WO2021193510A1

WO2021193510A1 - Biaxially oriented polypropylene film

Info

Publication number: WO2021193510A1
Application number: PCT/JP2021/011662
Authority: WO
Inventors: 今井　徹; 山田　浩司; 一仁堀之内; 麻洋中野; 健一船城
Original assignee: 東洋紡株式会社
Priority date: 2020-03-24
Filing date: 2021-03-22
Publication date: 2021-09-30
Also published as: JPWO2021193510A1; TW202140647A

Abstract

The present invention provides a biaxially oriented polypropylene film which has high rigidity and excellent heat resistance even at a temperature as high as 150°C, and which easily maintains the bag shape when formed into a packaging bag, while undergoing little pitch shift during printing and having few wrinkles in a seal part when heat sealed.　A biaxially oriented polypropylene film which satisfies the requirements (1) to (3) described below. (1) With respect to the temperature dependence of the maximum intensity of the azimuthal profile as obtained by scanning, in the circumferential direction, the scattering associated with the (110) plane of an α-form crystal of the polypropylene in a wide-angle X-ray diffraction measurement that is performed by restraining the film in four directions and irradiating the film with an X-ray in a direction that is perpendicular to the film surface, while heating the film from 40°C to 180°C at a rate of 10°C/minute, the ratio of the maximum value of the maximum intensity within the range from 40°C to 130°C to the maximum intensity at 40°C (namely, the (110) intensity ratio) is 115% or more. (2) The orientation degree in the width direction is 0.85 or more. (3) The thermal shrinkage ratio at 150°C is 10% or less in the longitudinal direction, while being 30% or less in the width direction.

Description

Biaxially oriented polypropylene film

The present invention relates to a biaxially oriented polypropylene film having excellent rigidity and heat resistance. More specifically, the present invention relates to a biaxially oriented polypropylene film that can be suitably used for a packaging bag because it easily retains the shape of the packaging bag and has few wrinkles in the sealed portion when heat-sealed.

Biaxially oriented polypropylene film is used for packaging and industrial applications because it has moisture resistance and the required rigidity and heat resistance. In recent years, as the applications used have expanded, higher performance has been required, and in particular, improvement in rigidity is expected. Further, from the consideration of the environment, it is required to maintain the strength even if the volume is reduced (the film thickness is thinned), but for that purpose, it is indispensable to remarkably improve the rigidity. As a means for improving the rigidity, it is known that the crystallinity and melting point of the polypropylene resin are improved by improving the catalyst and the process technology at the time of polymerization of the polypropylene resin. Until now, there was no biaxially oriented polypropylene film having sufficient rigidity.

In the manufacturing process of biaxially oriented polypropylene film, after stretching in the width direction, the first stage heat treatment is performed while relaxing the film at a temperature lower than the temperature at the time of width direction stretching, and the second stage heat treatment is performed at the first stage temperature to the width direction stretching temperature. (See, for example, Patent Document 1 and the like), and a method of further stretching in the longitudinal direction after stretching in the width direction (see, for example, Patent Document 2 and the like) have been proposed. However, although the film described in Patent Document 2 is excellent in rigidity, wrinkles are likely to occur in the sealed portion after heat sealing, and the heat resistance is inferior. Further, the orientation of the film described in Patent Document 1 is low, and the rigidity is not sufficient.

WO2016 / 182003 International Bulletin Japanese Unexamined Patent Publication No. 2013-177645

An object of the present invention is to solve the above-mentioned problems. That is, the present invention relates to a biaxially oriented polypropylene film having excellent film rigidity and heat resistance at a high temperature of 150 ° C. More specifically, it is an object of the present invention to provide a biaxially oriented polypropylene film which can easily maintain the shape of a packaging bag and has less wrinkles in and around the sealing portion when heat-sealed.

As a result of diligent studies to achieve such an object, the present inventors have made a biaxially oriented polypropylene film satisfying the following (1) to (3), thereby increasing the rigidity of the film and heat resistance at a high temperature of 150 ° C. It has been found that a biaxially oriented polypropylene film having excellent properties can be obtained.
(1) When the film is constrained in all directions and the temperature is raised from 40 ° C. to 180 ° C. at a rate of 10 ° C./min, X-rays are incident in the direction perpendicular to the film surface, and wide-angle X-ray diffraction measurement is performed. , The maximum intensity in the range of 40 ° C to 130 ° C in the temperature dependence of the maximum intensity of the azimuth profile obtained by scanning the scattering derived from the (110) plane of the α-type crystal of polypropylene in the circumferential direction. The ratio of the value to the maximum intensity at 40 ° C. ((110) intensity ratio) is 115% or more.
(2) The degree of orientation in the width direction is 0.85 or more.
(3) The heat shrinkage rate at 150 ° C. is 10% or less in the longitudinal direction and 30% or less in the width direction.

In this case, the loss elastic modulus (E ") at 100 ° C. or higher in the temperature dependence of the loss elastic modulus (E") in the width direction obtained by the dynamic viscoelasticity measurement (DMA) of the biaxially oriented polypropylene film. The ratio (E " _h / E" _g ) of the maximum value (E " _h _{) to the maximum value (E" g} ) of the loss elastic modulus (E ") between -25 ° C and 25 ° C is 70% or more. It is preferable to have.

Further, in this case, it is preferable that the tensile elongation at break of the biaxially oriented polypropylene film is 25% or more in the longitudinal direction and 195% or more in the width direction at 23 ° C.

Further, in this case, the heat shrinkage rate of the biaxially oriented polypropylene film at 120 ° C. is 2.0% or less in the longitudinal direction, 5.0% or less in the width direction, and 120 ° C. heat shrinkage in the longitudinal direction. It is preferable that the rate is smaller than the 120 ° C. heat shrinkage rate in the width direction.

Furthermore, in this case, it is preferable that the refractive index Ny in the longitudinal direction of the biaxially oriented polypropylene film is 1.5230 or more and ΔNy is 0.0220 or more.

Furthermore, in this case, it is preferable that the haze of the biaxially oriented polypropylene film is 5.0% or less.

Furthermore, in this case, it is preferable that the mesopentad fraction of the polypropylene resin constituting the biaxially oriented polypropylene film is 97.0% or more.

Furthermore, in this case, it is preferable that the polypropylene resin constituting the biaxially oriented polypropylene film has a crystallization temperature of 105 ° C. or higher and a melting point of 161 ° C. or higher.

Furthermore, in this case, it is preferable that the melt flow rate of the polypropylene resin constituting the biaxially oriented polypropylene film is 4.0 g / 10 minutes or more.

Furthermore, in this case, it is preferable that the component amount of the polypropylene resin constituting the biaxially oriented polypropylene film having a molecular weight of 100,000 or less is 35% by mass or more.

Since the biaxially oriented polypropylene film of the present invention has high rigidity and excellent heat resistance at a high temperature of 150 ° C., it is easy to maintain the bag shape when it is used as a packaging bag, and wrinkles of the sealed portion when heat-sealed. A biaxially oriented polypropylene film that can be suitably used for packaging bags can be obtained. Further, since the biaxially oriented polypropylene film is also excellent in rigidity, the strength can be maintained even if the thickness of the film is reduced, and it can be suitably used for applications requiring higher rigidity. ..

The maximum intensity at 40 ° C. in the maximum intensity in the azimuth angle profile of the diffraction intensity of wide-angle X-ray diffraction derived from the polypropylene α-type crystal (110) plane of the films obtained in Example 1, Comparative Example 1, and Comparative Example 2. The diffraction intensity ratio-temperature curve based on is shown. The elastic modulus-temperature curve in the width direction of the films obtained in Example 1, Comparative Example 1, and Comparative Example 2 is shown.

Hereinafter, the biaxially oriented polypropylene film of the present invention will be described in more detail.
The biaxially oriented polypropylene film of the present invention comprises a polypropylene resin composition containing a polypropylene resin as a main component. The "main component" means that the proportion of the polypropylene resin in the polypropylene resin composition is 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, and particularly preferably. Is 97% by mass or more.

(Polypropylene resin)
As the polypropylene resin used in the present invention, a polypropylene homopolymer or a copolymer with ethylene and / or an α-olefin having 4 or more carbon atoms can be used. A propylene homopolymer substantially free of ethylene and / or an α-olefin having 4 or more carbon atoms is preferable, and even when ethylene and / or an α-olefin component having 4 or more carbon atoms is contained, ethylene and / or The amount of the α-olefin component having 4 or more carbon atoms is preferably 1 mol% or less, more preferably 0.5 mol% or less, still more preferably 0.3 mol% or less, and particularly preferably 0. It is 1 mol or less. Within the above range, crystallinity tends to improve. Examples of the α-olefin component having 4 or more carbon atoms constituting such a copolymer include 1-butene, 1-pentene, 3-methylpentene-1, 3-methylbutene-1, 1-hexene, and 4-methyl. Examples thereof include pentene-1,5-ethylhexene-1,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene and the like.
As the polypropylene resin, two or more different polypropylene homopolymers, a copolymer with ethylene and / or an α-olefin having 4 or more carbon atoms, and a mixture thereof can be used.

(Tacticity)
The mesopentad fraction ([mmmm]%), which is an index of the stereoregularity of the polypropylene resin used in the present invention, is preferably in the range of 97.0 to 99.9%, preferably 97.5 to 99.7. It is more preferably in the range of%, further preferably in the range of 98.0 to 99.5%, and particularly preferably in the range of 98.5 to 99.3%.
When it is 97.0% or more, the crystallinity of the polypropylene resin is enhanced, the melting point, crystallinity, and crystallinity of the crystals in the film are improved, and rigidity and heat resistance at high temperature can be easily obtained. When it is 99.9% or less, it is easy to suppress the cost in terms of polypropylene production, and it is difficult to break during film formation. The mesopentad fraction is measured by a nuclear magnetic resonance method (so-called NMR method).
More preferably, it is 99.5% or less. The mesopentad fraction is measured by a nuclear magnetic resonance method (so-called NMR method).
In order to keep the mesopentad fraction of the polypropylene resin within the above range, a method of washing the obtained polypropylene resin powder with a solvent such as n-heptane, selection of a catalyst and / or a co-catalyst, and a polypropylene resin composition A method of appropriately selecting the components is preferably adopted.

(Melting temperature)
The lower limit of the melting temperature (Tm) measured by DSC of the polypropylene resin constituting the biaxially oriented polypropylene film of the present invention is preferably 160 ° C., more preferably 161 ° C., and further preferably 162 ° C. , More preferably 163 ° C, even more preferably 164 ° C. When Tm is 160 ° C. or higher, rigidity and heat resistance at high temperature can be easily obtained. The upper limit of Tm is preferably 170 ° C., more preferably 169 ° C., even more preferably 168 ° C., even more preferably 167 ° C., and particularly preferably 166 ° C. When Tm is 170 ° C. or lower, it is easy to suppress an increase in cost in terms of polypropylene production, and it is difficult to break during film formation. The melting temperature can be further raised by blending the crystal nucleating agent with the polypropylene resin described above.
Tm is a sample of 1 to 10 mg packed in an aluminum pan, set in a differential scanning calorimeter (DSC), melted at 230 ° C for 5 minutes in a nitrogen atmosphere, and up to 30 ° C at a scanning speed of -10 ° C / min. This is the main peak temperature of the endothermic peak associated with melting, which is observed when the temperature is lowered, held for 5 minutes, and the temperature is raised at a scanning speed of 10 ° C./min.

(Crystallization temperature)
The lower limit of the crystallization temperature (Tc) measured by DSC of the polypropylene resin constituting the biaxially oriented polypropylene film of the present invention is 105 ° C., preferably 108 ° C., and more preferably 110 ° C. When Tc is 105 ° C. or higher, crystallization is likely to proceed in the widthwise stretching and subsequent cooling steps, and rigidity and heat resistance at high temperatures are likely to be obtained. The upper limit of Tc is preferably 135 ° C., more preferably 133 ° C., still more preferably 132 ° C., even more preferably 130 ° C., particularly preferably 128 ° C., and most preferably 127 ° C. Is. If the Tc is 135 ° C. or lower, it is difficult to increase the cost in terms of polypropylene production, and it is difficult to break during film formation. The crystallization temperature can be further raised by blending the crystal nucleating agent with the polypropylene resin described above.
Tc is observed when a sample of 1 to 10 mg is packed in an aluminum pan, set in a DSC, melted at 230 ° C. for 5 minutes in a nitrogen atmosphere, and cooled to 30 ° C. at a scanning speed of -10 ° C./min. This is the main peak temperature of the exothermic peak.

(Melt flow rate)
The melt flow rate (MFR) of the polypropylene resin constituting the biaxially oriented polypropylene film of the present invention is 4 when measured in accordance with the condition M (230 ° C., 2.16 kgf) of JIS K 7210 (1995). It is preferably 0.0 to 30 g / 10 minutes, more preferably 4.5 to 25 g / 10 minutes, further preferably 4.8 to 22 g / 10 minutes, and 5.0 to 20 g / 10 minutes. It is particularly preferable to have it, and it is most preferably 6.0 to 20 g / 10 minutes.
When the melt flow rate (MFR) of the polypropylene resin is 4.0 g / 10 minutes or more, it is easy to obtain a biaxially oriented polypropylene film having a low heat shrinkage rate.
Further, when the melt flow rate (MFR) of the polypropylene resin is 30 g / 10 minutes or less, it is easy to maintain the film-forming property of the film.

From the viewpoint of film characteristics, the lower limit of the melt flow rate (MFR) (230 ° C., 2.16 kgf) of the polypropylene resin constituting the film is preferably 5.0 g / 10 minutes, more preferably 5.5 g / 10 minutes. It is more preferably 6.0 g / 10 minutes, particularly preferably 6.3 g / 10 minutes, and most preferably 6.5 g / 10 minutes.
When the melt flow rate (MFR) of the polypropylene resin is 5.0 g / 10 minutes or more, the amount of low molecular weight components of the polypropylene resin constituting the film increases. By adopting it, the orientation crystallization of the polypropylene resin is further promoted, the degree of crystallization in the film is more likely to be increased, and the polypropylene molecular chains in the amorphous portion are less entangled with each other, resulting in heat resistance. It is easier to improve sex.
In order to keep the melt flow rate (MFR) of the polypropylene resin within the above range, it is preferable to adopt a method of controlling the average molecular weight and the molecular weight distribution of the polypropylene resin.

That is, the lower limit of the amount of the component having a molecular weight of 100,000 or less in the GPC integration curve of the polypropylene resin constituting the film of the present invention is 35% by mass, preferably 38% by mass, and more preferably 40% by mass. It is more preferably 41% by mass, and particularly preferably 42% by mass.
The upper limit of the amount of the component having a molecular weight of 100,000 or less on the GPC integration curve is preferably 65% by mass, more preferably 60% by mass, and further preferably 58% by mass. When the amount of the component having a molecular weight of 100,000 or less in the GPC integration curve is 65% by mass or less, the film strength is unlikely to decrease.
At this time, if a high molecular weight component or a long chain branched component having a long relaxation time is included, the amount of the component having a molecular weight of 100,000 or less contained in the polypropylene resin can be easily adjusted without significantly changing the overall viscosity, so that the rigidity is increased. It is easy to improve the film-forming property without affecting the heat shrinkage.

(Molecular weight distribution)
The polypropylene resin used in the present invention has a lower limit of mass average molecular weight (Mw) / number average molecular weight (Mn), which is an index of the breadth of molecular weight distribution, preferably 3.5, more preferably 4, and further. It is preferably 4.5, and particularly preferably 5. The upper limit of Mw / Mn is preferably 30, more preferably 25, still more preferably 23, particularly preferably 21 and most preferably 20.
Mw / Mn can be obtained using gel permeation chromatography (GPC). When Mw / Mn is in the above range, it is easy to increase the amount of the component having a molecular weight of 100,000 or less.

Regarding the molecular weight distribution of polypropylene resin, components of different molecular weights are polymerized in a series of plants in multiple stages, components of different molecular weights are blended offline with a kneader, or catalysts having different performances are blended and polymerized. It can be adjusted by using a catalyst capable of achieving a desired molecular weight distribution. The shape of the molecular weight distribution obtained by GPC has a single peak in a GPC chart in which the horizontal axis is the logarithm of the molecular weight (M) (logM) and the vertical axis is the differential distribution value (weight fraction per logM). It may have a gentle molecular weight distribution, or it may have a molecular weight distribution having a plurality of peaks and shoulders.

(Method for forming biaxially oriented polypropylene film)
The biaxially oriented polypropylene film of the present invention is preferably obtained by preparing an unstretched sheet made of the polypropylene resin composition containing the above-mentioned polypropylene resin as a main component and biaxially stretching the film. As a biaxial stretching method, any of the inflation simultaneous biaxial stretching method, the tenter simultaneous biaxial stretching method, and the tenter sequential biaxial stretching method can be obtained, but from the viewpoint of film forming stability and thickness uniformity, the tenter sequential biaxial stretching method can be obtained. It is preferable to adopt the axial stretching method. In particular, it is preferable to stretch in the longitudinal direction and then in the width direction, but a method of stretching in the width direction and then stretching in the longitudinal direction may also be used.

Next, the method for producing the biaxially oriented polypropylene film of the present invention will be described below, but the method is not necessarily limited to this. In addition, in the biaxially oriented polypropylene film of the present invention, a layer having another function may be laminated on at least one side. It may be laminated on one side or both sides. At that time, the polypropylene resin composition described above may be used as the resin composition of the other one layer or the central layer. Further, it may be different from the polypropylene resin composition described above. The number of layers to be laminated may be one layer, two layers, three layers or more per one side, but one layer or two layers is preferable from the viewpoint of production. As a laminating method, for example, coextrusion by a feed block method or a multi-manifold method is preferable. In particular, for the purpose of improving the processability of the biaxially oriented polypropylene film, a resin layer having a heat-sealing property can be laminated within a range that does not deteriorate the characteristics. Further, in order to impart printability, one side or both sides may be subjected to corona treatment.

The case where the tenter sequential biaxial stretching method is adopted will be described below as an example in the case of a single layer.
First, the resin composition containing the polypropylene resin is heated and melted by a single-screw or twin-screw extruder, extruded into a sheet from a T-die, and grounded on a cooling roll to be cooled and solidified. For the purpose of promoting solidification, it is preferable to further cool the sheet cooled by a cooling roll by immersing it in a water tank or the like.

Next, the sheet is stretched in the longitudinal direction by increasing the number of rotations of the rear stretching rolls with two pairs of stretching rolls in which the sheet is heated to obtain a uniaxially stretched film.

Subsequently, after preheating the uniaxially stretched film, the uniaxially stretched film is stretched in the width direction at a specific temperature while grasping the end of the film with a tenter type stretching machine to obtain a biaxially stretched film. This width direction stretching step will be described in detail later.

After the width direction stretching step is completed, the biaxially stretched film is heat-treated at a specific temperature to obtain a biaxially oriented film. In the heat treatment step, the film may be relaxed in the width direction.

If necessary, the biaxially oriented polypropylene film thus obtained is subjected to, for example, corona discharge treatment on at least one side, and then wound with a winder to obtain a film roll.

Each process will be described in detail below.
(Extrusion process)
First, a polypropylene resin composition containing polypropylene resin as a main component is heated and melted in a range of 200 ° C. to 300 ° C. with a single-screw or twin-screw extruder, and a sheet-shaped molten polypropylene resin composition discharged from a T-die is extruded. , Contact with a metal cooling roll to cool and solidify. It is preferable that the obtained unstretched sheet is further put into a water tank.
The temperature of the cooling roll or the cooling roll and the water tank is preferably in the range of 10 ° C. to Tc, and if it is desired to increase the transparency of the film, it is cooled and solidified with a cooling roll having a temperature in the range of 10 to 50 ° C. Is preferable. When the cooling temperature is 50 ° C. or lower, the transparency of the unstretched sheet tends to increase, preferably 40 ° C. or lower, and more preferably 30 ° C. or lower. In order to increase the crystal orientation after sequential biaxial stretching, it may be preferable to set the cooling temperature to 40 ° C. or higher, but as described above, a propylene homopolymer having a mesopendat fraction of 97.0% or higher is used. In this case, the cooling temperature is preferably 40 ° C. or lower in order to facilitate the stretching of the next step and to reduce the thickness unevenness, and more preferably 30 ° C. or lower.
The thickness of the unstretched sheet is preferably 3500 μm or less, more preferably 3000 μm or less in terms of cooling efficiency, and can be appropriately adjusted according to the film thickness after sequential biaxial stretching. The thickness of the unstretched sheet can be controlled by the extrusion speed of the polypropylene resin composition, the lip width of the T-die, and the like.

(Longitudinal stretching process)
The lower limit of the longitudinal stretching ratio is preferably 3 times, more preferably 3.5 times, and particularly preferably 3.8 times. Within the above range, the strength can be easily increased and the film thickness unevenness can be reduced. The upper limit of the longitudinal stretching ratio is preferably 8 times, more preferably 7.5 times, and particularly preferably 7 times. Within the above range, the width direction stretching in the width direction stretching step is easy, and the productivity is improved.
The lower limit of the longitudinal stretching temperature is preferably Tm-40 ° C, more preferably Tm-37 ° C, and even more preferably Tm-35 ° C. Within the above range, the subsequent stretching in the width direction becomes easy and the thickness unevenness is reduced. The upper limit of the longitudinal stretching temperature is preferably Tm-7 ° C, more preferably Tm-10 ° C, and even more preferably Tm-12 ° C. Within the above range, the heat shrinkage rate is likely to be reduced, and it is unlikely that the heat shrinkage rate will be deteriorated due to adhesion to the stretching roll and difficulty in stretching, or an increase in surface roughness.
The longitudinal stretching may be performed by using three or more pairs of stretching rolls and stretching in two or more stages.

(Preheating process)
Before the width direction stretching step, it is necessary to heat the uniaxially stretched film after the longitudinal stretching in the range of Tm to Tm + 25 ° C. to soften the polypropylene resin composition. When it is set to Tm or more, softening progresses and stretching in the width direction becomes easy. By setting the temperature to Tm + 25 ° C. or lower, the orientation at the time of lateral stretching proceeds, and the rigidity is easily developed. More preferably, it is Tm + 2 to Tm + 22 ° C, and particularly preferably Tm + 3 to Tm + 20 ° C. Here, the maximum temperature in the preheating process is defined as the preheating temperature.

(Width direction stretching process)
In the width direction stretching step after the preheating step, a preferable method is as follows.

In the width direction stretching step, it is preferable to stretch at a temperature of Tm-10 ° C. or higher and a preheating temperature or lower. At this time, the start of stretching in the width direction may be when the preheating temperature is reached, or when the temperature is lowered after reaching the preheating temperature and reaches a temperature lower than the preheating temperature.
The lower limit of the temperature in the width direction stretching step is more preferably Tm-9 ° C, further preferably Tm-7 ° C, and particularly preferably Tm-5 ° C. When the stretching temperature in the width direction is in this range, the rigidity of the obtained biaxially oriented film can be easily improved.
The upper limit of the temperature in the width direction stretching step is preferably Tm + 10 ° C., more preferably Tm + 7 ° C., and particularly preferably Tm + 5 ° C. When the stretching temperature in the width direction is in this range, stretching unevenness is unlikely to occur.
Immediately after the end of widthwise stretching, that is, immediately after reaching the widthwise final stretching ratio, the film is cooled. The cooling temperature at this time is preferably not more than the temperature of stretching in the width direction and preferably Tm-80 ° C. or higher and Tm-15 ° C. or lower, and is preferably Tm-80 ° C. or higher and Tm-20 ° C. or lower. It is more preferable to set the temperature to Tm-80 ° C. or higher and Tm-30 ° C. or lower, and it is particularly preferable to set the temperature to Tm-70 ° C. or higher and Tm-40 ° C. or lower.
The temperature at the end of stretching in the width direction can be gradually lowered to the temperature at the time of cooling, but it can also be lowered stepwise or in one step. It is preferable to lower the temperature stepwise or stepwise because the crystal orientation in the film tends to be increased.

The lower limit of the final width direction stretching ratio in the width direction stretching step is preferably 10 times, more preferably 11 times. If it is 12 times or more, the rigidity is likely to be increased and the film thickness unevenness is likely to be reduced. The upper limit of the stretching ratio in the width direction is preferably 20 times, more preferably 17 times, and further preferably 15 times. When it is 20 times or less, the heat shrinkage rate is likely to be reduced, and it is difficult to break during stretching.

As described above, by using the polypropylene resin having high stereoregularity and high crystallinity and adopting the above-mentioned width direction stretching step, the molecules of the polypropylene resin are highly oriented in the main orientation direction (the above-mentioned width). In the directional stretching step, the width direction is applicable.) Therefore, the crystal orientation in the obtained biaxially oriented film is very strong, and crystals having a high melting point are easily generated.
In addition, the orientation of the amorphous part between the crystals also increases in the main orientation direction (the width direction corresponds to the width direction stretching step described above), and many crystals having a high melting point exist around the amorphous part. At a temperature lower than the melting point, the elongated polypropylene molecule in the amorphous part is difficult to relax and tends to maintain its tense state. Therefore, the entire biaxially oriented film can maintain high rigidity even at high temperatures.
In addition, it should be noted that by adopting such a stretching step in the width direction, the heat shrinkage rate at a high temperature of 150 ° C. is likely to be further reduced. The reason is that since there are more crystals with a high melting point around the amorphous part, the elongated polypropylene resin molecules in the amorphous part are difficult to relax at a temperature lower than the melting point of the crystals, and the molecules are less entangled with each other. It is in.

It should be further noted that by increasing the low molecular weight component of the polypropylene resin, the crystallinity of the film is more likely to be increased, and the polypropylene resin molecular chains in the amorphous portion are less entangled with each other, resulting in less heat shrinkage stress. By weakening it, the heat shrinkage rate can be further reduced. Conventionally, it can be said that it is epoch-making considering that if either the strength or the heat shrinkage rate is improved, the other property tends to be lowered.

(Heat treatment process)
If necessary, the biaxially stretched film can be heat-treated to further reduce the heat shrinkage rate. The upper limit of the heat treatment temperature is preferably Tm + 10 ° C, more preferably Tm + 7 ° C, and particularly preferably Tm + 5 ° C. By setting the temperature to Tm + 10 ° C. or lower, rigidity is likely to be developed, the roughness of the film surface does not become too large, and the film is less likely to whiten. The lower limit of the heat treatment temperature is preferably Tm-5 ° C, more preferably Tm-2 ° C, and particularly preferably Tm ° C. If it is less than Tm-5 ° C, the heat shrinkage rate may increase.
By adopting the above-mentioned width direction stretching step, even if heat treatment is performed at a temperature between Tm-5 ° C. and Tm + 10, the highly oriented crystals produced in the stretching step are difficult to melt, and the rigidity of the obtained film is reduced. The heat shrinkage rate can be made smaller without lowering. The film may be relaxed (relaxed) in the width direction during heat treatment for the purpose of adjusting the heat shrinkage rate, but the upper limit of the relaxation rate is preferably 4%. When it is within the above range, the film strength is unlikely to decrease, and the fluctuation in film thickness tends to be small. It is more preferably 3%, even more preferably 2%, even more preferably 1%, and particularly preferably 0%.

(Film thickness)
The thickness of the biaxially oriented polypropylene film of the present invention is set according to each application, but in order to obtain the strength of the film, the lower limit of the film thickness is preferably 2 μm, more preferably 3 μm, still more preferably. It is 4 μm, particularly preferably 8 μm, and most preferably 10 μm. When the film thickness is 2 μm or more, the rigidity of the film can be easily obtained. The upper limit of the film thickness is preferably 100 μm, more preferably 80 μm, further preferably 60 μm, particularly preferably 50 μm, and most preferably 40 μm. When the film thickness is 100 μm or less, the cooling rate of the unstretched sheet during the extrusion process is unlikely to decrease.
The biaxially oriented polypropylene film of the present invention is usually formed as a roll having a width of 2000 to 12000 mm and a length of about 1000 to 50000 m, and is wound into a film roll. Further, it is slit according to each application and is provided as a slit roll having a width of 300 to 2000 mm and a length of about 500 to 5000 m. The biaxially oriented polypropylene film of the present invention can obtain a longer film roll.

(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%, still more preferably 0.5%, and particularly preferably 1%. The upper limit of the thickness uniformity is preferably 20%, more preferably 17%, still more preferably 15%, particularly preferably 12%, and most preferably 10%. Within the above range, defects are less likely to occur during post-processing such as coating and printing, and it is easy to use for applications that require precision.
The measurement method was as follows. A test piece having a width of 40 mm is cut out from a steady region where the physical properties of the film are stable in the length direction of the film, and a film feeder manufactured by Micrometer Measuring Instruments Co., Ltd. (manufacturing number: A90172 is used) and a film manufactured by Anritsu Co., Ltd. Using a continuous thickness measuring device (product name: K-313A wide range high-sensitivity electronic micrometer), the film thickness was continuously measured over 20000 mm, and the thickness uniformity was calculated from the following formula.
Thickness uniformity (%) = [(maximum thickness-minimum thickness) / average thickness] x 100

Polypropylene when wide-angle X-ray diffraction measurement was performed by injecting X-rays in the direction perpendicular to the film surface while restraining the film in all directions and raising the temperature from 40 ° C to 180 ° C at a rate of 10 ° C / min. In the temperature dependence of the maximum intensity of the azimuth angle profile obtained by scanning the diffraction derived from the (110) plane of the α-type crystal in the circumferential direction, the maximum value of the maximum intensity in the range of 40 ° C. to 130 ° C. The feature is that the ratio ((110) intensity ratio) to the maximum intensity at 40 ° C. is 115% or more. The case of the film of Example 1 is shown in FIG.
The (110) strength ratio is preferably 120% or more, more preferably 123% or more, further preferably 125% or more, and particularly preferably 126% or more.
When the biaxially oriented film in which polypropylene molecules are highly aligned in the main orientation direction (the width direction is applicable in the above-mentioned width direction stretching step) is constrained in all directions and the temperature is raised from around room temperature, the main orientation direction is obtained. Secondary crystallization is likely to proceed along the line, and the degree of crystallinity increases. This is contributed by the large number of polypropylene molecules having a low molecular weight and high stereoregularity, which are easy to move and crystallize. The crystallinity becomes maximum at around 100 ° C., and then the diffraction intensity decreases as the crystals melt. Further, the diffraction intensity increases again with recrystallization from a high temperature of around 140 ° C. or higher. As described above, the biaxially stretched polypropylene film of the present invention has preferable characteristics of excellent rigidity and low heat shrinkage.

(Orientation)
The lower limit of the degree of orientation calculated from Wh of the biaxially oriented polypropylene film of the present invention by the following formula is preferably 0.850, more preferably 0.855, and even more preferably 0.861. It is easy to increase the rigidity by setting it to 0.850 or more.
Orientation = (180-Wh) / 180
The upper limit of the degree of orientation is preferably 0.928, more preferably 0.922, and even more preferably 0.917. When it is 0.928 or less, the film formation is easy to stabilize.

(Film characteristics)
The biaxially oriented polypropylene film of the present invention is characterized by the following characteristics. Here, the "longitudinal direction" in the biaxially oriented polypropylene film of the present invention is a direction corresponding to the flow direction in the film manufacturing process, and the "width direction" is a direction orthogonal to the flow direction in the film manufacturing process. Is. For polypropylene films whose flow direction is unknown in the film manufacturing process, wide-angle X-rays are incident in the direction perpendicular to the film surface, and the scattering peaks derived from the (110) plane of the α-type crystal are scanned in the circumferential direction. The direction in which the obtained diffraction intensity distribution has the largest diffraction intensity is referred to as the "longitudinal direction", and the direction orthogonal to it is referred to as the "width direction".

(150 ° C heat shrinkage rate)
The upper limit of the heat shrinkage in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 150 ° C. is preferably 10%, more preferably 7.0%, still more preferably 6.0%, and more. It is more preferably 5.0%, and particularly preferably 4.0% or less. The upper limit of the heat shrinkage rate in the width direction at 150 ° C. is preferably 30%, more preferably 24%, further preferably 21%, and particularly preferably 18% or less.
When the heat shrinkage rate in the longitudinal direction is 10% or less and the heat shrinkage rate in the width direction is 30% or less, wrinkles during heat sealing are less likely to occur, and in particular, the heat shrinkage rate in the longitudinal direction at 150 ° C. is 8. When the heat shrinkage rate in the width direction at 0% or less and 150 ° C. is 20% or less, the strain when the chuck portion is fused to the open portion is small, which is preferable. In order to reduce the heat shrinkage rate at 150 ° C., the lower limit of the amount of components having a molecular weight of 100,000 or less when measuring the gel permeation chromatography (GPC) integration curve of the polypropylene resin constituting the film is set to 35% by mass. It is effective to adjust the stretching ratio, stretching temperature, and heat fixing temperature.
(Loss modulus)
The biaxially oriented polypropylene film of the present invention uses polypropylene having high stereoregularity, and by adopting the above-mentioned stretching step in the width direction, the crystallinity and crystal distribution height in the film having a large contribution to rigidity are high. As a result, relaxation due to melting of the crystal near the glass transition temperature of the polypropylene resin is less likely to occur, and relaxation of the amorphous portion is also suppressed due to the effect. At high temperatures, the melting of crystals with a high degree of orientation is completed, and the relaxation of the amorphous parts, which had been suppressed until then, also progresses, so that large relaxation occurs at high temperatures.
That is, the biaxially oriented polypropylene film of the present invention has a small elastic modulus near the glass transition temperature, and conversely has a large elastic modulus at high temperatures (particularly at 100 ° C. or higher).
Therefore, in the temperature dependence of the loss elastic modulus (E ″) in the width direction obtained by the dynamic viscoelasticity measurement (DMA) of the biaxially oriented polypropylene film of the present invention, the loss elastic modulus (E ″) at 100 ° C. or higher. The ratio (E " _h / E" _g ) of the maximum value (E " _h _{) to the maximum value (E" g} ) of the loss elastic modulus (E ") between -25 ° C and 25 ° C is preferably 70. % Or more, more preferably 73% or more, further preferably 75% or more, particularly preferably 77% or more, and most preferably 78% or more. Ratio (E " _h / E" _g ) Is 70% or more, the rigidity and heat resistance in the practical temperature range close to room temperature are more likely to be improved. In order to increase the ratio (E " _h / E" _g ), the polypropylene resin constituting the film is used. It is effective to set the lower limit of the amount of the component having a molecular weight of 100,000 or less when measuring the gel permeation chromatography (GPC) integration curve to 35% by mass, and adjust the draw ratio, the draw temperature, and the heat fixation temperature.

(23 ° C tensile elongation at break)
The lower limit of the tensile elongation at break in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 23 ° C. is preferably 195%, more preferably 200%, still more preferably 210%, and particularly preferably. It is 220% or more. If it is 195% or more, the breakage of the film and the breakage of the packaging bag are likely to decrease. The upper limit of the tensile elongation at break in the longitudinal direction at 23 ° C. is preferably 300% as a realistic value, and more preferably 280%.

The lower limit of the tensile elongation at break in the width direction of the biaxially oriented polypropylene film of the present invention at 23 ° C. is preferably 25%, more preferably 30%, still more preferably 32%, and particularly preferably. It is 35%. If it is 25% or more, the breakage of the film and the breakage of the packaging bag are likely to occur. The upper limit of the tensile elongation at break in the width direction at 23 ° C. is preferably 60%, more preferably 55%, and even more preferably 50%. If it is 60% or less, the printing pitch shift when transferring the printing ink is less likely to occur, and the durability of the packaging bag is likely to be excellent.
The tensile elongation at break can be within the range by adjusting the draw ratio, the draw temperature, and the heat fixation temperature.

(23 ° C tensile breaking strength)
The lower limit of the tensile breaking strength in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 23 ° C. is preferably 90 MPa, more preferably 100 MPa, still more preferably 110 MPa, and particularly preferably 120 MPa. If it is 90 MPa or more, the printing pitch shift when transferring the printing ink is less likely to occur, and the durability of the packaging bag is likely to be excellent. The upper limit of the tensile breaking strength in the longitudinal direction at 23 ° C. is preferably 200 MPa, more preferably 180 MPa, and further preferably 160 MPa as a realistic value. If it is 200 MPa or less, the breakage of the film and the breakage of the packaging bag are likely to decrease.
The lower limit of the tensile breaking strength in the width direction of the biaxially oriented polypropylene film of the present invention at 23 ° C. is preferably 380 MPa, more preferably 400 MPa, further preferably 430 MPa, and particularly preferably 450 MPa. If it is 380 MPa or more, the printing pitch shift when transferring the printing ink is less likely to occur, and the durability of the packaging bag is likely to be excellent. The upper limit of the tensile breaking strength in the width direction at 23 ° C. is preferably 550 MPa, more preferably 520 MPa, and further preferably 500 MPa as a realistic value. If it is 550 MPa or less, the breakage of the film and the breakage of the packaging bag are likely to decrease. In order to increase the tensile elongation at break, the lower limit of the amount of components having a molecular weight of 100,000 or less when the gel permeation chromatography (GPC) integration curve of the polypropylene resin constituting the film is measured is set to 35% by mass, and the draw ratio is set to 35% by mass. It is effective to adjust the stretching temperature and the heat fixing temperature.

(Stress at 23 ° C. 5% elongation)
The lower limit of the stress (F5) of the biaxially oriented polypropylene film of the present invention at 5% elongation in the longitudinal direction at 23 ° C. is preferably 40 MPa, more preferably 42 MPa, still more preferably 44 MPa, and further. It is preferably 46 MPa, particularly preferably 48 MPa. At 40 MPa or more, since the rigidity is high, it is easy to maintain the bag shape when it is used as a packaging bag, and the film is less likely to be deformed during processing such as printing.
The upper limit of F5 in the longitudinal direction at 23 ° C. is preferably 70 MPa, more preferably 65 MPa, still more preferably 62 MPa, and particularly preferably 60 MPa. At 70 MPa or less, realistic manufacturing is easy, and the vertical-width balance is easy to improve.
The lower limit of F5 in the width direction of the biaxially oriented polypropylene film of the present invention at 23 ° C. is preferably 160 MPa, more preferably 170 MPa, still more preferably 180 MPa, and particularly preferably 190 MPa. At 160 MPa or more, since the rigidity is high, it is easy to maintain the bag shape when it is used as a packaging bag, and the film is less likely to be deformed during processing such as printing. The upper limit of F5 in the width direction at 23 ° C. is preferably 250 MPa, more preferably 230 MPa, and even more preferably 220 MPa. If it is 250 MPa or less, realistic manufacturing is easy and the vertical width balance is easy to improve.
F5 can be set within the range by adjusting the stretching ratio and the relaxing rate, and adjusting the temperature at the time of film formation.

(120 ° C. heat shrinkage rate)
The upper limit of the heat shrinkage in the longitudinal direction of the biaxially oriented polypropylene film of the present invention at 120 ° C. is preferably 2.0%, more preferably 1.5%, and even more preferably 1.2%. , Particularly preferably 1.0%. When it is 2.0% or less, the printing pitch shift when transferring the printing ink is less likely to occur. The upper limit of the heat shrinkage rate in the width direction at 120 ° C. is 5.0%, preferably 4.0%, more preferably 3.5%, and particularly preferably 2.5%. If it is 5.0% or less, wrinkles during heat sealing are unlikely to occur.
When the longitudinal heat shrinkage rate at 120 ° C. is smaller than the width direction heat shrinkage rate at 120 ° C., the printing pitch shift when transferring the printing ink is less likely to occur. The balance between the heat shrinkage rate at 120 ° C. and the heat shrinkage rate in the longitudinal direction to the width direction can be within the range by adjusting the draw ratio, the draw temperature, and the heat fixation temperature.

(Refractive index)
The lower limit of the refractive index (Nx) in the longitudinal direction of the biaxially oriented polypropylene film of the present invention is preferably 1.4950, more preferably 1.4970, and even more preferably 1.4980. If it is 1.4950 or more, it is easy to increase the rigidity of the film. The upper limit of the refractive index (Nx) in the longitudinal direction is preferably 1.5100, more preferably 1.5070, and even more preferably 1.5050. If it is 1.5100 or less, the balance of the characteristics in the longitudinal direction and the width direction of the film tends to be excellent.

The lower limit of the refractive index (Ny) in the width direction of the biaxially oriented polypropylene film of the present invention is 1.5230, preferably 1.5235, and more preferably 1.5240. If it is 1.5230 or more, it is easy to increase the rigidity of the film. The upper limit of the refractive index (Ny) in the width direction is preferably 1.5280, more preferably 1.5275, and even more preferably 1.5270. If it is 1.5280 or less, the balance of the characteristics in the longitudinal direction and the width direction of the film tends to be excellent.

The lower limit of the refractive index (Nz) in the thickness direction of the biaxially oriented polypropylene film of the present invention is preferably 1.4960, more preferably 14965, and even more preferably 1.4970. If it is 1.4960 or more, it is easy to increase the rigidity of the film. The upper limit of the refractive index (Nz) in the thickness direction is preferably 1.5020, more preferably 1.5015, and even more preferably 1.5010. If it is 1.5020 or less, the heat resistance of the film can be easily increased.
The refractive index can be set within the range by adjusting the stretching ratio, stretching temperature, and heat fixing temperature.

(△ Ny)
The lower limit of ΔNy of the biaxially oriented polypropylene film of the present invention of the present invention is 0.0220, preferably 0.0225, more preferably 0.0228, and further preferably 0.0230. If it is 0.0220 or more, the rigidity of the film tends to increase. The upper limit of ΔNy is preferably 0.0270, more preferably 0.0265, still more preferably 0.0262, and particularly preferably 0.0260 as a realistic value. If it is 0.0270 or less, the thickness unevenness tends to be good. ΔNy can be set within the range by adjusting the stretching ratio, stretching temperature, and heat fixing temperature of the film.
ΔNy is calculated by the following formula, where the refractive indexes along the longitudinal direction, the width direction, and the thickness direction of the film are Nx, Ny, and Nz, respectively. It means the degree of orientation in the direction.
ΔNy = Ny− [(Nx + Nz) / 2]

(Surface orientation coefficient)
The lower limit of the plane orientation coefficient (ΔP) of the biaxially oriented polypropylene film of the present invention is preferably 0.0135, more preferably 0.0138, and even more preferably 0.0140. When it is 0.0135 or more, the balance in the surface direction of the film is good, and the thickness unevenness is also good. The upper limit of the plane orientation coefficient (ΔP) is preferably 0.0155, more preferably 0.0152, and even more preferably 0.0150 as a realistic value. If it is 0.0155 or less, the heat resistance at high temperature is likely to be excellent. The plane orientation coefficient (ΔP) can be set within the range by adjusting the stretching ratio, stretching temperature, and heat fixing temperature.
The plane orientation coefficient (ΔP) was calculated using (Equation) [(Nx + Ny) / 2] -Nz.

(Half width of diffraction peak derived from oriented crystal)
In the orientation angle dependence of the diffraction peak of the (110) plane of the polypropylene α-type crystal obtained by wide-angle X-ray measurement vertically incident on the film plane of the biaxially oriented polypropylene film of the present invention, the oriented crystal in the width direction of the film. The upper limit of the half-value width (Wh) of the diffraction peak derived from is 27 °, preferably 26 °, more preferably 25 °, particularly preferably 24 °, and most preferably 23 °. When the full width at half maximum (Wh) is 27 ° or less, the rigidity of the film tends to be increased. The lower limit of Wh is preferably 13 °, more preferably 14 °, and even more preferably 15 °.

(Haze)
The upper limit of the haze of the biaxially oriented polypropylene film of the present invention is preferably 5.0%, more preferably 4.5%, further preferably 4.0%, and particularly preferably 3.5%. Yes, most preferably 3.0%. If it is 5.0% or less, it is easy to use in applications where transparency is required. The lower limit of the haze is preferably 0.1%, more preferably 0.2%, still more preferably 0.3%, and particularly preferably 0.4% as a realistic value. If it is 0.1% or more, it is easy to manufacture. The haze adjusts the cooling roll (CR) temperature, the stretching temperature in the width direction, the preheating temperature before stretching in the tenter width direction, the stretching temperature in the width direction, or the heat fixing temperature, or the amount of components having a molecular weight of 100,000 or less of the polypropylene resin. However, it may increase due to the addition of an antiblocking agent or the addition of a seal layer.

(Practical characteristics of film)
The practical characteristics of the biaxially oriented polypropylene film of the present invention will be described.

(Wrinkles during heat sealing)
To form a bag for wrapping food, the pre-made bag is filled with the contents and heated to melt the film, fuse it and seal it. In many cases, the same procedure is used when making a bag while filling food. Usually, a sealant film made of polyethylene, polypropylene, or the like is laminated on the base film, and the sealant film surfaces are fused to each other. In the heating method, pressure is applied from the base film side with a heating plate to press the film to seal it, but the sealing width is often about 10 mm. At this time, the base film is also heated, and the shrinkage at that time causes wrinkles. It is better to have less wrinkles in the durability of the bag, and it is better to have less wrinkles in order to increase purchasing motivation. The sealing temperature may be about 120 ° C., but in order to increase the bag making processing speed, a higher sealing temperature is required, and even in that case, it is preferable that the shrinkage is small. When the chuck is fused to the opening portion of the bag, it is required to seal at a higher temperature.

(Print pitch shift)
As a basic structure of the packaging film, it is often composed of a laminated film of a printed base film and a sealant film. A bag making machine is used to manufacture bags, and there are three-sided bags, standing bags, gusset bags, etc., and various bag making machines are used. It is considered that the printing pitch shift occurs because the base material of the film expands and contracts because tension and heat are applied to the film during the printing process. Eliminating defective products due to printing pitch deviation is important in terms of effective use of resources, and is also important in increasing purchasing motivation.

(Film processing)
The biaxially oriented polypropylene film of the present invention can be printed by letterpress printing, lithographic printing, intaglio printing, stencil printing, and transfer printing, depending on the application.
In addition, low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, unstretched sheet made of polyester, uniaxially stretched film, and biaxially stretched fill are bonded as a sealant film to impart heat sealability. It can also be used as a laminated body. If you want to further improve gas barrier properties and heat resistance, use aluminum foil, polyvinylidene chloride, nylon, ethylene-vinyl alcohol copolymer, unstretched sheet made of polyvinyl alcohol, uniaxially stretched film, and biaxially stretched film as biaxially oriented polypropylene film. It can be provided as an intermediate layer between the and the sealant film. An adhesive applied by a dry lamination method or a hot melt lamination method can be used for laminating the sealant film.
In order to enhance the gas barrier property, aluminum or an inorganic oxide can be vapor-deposited on a biaxially oriented polypropylene film, an intermediate layer film, or a sealant film. Vacuum vapor deposition, sputtering, and ion plating methods can be adopted as the vapor deposition method, but silica, allumina, or a mixture thereof is particularly preferable.

The biaxially oriented polypropylene film of the present invention contains, for example, antifogging agents such as fatty acid esters of polyhydric alcohols, amines of higher fatty acids, amides of higher fatty acids, amines of higher fatty acids and ethylene oxide adducts of amide. By setting the abundance in the film in the range of 0.2 to 5% by mass, it is possible to make it suitable for packaging fresh products made of plants that require high freshness such as vegetables, fruits, and flowers. can.

Further, as long as the effects of the present invention are not impaired, various additives for improving quality such as slipperiness and antistatic property, for example, lubricants such as wax and metal soap for improving productivity, and plasticizers. It is also possible to add agents, processing aids, heat stabilizers, antioxidants, antistatic agents, ultraviolet absorbers and the like.

(Industrial applicability)
Since the biaxially oriented polypropylene film of the present invention has excellent properties as described above, it can be preferably used for packaging bags, and the thickness of the film can be made thinner than before.

Furthermore, it is required to be used at high temperatures such as insulating films for capacitors and motors, back sheets for solar cells, barrier films for inorganic oxides, and base films for transparent conductive films such as ITO, and to have rigidity such as separate films. It is also suitable for various applications. In addition, it is possible to coat and print at high temperatures by using coating agents, inks, laminating adhesives, etc., which have been difficult to use in the past, and it is expected that production efficiency will be improved.

Hereinafter, the present invention will be described in detail with reference to Examples. The characteristics were measured and evaluated by the following methods.
(1) Melt flow rate The melt flow rate (MFR) was measured at a temperature of 230 ° C. and a load of 2.16 kgf in accordance with JIS K7210.

(2) Mesopendat fraction The mesopentad fraction ([mmmm]%) of the polypropylene resin was measured using 13C-NMR. The mesopentad fraction was calculated according to the method described in Zambelli et al., Macromolecules, Vol. 6, p. 925 (1973). The 13C-NMR measurement was carried out at 110 ° C. by dissolving 200 mg of a sample in an 8: 2 mixture of o-dichlorobenzene and heavy benzene using AVANCE500 manufactured by Bruker.

(3) Number average molecular weight, weight average molecular weight, component weight of molecular weight 100,000 or less, and molecular weight distribution of polypropylene resin It was determined as a PP-equivalent molecular weight based on monodisperse polystyrene using gel permeation chromatography (GPC). When the baseline was not clear, it was decided to set the baseline up to the lowest position of the high molecular weight side skirt of the high molecular weight side elution peak closest to the elution peak of the standard substance.
The GPC measurement conditions are as follows.
Equipment: HLC-8321PC / HT (manufactured by Tosoh Corporation)
Detector: RI
Solvent: 1,2,4-trichlorobenzene + dibutylhydroxytoluene (0.05%)
Column: TSKgelgradecolum HHR (30) HT (7.5 mm I.D. x 7.5 cm) x 1 + TSKgelGMHHR-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 ° C
The number average molecular weight (Mn) and the mass average molecular weight (Mw) are each defined by the following equations by the number of molecules (Ni) of the molecular weight (Mi) at each elution position of the GPC curve obtained via the molecular weight calibration curve.
Number average molecular weight: Mn = Σ (Ni ・ Mi) / ΣNi
Mass average molecular weight: Mw = Σ (Ni ・ Mi ² ) / Σ (Ni ・ Mi)
Here, the molecular weight distribution can be obtained by Mw / Mn.
Moreover, the ratio of the components having a molecular weight of 100,000 or less was obtained from the integral curve of the molecular weight distribution obtained by GPC.

(4) Crystallization temperature (Tc), melting temperature (Tm)
Heat measurement was performed in a nitrogen atmosphere using a Q1000 differential scanning calorimeter manufactured by TA Instruments. Approximately 5 mg was cut out from polypropylene resin pellets and sealed in an aluminum pan for measurement. The temperature was raised to 230 ° C. and held for 5 minutes, then cooled to 30 ° C. at a rate of −10 ° C./min, and the exothermic peak temperature was defined as the crystallization temperature (Tc). The amount of heat of crystallization (ΔHc) was determined by setting a baseline so that the area of the exothermic peak could be smoothly connected from the start of the peak to the end of the peak. The temperature was kept as it was at 30 ° C. for 5 minutes, the temperature was raised to 230 ° C. at 10 ° C./min, and the main endothermic peak temperature was defined as the melting temperature (Tm).

(5) Film Thickness The film thickness was measured using a Millitron 1202D manufactured by Seiko EM.

(6) Haze Using NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd., the measurement was carried out at 23 ° C. according to JIS K7105.

(7) Tensile test The tensile strength of the film in the longitudinal direction and the width direction was measured at 23 ° C. according to JIS K 7127. The sample was cut out from a film to a size of 15 mm × 200 mm, had a chuck width of 100 mm, and was set in a tensile tester (dual column desktop tester Instron 5965 manufactured by Instron Japan Company Limited). A tensile test was performed at a tensile speed of 200 mm / min. From the obtained strain-stress curve, the stress at 5% elongation was defined as F5. The tensile breaking strength and the tensile breaking elongation were taken as the strength and elongation at the time when the sample broke, respectively.
F5 at 80 ° C. was determined by performing the measurement in a constant temperature bath at 80 ° C. The measurement was carried out by setting the chuck in a constant temperature bath set to 80 ° C. in advance, mounting the sample until the measurement was performed, and then holding the sample for 1 minute.

(8) Heat shrinkage rate Measured by the following method in accordance with JIS Z 1712. The film was cut with a width of 20 mm and a length of 200 mm in the longitudinal direction and the width direction of the film, respectively, and hung in a hot air oven at 120 ° C. or 150 ° C. and heated for 5 minutes. The length after heating was measured, and the heat shrinkage rate was determined by the ratio of the contracted length to the original length.

(9) Refractive index, ΔNy, plane orientation coefficient Measured at a wavelength of 589.3 nm and a temperature of 23 ° C. using an Abbe refractometer manufactured by Atago Co., Ltd. The refractive indexes along the longitudinal direction and the width direction of the film were Nx and Ny, respectively, and the refractive indexes in the thickness direction were Nz. ΔNy was determined using (formula) Ny− [(Nx + Nz) / 2] using Nx, Ny, and Nz. The plane orientation coefficient (ΔP) was calculated using (Equation) [(Nx + Ny) / 2] -Nz.

(10) Diffraction intensity ratio derived from the (110) plane of α-type crystal The wide-angle X-ray (WAXS) measurement of the film is owned by the Frontier Soft Matter Development Industry-Academia Union (FSBL) in the large radiation facility SPring-8. It was done at the second hatch of the beam line BL03XU. The X-ray wavelength was 0.1 nm, a two-dimensional detector SOPHIAS was used as a detector, and the transmittance was calculated from the values of the ion chambers set before and after the sample.
The film is sandwiched between two non-slip SUS plates with a hole with a diameter of 4 mm in the center, placed in a self-made holder, restrained in all directions, and blown with temperature-controlled air from 40 ° C to 180 ° C. While raising the temperature at a rate of 10 ° C./min, X-rays were incident on the film surface in the direction perpendicular to the film surface to obtain wide-angle X-ray diffraction images at each temperature.
Air scattering correction was performed on the obtained two-dimensional image in consideration of the transmittance. _{Cerium oxide (CeO 2} ) was used to measure the camera length, and Fit2D (software made by European Synchrotron Radiation Facility [http://www.esrf.eu/computing/scientific/FIT2D/]) was used to measure polypropylene α. The azimuth profile of the (110) plane of the type crystal was calculated. In the temperature dependence of the maximum value of the diffraction intensity derived from the (110) plane of the α-type crystal oriented in the width direction, the maximum value of the maximum intensity in the range of 40 ° C. to 130 ° C., the maximum intensity at 40 ° C. The ratio (diffraction intensity ratio) to the ratio (diffraction intensity ratio) (%) was calculated.

(11) Half width at half maximum and degree of orientation The measurement was performed by a transmission method using an X-ray diffractometer (RINT2500 manufactured by Rigaku Co., Ltd.). An X-ray having a wavelength of 0.15418 nm was used, and a scintillation counter was used as a detector. A sample was prepared by superimposing films so as to have a thickness of 500 μm. A sample table is placed at the diffraction peak position (diffraction angle 2θ = 14.1 °) on the (110) plane of the α-type crystal of polypropylene resin, and the sample is rotated 360 ° about the thickness direction of the film to rotate the sample on the (110) plane. The azimuth dependence of the diffraction intensity was obtained. From this azimuth dependence, the full width at half maximum Wh of the diffraction peak derived from the oriented crystal in the width direction of the film was obtained.
Further, using Wh, the degree of orientation was calculated from the following formula.

(12) Dynamic Viscoelasticity Measurement (DMA)
For dynamic viscoelasticity measurement, use RSA-G2 manufactured by TA Instruments Japan Co., Ltd., set a film sample with a width of 4 mm in the device with a chuck spacing of 10 mm, load 10 g, and under a nitrogen atmosphere, -60. The temperature was raised from ° C. to 160 ° C. at 5 ° C./min and measured at a frequency of 10 Hz to obtain the temperature dependence of the loss elastic modulus (E ") (Pa). From the loss elastic modulus-temperature curve, -25 ° C. _{The maximum value (E "g} ) of the loss elastic modulus (E") between 25 ° C. _{and the maximum value (E "h} ) of the loss elastic modulus (E") at 100 ° C. or higher were obtained.

(Example 1)
As a polypropylene resin, propylene homopolymer PP-1 (Sumitomo Chemical Co., Ltd.) having MFR = 7.5 g / 10 minutes, [mmmm] = 98.9%, Tc = 116.2 ° C., and Tm = 162.5 ° C. , Sumitomo Noblen FLX80E4) with 80 parts by weight, MFR = 11 g / 10 minutes, [mmmm] = 98.8%, Tc = 116.5 ° C, Tm = 161.5 ° C, propylene homopolymer PP-2 (EL80F5 manufactured by Sumitomo Chemical Co., Ltd.) was used by blending with 20 parts by weight.
It was extruded into a sheet from a T-die at 250 ° C., brought into contact with a cooling roll at 20 ° C., and put into a water tank at 20 ° C. as it was. Then, it is stretched 4.5 times in the longitudinal direction with two pairs of rolls at 142 ° C., then both ends are clipped, guided into a hot air oven, preheated at 170 ° C., and stretched 12 times in the width direction at 167 ° C. Was done. Immediately after stretching in the width direction, the mixture was cooled at 100 ° C. while being held by the clip, and then heat-treated at 165 ° C. without relaxation in the width direction. The thickness of the film thus obtained was 20.3 μm.
Table 1 shows the structure of the polypropylene resin, and Table 2 shows the film forming conditions. As for the physical characteristics, as shown in Table 3, a film having high rigidity and low heat shrinkage at high temperature was obtained.

(Comparative Example 1)
As a polypropylene resin, PP-3 (manufactured by Japan Polypropylene Corporation, FL203D) having MFR = 3.0 g / 10 minutes, [mm mm] = 94.8%, Tc = 117.2 ° C., and Tm = 160.6 ° C. Was used. It was extruded into a sheet from a T-die at 250 ° C., brought into contact with a cooling roll at 20 ° C., and put into a water tank at 20 ° C. as it was. Then, after stretching 4.5 times in the longitudinal direction at 134 ° C., the film was heated at a preheating temperature of 170 ° C. with a tenter, followed by stretching 8.2 times in the width direction at a stretching temperature of 161 ° C., and then. , Heat fixation was performed at 165 ° C. with 6.6% relaxation. The thickness of the obtained film was 20.3 μm. Table 1 shows the structure of the polypropylene resin, Table 2 shows the film forming conditions, and Table 3 shows the physical properties. As shown in Table 3, its physical properties were inferior in rigidity and heat shrinkage at 150 ° C.

(Comparative Example 2)
As a polypropylene resin, PP-1 is 70 parts by weight, MFR = 2.7 g / 10 minutes, [mmmm] = 98.7%, Tc = 114.7 ° C., Tm = 163.0 ° C., PP-4 ( FS2012) manufactured by Sumitomo Chemical Co., Ltd. was used by blending 30 parts by weight. It was extruded into a sheet from a T-die at 250 ° C., brought into contact with a cooling roll at 20 ° C., and put into a water tank at 20 ° C. as it was. Then, after stretching 4.5 times in the longitudinal direction at 135 ° C., the film was heated with a tenter at a preheating temperature of 173 ° C., and subsequently stretched 8.2 times in the width direction at a stretching temperature of 165 ° C., and then. , Heat fixation was performed at 171 ° C. with 6.6% relaxation. The thickness of the obtained film was 20.9 μm. Table 1 shows the structure of the polypropylene resin, Table 2 shows the film forming conditions, and Table 3 shows the physical properties. As shown in Table 3, its physical properties were inferior in rigidity.

Claims

A biaxially oriented polypropylene film that satisfies the following (1) to (3).
(1) When the film is constrained in all directions and the temperature is raised from 40 ° C. to 180 ° C. at a rate of 10 ° C./min, X-rays are incident in the direction perpendicular to the film surface, and wide-angle X-ray diffraction measurement is performed. , The maximum intensity in the range of 40 ° C to 130 ° C in the temperature dependence of the maximum intensity of the azimuth profile obtained by scanning the scattering derived from the (110) plane of the α-type crystal of polypropylene in the circumferential direction. The ratio of the value to the maximum intensity at 40 ° C. ((110) intensity ratio) is 115% or more.
(2) The degree of orientation in the width direction obtained by wide-angle X-ray measurement is 0.85 or more.
(3) The heat shrinkage rate at 150 ° C. is 10% or less in the longitudinal direction and 30% or less in the width direction.
In the temperature dependence of the loss elastic modulus (E ") in the width direction obtained by the dynamic viscoelasticity measurement (DMA) of the biaxially oriented polypropylene film, the maximum value of the loss elastic modulus (E") at 100 ° C. or higher ( E claim 1 "h), loss modulus between 25 ° C. from -25 ° C. (E" maximum value) (E "ratio to g) (E" h / E "g) of at least 70% Biaxially oriented polypropylene film according to.
The biaxially oriented polypropylene film according to claim 1 or 2, wherein the tensile elongation at break of the biaxially oriented polypropylene film is 25% or more in the longitudinal direction and 195% or more in the width direction at 23 ° C.
The heat shrinkage rate of the biaxially oriented polypropylene film at 120 ° C. is 2.0% or less in the longitudinal direction, 5.0% or less in the width direction, and the heat shrinkage rate at 120 ° C. in the longitudinal direction is 120 in the width direction. The biaxially oriented polypropylene film according to any one of claims 1 to 3, which is smaller than the ° C. heat shrinkage rate.
The biaxially oriented polypropylene film according to any one of claims 1 to 4, wherein the biaxially oriented polypropylene film has a refractive index Ny in the width direction of 1.5230 or more and ΔNy of 0.0220 or more.
The biaxially oriented polypropylene film according to any one of claims 1 to 5, wherein the haze of the biaxially oriented polypropylene film is 5.0% or less.
The biaxially oriented polypropylene film according to any one of claims 1 to 6, wherein the polypropylene resin constituting the biaxially oriented polypropylene film has a mesopentad fraction of 97.0% or more.
The biaxially oriented polypropylene film according to any one of claims 1 to 7, wherein the polypropylene resin constituting the biaxially oriented polypropylene film has a crystallization temperature of 105 ° C. or higher and a melting point of 160 ° C. or higher.
The biaxially oriented polypropylene film according to any one of claims 1 to 8, wherein the melt flow rate of the polypropylene resin constituting the biaxially oriented polypropylene film is 4.0 g / 10 minutes or more.
The biaxially oriented polypropylene film according to any one of claims 1 to 9, wherein the polypropylene resin constituting the biaxially oriented polypropylene film has a molecular weight of 100,000 or less and a component amount of 35% by mass or more.