer A/intermediate layer C/sealing layer B, and except for Comparative Example 3, the thickness structure was also the same as in Example 7, with a total thickness of 20 ⁇ m, that is, 1 ⁇ m/16 ⁇ m/2 ⁇ m/1 ⁇ m. In Comparative Example 3, the thicknesses of the layers were 1 ⁇ m/31 ⁇ m/2 ⁇ m/1 ⁇ m, and the total thickness was 35 ⁇ m.
- the film-forming conditions for Comparative Examples 1 to 6 are shown in Table 3, and various physical properties of the films are shown in Table 4.
- Comparative Example 7 In Comparative Example 7, the layer structure was the same as in Example 7, that is, functional layer D/substrate layer A/intermediate layer C/sealing layer B, and the thickness structure was also the same as in Example 7, that is, 1 ⁇ m/16 ⁇ m/2 ⁇ m/1 ⁇ m, for a total thickness of 20 ⁇ m.
- the base layer A was made from a polypropylene resin composition containing 43% by mass of PP-6 ("FY6H" manufactured by Japan Polypropylene Corporation, MFR: 1.9 g/10 min, melting point: 163°C, mesopentad fraction: 98.9%), a propylene homopolymer, and 57% by mass of PP-7 (a composition obtained by adding 0.16% by mass of glycerin monostearate (TB-123 manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), 0.2% by mass of polyoxyethylene (2) stearylamine (TB-12 manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), and 0.6% by mass of polyoxyethylene (2) stearylamine monostearate (Elex 334 manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) to 100% by mass of the above PP-1).
- the film formation conditions are shown in Table 3, and the physical properties of the film are shown in Table 4.
- Fig. 1 is a diagram showing the relationship between temperature and the length in the width direction of the film in Example 1, Comparative Example 1, and Comparative Example 4, and more precisely, the relationship between temperature and the percentage of (X 1 - X 0 )/X 0.
- Fig. 2 is a diagram showing the relationship between temperature and loss modulus in Example 1 and Comparative Example 1
- Fig. 3 is a diagram showing the relationship between temperature and storage modulus in Example 1 and Comparative Example 1.
- the biaxially oriented polypropylene film of the present invention has excellent rigidity and heat resistance, making it easy to process into bags and easily retaining the shape of the bags when made into packaging bags. Therefore, the biaxially oriented polypropylene film of the present invention can be used for packaging bags, and packaging bags to which an anti-fog agent has been added are particularly suitable for packaging fresh produce. Furthermore, the biaxially oriented polypropylene film of the present invention can be suitably used in applications requiring high rigidity even without laminating a sealant film, and since it can maintain its strength even when the film is thin, it can reduce the burden on the environment.
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Abstract
Description
本発明は、二軸配向ポリプロピレンフィルムに関する。 The present invention relates to a biaxially oriented polypropylene film.
従来から、包装用に使用するヒートシール性フィルムとして、ポリプロピレン系樹脂フィルムが広く用いられている。ヒートシール性を有するポリプロピレン系樹脂フィルムの一例として、無延伸ポリエチレン系樹脂フィルム又は無延伸ポリプロピレン系樹脂フィルムと延伸ポリプロピレン系樹脂フィルムとをラミネートした積層ポリプロピレン系樹脂フィルムが挙げられる。しかし、上記積層ポリプロピレン系樹脂フィルムは、十分なシール強度を有するものの、有機溶剤などを使用するラミネート工程が必要であり、コスト面からも地球環境に与える影響の面からも好ましくない。 Conventionally, polypropylene-based resin films have been widely used as heat-sealable films for packaging. One example of a polypropylene-based resin film with heat-sealability is a laminated polypropylene-based resin film made by laminating an unstretched polyethylene-based resin film or an unstretched polypropylene-based resin film with an oriented polypropylene-based resin film. However, while the above-mentioned laminated polypropylene-based resin film has sufficient sealing strength, it requires a lamination process that uses organic solvents, making it undesirable from both a cost perspective and an environmental impact perspective.
別の例として、高融点のポリプロピレン系樹脂からなる層と低融点のポリオレフィン系樹脂からなる層を共押出しで積層したシートを延伸して得られた積層ポリプロピレン系樹脂フィルムが挙げられる。例えば、特許文献1,2には、剛性や透明性に優れたヒートシール性を有する二軸配向ポリプロピレン系樹脂フィルムが開示されている。 Another example is a laminated polypropylene resin film obtained by stretching a sheet in which a layer of high-melting-point polypropylene resin and a layer of low-melting-point polyolefin resin are co-extruded together. For example, Patent Documents 1 and 2 disclose biaxially oriented polypropylene resin films that have excellent rigidity, transparency, and heat sealability.
しかし、特許文献1,2のフィルムには、加工性に劣るという問題があった。また、透明性も向上が求められていた。 However, the films in Patent Documents 1 and 2 had the problem of poor processability. There was also a demand for improved transparency.
本発明は、クラリティが大きく、高温での貯蔵弾性率が高く、高温での熱収縮率が小さい二軸配向ポリプロピレンフィルムを提供することを目的とする。 The object of the present invention is to provide a biaxially oriented polypropylene film that has high clarity, a high storage modulus at high temperatures, and a low heat shrinkage rate at high temperatures.
本発明は、かかる目的を達成するために鋭意検討した結果、クラリティが大きく、高温での貯蔵弾性率が高く、高温での熱収縮率が小さい二軸配向ポリプロピレンフィルムを開発し、本発明を完成した。すなわち、本発明は、以下の発明を含む。
[1] ポリプロピレン系樹脂組成物からなる基材層A、及びポリプロピレン系樹脂組成物からなるシール層Bを有し、下記(1)~(4)を満足することを特徴とする二軸配向ポリプロピレンフィルム。
(1)シール層Bを少なくとも一方の最表面に有する。
(2)クラリティが90%以上100%以下である。
(3)幅方向の140℃での貯蔵弾性率が0.7GPa以上5.0GPa以下である。
(4)幅方向の150℃熱収縮率が10%以下である。
[2] 熱機械分析において、30℃から160℃まで昇温速度10℃/分で昇温したとき、30℃での幅方向の長さX0に対して幅方向の長さが0.9950×X0以下となる温度が129℃以上であり、23℃での長手方向の貯蔵弾性率が2.0GPa以上、23℃での幅方向の貯蔵弾性率が7.0GPa以上である前記[1]に記載の二軸配向ポリプロピレンフィルム。
[3] 120℃での長手方向の貯蔵弾性率が0.5GPa以上、120℃での幅方向の貯蔵弾性率が1.5GPa以上である前記[1]または[2]に記載の二軸配向ポリプロピレンフィルム。
[4] 120℃での長手方向の熱収縮率が2.5%以下、120℃での幅方向の熱収縮率が1.1%以下である前記[1]~[3]のいずれかに記載の二軸配向ポリプロピレンフィルム。
[5] 23℃での幅方向の5%伸長時応力が120MPa以上である前記[1]~[4]のいずれかに記載の二軸配向ポリプロピレンフィルム。
[6] ヘイズが7.0%以下である前記[1]~[5]のいずれかに記載の二軸配向ポリプロピレンフィルム。
[7] 防曇剤を0.2質量%以上2.0質量%以下含む前記[1]~[6]のいずれかに記載の二軸配向ポリプロピレンフィルム。
[8] 前記基材層Aが、メソペンタッド分率が97.0%以上であるポリプロピレン樹脂を90質量%以上含む前記[1]~[7]のいずれかに記載の二軸配向ポリプロピレンフィルム。
[9] 前記シール層Bがポリプロピレン共重合体を70質量%以上含み、前記ポリプロピレン共重合体はプロピレン以外のα-オレフィンを4モル%以上含む前記[1]~[8]のいずれかに記載の二軸配向ポリプロピレンフィルム。
[10] 前記基材層Aと前記シール層Bとの間にポリプロピレン系樹脂組成物からなる中間層Cを有し、前記中間層Cを構成するポリプロピレン系樹脂組成物の融点が前記シール層Bを構成するポリプロピレン系樹脂組成物の融点より高い前記[1]~[9]のいずれかに記載の二軸配向ポリプロピレンフィルム。
[11] 厚みが10μm以上100μm以下である前記[1]~[10]のいずれかに記載の二軸配向ポリプロピレンフィルム。
As a result of extensive research to achieve the above object, the inventors have developed a biaxially oriented polypropylene film with high clarity, high storage modulus at high temperatures, and low heat shrinkage at high temperatures, thereby completing the present invention. That is, the present invention includes the following inventions.
[1] A biaxially oriented polypropylene film having a base layer A made of a polypropylene-based resin composition and a seal layer B made of a polypropylene-based resin composition, and satisfying the following (1) to (4):
(1) The seal layer B is provided on at least one outermost surface.
(2) Clarity is between 90% and 100%.
(3) The storage modulus in the width direction at 140° C. is 0.7 GPa or more and 5.0 GPa or less.
(4) The thermal shrinkage rate at 150°C in the width direction is 10% or less.
[2] The biaxially oriented polypropylene film according to [1 ] , wherein, in a thermomechanical analysis, when heated from 30°C to 160°C at a heating rate of 10°C/min, the temperature at which the widthwise length is 0.9950 x X0 or less relative to the widthwise length X0 at 30°C is 129°C or higher, and the storage modulus in the longitudinal direction at 23°C is 2.0 GPa or higher and the storage modulus in the widthwise direction at 23°C is 7.0 GPa or higher.
[3] The biaxially oriented polypropylene film according to [1] or [2], wherein the storage modulus in the longitudinal direction at 120°C is 0.5 GPa or more and the storage modulus in the width direction at 120°C is 1.5 GPa or more.
[4] The biaxially oriented polypropylene film according to any one of [1] to [3], wherein the heat shrinkage rate in the longitudinal direction at 120 ° C is 2.5% or less and the heat shrinkage rate in the width direction at 120 ° C is 1.1% or less.
[5] The biaxially oriented polypropylene film according to any one of [1] to [4], wherein the stress at 5% elongation in the width direction at 23°C is 120 MPa or more.
[6] The biaxially oriented polypropylene film according to any one of [1] to [5], having a haze of 7.0% or less.
[7] The biaxially oriented polypropylene film according to any one of [1] to [6], containing an anti-fogging agent in an amount of 0.2% by mass or more and 2.0% by mass or less.
[8] The biaxially oriented polypropylene film according to any one of [1] to [7], wherein the base layer A contains 90% by mass or more of a polypropylene resin having a mesopentad fraction of 97.0% or more.
[9] The biaxially oriented polypropylene film according to any one of [1] to [8], wherein the seal layer B contains 70% by mass or more of a polypropylene copolymer, and the polypropylene copolymer contains 4% by mol or more of an α-olefin other than propylene.
[10] The biaxially oriented polypropylene film according to any one of [1] to [9], which has an intermediate layer C made of a polypropylene-based resin composition between the base layer A and the seal layer B, and the melting point of the polypropylene-based resin composition constituting the intermediate layer C is higher than the melting point of the polypropylene-based resin composition constituting the seal layer B.
[11] The biaxially oriented polypropylene film according to any one of [1] to [10], having a thickness of 10 μm or more and 100 μm or less.
本発明のポリプロピレンフィルムは、剛性および耐熱性に優れているヒートシール性を有するフィルムであるため、包装袋としたときに袋形状を保持しやすい。また、シーラントフィルムをラミネートすることなく、高い剛性が必要とされる用途にも好適に用いることができ、フィルムの厚みを薄くしても強度を維持することができる。また、耐熱性に優れているのでヒートシールしたときにシール部のシワが少なく、袋形状としたときの外観に優れている。 The polypropylene film of the present invention is a heat-sealable film with excellent rigidity and heat resistance, so it easily maintains its bag shape when made into a packaging bag. It can also be used suitably in applications requiring high rigidity without laminating a sealant film, and can maintain its strength even when the film is thin. Furthermore, because it has excellent heat resistance, there are fewer wrinkles in the sealed area when heat-sealed, resulting in an excellent appearance when made into a bag.
以下、本発明の二軸配向ポリプロピレンフィルムについて説明する。 The biaxially oriented polypropylene film of the present invention will be described below.
二軸配向ポリプロピレンフィルムの層構成
本発明の二軸配向ポリプロピレンフィルムは、ポリプロピレン系樹脂組成物からなる基材層A、及びポリプロピレン系樹脂組成物からなるシール層Bを有する。本発明の二軸配向ポリプロピレンフィルムは、前記基材層Aと前記シール層Bとの間にポリプロピレン系樹脂組成物からなる中間層Cを有してもよい。さらに、本発明の二軸配向ポリプロピレンフィルムは、機能層Dを有していてもよい。
以下に基材層A、シール層B、中間層C、及び機能層Dについて、詳しく説明する。
Layer structure of biaxially oriented polypropylene film The biaxially oriented polypropylene film of the present invention has a base layer A made of a polypropylene-based resin composition and a seal layer B made of a polypropylene-based resin composition. The biaxially oriented polypropylene film of the present invention may have an intermediate layer C made of a polypropylene-based resin composition between the base layer A and the seal layer B. Furthermore, the biaxially oriented polypropylene film of the present invention may have a functional layer D.
The substrate layer A, the seal layer B, the intermediate layer C, and the functional layer D will be described in detail below.
1.基材層A
ポリプロピレン系樹脂組成物からなる基材層Aは、ポリプロピレン単独重合体を主成分とするポリプロピレン系樹脂組成物からなることが好ましい。なお、「主成分」とは、基材層A全体の80質量%以上がポリプロピレン単独重合体であることを意味し、基材層A全体の90質量%以上がポリプロピレン単独重合体であることがより好ましく、基材層A全体の95質量%以上がポリプロピレン単独重合体であることがよりさらに好ましく、基材層A全体の97質量%以上がポリプロピレン単独重合体であることが特に好ましく、基材層A全体の99質量%以上がポリプロピレン単独重合体であることが最も好ましい。当該割合の上限は特に制限されないが、基材層A全体の100質量%以下がポリプロピレン単独重合体であってもよい。
1. Base material layer A
The base layer A made of a polypropylene-based resin composition is preferably made of a polypropylene-based resin composition containing a polypropylene homopolymer as a main component. The term "main component" means that 80% by mass or more of the entire base layer A is polypropylene homopolymer, more preferably 90% by mass or more of the entire base layer A is polypropylene homopolymer, even more preferably 95% by mass or more of the entire base layer A is polypropylene homopolymer, particularly preferably 97% by mass or more of the entire base layer A is polypropylene homopolymer, and most preferably 99% by mass or more of the entire base layer A is polypropylene homopolymer. The upper limit of this ratio is not particularly limited, but 100% by mass or less of the entire base layer A may be polypropylene homopolymer.
1-1.ポリプロピレン単独重合体
基材層Aに用いられるポリプロピレン単独重合体は、実質的にプロピレン以外のα-オレフィン成分を含まないポリプロピレン重合体であり、具体的には、100モル%のプロピレンの単独重合体、又は0モル%超1モル%以下のプロピレン以外のα-オレフィン成分と99モル%以上100モル%未満のプロピレン(合計100モル%)とを構成単位とするポリプロピレン共重合体である。プロピレン以外のα-オレフィン成分とは、エチレン、及び炭素数4以上のα-オレフィンをいう。プロピレン以外のα-オレフィン成分を含む場合であっても、プロピレン以外のα-オレフィン成分の含有量は上述のとおり1モル%以下であり、好ましくは0.3モル%以下であり、より好ましくは0.2モル%以下であり、よりさらに好ましくは0.1モル%以下である。上記範囲内であると結晶性が向上しやすい。
1-1. Polypropylene Homopolymer The polypropylene homopolymer used in the base layer A is a polypropylene polymer that is substantially free of α-olefin components other than propylene. Specifically, it is a 100 mol% propylene homopolymer or a polypropylene copolymer having structural units of more than 0 mol% and 1 mol% or less of α-olefin components other than propylene and 99 mol% or more but less than 100 mol% of propylene (total 100 mol%). α-olefin components other than propylene refer to ethylene and α-olefins having 4 or more carbon atoms. Even when α-olefin components other than propylene are contained, the content of α-olefin components other than propylene is 1 mol% or less, as described above, preferably 0.3 mol% or less, more preferably 0.2 mol% or less, and even more preferably 0.1 mol% or less. Within the above range, crystallinity is likely to be improved.
炭素数4以上のα-オレフィン成分として、例えば、1-ブテン、1-ペンテン、3-メチル-1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、5-エチル-1-ヘキセン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-ヘプタデセン、1-オクタデセン、1-エイコセンなどが挙げられる。 Examples of α-olefin components having 4 or more carbon atoms include 1-butene, 1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 5-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
ポリプロピレン単独重合体は、異なる2種以上のポリプロピレン単独重合体を用いることもでき、その場合、合計の含有量が上記範囲内であることが好ましい。なお、基材層Aに用いられるポリプロピレン単独重合体については、プロピレン以外のα-オレフィン成分を全く含まないポリプロピレン単独重合体のみならず、0モル%超1モル%以下のプロピレン以外のα-オレフィン成分と99モル%以上100モル%未満のプロピレンとを構成単位とするポリプロピレン共重合体もポリプロピレン単独重合体に含むものとする。 Two or more different types of polypropylene homopolymers can also be used, in which case it is preferable that the total content is within the above range. The polypropylene homopolymer used in base layer A includes not only polypropylene homopolymers containing no α-olefin components other than propylene, but also polypropylene copolymers whose constituent units are more than 0 mol% and not more than 1 mol% α-olefin components other than propylene and 99 mol% or more but less than 100 mol% propylene.
以下にポリプロピレン単独重合体の好適な各種物性について記載する。なお、異なる2種以上のポリプロピレン単独重合体を用いる場合、物性値は各ポリプロピレン単独重合体の物性を質量平均した値とする。 The following describes various suitable physical properties of polypropylene homopolymer. When two or more different types of polypropylene homopolymer are used, the physical property values are the mass average values of the physical properties of each polypropylene homopolymer.
基材層Aに用いられるポリプロピレン単独重合体の融点Tmaとしては、160℃以上170℃以下が好ましい。Tmaが160℃以上であれば、剛性と高温での耐熱性が得られやすい。Tmaが170℃以下であると、ポリプロピレン製造でのコストアップを抑制しやすく、また製膜時に破断しにくくなる。Tmaとしては、161℃以上がより好ましく、162℃以上がよりさらに好ましく、また、169℃以下がより好ましく、168℃以下がよりさらに好ましく、167℃以下が特に好ましく、166℃以下が最も好ましい。前述のポリプロピレン樹脂に結晶核剤を配合することによって、Tmaをより上げることもできる。
樹脂の融点は、ポリプロピレン単独重合体5mgをアルミパンに詰めて示差走査熱量計(DSC)にセットし、窒素雰囲気下で昇温速度20℃/分で30℃から230℃まで昇温し230℃で5分間保持することでポリプロピレン単独重合体を融解し、その後、降温速度-10℃/分で30℃まで降温し30℃で5分間保持した後、昇温速度10℃/分で昇温した際に観察される、融解にともなう吸熱ピークの主たるピーク温度である。
The melting point Tm a of the polypropylene homopolymer used in the base layer A is preferably 160°C or higher and 170°C or lower. If Tm a is 160°C or higher, rigidity and heat resistance at high temperatures are likely to be obtained. If Tm a is 170°C or lower, it is easy to suppress an increase in the cost of polypropylene production and the film is less likely to break during film formation. Tm a is more preferably 161°C or higher, even more preferably 162°C or higher, more preferably 169°C or lower, even more preferably 168°C or lower, particularly preferably 167°C or lower, and most preferably 166°C or lower. Tm a can also be further increased by blending a crystal nucleating agent with the above-mentioned polypropylene resin.
The melting point of the resin is the main peak temperature of the endothermic peak accompanying melting, which is observed when 5 mg of polypropylene homopolymer is packed into an aluminum pan, set in a differential scanning calorimeter (DSC), heated from 30°C to 230°C at a heating rate of 20°C/min in a nitrogen atmosphere, and held at 230°C for 5 minutes to melt the polypropylene homopolymer, then cooled to 30°C at a heating rate of -10°C/min, held at 30°C for 5 minutes, and then heated at a heating rate of 10°C/min.
基材層Aに用いられるポリプロピレン単独重合体は、立体規則性の指標であるメソペンタッド分率([mmmm]%)が97.0%以上99.9%以下であることが好ましい。当該メソペンタッド分率が97.0%以上であると、ポリプロピレン樹脂の結晶性が高まり、基材層Aにおける結晶の融点Tma、結晶化度、結晶配向度が向上し、剛性と高温での耐熱性が得られやすい。当該メソペンタッド分率が99.9%以下であると、ポリプロピレン製造でのコストを抑えやすく、製膜時に破断しにくくなる。上記メソペンタッド分率としては、97.5%以上がより好ましく、98.0%以上がよりさらに好ましく、また、99.7%以下がより好ましく、99.5%以下がよりさらに好ましい。メソペンタッド分率は、核磁気共鳴法(所謂NMR法)で測定される。ポリプロピレン単独重合体のメソペンタッド分率を上述の範囲内とするためには、得られたポリプロピレン重合体のパウダーをn-ヘプタンなどの溶媒で洗浄する方法、触媒および/または助触媒の選定、ポリプロピレン系樹脂組成物の成分の選定を適宜行う方法などが好ましく採用される。 The polypropylene homopolymer used in the base layer A preferably has a mesopentad fraction ([mmmm]%), which is an index of stereoregularity, of 97.0% or more and 99.9% or less. A mesopentad fraction of 97.0% or more enhances the crystallinity of the polypropylene resin, improving the melting point Tm a of the crystals in the base layer A, the degree of crystallinity, and the degree of crystal orientation, making it easier to obtain rigidity and heat resistance at high temperatures. A mesopentad fraction of 99.9% or less makes it easier to reduce the cost of polypropylene production and makes the film less susceptible to breakage during film formation. The mesopentad fraction is more preferably 97.5% or more, even more preferably 98.0% or more, and more preferably 99.7% or less, and even more preferably 99.5% or less. The mesopentad fraction is measured by nuclear magnetic resonance (NMR) spectroscopy. In order to control the mesopentad fraction of the polypropylene homopolymer within the above range, a method of washing the obtained polypropylene polymer powder with a solvent such as n-heptane, a method of appropriately selecting a catalyst and/or a co-catalyst, and a method of appropriately selecting components of the polypropylene resin composition are preferably employed.
基材層Aに用いられるポリプロピレン単独重合体のメルトフローレート(MFR)は、JIS K 7210(1995)の条件Mに準拠して、温度230℃、荷重2.16kgfで測定した場合において、5.0g/10分以上30g/10分以下が好ましい。
ポリプロピレン樹脂のMFRが5.0g/10分以上であると、基材層Aを構成するポリプロピレン樹脂の低分子量成分が多くなるため、後述するフィルム製膜工程での幅方向延伸工程を採用することにより、ポリプロピレン樹脂の配向結晶化がより促進されること、基材層Aにおける結晶化度がより高まりやすくなることに加えて、非晶部分のポリプロピレン分子鎖同士の絡み合いがより少なくなることから、耐熱性をより高めやすい。また、ポリプロピレン樹脂のMFRが30g/10分以下であると、フィルムの製膜性を維持しやすい。
上記MFRとしては、5.5g/10分以上がより好ましく、6.0g/10分以上がよりさらに好ましく、6.3g/10分以上が特に好ましく、6.5g/10分以上が最も好ましく、また、25g/10分以下がより好ましく、22g/10分以下がよりさらに好ましく、20g/10分以下が特に好ましく、10g/10分以下が最も好ましい。
ポリプロピレン単独重合体のMFRを上記の範囲内とするためには、ポリプロピレン単独重合体の分子量や分子量分布を制御する方法などを採用するのが好ましい。
The melt flow rate (MFR) of the polypropylene homopolymer used in the base layer A is preferably 5.0 g/10 min or more and 30 g/10 min or less when measured at a temperature of 230°C and a load of 2.16 kgf in accordance with condition M of JIS K 7210 (1995).
When the polypropylene resin has an MFR of 5.0 g/10 min or more, the polypropylene resin constituting the base layer A contains a large amount of low-molecular-weight components, and therefore, by employing a width direction stretching step in the film formation process described below, oriented crystallization of the polypropylene resin is further promoted, the crystallinity of the base layer A is more likely to be increased, and entanglement of polypropylene molecular chains in the amorphous portion is reduced, making it easier to improve heat resistance. Furthermore, when the polypropylene resin has an MFR of 30 g/10 min or less, the film formability of the film is easily maintained.
The MFR is more preferably 5.5 g/10 min or more, even more preferably 6.0 g/10 min or more, particularly preferably 6.3 g/10 min or more, and most preferably 6.5 g/10 min or more. It is more preferably 25 g/10 min or less, even more preferably 22 g/10 min or less, particularly preferably 20 g/10 min or less, and most preferably 10 g/10 min or less.
In order to set the MFR of the polypropylene homopolymer within the above range, it is preferable to employ a method for controlling the molecular weight or molecular weight distribution of the polypropylene homopolymer.
基材層Aに用いられるポリプロピレン単独重合体は、分子量分布の指標であるMw/Mnの下限が好ましくは3.5であり、より好ましくは4.0であり、よりさらに好ましくは4.5であり、特に好ましくは5.0である。Mw/Mnの上限は、好ましくは30であり、より好ましくは25であり、よりさらに好ましくは23であり、特に好ましくは21であり、最も好ましくは20である。
Mw/Mnが上記範囲内であると、分子量10万以下の成分の量を多くすることが容易である。Mw/Mnは、ゲルパーミエーションクロマトグラフィー(GPC)を用いて得ることができる。
The polypropylene homopolymer used in the base layer A has a lower limit of Mw / Mn , which is an index of molecular weight distribution, of preferably 3.5, more preferably 4.0, even more preferably 4.5, and particularly preferably 5.0. The upper limit of Mw / Mn is preferably 30, more preferably 25, even more preferably 23, particularly preferably 21, and most preferably 20.
When Mw / Mn is within the above range, it is easy to increase the amount of components having a molecular weight of 100,000 or less. Mw / Mn can be obtained using gel permeation chromatography (GPC).
なお、ポリプロピレン重合体の分子量分布は、異なる分子量の成分を多段階に一連のプラントで重合したり、異なる分子量の成分をオフラインで混練機にてブレンドしたり、異なる性能をもつ触媒をブレンドして重合したり、所望の分子量分布を実現できる触媒を用いたりすることで調整することが可能である。GPCで得られる分子量分布の形状としては、横軸に分子量(M)の対数(logM)、縦軸に微分分布値(logMあたりの質量分率)をとったGPCチャートにおいて、単一ピークを有するなだらかな分子量分布であってもよく、複数のピークやショルダーを有する分子量分布であってよい。 The molecular weight distribution of polypropylene polymers can be adjusted by polymerizing components of different molecular weights in multiple stages in a series of plants, blending components of different molecular weights offline in a kneader, polymerizing by blending catalysts with different performance, or using a catalyst that can achieve the desired molecular weight distribution. The shape of the molecular weight distribution obtained by GPC may be a gentle molecular weight distribution with a single peak on a GPC chart with the logarithm (logM) of molecular weight (M) on the horizontal axis and the differential distribution value (mass fraction per logM) on the vertical axis, or a molecular weight distribution with multiple peaks or shoulders.
基材層Aを構成するプロピレン系樹脂組成物のGPC積算カーブにおける分子量10万以下の成分の量は、38質量%以上が好ましく、38質量%以上65質量%以下がより好ましい。分子量10万以下の成分の量を38質量%以上とすることにより、耐熱性を高めやすい。分子量10万以下の成分の量が65質量%以下であると、フィルム強度が低下しにくい。このとき、緩和時間の長い高分子量成分や長鎖分岐成分を含むと、全体の粘度を大きく変えずに、ポリプロピレン樹脂に含まれる分子量10万以下の成分の量を調整しやすくなるので、剛性や耐熱性にあまり影響を与えずに製膜性を改善しやすい。上記量としては、40質量%以上がよりさらに好ましく、41質量%以上が特に好ましく、42質量%以上が最も好ましく、また、60質量%以下がよりさらに好ましく、55質量%以下が特に好ましく、50質量%以下が最も好ましい。 The amount of components with a molecular weight of 100,000 or less in the GPC cumulative curve of the propylene-based resin composition constituting the base layer A is preferably 38% by mass or more, and more preferably 38% by mass or more and 65% by mass or less. By ensuring that the amount of components with a molecular weight of 100,000 or less is 38% by mass or more, heat resistance is easily improved. If the amount of components with a molecular weight of 100,000 or less is 65% by mass or less, film strength is less likely to decrease. In this case, if high-molecular-weight components with long relaxation times or long-chain branched components are included, it becomes easier to adjust the amount of components with a molecular weight of 100,000 or less contained in the polypropylene resin without significantly changing the overall viscosity, making it easier to improve film formability without significantly affecting rigidity or heat resistance. The above amount is even more preferably 40% by mass or more, particularly preferably 41% by mass or more, most preferably 42% by mass or more, even more preferably 60% by mass or less, particularly preferably 55% by mass or less, and most preferably 50% by mass or less.
1-2.防曇剤
基材層Aを構成するポリプロピレン系樹脂組成物に防曇剤を配合することが好ましい。本発明の二軸配向ポリプロピレンフィルムは包装袋に加工して用いることができるが、特に包装袋に青果物を入れた場合、青果物は収穫後も生理作用を持続するため、防曇剤を添加することにより、包装袋に生じる曇りを防止できる。
1-2. Anti-Fog Agent It is preferable to blend an anti-fogging agent into the polypropylene resin composition constituting the base layer A. The biaxially oriented polypropylene film of the present invention can be processed into packaging bags, and when fruits and vegetables are placed in the packaging bags, the addition of an anti-fogging agent can prevent fogging of the packaging bags, since the physiological functions of the fruits and vegetables continue even after harvest.
防曇剤としては、例えば、脂肪族アミンのエチレンオキサイド付加物、脂肪族アミドのエチレンオキサイド付加物、脂肪族アミンのエチレンオキサイド付加物と脂肪酸とのエステル、多価アルコ-ルの脂肪酸エステル、脂肪酸アミン、脂肪酸アミドなどの公知の防曇剤を用いることができる。中でも、脂肪族アミンのエチレンオキサイド付加物および脂肪族アミンのエチレンオキサイド付加物と脂肪酸とのエステルからなる群から選択される少なくとも1種を含むことが好ましく、脂肪族アミンのエチレンオキサイド付加物および脂肪族アミンのエチレンオキサイド付加物と脂肪酸とのエステルを含むことがより好ましい。
脂肪族アミンのエチレンオキサイド付加物と脂肪酸とのエステルは、ステアリルジエタノールアミンモノエステル及びステアリルジエタノールアミンジエステルからなる群から選択される少なくとも1種を含むことが好ましい。なお、包装袋は冷凍保存よりもむしろ室温雰囲気で保存されることが多く、流通過程で長期的に優れた防曇性を持続させるためには、保存または流通時の気温変化を考慮して、5℃以上30℃以下の間で温度変化を繰り返す経過中、継続して防曇性を示すような防曇剤とすることが好ましいが、上記好適な態様に限定されず、用途に応じて適宜選択すればよい。防曇剤は1種のみでもよく、2種以上併用してもよい。
Examples of the antifogging agent that can be used include known antifogging agents such as ethylene oxide adducts of aliphatic amines, ethylene oxide adducts of aliphatic amides, esters of ethylene oxide adducts of aliphatic amines and fatty acids, fatty acid esters of polyhydric alcohols, fatty acid amines, fatty acid amides, etc. Among these, it is preferable to include at least one selected from the group consisting of ethylene oxide adducts of aliphatic amines and esters of ethylene oxide adducts of aliphatic amines and fatty acids, and it is more preferable to include ethylene oxide adducts of aliphatic amines and esters of ethylene oxide adducts of aliphatic amines and fatty acids.
The ester of an ethylene oxide adduct of an aliphatic amine and a fatty acid preferably comprises at least one selected from the group consisting of stearyl diethanolamine monoester and stearyl diethanolamine diester. Packaging bags are often stored at room temperature rather than frozen, and in order to maintain excellent anti-fogging properties over the long term during distribution, it is preferable to use an anti-fogging agent that continuously exhibits anti-fogging properties over repeated temperature changes between 5°C and 30°C, taking into account temperature changes during storage or distribution. However, the anti-fogging agent is not limited to the above preferred embodiment and may be selected appropriately depending on the application. One type of anti-fogging agent may be used alone, or two or more types may be used in combination.
ステアリルジエタノールアミンモノエステルとしては、ステアリルジエタノールアミンモノラウレート、ステアリルジエタノールアミンモノミリステート、ステアリルジエタノールアミンモノパルミテート、ステアリルジエタノールアミンモノステアレート、ステアリルジエタノールアミンモノオレート等が挙げられ、中でもステアリルジエタノールアミンモノステアレートが好ましい。
ステアリルジエタノールアミンジエステルとしては、ステアリルジエタノールアミンジラウレート、ステアリルジエタノールアミンジミリステート、ステアリルジエタノールアミンジパルミテート、ステアリルジエタノールアミンジステアレート、ステアリルジエタノールアミンジオレート等が挙げられ、中でもステアリルジエタノールアミンジステアレートが好ましい。
脂肪族アミンのエチレンオキサイド付加物は、例えば、ラウリルジエタノールアミン、ミリスチルジエタノールアミン、パルミチルジエタノールアミン、ステアリルジエタノールアミン等が挙げられ、ステアリルジエタノールアミンが好ましい。脂肪族アミンのエチレンオキサイド付加物は1種のみでもよく、2種以上併用してもよい。
Examples of stearyl diethanolamine monoesters include stearyl diethanolamine monolaurate, stearyl diethanolamine monomyristate, stearyl diethanolamine monopalmitate, stearyl diethanolamine monostearate, and stearyl diethanolamine monooleate, with stearyl diethanolamine monostearate being preferred.
Examples of stearyl diethanolamine diesters include stearyl diethanolamine dilaurate, stearyl diethanolamine dimyristate, stearyl diethanolamine dipalmitate, stearyl diethanolamine distearate, and stearyl diethanolamine dioleate, with stearyl diethanolamine distearate being preferred.
Examples of the ethylene oxide adducts of aliphatic amines include lauryldiethanolamine, myristyldiethanolamine, palmityldiethanolamine, and stearyldiethanolamine, with stearyldiethanolamine being preferred. The ethylene oxide adducts of aliphatic amines may be used alone or in combination of two or more.
基材層Aを構成するプロピレン系樹脂組成物中における防曇剤の量は、0.2質量%以上2.0質量%以下が好ましい。当該量としては、0.3質量%以上がより好ましく、0.35質量%以上がよりさらに好ましく、また、1.8質量%以下がより好ましく、1.6質量%以下がよりさらに好ましい。ただし、後述のように、製膜工程において、基材層Aから中間層C等の他の層に防曇剤が移動することがある。 The amount of antifogging agent in the propylene-based resin composition constituting base layer A is preferably 0.2% by mass or more and 2.0% by mass or less. This amount is more preferably 0.3% by mass or more, even more preferably 0.35% by mass or more, more preferably 1.8% by mass or less, and even more preferably 1.6% by mass or less. However, as described below, the antifogging agent may migrate from base layer A to other layers such as intermediate layer C during the film-forming process.
1-3.その他
本発明の効果を損なわない範囲であれば、基材層Aを構成するポリプロピレン系樹脂組成物には、ポリプロピレン単独重合体以外の樹脂や公知の熱安定剤、酸化防止剤、紫外線吸収剤、造核剤、粘着剤、難燃剤、無機または有機の充填剤などの添加剤を含有させてもよい。
しかし、これらの添加は少量であることが好ましく、基材層Aを構成するポリプロピレン系樹脂組成物中、ポリプロピレン単独重合体以外の樹脂の量は20質量%以下であることが好ましく、10質量%以下であることがより好ましく、5質量%以下であることがよりさらに好ましく、2質量%以下であることが特に好ましく、1質量%以下であることが最も好ましい。また、基材層Aを構成するポリプロピレン系樹脂組成物中、樹脂以外の添加剤の量は10質量%以下であることが好ましく、5質量%以下であることがより好ましく、2質量%以下であることがよりさらに好ましく、1質量%以下であることが特に好ましい。これらポリプロピレン単独重合体以外の樹脂および/または樹脂以外の添加剤は、基剤層Aに配合しなくてもよい。すなわち、基材層Aにおけるポリプロピレン単独重合体以外の樹脂および/または樹脂以外の添加剤の量は、0質量%以上である。
ポリプロピレン単独重合体以外の樹脂としては、基材層Aで用いられるポリプロピレン単独重合体以外のポリオレフィン樹脂や、各種エラストマー等が挙げられる。これらは、多段の反応器を用いて逐次重合するか、ポリプロピレン樹脂とヘンシェルミキサーでブレンドするか、事前に溶融混錬機を用いて作製したマスターペレットを所定の濃度になるようにポリプロピレンで希釈するか、予め全量を溶融混練して使用してもよい。基材層Aで用いられるポリプロピレン単独重合体単体であると表面抵抗値が大きすぎる場合には、界面活性剤を添加して表面抵抗値を小さくしてもよい。
1-3. Others The polypropylene resin composition constituting the base layer A may contain resins other than polypropylene homopolymers, as well as known additives such as heat stabilizers, antioxidants, ultraviolet absorbers, nucleating agents, adhesives, flame retardants, and inorganic or organic fillers, as long as the effects of the present invention are not impaired.
However, it is preferable that these be added in small amounts, and in the polypropylene resin composition constituting the base layer A, the amount of resins other than polypropylene homopolymers is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 2% by mass or less, and most preferably 1% by mass or less. Furthermore, in the polypropylene resin composition constituting the base layer A, the amount of additives other than resins is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less. These resins other than polypropylene homopolymers and/or additives other than resins do not need to be blended into the base layer A. That is, the amount of resins other than polypropylene homopolymers and/or additives other than resins in the base layer A is 0% by mass or more.
Examples of resins other than polypropylene homopolymers include polyolefin resins other than the polypropylene homopolymer used in the base layer A, various elastomers, etc. These may be used by sequential polymerization using a multi-stage reactor, blending with polypropylene resin in a Henschel mixer, diluting master pellets prepared in advance using a melt kneader with polypropylene to a predetermined concentration, or melt-kneading the entire amount in advance. If the surface resistance of the polypropylene homopolymer used in the base layer A is too high, a surfactant may be added to reduce the surface resistance.
2.シール層B
2-1.ポリプロピレン系樹脂組成物
ポリプロピレン系樹脂組成物からなるシール層Bは、プロピレン以外のα-オレフィンを含むポリプロピレン共重合体を含むことが好ましい。すなわち、シール層Bを構成するポリプロピレン系樹脂組成物は、プロピレン以外のα-オレフィンを含むポリプロピレン共重合体を含むことが好ましい。なお、シール層Bに関する説明では、単に「(シール層Bに含まれる)ポリプロピレン共重合体」と記載した場合であっても、プロピレンに加えて、プロピレン以外のα-オレフィンを含むポリプロピレン共重合体を指す。シール層Bはポリプロピレン共重合体を70質量%以上含有することが好ましい。ポリプロピレン共重合体を70質量%以上とすることにより、シール層Bと中間層Cとの層間密着性を高めやすく、二軸配向ポリプロピレンフィルムのヒートシール強度をより高めることができる。当該割合としては、80質量%以上がより好ましく、90質量%以上がよりさらに好ましく、95質量%以上が特に好ましい。なお、シール層Bに含まれるポリプロピレン共重合体としては、異なる2種以上のポリプロピレン共重合体を用いることもでき、合計の含有量が上記範囲内であることが好ましい。同割合の上限は特に制限されないが、シール層B全体の100質量%以下がポリプロピレン共重合体であってもよい。
シール層Bに含まれるポリプロピレン共重合体におけるプロピレン以外のα-オレフィン成分の含有量は4.0モル%以上が好ましい。この場合、ポリプロピレン共重合体におけるプロピレンの含有量は96モル%以下であり、プロピレンの含有量とプロピレン以外のα-オレフィン成分の含有量の合計は100モル%である。α-オレフィン成分の含有量は、エチレンと炭素数4以上のα-オレフィンとの合計量である。プロピレン以外のα-オレフィン成分の含有量は、5.0モル%以上がより好ましく、6.0モル%以上がよりさらに好ましく、7.0モル%以上が特に好ましく、また、15モル%以下がより好ましく、12モル%以下がよりさらに好ましく、10モル%以下が特に好ましい。
炭素数4以上のα-オレフィン成分として、例えば、1-ブテン、1-ペンテン、3-メチル-1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、5-エチル-1-ヘキセン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-ヘプタデセン、1-オクタデセン、1-エイコセンなどが挙げられる。
プロピレン以外のα-オレフィン成分は、炭素数が2以上20以下であるプロピレン以外のα-オレフィン成分が好ましく、炭素数が2以上10以下であるプロピレン以外のα-オレフィン成分がより好ましく、炭素数が2以上6以下であるプロピレン以外のα-オレフィン成分がよりさらに好ましく、炭素数が2以上4以下であるプロピレン以外のα-オレフィン成分が特に好ましい。
2. Sealing layer B
2-1. Polypropylene Resin Composition The seal layer B made of a polypropylene resin composition preferably contains a polypropylene copolymer containing an α-olefin other than propylene. That is, the polypropylene resin composition constituting the seal layer B preferably contains a polypropylene copolymer containing an α-olefin other than propylene. In the description of the seal layer B, even if the term "polypropylene copolymer (contained in seal layer B)" is simply used, it refers to a polypropylene copolymer containing propylene and an α-olefin other than propylene. The seal layer B preferably contains 70% by mass or more of the polypropylene copolymer. By containing 70% by mass or more of the polypropylene copolymer, it is easy to improve the interlayer adhesion between the seal layer B and the intermediate layer C, thereby further increasing the heat seal strength of the biaxially oriented polypropylene film. The proportion is more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The polypropylene copolymer contained in the seal layer B can also be two or more different polypropylene copolymers, and the total content is preferably within the above range. There is no particular upper limit to this proportion, but the polypropylene copolymer may account for up to 100% by mass of the entire seal layer B.
The content of α-olefin components other than propylene in the polypropylene copolymer contained in the seal layer B is preferably 4.0 mol% or more. In this case, the propylene content in the polypropylene copolymer is 96 mol% or less, and the sum of the propylene content and the content of α-olefin components other than propylene is 100 mol%. The content of α-olefin components is the total amount of ethylene and α-olefins having 4 or more carbon atoms. The content of α-olefin components other than propylene is more preferably 5.0 mol% or more, even more preferably 6.0 mol% or more, particularly preferably 7.0 mol% or more, and more preferably 15 mol% or less, even more preferably 12 mol% or less, and particularly preferably 10 mol% or less.
Examples of the α-olefin component having 4 or more carbon atoms include 1-butene, 1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 5-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
The α-olefin component other than propylene is preferably an α-olefin component other than propylene having 2 or more and 20 or less carbon atoms, more preferably an α-olefin component other than propylene having 2 or more and 10 or less carbon atoms, even more preferably an α-olefin component other than propylene having 2 or more and 6 or less carbon atoms, and particularly preferably an α-olefin component other than propylene having 2 or more and 4 or less carbon atoms.
シール層Bを構成するポリプロピレン系樹脂組成物の融点Tmbとしては、150℃以下が好ましく、145℃以下がより好ましく、140℃以下がよりさらに好ましく、135℃以下が特に好ましく、130℃以下が最も好ましい。Tmbを上記範囲内とすることにより、ヒートシール立上がり温度を低くしやすい上にヒートシール強度を高めることができる。シール層Bを構成するポリプロピレン系樹脂組成物の融点Tmbの下限は特に限定されず、例えば、110℃以上である。また、ヒートシール強度を高める観点から、シール層Bを構成するポリプロピレン系樹脂組成物の融点Tmbは中間層Cを構成するポリプロピレン系樹脂組成物の融点Tmcより低いことが好ましい。 The melting point Tmb of the polypropylene resin composition constituting the seal layer B is preferably 150°C or lower, more preferably 145°C or lower, even more preferably 140°C or lower, particularly preferably 135°C or lower, and most preferably 130°C or lower. By setting Tmb within the above range, it is easy to lower the heat seal start temperature and also to increase the heat seal strength. There is no particular restriction on the lower limit of the melting point Tmb of the polypropylene resin composition constituting the seal layer B, and it is, for example, 110°C or higher. Furthermore, from the viewpoint of increasing the heat seal strength, it is preferable that the melting point Tmb of the polypropylene resin composition constituting the seal layer B is lower than the melting point Tmc of the polypropylene resin composition constituting the intermediate layer C.
シール層Bを構成するポリプロピレン系樹脂組成物の温度230℃、荷重2.16kgfで測定したメルトフローレート(MFR)は、5.0g/10分以上8.0g/10分以下が好ましい。当該MFRとしては、5.5g/10分以上がより好ましく、6.0g/10分以上がよりさらに好ましく、6.3g/10分以上が特に好ましく、また、7.5g/10分以下がより好ましく、7.0g/10分以下がよりさらに好ましく、6.8g/10分以下が特に好ましい。また、ヒートシール強度を高める観点から、シール層Bを構成するポリプロピレン系樹脂組成物のメルトフローレートは、中間層Cを構成するポリプロピレン系樹脂組成物のメルトフローレートより大きいことが好ましい。 The melt flow rate (MFR) of the polypropylene resin composition constituting seal layer B, measured at a temperature of 230°C and a load of 2.16 kgf, is preferably 5.0 g/10 min or more and 8.0 g/10 min or less. The MFR is more preferably 5.5 g/10 min or more, even more preferably 6.0 g/10 min or more, and particularly preferably 6.3 g/10 min or more, and more preferably 7.5 g/10 min or less, even more preferably 7.0 g/10 min or less, and particularly preferably 6.8 g/10 min or less. Furthermore, from the perspective of increasing heat seal strength, the melt flow rate of the polypropylene resin composition constituting seal layer B is preferably higher than the melt flow rate of the polypropylene resin composition constituting intermediate layer C.
シール層Bに含まれるポリプロピレン共重合体としては、例えばプロピレン・ブテン共重合体、プロピレン・エチレン・ブテン共重合体、及びプロピレン・エチレン共重合体からなる群から選択される少なくとも1種を含むことが好ましく、プロピレン・ブテン共重合体を含むことがより好ましい。 The polypropylene copolymer contained in sealing layer B preferably includes at least one selected from the group consisting of propylene-butene copolymer, propylene-ethylene-butene copolymer, and propylene-ethylene copolymer, and more preferably includes propylene-butene copolymer.
2-2.プロピレン・エチレン・ブテン共重合体
プロピレン・エチレン・ブテン共重合体におけるプロピレン以外のα-オレフィン成分の含有量は4モル%以上が好ましい。プロピレン以外のα-オレフィン成分の含有量が4モル%以上であると、中間層Cとシール層Bとの層間密着性が向上しやすく、その結果、ヒートシール強度や密封性が向上しやすい。プロピレン以外のα-オレフィン成分の含有量は5モル%以上がより好ましく、6モル%以上がよりさらに好ましい。プロピレン以外のα-オレフィン成分の含有量の上限は特に限定されず、例えば、25モル%以下である。なお、プロピレン以外のα-オレフィン成分が2種以上である場合、合計量をプロピレン以外のα-オレフィン成分の含有量とする。
エチレン含有量は1モル%以上が好ましく、2モル%以上がより好ましい。エチレン含有量の上限は特に限定されないが、エチレン含有量が多すぎるとフィルム表面がべたつき、滑り性や耐ブロッキング性が低下するおそれがあるため、例えば、12モル%以下である。
ブテン含有量は1モル%以上が好ましく、2モル%以上がより好ましい。ブテン含有量の上限は特に限定されないが、ブテン含有量が多すぎるとフィルム表面がべたつき、滑り性や耐ブロッキング性が低下するおそれがあるため、例えば、16モル%以下である。
プロピレン以外のα-オレフィン成分の合計含有量が4モル%以上であるプロピレン・エチレン・ブテン共重合体としては、市販品を用いてもよく、例えば、住友化学社製FSX66E8などが挙げられる。
2-2. Propylene-Ethylene-Butene Copolymer The content of α-olefin components other than propylene in the propylene-ethylene-butene copolymer is preferably 4 mol% or more. When the content of α-olefin components other than propylene is 4 mol% or more, the interlayer adhesion between the intermediate layer C and the seal layer B is likely to be improved, and as a result, the heat seal strength and hermetic sealability are likely to be improved. The content of α-olefin components other than propylene is more preferably 5 mol% or more, and even more preferably 6 mol% or more. There is no particular upper limit for the content of α-olefin components other than propylene, and it is, for example, 25 mol% or less. When there are two or more α-olefin components other than propylene, the total amount is taken as the content of the α-olefin components other than propylene.
The ethylene content is preferably 1 mol% or more, more preferably 2 mol% or more. Although there is no particular upper limit to the ethylene content, if the ethylene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may decrease, so the upper limit is, for example, 12 mol% or less.
The butene content is preferably 1 mol% or more, more preferably 2 mol% or more. Although there is no particular upper limit to the butene content, if the butene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may be reduced, so the upper limit is, for example, 16 mol% or less.
As the propylene-ethylene-butene copolymer having a total content of α-olefin components other than propylene of 4 mol % or more, a commercially available product may be used, for example, FSX66E8 manufactured by Sumitomo Chemical Co., Ltd.
2-3.プロピレン・ブテン共重合体
プロピレン・ブテン共重合体におけるブテン含有量は、4モル%以上が好ましい。ブテン含有量が4モル%以上であると、中間層Cとシール層Bとの層間密着力が向上しやすく、その結果、ヒートシール強度や密封性が向上しやすい。ブテン含有量は5モル%以上がより好ましく、6モル%以上がよりさらに好ましい。ブテン含有量の上限は特に限定されないが、ブテン含有量が多すぎるとフィルム表面がべたつき、滑り性や耐ブロッキング性が低下するおそれがあるため、例えば、16モル%以下であり、好ましくは12モル%以下である。ブテン含有量が4モル%以上であるプロピレン・ブテン共重合体としては、市販品を用いてもよく、例えば、住友化学社製SP7843、住友化学社製SPX78J1、三井化学社製XR110Hなどを例示することができる。
2-3. Propylene-Butene Copolymer The butene content in the propylene-butene copolymer is preferably 4 mol% or more. A butene content of 4 mol% or more tends to improve the interlayer adhesion between the intermediate layer C and the seal layer B, and as a result, tends to improve heat seal strength and hermetic sealability. The butene content is more preferably 5 mol% or more, and even more preferably 6 mol% or more. There is no particular upper limit for the butene content, but if the butene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may decrease, so for example, it is 16 mol% or less, preferably 12 mol% or less. As a propylene-butene copolymer having a butene content of 4 mol% or more, commercially available products may be used, such as SP7843 manufactured by Sumitomo Chemical Co., Ltd., SPX78J1 manufactured by Sumitomo Chemical Co., Ltd., and XR110H manufactured by Mitsui Chemicals, Inc.
2-4.プロピレン・エチレン共重合体
プロピレン・エチレン共重合体におけるエチレン含有量は、4モル%以上が好ましい。エチレン含有量が4モル%以上であると、中間層Cとシール層Bとの層間密着力が向上しやすく、その結果、ヒートシール強度や密封性が向上しやすい。エチレン含有量は5モル%以上がより好ましく、6モル%以上がよりさらに好ましい。エチレン含有量の上限は特に限定されないが、エチレン含有量が多すぎるとフィルム表面がべたつき、滑り性や耐ブロッキング性が低下するおそれがあるため、例えば、12モル%以下である。エチレン含有量が4モル%以上であるプロピレン・エチレン共重合体としては、市販品を用いてもよく、例えば、サンアロマー社製PC540R、三井化学社製VM3588FLなどが挙げられる。
2-4. Propylene-Ethylene Copolymer The ethylene content of the propylene-ethylene copolymer is preferably 4 mol% or more. When the ethylene content is 4 mol% or more, the interlayer adhesion between the intermediate layer C and the seal layer B is likely to be improved, and as a result, the heat seal strength and hermetic sealability are likely to be improved. The ethylene content is more preferably 5 mol% or more, and even more preferably 6 mol% or more. There is no particular upper limit for the ethylene content, but if the ethylene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may be reduced, so for example, it is 12 mol% or less. As a propylene-ethylene copolymer having an ethylene content of 4 mol% or more, commercially available products may be used, such as PC540R manufactured by SunAllomer Co., Ltd. and VM3588FL manufactured by Mitsui Chemicals, Inc.
2-5.防曇剤
シール層Bを構成するポリプロピレン系樹脂組成物は、防曇剤を含んでいてもよいし含んでいなくてもよい。防曇剤としては、基材層Aの説明に記載した防曇剤を用いることができる。なお、シール層Bを構成するポリプロピレン系樹脂組成物中には防曇剤を含まない場合であっても、製膜工程において、基材層Aからシール層Bに防曇剤が移動してくる場合があり、得られた二軸配向ポリプロピレンフィルムにおいてはシール層Bに防曇剤が含まれる場合がある。
また、本発明の効果を損なわない範囲であれば、シール層Bを構成するポリプロピレン系樹脂組成物には、ポリプロピレン共重合体以外の樹脂、上述の防曇剤、公知の熱安定剤、酸化防止剤、紫外線吸収剤、造核剤、粘着剤、難燃剤、無機または有機の充填剤などの添加剤が添加されていてもよい。ポリプロピレン共重合体以外の樹脂としては、シール層Bで用いられるポリプロピレン共重合体以外のポリオレフィン樹脂や、各種エラストマー等が挙げられる。しかし、これらの添加は少量であることが好ましく、シール層Bを構成するポリプロピレン系樹脂組成物中、ポリプロピレン共重合体以外の樹脂の量は30質量%以下が好ましく、10質量%以下がより好ましく、5質量%以下がよりさらに好ましく、2質量%以下が特に好ましく、0質量%以上であってもよい。また、シール層Bを構成するポリプロピレン系樹脂組成物中、樹脂以外の添加剤の量は10質量%以下が好ましく、5質量%以下がより好ましく、2質量%以下がよりさらに好ましく、1質量%以下が特に好ましく、0質量%以上であってもよい。
2-5. Anti-Fog Agent The polypropylene resin composition constituting the seal layer B may or may not contain an anti-fogging agent. The anti-fogging agents described in the description of the substrate layer A can be used as the anti-fogging agent. Even if the polypropylene resin composition constituting the seal layer B does not contain an anti-fogging agent, the anti-fogging agent may migrate from the substrate layer A to the seal layer B during the film formation process, and the obtained biaxially oriented polypropylene film may contain the anti-fogging agent in the seal layer B.
Furthermore, as long as the effects of the present invention are not impaired, the polypropylene-based resin composition constituting the sealing layer B may contain additives such as resins other than polypropylene copolymers, the above-mentioned antifogging agents, known heat stabilizers, antioxidants, UV absorbers, nucleating agents, adhesives, flame retardants, inorganic or organic fillers, etc. Examples of resins other than polypropylene copolymers include polyolefin resins other than the polypropylene copolymers used in the sealing layer B, and various elastomers. However, it is preferable that these be added in small amounts, and the amount of resins other than polypropylene copolymers in the polypropylene-based resin composition constituting the sealing layer B is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 2% by mass or less, and may even be 0% by mass or more. Furthermore, the amount of additives other than resins in the polypropylene-based resin composition constituting the sealing layer B is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, particularly preferably 1% by mass or less, and may even be 0% by mass or more.
3.中間層C
3-1.ポリプロピレン系樹脂組成物
ポリプロピレン系樹脂組成物からなる中間層Cは、プロピレン以外のα-オレフィンを含むポリプロピレン共重合体を含むことが好ましい。すなわち、中間層Cを構成するポリプロピレン系樹脂組成物は、プロピレン以外のα-オレフィンを含むポリプロピレン共重合体を含むことが好ましい。中間層Cを設けることでヒートシール強度を向上させることができる。なお、中間層Cに関する説明では、単に「ポリプロピレン共重合体」と記載した場合であっても、プロピレン以外のα-オレフィンを含むポリプロピレン共重合体を指す。中間層Cはポリプロピレン共重合体を70質量%以上含有することが好ましい。ポリプロピレン共重合体を70質量%以上とすることにより、中間層Cとシール層Bとの層間密着性や基材層Aと中間層Cとの層間密着性を高めやすく、二軸配向ポリプロピレンフィルムのヒートシール強度をより高めることができる。中間層Cにおけるポリプロピレン共重合体の割合としては、80質量%以上がより好ましく、90質量%以上がよりさらに好ましく、95質量%以上が特に好ましく、100質量%以上であってもよい。なお、中間層Cに含まれるポリプロピレン共重合体としては、異なる2種以上のポリプロピレン共重合体を用いることもでき、合計の含有量が上記範囲内であることが好ましい。
中間層Cに含まれるポリプロピレン共重合体におけるプロピレン以外のα-オレフィン成分の含有量、すなわちエチレンと炭素数4以上のα-オレフィンとの合計量は、4.0モル%以上が好ましい。この場合、ポリプロピレン共重合体におけるプロピレンの含有量は96モル%以下であり、プロピレンの含有量とプロピレン以外のα-オレフィン成分の含有量の合計は100モル%である。当該量としては、4.0モル%以上がより好ましく、5.0モル%以上がよりさらに好ましく、6.0モル%以上が特に好ましく、また、12モル%以下がより好ましく、11モル%以下がよりさらに好ましく、10モル%以下が特に好ましい。
炭素数4以上のα-オレフィン成分として、例えば、1-ブテン、1-ペンテン、3-メチル-1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、5-エチル-1-ヘキセン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-ヘプタデセン、1-オクタデセン、1-エイコセンなどが挙げられる。
プロピレン以外のα-オレフィン成分は、炭素数が2以上20以下であるプロピレン以外のα-オレフィン成分であることが好ましく、炭素数が2以上10以下であるプロピレン以外のα-オレフィン成分であることがより好ましく、炭素数が2以上6以下であるプロピレン以外のα-オレフィン成分であることがよりさらに好ましく、炭素数が2以上4以下であるプロピレン以外のα-オレフィン成分であることが特に好ましい。
3. middle class C
3-1. Polypropylene Resin Composition The intermediate layer C made of a polypropylene resin composition preferably contains a polypropylene copolymer containing an α-olefin other than propylene. That is, the polypropylene resin composition constituting the intermediate layer C preferably contains a polypropylene copolymer containing an α-olefin other than propylene. The provision of the intermediate layer C can improve heat seal strength. In the description of the intermediate layer C, even when the term "polypropylene copolymer" is simply used, it refers to a polypropylene copolymer containing an α-olefin other than propylene. The intermediate layer C preferably contains 70% by mass or more of the polypropylene copolymer. By containing 70% by mass or more of the polypropylene copolymer, it is easy to improve the interlayer adhesion between the intermediate layer C and the seal layer B and between the base layer A and the intermediate layer C, thereby further increasing the heat seal strength of the biaxially oriented polypropylene film. The proportion of the polypropylene copolymer in the intermediate layer C is more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may even be 100% by mass or more. In addition, two or more different polypropylene copolymers can be used as the polypropylene copolymer contained in the intermediate layer C, and it is preferable that the total content is within the above range.
The content of α-olefin components other than propylene in the polypropylene copolymer contained in the intermediate layer C, i.e., the total amount of ethylene and α-olefins having 4 or more carbon atoms, is preferably 4.0 mol% or more. In this case, the propylene content in the polypropylene copolymer is 96 mol% or less, and the sum of the propylene content and the content of α-olefin components other than propylene is 100 mol%. The amount is more preferably 4.0 mol% or more, even more preferably 5.0 mol% or more, particularly preferably 6.0 mol% or more, more preferably 12 mol% or less, even more preferably 11 mol% or less, and particularly preferably 10 mol% or less.
Examples of the α-olefin component having 4 or more carbon atoms include 1-butene, 1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 5-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
The α-olefin component other than propylene is preferably an α-olefin component other than propylene having 2 or more and 20 or less carbon atoms, more preferably an α-olefin component other than propylene having 2 or more and 10 or less carbon atoms, even more preferably an α-olefin component other than propylene having 2 or more and 6 or less carbon atoms, and particularly preferably an α-olefin component other than propylene having 2 or more and 4 or less carbon atoms.
以下、ポリプロピレン系樹脂組成物の好適な各種物性について記載する。なお、異なる2種以上のポリプロピレン共重合体を用いる場合、物性値は各ポリプロピレン共重合体の物性を質量平均した値とする。前述のシール層B、及び後述の機能層Dでも同様とする。 The following describes various suitable physical properties of the polypropylene resin composition. When two or more different polypropylene copolymers are used, the physical property values are the mass average values of the physical properties of each polypropylene copolymer. The same applies to the sealing layer B described above and the functional layer D described below.
中間層Cを構成するポリプロピレン系樹脂組成物の融点Tmcは、150℃以下が好ましく、145℃以下がより好ましく、140℃以下がよりさらに好ましい。Tmcを上記範囲内とすることにより、ヒートシール強度を高めることができる。中間層Cを構成するポリプロピレン系樹脂組成物の融点Tmcの下限は特に限定されず、例えば、120℃以上である。また、ヒートシール強度を高める観点から、中間層Cを構成するポリプロピレン系樹脂組成物の融点Tmcは、シール層Bを構成するポリプロピレン系樹脂組成物の融点Tmbより高いことが好ましい。 The melting point Tmc of the polypropylene resin composition constituting the intermediate layer C is preferably 150°C or lower, more preferably 145°C or lower, and even more preferably 140°C or lower. By setting Tmc within the above range, the heat seal strength can be increased. The lower limit of the melting point Tmc of the polypropylene resin composition constituting the intermediate layer C is not particularly limited, and is, for example, 120°C or higher. Furthermore, from the viewpoint of increasing the heat seal strength, it is preferable that the melting point Tmc of the polypropylene resin composition constituting the intermediate layer C is higher than the melting point Tmb of the polypropylene resin composition constituting the seal layer B.
中間層Cを構成するポリプロピレン系樹脂組成物の温度230℃、荷重2.16kgfで測定したメルトフローレート(MFR)は、3.0g/10分以上6.0g/10分以下が好ましい。当該メルトフローレート値は、3.5g/10分以上がより好ましく、4.0g/10分以上がよりさらに好ましく、4.3g/10分以上が特に好ましく、また、5.5g/10分以下がより好ましく、5.0g/10分以下がよりさらに好ましく、4.8g/10分以下が特に好ましい。また、ヒートシール強度を高める観点から、中間層Cを構成するポリプロピレン系樹脂組成物のメルトフローレートは、シール層Bを構成するポリプロピレン系樹脂組成物のメルトフローレートより小さいことが好ましい。 The melt flow rate (MFR) of the polypropylene resin composition constituting intermediate layer C, measured at a temperature of 230°C and a load of 2.16 kgf, is preferably 3.0 g/10 min or more and 6.0 g/10 min or less. The melt flow rate value is more preferably 3.5 g/10 min or more, even more preferably 4.0 g/10 min or more, particularly preferably 4.3 g/10 min or more, more preferably 5.5 g/10 min or less, even more preferably 5.0 g/10 min or less, and particularly preferably 4.8 g/10 min or less. Furthermore, from the perspective of increasing heat seal strength, the melt flow rate of the polypropylene resin composition constituting intermediate layer C is preferably lower than the melt flow rate of the polypropylene resin composition constituting seal layer B.
中間層Cに含まれるポリプロピレン共重合体としては、例えばプロピレン・ブテン共重合体、プロピレン・エチレン・ブテン共重合体、及びプロピレン・エチレン共重合体からなる群から選択される少なくとも1種が好ましく、プロピレン・エチレン・ブテン共重合体がより好ましい。 The polypropylene copolymer contained in the intermediate layer C is preferably at least one selected from the group consisting of propylene-butene copolymer, propylene-ethylene-butene copolymer, and propylene-ethylene copolymer, with propylene-ethylene-butene copolymer being more preferred.
3-2.プロピレン・エチレン・ブテン共重合体
中間層Cにおけるプロピレン・エチレン・ブテン共重合体におけるプロピレン以外のα-オレフィン成分の含有量は、4モル%以上が好ましい。プロピレン以外のα-オレフィン成分の含有量が4モル%以上であると、中間層Cとシール層Bとの層間密着性が向上しやすく、その結果、ヒートシール強度や密封性が向上しやすい。プロピレン以外のα-オレフィン成分の含有量は、5モル%以上がより好ましく、6モル%以上がよりさらに好ましい。プロピレン以外のα-オレフィン成分の含有量の上限は特に限定されず、例えば、25モル%以下である。なお、プロピレン以外のα-オレフィン成分が2種以上である場合、合計量をプロピレン以外のα-オレフィン成分の含有量とする。
エチレン含有量は1モル%以上が好ましく、2モル%以上がより好ましい。エチレン含有量の上限は特に限定されないが、エチレン含有量が多すぎると結晶化が抑制されすぎて、プロピレン単独重合体に比べて結晶性が低く、結果としてフィルムの腰感を低下させるおそれがあるため、例えば、10モル%以下である。
ブテン含有量は1モル%以上が好ましく、2モル%以上がより好ましい。ブテン含有量の上限は特に限定されないが、ブテン含有量が多すぎると結晶化が抑制されすぎて、プロピレン単独重合体に比べて結晶性が低く、結果としてフィルムの腰感を低下させるおそれがあるため、例えば、16モル%以下である。
プロピレン以外のα-オレフィン成分の合計含有量が4モル%以上であるプロピレン・エチレン・ブテン共重合体としては、市販品を用いてもよく、例えば、住友化学社製FSX66E8などが挙げられる。
3-2. Propylene-Ethylene-Butene Copolymer The content of the α-olefin component other than propylene in the propylene-ethylene-butene copolymer in the intermediate layer C is preferably 4 mol% or more. When the content of the α-olefin component other than propylene is 4 mol% or more, the interlayer adhesion between the intermediate layer C and the seal layer B is likely to be improved, and as a result, the heat seal strength and hermetic sealability are likely to be improved. The content of the α-olefin component other than propylene is more preferably 5 mol% or more, and even more preferably 6 mol% or more. There is no particular upper limit for the content of the α-olefin component other than propylene, and it is, for example, 25 mol% or less. When there are two or more types of α-olefin components other than propylene, the total amount is taken as the content of the α-olefin components other than propylene.
The ethylene content is preferably 1 mol% or more, more preferably 2 mol% or more. Although there is no particular upper limit for the ethylene content, if the ethylene content is too high, crystallization is too suppressed, resulting in lower crystallinity compared to propylene homopolymer, which may result in a decrease in the stiffness of the film. Therefore, for example, the upper limit is 10 mol% or less.
The butene content is preferably 1 mol% or more, more preferably 2 mol% or more. Although there is no particular upper limit for the butene content, if the butene content is too high, crystallization is too suppressed, resulting in lower crystallinity compared to propylene homopolymer, which may result in a decrease in the stiffness of the film. Therefore, for example, the upper limit is 16 mol% or less.
As the propylene-ethylene-butene copolymer having a total content of α-olefin components other than propylene of 4 mol % or more, a commercially available product may be used, for example, FSX66E8 manufactured by Sumitomo Chemical Co., Ltd.
3-3.プロピレン・ブテン共重合体
プロピレン・ブテン共重合体におけるブテン含有量は、4モル%以上が好ましい。ブテン含有量が4モル%以上であると中間層Cとシール層Bとの層間密着力が向上しやすく、その結果、ヒートシール強度や密封性が向上しやすい。ブテン含有量は5モル%以上が好ましく、6モル%以上がよりさらに好ましい。ブテン含有量の上限は特に限定されないが、ブテン含有量が多すぎると結晶化が抑制されすぎて、プロピレン単独重合体に比べて結晶性が低く、結果としてフィルムの腰感を低下させるおそれがあるため、例えば、16モル%以下であり、好ましくは12モル%以下である。ブテン含有量が4モル%以上であるプロピレン・ブテン共重合体としては、市販品を用いてもよく、例えば、住友化学社製SP7843、住友化学社製SPX78J1、三井化学社製XR110Hなどを例示することができる。
3-3. Propylene-Butene Copolymer The butene content in the propylene-butene copolymer is preferably 4 mol% or more. A butene content of 4 mol% or more tends to improve the interlayer adhesion between the intermediate layer C and the seal layer B, and as a result, the heat seal strength and hermetic sealability are likely to be improved. The butene content is preferably 5 mol% or more, and even more preferably 6 mol% or more. There is no particular upper limit for the butene content, but if the butene content is too high, crystallization is too suppressed, resulting in lower crystallinity compared to propylene homopolymer, which may result in a decrease in the stiffness of the film. Therefore, for example, the upper limit is 16 mol% or less, and preferably 12 mol% or less. As a propylene-butene copolymer having a butene content of 4 mol% or more, commercially available products may be used, such as SP7843 manufactured by Sumitomo Chemical Co., Ltd., SPX78J1 manufactured by Sumitomo Chemical Co., Ltd., and XR110H manufactured by Mitsui Chemicals, Inc.
3-4.プロピレン・エチレン共重合体
プロピレン・エチレン共重合体におけるエチレン含有量は、4モル%以上が好ましい。エチレン含有量が4モル%以上であると中間層Cとシール層Bとの層間密着力が向上しやすく、その結果、ヒートシール強度や密封性が向上しやすい。エチレン含有量は5モル%以上がより好ましく、6モル%以上がよりさらに好ましい。エチレン含有量の上限は特に限定されないが、エチレン含有量が多すぎると結晶化が抑制されすぎて、プロピレン単独重合体に比べて結晶性が低く、結果としてフィルムの腰感を低下させるおそれがあるため、例えば、12モル%以下である。エチレン含有量が4モル%以上であるプロピレン・エチレン共重合体としては、市販品を用いてもよく、例えば、サンアロマー社製PC540R、三井化学社製VM3588FLなどが挙げられる。
3-4. Propylene-Ethylene Copolymer The ethylene content of the propylene-ethylene copolymer is preferably 4 mol% or more. An ethylene content of 4 mol% or more tends to improve the interlayer adhesion between the intermediate layer C and the seal layer B, and as a result, tends to improve heat seal strength and hermetic sealability. The ethylene content is more preferably 5 mol% or more, and even more preferably 6 mol% or more. There is no particular upper limit for the ethylene content, but if the ethylene content is too high, crystallization is too suppressed, resulting in lower crystallinity compared to propylene homopolymer, which may result in a decrease in the stiffness of the film. Therefore, for example, the upper limit is 12 mol% or less. As a propylene-ethylene copolymer having an ethylene content of 4 mol% or more, commercially available products may be used, such as PC540R manufactured by SunAllomer Co., Ltd. and VM3588FL manufactured by Mitsui Chemicals, Inc.
3-5.防曇剤
中間層Cを構成するポリプロピレン系樹脂組成物は、防曇剤を含んでいてもよいし含んでいなくてもよい。防曇剤としては、基材層Aの説明に記載した防曇剤を用いることができる。なお、中間層Cを構成するポリプロピレン系樹脂組成物中には防曇剤を含まない場合であっても、製膜工程において、基材層Aから中間層Cに防曇剤が移動してくる場合があり、得られた二軸配向ポリプロピレンフィルムにおいては中間層Cに防曇剤が含まれる場合がある。
また、本発明の効果を損なわない範囲であれば、中間層Cを構成するポリプロピレン系樹脂組成物には、ポリプロピレン共重合体以外の樹脂、上述の防曇剤、公知の熱安定剤、酸化防止剤、紫外線吸収剤、造核剤、粘着剤、難燃剤、無機または有機の充填剤などの添加剤が添加されていてもよい。ポリプロピレン共重合体以外の樹脂としては、中間層Bで用いられるポリプロピレン共重合体以外のポリオレフィン樹脂や、各種エラストマー等が挙げられる。しかし、これらの添加は少量であることが好ましく、中間層Cを構成するポリプロピレン系樹脂組成物中、ポリプロピレン共重合体以外の樹脂の量は30質量%以下が好ましく、10質量%以下がより好ましく、5質量%以下がよりさらに好ましく、2質量%以下が特に好ましく、0質量%以上であってもよい。また、中間層Cを構成するポリプロピレン系樹脂組成物中、樹脂以外の添加剤の量は10質量%以下が好ましく、5質量%以下がより好ましく、2質量%以下がよりさらに好ましく、1質量%以下が特に好ましく、0質量%以上であってもよい。
3-5. Anti-Fog Agent The polypropylene resin composition constituting the intermediate layer C may or may not contain an anti-fogging agent. As the anti-fogging agent, the anti-fogging agents described in the description of the base layer A can be used. Even if the polypropylene resin composition constituting the intermediate layer C does not contain an anti-fogging agent, the anti-fogging agent may migrate from the base layer A to the intermediate layer C during the film formation process, and the obtained biaxially oriented polypropylene film may contain the anti-fogging agent in the intermediate layer C.
Furthermore, as long as the effects of the present invention are not impaired, the polypropylene-based resin composition constituting the intermediate layer C may contain additives such as resins other than polypropylene copolymers, the above-mentioned antifogging agents, known heat stabilizers, antioxidants, UV absorbers, nucleating agents, adhesives, flame retardants, inorganic or organic fillers, etc. Examples of resins other than polypropylene copolymers include polyolefin resins other than the polypropylene copolymers used in the intermediate layer B, and various elastomers. However, the amount of these additives is preferably small, and the amount of resins other than polypropylene copolymers in the polypropylene-based resin composition constituting the intermediate layer C is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 2% by mass or less, and may even be 0% by mass or more. Furthermore, the amount of additives other than resins in the polypropylene-based resin composition constituting the intermediate layer C is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, particularly preferably 1% by mass or less, and may even be 0% by mass or more.
4.機能層D
機能層Dは、基材層Aのシール層Bが設けられていない側の面に設けることが好ましい。機能層Dは、特に限定されず、中間層Cと同じ組成の層であってもよいし、フィルム同士の易滑性やフィルムと加工器具との易滑性や帯電防止性などの機能を機能層Dに付与するために、機能層Dを構成するポリプロピレン系樹脂組成物にアンチブロッキング剤、ワックスや金属石鹸などの潤滑剤、可塑剤、加工助剤、帯電防止剤などを配合してもよい。
4. Functional layer D
The functional layer D is preferably provided on the surface of the base layer A on which the seal layer B is not provided. The functional layer D is not particularly limited and may be a layer of the same composition as the intermediate layer C. In order to impart functions such as easy lubricity between films or between the film and a processing tool, or antistatic properties to the functional layer D, an antiblocking agent, a lubricant such as wax or metal soap, a plasticizer, a processing aid, an antistatic agent, etc. may be blended into the polypropylene resin composition constituting the functional layer D.
4-1.ポリプロピレン系樹脂組成物
機能層Dは、ポリプロピレン系樹脂組成物からなる層であることが好ましく、プロピレン以外のα-オレフィンを含むポリプロピレン共重合体を含むことがより好ましい。すなわち、機能層Dを構成するポリプロピレン系樹脂組成物は、プロピレン以外のα-オレフィンを含むポリプロピレン共重合体を含むことがより好ましい。なお、機能層Dに関する説明では、単に「ポリプロピレン共重合体」と記載した場合であっても、プロピレン以外のα-オレフィンを含むポリプロピレン共重合体を指す。機能層Dはポリプロピレン共重合体を70質量%以上含有することが好ましく、80質量%以上含有することがより好ましく、90質量%以上含有することがよりさらに好ましく、95質量%以上含有することが特に好ましい。当該割合は100質量%以下であってもよい。なお、機能層Dに含まれるポリプロピレン共重合体としては、異なる2種以上のポリプロピレン共重合体を用いることもでき、合計の含有量が上記範囲内であることが好ましい。ポリプロピレン共重合体を70質量%以上100質量%以下とすることにより、機能層Dと機能層Dに隣接する層との層間密着性を高めやすく、二軸配向ポリプロピレンフィルムのヒートシール強度をより高めることができる。
機能層Dに含まれるポリプロピレン共重合体におけるプロピレン以外のα-オレフィン成分の含有量、すなわちエチレンと炭素数4以上のα-オレフィンとの合計量は、4.0モル%以上が好ましい。この場合、ポリプロピレン共重合体におけるプロピレンの含有量は96モル%以下であり、プロピレンの含有量とプロピレン以外のα-オレフィン成分の含有量の合計は100モル%である。当該量としては、4.0モル%以上がより好ましく、5.0モル%以上がよりさらに好ましく、6.0モル%以上が特に好ましく、また、12モル%以下がより好ましく、11モル%以下がよりさらに好ましく、10モル%以下が特に好ましい。
炭素数4以上のα-オレフィン成分として、例えば、1-ブテン、1-ペンテン、3-メチル-1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、5-エチル-1-ヘキセン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-ヘプタデセン、1-オクタデセン、1-エイコセンなどが挙げられる。
プロピレン以外のα-オレフィン成分は、炭素数が2以上20以下であるプロピレン以外のα-オレフィン成分が好ましく、炭素数が2以上10以下であるプロピレン以外のα-オレフィン成分がより好ましく、炭素数が2以上6以下であるプロピレン以外のα-オレフィン成分がよりさらに好ましく、炭素数が2以上4以下であるプロピレン以外のα-オレフィン成分が特に好ましい。
4-1. Polypropylene Resin Composition The functional layer D is preferably a layer made of a polypropylene resin composition, and more preferably contains a polypropylene copolymer containing an α-olefin other than propylene. That is, the polypropylene resin composition constituting the functional layer D more preferably contains a polypropylene copolymer containing an α-olefin other than propylene. In the description of the functional layer D, even when the term "polypropylene copolymer" is simply used, it refers to a polypropylene copolymer containing an α-olefin other than propylene. The functional layer D preferably contains 70% by mass or more of the polypropylene copolymer, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more. This proportion may be 100% by mass or less. The polypropylene copolymer contained in the functional layer D can also be two or more different polypropylene copolymers, with the total content preferably being within the above range. By containing the polypropylene copolymer in an amount of 70% by mass or more and 100% by mass or less, it is easy to improve the interlayer adhesion between the functional layer D and the layer adjacent to the functional layer D, thereby further increasing the heat seal strength of the biaxially oriented polypropylene film.
The content of α-olefin components other than propylene in the polypropylene copolymer contained in the functional layer D, i.e., the total amount of ethylene and α-olefins having 4 or more carbon atoms, is preferably 4.0 mol% or more. In this case, the propylene content in the polypropylene copolymer is 96 mol% or less, and the sum of the propylene content and the content of α-olefin components other than propylene is 100 mol%. The amount is more preferably 4.0 mol% or more, even more preferably 5.0 mol% or more, particularly preferably 6.0 mol% or more, more preferably 12 mol% or less, even more preferably 11 mol% or less, and particularly preferably 10 mol% or less.
Examples of the α-olefin component having 4 or more carbon atoms include 1-butene, 1-pentene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 5-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene.
The α-olefin component other than propylene is preferably an α-olefin component other than propylene having 2 or more and 20 or less carbon atoms, more preferably an α-olefin component other than propylene having 2 or more and 10 or less carbon atoms, even more preferably an α-olefin component other than propylene having 2 or more and 6 or less carbon atoms, and particularly preferably an α-olefin component other than propylene having 2 or more and 4 or less carbon atoms.
機能層Dを構成するポリプロピレン系樹脂組成物の融点Tmdは、150℃以下が好ましく、145℃以下がより好ましく、140℃以下がよりさらに好ましい。Tmdを上記範囲内とすることにより、ヒートシール強度を高めることができる。機能層Dを構成するポリプロピレン系樹脂組成物の融点Tmdの下限は特に限定されず、例えば、120℃以上である。 The melting point Tmd of the polypropylene resin composition constituting the functional layer D is preferably 150°C or lower, more preferably 145°C or lower, and even more preferably 140°C or lower. By setting Tmd within the above range, the heat seal strength can be increased. The lower limit of the melting point Tmd of the polypropylene resin composition constituting the functional layer D is not particularly limited, and is, for example, 120°C or higher.
機能層Dを構成するポリプロピレン系樹脂組成物の温度230℃、荷重2.16kgfで測定されるメルトフローレート(MFR)は、3.0g/10分以上6.0g/10分以下が好ましい。当該メルトフローレートとしては、3.5g/10分以上がより好ましく、4.0g/10分以上がよりさらに好ましく、4.3g/10分以上が特に好ましく、また、5.5g/10分以下がより好ましく、5.0g/10分以下がよりさらに好ましく、4.8g/10分以下が特に好ましい。 The melt flow rate (MFR) of the polypropylene resin composition constituting functional layer D, measured at a temperature of 230°C and a load of 2.16 kgf, is preferably 3.0 g/10 min or more and 6.0 g/10 min or less. The melt flow rate is more preferably 3.5 g/10 min or more, even more preferably 4.0 g/10 min or more, and particularly preferably 4.3 g/10 min or more. It is more preferably 5.5 g/10 min or less, even more preferably 5.0 g/10 min or less, and particularly preferably 4.8 g/10 min or less.
機能層Dに含まれるポリプロピレン共重合体としては、例えばプロピレン・ブテン共重合体、プロピレン・エチレン・ブテン共重合体、及びプロピレン・エチレン共重合体からなる群から選択される少なくとも1種を含むことが好ましく、プロピレン・エチレン・ブテン共重合体を含むことがより好ましい。 The polypropylene copolymer contained in functional layer D preferably contains at least one selected from the group consisting of propylene-butene copolymer, propylene-ethylene-butene copolymer, and propylene-ethylene copolymer, and more preferably contains propylene-ethylene-butene copolymer.
4-2.プロピレン・エチレン・ブテン共重合体
プロピレン・エチレン・ブテン共重合体におけるプロピレン以外のα-オレフィン成分の含有量は、4モル%以上が好ましい。プロピレン以外のα-オレフィン成分の含有量が4モル%以上であると、機能層Dと機能層Dに隣接する層との層間密着性が向上しやすく、その結果、ヒートシール強度や密封性が向上しやすい。プロピレン以外のα-オレフィン成分の含有量は5モル%以上がより好ましく、6モル%以上がよりさらに好ましい。プロピレン以外のα-オレフィン成分の含有量の上限は特に限定されず、例えば、25モル%以下である。なお、プロピレン以外のα-オレフィン成分が2種以上である場合、合計量をプロピレン以外のα-オレフィン成分の含有量とする。
エチレン含有量は1モル%以上が好ましく、2モル%以上がより好ましい。エチレン含有量の上限は特に限定されないが、エチレン含有量が多すぎるとフィルム表面がべたつき、滑り性や耐ブロッキング性が低下するおそれがあるため、例えば、10モル%以下である。
ブテン含有量は1モル%以上が好ましく、2モル%以上がより好ましい。ブテン含有量の上限は特に限定されないが、ブテン含有量が多すぎるとフィルム表面がべたつき、滑り性や耐ブロッキング性が低下するおそれがあるため、例えば、16モル%以下である。
プロピレン以外のα-オレフィン成分の合計含有量が4モル%以上であるプロピレン・エチレン・ブテン共重合体としては、市販品を用いてもよく、例えば、住友化学社製FSX66E8などが挙げられる。
4-2. Propylene-Ethylene-Butene Copolymer The content of α-olefin components other than propylene in the propylene-ethylene-butene copolymer is preferably 4 mol% or more. When the content of α-olefin components other than propylene is 4 mol% or more, the interlayer adhesion between the functional layer D and the layer adjacent to the functional layer D is likely to be improved, and as a result, the heat seal strength and hermetic sealability are likely to be improved. The content of α-olefin components other than propylene is more preferably 5 mol% or more, and even more preferably 6 mol% or more. There is no particular upper limit for the content of α-olefin components other than propylene, and it is, for example, 25 mol% or less. When there are two or more types of α-olefin components other than propylene, the total amount is taken as the content of the α-olefin components other than propylene.
The ethylene content is preferably 1 mol% or more, more preferably 2 mol% or more. Although there is no particular upper limit to the ethylene content, if the ethylene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may decrease, so the upper limit is, for example, 10 mol% or less.
The butene content is preferably 1 mol% or more, more preferably 2 mol% or more. Although there is no particular upper limit to the butene content, if the butene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may be reduced, so the upper limit is, for example, 16 mol% or less.
As the propylene-ethylene-butene copolymer having a total content of α-olefin components other than propylene of 4 mol % or more, a commercially available product may be used, for example, FSX66E8 manufactured by Sumitomo Chemical Co., Ltd.
4-3.プロピレン・ブテン共重合体
プロピレン・ブテン共重合体におけるブテン含有量は、4モル%以上が好ましい。ブテン含有量が4モル%以上であると、機能層Dと機能層Dに隣接する層との層間密着力が向上しやすく、その結果、ヒートシール強度や密封性が向上しやすい。ブテン含有量は5モル%以上がより好ましく、6モル%以上がよりさらに好ましい。ブテン含有量の上限は特に限定されないが、ブテン含有量が多すぎるとフィルム表面がべたつき、滑り性や耐ブロッキング性が低下するおそれがあるため、例えば、16モル%以下であり、好ましくは12モル%以下である。ブテン含有量が4モル%以上であるプロピレン・ブテン共重合体としては、市販品を用いてもよく、例えば、住友化学社製SP7843、住友化学社製SPX78J1、三井化学社製XR110Hなどを例示することができる。
4-3. Propylene-Butene Copolymer The butene content in the propylene-butene copolymer is preferably 4 mol% or more. A butene content of 4 mol% or more tends to improve the interlayer adhesion between the functional layer D and the layer adjacent to the functional layer D, and as a result, tends to improve heat seal strength and hermetic sealability. The butene content is more preferably 5 mol% or more, and even more preferably 6 mol% or more. There is no particular upper limit for the butene content, but if the butene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may decrease. Therefore, for example, it is 16 mol% or less, preferably 12 mol% or less. As a propylene-butene copolymer having a butene content of 4 mol% or more, commercially available products may be used, such as SP7843 manufactured by Sumitomo Chemical Co., Ltd., SPX78J1 manufactured by Sumitomo Chemical Co., Ltd., and XR110H manufactured by Mitsui Chemicals, Inc.
4-4.プロピレン・エチレン共重合体
プロピレン・エチレン共重合体におけるエチレン含有量は、4モル%以上が好ましい。エチレン含有量が4モル%以上であると、機能層Dと機能層Dに隣接する層との層間密着力が向上しやすく、その結果、ヒートシール強度や密封性が向上しやすい。エチレン含有量は5モル%以上がより好ましく、6モル%以上がよりさらに好ましい。エチレン含有量の上限は特に限定されないが、エチレン含有量が多すぎるとフィルム表面がべたつき、滑り性や耐ブロッキング性が低下するおそれがあるため、例えば、12モル%以下である。エチレン含有量が4モル%以上であるプロピレン・エチレン共重合体としては、市販品を用いてもよく、例えば、サンアロマー社製PC540R、三井化学社製VM3588FLなどが挙げられる。
4-4. Propylene-Ethylene Copolymer The ethylene content of the propylene-ethylene copolymer is preferably 4 mol% or more. When the ethylene content is 4 mol% or more, the interlayer adhesion between the functional layer D and the layer adjacent to the functional layer D is likely to be improved, and as a result, the heat seal strength and hermetic sealability are likely to be improved. The ethylene content is more preferably 5 mol% or more, and even more preferably 6 mol% or more. There is no particular upper limit for the ethylene content, but if the ethylene content is too high, the film surface may become sticky and the slipperiness and blocking resistance may be reduced, so for example, it is 12 mol% or less. As a propylene-ethylene copolymer having an ethylene content of 4 mol% or more, commercially available products may be used, such as PC540R manufactured by SunAllomer Co., Ltd. and VM3588FL manufactured by Mitsui Chemicals, Inc.
4-5.防曇剤
機能層Dを構成するポリプロピレン系樹脂組成物は、防曇剤を含んでいてもよいし含んでいなくてもよい。防曇剤としては、基材層Aの説明に記載した防曇剤を用いることができる。なお、機能層Dを構成するポリプロピレン系樹脂組成物中には防曇剤を含まない場合であっても、製膜工程において、基材層Aから機能層Dに防曇剤が移動してくる場合があり、得られた二軸配向ポリプロピレンフィルムにおいては機能層Dに防曇剤が含まれる場合がある。
また、本発明の効果を損なわない範囲であれば、機能層Dを構成するポリプロピレン系樹脂組成物には、ポリプロピレン共重合体以外の樹脂、上述の防曇剤、公知の熱安定剤、酸化防止剤、紫外線吸収剤、造核剤、粘着剤、難燃剤、無機または有機の充填剤などの添加剤が添加されていてもよい。
ポリプロピレン共重合体以外の樹脂としては、機能層Dで用いられるポリプロピレン共重合体以外のポリオレフィン樹脂や、各種エラストマー等が挙げられる。しかし、これらの添加は少量であることが好ましく、機能層Dを構成するポリプロピレン系樹脂組成物中、ポリプロピレン共重合体以外の樹脂の量は30質量%以下が好ましく、10質量%以下がより好ましく、5質量%以下がよりさらに好ましく、2質量%以下が特に好ましく、0質量%以上とすることができる。また、機能層Dを構成するポリプロピレン系樹脂組成物中、樹脂以外の添加剤の量は10質量%以下が好ましく、5質量%以下がより好ましく、2質量%以下がよりさらに好ましく、1質量%以下が特に好ましく、0質量%以上とすることができる。
4-5. Anti-Fog Agent The polypropylene resin composition constituting the functional layer D may or may not contain an anti-fogging agent. As the anti-fogging agent, the anti-fogging agents described in the description of the base layer A can be used. Even if the polypropylene resin composition constituting the functional layer D does not contain an anti-fogging agent, the anti-fogging agent may migrate from the base layer A to the functional layer D during the film formation process, and the functional layer D may contain the anti-fogging agent in the obtained biaxially oriented polypropylene film.
Furthermore, as long as the effects of the present invention are not impaired, the polypropylene-based resin composition constituting the functional layer D may contain additives such as resins other than polypropylene copolymers, the above-mentioned anti-fogging agents, known heat stabilizers, antioxidants, ultraviolet absorbers, nucleating agents, adhesives, flame retardants, inorganic or organic fillers, etc.
Examples of resins other than polypropylene copolymers include polyolefin resins other than the polypropylene copolymers used in the functional layer D, various elastomers, and the like. However, it is preferable that these be added in small amounts, and the amount of resins other than polypropylene copolymers in the polypropylene-based resin composition constituting the functional layer D is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 2% by mass or less, and can be 0% by mass or more. Furthermore, the amount of additives other than resins in the polypropylene-based resin composition constituting the functional layer D is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, particularly preferably 1% by mass or less, and can be 0% by mass or more.
5.フィルム中における防曇剤の含有量
本発明の二軸配向ポリプロピレンフィルム中における防曇剤の含有量は、0.1質量%以上10質量%以下が好ましい。当該含有量としては、0.15質量%以上がより好ましく、0.2質量%以上がよりさらに好ましく、0.25質量%以上が特に好ましく、0.3質量%以上が最も好ましく、また、5.0質量%以下がより好ましく、3.0質量%以下がよりさらに好ましく、2.0質量%以下が特に好ましく、1.5質量%以下が最も好ましい。基材層Aを構成するポリプロピレン系樹脂組成物のみに防曇剤を添加した場合であっても、フィルム製膜時およびフィルム製膜後の保管時に、防曇剤が基材層Aから他の層へと移動し、防曇剤が最表面であるシール層Bへと移動すると、シール層Bの表面に防曇剤が存在するようになり、防曇性を有する状態になる。
5. Content of Anti-Fog Agent in Film The content of the anti-fogging agent in the biaxially oriented polypropylene film of the present invention is preferably 0.1% by mass or more and 10% by mass or less. The content is more preferably 0.15% by mass or more, even more preferably 0.2% by mass or more, particularly preferably 0.25% by mass or more, most preferably 0.3% by mass or more, more preferably 5.0% by mass or less, even more preferably 3.0% by mass or less, particularly preferably 2.0% by mass or less, and most preferably 1.5% by mass or less. Even if the anti-fogging agent is added only to the polypropylene resin composition constituting the base layer A, the anti-fogging agent may migrate from the base layer A to other layers during film formation and storage after film formation, and the anti-fogging agent may migrate to the outermost seal layer B, causing the anti-fogging agent to be present on the surface of the seal layer B, thereby providing anti-fogging properties.
6.二軸配向ポリプロピレンフィルムの層構成と厚み構成
本発明の二軸配向ポリプロピレンフィルムは、基材層A及びシール層Bを有する。基材層Aとシール層Bとの間に中間層Cを有してもよい。本発明の二軸配向ポリプロピレンフィルムの層構成は、基材層Aとシール層Bを有しており、シール層Bを少なくとも一方の最表面に有してさえいれば、基材層Aとシール層Bの間に中間層Cを有してもよく、基材層Aと中間層Cとの間に他の層を有していてもよく、中間層Cが基材層A上に直接積層されていてもよい。また、中間層Cとシール層Bとの間に他の層を有していてもよく、シール層Bが中間層Cに直接積層されていてもよい。本発明の二軸配向ポリプロピレンフィルムとして、例えば、基材層A/シール層Bの2層構造、基材層A/中間層C/シール層Bの3層構造、シール層B1/基材層A/シール層B2の3層構造、シール層B1/基材層A/中間層C/シール層B2の4層構造、シール層B1/中間層C1/基材層A/中間層C2/シール層B2の5層構造、シール層B1/基材層A1/中間層C1/基材層A2/中間層C2/シール層B2の6層構造などが挙げられる。このとき基材層A1と基材層A2はお互い異なるポリプロピレン系樹脂組成物からなるものであってもよく、同じであってもよく、中間層C1と中間層C2はお互い異なるポリプロピレン系樹脂組成物からなるものであってもよく、同じであってもよく、シール層B1とシール層B2はお互い異なるポリプロピレン系樹脂組成物からなるものであってもよく、同じであってもよい。
6. Layer structure and thickness structure of biaxially oriented polypropylene film The biaxially oriented polypropylene film of the present invention has a base layer A and a seal layer B. An intermediate layer C may be present between the base layer A and the seal layer B. The layer structure of the biaxially oriented polypropylene film of the present invention has the base layer A and the seal layer B, and as long as the seal layer B is present on at least one outermost surface, the intermediate layer C may be present between the base layer A and the seal layer B, or another layer may be present between the base layer A and the intermediate layer C, or the intermediate layer C may be laminated directly on the base layer A. Furthermore, another layer may be present between the intermediate layer C and the seal layer B, or the seal layer B may be laminated directly on the intermediate layer C. Examples of the biaxially oriented polypropylene film of the present invention include a two-layer structure of base layer A/seal layer B, a three-layer structure of base layer A/intermediate layer C/seal layer B, a three-layer structure of seal layer B1/base layer A/seal layer B2, a four-layer structure of seal layer B1/base layer A/intermediate layer C/seal layer B2, a five-layer structure of seal layer B1/intermediate layer C1/base layer A/intermediate layer C2/seal layer B2, and a six-layer structure of seal layer B1/base layer A1/intermediate layer C1/base layer A2/intermediate layer C2/seal layer B2. In this case, the base layer A1 and the base layer A2 may be made of different polypropylene-based resin compositions or may be the same, the intermediate layers C1 and C2 may be made of different polypropylene-based resin compositions or may be the same, and the seal layer B1 and the seal layer B2 may be made of different polypropylene-based resin compositions or may be the same.
本発明の二軸配向ポリプロピレンフィルムが機能層Dを有する場合、基材層Aの表面に機能層Dが直接積層されていてもよく、基材層Aと機能層Dとの間に中間層Cを介していてもよい。また、機能層Dは、基材層Aと中間層Cとの間に位置していてもよく、中間層Cとシール層Bとの間に位置していてもよい。機能層Dを有する場合も、基材層A、中間層C、シール層Bをこの順で有しており、シール層Bを少なくとも一方の最表面に有してさえいれば、特に限定されず、例えば、基材層A/中間層C/シール層Bの構成にさらに機能層Dを有した機能層D/基材層A/中間層C/シール層Bの4層構造、中間層C/基材層A/中間層C/シール層Bの構成にさらに機能層Dを有した機能層D/中間層C/基材層A/中間層C/シール層Bの5層構造などが挙げられる。 When the biaxially oriented polypropylene film of the present invention has a functional layer D, the functional layer D may be laminated directly on the surface of the substrate layer A, or an intermediate layer C may be interposed between the substrate layer A and the functional layer D. The functional layer D may also be located between the substrate layer A and the intermediate layer C, or between the intermediate layer C and the sealing layer B. When the functional layer D is present, there are no particular limitations as long as the substrate layer A, intermediate layer C, and sealing layer B are present in this order, with sealing layer B on at least one outermost surface. Examples of such a structure include a four-layer structure of functional layer D/substrate layer A/intermediate layer C/sealing layer B, in which the substrate layer A/intermediate layer C/sealing layer B structure further has a functional layer D, and a five-layer structure of functional layer D/intermediate layer C/substrate layer A/intermediate layer C/sealing layer B, in which the intermediate layer C/substrate layer A/intermediate layer C/sealing layer B structure further has a functional layer D.
本発明の二軸配向ポリプロピレンフィルム全体の厚みは、その用途や使用方法によって異なるが、フィルム強度、密封性および水蒸気バリア性の観点から、5μm以上100μm以下が好ましい。当該厚さとしては、10μm以上がより好ましく、18μm以上がよりさらに好ましく、また、80μm以下がより好ましく、50μm以下がよりさらに好ましい。本発明の二軸配向ポリプロピレンフィルムを鮮度保持用包材として使用する場合、厚みは33μm以下が好ましく、28μm以下がより好ましく、23μm以下がよりさらに好ましく、18μm以下が特に好ましい。 The overall thickness of the biaxially oriented polypropylene film of the present invention will vary depending on the application and method of use, but from the viewpoints of film strength, airtightness, and water vapor barrier properties, it is preferably 5 μm or more and 100 μm or less. The thickness is more preferably 10 μm or more, even more preferably 18 μm or more, more preferably 80 μm or less, and even more preferably 50 μm or less. When the biaxially oriented polypropylene film of the present invention is used as a freshness-preserving packaging material, the thickness is preferably 33 μm or less, more preferably 28 μm or less, even more preferably 23 μm or less, and particularly preferably 18 μm or less.
基材層Aの厚みは、その用途や使用方法によって異なるが、5μm以上90μm以下が好ましい。厚みを5μm以上とすることでフィルム強度や密封性または水蒸気バリア性を高めることができる。また、厚みを90μm以下とすることで減容化による環境負荷低減を行うことができる。基材層Aの厚みとしては、10μm以上がより好ましく、15μm以上がよりさらに好ましく、また、50μm以下がより好ましく、30μm以下がよりさらに好ましい。 The thickness of the base layer A varies depending on the application and method of use, but is preferably 5 μm or more and 90 μm or less. A thickness of 5 μm or more can improve film strength, sealing properties, and water vapor barrier properties. Furthermore, a thickness of 90 μm or less can reduce the environmental impact by reducing the volume. The thickness of the base layer A is more preferably 10 μm or more, even more preferably 15 μm or more, more preferably 50 μm or less, and even more preferably 30 μm or less.
中間層Cの厚みは、その用途や使用方法によって異なるが、0.5μm以上4μm以下が好ましい。厚みを0.5μm以上とすることで基材層Aとシール層Bとの密着性を高くしてシール強度を高めることができる。また、厚みを4μm以下とすることで減容化による環境負荷低減を行うことができる。中間層Cの厚みとしては、1μm以上3μm以下がより好ましい。 The thickness of intermediate layer C varies depending on its application and method of use, but is preferably 0.5 μm or more and 4 μm or less. A thickness of 0.5 μm or more can improve adhesion between base layer A and seal layer B, thereby increasing seal strength. Furthermore, a thickness of 4 μm or less can reduce the environmental impact by reducing volume. The thickness of intermediate layer C is more preferably 1 μm or more and 3 μm or less.
シール層Bの厚みは、その用途や使用方法によって異なるが、0.3μm以上2μm以下が好ましい。厚みを0.3μm以上とすることでヒートシール強度を高めることができる。また、厚みを2μm以下とすることで減容化による環境負荷低減を行うことができる。シール層Bの厚みとしては、0.5μm以上1.5μm以下がより好ましい。 The thickness of sealing layer B varies depending on its application and method of use, but is preferably 0.3 μm or more and 2 μm or less. A thickness of 0.3 μm or more can increase heat seal strength. Furthermore, a thickness of 2 μm or less can reduce the environmental impact by reducing the volume. The thickness of sealing layer B is more preferably 0.5 μm or more and 1.5 μm or less.
機能層Dの厚みは、その用途や使用方法によって異なるが、0.3μm以上2μm以下が好ましい。厚みを0.3μm以上とすることでヒートシール強度を高めることができる。また、厚みを2μm以下とすることで減容化による環境負荷低減を行うことができる。機能層Dの厚みとしては、0.5μm以上1.5μm以下がより好ましい。 The thickness of functional layer D varies depending on its application and method of use, but is preferably 0.3 μm or more and 2 μm or less. A thickness of 0.3 μm or more can increase heat seal strength. Furthermore, a thickness of 2 μm or less can reduce the environmental impact by reducing the volume. The thickness of functional layer D is more preferably 0.5 μm or more and 1.5 μm or less.
7.二軸配向ポリプロピレンフィルムの製造方法
本発明の二軸配向ポリプロピレンフィルムの製造方法は特に限定されないが、例えば、積層数に見合う押出し機を用いてTダイ法またはインフレーション法などで溶融積層した後、冷却ロール法、水冷法または空冷法で冷却して得た未延伸の積層フィルムを、逐次二軸延伸法、同時二軸延伸法、チューブ延伸法などで延伸する方法を例示することができる。
7. Method for Producing Biaxially Oriented Polypropylene Film The method for producing the biaxially oriented polypropylene film of the present invention is not particularly limited, but examples thereof include a method in which melt lamination is performed by a T-die method, inflation method, or the like using an extruder suitable for the number of layers, followed by cooling by a cooling roll method, water cooling method, or air cooling method to obtain an unstretched laminated film, and then stretching the obtained film by a sequential biaxial stretching method, simultaneous biaxial stretching method, tube stretching method, or the like.
以下、機能層D/基材層A/中間層C/シール層Bの構成からなる二軸配向ポリプロピレンフィルムを逐次二軸延伸法で製造する方法を例示する。なお、層構成などに応じて、以下の例示を適宜変更することができる。基材層A、中間層C、シール層B、機能層Dのそれぞれを構成するポリプロピレン樹脂組成物は前述のとおりである。また、基材層A、中間層C、シール層Bに添加する防曇剤の量は、フィルムの製造工程で高温に晒される際に大気中に蒸散することを考慮して調整することが好ましい。 Below is an example of a method for producing a biaxially oriented polypropylene film consisting of functional layer D/substrate layer A/intermediate layer C/sealing layer B using the sequential biaxial stretching method. Note that the following example can be modified as appropriate depending on the layer configuration, etc. The polypropylene resin compositions that make up each of the substrate layer A, intermediate layer C, sealing layer B, and functional layer D are as described above. Furthermore, it is preferable to adjust the amount of anti-fogging agent added to the substrate layer A, intermediate layer C, and sealing layer B, taking into account that the anti-fogging agent will evaporate into the atmosphere when exposed to high temperatures during the film manufacturing process.
機能層D、基材層A、中間層C、シール層Bの各層を構成するポリプロピレン系樹脂組成物を1台または複数台の押出機により溶融押出しし、押し出された多層シートを冷却ロールで冷却して、未延伸シートを形成する。次に、得られた未延伸シートを長手方向(MD)に延伸する。続いて、延伸後のシートに予熱を加えた後、幅方向(TD)に延伸し、最後に熱固定処理することによって本発明の二軸配向ポリプロピレンフィルムを得ることができる。なお、必要に応じて、二軸配向ポリプロピレンフィルムの少なくとも片面に表面処理を施した後、ワインダーで巻取ることによりフィルムロールを得ることができる。 The polypropylene resin composition constituting each of the functional layer D, substrate layer A, intermediate layer C, and seal layer B is melt-extruded using one or more extruders, and the extruded multilayer sheet is cooled on a cooling roll to form an unstretched sheet. The resulting unstretched sheet is then stretched in the longitudinal direction (MD). The stretched sheet is then preheated, stretched in the transverse direction (TD), and finally heat-set to obtain the biaxially oriented polypropylene film of the present invention. If necessary, at least one side of the biaxially oriented polypropylene film can be surface-treated, and then wound up on a winder to obtain a film roll.
7-1.押出工程
機能層D、基材層A、中間層C、シール層Bのそれぞれを構成するポリプロピレン樹脂組成物を各々例えば200℃以上260℃以下で溶融し、4台の押出機を用いて異なる流路から溶融されたポリプロピレン系樹脂組成物を送り出す。送り出された各ポリプロピレン系樹脂組成物を多層フィードブロックやスタティックミキサー、多層マルチマニホールドダイ等を用いて多層に積層し、機能層D/基材層A/中間層C/シール層Bの順に積層された多層シートをTダイから押出す。なお、1台の押出機のみを用いて、押出機からTダイまでのメルトラインに多層化装置を導入して多層シートを得ることも可能である。また、背圧の安定化および厚み変動の抑制の観点から、ポリマー流路にギヤポンプを設置することが好ましい。
7-1. Extrusion Process The polypropylene resin compositions constituting the functional layer D, base layer A, intermediate layer C, and seal layer B are each melted at, for example, 200°C or higher and 260°C or lower, and the molten polypropylene resin compositions are delivered from different flow paths using four extruders. The delivered polypropylene resin compositions are laminated in multiple layers using a multi-layer feed block, static mixer, multi-layer multi-manifold die, or the like, and a multi-layer sheet laminated in the order of functional layer D/base layer A/intermediate layer C/seal layer B is extruded from a T-die. It is also possible to obtain a multi-layer sheet using only one extruder by introducing a multi-layering device into the melt line from the extruder to the T-die. Furthermore, from the viewpoints of stabilizing back pressure and suppressing thickness fluctuations, it is preferable to install a gear pump in the polymer flow path.
未延伸の多層シートの厚みは3500μm以下とするのが、冷却効率を高める観点から好ましく、3000μm以下とするのがより好ましいが、逐次二軸延伸後のフィルム厚みに応じて、適宜調整できる。未延伸多層シートの厚みは、ポリプロピレン樹脂組成物の押出し速度およびTダイのリップ幅などで調整できる。未延伸多層シートの厚みの下限は特に制限されないが、例えば500μmとすることができる。 The thickness of the unstretched multilayer sheet is preferably 3500 μm or less from the perspective of improving cooling efficiency, and more preferably 3000 μm or less, but this can be adjusted appropriately depending on the film thickness after sequential biaxial stretching. The thickness of the unstretched multilayer sheet can be adjusted by the extrusion speed of the polypropylene resin composition and the lip width of the T-die, etc. There is no particular lower limit to the thickness of the unstretched multilayer sheet, but it can be set to 500 μm, for example.
7-2.冷却工程
Tダイからシート状に共押出した未延伸多層シートを金属製冷却ロール上に接触させて冷却固化する。このとき、シール層B側を冷却ロール上に接地させることが好ましい。また、固化を促進する目的で、冷却ロールで冷却した未延伸多層シートを水槽に浸漬するなどして、さらに冷却することが好ましい。
冷却ロールの温度は、10℃以上、ポリプロピレン樹脂組成物の結晶化温度以下であることが好ましく、フィルムの透明性を上げたい場合は、10℃以上50℃以下の冷却ロールで冷却固化するのが好ましい。冷却ロールの温度を50℃以下にすると未延伸多層シートの透明性が高まりやすく、より好ましくは40℃以下であり、よりさらに好ましくは30℃以下である。逐次二軸延伸後の結晶配向度を増大させるには冷却温度を40℃以上とするのが好ましい場合もあるが、上述のようにメソペンタッド分率が97.0%以上のプロピレン単独重合体を用いる場合は、次工程の延伸を容易に行い、また厚み斑を低減する観点から、冷却ロールの温度を40℃以下とするのが好ましく、30℃以下とするのがより好ましい。水槽を用いる場合、水槽の温度も上記と同様の理由により、10℃以上50℃以下であることが好ましく、より好ましくは40℃以下であり、よりさらに好ましくは30℃以下である。
7-2. Cooling step The unstretched multilayer sheet co-extruded from the T-die into a sheet form is brought into contact with a metal cooling roll and cooled and solidified. At this time, it is preferable that the seal layer B side is grounded on the cooling roll. In order to promote solidification, it is also preferable to further cool the unstretched multilayer sheet cooled by the cooling roll by, for example, immersing it in a water bath.
The temperature of the chill roll is preferably 10°C or higher and lower than the crystallization temperature of the polypropylene resin composition. When increasing the transparency of the film, it is preferable to cool and solidify using a chill roll at 10°C or higher and 50°C or lower. Setting the chill roll temperature to 50°C or lower tends to increase the transparency of the unstretched multilayer sheet, and it is more preferably 40°C or lower, and even more preferably 30°C or lower. In order to increase the degree of crystalline orientation after sequential biaxial stretching, a cooling temperature of 40°C or higher may be preferable. However, when using a propylene homopolymer with a mesopentad fraction of 97.0% or higher as described above, the chill roll temperature is preferably 40°C or lower, more preferably 30°C or lower, from the viewpoint of facilitating the subsequent stretching step and reducing thickness unevenness. When a water bath is used, the temperature of the water bath is also preferably 10°C or higher and 50°C or lower, more preferably 40°C or lower, and even more preferably 30°C or lower, for the same reasons as above.
7-3.長手方向の延伸工程
長手方向の延伸温度は、Tm-30℃以上Tm-7℃以下が好ましい。当該温度がTm-30℃以上であると、引き続いて行われる幅方向の延伸が容易になり、膜厚ムラも少なくしやすい。また、Tm-7℃以下であると熱収縮率を小さくしやすい上に、延伸ロールに付漕し延伸しにくくなったり、表面の粗さが大きくなることにより品位が低下することも少ない。上記温度としては、Tm-27℃以上がより好ましく、Tm-25℃以上がよりさらに好ましく、また、Tm-12℃以下がより好ましく、Tm-10℃以下がよりさらに好ましい。なお、ここでのTmは、最も厚い層を形成する樹脂のTmをいうものとする。
長手方向の延伸倍率は、3.5倍以上8.0倍以下が好ましい。当該延伸倍率が3.5倍以上であると、強度を高めやすく、膜厚ムラも少なくしやすい。また、8.0倍以下であると、幅方向延伸工程での幅方向延伸がしやすく、生産性を向上させやすい。上記延伸倍率としては、3.8倍以上がより好ましく、4.2倍以上がよりさらに好ましく、また、7.0倍以下がより好ましく、6.0倍以下がよりさらに好ましい。
なお、長手方向の延伸は、3対以上の延伸ロールを使用して、2段階以上の多段階に分けて延伸してもよいが、2対の延伸ロールを使用して1段階で延伸することが好ましい。多段階に分けて延伸する場合、最も高い延伸温度が上記範囲内であることが好ましい。
7-3. Longitudinal Stretching Process The longitudinal stretching temperature is preferably Tm-30°C or higher and Tm-7°C or lower. If the temperature is Tm-30°C or higher, the subsequent widthwise stretching becomes easier and film thickness unevenness tends to be reduced. If the temperature is Tm-7°C or lower, the thermal shrinkage rate is easily reduced, and there is little risk of the film becoming difficult to stretch when applied to the stretching rolls or of the film becoming rough on the surface, resulting in a decrease in quality. The temperature is more preferably Tm-27°C or higher, even more preferably Tm-25°C or higher, more preferably Tm-12°C or lower, and even more preferably Tm-10°C or lower. Here, Tm refers to the Tm of the resin forming the thickest layer.
The stretching ratio in the longitudinal direction is preferably 3.5 times or more and 8.0 times or less. When the stretching ratio is 3.5 times or more, it is easy to increase the strength and reduce thickness unevenness. Furthermore, when the stretching ratio is 8.0 times or less, it is easy to perform width direction stretching in the width direction stretching step, and it is easy to improve productivity. The stretching ratio is more preferably 3.8 times or more, even more preferably 4.2 times or more, and more preferably 7.0 times or less, and even more preferably 6.0 times or less.
The longitudinal stretching may be performed in two or more stages using three or more pairs of stretching rolls, but it is preferable to perform stretching in one stage using two pairs of stretching rolls. When performing stretching in multiple stages, it is preferable that the highest stretching temperature is within the above range.
7-4.予熱工程
予熱工程にて長手方向延伸後の一軸延伸フィルムを加熱して、幅方向の延伸工程の前にポリプロピレン樹脂組成物を十分に軟化させることが好ましい。予熱工程での加熱温度はTm以上、Tm+25℃以下が好ましい。予熱工程での加熱温度を融点以上とすることにより、軟化が進み、幅方向の延伸が容易になる。また、予熱工程での加熱温度をTm+25℃以下とすることで、幅方向の延伸時に配向が進み、剛性が発現しやすくなる。上記加熱温度としては、Tm+2℃以上がより好ましく、Tm+3℃以上がよりさらに好ましく、また、Tm+20℃以下がより好ましく、Tm+15℃以下がよりさらに好ましい。なお、予熱工程が複数のゾーンからなる場合は、その中の最高温度のゾーンの温度を予熱温度とする。また、ここでのTmは、最も厚い層を形成する樹脂のTmをいうものとする。
7-4. Preheating Step It is preferable to heat the uniaxially stretched film after longitudinal stretching in a preheating step to sufficiently soften the polypropylene resin composition before the widthwise stretching step. The heating temperature in the preheating step is preferably Tm or higher and Tm + 25°C or lower. By setting the heating temperature in the preheating step to the melting point or higher, softening proceeds, facilitating widthwise stretching. Furthermore, by setting the heating temperature in the preheating step to Tm + 25°C or lower, orientation proceeds during widthwise stretching, making it easier to develop rigidity. The heating temperature is more preferably Tm + 2°C or higher, even more preferably Tm + 3°C or higher, more preferably Tm + 20°C or lower, and even more preferably Tm + 15°C or lower. Note that if the preheating step consists of multiple zones, the temperature of the hottest zone among them is taken as the preheating temperature. Note that Tm here refers to the Tm of the resin forming the thickest layer.
7-5.幅方向の延伸工程
幅方向の延伸温度は、Tm-10℃以上、予熱工程での加熱温度以下が好ましい。当該温度がTm-10℃以上であると、得られるフィルムの剛性を向上させやすく、予熱工程での加熱温度以下であると、延伸ムラが生じにくい。上記温度としては、Tm-9℃以上がより好ましく、Tm-7℃以上がよりさらに好ましく、Tm-5℃以上が特に好ましく、また、Tm+10℃以下がより好ましく、Tm+7℃以下がよりさらに好ましく、Tm+5℃以下が特に好ましい。なお、ここでのTmは、最も厚い層を形成する樹脂のTmをいうものとする。
幅方向延伸工程において、上記の温度範囲での幅方向の延伸工程(以下、「前期延伸工程」ということがある)に引き続き、より低温で延伸する後期延伸工程を加えることが好ましい。後期延伸工程を設けることでフィルムの剛性を高めやすい。
幅方向の延伸倍率は、10倍以上20倍以下が好ましい。当該延伸倍率が10倍以上であると、剛性を高めやすく、膜厚ムラも少なくなりやすい。また、20倍以下であると、熱収縮率を小さくしやすく、延伸時に破断しにくい。上記延伸倍率としては、11倍以上がより好ましく、12倍以上がよりさらに好ましく、12.5倍以上が特に好ましく、また、17倍以下がより好ましく、15倍以下がよりさらに好ましい。
なお、後期延伸工程を加える場合は、合計の延伸倍率が上記範囲となるようにすることが好ましい。
7-5. Width Direction Stretching Process The width direction stretching temperature is preferably Tm-10°C or higher and the heating temperature in the preheating process or lower. If the temperature is Tm-10°C or higher, the rigidity of the resulting film is easily improved, and if the temperature is lower than the heating temperature in the preheating process, stretching unevenness is less likely to occur. The temperature is more preferably Tm-9°C or higher, even more preferably Tm-7°C or higher, particularly preferably Tm-5°C or higher, and more preferably Tm+10°C or lower, even more preferably Tm+7°C or lower, and particularly preferably Tm+5°C or lower. Note that Tm here refers to the Tm of the resin forming the thickest layer.
In the width direction stretching step, it is preferable to add a later stretching step in which the film is stretched at a lower temperature following the width direction stretching step in the above temperature range (hereinafter sometimes referred to as the "early stretching step"). By providing the later stretching step, the rigidity of the film can be easily increased.
The stretching ratio in the width direction is preferably 10 times or more and 20 times or less. When the stretching ratio is 10 times or more, rigidity is easily increased and thickness unevenness is easily reduced. Furthermore, when the stretching ratio is 20 times or less, the heat shrinkage rate is easily reduced and the film is less likely to break during stretching. The stretching ratio is more preferably 11 times or more, even more preferably 12 times or more, particularly preferably 12.5 times or more, and more preferably 17 times or less, and even more preferably 15 times or less.
When a later stretching step is added, it is preferable that the total stretching ratio is set within the above range.
7-6.熱処理工程
幅方向の延伸工程の終了後に熱処理を行うことが好ましい。熱処理の具体的な手段としては、幅方向の延伸終了後に延伸ゾーンより高温のゾーンを設ける方法、延伸後半でゾーン温度を上げ延伸終了後も同じ温度のゾーンを通過させてフィルムの温度を上昇させる方法などが挙げられる。加熱する手段としては、熱風を吹き付ける方法、赤外線ヒーターで加熱する方法などが挙げられるが、幅方向の延伸工程終了時よりフィルムの温度を上げる方法であれば特に限定されるものではない。
7-6. Heat Treatment Step It is preferable to perform heat treatment after the width direction stretching step. Specific means for heat treatment include providing a zone with a higher temperature than the stretching zone after the width direction stretching is completed, or increasing the zone temperature in the latter half of stretching and passing the film through a zone at the same temperature after the stretching is completed to increase the film temperature. Examples of heating methods include blowing hot air or heating with an infrared heater, but there are no particular limitations as long as the method increases the film temperature from the temperature at the end of the width direction stretching step.
熱処理工程は、幅方向の延伸工程の終了した直後、すなわち、幅方向への延伸が最終延伸倍率に到達した直後に行うことが好ましい。熱処理工程での温度は、幅方向の延伸工程終了時よりも高い温度とすることが好ましく、具体的には、幅方向の延伸温度+1℃以上であることが好ましい。また、熱処理工程は2段階行うことが好ましく、前期熱処理工程で幅方向の延伸工程終了時よりも高い温度で熱処理した後、後期熱処理工程で前期熱処理工程よりも低い温度で熱処理することが好ましい。以下、前期熱処理工程と後期熱処理工程について説明する。 The heat treatment step is preferably carried out immediately after the widthwise stretching step is completed, i.e., immediately after the widthwise stretching has reached the final stretch ratio. The temperature in the heat treatment step is preferably higher than that at the end of the widthwise stretching step, and specifically, is preferably at least 1°C higher than the widthwise stretching temperature. It is also preferable to carry out the heat treatment step in two stages, with the early heat treatment step being performed at a temperature higher than that at the end of the widthwise stretching step, and the later heat treatment step being performed at a temperature lower than that in the early heat treatment step. The early and later heat treatment steps are explained below.
7-6-1.前期熱処理工程
前期熱処理工程での加熱温度は、Tm以上、Tm+20℃以下が好ましい。Tm以上で加熱することにより、緩和が進行し、分子鎖の緊張を軽減し、結晶化がより確実に進行し得る。一方、Tm+20℃以下で加熱することにより、融解を抑制しつつ、配向した分子鎖の緩和を抑制できるため、剛性の低下をより確実に阻害し得る。上記加熱温度としては、Tm+3℃以上がより好ましく、Tm+4℃以上がよりさらに好ましく、Tm+5℃以上が特に好ましく、また、Tm+18℃以下がより好ましく、Tm+14℃以下がよりさらに好ましく、Tm+10℃以下が特に好ましい。延伸工程の後に熱処理工程にて加熱することで、延伸時に形成した分子鎖配向が緩和され、後期熱処理工程で結晶化が起こりやすくなる。幅方向延伸終了時の温度から加熱時の温度へは徐々に昇温させることもできるが、段階的にあるいは一段階で昇温させることもできる。温度を段階的にあるいは一段階で昇温させると、フィルム中の分子鎖の配向を制御しやすいため、好ましい。なお、ここでのTmは、最も厚い層を形成する樹脂のTmをいうものとする。
前期熱処理工程では、幅方向にフィルムを弛緩させても弛緩させなくてもよい。具体的には、弛緩率は0%以上3%以下が好ましい。弛緩率が当該範囲内であると、剛性が低下しにくく、フィルム厚み変動が小さくなりやすい。上記弛緩率としては、0%以上1%以下がより好ましく、0%、すなわち弛緩させないことがよりさらに好ましい。なお、剛性をより高めたいときは、弛緩させなくてもよい。また、本発明の効果を損なわないのであれば、フィルムのたるみなどを抑制するためにわずかに拡張してもよい。
7-6-1. Preliminary Heat Treatment Step The heating temperature in the preliminary heat treatment step is preferably Tm or higher and Tm + 20°C or lower. Heating at a temperature above Tm promotes relaxation, reducing tension in the molecular chains and allowing crystallization to proceed more reliably. On the other hand, heating at a temperature below Tm + 20°C suppresses melting while suppressing relaxation of the oriented molecular chains, thereby more reliably preventing a decrease in rigidity. The heating temperature is more preferably Tm + 3°C or higher, even more preferably Tm + 4°C or higher, particularly preferably Tm + 5°C or higher, more preferably Tm + 18°C or lower, even more preferably Tm + 14°C or lower, and particularly preferably Tm + 10°C or lower. Heating in the heat treatment step after the stretching step relaxes the molecular chain orientation formed during stretching, making crystallization more likely to occur in the final heat treatment step. The temperature can be gradually increased from the temperature at the end of width direction stretching to the temperature during heating, or it can be increased in stages or in a single step. It is preferable to raise the temperature stepwise or in one step, since this makes it easier to control the orientation of molecular chains in the film. Note that Tm here refers to the Tm of the resin that forms the thickest layer.
In the heat treatment step, the film may or may not be relaxed in the width direction. Specifically, the relaxation rate is preferably 0% or more and 3% or less. If the relaxation rate is within this range, the rigidity is less likely to decrease and the film thickness fluctuation is likely to be small. The relaxation rate is more preferably 0% or more and 1% or less, and even more preferably 0%, i.e., no relaxation. If it is desired to further increase the rigidity, relaxation is not necessary. Furthermore, the film may be slightly expanded to suppress sagging, etc., as long as it does not impair the effects of the present invention.
7-6-2.後期熱処理工程
後期熱処理工程での加熱温度は、Tm-70℃以上、Tm以下が好ましい。当該加熱温度がTm-70℃以上であれば、ラメラ厚化が進行し、フィルムの融点が上がりやすい。つまり、高温での耐熱性が得られる。一方、上記加熱温度がTm以下であれば、結晶化が進行して熱収縮率が低下しやすい。上記加熱温度としては、Tm-50℃以上がより好ましく、Tm-40℃以上がよりさらに好ましく、Tm-30℃以上が特に好ましく、また、Tm-1℃以下がより好ましく、Tm-2℃以下がよりさらに好ましく、Tm-3℃以下が特に好ましい。なお、ここでのTmは、最も厚い層を形成する樹脂のTmをいうものとする。
後期熱処理工程では、熱収縮率を調整する目的で幅方向にフィルムを弛緩させてもよい。弛緩させる場合、弛緩率は1%以上8%以下が好ましい。弛緩率が当該範囲内であると、剛性が低下しにくく、フィルム厚み変動が小さくなりやすい。上記弛緩率としては、2%以上がより好ましく、3%以上がよりさらに好ましく、また、6%以下がより好ましく、5%以下がよりさらに好ましい。ただし、剛性をより高めたいときは弛緩させなくてもよい。
7-6-2. Later Heat Treatment Step The heating temperature in the later heat treatment step is preferably Tm-70°C or higher and Tm or lower. If the heating temperature is Tm-70°C or higher, lamellar thickening proceeds and the melting point of the film is likely to increase. In other words, heat resistance at high temperatures can be obtained. On the other hand, if the heating temperature is Tm or lower, crystallization proceeds and the heat shrinkage rate is likely to decrease. The heating temperature is more preferably Tm-50°C or higher, even more preferably Tm-40°C or higher, particularly preferably Tm-30°C or higher, more preferably Tm-1°C or lower, even more preferably Tm-2°C or lower, and particularly preferably Tm-3°C or lower. Note that Tm here refers to the Tm of the resin forming the thickest layer.
In the latter heat treatment step, the film may be relaxed in the width direction in order to adjust the thermal shrinkage rate. When the film is relaxed, the relaxation rate is preferably 1% or more and 8% or less. When the relaxation rate is within this range, the rigidity is less likely to decrease and the film thickness fluctuation tends to be small. The relaxation rate is more preferably 2% or more, even more preferably 3% or more, and more preferably 6% or less, and even more preferably 5% or less. However, if it is desired to further increase the rigidity, relaxation is not necessary.
幅方向の延伸工程においては、延伸により分子鎖は配向するが絡み合いが強く残るため、分子鎖は過度に拘束された状態である。この状態で熱処理工程を行うと、絡み合いに伴う過度に拘束された分子鎖が多いため、結晶化度が上がりにくく、さらに結晶部のラメラの厚みの増加が起こりにくく、より低温で融解する結晶部を形成するので、高温では十分な耐熱性を発現することができない。そのため、従来の製膜プロセスでは、幅方向への延伸後の分子鎖の絡み合いを解消するため、熱処理工程でフィルムを数%から数十%の弛緩を施すことで結晶化を促進していた。しかし、弛緩を施すことで幅方向の延伸工程で生成した分子鎖の配向が低下して、フィルムの剛性が低下してしまい、従来の製膜プロセスでは耐熱性と剛性を両立することは困難であった。また、高温で熱処理すると過度に融解が進行し、フィルムが白化する問題もあった。
この課題を解消するためには、幅方向の延伸工程の終了直後に幅方向の延伸よりも高い温度で、例えば1%以上5%以下、好ましくは3%以下の弛緩率で熱処理を行うことにより、分子鎖の配向は残しつつ、過度な絡み合いによる分子鎖の拘束を解消させることが好ましい。この熱処理工程を行うと、分子鎖の絡み合いに伴う拘束された分子鎖の存在が少ないため、結晶化度が上がり、結晶部のラメラの厚みを増加しやすくなり、高温でも十分な耐熱性を発現することができる。
During the widthwise stretching process, molecular chains are oriented by stretching, but remain strongly entangled, resulting in an excessively constrained state of the molecular chains. If a heat treatment process is performed in this state, the excessively constrained molecular chains due to entanglement make it difficult to increase the crystallinity, and the lamellae in the crystalline region do not increase in thickness. This leads to the formation of crystalline regions that melt at lower temperatures, resulting in insufficient heat resistance at high temperatures. Therefore, in conventional film-forming processes, in order to eliminate the entanglement of molecular chains after widthwise stretching, the film is relaxed by several percent to several tens of percent during the heat treatment process to promote crystallization. However, relaxation reduces the molecular chain orientation generated during the widthwise stretching process, resulting in a decrease in the rigidity of the film. Therefore, it is difficult to achieve both heat resistance and rigidity in conventional film-forming processes. Furthermore, heat treatment at high temperatures can cause excessive melting, resulting in the whitening of the film.
To solve this problem, it is preferable to perform heat treatment immediately after the end of the width direction stretching step at a temperature higher than that used for width direction stretching, for example, at a relaxation rate of 1% to 5%, preferably 3% or less, to relieve the constraint of the molecular chains due to excessive entanglement while maintaining the molecular chain orientation. By performing this heat treatment step, the presence of constrained molecular chains due to entanglement is reduced, which increases the crystallinity and makes it easier to increase the thickness of the lamellae in the crystalline portion, thereby enabling the film to exhibit sufficient heat resistance even at high temperatures.
また、二軸配向ポリプロピレンフィルムを構成するポリプロピレン樹脂組成物中の低分子量ポリプロピレン成分を増やすと、分子鎖の絡み合いがより少なくすることができるので、結晶部のラメラ以外の部分の熱収縮応力が弱くなり、熱収縮率をさらに低下させることができ好ましい。 Furthermore, increasing the amount of low-molecular-weight polypropylene components in the polypropylene resin composition that makes up the biaxially oriented polypropylene film can reduce entanglement of molecular chains, thereby weakening the heat shrinkage stress in areas other than the lamellae of the crystalline portion and further reducing the heat shrinkage rate, which is preferable.
7-7.冷却工程
熱処理工程直後にフィルムを冷却することが好ましい。冷却温度は、10℃以上140℃以下が好ましい。当該冷却温度としては、15℃以上がより好ましく、20℃以上がよりさらに好ましく、また、135℃以下がより好ましく、130℃以下がよりさらに好ましく、80℃以下が特に好ましく、50℃以下が最も好ましい。冷却工程を設けることで、フィルム内の分子配向の状態を固定することができる。
7-7. Cooling Step It is preferable to cool the film immediately after the heat treatment step. The cooling temperature is preferably 10°C or higher and 140°C or lower. The cooling temperature is more preferably 15°C or higher, even more preferably 20°C or higher, more preferably 135°C or lower, even more preferably 130°C or lower, particularly preferably 80°C or lower, and most preferably 50°C or lower. By providing a cooling step, the state of molecular orientation within the film can be fixed.
7-8.表面処理工程
本発明の二軸配向ポリプロピレンフィルムは、印刷性やラミネート性などを向上させるために、シール層B、及びシール層Bとは反対側の表面層の少なくとも一方を表面処理することが好ましく、シール層Bの表面張力を高める観点から、シール層Bを表面処理することがより好ましい。表面処理の方法としては、コロナ放電処理、プラズマ処理、火炎処理、酸処理などが例示でき、特に制限はないが、連続処理が可能であり、このフィルムの製膜過程の巻き取り工程前に容易に実施できるという観点から、コロナ放電処理、プラズマ処理、火炎処理のいずれかを行うのが好ましく、防曇性を高める観点からコロナ放電処理を行うことがより好ましい。
7-8. Surface Treatment Step In order to improve printability and lamination properties, the biaxially oriented polypropylene film of the present invention is preferably surface-treated on at least one of the seal layer B and the surface layer opposite to the seal layer B, and it is more preferable to surface-treat the seal layer B from the viewpoint of increasing the surface tension of the seal layer B. Examples of the surface treatment method include corona discharge treatment, plasma treatment, flame treatment, and acid treatment, and there are no particular restrictions on the method. However, from the viewpoints that continuous treatment is possible and that it can be easily carried out before the winding step in the film production process, it is preferable to carry out corona discharge treatment, plasma treatment, or flame treatment, and from the viewpoint of improving anti-fogging properties, it is more preferable to carry out corona discharge treatment.
8.本発明の二軸配向ポリプロピレンフィルムの各種特性
本発明の二軸配向ポリプロピレンフィルムは、下記特性を有することが好ましい。ここで本発明の二軸配向ポリプロピレンフィルムにおける「長手方向(MD方向)」とは、フィルム製造工程における流れ方向に対応する方向であり、「幅方向(TD方向)」とは、前記のフィルム製造工程における流れ方向と直交する方向であり、以下も同様である。
なお、フィルム製造工程における流れ方向が不明なポリプロピレンフィルムについては、フィルム表面に対して垂直方向に広角X線を入射し、α型結晶の(110)面に由来する散乱ピークを円周方向にスキャンし、得られた回折強度分布の回折強度が最も大きい方向を「長手方向」、それと直交する方向を「幅方向」とする。
8. Various Properties of the Biaxially Oriented Polypropylene Film of the Present Invention The biaxially oriented polypropylene film of the present invention preferably has the following properties. Here, the "longitudinal direction (MD direction)" of the biaxially oriented polypropylene film of the present invention refers to the direction corresponding to the flow direction in the film production process, and the "transverse direction (TD direction)" refers to the direction perpendicular to the flow direction in the film production process, and the same applies hereinafter.
For polypropylene films whose flow direction in the film manufacturing process is unknown, wide-angle X-rays are incident perpendicularly to the film surface, and the scattering peaks resulting from the (110) plane of the α-type crystals are scanned in the circumferential direction. The direction with the greatest diffraction intensity in the obtained diffraction intensity distribution is designated the "longitudinal direction," and the direction perpendicular to that is designated the "width direction."
8-1.幅方向の長さ
熱機械分析において、30℃から130℃まで昇温速度10℃/分で昇温したとき、本発明の二軸配向ポリプロピレンフィルムにおける30℃での幅方向の長さをX0、前記昇温中における幅方向の長さの最大値をX1、前記昇温中における幅方向の長さの最小値をX2とすると、(X1-X0)/X0の百分率は0.50%以下が好ましい。当該百分率が0.50%以下であると、ロールでの加熱加工時、印刷時、ヒートシール時のように高温でフィルムを加熱した後であってもフィルムの変形を抑制できるため、フィルムの平面性が悪くなりにくい上にフィルムの加工性を向上させることができる。また、印刷時には高温の印刷インキを転写するが、その際に印刷ピッチずれが生じにくくなる。上記百分率として、より好ましくは0.45%以下であり、よりさらに好ましくは0.40%以下であり、特に好ましくは0.35%以下であり、最も好ましくは0.30%以下である。(X1-X0)/X0の百分率は小さい方が好ましく、下限は特に限定されないが、技術上の困難性から例えば0.01%以上であり、好ましくは0.02%以上である。
本発明の二軸配向ポリプロピレンフィルムの(X2-X0)/X0の百分率は-0.50%以上が好ましい。当該百分率が-0.50%以上であると、ロールでの加熱加工時、印刷時、ヒートシール時のように高温でフィルムを加熱した後であってもフィルムの変形を抑制できるため、フィルムの平面性が悪くなりにくい上にフィルムの加工性を向上させることができる。上記百分率として、より好ましくは-0.45%以上であり、よりさらに好ましくは-0.40%以上であり、特に好ましくは-0.35%以上であり、最も好ましくは-0.30%以上である。(X2-X0)/X0の百分率は大きい方が好ましく、上限は特に限定されないが、技術上の困難性から例えば0.01%以下であり、好ましくは0.00%以下である。
8-1. Width Direction Length In thermomechanical analysis, when the temperature of the biaxially oriented polypropylene film of the present invention is increased from 30°C to 130°C at a rate of 10°C/min, where X0 is the width direction length at 30°C, X1 is the maximum width direction length during the temperature increase, and X2 is the minimum width direction length during the temperature increase, the percentage of ( X1 - X0 )/ X0 is preferably 0.50% or less. When this percentage is 0.50% or less, film deformation can be suppressed even after heating at high temperatures, such as during heat processing with a roll, printing, or heat sealing. This reduces the deterioration of film flatness and improves film processability. Furthermore, high-temperature printing ink is transferred during printing, which reduces the occurrence of printing pitch deviation. The percentage is more preferably 0.45% or less, even more preferably 0.40% or less, particularly preferably 0.35% or less, and most preferably 0.30% or less. The percentage of (X 1 -X 0 )/X 0 is preferably small, and although there is no particular lower limit, it is, for example, 0.01% or more, preferably 0.02% or more, in view of technical difficulties.
The percentage of (X 2 -X 0 )/X 0 of the biaxially oriented polypropylene film of the present invention is preferably -0.50% or more. When this percentage is -0.50% or more, deformation of the film can be suppressed even after heating at high temperatures, such as during heat processing with a roll, printing, or heat sealing. This prevents deterioration of the film's flatness and improves the film's processability. The percentage is more preferably -0.45% or more, even more preferably -0.40% or more, particularly preferably -0.35% or more, and most preferably -0.30% or more. A larger percentage of (X 2 -X 0 )/X 0 is preferable. While there is no particular upper limit, it is, for example, 0.01% or less, preferably 0.00% or less, due to technical difficulties.
熱機械分析において、30℃から160℃まで昇温速度10℃/分で昇温したとき、本発明の二軸配向ポリプロピレンフィルムにおける幅方向の長さが0.9950×X0以下となる温度、すなわち0.5%収縮時の温度は、129℃以上が好ましく、130℃以上がより好ましく、131℃以上がよりさらに好ましく、132℃以上が特に好ましく、133℃以上が最も好ましい。なお、「幅方向の長さが0.9950×X0以下となる温度」は、30℃から160℃まで昇温速度10℃/分で昇温したときに幅方向の長さが0.9950×X0以下となる温度の中で最も低い温度を指す。0.9950×X0以下となる温度が129℃以上であると、ロールでの加熱加工時、印刷時、ヒートシール時のように高温でフィルムを加熱した後であってもフィルムの変形を抑制できるため、フィルムの平面性が悪くなりにくい上にフィルムの加工性を向上させることができる。0.9950×X0以下となる温度は高い方が好ましく、上限は特に限定されないが、例えば160℃以下であり、好ましくは156℃以下である。160℃以下であると、現実的な製造が容易であったり、透明性を維持しやすい。 In thermomechanical analysis, when the biaxially oriented polypropylene film of the present invention is heated from 30°C to 160°C at a heating rate of 10°C/min, the temperature at which the width direction length of the film is 0.9950 x X0 or less, i.e., the temperature at which the film shrinks by 0.5%, is preferably 129°C or higher, more preferably 130°C or higher, even more preferably 131°C or higher, particularly preferably 132°C or higher, and most preferably 133°C or higher. The "temperature at which the width direction length is 0.9950 x X0 or less" refers to the lowest temperature at which the width direction length is 0.9950 x X0 or less when the film is heated from 30°C to 160°C at a heating rate of 10°C/min. When the temperature at which the width direction length is 0.9950 x X0 or less is 129°C or higher, deformation of the film can be suppressed even after heating at high temperatures, such as during heat processing with a roll, printing, or heat sealing. This makes it less likely that the flatness of the film will deteriorate and improves the processability of the film. The temperature at which 0.9950 × X 0 or less is preferably higher, and the upper limit is not particularly limited, but is, for example, 160° C. or less, preferably 156° C. or less. When the temperature is 160° C. or less, practical production is easy and transparency is easily maintained.
8-2.損失弾性率
損失弾性率は動的粘弾性測定により求める。具体的には、測定荷重10g、周波数10Hzで、窒素雰囲気下、-60℃から160℃まで昇温速度5℃/分で昇温し、昇温中の各温度における損失弾性率を測定する。本発明者らは、剛性と耐熱性を高めるだけではフィルム加熱後に平面性が保てない場合がある一方で、所定の温度領域における損失弾性率を所定の範囲内となるように制御すれば、フィルム加熱後であっても平面性を保つことができることを見出した。
8-2. Loss Modulus The loss modulus is determined by dynamic viscoelasticity measurement. Specifically, the temperature is raised from -60°C to 160°C at a rate of 5°C/min under a nitrogen atmosphere with a measurement load of 10 g and a frequency of 10 Hz, and the loss modulus is measured at each temperature during the temperature rise. The inventors have found that while increasing the rigidity and heat resistance alone may not be enough to maintain the flatness of the film after heating, controlling the loss modulus in a predetermined temperature range to fall within a predetermined range makes it possible to maintain the flatness of the film even after heating.
以下、-25℃~25℃での損失弾性率の最大値E”(A)、25℃~75℃での損失弾性率の最小値E”(B)、100℃~160℃での損失弾性率の最大値E”(C)、E”(C)/E”(A)、及びE”(B)/E”(C)の5つの損失弾性率に関するパラメータについて説明する。なお、本明細書では、単に「損失弾性率」と記載している場合であっても、全て幅方向の損失弾性率を指す。 Below, we will explain five parameters related to the loss modulus: E"(A), the maximum value of the loss modulus between -25°C and 25°C; E"(B), the minimum value of the loss modulus between 25°C and 75°C; E"(C), the maximum value of the loss modulus between 100°C and 160°C; E"(C)/E"(A); and E"(B)/E"(C). Note that in this specification, even when simply referring to "loss modulus," it always refers to the loss modulus in the width direction.
8-2-1.-25℃から25℃での損失弾性率の最大値E”(A)
高柳素夫,「結晶性高分子の温度分散」,高分子,高分子学会,1961年,第10巻,第3号,p.289~295には、ポリプロピレンフィルムは、主鎖のミクロブラウン運動に起因する緩和(主分散)が-25℃から25℃で起こることが記載されており、また、延伸による配向度が上がるにつれて-25℃から25℃の損失弾性率が大きくなることが記載されている。本発明者らは、高立体規則性のポリプロピレンを使用し、上述の幅方向延伸工程を採用することで、フィルム中の配向を高くすることができ、すなわち、-25℃から25℃での損失弾性率の値を大きくできることを見出した。
8-2-1. Maximum loss modulus E" (A) from -25°C to 25°C
Takayanagi Motoo, "Temperature Dispersion of Crystalline Polymers," Polymer, Society of Polymer Science, 1961, Vol. 10, No. 3, pp. 289-295, describes that relaxation (main dispersion) due to micro-Brownian motion of the main chain occurs in polypropylene films at temperatures between -25°C and 25°C, and also describes that the loss modulus between -25°C and 25°C increases as the degree of orientation by stretching increases. The present inventors have found that by using highly stereoregular polypropylene and employing the above-mentioned width direction stretching process, it is possible to increase the orientation in the film, i.e., to increase the value of the loss modulus between -25°C and 25°C.
本発明の二軸配向ポリプロピレンフィルムのE”(A)は、0.40GPa以上が好ましい。E”(A)が0.40GPa以上であると、剛性が高くなりやすい。E”(A)としては、0.42GPa以上がより好ましく、0.44GPa以上がよりさらに好ましく、0.46GPa以上が特に好ましく、0.48GPa以上が最も好ましい。E”(A)の上限は特に限定されないが、現実的な値として例えば0.70GPa以下であり、0.60GPa以下であることが好ましい。 E"(A) of the biaxially oriented polypropylene film of the present invention is preferably 0.40 GPa or more. When E"(A) is 0.40 GPa or more, rigidity tends to be high. E"(A) is more preferably 0.42 GPa or more, even more preferably 0.44 GPa or more, particularly preferably 0.46 GPa or more, and most preferably 0.48 GPa or more. There is no particular upper limit for E"(A), but a realistic value is, for example, 0.70 GPa or less, and preferably 0.60 GPa or less.
8-2-2.25℃から75℃での損失弾性率の最小値E”(B)
高柳素夫,「結晶性高分子の温度分散」,高分子,高分子学会,1961年,第10巻,第3号,p.289~295には、耐熱性に寄与が大きいフィルム中の結晶化度を高め、ポリプロピレン樹脂のガラス転移点温度以上における比較的低温の領域(以下、低温領域という)で融解する結晶を少なくすることにより、融解に伴う緩和が生じにくくなり、その影響により非晶部の緩和も抑制される、すなわち、高温で処理しても非晶部の運動性が低くなり、耐熱性が良好となることが記載されている。本発明者らは、高立体規則性のポリプロピレンを使用し、上述の幅方向延伸工程を採用することで、上記低温領域で融解する結晶を少なくすることができ、ガラス転移点温度から75℃までの損失弾性率の変化が小さくなることを見出した。
8-2-2. Minimum loss modulus E" (B) from 25°C to 75°C
Takayanagi Motoo, "Temperature Dispersion of Crystalline Polymers," Polymer, Society of Polymer Science, 1961, Vol. 10, No. 3, pp. 289-295, describes that increasing the crystallinity in a film, which contributes greatly to heat resistance, and reducing the amount of crystals that melt in a relatively low temperature range above the glass transition temperature of the polypropylene resin (hereinafter referred to as the low temperature range) makes it difficult for relaxation to occur due to melting, which in turn suppresses relaxation of the amorphous portion, i.e., even when treated at high temperatures, the mobility of the amorphous portion is reduced, resulting in good heat resistance. The present inventors have found that by using a highly stereoregular polypropylene and employing the width direction stretching process described above, it is possible to reduce the amount of crystals that melt in the low temperature range, thereby reducing the change in loss modulus from the glass transition temperature to 75°C.
本発明の二軸配向ポリプロピレンフィルムのE”(B)は、0.16GPa以上が好ましい。E”(B)が0.16GPa以上であると、熱収縮率が低下しやすい。また、E”(B)が0.16GPa以上であると、上記低温領域で融解する結晶が少ないため、平面性を高めることができる。E”(B)としては、0.17GPa以上がより好ましく、0.18GPa以上がよりさらに好ましく、0.19GPa以上が特に好ましく、0.20GPa以上が最も好ましい。E”(B)の上限は特に限定されないが、現実的な値として例えば0.60GPa以下であり、0.50GPa以下であることが好ましい。 E"(B) of the biaxially oriented polypropylene film of the present invention is preferably 0.16 GPa or more. If E"(B) is 0.16 GPa or more, the heat shrinkage rate is likely to decrease. Furthermore, if E"(B) is 0.16 GPa or more, fewer crystals will melt in the above-mentioned low temperature range, thereby improving flatness. E"(B) is more preferably 0.17 GPa or more, even more preferably 0.18 GPa or more, particularly preferably 0.19 GPa or more, and most preferably 0.20 GPa or more. There is no particular upper limit for E"(B), but a realistic value is, for example, 0.60 GPa or less, and preferably 0.50 GPa or less.
8-2-3.100℃から160℃での損失弾性率の最大値E”(C)
高柳素夫,「結晶性高分子の温度分散」,高分子,高分子学会,1961年,第10巻,第3号,p.289~295には、ポリプロピレンの延伸フィルムを昇温させて温度毎の損失弾性率を測定すると、100℃以上に結晶分散に由来するピークが現れることが記載されている。この結晶分散のピークは結晶構造の面間の摩擦粘性が増大することに由来すると考えられており、製膜時に最適な温度でフィルムを延伸することで増大する。摩擦粘性が増大することは結晶相内での応力伝達が強いことを示しており、剛性の増大と相関すると考えられる。以上のことから、本発明者らは、高立体規則性のポリプロピレンを使用し、上述の幅方向延伸工程を採用することで、100℃以上の損失弾性率の最大値が大きくなることを見出した。
8-2-3. Maximum loss modulus E" (C) from 100°C to 160°C
Takayanagi Motoo, "Temperature Dispersion of Crystalline Polymers," Polymer, Society of Polymer Science, 1961, Vol. 10, No. 3, pp. 289-295, describes that when a stretched polypropylene film is heated and the loss modulus is measured at each temperature, a peak due to crystalline dispersion appears above 100°C. This crystalline dispersion peak is believed to be due to an increase in frictional viscosity between the planes of the crystalline structure, and increases when the film is stretched at an optimal temperature during film formation. Increased frictional viscosity indicates strong stress transmission within the crystalline phase and is thought to correlate with increased rigidity. Based on the above, the present inventors have discovered that the maximum value of the loss modulus above 100°C is increased by using highly stereoregular polypropylene and employing the above-described width direction stretching process.
本発明の二軸配向ポリプロピレンフィルムのE”(C)は、0.28GPa以上0.80GPa以下が好ましい。E”(C)が0.28GPa以上であると、剛性が高いため、包装袋としたときの袋形状を保持しやすく、印刷など加工時にフィルムの変形が起こりにくい。また、E”(C)が0.80GPa以下であると、現実的な製造が容易であったり、幅方向に裂けにくくなる。E”(C)としては、0.29GPa以上がより好ましく、0.30GPa以上がよりさらに好ましく、0.31GPa以上が特に好ましく、0.32GPa以上が最も好ましく、また、0.75GPa以下がより好ましく、0.70GPa以下がよりさらに好ましく、0.65GPa以下が特に好ましく、0.60GPa以下が最も好ましい。 The E"(C) of the biaxially oriented polypropylene film of the present invention is preferably 0.28 GPa or more and 0.80 GPa or less. When E"(C) is 0.28 GPa or more, the high rigidity makes it easier to maintain the shape of the bag when made into a packaging bag, and the film is less likely to deform during processing such as printing. Furthermore, when E"(C) is 0.80 GPa or less, practical manufacturing is easier and the film is less likely to tear in the width direction. E"(C) is more preferably 0.29 GPa or more, even more preferably 0.30 GPa or more, particularly preferably 0.31 GPa or more, and most preferably 0.32 GPa or more. It is more preferably 0.75 GPa or less, even more preferably 0.70 GPa or less, particularly preferably 0.65 GPa or less, and most preferably 0.60 GPa or less.
本発明の二軸配向ポリプロピレンフィルムのE”(C)/E”(A)は、0.55以上が好ましく、0.55以上1.30以下がより好ましい。E”(C)/E”(A)が0.55以上であると、剛性が高いため、包装袋としたときの袋形状を保持しやすく、印刷など加工時にフィルムの変形が起こりにくい。また、E”(C)/E”(A)が1.30以下であると、現実的な製造が容易であったり、幅方向に裂けにくくなる。E”(C)/E”(A)としては、0.60以上または0.62以上がよりさらに好ましく、0.64以上が特に好ましく、0.66以上が最も好ましく、また、1.20以下または1.10以下がよりさらに好ましく、1.00以下が特に好ましく、0.90以下が最も好ましい。 The E"(C)/E"(A) ratio of the biaxially oriented polypropylene film of the present invention is preferably 0.55 or greater, and more preferably 0.55 or greater and 1.30 or less. When E"(C)/E"(A) is 0.55 or greater, the film has high rigidity, making it easier to maintain the shape of the packaging bag when made into it, and the film is less likely to deform during processing such as printing. When E"(C)/E"(A) is 1.30 or less, practical manufacturing is easier and the film is less likely to tear in the width direction. E"(C)/E"(A) is more preferably 0.60 or greater or 0.62 or greater, particularly preferably 0.64 or greater, and most preferably 0.66 or greater. It is even more preferably 1.20 or less or 1.10 or less, particularly preferably 1.00 or less, and most preferably 0.90 or less.
本発明の二軸配向ポリプロピレンフィルムのE”(B)/E”(C)は、0.55以上が好ましく、0.55以上1.30以下がより好ましい。E”(B)/E”(C)が0.55以上であると、低温領域で融解する結晶が少ないため、融解に伴う緩和が生じにくくなり、その影響により非晶部の緩和も抑制され、その結果、高温で処理しても非晶部の運動性が低くなり、平面性や耐熱性を高めることができる。E”(B)/E”(C)が1.30以下であると、剛性が低下しにくく、フィルムの厚み変動が小さくなりやすい。E”(B)/E”(C)としては、0.60以上または0.61以上がよりさらに好ましく、0.62以上が特に好ましく、0.63以上が最も好ましく、また、1.25以下または1.20以下がよりさらに好ましく、1.15以下が特に好ましく、1.10以下が最も好ましい。 The E"(B)/E"(C) ratio of the biaxially oriented polypropylene film of the present invention is preferably 0.55 or greater, and more preferably 0.55 or greater and 1.30 or less. When E"(B)/E"(C) is 0.55 or greater, fewer crystals melt in the low-temperature range, making relaxation associated with melting less likely to occur. This in turn suppresses relaxation of the amorphous portion. As a result, the mobility of the amorphous portion is reduced even when processed at high temperatures, improving flatness and heat resistance. When E"(B)/E"(C) is 1.30 or less, rigidity is less likely to decrease and film thickness fluctuations tend to be small. E"(B)/E"(C) is more preferably 0.60 or greater or 0.61 or greater, particularly preferably 0.62 or greater, and most preferably 0.63 or greater. It is even more preferably 1.25 or less or 1.20 or less, particularly preferably 1.15 or less, and most preferably 1.10 or less.
8-3.貯蔵弾性率
貯蔵弾性率は動的粘弾性測定により求め、具体的には、測定荷重10g、周波数10Hzで、窒素雰囲気下、-60℃から160℃まで昇温速度5℃/分で昇温し、昇温中の各温度における貯蔵弾性率を測定する。
The storage modulus is determined by dynamic viscoelasticity measurement. Specifically, the temperature is increased from -60°C to 160°C at a rate of 5°C/min under a nitrogen atmosphere with a measurement load of 10 g and a frequency of 10 Hz, and the storage modulus is measured at each temperature during the temperature increase.
本発明の二軸配向ポリプロピレンフィルムの23℃における長手方向の貯蔵弾性率は、2.0GPa以上5.0GPa以下が好ましい。当該貯蔵弾性率としては、2.3GPa以上がより好ましく、2.5GPa以上がよりさらに好ましく、2.9GPa以上が特に好ましく、3.0GPa以上が最も好ましく、また、4.5GPa以下がより好ましく、4.3GPa以下がよりさらに好ましく、4.2GPa以下が特に好ましく、4.0GPa以下が最も好ましい。
本発明の二軸配向ポリプロピレンフィルムの23℃における幅方向の貯蔵弾性率は、7.0GPa以上15.0GPa以下が好ましい。当該貯蔵弾性率としては、7.3GPa以上がより好ましく、7.6GPa以上がよりさらに好ましく、8.0GPa以上が特に好ましく、また、14.0GPa以下がより好ましく、13.5GPa以下がよりさらに好ましく、13.0GPa以下が特に好ましい。
長手方向および幅方向の23℃の貯蔵弾性率が上記範囲内であると、二軸配向ポリプロピレンフィルムの強度が著しく大きくなり、フィルムが薄くても腰感や強度を保つことができ、フィルムの減容化に大きく貢献できる。
The storage modulus in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 23° C. is preferably 2.0 GPa or more and 5.0 GPa or less. The storage modulus is more preferably 2.3 GPa or more, even more preferably 2.5 GPa or more, particularly preferably 2.9 GPa or more, most preferably 3.0 GPa or more, and more preferably 4.5 GPa or less, even more preferably 4.3 GPa or less, particularly preferably 4.2 GPa or less, and most preferably 4.0 GPa or less.
The storage modulus in the width direction of the biaxially oriented polypropylene film of the present invention at 23° C. is preferably 7.0 GPa or more and 15.0 GPa or less. The storage modulus is more preferably 7.3 GPa or more, even more preferably 7.6 GPa or more, and particularly preferably 8.0 GPa or more, and more preferably 14.0 GPa or less, even more preferably 13.5 GPa or less, and particularly preferably 13.0 GPa or less.
When the storage modulus at 23°C in the longitudinal and transverse directions is within the above range, the strength of the biaxially oriented polypropylene film is significantly increased, and even if the film is thin, it can maintain its stiffness and strength, which greatly contributes to reducing the volume of the film.
本発明の二軸配向ポリプロピレンフィルムの120℃における長手方向の貯蔵弾性率は、0.5GPa以上2.5GPa以下が好ましい。当該貯蔵弾性率としては、0.6GPa以上がより好ましく、0.7GPa以上がよりさらに好ましく、0.8GPa以上が特に好ましく、また、2.3GPa以下がより好ましく、2.1GPa以下がよりさらに好ましく、2.0GPa以下が特に好ましい。長手方向の120℃の貯蔵弾性率が上記範囲内であると、高温での強度が大きくなりやすく、印刷時に高温の印刷インキを転写する際に印刷ピッチずれが生じにくくなる。 The storage modulus in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 120°C is preferably 0.5 GPa or more and 2.5 GPa or less. The storage modulus is more preferably 0.6 GPa or more, even more preferably 0.7 GPa or more, and particularly preferably 0.8 GPa or more, and is more preferably 2.3 GPa or less, even more preferably 2.1 GPa or less, and particularly preferably 2.0 GPa or less. When the storage modulus in the longitudinal direction at 120°C is within the above range, strength at high temperatures tends to be high, and printing pitch deviation is less likely to occur when hot printing ink is transferred during printing.
本発明の二軸配向ポリプロピレンフィルムの120℃における幅方向の貯蔵弾性率は、1.5GPa以上8.0GPa以下が好ましい。当該貯蔵弾性率としては、1.8GPa以上がより好ましく、2.0GPa以上がよりさらに好ましく、2.1GPa以上が特に好ましく、また、7.8GPa以下がより好ましく、7.6GPa以下がよりさらに好ましく、7.4GPa以下が特に好ましい。幅方向の120℃の貯蔵弾性率が上記範囲内であると、高温での強度が大きくなりやすく、印刷時に高温の印刷インキを転写する際に印刷ピッチずれが生じにくくなる。また、フィルムの平面性が悪くなりにくい上にフィルムの加工性を向上させることができる。 The storage modulus in the width direction of the biaxially oriented polypropylene film of the present invention at 120°C is preferably 1.5 GPa or more and 8.0 GPa or less. The storage modulus is more preferably 1.8 GPa or more, even more preferably 2.0 GPa or more, and particularly preferably 2.1 GPa or more, and is more preferably 7.8 GPa or less, even more preferably 7.6 GPa or less, and particularly preferably 7.4 GPa or less. When the storage modulus in the width direction at 120°C is within the above range, strength at high temperatures tends to be increased, and printing pitch deviation is less likely to occur when hot printing ink is transferred during printing. Furthermore, the flatness of the film is less likely to deteriorate, and the processability of the film can be improved.
本発明の二軸配向ポリプロピレンフィルムの140℃における長手方向の貯蔵弾性率は、0.3GPa以上1.5GPa以下が好ましい。当該貯蔵弾性率としては、0.35GPa以上がより好ましく、0.4GPa以上がよりさらに好ましく、0.45GPa以上が特に好ましく、また、1.45GPa以下がより好ましく、1.4GPa以下がよりさらに好ましく、1.35GPa以下が特に好ましい。
本発明の二軸配向ポリプロピレンフィルムの140℃における幅方向の貯蔵弾性率は、0.9GPa以上5.0GPa以下が好ましい。当該貯蔵弾性率としては、1.0GPa以上がより好ましく、1.2GPa以上がよりさらに好ましく、1.3GPa以上が特に好ましく、また、4.5GPa以下がより好ましく、4.0GPa以下がよりさらに好ましく、3.5GPa以下が特に好ましい。
長手方向および幅方向の140℃の貯蔵弾性率が上記範囲内であると、高温での強度が大きくなりやすく、印刷時に高温の印刷インキを転写する際に印刷ピッチずれが生じにくくなる。また、フィルムの平面性が悪くなりにくい上にフィルムの加工性を向上させることができる。
The storage modulus in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 140° C. is preferably 0.3 GPa or more and 1.5 GPa or less, more preferably 0.35 GPa or more, even more preferably 0.4 GPa or more, particularly preferably 0.45 GPa or more, and more preferably 1.45 GPa or less, even more preferably 1.4 GPa or less, particularly preferably 1.35 GPa or less.
The storage modulus in the width direction of the biaxially oriented polypropylene film of the present invention at 140° C. is preferably 0.9 GPa or more and 5.0 GPa or less, more preferably 1.0 GPa or more, even more preferably 1.2 GPa or more, and particularly preferably 1.3 GPa or more, and more preferably 4.5 GPa or less, even more preferably 4.0 GPa or less, and particularly preferably 3.5 GPa or less.
When the storage modulus at 140°C in the longitudinal and transverse directions is within the above range, the strength at high temperatures tends to be high, and printing pitch deviation is less likely to occur when transferring high-temperature printing ink during printing. In addition, the flatness of the film is less likely to deteriorate and the processability of the film can be improved.
本発明の二軸配向ポリプロピレンフィルムの150℃における長手方向の貯蔵弾性率は、0.1GPa以上1.0GPa以下が好ましい。当該貯蔵弾性率としては、0.15GPa以上がより好ましく、0.2GPa以上がよりさらに好ましく、0.25GPa以上が特に好ましく、また、0.9GPa以下がより好ましく、0.8GPa以下がよりさらに好ましく、0.7GPa以下が特に好ましい。
本発明の二軸配向ポリプロピレンフィルムの150℃における幅方向の貯蔵弾性率は、0.85GPa以上2.5GPa以下が好ましい。当該貯蔵弾性率としては、0.9GPa以上がより好ましく、0.95GPa以上がよりさらに好ましく、1.0GPa以上が特に好ましく、また、2.4GPa以下がより好ましく、2.3GPa以下がよりさらに好ましく、2.2GPa以下が特に好ましい。
長手方向および幅方向の150℃の貯蔵弾性率が上記範囲内であると、高温での強度が大きくなりやすく、印刷時に高温の印刷インキを転写する際に印刷ピッチずれが生じにくくなる。また、フィルムの平面性が悪くなりにくい上にフィルムの加工性を向上させることができる。
The storage modulus in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 150° C. is preferably 0.1 GPa or more and 1.0 GPa or less, more preferably 0.15 GPa or more, even more preferably 0.2 GPa or more, particularly preferably 0.25 GPa or more, and more preferably 0.9 GPa or less, even more preferably 0.8 GPa or less, particularly preferably 0.7 GPa or less.
The storage modulus in the width direction of the biaxially oriented polypropylene film of the present invention at 150° C. is preferably 0.85 GPa or more and 2.5 GPa or less, more preferably 0.9 GPa or more, even more preferably 0.95 GPa or more, and particularly preferably 1.0 GPa or more, and more preferably 2.4 GPa or less, even more preferably 2.3 GPa or less, and particularly preferably 2.2 GPa or less.
When the storage modulus at 150°C in the longitudinal and transverse directions is within the above range, the strength at high temperatures tends to be high, and printing pitch deviation is less likely to occur when transferring high-temperature printing ink during printing. In addition, the flatness of the film is less likely to deteriorate and the processability of the film can be improved.
本発明の二軸配向ポリプロピレンフィルムの23℃における長手方向の貯蔵弾性率と140℃における長手方向の貯蔵弾性率との和は、2.8GPa以上8.0GPa以下が好ましい。これら貯蔵弾性率の和としては、3.0GPa以上がより好ましく、3.1GPa以上がよりさらに好ましく、3.2GPa以上が特に好ましく、また、7.5GPa以下がより好ましく、7.0GPa以下がよりさらに好ましく、6.5GPa以下が特に好ましい。
本発明の二軸配向ポリプロピレンフィルムの23℃における幅方向の貯蔵弾性率と140℃における幅方向の貯蔵弾性率との和は、8.5GPa以上19.0GPa以下が好ましい。これら貯蔵弾性率の和としては、8.8GPa以上がより好ましく、9.1GPa以上がよりさらに好ましく、9.5GPa以上が特に好ましく、また、18.0GPa以下がより好ましく、17.0GPa以下がよりさらに好ましく、16.0GPa以下が特に好ましい。
上記和がそれぞれ上記範囲内であると、高温での強度が大きくなりやすく、印刷時に高温の印刷インキを転写する際に印刷ピッチずれが生じにくくなる。また、フィルムの平面性が悪くなりにくい上にフィルムの加工性を向上させることができる。
The sum of the longitudinal storage modulus at 23° C. and the longitudinal storage modulus at 140° C. of the biaxially oriented polypropylene film of the present invention is preferably 2.8 GPa or more and 8.0 GPa or less. The sum of these storage moduli is more preferably 3.0 GPa or more, even more preferably 3.1 GPa or more, and particularly preferably 3.2 GPa or more, and more preferably 7.5 GPa or less, even more preferably 7.0 GPa or less, and particularly preferably 6.5 GPa or less.
The sum of the storage modulus in the width direction at 23° C. and the storage modulus in the width direction at 140° C. of the biaxially oriented polypropylene film of the present invention is preferably 8.5 GPa or more and 19.0 GPa or less. The sum of these storage moduli is more preferably 8.8 GPa or more, even more preferably 9.1 GPa or more, and particularly preferably 9.5 GPa or more, and is more preferably 18.0 GPa or less, even more preferably 17.0 GPa or less, and particularly preferably 16.0 GPa or less.
When the sums are within the above ranges, the strength at high temperatures is likely to be high, and printing pitch deviation is unlikely to occur when transferring high-temperature printing ink during printing. In addition, the flatness of the film is unlikely to be deteriorated and the processability of the film can be improved.
8-4.損失弾性率および貯蔵弾性率以外の物性
8-4-1.5%伸長時の応力(F5)
本発明の二軸配向ポリプロピレンフィルムの23℃での長手方向の5%伸長時応力(F5)は、40MPa以上70MPa以下が好ましい。当該F5が40MPa以上であれば、フィルムの剛性が高いため、包装袋としたときの袋形状を保持しやすく、印刷など加工時にフィルムの変形が起こりにくい。70MPa以下では現実的な製造が容易となったり、長手方向と幅方向のバランスが良化しやすい。上記F5としては、42MPa以上がより好ましく、46MPa以上がよりさらに好ましく、48MPa以上が特に好ましく、また、65MPa以下がより好ましく、62MPa以下がよりさらに好ましく、60MPa以下が特に好ましい。長手方向のF5は、延伸倍率やリラックス率を調節したり、製膜時の温度を調整することで、上記範囲内とすることができる。
8-4. Physical properties other than loss modulus and storage modulus 8-4-1.5% elongation stress (F5)
The stress at 5% elongation in the longitudinal direction (F5) of the biaxially oriented polypropylene film of the present invention at 23°C is preferably 40 MPa or more and 70 MPa or less. If the F5 is 40 MPa or more, the film has high rigidity, making it easier to maintain the shape of the bag when made into a packaging bag, and the film is less likely to deform during processing such as printing. If the F5 is 70 MPa or less, practical production becomes easier and the balance between the longitudinal direction and the width direction tends to be improved. The F5 is more preferably 42 MPa or more, even more preferably 46 MPa or more, particularly preferably 48 MPa or more, and more preferably 65 MPa or less, even more preferably 62 MPa or less, and particularly preferably 60 MPa or less. The F5 in the longitudinal direction can be adjusted within the above range by adjusting the stretch ratio or relaxation rate or adjusting the temperature during film formation.
本発明の二軸配向ポリプロピレンフィルムの23℃での幅方向の5%伸長時応力(F5)は、90MPa以上280MPa以下が好ましい。当該F5が90MPa以上であれば、フィルムの剛性が高いため、包装袋としたときの袋形状を保持しやすく、印刷など加工時にフィルムの変形が起こりにくい。また、当該F5が90MPa以上であれば、平面性を高めることができる。280MPa以下だと、現実的な製造が容易であったり、幅方向に裂けにくい。上記F5として、110MPa以上または120MPa以上がより好ましく、130MPa以上がよりさらに好ましく、150MPa以上が特に好ましく、156MPa以上が最も好ましく、また、250MPa以下がより好ましく、230MPa以下がよりさらに好ましく、210MPa以下が特に好ましく、200MPa以下が最も好ましい。幅方向のF5は、延伸倍率やリラックス率を調節したり、製膜時の温度を調整することで上記範囲内とすることができる。 The stress at 5% elongation in the width direction (F5) of the biaxially oriented polypropylene film of the present invention at 23°C is preferably 90 MPa or more and 280 MPa or less. If the F5 is 90 MPa or more, the film has high rigidity, making it easier to maintain the shape of the bag when made into a packaging bag, and the film is less likely to deform during processing such as printing. Furthermore, if the F5 is 90 MPa or more, flatness can be improved. If the F5 is 280 MPa or less, practical manufacturing is easier and the film is less likely to tear in the width direction. The F5 is preferably 110 MPa or more or 120 MPa or more, more preferably 130 MPa or more, particularly preferably 150 MPa or more, most preferably 156 MPa or more, more preferably 250 MPa or less, even more preferably 230 MPa or less, particularly preferably 210 MPa or less, and most preferably 200 MPa or less. The F5 in the width direction can be adjusted within the above range by adjusting the stretch ratio and relaxation rate, or by adjusting the temperature during film formation.
8-4-2.120℃での熱収縮率
本発明の二軸配向ポリプロピレンフィルムの120℃での長手方向の熱収縮率は、2.5%以下が好ましい。当該熱収縮率が2.5%以下であると、印刷インキを転写する際の印刷ピッチずれが生じにくくなる。上記熱収縮率としては、2.0%以下がより好ましく、1.7%以下がよりさらに好ましく、1.5%以下が特に好ましい。120℃での長手方向の熱収縮率は低い方が好ましく、下限は特に限定されないが、技術上の困難性から例えば0.1%以上であり、好ましくは0.3%以上である。120℃での長手方向の熱収縮率は、延伸倍率、延伸温度、熱処理温度の調整により上記範囲内とすることができる。
8-4-2. Heat Shrinkage at 120°C The heat shrinkage in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 120°C is preferably 2.5% or less. If the heat shrinkage is 2.5% or less, printing pitch deviation is less likely to occur when transferring printing ink. The heat shrinkage is more preferably 2.0% or less, even more preferably 1.7% or less, and particularly preferably 1.5% or less. The lower the heat shrinkage in the longitudinal direction at 120°C, the more preferable it is. Although there is no particular lower limit, in view of technical difficulties, it is, for example, 0.1% or more, preferably 0.3% or more. The heat shrinkage in the longitudinal direction at 120°C can be adjusted to fall within the above range by adjusting the stretch ratio, stretching temperature, and heat treatment temperature.
本発明の二軸配向ポリプロピレンフィルムの120℃での幅方向の熱収縮率は、1.1%以下が好ましい。当該熱収縮率が1.1%以下であると、ヒートシール時のシワが生じにくい。上記熱収縮率としては、1.0%以下がより好ましく、0.7%以下がよりさらに好ましく、0.5%以下が特に好ましく、0.3%以下が最も好ましい。120℃での幅方向の熱収縮率の下限は特に限定されないが、例えば-0.2%である。120℃での幅方向の熱収縮率は、延伸倍率、延伸温度、熱処理温度の調整により上記範囲内とすることができる。 The heat shrinkage rate in the width direction of the biaxially oriented polypropylene film of the present invention at 120°C is preferably 1.1% or less. If the heat shrinkage rate is 1.1% or less, wrinkles are less likely to occur during heat sealing. The heat shrinkage rate is more preferably 1.0% or less, even more preferably 0.7% or less, particularly preferably 0.5% or less, and most preferably 0.3% or less. There is no particular restriction on the lower limit of the heat shrinkage rate in the width direction at 120°C, but it is, for example, -0.2%. The heat shrinkage rate in the width direction at 120°C can be kept within the above range by adjusting the stretch ratio, stretching temperature, and heat treatment temperature.
本発明の二軸配向ポリプロピレンフィルムの120℃での長手方向と幅方向の熱収縮率の和は、3.5%以下であることが好ましい。当該和が3.5%以下であると、平面性を高めやすく、また、印刷インキを転写する際の印刷ピッチずれがより生じにくくなる。当該和は、3.0%以下がより好ましく、2.5%以下がよりさらに好ましく、2.0%以下が特に好ましく、1.7%以下が最も好ましい。上記和は低い方が好ましく、下限は特に限定されないが、技術上の困難性から例えば1.0%以上であり、好ましくは1.3%以上である。120℃での長手方向と幅方向の熱収縮率の和は、延伸倍率、延伸温度、熱処理温度の調整により上記範囲内とすることができる。 The sum of the thermal shrinkage rates in the longitudinal and transverse directions of the biaxially oriented polypropylene film of the present invention at 120°C is preferably 3.5% or less. When this sum is 3.5% or less, flatness is easily improved and printing pitch deviation when transferring printing ink is less likely to occur. This sum is more preferably 3.0% or less, even more preferably 2.5% or less, particularly preferably 2.0% or less, and most preferably 1.7% or less. A lower sum is preferable, and although there is no particular lower limit, considering technical difficulties, it is, for example, 1.0% or more, preferably 1.3% or more. The sum of the thermal shrinkage rates in the longitudinal and transverse directions at 120°C can be kept within the above range by adjusting the stretch ratio, stretching temperature, and heat treatment temperature.
8-4-3.150℃での熱収縮率
本発明の二軸配向ポリプロピレンフィルムの150℃での長手方向の熱収縮率は、10%以下が好ましい。当該熱収縮率が10%以下であると、印刷インキを転写する際の印刷ピッチずれが生じにくくなる。上記熱収縮率としては、7.0%以下がより好ましく、6.0%以下がよりさらに好ましく、5.0%以下が特に好ましく、4.0%以下が最も好ましい。150℃での長手方向の熱収縮率は低い方が好ましく、下限は特に限定されないが、技術上の困難性から例えば0.1%以上であり、好ましくは0.5%以上である。150℃での長手方向の熱収縮率は、延伸倍率、延伸温度、熱処理温度の調整により上記範囲内とすることができる。
8-4-3. Heat Shrinkage at 150°C The heat shrinkage in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 150°C is preferably 10% or less. If the heat shrinkage is 10% or less, printing pitch deviation is less likely to occur when transferring printing ink. The heat shrinkage is more preferably 7.0% or less, even more preferably 6.0% or less, particularly preferably 5.0% or less, and most preferably 4.0% or less. The lower the heat shrinkage in the longitudinal direction at 150°C, the more preferable it is. Although there is no particular lower limit, considering technical difficulties, it is, for example, 0.1% or more, preferably 0.5% or more. The heat shrinkage in the longitudinal direction at 150°C can be adjusted to fall within the above range by adjusting the stretch ratio, stretching temperature, and heat treatment temperature.
本発明の二軸配向ポリプロピレンフィルムの150℃での幅方向の熱収縮率は、20%以下が好ましい。当該熱収縮率が20%以下であると、ヒートシール時のシワが生じにくい。上記熱収縮率としては、15%以下がより好ましく、12%以下がよりさらに好ましく、10%以下が特に好ましい。150℃での幅方向の熱収縮率の下限は特に限定されないが、例えば0%以上であり、好ましくは1%以上である。150℃での幅方向の熱収縮率は、延伸倍率、延伸温度、熱処理温度の調整により上記範囲内とすることができる。 The heat shrinkage rate in the width direction of the biaxially oriented polypropylene film of the present invention at 150°C is preferably 20% or less. If the heat shrinkage rate is 20% or less, wrinkles are less likely to occur during heat sealing. The heat shrinkage rate is more preferably 15% or less, even more preferably 12% or less, and particularly preferably 10% or less. There is no particular lower limit for the heat shrinkage rate in the width direction at 150°C, but it is, for example, 0% or more, and preferably 1% or more. The heat shrinkage rate in the width direction at 150°C can be kept within the above range by adjusting the stretch ratio, stretching temperature, and heat treatment temperature.
150℃での長手方向の熱収縮率が10%以下、かつ、幅方向の熱収縮率が20%以下であると、ヒートシール時のシワが生じにくく、特に150℃での長手方向の熱収縮率が8.0%以下、150℃での幅方向の熱収縮率が15%以下であると、開口部にチャック部を融着する際の歪みが小さいため好ましい。150℃での熱収縮率を小さくするには、フィルムを構成するポリプロピレン樹脂組成物のゲルパーミエーションクロマトグラフィー(GPC)積算カーブを測定した場合の分子量10万以下の成分の量を35質量%以上とするのが有効である。 If the heat shrinkage rate in the longitudinal direction at 150°C is 10% or less and the heat shrinkage rate in the width direction is 20% or less, wrinkles are less likely to occur during heat sealing. In particular, if the heat shrinkage rate in the longitudinal direction at 150°C is 8.0% or less and the heat shrinkage rate in the width direction at 150°C is 15% or less, distortion when the zipper part is fused to the opening is small, which is preferable. To reduce the heat shrinkage rate at 150°C, it is effective to set the amount of components with a molecular weight of 100,000 or less to 35% by mass or more when measuring the gel permeation chromatography (GPC) cumulative curve of the polypropylene resin composition that makes up the film.
8-4-4.厚み均一性
本発明の二軸配向ポリプロピレンフィルムの厚み均一性の下限は好ましくは0%であり、より好ましくは0.1%であり、よりさらに好ましくは0.5%であり、特に好ましくは1%である。厚み均一性の上限は好ましくは20%であり、より好ましくは17%であり、よりさらに好ましくは15%であり、特に好ましくは12%であり、最も好ましくは10%である。上記範囲内ではコートや印刷などの後加工時に不良が生じにくく、精密性を要求される用途に用いやすい。
厚み均一性の測定方法は下記のとおりとした。フィルムの長さ方向にフィルム物性が安定している定常領域から幅方向40mmの試験片を切り出し、ミクロン計測器社製のフィルム送り装置(製番:A90172)およびアンリツ社製フィルム厚み連続測定器(製品名:K-313A広範囲高感度電子マイクロメーター)を用い、20000mmにわたって連続してフィルム厚みを計測し、下式から厚み均一性を算出した。
厚み均一性(%)=[(厚みの最大値-厚みの最小値)/厚みの平均値]×100
8-4-4. Thickness Uniformity The lower limit of the thickness uniformity of the biaxially oriented polypropylene film of the present invention is preferably 0%, more preferably 0.1%, even more preferably 0.5%, and particularly preferably 1%. The upper limit of the thickness uniformity is preferably 20%, more preferably 17%, even more preferably 15%, particularly preferably 12%, and most preferably 10%. Within the above range, defects are unlikely to occur during post-processing such as coating or printing, making the film suitable for use in applications requiring precision.
The thickness uniformity was measured as follows: A test piece 40 mm in width was cut out from a steady region where the film properties were stable in the length direction of the film, and the film thickness was measured continuously over 20,000 mm using a film feeder manufactured by Micron Measurement Instruments (product number: A90172) and a continuous film thickness measuring instrument manufactured by Anritsu Corporation (product name: K-313A wide-range high-sensitivity electronic micrometer), and the thickness uniformity was calculated using the following formula.
Thickness uniformity (%) = [(maximum thickness - minimum thickness) / average thickness] x 100
8-4-5.ヘイズ
本発明の二軸配向ポリプロピレンフィルムのヘイズの上限は好ましくは7.0%である。ヘイズが7.0%以下であると、透明性が要求される用途で使いやすい。当該ヘイズとしては、より好ましくは5.0%以下であり、よりさらに好ましくは4.0%以下であり、特に好ましくは3.5%以下であり、最も好ましくは3.0%以下である。ヘイズの下限は、0%が好ましく、現実的値としては0.1%である。ヘイズは、冷却ロール温度、長手方向の延伸温度、テンター幅方向延伸前予熱温度、幅方向延伸温度、熱固定温度、又はポリプロピレン重合体の分子量が10万以下の成分の量を調節することで上記範囲内とすることができる。ヘイズは、ブロッキング防止剤の添加や、シール層Bの組成により、大きくなることがある。
8-4-5. Haze The upper limit of the haze of the biaxially oriented polypropylene film of the present invention is preferably 7.0%. A haze of 7.0% or less makes it easy to use in applications requiring transparency. The haze is more preferably 5.0% or less, even more preferably 4.0% or less, particularly preferably 3.5% or less, and most preferably 3.0% or less. The lower limit of the haze is preferably 0%, with 0.1% being a practical value. The haze can be adjusted within the above range by adjusting the cooling roll temperature, the longitudinal stretching temperature, the tenter preheating temperature before widthwise stretching, the widthwise stretching temperature, the heat setting temperature, or the amount of polypropylene polymer components with a molecular weight of 100,000 or less. The haze may increase depending on the addition of an antiblocking agent or the composition of the sealing layer B.
8-4-6.像鮮明度
本発明の二軸配向ポリプロピレンフィルムの像鮮明度の下限は好ましくは55%である。像鮮明度が55%以上であれば、透明性が要求される用途で使いやすい。当該像鮮明度は、より好ましくは57%以上であり、よりさらに好ましくは59%以上であり、特に好ましくは61%以上であり、最も好ましくは65%以上である。像鮮明度の上限は、100%が好ましく、現実的値としては95%である。像鮮明度は、冷却ロール温度、長手方向の延伸温度、テンター幅方向延伸前予熱温度、幅方向延伸温度、熱固定温度、又はポリプロピレン重合体の分子量が10万以下の成分の量を調節することで範囲内とすることができる。像鮮明度は、ブロッキング防止剤の添加や、シール層Bの組成により、大きくなることがある。
8-4-6. Image clarity The lower limit of the image clarity of the biaxially oriented polypropylene film of the present invention is preferably 55%. An image clarity of 55% or higher is easy to use in applications requiring transparency. The image clarity is more preferably 57% or higher, even more preferably 59% or higher, particularly preferably 61% or higher, and most preferably 65% or higher. The upper limit of the image clarity is preferably 100%, with 95% being a realistic value. The image clarity can be kept within the range by adjusting the chill roll temperature, longitudinal stretching temperature, tenter preheating temperature before widthwise stretching, widthwise stretching temperature, heat setting temperature, or the amount of polypropylene polymer components with a molecular weight of 100,000 or less. The image clarity may be increased by adding an antiblocking agent or by adjusting the composition of the sealing layer B.
8-4-7.クラリティ
本発明の二軸配向ポリプロピレンフィルムのクラリティの下限は好ましくは90%である。当該クラリティが90%以上であると、透明性が要求される用途で使いやすい。当該クラリティは、より好ましくは92%以上であり、よりさらに好ましくは93%以上であり、特に好ましくは94%以上であり、最も好ましくは95%以上である。クラリティの上限は、100%が好ましく、現実的値としては99%である。クラリティは、冷却ロール温度、長手方向の延伸温度、テンター幅方向延伸前予熱温度、幅方向延伸温度、熱固定温度、又はポリプロピレン重合体の分子量が10万以下の成分の量を調節することで上記範囲内とすることができる。クラリティは、ブロッキング防止剤の添加や、シール層Bの組成により、大きくなることがある。
8-4-7. Clarity The lower limit of the clarity of the biaxially oriented polypropylene film of the present invention is preferably 90%. A clarity of 90% or higher makes it easy to use in applications requiring transparency. The clarity is more preferably 92% or higher, even more preferably 93% or higher, particularly preferably 94% or higher, and most preferably 95% or higher. The upper limit of the clarity is preferably 100%, with 99% being a realistic value. The clarity can be adjusted within the above range by adjusting the cooling roll temperature, longitudinal stretching temperature, tenter preheating temperature before widthwise stretching, widthwise stretching temperature, heat setting temperature, or the amount of polypropylene polymer components with a molecular weight of 100,000 or less. The clarity may be increased by adding an antiblocking agent or by adjusting the composition of the sealing layer B.
9.用途
本発明の二軸配向ポリプロピレンフィルムは、室温から130℃までの全温度範囲において寸法変化が少ない。そのため、ロールでの加熱加工時、印刷時、ヒートシール時のように高温で加熱した後であってもフィルムの変形を抑制でき、フィルムの平面性が悪くなりにくい上にフィルムの加工性を向上させることができる。また、より薄膜化が可能となり、包装材料の減容化にも貢献できる。
以上のことから、本発明の二軸配向ポリプロピレンフィルムを用いた場合、包装袋としたときに袋形状を保持しやすく、高温でのヒートシールなどの加工時のフィルムの変形が起こりにくく、印刷時に印刷ピッチずれが生じにくいため、包装用として好適である。また、シリコーン離型剤を塗布し加熱乾燥した後であっても平面性が失われにくく、光学用途などの高度の平面性が要求される離型フィルムとしても好適である。
9. Applications The biaxially oriented polypropylene film of the present invention exhibits little dimensional change over the entire temperature range from room temperature to 130°C. Therefore, deformation of the film can be suppressed even after heating at high temperatures, such as during heat processing with a roll, printing, or heat sealing. This makes it difficult for the film's flatness to deteriorate and improves its processability. Furthermore, it allows for thinner films, which contributes to reducing the volume of packaging materials.
From the above, when the biaxially oriented polypropylene film of the present invention is used to make a packaging bag, the bag shape is easily maintained, the film is less likely to deform during processing such as heat sealing at high temperatures, and printing pitch deviation is less likely to occur during printing, making it suitable for packaging. In addition, the film is less likely to lose flatness even after being coated with a silicone release agent and heated and dried, making it suitable as a release film for optical applications and other applications where a high degree of flatness is required.
食品を包装する袋を形成するには、製袋済みの袋に内容物を充填し、加熱してフィルムを溶融して融着して密封する。また、食品を充填しながら製袋する際にも同様に行う場合が多い。通常は基材フィルムとしての本発明の二軸配向ポリプロピレンフィルムにポリエチレン樹脂やポリプロピレン樹脂などからなるシーラントフィルムを積層し、このシーラントフィルム面同士を融着させる。加熱方法は基材フィルム側から加熱板で圧力をかけフィルムを押さえてシールするが、シール幅は10mm程度とする場合が多い。このとき基材フィルムも加熱されるため、その際の伸縮がシワを発生させる。袋の耐久性においてシワは少ない方が良く、購買意欲を高めるためにもシワは少ない方が良い。シール温度は120℃程度である場合もあるが、製袋加工速度を高めるためにはより高温でのシール温度が求められ、その場合でも伸縮は小さいことが好ましい。なお、袋の開口部にチャックを融着する場合には、さらに高温でのシールが求められる。 To form a bag for packaging food, the contents are filled into a pre-made bag, and the film is heated to melt and fuse, sealing it. This process is often repeated when making bags while filling them with food. Typically, a sealant film made of polyethylene resin, polypropylene resin, or the like is laminated onto the biaxially oriented polypropylene film of the present invention as the base film, and the sealant film surfaces are fused together. The heating method involves applying pressure from a heating plate from the base film side to hold down the film and seal it, with a seal width of approximately 10 mm being common. The base film is also heated during this process, and the resulting expansion and contraction causes wrinkles. Fewer wrinkles are preferable for bag durability and to increase consumer appetite. While the sealing temperature can be around 120°C, higher temperatures are required to increase the bag-making processing speed, and even in this case, small expansion and contraction are preferable. If a zipper is to be fused to the opening of the bag, sealing at even higher temperatures is required.
10.ヒートシール強度
本発明の二軸配向ポリプロピレンフィルムは、内容物の脱落を防止するためには、後述する測定方法で得られたシール層B側の130℃でのヒートシール強度が、4.8N/15mm以上であることが好ましく、より好ましくは5.0N/15mm以上であり、よりさらに好ましくは5.5N/15mm以上であり、特に好ましくは6.0N/15mm以上である。上限値は、8.0N/15mm程度である。それ以上大きい必要性が少なく、大きすぎると袋が開封しにくくなる場合がある。
また、本発明の二軸配向ポリプロピレンフィルムの一方の表面をシール層B、他方の表面を機能層Dとする場合、例えばゼット包装のように包装形態を維持するために、製袋加工後のヒートシール部を折り曲げて、機能層D同士を接着させているが、手で容易に袋を開封できるように機能層D側の130℃でのヒートシール強度はシール層B側の130℃でのヒートシール強度よりも低いヒートシール強度であることが好ましく、例えば、3.5N/15mm以下であり、2.0N/15mm以下が好ましく、1.0N/15mm以下がより好ましい。
10. Heat Seal Strength In order to prevent the contents from falling out, the biaxially oriented polypropylene film of the present invention preferably has a heat seal strength at 130°C on the seal layer B side, measured by the measurement method described below, of 4.8 N/15 mm or more, more preferably 5.0 N/15 mm or more, even more preferably 5.5 N/15 mm or more, and particularly preferably 6.0 N/15 mm or more. The upper limit is about 8.0 N/15 mm. There is little need for a strength greater than this, and if it is too great, the bag may be difficult to open.
Furthermore, when one surface of the biaxially oriented polypropylene film of the present invention is a sealing layer B and the other surface is a functional layer D, in order to maintain the packaging form, for example, as in Z-packaging, the heat-sealed portion after bag-making processing is folded to bond the functional layers D together.However, so that the bag can be easily opened by hand, it is preferable that the heat seal strength at 130°C on the functional layer D side is lower than the heat seal strength at 130°C on the sealing layer B side, for example, 3.5 N/15 mm or less, preferably 2.0 N/15 mm or less, and more preferably 1.0 N/15 mm or less.
11.ヒートシール立上がり温度
本発明の二軸配向ポリプロピレンフィルムのシール層Bのヒートシール立上がり温度は、90℃以上130℃以下が好ましい。シール層Bのヒートシール立上がり温度が130℃以下であると、130℃程度の比較的低温で高いヒートシール強度を発現できるため、ヒートシール時の加工器具の温度を比較的低温とすることができ、自動包装する際に高速で運転することができる。また、比較的低温でヒートシール加工ができるためフィルム全体が収縮しにくく、シール部にしわが生じにくい。シール層Bのヒートシール立上がり温度を90℃以上とすることにより、フィルム製膜装置にフィルムが融着しにくくすることができる。上記温度としては、100℃以上がより好ましく、110℃以上がよりさらに好ましく、また、125℃以下がより好ましく、120℃以下がよりさらに好ましい。
ヒートシール立上がり温度は、上述の各層の原料組成、特に基材層Aの原料組成、製膜時の延伸倍率、リラックス率、各製膜工程の温度などを調整することで上記範囲内とすることができる。
11. Heat-sealing start temperature The heat-sealing start temperature of the seal layer B of the biaxially oriented polypropylene film of the present invention is preferably 90°C or higher and 130°C or lower. When the heat-sealing start temperature of the seal layer B is 130°C or lower, high heat-sealing strength can be achieved at a relatively low temperature of around 130°C, allowing the temperature of the processing equipment during heat-sealing to be relatively low, enabling high-speed operation during automatic packaging. Furthermore, since heat-sealing processing can be performed at a relatively low temperature, the entire film is less likely to shrink and wrinkles are less likely to form in the sealed area. By setting the heat-sealing start temperature of the seal layer B to 90°C or higher, the film can be made less likely to fuse to the film-forming equipment. The above temperature is more preferably 100°C or higher, even more preferably 110°C or higher, and more preferably 125°C or lower, and even more preferably 120°C or lower.
The heat seal rise temperature can be set within the above range by adjusting the raw material composition of each layer, particularly the raw material composition of the base layer A, the stretching ratio during film formation, the relaxation rate, the temperature of each film formation step, etc.
12.動摩擦係数
本発明の二軸配向ポリプロピレンフィルムの動摩擦係数は両面、すなわちシール層Bおよびシール層Bとは反対側の表面層共に0.50以下であることが好ましい。動摩擦係数が両面共に0.50以下であると、ロールフィルムからのフィルムの巻き出しがスムーズに行え、印刷加工しやすい。上記動摩擦係数としては、0.48以下がより好ましく、0.45以下がよりさらに好ましい。動摩擦係数の下限は特に限定されないが、例えば0.10以上である。
12. Coefficient of Dynamic Friction The coefficient of dynamic friction of the biaxially oriented polypropylene film of the present invention is preferably 0.50 or less on both sides, i.e., on both the seal layer B and the surface layer opposite to the seal layer B. If the coefficient of dynamic friction is 0.50 or less on both sides, the film can be smoothly unwound from the roll film, facilitating printing processing. The coefficient of dynamic friction is more preferably 0.48 or less, and even more preferably 0.45 or less. There is no particular restriction on the lower limit of the coefficient of dynamic friction, but it is, for example, 0.10 or more.
13.濡れ張力
本発明の二軸配向ポリプロピレンフィルムのシール層Bの表面の濡れ張力は、35mN/m以上が好ましい。濡れ張力が35mN/m以上であると、シール層Bとは反対側の表面層との密着性を高めることができる。また、濡れ張力が35mN/m以上であると、フィルムの防曇性を高めることができる。濡れ張力を35mN/m以上とするには、コロナ処理、火炎処理などの物理化学的な表面処理を行うことが好ましい。コロナ処理では、予熱ロールおよび処理ロールを用い、空中で放電を行うことが好ましい。濡れ張力としては、37mN/m以上がより好ましい。濡れ張力は高すぎても効果が飽和するため、43mN/m以下であることが好ましい。
13. Wet Tension The wet tension of the surface of the seal layer B of the biaxially oriented polypropylene film of the present invention is preferably 35 mN/m or more. A wet tension of 35 mN/m or more can improve adhesion to the surface layer opposite the seal layer B. Furthermore, a wet tension of 35 mN/m or more can improve the anti-fogging properties of the film. To achieve a wet tension of 35 mN/m or more, it is preferable to perform a physicochemical surface treatment such as corona treatment or flame treatment. In corona treatment, it is preferable to use a preheating roll and a treatment roll and perform discharge in the air. The wet tension is more preferably 37 mN/m or more. If the wet tension is too high, the effect will saturate, so it is preferably 43 mN/m or less.
14.防曇性
本発明の二軸配向ポリプロピレンフィルムのシール層Bの表面の防曇性は、後述する評価方法で得られる評価が1~3級であることが好ましく、1~2級であることがより好ましく、1級であることがよりさらに好ましい。
14. Anti-Fog Property The anti-fogging property of the surface of the seal layer B of the biaxially oriented polypropylene film of the present invention is preferably grade 1 to 3, more preferably grade 1 or 2, and even more preferably grade 1, as determined by the evaluation method described below.
15.包装用材料
本発明の二軸延伸ポリプロピレンフィルムを包装用材料として使用する場合、単独で用いてもよく、印刷層を設けて用いてもよい。
本発明の二軸延伸ポリプロピレンフィルムを使用した包装用材料は、シール強度およびシール部の外観が良好な三方シールタイプ、ピロータイプ及びガゼットタイプの包装袋を作製できる。
本発明の二軸延伸ポリプロピレンフィルムは、用途に応じて、凸版印刷、平版印刷、凹版印刷、孔版印刷、転写印刷を行うことができる。
15. Packaging Materials When the biaxially oriented polypropylene film of the present invention is used as a packaging material, it may be used alone or with a printed layer provided thereon.
The biaxially oriented polypropylene film of the present invention can be used as a packaging material to produce three-side seal type, pillow type and gusset type packaging bags having good seal strength and good appearance of the sealed portion.
The biaxially oriented polypropylene film of the present invention can be subjected to relief printing, lithographic printing, intaglio printing, stencil printing and transfer printing depending on the application.
本願は、2024年2月1日に出願された日本国特許出願第2024-14405号に基づく優先権の利益を主張するものである。2024年2月1日に出願された日本国特許出願第2024-14405号の明細書の全内容が、本願に参考のため援用される。 This application claims the benefit of priority from Japanese Patent Application No. 2024-14405, filed February 1, 2024. The entire contents of the specification of Japanese Patent Application No. 2024-14405, filed February 1, 2024, are incorporated herein by reference.
以下、本発明を実施例により説明するが、本発明はもとよりこれらの実施例に限定されるものではない。
なお、各実施例および比較例において用いた評価方法は、以下の通りである。
また、「シール層Bとは反対側の表面層」とは、実施例3及び4では基材層Aのことを指し、実施例1,2,及び比較例1~4では機能層Dのことを指す。
The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
The evaluation methods used in each of the examples and comparative examples are as follows.
Furthermore, the "surface layer opposite to the sealing layer B" refers to the base material layer A in Examples 3 and 4, and to the functional layer D in Examples 1 and 2 and Comparative Examples 1 to 4.
(1)ポリプロピレン樹脂のメルトフローレート
メルトフローレート(MFR)は、JIS K7210に準拠し、温度230℃、荷重2.16kgfで測定した。
(1) Melt Flow Rate of Polypropylene Resin The melt flow rate (MFR) was measured in accordance with JIS K7210 at a temperature of 230°C and a load of 2.16 kgf.
(2)ポリプロピレン樹脂のメソペンタッド分率
ポリプロピレン樹脂のメソペンタッド分率([mmmm]%)の測定は、13C-NMRを用いて行った。メソペンタッド分率は、Zambelliら,Macromolecules,第6巻,925頁(1973)に記載の方法に従って算出した。13C-NMR測定は、「AVANCE500」BRUKER社製を用い、試料200mgをo-ジクロロベンゼンと重ベンゼンの8:2の混合液に135℃で溶解し、110℃で行った。
(2) Mesopentad Fraction of Polypropylene Resin The mesopentad fraction ([mmmm]%) of polypropylene resin was measured using 13 C-NMR. The mesopentad fraction was calculated according to the method described in Zambelli et al., Macromolecules, Vol. 6, p. 925 (1973). 13 C-NMR measurement was performed using an "AVANCE 500" manufactured by BRUKER Corporation, by dissolving 200 mg of a sample in an 8:2 mixture of o-dichlorobenzene and deuterated benzene at 135°C, and then at 110°C.
(3)分子量10万以下の成分量
ゲルパーミエーションクロマトグラフィー(GPC)を用い、単分散ポリスチレン基準でポリプロピレン換算分子量の積分曲線を得た。ベースラインが明確でないときは、標準物質の溶出ピークに最も近い高分子量側の溶出ピークの高分子量側のすそ野の最も低い位置までの範囲でベースラインを設定することとした。
GPC測定条件は次のとおりである。
・装置: 「HLC-8321PC/HT」東ソー社製
・検出器: RI
・溶媒: 1,2,4-トリクロロベンゼン+ジブチルヒドロキシトルエン(0.05%)
・カラム: TSKgelguardcolumnHHR(30)HT(7.5mmI.D.×7.5cm)×1本+TSKgelGMHHR-H(20)HT(7.8mmI.D.×30cm)×3本
・流量: 1.0mL/分
・注入量: 0.3mL
・測定温度: 140℃
GPCで得られた分子量の積分曲線から、分子量10万以下の成分の質量割合を求めた。
(3) Amount of components with a molecular weight of 100,000 or less: Using gel permeation chromatography (GPC), an integral curve of the polypropylene-equivalent molecular weight was obtained using monodisperse polystyrene as a standard. When the baseline was unclear, the baseline was set in the range from the lowest point of the high-molecular-weight side base of the elution peak closest to the elution peak of the standard substance.
The GPC measurement conditions are as follows.
・Device: "HLC-8321PC/HT" manufactured by Tosoh Corporation ・Detector: RI
Solvent: 1,2,4-trichlorobenzene + dibutylhydroxytoluene (0.05%)
Column: TSK gelguard column HHR (30) HT (7.5 mm I.D. x 7.5 cm) x 1 + TSK gel GMHHR-H (20) HT (7.8 mm I.D. x 30 cm) x 3 Flow rate: 1.0 mL/min Injection volume: 0.3 mL
・Measurement temperature: 140℃
The mass proportion of components having a molecular weight of 100,000 or less was determined from the integral curve of the molecular weight obtained by GPC.
(4)融点と結晶化温度
示差走査熱量計(「Q1000」ティー・エイ・インスツルメント社製)を用いて熱測定を行った。ペレットから約5mgを切り出して測定用のアルミパンに詰めて示差走査熱量計にセットし、窒素雰囲気下で、昇温速度20℃/分で30℃から230℃まで昇温し230℃で5分間保持することで樹脂を融解した後、降温速度-10℃/分で30℃まで降温し30℃で5分間保持した後、昇温速度10℃/分で230℃まで昇温した。融点は2回目に昇温した際に観察される、融解にともなう吸熱ピークの主たるピーク温度とした。結晶化温度は、230℃から30℃に降温したときに観察される発熱ピークの主たるピーク温度とした。
(4) Melting point and crystallization temperature Thermal measurements were performed using a differential scanning calorimeter ("Q1000" manufactured by TA Instruments). Approximately 5 mg was cut out from the pellet, placed in an aluminum pan for measurement, and set in a differential scanning calorimeter. Under a nitrogen atmosphere, the resin was melted by heating from 30 ° C. to 230 ° C. at a heating rate of 20 ° C./min and holding at 230 ° C. for 5 minutes, and then cooled to 30 ° C. at a heating rate of -10 ° C./min and held at 30 ° C. for 5 minutes. The temperature was then increased to 230 ° C. at a heating rate of 10 ° C./min. The melting point was the main peak temperature of the endothermic peak associated with melting observed during the second heating. The crystallization temperature was the main peak temperature of the exothermic peak observed when the temperature was lowered from 230 ° C. to 30 ° C.
(5)フィルム厚み
触針式膜厚計(「ミリトロン1202D」セイコー・イーエム社製)を用いて、フィルムの厚みを計測した。
(5) Film Thickness The thickness of the film was measured using a stylus film thickness meter ("Militron 1202D" manufactured by Seiko EM Corporation).
(6)熱機械分析(TMA)測定(30℃から130℃までのフィルム幅方向の長さ測定)
フィルムの幅方向が40mm、フィルムの長手方向が4mmとなるようにフィルムを切り取り、チャック幅が10mmとなるように熱機械分析装置(「TMA-60」島津製作所社製)にセットした。測定荷重0.5gで、30℃から130℃まで昇温速度10℃/分で昇温し、昇温中におけるサンプルの幅方向の長さXを測定しつづけた。前記昇温中におけるチャック間の長さの最大値をX1(mm)、前記昇温中におけるチャック間の長さの最小値をX2(mm)とし、(X1-10)/10の百分率と(X2-10)/10の百分率とを算出した。
(6) Thermomechanical analysis (TMA) measurement (measurement of film width direction length from 30°C to 130°C)
A film was cut out so that the width direction of the film was 40 mm and the length direction of the film was 4 mm, and the film was set in a thermomechanical analyzer ("TMA-60", manufactured by Shimadzu Corporation) so that the chuck width was 10 mm. The temperature was raised from 30°C to 130°C at a temperature increase rate of 10°C/min with a measurement load of 0.5 g, and the length X of the sample in the width direction during the temperature increase was continuously measured. The maximum value of the length between the chucks during the temperature increase was defined as X1 (mm), and the minimum value of the length between the chucks during the temperature increase was defined as X2 (mm), and the percentages of (X1 - 10 )/10 and (X2 - 10)/10 were calculated.
(7)熱機械分析(TMA)測定(0.5%収縮時の温度測定)
フィルムの幅方向が40mm、フィルムの長手方向が4mmとなるようにフィルムを切り取り、チャック幅が10mmとなるように熱機械分析装置(「TMA-60」島津製作所社製)にセットした。測定荷重0.5gで、30℃から160℃まで昇温速度10℃/分で昇温し、昇温中におけるサンプルの幅方向の長さを測定しつづけた。測定結果から、サンプルの幅方向の長さが9.95mm以下となる温度の中で最も低い温度を0.5%収縮時の温度とした。
(7) Thermomechanical analysis (TMA) measurement (temperature measurement at 0.5% shrinkage)
A film was cut out so that the width direction of the film was 40 mm and the length direction of the film was 4 mm, and the film was set in a thermomechanical analyzer ("TMA-60", manufactured by Shimadzu Corporation) so that the chuck width was 10 mm. The temperature was raised from 30°C to 160°C at a heating rate of 10°C/min with a measurement load of 0.5 g, and the width direction length of the sample was continuously measured during the temperature rise. From the measurement results, the lowest temperature at which the width direction length of the sample was 9.95 mm or less was determined to be the temperature at which 0.5% shrinkage occurred.
(8)動的粘弾性測定(DMA)による損失弾性率
フィルムの幅方向が40mm、フィルムの長手方向が4mmとなるようにフィルムを切り取り、チャック幅が10mmとなるように固体粘弾性アナライザー(「RSA-G2」ティー・エイ・インスツルメント・ジャパン社製)にセットした。測定荷重10g、周波数10Hzで、窒素雰囲気下、-60℃から160℃まで昇温速度5℃/分で昇温し、フィルムの幅方向の昇温中の損失弾性率を測定した。温度を横軸、損失弾性率を縦軸としたグラフを描き、-25℃から25℃までの損失弾性率の最大値E”(A)、25℃から75℃までの損失弾性率の最小値E”(B)、100℃以上の損失弾性率の最大値E”(C)をそれぞれ求めた。また、E”(C)/E”(A)の値とE”(B)/E”(C)の値も算出した。
(8) Loss modulus by dynamic mechanical analysis (DMA) A film was cut to a width of 40 mm and a length of 4 mm, and set in a solid viscoelastic analyzer (RSA-G2, manufactured by TA Instruments Japan) with a chuck width of 10 mm. The film was heated from -60°C to 160°C at a heating rate of 5°C/min under a nitrogen atmosphere with a measuring load of 10 g and a frequency of 10 Hz, and the loss modulus of the film was measured during the heating in the width direction. A graph was drawn with temperature on the horizontal axis and loss modulus on the vertical axis, and the maximum loss modulus E"(A) from -25°C to 25°C, the minimum loss modulus E"(B) from 25°C to 75°C, and the maximum loss modulus E"(C) at 100°C or higher were calculated. The values of E"(C)/E"(A) and E"(B)/E"(C) were also calculated.
(9)動的粘弾性測定(DMA)による貯蔵弾性率
フィルムの長手方向および幅方向の貯蔵弾性率を以下の方法で測定した。測定する方向が40mm、これに垂直な方向が4mmとなるようにフィルムを切り取り、チャック幅が10mmとなるように固体粘弾性アナライザー(「RSA-G2」ティー・エイ・インスツルメント・ジャパン社製)にセットした。測定荷重10g、周波数10Hzで、窒素雰囲気下、-60℃から160℃まで昇温速度5℃/分で昇温し、23℃、120℃、140℃、150℃の貯蔵弾性率を求めた。また、得られた値から長手方向の23℃と140℃との貯蔵弾性率の和、幅方向の23℃と140℃との貯蔵弾性率の和をそれぞれ算出した。
(9) Storage modulus by dynamic mechanical analysis (DMA) The storage modulus in the longitudinal and transverse directions of the film was measured by the following method. A film was cut so that the measurement direction was 40 mm and the direction perpendicular thereto was 4 mm, and the film was set in a solid viscoelasticity analyzer ("RSA-G2" manufactured by TA Instruments Japan) so that the chuck width was 10 mm. The temperature was raised from -60 ° C to 160 ° C at a heating rate of 5 ° C / min under a nitrogen atmosphere with a measurement load of 10 g and a frequency of 10 Hz, and the storage moduli at 23 ° C, 120 ° C, 140 ° C, and 150 ° C were determined. Furthermore, the sum of the storage moduli at 23 ° C and 140 ° C in the longitudinal direction and the sum of the storage moduli at 23 ° C and 140 ° C in the transverse direction were calculated from the obtained values.
(10)ヘイズ
濁度計(「NDH5000」日本電色工業社製)を用い、23℃にて、JIS K7105に従って測定した。
(10) Haze: Measured at 23° C. in accordance with JIS K7105 using a turbidity meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).
(11)像鮮明度
写像性測定器(「ICM-1T」スガ試験機社製)を使用し、JIS K7374:2007の透過法に準拠して、光学くしのスリット幅は0.5mmとし、像鮮明度を測定した。測定時にサンプルの幅方向が測定器の光学くしと垂直となるようにセットした。
(11) Image clarity Using an image clarity measuring instrument ("ICM-1T" manufactured by Suga Test Instruments Co., Ltd.), image clarity was measured in accordance with the transmission method of JIS K7374: 2007, with the slit width of the optical comb set to 0.5 mm. During measurement, the sample was set so that the width direction was perpendicular to the optical comb of the measuring instrument.
(12)クラリティ
透明性測定器(「ヘイズガードi」BYK社製)を使用し、クラリティを測定した。
測定時にフィルムを透過した光には、入射した平行光の光軸に沿って直進する直進光と、平行光の光軸に対し±2.5°以内の角度を有する狭角散乱光とが含まれる。
直進光の光量をIc、±2.5°以内の挟角散乱光の光量をIsとした時に、クラリティは下記の式で算出される。
クラリティ(%)=(Ic-Is)/(Ic+Is)×100
(12) Clarity Clarity was measured using a transparency measuring device ("Hazeguard i" manufactured by BYK).
The light transmitted through the film during measurement includes straight light that travels straight along the optical axis of the incident parallel light and narrow-angle scattered light that has an angle of ±2.5° or less with respect to the optical axis of the parallel light.
When the amount of light of straight light is I c and the amount of light of narrow-angle scattered light within ±2.5° is I s , the clarity is calculated by the following formula.
Clarity (%) = (I c - I s ) / (I c + I s ) × 100
(13)5%伸長時の応力(F5)、引張弾性率、引張破断強度、引張破断伸度
JIS K7127に準拠してフィルムの長手方向および幅方向の引張試験時の各種物性を23℃にて測定した。測定する方向が200mm、これに垂直な方向が15mmとなるようにフィルムを切り取り、チャック幅は100mmで、引張試験機(「デュアルコラム卓上型試験機インストロン5965」インストロンジャパンカンパニイリミテッド社製)にセットした。引張速度200mm/分にて引張試験を行った。得られた歪み-応力カーブより、伸長初期の直線部分の傾きから引張弾性率を求め、5%伸長時の応力をF5とした。引張破断強度および引張破断伸度は、それぞれ、サンプルが破断した時点での強度および伸度とした。
(13) Stress at 5% Elongation (F5), Tensile Modulus, Tensile Breaking Strength, and Tensile Breaking Elongation Various physical properties were measured at 23°C during tensile testing of the film in the longitudinal and transverse directions in accordance with JIS K7127. The film was cut so that the measurement direction was 200 mm and the direction perpendicular thereto was 15 mm, and the chuck width was 100 mm. The film was set in a tensile testing machine ("Dual Column Tabletop Tester Instron 5965" manufactured by Instron Japan Co., Ltd.). The tensile test was performed at a pulling rate of 200 mm/min. From the obtained strain-stress curve, the tensile modulus was calculated from the slope of the linear portion at the beginning of elongation, and the stress at 5% elongation was designated as F5. The tensile breaking strength and tensile breaking elongation were defined as the strength and elongation, respectively, at the time the sample broke.
(14)熱収縮率
JIS Z1712に準拠してフィルムの長手方向および幅方向の熱収縮率を以下の方法で測定した。測定する方向が200mm、これに垂直な方向が20mmとなるようにフィルムを切り取り、120℃の熱風オーブン中に吊るして5分間加熱した。加熱後の長さを測定し、元の長さに対する収縮した長さの割合で熱収縮率を求めた。
(14) Heat Shrinkage Ratio The heat shrinkage ratios of the film in the longitudinal and transverse directions were measured according to JIS Z1712 by the following method. A film was cut so that the measurement direction was 200 mm and the direction perpendicular to this was 20 mm, and the film was hung in a hot air oven at 120°C and heated for 5 minutes. The length after heating was measured, and the heat shrinkage ratio was calculated as the ratio of the shrunken length to the original length.
(15)動摩擦係数
フィルムから長手方向400mm、幅方向100mmのサンプルを切り出した。これを23℃、65%RHの雰囲気下で12時間エージングし、上記サンプルを長手方向300mm×幅方向100mmの試験テーブル用サンプルと、長手方向100mm×幅方向100mmの滑り片用サンプルとに分けた。
試験テーブル用サンプルを試験テーブルにセットし、滑り片用サンプルは、金属製の荷重が1.5kgの滑り片の底面(面積39.7mm2の正方形)に、シール層B同士が接するように貼りつけた。
JIS K-7125に準拠し、引張試験機(「テンシロンRTG-1210」A&D社製)を用い、試験片の滑り速度を200mm/分、23℃、65%RH条件下でシール層B面の動摩擦係数を測定し、3回の測定の平均を用いた。
また、シール層Bとは反対側の表面同士が接するように貼り付ける以外は上記と同様の方法で、シール層Bとは反対側の表面の動摩擦係数も求めた。
(15) Dynamic friction coefficient A sample measuring 400 mm in length and 100 mm in width was cut out from the film. This was aged for 12 hours in an atmosphere of 23°C and 65% RH, and then divided into a sample for a test table measuring 300 mm in length and 100 mm in width and a sample for a sliding piece measuring 100 mm in length and 100 mm in width.
The test table sample was set on the test table, and the slider sample was attached to the bottom surface (square with an area of 39.7 mm 2 ) of a metal slider with a load of 1.5 kg so that the sealing layers B were in contact with each other.
In accordance with JIS K-7125, a tensile tester ("Tensilon RTG-1210" manufactured by A&D Co., Ltd.) was used to measure the dynamic friction coefficient of the seal layer surface B under conditions of a sliding speed of the test piece of 200 mm/min, 23°C, and 65% RH, and the average of three measurements was used.
The coefficient of dynamic friction of the surface opposite to the sealing layer B was also determined in the same manner as above, except that the surfaces opposite to the sealing layer B were attached so as to be in contact with each other.
(16)濡れ張力(mN/m)
フィルムを長手方向に297mm、幅方向に210mmのサイズで切り出し、温度23℃、相対湿度50%で24時間エージング後、サンプルのシール層B側の面の濡れ張力をJIS K 6768に準拠して下記手順で測定した。なお、濡れ張力の測定時の雰囲気は、JIS K7100に準拠し、温度23℃、相対湿度50%の試験室雰囲気で行った。
サンプルを平面基板の上に置き、サンプルのシール層Bの上に濡れ張力標準液(JIS K 6768に記載の試験用混合液)を数滴滴下して、濡れ張力標準液を綿棒によりシール層Bの表面に6cm2以上の面積となるように塗り広げ、塗布から3秒経過した時点の液膜の状態を明るいところで目視した。液膜の形成から3秒経過した時点で液膜破れが生じておらず、塗布されたときの状態を保っている場合、濡れていることを意味するため、液膜の形成に用いた濡れ張力標準液より表面張力が一段階高い濡れ張力標準液を用いて液膜形成を行った。一方、3秒未満で液膜が破れる場合は、液膜の形成に用いた濡れ張力標準液より表面張力が一段階低い濡れ張力標準液を用いて液膜形成を行った。なお、液膜の形成毎に新しい綿棒を使用した。
上記液膜形成を繰り返し、シール層Bの表面を3秒間で濡らすことができる濡れ張力標準液の中で最大の数値の濡れ張力標準液の値を濡れ張力とした。なお、最大の数値の濡れ張力標準液を用いて3回液膜の形成を行って、3秒経過した時点で塗布されたときの状態を保っていることを確認した。
また、シール層Bとは反対側の表面層についても、上記と同様の測定方法および算出方法で濡れ張力を測定した。
(16) Wetting tension (mN/m)
The film was cut into a size of 297 mm in the longitudinal direction and 210 mm in the width direction, and after aging for 24 hours at a temperature of 23°C and a relative humidity of 50%, the wet tension of the surface on the seal layer B side of the sample was measured by the following procedure in accordance with JIS K 6768. The wet tension was measured in a laboratory atmosphere at a temperature of 23°C and a relative humidity of 50%, in accordance with JIS K7100.
The sample was placed on a flat substrate, and several drops of a wetting tension standard solution (a test mixture according to JIS K 6768) were placed on the sealing layer B of the sample. The wetting tension standard solution was then spread over the surface of the sealing layer B with a cotton swab to an area of 6 cm2 or more. The state of the liquid film was visually observed in a bright place 3 seconds after application. If the liquid film did not break 3 seconds after formation and remained in the same state as when it was applied, this meant that the liquid film was wet. Therefore, a liquid film was formed using a wetting tension standard solution with a surface tension one level higher than the wetting tension standard solution used to form the liquid film. On the other hand, if the liquid film broke within 3 seconds, a liquid film was formed using a wetting tension standard solution with a surface tension one level lower than the wetting tension standard solution used to form the liquid film. A new cotton swab was used for each liquid film formation.
The above liquid film formation was repeated, and the value of the maximum wetting tension standard solution among the wetting tension standard solutions that could wet the surface of the sealing layer B in 3 seconds was taken as the wetting tension. Note that a liquid film was formed three times using the wetting tension standard solution with the maximum value, and it was confirmed that the state at the time of application was maintained after 3 seconds had elapsed.
The wetting tension of the surface layer on the opposite side to the sealing layer B was also measured using the same measuring and calculation methods as above.
(17)防曇性
フィルムを用いて、シール層B側のフィルム表面の防曇性とシール層Bとは反対側のフィルム表面の防曇性を下記の手順で評価した。
1)500mLの上部開口容器に50℃の温水を300mL入れた。
2)フィルムの防曇性を測定する側のフィルム表面を内側にして、フィルムで容器開口部を密閉した。
3)5℃の冷室中に30分間放置し、その後、防曇性を測定する側のフィルム表面の露付着状況を以下の5段階で評価した。
評価1級: 全面露なし(付着面積0)
評価2級: 面のわずかな部分に露付着(付着面積0超1/4以下)
評価3級: 面の半分弱に露付着(付着面積1/4超2/4以下)
評価4級: 面のほとんどに露付着(付着面積2/4超3/4以下)
評価5級: ほぼ全面に露付着(付着面積3/4超)
(17) Anti-Fogging Properties Using a film, the anti-fogging properties of the film surface on the seal layer B side and the film surface on the opposite side to the seal layer B were evaluated according to the following procedure.
1) 300 mL of hot water at 50°C was placed in a 500 mL open-top container.
2) The opening of the container was sealed with the film, with the surface of the film on the side where the anti-fogging properties of the film were to be measured facing inward.
3) The film was left in a cold room at 5° C. for 30 minutes, and then the state of dew on the film surface on the side where the anti-fogging property was to be measured was evaluated on the following 5-point scale.
Grade 1: No dew on the entire surface (0 adhesion area)
Grade 2: Dew adheres to a small area of the surface (adhesion area is greater than 0 and less than 1/4)
Grade 3: Dew on just under half of the surface (adhesion area: over 1/4 and less than 2/4)
Grade 4: Dew on most of the surface (adhesion area: over 2/4 and less than 3/4)
Grade 5: Dew on almost the entire surface (more than 3/4 of the surface area)
(18)ヒートシール立上がり温度
フィルムから長手方向が20cm、幅方向が5cmであるサンプルを2枚切り出した。切り出した2枚のサンプルのシール層B同士を向かい合わせて重ねた後、熱傾斜試験機(東洋精機社製)を用いてヒートシールを行い、サンプルの幅方向の中央部に一列、かつ、サンプルの長手方向と平行になるように矩形状のヒートシール面5個を設置した。ヒートシール面はサンプルの長手方向に1cm、サンプルの幅方向に3cmとなるように、隣り合うヒートシール面同士の間隔が1.5cmとなるように設置された。ヒートシール温度はヒートシール面ごとに異なり、80℃、85℃、90℃、95℃、100℃とした。ヒートシール圧力は1kg/cm2、時間は1秒とした。
その後、5つのヒートシール面が含まれるようにサンプルの長手方向19cm、幅方向の中央部1.5cmをカットした。なお、長手方向については、サンプルの長手方向とカットしたサンプルの長手方向が平行になるようにサンプルをカットし、長手方向の中央部に90℃でヒートシールしたヒートシール面が位置するようにした。カットしたサンプルを引張試験機(「5965デュアルコラム卓上型試験機」インストロン社製)の上下チャックに取付け、引張速度200mm/minで引っ張った際のヒートシール強度をヒートシール面毎に測定した(単位はN/15mm)。
また、切り出した2枚のサンプルを新たに準備し、105℃、110℃、115℃、120℃、125℃でヒートシールした以外は上記と同様の方法で5つの測定用サンプルを準備しヒートシール強度の測定を行った。
横軸を温度、縦軸をヒートシール強度とする線形グラフを描き、ヒートシール強度が1N/15mmとなる温度をヒートシール立上がり温度とした。別のサンプルを準備して80~125℃でのヒートシール強度の測定をさらに2回行ってヒートシール立上がり温度を求めた後、算出した3つの値の平均値をフィルムのヒートシール立上がり温度とした。
シール層Bとは反対側の表面層についても、シール層Bとは反対側の表面層同士を向かい合わせて重ねた以上は上記と同様の測定方法および算出方法で、フィルムのヒートシール立上がり温度を求めた。
(18) Heat-sealing Rise Temperature Two samples measuring 20 cm in the longitudinal direction and 5 cm in the width direction were cut out from the film. The two cut-out samples were stacked with the seal layers B facing each other, and then heat-sealed using a thermal gradient tester (manufactured by Toyo Seiki Co., Ltd.). Five rectangular heat-sealed surfaces were placed in a row in the center of the width direction of the sample, parallel to the longitudinal direction of the sample. The heat-sealed surfaces were placed 1 cm in the longitudinal direction of the sample and 3 cm in the width direction of the sample, with a 1.5 cm gap between adjacent heat-sealed surfaces. The heat-sealing temperatures were different for each heat-sealed surface, and were 80°C, 85°C, 90°C, 95°C, and 100°C. The heat-sealing pressure was 1 kg/ cm2 , and the heat-sealing time was 1 second.
The sample was then cut to a length of 19 cm in the longitudinal direction and a central 1.5 cm in the width direction so that five heat-sealed surfaces were included. The sample was cut in the longitudinal direction so that the longitudinal direction of the sample and the longitudinal direction of the cut sample were parallel, and the heat-sealed surface heat-sealed at 90°C was located in the longitudinal center. The cut sample was attached to the upper and lower chucks of a tensile tester ("5965 Dual Column Tabletop Tester" manufactured by Instron), and the heat-seal strength was measured for each heat-sealed surface when pulled at a pulling speed of 200 mm/min (unit: N/15 mm).
In addition, two new cut-out samples were prepared and heat-sealed at 105°C, 110°C, 115°C, 120°C, and 125°C in the same manner as above, except that five measurement samples were prepared and the heat-seal strength was measured.
A linear graph was drawn with the horizontal axis representing temperature and the vertical axis representing heat seal strength, and the temperature at which the heat seal strength reached 1 N/15 mm was taken as the heat seal initiation temperature. Another sample was prepared and the heat seal strength was measured two more times at 80 to 125°C to determine the heat seal initiation temperature, and the average of the three calculated values was taken as the heat seal initiation temperature of the film.
For the surface layer on the opposite side to seal layer B, the heat seal rise temperature of the film was determined using the same measurement and calculation methods as above, except that the surface layers on the opposite side to seal layer B were stacked facing each other.
(19)ヒートシール強度
フィルムから長手方向が29.7cm、幅方向が21.0cmであるサンプルを2枚切り出した。切出した2枚のサンプルのシール層B同士を向かい合わせて重ねた後、熱傾斜試験機(東洋精機社製)を用いて130℃でヒートシールを行い、サンプルの幅方向の中央部に、サンプルの長手方向と平行になるように矩形状のヒートシール面を設置した。ヒートシール面はサンプルの長手方向に1.5cm、サンプルの幅方向に3cmとなるように設置された。その後、サンプルの長手方向9.5cm、幅方向の中央部1.5cmをカットした。なお、長手方向については、サンプルの長手方向とカットしたサンプルの長手方向が平行になるようにサンプルをカットし、長手方向の中央部にヒートシール面が位置するようにした。カットしたサンプルを引張試験機(「5965デュアルコラム卓上型試験機」インストロン社製)の上下チャックに取付け、引張速度200mm/minで引っ張った際のヒートシール強度(単位はN/15mm)を測定した。別のサンプルを2個準備してヒートシール強度の測定を行った後、算出した3つの値の平均値をフィルムのヒートシール強度とした。
また、切出した2枚のサンプルのシール層Bとは反対側の表面層同士を向かい合わせて重ねた以外は上記と同様の測定方法および算出方法で、フィルムのヒートシール強度を求めた。
さらに、ヒートシール温度を140℃とした以外は上記と同様の測定方法および算出方法で、シール層Bのヒートシール強度およびシール層Bとは反対側の表面層のヒートシール強度を求めた。
(19) Heat Seal Strength Two samples measuring 29.7 cm in the longitudinal direction and 21.0 cm in the width direction were cut out from the film. The seal layers B of the two cut out samples were placed face to face, and then heat sealed at 130 ° C. using a thermal gradient tester (manufactured by Toyo Seiki Co., Ltd.). A rectangular heat seal surface was placed in the center of the width direction of the sample so that it was parallel to the longitudinal direction of the sample. The heat seal surface was placed so that it was 1.5 cm in the longitudinal direction of the sample and 3 cm in the width direction of the sample. Then, the sample was cut to a length of 9.5 cm in the longitudinal direction and 1.5 cm in the central part of the width direction. In the longitudinal direction, the sample was cut so that the longitudinal direction of the sample and the longitudinal direction of the cut sample were parallel, and the heat seal surface was located in the center of the longitudinal direction. The cut sample was attached to the upper and lower chucks of a tensile tester (Instron's "5965 Dual Column Tabletop Tester") and pulled at a pulling speed of 200 mm/min to measure the heat seal strength (unit: N/15 mm). Two other samples were prepared and their heat seal strengths were measured, and the average of the three calculated values was used as the heat seal strength of the film.
The heat seal strength of the film was determined using the same measuring and calculating methods as above, except that the surface layers of the two cut-out samples on the side opposite to the seal layer B were placed face to face.
Furthermore, the heat seal strength of the seal layer B and the heat seal strength of the surface layer opposite to the seal layer B were determined using the same measuring and calculation methods as above, except that the heat seal temperature was set to 140°C.
(20)ヒートシール部の外観評価
得られたフィルムをヒートシーラーにて130mm×180mmの三方シール袋となるように積層体のシーラントフィルム同士をヒートシールして、三方シール袋を作製した。0.2MPaの圧力で1秒間、シールバーの幅を10mm、ヒートシール温度を150℃とした。ヒートシール部のシワの外観を目視評価した。
A: フィルムの幅方向、長さ方向ともにヒートシール部にシワが確認できない
B: フィルムの幅方向、長さ方向の一方のみのヒートシール部にシワが確認できる
C: フィルムの幅方向、長さ方向ともにヒートシール部にシワが確認できる
(20) Appearance Evaluation of Heat-Sealed Portions The obtained film was heat-sealed to form a 130 mm x 180 mm three-sided sealed bag using a heat sealer, with the sealant films of the laminate heat-sealed to each other. The pressure was 0.2 MPa for 1 second, the seal bar width was 10 mm, and the heat-sealing temperature was 150°C. The appearance of wrinkles in the heat-sealed portions was visually evaluated.
A: No wrinkles can be seen in the heat-sealed area in either the width or length direction of the film. B: Wrinkles can be seen in the heat-sealed area in only one of the width or length directions of the film. C: Wrinkles can be seen in the heat-sealed area in both the width and length directions of the film.
(21)平面性評価(130℃処理後の平面性)
フィルムの幅方向、長手方向が共に200mmとなるようにサンプルを切り出し、評価用サンプルとした。130℃の熱風オーブン中にサンプルを吊るして5分間加熱した。室温に冷却後、黒台紙の上にフィルムをのせ、蛍光灯下で斜め45度の角度からフィルム表面を観察した。
A: 熱シワも5mm以上の大きなうねりも存在しない
B: 熱シワは確認できないが、5mm以上の大きなうねりが確認できる
C: 熱シワが確認できる
(21) Flatness Evaluation (Flatness after 130°C Treatment)
A sample was cut out from the film so that both the width and length directions were 200 mm, and used as an evaluation sample. The sample was hung in a hot air oven at 130°C and heated for 5 minutes. After cooling to room temperature, the film was placed on a black mount, and the film surface was observed at a 45-degree angle under a fluorescent lamp.
A: No heat wrinkles or large swells of 5 mm or more exist. B: No heat wrinkles are visible, but large swells of 5 mm or more can be seen. C: Heat wrinkles can be seen.
使用した原料
下記実施例および比較例のフィルムの各層を構成するポリプロピレン系樹脂は、次の通りである。
PP-1: プロピレン単独重合体(「FLX80H5」住友化学社製,メソペンタッド分率:98.9%,融点:163℃,MFR:7.5g/10分,分子量1万以下の成分量:4.0質量%,分子量10万以下の成分量:40.5質量%)
PP-2: プロピレン単独重合体(「EL80F5」住友化学社製,メソペンタッド分率:98.8%,融点:162℃,MFR:11g/10分,分子量1万以下の成分量:6.9質量%,分子量10万以下の成分量:53.1質量%)
PP-3: PP-1に防曇剤としてステアリルジエタノールアミンモノステアレート、ステアリルジエタノールアミンジステアレート及びステアリルジエタノールアミンを合計で1.7質量%、グリセリンモノステアレート0.25質量%を含む組成物
PP-4: プロピレン単独重合体(「FY6H」日本ポリプロ社製,MFR:1.9g/10分,融点:163℃,メソペンタッド分率:98.9%)
PP-5: プロピレン単独重合体(「FL203D」日本ポリプロ社製,メソペンタッド分率:94.8%,融点:161℃,MFR:3g/10分,分子量1万以下の成分量:3.0質量%,分子量10万以下の成分量:37.1質量%)に対して、防曇剤としてステアリルジエタノールアミンモノステアレートを1.7質量%、グリセリンモノステアレート0.25質量%を含む組成物
PP-6: プロピレン・エチレン・ブテン共重合体(「FSX66M4」住友化学社製,融点:138℃,MFR:4.5g/10分,エチレン含有量:3.3モル%,ブテン含有量:2.9モル%,グリセリンモノステアレート含有量:0.45質量%)
PP-7: プロピレン・ブテン共重合体(「SP7843」住友化学社製,融点:128℃,MFR:6.5g/10分,ブテン含有量:8.2モル%)
Raw Materials Used The polypropylene resins constituting the layers of the films in the following Examples and Comparative Examples are as follows.
PP-1: Propylene homopolymer ("FLX80H5" manufactured by Sumitomo Chemical Co., Ltd., mesopentad fraction: 98.9%, melting point: 163°C, MFR: 7.5g/10min, amount of components with molecular weight of 10,000 or less: 4.0% by mass, amount of components with molecular weight of 100,000 or less: 40.5% by mass)
PP-2: Propylene homopolymer ("EL80F5" manufactured by Sumitomo Chemical Co., Ltd., mesopentad fraction: 98.8%, melting point: 162°C, MFR: 11 g/10 min, amount of components with a molecular weight of 10,000 or less: 6.9% by mass, amount of components with a molecular weight of 100,000 or less: 53.1% by mass)
PP-3: A composition containing PP-1 and, as an anti-fogging agent, stearyl diethanolamine monostearate, stearyl diethanolamine distearate, and stearyl diethanolamine in a total amount of 1.7% by mass, and glycerin monostearate in an amount of 0.25% by mass. PP-4: Propylene homopolymer ("FY6H", manufactured by Japan Polypropylene Corporation, MFR: 1.9 g/10 min, melting point: 163°C, mesopentad fraction: 98.9%)
PP-5: A composition containing propylene homopolymer ("FL203D" manufactured by Japan Polypropylene Corporation, mesopentad fraction: 94.8%, melting point: 161°C, MFR: 3g/10 min, amount of components with a molecular weight of 10,000 or less: 3.0% by mass, amount of components with a molecular weight of 100,000 or less: 37.1% by mass), 1.7% by mass of stearyl diethanolamine monostearate as an anti-fogging agent, and 0.25% by mass of glycerin monostearate. PP-6: A composition containing propylene-ethylene-butene copolymer ("FSX66M4" manufactured by Sumitomo Chemical Co., Ltd., melting point: 138°C, MFR: 4.5g/10 min, ethylene content: 3.3 mol%, butene content: 2.9 mol%, glycerin monostearate content: 0.45% by mass).
PP-7: Propylene-butene copolymer ("SP7843" manufactured by Sumitomo Chemical Co., Ltd., melting point: 128°C, MFR: 6.5 g/10 min, butene content: 8.2 mol%)
実施例1
(1)基材層Aの原料の作製
プロピレン単独重合体PP-1を20質量%、プロピレン単独重合体PP-2を20質量%、プロピレン単独重合体PP-3を60質量%配合したポリプロピレン系樹脂組成物を原料とした。各ポリプロピレン単独重合体の物性を質量平均すると、基材層Aを構成するポリプロピレン系樹脂組成物のメソペンタッド分率は98.88%、融点は162.8℃、MFRは8.2g/10分、分子量1万以下の成分量は4.58質量%、分子量10万以下の成分量は43.02質量%となる。
(2)シール層Bの原料
プロピレン・ブテン共重合体PP-7を原料とした。
(3)機能層Dの原料
プロピレン・エチレン・ブテン共重合体PP-6を原料とした。
(4)フィルムの作製
まず、機能層D/基材層A/シール層Bのそれぞれを構成するポリプロピレン系樹脂組成物を、多層フィードブロックを用い、押出機でそれぞれ250℃、250℃、210℃で加熱溶融させ、250℃でTダイから溶融ポリプロピレン系樹脂組成物を積層しながら厚みが1.8mmの積層溶融シートを機能層D/基材層A/シール層Bのそれぞれの厚みの割合が1/14/1となるように共押出した。
溶融シートの機能層D側を20℃の冷却ロールに接触させ、そのまま20℃の水槽に投入した。その後、142℃で二対のロールで長手方向に4.5倍の延伸を行い、ついで両端をクリップで挟み、熱風オーブン中に導いて172℃で予熱後、幅方向に162℃で12.7倍の延伸を行った。幅方向延伸直後に、クリップに把持したまま弛緩することなく170℃で熱処理し、その後、140℃で熱処理し幅方向に弛緩率3%の弛緩を行った。最後に室温にて冷却した。得られた二軸配向ポリプロピレンフィルムのシール層B側のフィルム表面にコロナ処理機(ソフタル・コロナ・アンド・プラズマGmbH社製)を用いて、印加電流値0.75A、印加電圧1.8kWの条件でコロナ処理を施した後、ワインダーで巻き取ったものを本発明の二軸配向ポリプロピレンフィルムとした。得られたフィルムの厚みは16μmであった。得られたフィルムにおいて、機能層D/基材層A/シール層Bの各層の厚みは1μm/14μm/1μmであった。
各層の原料組成とフィルムの製膜条件を表1に示し、フィルムの各種物性を表2に示す。なお、表中、「%」は質量%を示す。
二軸配向ポリプロピレンフィルムは、剛性が高いにもかかわらず、高温での熱収縮率が低く、シール強度が高く、かつ、防曇性に優れていた。また、130℃で処理した後の平面性に優れていた。実施例1のフィルムを用いて製造された三方シール袋は、ヒートシール外観が良好である上、製袋品の腰に優れるためハンドリング性が良好であった。
Example 1
(1) Preparation of raw materials for base layer A A polypropylene-based resin composition containing 20% by mass of propylene homopolymer PP-1, 20% by mass of propylene homopolymer PP-2, and 60% by mass of propylene homopolymer PP-3 was used as the raw material. When the physical properties of each polypropylene homopolymer were averaged by mass, the polypropylene-based resin composition constituting base layer A had a mesopentad fraction of 98.88%, a melting point of 162.8°C, an MFR of 8.2 g/10 min, a content of components with a molecular weight of 10,000 or less of 4.58% by mass, and a content of components with a molecular weight of 100,000 or less of 43.02% by mass.
(2) Raw Materials for Sealing Layer B Propylene-butene copolymer PP-7 was used as the raw material.
(3) Raw Materials for Functional Layer D Propylene-ethylene-butene copolymer PP-6 was used as the raw material.
(4) Film Preparation First, the polypropylene resin compositions constituting each of the functional layer D, base layer A, and seal layer B were heated and melted in an extruder using a multi-layer feed block at 250°C, 250°C, and 210°C, respectively, and the molten polypropylene resin compositions were then laminated from a T-die at 250°C to produce a 1.8 mm thick laminated molten sheet, with the thickness ratio of the functional layer D, base layer A, and seal layer B being 1/14/1.
The functional layer D side of the molten sheet was brought into contact with a cooling roll at 20 ° C. and then placed in a water bath at 20 ° C. The sheet was then stretched 4.5 times in the longitudinal direction using two pairs of rolls at 142 ° C., then clamped at both ends with clips and introduced into a hot air oven, preheated to 172 ° C., and then stretched 12.7 times in the width direction at 162 ° C. Immediately after stretching in the width direction, the sheet was heat-treated at 170 ° C. while still held by the clips without relaxation, and then heat-treated at 140 ° C. to achieve a relaxation rate of 3% in the width direction. Finally, the sheet was cooled to room temperature. The surface of the seal layer B side of the obtained biaxially oriented polypropylene film was subjected to corona treatment using a corona treatment machine (manufactured by Softal Corona & Plasma GmbH) at an applied current of 0.75 A and an applied voltage of 1.8 kW, and then wound up on a winder to obtain the biaxially oriented polypropylene film of the present invention. The thickness of the obtained film was 16 μm. In the obtained film, the thicknesses of the functional layer D, the base layer A and the seal layer B were 1 μm, 14 μm and 1 μm, respectively.
The raw material composition of each layer and the film-forming conditions are shown in Table 1, and various physical properties of the film are shown in Table 2. In the table, "%" indicates % by mass.
Despite its high rigidity, the biaxially oriented polypropylene film had low heat shrinkage at high temperatures, high seal strength, and excellent anti-fogging properties. It also had excellent flatness after treatment at 130°C. The three-side sealed bag produced using the film of Example 1 had a good heat-sealed appearance and excellent handleability due to the excellent stiffness of the bag.
実施例2~4
実施例2~4では、フィルムの製造条件を表1に記載の製造条件に変更した以外は実施例1と同じ製造方法でフィルムを製造した。フィルムの各種物性を表2に示す。実施例2~4の二軸配向ポリプロピレンフィルムは、実施例1同様に剛性が高いにもかかわらず、高温での熱収縮率が低く、シール強度が高く、かつ、防曇性に優れていた。
Examples 2 to 4
In Examples 2 to 4, films were produced using the same production method as in Example 1, except that the film production conditions were changed to those shown in Table 1. Various physical properties of the films are shown in Table 2. The biaxially oriented polypropylene films of Examples 2 to 4 had high rigidity like that of Example 1, but also had low heat shrinkage at high temperatures, high seal strength, and excellent anti-fogging properties.
実施例5,6
基材層Aとシール層Bの原料として実施例1~4と同じ原料を用い、中間層Cの原料として、プロピレン・エチレン・ブテン共重合体PP-6を用いた。
まず、基材層A/中間層C/シール層Bのそれぞれを構成するポリプロピレン系樹脂組成物を、多層フィードブロックを用い、押出機でそれぞれ250℃、250℃、210℃で加熱溶融させ、250℃でTダイから溶融ポリプロピレン系樹脂組成物を積層しながら厚みが1.8mmの積層溶融シートを基材層A/中間層C/シール層Bのそれぞれの厚みの割合が13/2/1となるように共押出した。
実施例1と同様にして溶融シートを得て長手方向と幅方向に延伸を行った後、幅方向延伸直後に、クリップに把持したまま弛緩することなく170℃で熱処理し、その後、140℃で熱処理し幅方向に弛緩率3%の弛緩を行い、最後に室温にて冷却した。得られた二軸配向ポリプロピレンフィルムのシール層B側のフィルム表面にコロナ処理を施した後、ワインダーで巻き取ったものを本発明の二軸配向ポリプロピレンフィルムとした。得られたフィルムの厚みは16μmであった。得られたフィルムにおいて、基材層A/中間層C/シール層Bの各層の厚みは13μm/2μm/1μmであった。
各層の原料組成およびフィルムの製膜条件を表1に示し、フィルムの各種物性を表2に示す。
実施例5,6の二軸配向ポリプロピレンフィルムは、剛性が高いにもかかわらず、高温での熱収縮率が低く、シール強度が高く、かつ、防曇性に優れていた。
Examples 5 and 6
The same materials as those used in Examples 1 to 4 were used as the raw materials for the base layer A and the seal layer B, and the propylene-ethylene-butene copolymer PP-6 was used as the raw material for the intermediate layer C.
First, the polypropylene resin compositions constituting each of the base layer A, intermediate layer C, and seal layer B were heated and melted in an extruder using a multi-layer feed block at 250°C, 250°C, and 210°C, respectively, and the molten polypropylene resin compositions were laminated from a T-die at 250°C to produce a 1.8 mm thick laminated molten sheet, with the thickness ratio of the base layer A, intermediate layer C, and seal layer B being 13/2/1.
A molten sheet was obtained in the same manner as in Example 1 and stretched in the longitudinal and width directions. Immediately after stretching in the width direction, the sheet was heat-treated at 170°C while held by the clips without relaxation, then heat-treated at 140°C to relax the sheet in the width direction by 3%, and finally cooled to room temperature. The surface of the resulting biaxially oriented polypropylene film on the side of the seal layer B was corona-treated, and the resulting film was wound up on a winder to form a biaxially oriented polypropylene film of the present invention. The thickness of the resulting film was 16 μm. In the resulting film, the thicknesses of the base layer A, intermediate layer C, and seal layer B were 13 μm, 2 μm, and 1 μm.
The raw material composition of each layer and the film-forming conditions are shown in Table 1, and various physical properties of the film are shown in Table 2.
The biaxially oriented polypropylene films of Examples 5 and 6 had high rigidity, but also had low heat shrinkage at high temperatures, high seal strength, and excellent anti-fogging properties.
実施例7
基材層A、シール層B、機能層Dの原料として実施例1~4と同じ原料を用い、中間層Cの原料としてプロピレン・エチレン・ブテン共重合体PP-6を用いた。
まず、機能層D/基材層A/中間層C/シール層Bのそれぞれを構成するポリプロピレン系樹脂組成物を多層フィードブロックを用い、押出機でそれぞれ250℃、250℃、250℃、210℃で加熱溶融させ、250℃でTダイから溶融ポリプロピレン系樹脂組成物を積層しながら厚みが1.8mmの積層溶融シートを機能層D/基材層A/中間層C/シール層Bのそれぞれの厚みの割合が1/16/2/1となるように共押出した。
実施例1と同様にして溶融シートを得て長手方向と幅方向に延伸を行った後、幅方向延伸直後に、クリップに把持したまま弛緩することなく170℃で熱処理し、その後、140℃で熱処理し幅方向に弛緩率3%の弛緩を行い、最後に室温にて冷却した。得られた二軸配向ポリプロピレンフィルムのシール層B側のフィルム表面にコロナ処理を施した後、ワインダーで巻き取ったものを本発明の二軸配向ポリプロピレンフィルムとした。得られたフィルムの厚みは20μmであった。得られたフィルムにおいて、機能層D/基材層A/中間層C/シール層Bの各層の厚みは1μm/16μm/2μm/1μmであった。
各層の原料組成およびフィルムの製膜条件を表1に示し、フィルムの各種物性を表2に示す。
実施例7の二軸配向ポリプロピレンフィルムは、剛性が高いにもかかわらず、高温での熱収縮率が低く、シール強度が高く、かつ、防曇性に優れていた。
Example 7
The same materials as those used in Examples 1 to 4 were used as the raw materials for the base layer A, the sealing layer B, and the functional layer D, and the propylene-ethylene-butene copolymer PP-6 was used as the raw material for the intermediate layer C.
First, the polypropylene resin compositions constituting each of the functional layer D, base layer A, intermediate layer C, and seal layer B were heated and melted in an extruder using a multi-layer feed block at 250°C, 250°C, 250°C, and 210°C, respectively, and the molten polypropylene resin compositions were laminated from a T-die at 250°C to produce a 1.8 mm thick laminated molten sheet, with the thickness ratio of the functional layer D, base layer A, intermediate layer C, and seal layer B being 1/16/2/1.
A molten sheet was obtained in the same manner as in Example 1 and stretched in the longitudinal and width directions. Immediately after stretching in the width direction, the sheet was heat-treated at 170°C while held by the clips without relaxation, then heat-treated at 140°C to relax the sheet in the width direction by 3%, and finally cooled to room temperature. The surface of the resulting biaxially oriented polypropylene film on the side of the seal layer B was corona-treated, and the resulting film was wound up on a winder to form a biaxially oriented polypropylene film of the present invention. The thickness of the resulting film was 20 μm. In the resulting film, the thicknesses of the functional layer D, base layer A, intermediate layer C, and seal layer B were 1 μm, 16 μm, 2 μm, and 1 μm.
The raw material composition of each layer and the film-forming conditions are shown in Table 1, and various physical properties of the film are shown in Table 2.
The biaxially oriented polypropylene film of Example 7 had high rigidity, but also had low heat shrinkage at high temperatures, high seal strength, and excellent anti-fogging properties.
比較例1~6
比較例1~6では、実施例7と同じ原料を用いて機能層D/基材層A/中間層C/シール層Bの層構成とし、比較例3を除き厚み構成も実施例7と同じく1μm/16μm/2μm/1μmで全厚み20μmにした。比較例3の各層の厚みは1μm/31μm/2μm/1μmであり、全厚みは35μmであった。
比較例1~6の製膜条件を表3に示し、フィルムの各種物性を表4に示す。
Comparative Examples 1 to 6
In Comparative Examples 1 to 6, the same raw materials as in Example 7 were used to form a layer structure of functional layer D/substrate layer A/intermediate layer C/sealing layer B, and except for Comparative Example 3, the thickness structure was also the same as in Example 7, with a total thickness of 20 μm, that is, 1 μm/16 μm/2 μm/1 μm. In Comparative Example 3, the thicknesses of the layers were 1 μm/31 μm/2 μm/1 μm, and the total thickness was 35 μm.
The film-forming conditions for Comparative Examples 1 to 6 are shown in Table 3, and various physical properties of the films are shown in Table 4.
比較例7
比較例7では、実施例7と同じ機能層D/基材層A/中間層C/シール層Bの層構成とし、厚み構成も実施例7と同じく1μm/16μm/2μm/1μmで全厚み20μmにした。ただし、基材層Aの原料には、プロピレン単独重合体であるPP-6(「FY6H」日本ポリプロ社製,MFR:1.9g/10分,融点:163℃,メソペンタッド分率:98.9%)を43質量%、PP-7(100質量%の上記PP-1に対して、グリセリンモノステアレート(松本油脂製薬社製TB-123)を0.16質量%、ポリオキシエチレン(2)ステアリルアミン(松本油脂製薬社製TB-12)を0.2質量%、ポリオキシエチレン(2)ステアリルアミンモノステアレート(松本油脂製薬社製エレックス334)を0.6質量%添加した組成物)を57質量%配合したポリプロピレン系樹脂組成物を原料とした。製膜条件を表3に示し、フィルムの各種物性を表4に示す。
Comparative Example 7
In Comparative Example 7, the layer structure was the same as in Example 7, that is, functional layer D/substrate layer A/intermediate layer C/sealing layer B, and the thickness structure was also the same as in Example 7, that is, 1 μm/16 μm/2 μm/1 μm, for a total thickness of 20 μm. The base layer A was made from a polypropylene resin composition containing 43% by mass of PP-6 ("FY6H" manufactured by Japan Polypropylene Corporation, MFR: 1.9 g/10 min, melting point: 163°C, mesopentad fraction: 98.9%), a propylene homopolymer, and 57% by mass of PP-7 (a composition obtained by adding 0.16% by mass of glycerin monostearate (TB-123 manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), 0.2% by mass of polyoxyethylene (2) stearylamine (TB-12 manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), and 0.6% by mass of polyoxyethylene (2) stearylamine monostearate (Elex 334 manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) to 100% by mass of the above PP-1). The film formation conditions are shown in Table 3, and the physical properties of the film are shown in Table 4.
表4に示す通り、比較例1~7では、(X1-X0)/X0または(X2-X0)/X0の百分率(X0:10mm,X1:昇温中におけるチャック間最大値(mm),X2:昇温中におけるチャック間最小値(mm))の少なくとも一方が所定の範囲を外れているため、比較例1~7のフィルムは150℃でヒートシールしたシール部にシワが発生した。また、フィルムを130℃で処理した後の平面性に劣っていた。
一方、表3に示す通り、(X1-X0)/X0および(X2-X0)/X0の百分率が所定値であれば、昇温途中や昇温終了後においてもフィルムの長さ、特に幅方向の長さの変化が小さく、シワの発生が抑制されており、また平面性に優れていた。
As shown in Table 4, in Comparative Examples 1 to 7, at least one of the percentages ( X1 - X0 )/ X0 or ( X2 - X0 )/ X0 ( X0 : 10 mm, X1 : maximum value of chuck gap during temperature increase (mm), X2 : minimum value of chuck gap during temperature increase (mm)) was outside the specified range, and therefore the films of Comparative Examples 1 to 7 developed wrinkles in the sealed portion heat-sealed at 150°C. In addition, the flatness of the films after treatment at 130°C was poor.
On the other hand, as shown in Table 3, when the percentages of (X 1 −X 0 )/X 0 and (X 2 −X 0 )/X 0 were predetermined values, the change in the length of the film, particularly the length in the width direction, was small even during and after the temperature increase, the occurrence of wrinkles was suppressed, and the flatness was excellent.
なお、図1は、実施例1、比較例1、及び比較例4における温度とフィルム幅方向の長さとの関係を示す図であり、厳密には温度と(X1-X0)/X0の百分率との関係を示している。また、図2は、実施例1及び比較例1における温度と損失弾性率との関係を示す図であり、図3は、実施例1及び比較例1における温度と貯蔵弾性率との関係を示す図である。 Fig. 1 is a diagram showing the relationship between temperature and the length in the width direction of the film in Example 1, Comparative Example 1, and Comparative Example 4, and more precisely, the relationship between temperature and the percentage of (X 1 - X 0 )/X 0. Fig. 2 is a diagram showing the relationship between temperature and loss modulus in Example 1 and Comparative Example 1, and Fig. 3 is a diagram showing the relationship between temperature and storage modulus in Example 1 and Comparative Example 1.
本発明の二軸配向ポリプロピレンフィルムは、剛性と耐熱性に優れているため、製袋加工性に優れており、包装袋としたときの袋形状を保持しやすい。そのため、本発明の二軸配向ポリプロピレンフィルムは包装袋に用いることができ、特に防曇剤を添加した包装袋は、青果物の包装に好適である。また、本発明の二軸配向ポリプロピレンフィルムは、シーラントフィルムをラミネートしなくても、高い剛性が必要とされる用途にも好適に用いることができ、フィルムの厚みを薄くしても強度を維持することができるため、環境への負荷を少なくすることができる。 The biaxially oriented polypropylene film of the present invention has excellent rigidity and heat resistance, making it easy to process into bags and easily retaining the shape of the bags when made into packaging bags. Therefore, the biaxially oriented polypropylene film of the present invention can be used for packaging bags, and packaging bags to which an anti-fog agent has been added are particularly suitable for packaging fresh produce. Furthermore, the biaxially oriented polypropylene film of the present invention can be suitably used in applications requiring high rigidity even without laminating a sealant film, and since it can maintain its strength even when the film is thin, it can reduce the burden on the environment.
Claims (11)
(1)シール層Bを少なくとも一方の最表面に有する。
(2)クラリティが90%以上100%以下である。
(3)幅方向の140℃での貯蔵弾性率が0.7GPa以上5.0GPa以下である。
(4)幅方向の150℃熱収縮率が10%以下である。 A biaxially oriented polypropylene film having a substrate layer A made of a polypropylene-based resin composition and a seal layer B made of a polypropylene-based resin composition, and satisfying the following (1) to (4):
(1) The seal layer B is provided on at least one outermost surface.
(2) Clarity is between 90% and 100%.
(3) The storage modulus in the width direction at 140° C. is 0.7 GPa or more and 5.0 GPa or less.
(4) The thermal shrinkage rate at 150°C in the width direction is 10% or less.
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