JP6221481B2 - Polypropylene film - Google Patents

Description

  The present invention relates to a polypropylene film. More specifically, the present invention relates to a polypropylene film excellent in heat resistance and mechanical properties that can be suitably used in various fields that require dimensional stability at high temperatures and high rigidity.

  Conventionally, a stretched polypropylene film has been widely used in a wide range of applications such as packaging of food and various products, electrical insulation, and surface protection films. However, the conventional polypropylene film has a shrinkage rate of several tens of percent at 150 ° C., and has low heat resistance and low rigidity as compared with PET and the like, and its application has been limited.

In order to solve these problems, there has been known a technique for producing a film having high-temperature rigidity and heat resistance by forming a stretched film using polypropylene having high stereoregularity and a narrow molecular weight distribution (for example, Patent Document 1). Etc.).
In addition, a technology has been known that can be suitably used as a capacitor film having excellent electrical insulation, mechanical properties and the like by using a polypropylene film having high stereoregularity and having a wide molecular weight distribution as a stretched film ( For example, see Patent Document 2).

  Furthermore, a technology for forming a separator film using polypropylene having a low molecular weight and a soluble content of 0 ° C. by a temperature rising fractionation method in a specific range is known. This film has dimensions in a drying process and a printing process. It was also said to be excellent in stability (see, for example, Patent Document 3).

  However, the films described in Patent Documents 1 to 3 have difficulty in stretchability and inferior mechanical properties such as impact resistance.

  By adding a small amount of long-chain branched or cross-linked polypropylene to the medium molecular weight component, it promotes the formation of a child lamella, improves the stretchability, has excellent mechanical properties, heat resistance, withstand voltage properties, and excellent uniformity of various properties. A technique for forming a film has been known (see, for example, Patent Document 4).

  In addition, it balances rigidity and workability by using a film made of polypropylene that contains almost the same amount of high molecular weight component and medium molecular weight component (low molecular weight component is small), has a wide molecular weight distribution, and has a small amount of decalin soluble matter. Is known (see, for example, Patent Document 5).

  The films described in Patent Documents 4 to 5 cannot be said to have sufficient heat resistance at high temperatures, and polypropylene films having high heat resistance and excellent impact resistance and transparency have not been known. That is, they do not exceed the range of conventional polypropylene films, and their uses are limited. For example, no attention has been paid to heat resistance at high temperatures exceeding 150 ° C.

In order to improve the heat resistance of the film, a technique has been known in which the elongation at 120 ° C. and 0.5 kgf / mm ² load in TMA (mechanical thermal analysis) measurement is 10% or less (see, for example, Patent Document 6). . However, the film described in Patent Document 6 does not have sufficient heat resistance when performing printing or processing.

Conventionally, when printing or laminating a polypropylene film, the drying process is known to cause various problems because the film is stretched because it is heated under tension. ing. For example, printed designs are printed in layers for each color to be printed, but if the film is not heat resistant, problems such as the pitch not matching during the overprinting and the difficulty of adjusting it are known. It has been. When the film has wrinkles or the like, the film is generally processed after the wrinkles are apparently eliminated by increasing the tension applied to the film during processing. However, in this case as well, if the film is not heat resistant, it may be stretched too much or, in extreme cases, it may break.
Because of these problems, in polypropylene film, it is common to set the tension during printing and laminating low, but if set too low, it will cause wrinkles during processing, It is known to meander.
For example, in the case of a processed product in which the printing pitch is particularly important, the front substrate is not a polypropylene film, but a polyethylene terephthalate film made of a resin material having excellent heat resistance is used. The range of use of the film has been limited.

JP-A-8-325327 JP 2004-175932 A JP 2001-146536 A JP 2007-84813 A Special table 2008-540815 JP 2001-106804 A

  The present invention has been made against the background of such prior art problems. That is, an object of the present invention is to provide a polypropylene film that is excellent in heat resistance and dimensional stability and is suitable for printing processing, and more specifically, has little elongation under a load at a high temperature. Another object is to provide a polypropylene film having a low shrinkage at 150 ° C. and having high rigidity.

The inventors of the present invention have intensively studied to achieve the object, and as a result, the present invention has been completed. That is, the present invention has a haze of 6% or less, a thermal shrinkage at 150 ° C. of 15% or less, a temperature rising rate of 5 ° C./min, and a load of 0.5 kg / mm ^2. Analysis) The polypropylene film is characterized in that the heating elongation E (%) in the MD direction when the measurement is performed satisfies the formula (1) at 120 ° C. to 150 ° C.
log (E) ≦ 0.0275T−2.4839 (1)
(However, T is temperature (° C))

  In this case, it is preferable that the lower limit of the isotactic mesopentad fraction of the polypropylene resin constituting the film is 96%, and the lower limit of the plane orientation coefficient of the film is 0.0125.

  In this case, it is preferable that the upper limit of the amount of the copolymerization monomer of the polypropylene resin constituting the film is 0.1 mol%.

  Furthermore, in this case, it is preferable that the polypropylene resin constituting the film has a normal temperature xylene soluble content of 7% by mass or less.

Since the polypropylene film of the present invention is excellent in heat resistance and dimensional stability, misregistration and deformation during printing are suppressed, and the efficiency of printing processing is remarkably improved.
Furthermore, since the polypropylene film of the present invention can maintain various physical properties even when exposed to an environment of 150 ° C. or higher, it can be used in a high-temperature environment that has not been considered in conventional polypropylene films. .

2 is a DSC chart of a polypropylene film described in Example 1 and Comparative Example 1.

(Film characteristics)
The present invention relates to a polypropylene film having excellent dimensional stability and mechanical properties at high temperature. The polypropylene film is measured by TMA (mechanical thermal analysis) under the conditions of a heating rate of 5 ° C./min and a load of 0.5 kg / mm ^2. When the heating elongation E (%) in the MD direction is 120 to 150 ° C., the formula (1) is satisfied, preferably the formula (2) is satisfied, and the formula (3) is more preferable. Is satisfied.
log (E) ≦ 0.0275T−2.4839 (1)
log (E) ≦ 0.0263T−2.3572 (2)
log (E) ≦ 0.0239T−2.0776 Formula (3)
(In formulas (1) to (3), T is temperature (° C.))
When the heating elongation E (%) does not satisfy the formula (1), the deformation of the film in the printing process becomes large, and the printing accuracy and efficiency are remarkably lowered.
The lower limit of the heating elongation E (%) is 1% at 120 ° C, 2% at 130 ° C, 5% at 140 ° C, and 8% at 150 ° C. If the heating elongation E (%) at each temperature is smaller than the lower limit, the stability during printing may be lowered.

The lower limit of the heat shrinkage rate at 150 ° C. in the MD direction and the TD direction of the polypropylene film of the present invention is preferably 0.5%, more preferably 1%, still more preferably 1.5%, particularly preferably. Is 2%, most preferably 2.5%. When the heat shrinkage rate is 0.5% or more, realistic production may be facilitated in terms of cost or the like, and thickness spots may be reduced. The MD direction is the film flow direction, and the TD direction is the direction perpendicular to the film flow direction.
The upper limit of the heat shrinkage rate at 150 ° C. in the MD direction and the TD direction is 15%, preferably 13%, more preferably 12%, still more preferably 11%, and most preferably 10%. . When the heat shrinkage rate is 15% or less, a film having excellent heat resistance can be obtained, and use in applications that may be exposed to a high temperature of about 150 ° C. becomes easier. When the heat shrinkage at 150 ° C. is about 2.5% or more, for example, the low molecular weight polypropylene (hereinafter referred to as low molecular weight component) having a molecular weight of about 100,000 is increased, and the stretching conditions and heat setting conditions are adjusted. Although it is possible, if it is lower than about 2.5%, it is preferable to perform the annealing treatment off-line. In the conventional polypropylene film, the thermal shrinkage rate at 150 ° C. in the MD direction and the TD direction is 15% or more, and the thermal shrinkage rate at 120 ° C. is about 3%.

  The lower limit as a practical value of the haze of the polypropylene film of the present invention is preferably 0.1%, more preferably 0.2%, still more preferably 0.3%, and particularly preferably 0.4%. %, And most preferably 0.5%. The upper limit of the haze of the film is 6%, preferably 5%, more preferably 4.5%, still more preferably 4%, and most preferably 3.5%. When the haze is 6% or less, it may be easy to use in applications where transparency is required. The haze tends to increase when the stretching temperature or heat setting temperature is too high, when the cooling roll temperature is high and the stretching rate of the stretched raw fabric is slow, or when there are too many low molecular weight components. It can be within the range.

(Polypropylene resin)

Polypropylene resin used in the present invention, for example, weight average molecular weight (M _w) of 100,000 as low molecular weight polypropylene (low molecular weight component) as main, further for example M _w of high molecular weight having a molecular weight extremely about 1.5 million Polypropylene (hereinafter referred to as a high molecular weight component) is preferably contained. Crystallinity can be greatly increased by mainly using a low molecular weight component, and it is considered that a polypropylene film having a high rigidity and high heat resistance, which has not been conventionally obtained, is obtained. On the other hand, a low molecular weight polypropylene resin has a low melt tension when softened by heating, and it is generally difficult to obtain a stretched film. The polypropylene film of the present invention has the effect of stretching by allowing the high molecular weight component to exist in the range of several percent to several tens of percent, the high molecular weight component serving as a crystal nucleus, and further improving the crystallinity of the film. It seems that it is suitable for obtaining.
Parameters representing the molecular weight of the polymer include number average molecular weight (M _n ), mass average molecular weight (M _w ), Z average molecular weight (M _z ), Z + 1 average molecular weight (M _{z + 1} ), peak molecular weight (M _p ). These are defined by the number of molecules (Ni) of the molecular weight (Mi) as follows.
Number average molecular weight: M _n = Σ (N _i · M _i ) / ΣN _i
Mass average molecular weight: M _w = Σ (N _i · M _i ² ) / Σ (N _i · M _i )
Z average molecular weight: M _z = Σ (N _i · M _i ³ ) / Σ (N _i · M _i ² )
Z + 1 average molecular weight: M _{z + 1} = Σ (N _i · M _i ⁴ ) / Σ (N _i · M _i ³ )
Peak molecular weight: M _p (Molecular weight at the peak position of the gel permeation chromatography (GPC) curve)
As a parameter representing the molecular weight distribution, a ratio of these average molecular weights is generally used, and examples thereof include M _w / M _n , M _{z + 1} / M _n, and the polypropylene used in the present invention. M _{z + 1} / M _n is suitable for expressing the characteristic molecular weight distribution of the resin. GPC is generally used as a method for measuring such molecular weight and molecular weight distribution.

The lower limit of M _{z + 1} / M _n is preferably 50, more preferably 60, still more preferably 70, particularly preferably 80, and most preferably 90. If M _{z + 1} / M _n is less than 50, it may be difficult to obtain the effects of the present invention such as a low thermal shrinkage at a high temperature. The upper limit of M _{z + 1} / M _n is preferably 300, more preferably 200. If M _{z + 1} / M _n exceeds 300, it may actually be difficult to produce a resin.

The lower limit of M _{z + 1} of the entire polypropylene resin constituting the film is preferably 2500,000, more preferably 3000,000, still more preferably 3300000, particularly preferably 3500000, and most preferably 3700000. When M _{z + 1} is 2500,000 or more, the high molecular weight component is sufficient, and the effects of the present invention are easily obtained. The upper limit of M _{z + 1} of the entire polypropylene resin constituting the film is preferably 40000000, more preferably 35000000, and further preferably 30000000. When M _{z + 1} is 4000000 or less, the production of the resin is actually easy, stretching may be easy, and fish eyes in the film may be reduced.

The lower limit of M _n of the entire polypropylene resin constituting the film is preferably 20000, more preferably 22000, still more preferably 24000, particularly preferably 26000, and most preferably 27000. When _Mn is 20000 or more, there are the advantages that stretching is easy, thickness unevenness is small, stretching temperature and heat setting temperature are easily raised, and thermal shrinkage is lowered. The upper limit of M _n of the entire polypropylene resin constituting the film is preferably 65000, more preferably 60000, still more preferably 55000, particularly preferably 53000, and most preferably 52000. When _Mn is 65000 or less, the effect of a low molecular weight component is more easily exhibited, and a low thermal shrinkage rate at a high temperature is likely to be obtained, or stretching may be facilitated.

The lower limit of M _w of the entire polypropylene resin constituting the film is preferably 250,000, more preferably 260000, still more preferably 270000, particularly preferably 280000, and most preferably 290000. When _Mw is 250,000 or more, there are the advantages that stretching becomes easy, thickness spots are reduced, stretching temperature and heat setting temperature are easily raised, and thermal shrinkage rate is lowered. The upper limit of M _w of the entire polypropylene resin constituting the film is preferably 500,000, more preferably 450,000, still more preferably 400,000, particularly preferably 380000, and most preferably 370000. M _w of sometimes becomes easy mechanical load is small extrusion and stretching When it is 500,000 or less.

  The lower limit of the melt flow rate (MFR) (230 ° C., 2.16 kgf) of the entire polypropylene resin constituting the film is preferably 1 g / 10 minutes, more preferably 1.2 g / 10 minutes, and even more preferably 1 0.4 g / 10 min, particularly preferably 1.5 g / 10 min, most preferably 1.6 g / 10 min. When the MFR is 1 g / 10 min or more, the mechanical load is small and stretching may be easy. The upper limit of the MFR of the entire polypropylene resin constituting the film is preferably 11 g / 10 minutes, more preferably 10 g / 10 minutes, still more preferably 9 g / 10 minutes, and particularly preferably 8.5 g / 10 minutes. It is. When the MFR is 11 g / 10 min or less, stretching may be facilitated, thickness unevenness may be reduced, and the stretching temperature and heat setting temperature may be easily increased, resulting in a lower thermal shrinkage rate.

When the gel permeation chromatography (GPC) integration curve of the entire polypropylene resin constituting the film is measured, the lower limit of the ratio of components having a molecular weight of 10,000 or less in the entire polypropylene resin is preferably 2% by mass, more preferably 2 0.5% by mass, more preferably 3% by mass, particularly preferably 3.3% by mass, and most preferably 3.5% by mass. When the ratio of the component having a molecular weight of 10,000 or less is 2% by mass or more, the effects of the present application such as a low heat shrinkage rate at a high temperature, which is an effect of a low molecular weight product, may be more easily obtained, and stretching may be facilitated. .
The upper limit of the ratio of components having a molecular weight of 10,000 or less in the entire polypropylene resin in the GPC integration curve is preferably 20% by mass, more preferably 17% by mass, still more preferably 15% by mass, and particularly preferably 14%. % By mass, most preferably 13% by mass. When the ratio of the component having a molecular weight of 10,000 or less is 20% by mass or less, stretching may be facilitated, thickness unevenness may be reduced, and the stretching temperature and heat setting temperature may be easily increased, resulting in a low thermal shrinkage rate.
Molecules with a molecular weight of 10,000 or less do not contribute to the entanglement between the molecular chains, and have the effect of loosening the entanglement between the molecules like a plasticizer. The inclusion of a specific amount of a component with a molecular weight of 10,000 or less facilitates the entanglement of molecules during stretching, and enables stretching with low stretching stress, resulting in low residual stress and low shrinkage at high temperatures. It is thought that.

The lower limit of the ratio of components having a molecular weight of 100,000 or less in the entire polypropylene resin in the GPC integration curve is preferably 35% by mass, more preferably 38% by mass, still more preferably 40% by mass, and particularly preferably 41%. % By mass, most preferably 42% by mass. When the ratio of the component having a molecular weight of 100,000 or less is 35% by mass or more, the effect of a low molecular weight product is likely to be exhibited, and a low heat shrinkage rate at a high temperature may be easily obtained or stretching may be facilitated.
The upper limit of the ratio of components having a molecular weight of 100,000 or less in the entire polypropylene resin in the GPC integration curve is preferably 65% by mass, more preferably 60% by mass, still more preferably 58% by mass, and particularly preferably 56% by mass. % By mass, most preferably 55% by mass. When the ratio of the component having a molecular weight of 100,000 or less is 65% by mass or less, stretching is facilitated, thickness unevenness is reduced, stretching temperature and heat setting temperature are easily increased, and heat shrinkage rate is easily reduced. May be.

  Conventionally, a polypropylene mainly composed of low molecular weight components could not be sufficiently stretched, but by using a polypropylene resin having such a characteristic molecular weight distribution, It is considered that the heat shrinkage rate at high temperatures can be lowered by the synergistic effect of high crystallinity and strong heat fixation. .

  A high molecular weight component and a low molecular weight component that are preferably used to obtain a polypropylene resin having such a molecular weight distribution characteristic will be described below.

(High molecular weight component)
The lower limit of MFR (230 ° C., 2.16 kgf) of the high molecular weight component is preferably 0.0001 g / 10 minutes, more preferably 0.0005 g / 10 minutes, and further preferably 0.001 g / 10 minutes. Particularly preferred is 0.005 g / 10 min. When the MFR of the high molecular weight component is 0.0001 g / 10 min or more, the production of the resin may actually be easy, or the fish eyes of the film may be reduced.
The MFR at 230 ° C. and 2.16 kgf, which is a high molecular weight component, is too small and may be difficult to measure in practice. When expressed in terms of MFR at a load 10 times that of 2.16 kgf (21.6 kgf), the preferred lower limit is 0.1 g / 10 minutes, more preferably 0.5 g / 10 minutes, and even more preferably 1 g / 10. Minute, particularly preferably 5 g / 10 minutes.
The upper limit of the MFR of the high molecular weight component is preferably 0.5 g / 10 min, more preferably 0.35 g / 10 min, still more preferably 0.3 g / 10 min, particularly preferably 0.2 g / min. 10 minutes, most preferably 0.1 g / 10 minutes. When the MFR of the high molecular weight component is 0.5 g / 10 min or less, many high molecular weight components are not necessary to maintain the MFR of the entire polypropylene resin, and the effect of the low molecular weight component is easily manifested and is low at high temperatures. A thermal contraction rate may be more easily obtained.

The lower limit of M _w of the high molecular weight component is preferably 500,000, more preferably 600,000, still more preferably 700,000, particularly preferably 800,000, and most preferably 1000000. Not require the amount of number of polymeric component to M _w of the high molecular weight component to maintain MFR of the whole polypropylene resin If it is 500,000 or more, the effect of the low molecular weight component is likely to express, low thermal shrinkage at high temperatures The rate may be more easily obtained.
The upper limit of M _w of the high molecular weight component is preferably 10000000, more preferably 8000000, still more preferably 6000000, and particularly preferably 5000000. If the _{Mw of the} high molecular weight component is 10000000 or less, the production of the resin may actually be easy, or the fish eyes of the film may be reduced.

The lower limit of the amount of the high molecular weight component is preferably 2% by mass, more preferably 3% by mass, still more preferably 4% by mass, and particularly preferably 5% by mass. When the amount of the high molecular weight component is 2% by mass or more, it is not necessary to increase the molecular weight of the low molecular weight component in order to maintain the MFR of the entire polypropylene resin, and a low heat shrinkage rate at high temperatures may be more easily obtained.
The upper limit of the amount of the high molecular weight component is preferably 30% by mass, more preferably 25% by mass, still more preferably 22% by mass, and particularly preferably 20% by mass. When the amount of the high molecular weight component is 30% by mass or less, the effect of the low molecular weight component is easily exhibited, and a low heat shrinkage rate at a high temperature may be more easily obtained. The ratio of the high molecular weight component to the entire polypropylene resin constituting the film is determined by performing peak separation from the molecular weight distribution curve measured using GPC, and the same applies to other components such as a low molecular weight component described later.

Here, as the high molecular weight component, a polypropylene resin having a long chain branching or a crosslinked structure can be used in place of the linear polypropylene resin, which is known as a high melt tension polypropylene, and is made by Borealis Corporation. There are “WB130HMS”, “WB135HMS” and the like.
(Low molecular weight component)

The lower limit of the low molecular weight component MFR (230 ° C., 2.16 kgf) is preferably 70 g / 10 min, more preferably 80 g / 10 min, still more preferably 100 g / 10 min, and particularly preferably 150 g / min. 10 minutes, most preferably 200 g / 10 minutes. When the MFR of the low molecular weight component is 70 g / 10 min or more, the crystallinity is improved, and a low heat shrinkage rate at a high temperature may be more easily obtained.
The upper limit of the MFR of the low molecular weight component is preferably 2000 g / 10 minutes, more preferably 1800 g / 10 minutes, still more preferably 1600 g / 10 minutes, particularly preferably 1500 g / 10 minutes, most preferably 1500 g / 10 minutes. When the MFR of the low molecular weight component is 2000 g / 10 min or less, it becomes easy to maintain the MFR in the entire polypropylene resin, and the film forming property may be excellent.

The lower limit of M _w of the low molecular weight component is preferably 50000, more preferably 53000, still more preferably 55000, particularly preferably 60000, and most preferably 70000. When the _{Mw of the} low molecular weight component is 50000 or more, it becomes easy to maintain the MFR in the entire polypropylene resin and the film forming property may be excellent.
The upper limit of the M _w of the low molecular weight component is preferably 170000, more preferably 165000, still more preferably 160000, particularly preferably 155000, and most preferably 150,000. When the _{Mw of the} low molecular weight component is 170000 or less, the crystallinity is improved, and a low heat shrinkage rate at a high temperature may be more easily obtained.

The lower limit of the amount of the low molecular weight component is preferably 40% by mass, more preferably 50% by mass, still more preferably 55% by mass, and particularly preferably 60% by mass. When the amount of the low molecular weight component is 40% by mass or more, a low heat shrinkage rate at a high temperature, which is an effect of the low molecular weight component, may be more easily obtained.
The upper limit of the amount of the low molecular weight component is preferably 98% by mass, more preferably 97% by mass, still more preferably 96% by mass, and particularly preferably 95% by mass. If the amount of the low molecular weight component is 98% by mass or less, it is not necessary to increase the molecular weight of the low molecular weight component in order to maintain the MFR in the entire polypropylene resin, and a low heat shrinkage rate at a high temperature can be easily obtained. is there.

  The lower limit of the MFR of the low molecular weight component / the MFR ratio of the high molecular weight component is preferably 500, more preferably 1000, still more preferably 2000, and particularly preferably 4000. When the MFR ratio of the low molecular weight component / MFR of the high molecular weight component is 500 or more, a low thermal shrinkage rate at high temperatures may be more easily obtained. The upper limit of the MFR ratio of the low molecular weight component / the MFR ratio of the high molecular weight component is preferably 1,000,000.

The high molecular weight component and the low molecular weight component may be a mixture of two or more resins corresponding to each component, and the blending amount in that case is a total amount.
In addition to the above high molecular weight component and low molecular weight component, a component having a molecular weight other than the low molecular weight component and high molecular weight component of the present invention may be added in order to adjust the MFR of the entire polypropylene resin. For example, polypropylene (hereinafter, referred to as a medium molecular weight component) having a M _w that is larger than the low molecular weight component and smaller than the high molecular weight component may be included. Further, preferably to regulate the like to stretchability easily loosened entanglement of molecular chains of less than M _{w 5} million in polypropylene, more preferably M _w 3 10,000 or less polypropylene resin, particularly preferably M _w 1 10,000 or less Polypropylene resin may be added.
The lower limit of the ratio of medium molecular weight component to the entire polypropylene resin constituting the film, depending on the M _w molecular weight component in used, is preferably 5 wt%, more preferably 10 wt%, more preferably 13 % By weight, particularly preferably 15% by weight, and most preferably 16% by weight. When the ratio of the medium molecular weight component is 5% by mass or more, fish eyes may be reduced or stretching may be facilitated.
The upper limit of the ratio of the medium molecular weight component to the entire polypropylene resin constituting the film is preferably 58% by mass, more preferably 56% by mass, still more preferably 54% by mass, and particularly preferably 52% by mass. Most preferably, it is 50 mass%. When the ratio of the medium molecular weight component is 58% by mass or less, stretching may be facilitated, thickness unevenness may be reduced, and the stretching temperature and heat setting temperature may be easily increased, resulting in a low thermal shrinkage rate.
The lower limit of the ratio of polypropylene having an M _{w of} less than 50,000 to the total polypropylene resin constituting the film is preferably 0% by mass, more preferably 1% by mass, still more preferably 2% by mass, and particularly preferably 3%. % By weight, most preferably 4% by weight. By adding a polypropylene having a M _{w of} less than 50,000, the effects of the present invention such as a low heat shrinkage at high temperatures may be more easily obtained.
The upper limit of the ratio of polypropylene having an _{Mw of} less than 50,000 to the total polypropylene resin constituting the film is preferably 20% by mass, more preferably 18% by mass, still more preferably 17% by mass, and particularly preferably 16%. % By mass, most preferably 15% by mass. When the ratio of the polypropylene having an _{Mw of} less than 50,000 is 20% by mass or less, stretching may be facilitated, and thickness unevenness may be reduced.
Polypropylene molecules having an _{Mw of} less than 50,000 are difficult to form entanglement between molecular chains, and have an effect of loosening the entanglement between molecules like a plasticizer. By including a specific amount of polypropylene component of less than 50,000 _Mw, it is easy to entangle the molecules at the time of stretching, and it is possible to stretch at a low stretching stress. As a result, the residual stress is also low and the shrinkage rate at high temperature is reduced. It is thought that it is made low.

  In order to achieve a favorable molecular weight distribution of the polypropylene resin using a high molecular weight component and a low molecular weight component, for example, when the molecular weight of the low molecular weight component used is low, the molecular weight of the high molecular weight component is increased. It is possible to adjust the molecular weight distribution by increasing the MFR and adjust the MFR so that it can be easily produced as a stretched film.

(Stereoregularity of polypropylene resin)
The lower limit of the isotactic mesopentad fraction (hereinafter sometimes referred to as mmmm), which is an index of the stereoregularity of the polypropylene resin constituting the film, is preferably 96%, more preferably 96.5%, More preferably, it is 97%. When mmmm is 96% or more, the crystallinity is improved, and the thermal shrinkage rate at a high temperature may be lower.
The upper limit of mmmm is preferably 99.5%, more preferably 99.3%, and still more preferably 99%. When mmmm is 99.5% or less, production may be facilitated in practice.

In the polypropylene resin constituting the film, it is preferable that heterogeneous bonds such as head-to-head bonds of propylene monomer are not observed. In addition, “a heterogeneous bond is not recognized” means that no peak is observed in ¹³ C-NMR.

  The lower limit of the isotactic meso average chain length (hereinafter referred to as “meso average chain length”) of the polypropylene resin constituting the film is preferably 100, more preferably 120, and still more preferably 130. When the meso average chain length is 100 or more, the crystallinity is improved, and the thermal shrinkage rate at a high temperature may be reduced. The upper limit of the meso average chain length of the polypropylene resin constituting the film is preferably 5000 from a practical aspect.

  The lower limit of the xylene soluble content of the polypropylene resin constituting the film is preferably 0.1% by mass from a practical aspect. The upper limit of the xylene-soluble content is preferably 7% by mass, more preferably 6% by mass, and further preferably 5% by mass. When the xylene-soluble content of the propylene resin is 7% by mass or less, the crystallinity is improved, and the thermal shrinkage rate at a high temperature may be reduced.

  The polypropylene resin constituting the film is most preferably a propylene homopolymer (complete homopolypropylene) obtained only from propylene monomer, but may be a copolymer of a propylene monomer and a small amount of monomer other than propylene monomer. . As the monomer species (copolymer monomer species) other than the propylene monomer, ethylene, butene, hexene, octene and the like can be used.

  The upper limit of the proportion of monomers other than the propylene monomer is preferably 0.1 mol%, more preferably 0.05 mol%, and still more preferably 0.01 mol%. When the proportion of the monomer other than the propylene monomer is 0.1 mol% or less, the crystallinity may be improved and the thermal shrinkage rate at high temperature may be reduced.

  In addition, when a conventional polypropylene film is used as a propylene homopolymer, it has an extremely narrow range of conditions that can be stretched, such as high crystallinity and a rapid drop in melt tension after melt softening. It is difficult to add a copolymer component (mainly ethylene) of about 0.5 mol%. However, in the polypropylene resin having the molecular weight distribution as described above, the decrease in tension after melt softening is moderate even if it contains little or no copolymerization component, and industrial stretching is possible.

(Production method of polypropylene resin)
The polypropylene resin is obtained by polymerizing propylene as a raw material using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. Among these, it is preferable to use a catalyst such as a Ziegler-Natta catalyst that is unlikely to contain heterogeneous bonds and can be polymerized with high stereoregularity.
As a polymerization method of propylene, a known polymerization method can be used, but a method of polymerizing in an inert solvent such as hexane, heptane, toluene, xylene, a method of polymerizing in liquid propylene or ethylene, or a gas. Examples thereof include a method in which a catalyst is added to propylene and ethylene and polymerization is performed in a gas phase state, or a method in which these are combined for polymerization.
The method for realizing the polypropylene having the molecular weight distribution of the present invention is not particularly limited, but it is necessary to substantially include a high molecular weight component and a low molecular weight component. For example, the high molecular weight component and the low molecular weight component may be separately polymerized and then mixed, or may be produced in a series of plants using a multistage reactor. In particular, a method is preferred in which a plant having a multi-stage reactor is used, and a high molecular weight component is first polymerized and then a low molecular weight component is polymerized in the presence thereof.

  In addition to the polypropylene resin and the like, additives and other resins may be added to the polypropylene film molding resin composition of the present invention as necessary, but the mass of these may be 30% by mass or less. preferable. Examples of the additive include an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a nucleating agent, an adhesive, an antifogging agent, a flame retardant, an antiblocking agent, and an inorganic or organic filler. Examples of other resins include polypropylene resins other than the polypropylene resin used in the present invention, random copolymers that are copolymers of propylene and ethylene and / or α-olefins having 4 or more carbon atoms, and various elastomers. Examples of the α-olefin having 4 or more carbon atoms include butene, hexene, octene and the like. These can be blended with polypropylene resin and a Henschel mixer, or master pellets prepared using a melt kneader in advance can be diluted with polypropylene to a predetermined concentration, or the total amount can be melt-kneaded in advance. Also good.

(Film physical properties)
The lower limit of the plane orientation coefficient of the polypropylene film of the present invention is preferably 0.0125, more preferably 0.0126, still more preferably 0.0127, and particularly preferably 0.0128. The upper limit of the plane orientation coefficient of the polypropylene film of the present invention is preferably 0.0155 as a realistic value, more preferably 0.0150, still more preferably 0.0148, and particularly preferably 0.0145. is there. The plane orientation coefficient can be adjusted by adjusting the draw ratio in the MD direction and the TD direction. When the plane orientation coefficient of the film is 0.0125 or more and 0.0155 or less, the thickness unevenness of the film is also good.

  The lower limit of the refractive index (Nx) in the MD direction of the polypropylene film of the present invention is preferably 1.502, more preferably 1.503, and still more preferably 1.504. The upper limit of Nx is preferably 1.520, more preferably 1.517, and even more preferably 1.515.

  The lower limit of the refractive index (Ny) in the TD direction of the polypropylene film of the present invention is preferably 1.523, and more preferably 1.525. The upper limit of Ny is preferably 1.535, more preferably 1.532.

  The lower limit of the refractive index (Nz) in the thickness direction of the polypropylene film of the present invention is preferably 1.480, more preferably 1.490, and still more preferably 1.501. The upper limit of Nz is preferably 1.510, more preferably 1.507, and even more preferably 1.505.

(Film crystallinity)
The polypropylene film of the present invention has the following highly crystalline characteristics.
The lower limit of the crystallinity of the polypropylene film of the present invention is preferably 55%, more preferably 56%, still more preferably 57%, particularly preferably 58%, most preferably 59%. . If the degree of crystallinity of the film is less than 55%, the thermal shrinkage at high temperatures may increase. The upper limit of the crystallinity of the polypropylene film of the present invention is preferably 85%, more preferably 80%, still more preferably 79%, particularly preferably 78%, and most preferably 77%. . When the crystallinity of the film exceeds 85%, realistic production may be difficult. The crystallinity of the film can be adjusted by techniques such as reducing or eliminating copolymerization monomers, increasing the amount of low molecular weight components, and setting the stretching temperature and heat setting temperature to a high temperature.

  The lower limit of the melting peak temperature of the polypropylene film of the present invention is preferably 168 ° C, more preferably 169 ° C. If the melting peak temperature of the film is 168 ° C. or higher, the thermal shrinkage at high temperatures may be small. The upper limit of the melting peak temperature of the polypropylene film of the present invention is preferably 180 ° C, more preferably 177 ° C, and further preferably 175 ° C. When the melting peak temperature of the film is 180 ° C. or lower, production may be facilitated in practice. The melting peak temperature can be adjusted by a technique such as reducing or eliminating the copolymerization monomer, setting the stretching temperature and the heat setting temperature to a high temperature.

Even if the conventional polypropylene film has a melting peak temperature in the vicinity of 170 ° C., the peak rise from around 140 ° C. when measured with a differential scanning calorimeter (hereinafter also referred to as DSC) ( Although the heat resistance at 140 ° C. could be expected, the heat shrinkage rate increased rapidly at 150 ° C. However, the polypropylene film of the present invention does not have a peak at 150 ° C., and the polypropylene film of the present invention is considered to have low heat shrinkage even at 150 ° C.
The polypropylene film of the present invention can maintain various physical properties even when exposed to an environment of 150 ° C. or higher, and can be used in a high-temperature environment that has not been considered with conventional polypropylene films. The melting start can be obtained from the DSC chart.

  The lower limit of the crystallinity at 150 ° C. is preferably 48%, more preferably 49%, still more preferably 50%, and particularly preferably 51%. When the degree of crystallinity at 150 ° C. is 48% or more, the thermal shrinkage rate at high temperatures may be smaller. The upper limit of the degree of crystallinity at 150 ° C. is preferably 85%, more preferably 80%, still more preferably 79%, and particularly preferably 78% from a practical aspect. The degree of crystallinity at 150 ° C. can be kept within the range by techniques such as reducing or eliminating the copolymerization monomer, increasing the low molecular weight component, and setting the stretching temperature and heat setting temperature to a high temperature.

The melting peak temperature (Tmp), the crystallinity of the film, and the crystallinity at 150 ° C. can be determined using a differential scanning calorimeter (DSC).
The melting endothermic peak temperature obtained when the temperature was raised from room temperature to 230 ° C. at a rate of 20 ° C./min was defined as Tmp. Then, the heat of fusion is obtained from the endothermic peak area, and the degree of crystallinity can be obtained by dividing the heat of fusion by 209 J / g which is the heat of fusion of the complete polypropylene crystal. Further, among the endothermic peak areas, the heat of fusion is obtained from the endothermic peak area of 150 ° C. or higher, and the heat of fusion is divided by 209 J / g, which is the heat of fusion of polypropylene complete crystal. Can be obtained. In addition, about the heat of fusion of a polypropylene complete crystal | crystallization, H.H. Bu, S .; Z. D. Cheng, B.M. The values described in Wunderlich et al., Makromoleculare Chemie, Rapid Communication, Vol. 9, page 75 (1988) were used, and the same values were used in the examples described later.

  The impact resistance of the polypropylene film largely depends on the thickness of the film, but when the commonly used thickness is 20 μm, the lower limit of the impact resistance (23 ° C.) of the polypropylene film of the present invention is preferably 0.5 J, More preferably, it is 0.6J. When the impact resistance of the film is 0.5 J or more, the film has sufficient toughness and does not break during handling. The upper limit of impact resistance may be 2J from a practical viewpoint, preferably 1.5J, and more preferably 1.2J. Impact resistance tends to decrease when there are many low molecular weight components, when the overall molecular weight is low, when there are few high molecular weight components, and when the molecular weight of high molecular weight components is low. These components can be adjusted to be within the range.

  When the polypropylene film is a biaxially stretched film, the lower limit of the Young's modulus (23 ° C.) in the MD direction is preferably 2 GPa, more preferably 2.1 GPa, still more preferably 2.2 GPa, particularly preferably 2.3 GPa, most preferably 2.4 GPa. The upper limit of the Young's modulus in the MD direction is preferably 4 GPa, more preferably 3.7 GPa, still more preferably 3.5 GPa, particularly preferably 3.4 GPa, and most preferably 3.3 GPa. When the Young's modulus in the MD direction is 2 GPa or more and 4 GPa or less, it may be practically easy to manufacture or the MD-TD balance may be improved.

When the polypropylene film is a biaxially stretched film, the lower limit of the Young's modulus (23 ° C.) in the TD direction is preferably 3.8 GPa, more preferably 4 GPa, still more preferably 4.2 GPa, and particularly preferably 4.3 GPa. The upper limit of the Young's modulus in the TD direction is preferably 8 GPa, more preferably 7.5 GPa, still more preferably 7 GPa, and particularly preferably 6.5 GPa. When the Young's modulus in the TD direction is 3.8 GPa or more and 8 GPa or less, it may be practically easy to manufacture or the MD-TD balance may be improved.
The Young's modulus can be increased by increasing the stretching ratio. In the case of MD-TD stretching, the stretching ratio in the MD direction is set lower, and the Young's modulus in the TD direction is increased by increasing the stretching ratio in the TD direction. The rate can be increased.

  The lower limit of the thickness unevenness of the 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 unevenness of the polypropylene film of the present invention is preferably 20%, more preferably 17%, still more preferably 15%, particularly preferably 12%, and most preferably 10%. When the thickness unevenness of the film is 0% or more and 20% or less, defects are unlikely to occur during post-processing such as coating and printing, and it is easy to use in applications that require precision.

The lower limit of the density of the polypropylene film of the present invention is preferably 0.910 g / cm ³ , more preferably 0.911 g / cm ³ , still more preferably 0.912 g / cm ³ , and particularly preferably 0.8. 913 g / cm ³ . When the density of the film is 0.910 g / cm ³ or more, the crystallinity is high and the thermal shrinkage rate may be small.
The upper limit of the density of the polypropylene film of the present invention is preferably 0.925 g / cm ^3, more preferably 0.922 g / cm ^3, more preferably from 0.920 g / cm ^3, particularly preferably 0. 918 g / cm ³ . When the density of the film is 0.925 g / cm ³ or less, production may be facilitated in practice. The density of the film can be increased by increasing the draw ratio and temperature, increasing the heat setting temperature, and further performing offline annealing.

(Method for producing polypropylene film)
The polypropylene film of the present invention may be a uniaxially stretched film in the longitudinal direction (MD direction) or the transverse direction (TD direction), but is preferably a biaxially stretched film. In the case of biaxial stretching, sequential biaxial stretching or simultaneous biaxial stretching may be used.
By producing a polypropylene film by stretching, a film having a low thermal shrinkage can be obtained even at 150 ° C., which could not be expected with a conventional polypropylene film.

Although the manufacturing method of the film of sequential biaxial stretching of the longitudinal stretch-lateral stretch which is the most preferable example is demonstrated below, the manufacturing method of a polypropylene film is not limited to this.
First, a polypropylene resin is heated and melted with a single or twin screw extruder and extruded onto a chill roll to obtain an unstretched sheet. The melt extrusion conditions are such that the resin temperature is 200 to 280 ° C., the sheet is extruded from a T-die and cooled and solidified by a cooling roll having a temperature of 10 to 100 ° C. Next, the film is stretched 3 to 8 times in the length direction (MD direction) with a stretching roll at 120 to 160 ° C., and subsequently 155 ° C. to 175 ° C., preferably 157 ° C. to 170 ° C. in the width direction (TD direction). Stretch 4 to 15 times at temperature.
Furthermore, heat treatment (heat setting) is performed while relaxing (relaxing) 1 to 15% at an ambient temperature of 165 to 175 ° C., preferably 166 to 173 ° C.
A roll film can be obtained by subjecting the polypropylene film thus obtained to corona discharge treatment on at least one side as necessary, and then winding it with a winder.

  The lower limit of the draw ratio in the MD direction is preferably 3 times, more preferably 3.5 times. If the draw ratio in the MD direction is less than 3 times, thickness unevenness may occur. The upper limit of the draw ratio in the MD direction is preferably 8 times, more preferably 7 times. If the stretching ratio in the MD direction exceeds 8 times, it may be difficult to continue stretching in the TD direction.

  The lower limit of the temperature at the time of stretching in the MD direction (hereinafter referred to as the stretching temperature) is preferably 120 ° C, more preferably 125 ° C, and further preferably 130 ° C. When the stretching temperature in the MD direction is less than 120 ° C., the mechanical load may increase, the thickness unevenness may increase, or the film may become rough. The upper limit of the stretching temperature in the MD direction is preferably 160 ° C, more preferably 155 ° C, and further preferably 150 ° C. A higher stretching temperature in the MD direction is preferable for lowering the thermal shrinkage, but may adhere to the roll and cannot be stretched.

  It is preferred to preheat the film before stretching in the TD direction. In order to quickly raise the film temperature to the stretching temperature in the TD direction, the preheating temperature (hereinafter referred to as the preheating temperature) is preferably set to be 10 to 15 ° C. higher than the stretching temperature in the TD direction.

  The lower limit of the draw ratio in the TD direction is preferably 4 times, more preferably 5 times, and even more preferably 6 times. If the draw ratio in the TD direction is less than 4 times, thickness unevenness may occur. The upper limit of the draw ratio in the TD direction is preferably 15 times, more preferably 14 times, and still more preferably 13 times. When the draw ratio in the TD direction exceeds 15 times, the thermal shrinkage rate may be increased or the film may be broken during stretching.

  The stretching in the TD direction can be performed at a higher temperature than the conventional polypropylene film, and the lower limit of the stretching temperature in the TD direction is preferably 155 ° C., more preferably 157 ° C. If the stretching temperature in the TD direction is less than 155 ° C., the film may be broken without being sufficiently softened or the heat shrinkage rate may be increased. The upper limit of the stretching temperature in the TD direction is preferably 175 ° C, more preferably 170 ° C. In order to lower the heat shrinkage rate, a higher temperature is preferable, but when the stretching temperature in the TD direction exceeds 175 ° C., low molecular components may melt and recrystallize, resulting in surface roughness and whitening of the film. .

  The stretched film is preferably heat-set by heat treatment. The heat setting can be performed at a temperature higher than that of a conventional polypropylene film, and the lower limit of the heat treatment temperature for performing the heat setting (hereinafter referred to as the heat setting temperature) is preferably 165 ° C., more preferably 166 ° C. . When the heat setting temperature is lower than 165 ° C., the heat shrinkage rate may be increased. In addition, a long time treatment is required to lower the heat shrinkage rate, and productivity may be inferior. The upper limit of the heat setting temperature is preferably 175 ° C, more preferably 173 ° C. When the heat setting temperature exceeds 175 ° C., low molecular weight components may melt and recrystallize, resulting in surface roughness and whitening of the film.

  It is preferable to relax during heat setting. The lower limit of the relaxation rate is preferably 1%, more preferably 2%. If the relaxation rate is less than 1%, the thermal shrinkage rate may increase. The upper limit of the relaxation rate is preferably 15%, more preferably 10%. If the relaxation rate exceeds 15%, the thickness unevenness may increase.

Further, in order to reduce the thermal shrinkage rate, the film produced in the above process can be once wound up into a roll and then annealed offline.
The lower limit of the annealing temperature (hereinafter referred to as offline annealing temperature) is preferably 160 ° C., more preferably 162 ° C., and further preferably 163 ° C. If the offline annealing temperature is lower than 160 ° C., the effect of annealing may not be obtained. The upper limit of the offline annealing temperature is preferably 175 ° C., more preferably 174 ° C., and further preferably 173 ° C. When the offline annealing temperature exceeds 175 ° C., the transparency may be lowered or the thickness unevenness may be increased.

  The lower limit of the time for annealing offline (hereinafter referred to as offline annealing time) is preferably 0.1 minutes, more preferably 0.5 minutes, and even more preferably 1 minute. If the offline annealing time is less than 0.1 minute, the effect of annealing may not be obtained. The upper limit of the offline annealing time is preferably 30 minutes, more preferably 25 minutes, and further preferably 20 minutes. If the offline annealing time exceeds 30 minutes, the productivity may decrease.

  Although the thickness of a film is set according to each use, Preferably the minimum of the thickness of a film is 2 micrometers, More preferably, it is 3 micrometers, More preferably, it is 4 micrometers. The upper limit of the thickness of the film is preferably 300 μm, more preferably 250 μm, still more preferably 200 μm, particularly preferably 150 μm, and most preferably 100 μm.

  The polypropylene film thus obtained is usually formed as a roll having a width of 2000 to 12000 mm and a length of 1000 to 50000 m, and is wound up into a roll. Furthermore, 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 polypropylene film of the present invention has excellent characteristics such as those described above which are not present in the prior art.
When the polypropylene film of the present invention is used as a packaging film, it can be thinned because of its high rigidity, and cost reduction and weight reduction can be achieved.
In addition, since the polypropylene film of the present invention has high heat resistance, it can be processed at high temperature during coating and printing, and it is possible to use a coating agent, an ink, a laminating adhesive, and the like, which are difficult to be used for production efficiency and conventionally used.
Furthermore, the polypropylene film of the present invention can also be used as an insulating film such as a capacitor and a motor, a back sheet of a solar cell, a barrier film of an inorganic oxide, and a base film of a transparent conductive film such as ITO.

  The present invention will be described in detail below based on examples, but the present invention is not limited to such examples. The measuring method of the physical property in an Example is as follows.

1) Melt flow rate (MFR, g / 10 min)
According to JIS K 7210, the measurement was performed at a temperature of 230 ° C. and a load of 2.16 kgf.

2) Molecular weight and molecular weight distribution The molecular weight and molecular weight distribution were determined on the basis of monodisperse polystyrene using gel permeation chromatography (GPC).
The columns and solvents used in the GPC measurement are as follows.
Solvent: 1,2,4-trichlorobenzene Column: TSKgel GMH _HR- H (20) HT × 3
Flow rate: 1.0 ml / min
Detector: RI
Measurement temperature: 140 ° C
Number average molecular weight (M _n ), mass average molecular weight (M _w ), Z average molecular weight (M _z ), and Z + 1 average molecular weight (M _{z + 1} ) are each eluted from the GPC curve obtained through the molecular weight calibration curve. The molecular weight (N _i ) of the molecular weight (M _i ) at the position is defined by the following formula.
Number average molecular weight: M _n = Σ (N _i · M _i ) / ΣN _i
Mass average molecular weight: M _w = Σ (N _i · M _i ² ) / Σ (N _i · M _i )
Z average molecular weight: M _z = Σ (N _i · M _i ³ ) / Σ (N _i · M _i ² )
Z + 1 average molecular weight: M _{z + 1} = Σ (N _i · M _i ⁴ ) / Σ (N _i · M _i ³ )
Molecular weight distribution: M _w / M _n , M _{z + 1} / M _n
The molecular weight at the peak position of the GPC curve was defined as M _p .
When the baseline is not clear, the baseline should be set in a range up to the lowest position on the high molecular weight side of the elution peak closest to the elution peak of the standard substance.
From the obtained GPC curve, two or more components having different molecular weights were subjected to peak separation. The molecular weight distribution of each component was assumed to be a Gaussian function, and the respective peak widths were set to be M _w / M _n = 4. The average molecular weight was calculated from the obtained curve of each component.
Moreover, from the GPC curve of the whole polypropylene resin which comprises a film, the ratio of the component used as the molecular weight of 10,000 or less in the whole polypropylene resin which comprises a film, and the ratio of the component used as a molecular weight of 100,000 or less were calculated | required.

3) Stereoregularity Measurement of mmmm and meso average chain length was performed using ¹³ C-NMR. mmmm is in accordance with the method described in Zambelli et al., Macromolecules, Vol. 6, 925 (1973). C. It was calculated according to the method described in Randall, “Polymer Sequence Distribution”, Chapter 2 (1977) (Academic Press, New York).
NMR measurement was performed at 110 ° C. using AVANCE 500 manufactured by BRUKER, dissolving 200 mg of a sample in an 8: 2 mixture of o-dichlorobenzene and heavy benzene at 135 ° C.

4) Heat elongation (%)
Heat elongation was performed by TMA measurement, and TMA measurement was performed using TMA-60 manufactured by Shimadzu Corporation. A strip was cut out from the film so that it had a length of 20 mm in the MD direction and a width of 4 mm in the TD direction. The distance between chucks was set to 10 mm, the dimensional change in the MD direction at a constant load of 0.5 kg / mm ² was measured at a heating rate of 5 ° C./min from room temperature, and the temperature of the sample at room temperature (23 ° C.) The rate of dimensional change in the MD direction of the sample at temperature was defined as the heating elongation E (%).

5) Density (g / cm ³ )
The density of the film was measured by a density gradient tube method according to JIS K7112.

6) Melting peak temperature (Tmp, ° C)
The heat was measured using a DSC-60 differential scanning calorimeter manufactured by Shimadzu Corporation. About 5 mg was cut out from the film as a sample, and the sample was sealed in an aluminum pan for measurement. The temperature was raised from room temperature to 230 ° C. at a rate of 20 ° C./min, and the melting peak temperature of the sample was defined as Tmp.

7) Crystallinity By obtaining the heat of fusion (ΔHm, J / g) from the endothermic peak area in the DSC melting profile and dividing the value of ΔHm by 209 J / g, which is the heat of fusion of the complete polypropylene crystal, the crystallinity. Asked.
Further, by obtaining the heat of fusion (ΔHm ′, J / g) from the endothermic peak area of 150 ° C. or higher in the DSC melting profile, and dividing the value of ΔHm ′ by 209 J / g, which is the heat of fusion of polypropylene complete crystal, The crystallinity in all samples at 150 ° C. was determined.

8) Cold xylene soluble part (CXS, mass%)
Dissolve 1 g of polypropylene sample in 200 ml of boiling xylene, allow to cool, recrystallize in a constant temperature water bath at 20 ° C. for 1 hour, and calculate the ratio of the mass dissolved in the filtrate to the original sample amount by CXS (mass%) It was.

9) Thermal contraction rate (%)
Measurement was performed in accordance with JIS Z 1712. That is, the polypropylene film was cut in the MD and TD directions with a width of 20 mm and a length of 200 mm, suspended in a hot air oven and heated for 5 minutes. The length after heating was measured, and the thermal contraction rate was determined by the ratio of the contracted length to the original length.

10) Impact resistance It measured at 23 degreeC using the Toyo Seiki Seisakusho film impact tester.

11) Young's modulus (GPa)
The Young's modulus in the MD and TD directions was measured at 23 ° C. in accordance with JIS K 7127.

12) Haze (%)
Measured according to JIS K 7105.

13) Refractive index It measured using the Atago Co., Ltd. Abbe refractometer. The refractive indexes along the MD and TD directions were Nx and Ny, respectively, and the refractive index in the thickness direction was Nz.

14) Plane Orientation Coefficient The plane orientation coefficient (P) was calculated from Nx, Ny, and Nz measured in 13) above using the following formula.
P = [(Nx + Ny) / 2] −Nz

15) Thickness spot A square sample having a length of 1 m was cut out from the wound film roll, and divided into 10 equal parts in the MD direction and the TD direction to prepare 100 measurement samples. The thickness was measured with a contact-type film thickness meter at the approximate center of the measurement sample.
The average value of the 100 points of data obtained was obtained, the difference between the minimum value and the maximum value (absolute value) was obtained, and the value obtained by dividing the absolute value of the difference between the minimum value and the maximum value by the average value was obtained. It was.

Example 1
As a polypropylene resin, a propylene homopolymer (Nippon Polypro Corp.) with M _w / M _n = 7.7, M _{z + 1} / M _n = 140, MFR = 5.0 / 10 min, mmmm = 97.3% ): Novatec (registered trademark) PP “SA4L” (hereinafter referred to as “PP-1”) was used. Extruded into a sheet form from a T-die at 250 ° C using a 60mm extruder, cooled and solidified with a cooling roll at 30 ° C, stretched 4.5 times in the length direction (MD direction) at 135 ° C, then both ends Is clipped and guided into a hot air oven, preheated at 170 ° C, stretched 8.2 times in the transverse direction (TD direction) at 160 ° C, and then relaxed at a relaxation rate of 6.7% at 168 ° C. And heat treated. Thereafter, one side of the film was subjected to corona treatment and wound up with a winder. The thickness of the film thus obtained is 20 μm, the characteristics of the polypropylene resin are shown in Tables 1 and 2, and the film forming conditions are shown in Table 3. As shown in Table 5, a film having a low thermal shrinkage and a high Young's modulus was obtained. The DSC chart of the stretched propylene film of Example 1 is shown in FIG.
(Example 2)
A film was obtained in the same manner as in Example 1 except that the thickness was 13 μm. Properties of the polypropylene resin are shown in Tables 1 and 2, and film forming conditions are shown in Table 3. Table 5 shows the physical properties of the obtained films.
(Example 3)
A film was obtained in the same manner as in Example 1 except that the thickness was 4 μm and the preheating temperature was 169 ° C. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 3, and physical properties of the obtained film are shown in Table 5.

Example 4
10 parts by weight of low molecular weight polypropylene having a molecular weight of 10,000 (high wax “NP105” manufactured by Mitsui Chemicals, Inc.) is added to 90 parts by weight of “PP-1” to make a total of 100 parts by weight, and a 30 mm twin screw extruder And kneaded to obtain pellets of the mixture “PP-2”. A film was obtained from the pellets in the same manner as in Example 1. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 3, and physical properties of the obtained film are shown in Table 5.

(Example 5)
Propylene alone with M _w / M _n = 4.6, M _{z + 1} / M _n = 22, MFR = 120 g / 10 min, mmmm = 98.1% with respect to 70 parts by weight of “PP-1”. 30 parts by weight of the polymer was added and dry blended to obtain a mixture “PP-3”. A film was obtained in the same manner as in Example 1 using “PP-3”. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 3, and physical properties of the obtained film are shown in Table 5.

(Example 6)
A film was obtained in the same manner as in Example 1 except that the above-mentioned “PP-1” was used, the preheating temperature was 173 ° C., the stretching temperature in the TD direction and the heat setting temperature were 167 ° C. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 3, and physical properties of the obtained film are shown in Table 5.

(Example 7)
A film was obtained in the same manner as in Example 4 except that the film was stretched 5.5 times in the length direction and 12 times in the transverse direction. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 3, and physical properties of the obtained film are shown in Table 5.

(Example 8)
The film produced in Example 1 was subjected to heat treatment (offline annealing) at 170 ° C. for 5 minutes in a tenter hot air oven. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 3, and physical properties of the obtained film are shown in Table 5.

Example 9
As a polypropylene resin, a propylene homopolymer having a M _w / M _n = 8.9, M _{z + 1} / M _n = 110, MFR = 3.0 g / 10 min, mmmm = 97.1% (Samsunthal Co., Ltd.) ) “HU300”) (hereinafter referred to as “PP-4”), except that the preheating temperature was 171 ° C., the stretching temperature in the TD direction was 161 ° C., and the heat setting temperature was 170 ° C. A polypropylene film was obtained by this method. The properties of the polypropylene resin are shown in Tables 1 and 2, the film forming conditions are shown in Table 3, and the physical properties are shown in Table 5.

  The polypropylene films described in Examples 1 to 9 had high rigidity and heat resistance, and there was little deformation of the film during printing.

(Comparative Example 1)
As a polypropylene resin, Sumitomo Nobrene manufactured by Sumitomo Chemical Co., Ltd. having M _w / M _n = 4, M _{z + 1} / M _n = 21, MFR = 2.5 g / 10 min, and ethylene content = 0.6 mol% ( Registered trademark) “FS2011DG3” (hereinafter referred to as “PP-5”), MD stretching temperature was 125 ° C., preheating temperature was 168 ° C., stretching temperature in the TD direction was 155 ° C., and heat setting temperature was 163 ° C. A film was obtained in the same manner as in Example 1. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 4, and physical properties of the obtained film are shown in Table 6. A DSC chart of the stretched propylene film of Comparative Example 1 is shown in FIG.

(Comparative Example 2)
A film was obtained in the same manner as in Comparative Example 1 except that the thickness was 12 μm and the preheating temperature was 167 ° C. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 4, and physical properties of the obtained film are shown in Table 6.

(Comparative Example 3)
A film was obtained in the same manner as in Comparative Example 1 except that the thickness was 4 μm and the preheating temperature was 165 ° C. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 4, and physical properties of the obtained film are shown in Table 6.

(Comparative Example 4)
A film was produced in the same manner as in Comparative Example 1, except that the preheating temperature was 171 ° C, the stretching temperature in the TD direction was 160 ° C, and the heat setting temperature was 165 ° C. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 4, and physical properties of the obtained film are shown in Table 6.

(Comparative Example 5)
As a polypropylene resin, a propylene homopolymer having M _w / M _n = 4.3, M _{z + 1} / M _n = 28, MFR = 0.5 g / 10 min, mmmm = 97.0% (hereinafter referred to as “PP- 6 ”) and a film was obtained under the same conditions as in Example 9. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, film forming conditions are shown in Table 4, and physical properties of the obtained film are shown in Table 6.

(Comparative Example 6)
As a polypropylene resin, Nippon Polypro Co., Ltd., which is a propylene homopolymer having M _w / M _n = 2.8, M _{z + 1} / M _n = 9.2, MFR = 30 g / 10 min, mmmm = 97.9% ) Manufactured by Novatec PP “SA03” (hereinafter referred to as “PP-7”), biaxial stretching was attempted in the same manner as in Example 1. However, the film could not be obtained by breaking at the time of stretching in the transverse direction. It was. Properties and the like of the polypropylene resin are shown in Tables 1 and 2, and film forming conditions are shown in Table 4.

  The polypropylene films described in Comparative Examples 1 to 5 had low rigidity and heat resistance, and the film was greatly deformed during printing.

The polypropylene film of the present invention can be widely used for packaging and industrial applications, but is particularly suitable for printing because it is excellent in heat resistance and dimensional stability.
In addition, since the polypropylene film of the present invention has high heat resistance, it can be processed at a high temperature during coating and printing, and the coating agent, ink, laminating adhesive, etc. that have been difficult to use conventionally can be produced. It can be used for polypropylene films.
Furthermore, it is also suitable for insulating films such as capacitors and motors, solar cell backsheets, inorganic oxide barrier films, and transparent conductive film base films such as ITO.

Claims (4)

TMA (Mechanical Thermal Analysis) measurement was performed under the conditions of a haze of 6% or less, a thermal shrinkage at 150 ° C. of 15% or less, a temperature rising rate of 5 ° C./min, and a load of 0.5 kg / mm ^2. A polypropylene film characterized by satisfying the formula (1) at a heating elongation E (%) in the MD direction of 120 ° C. to 150 ° C.
log (E) ≦ 0.0275T−2.4839 (1)
(However, T is temperature (° C))   The polypropylene film according to claim 1, wherein the lower limit of the isotactic mesopentad fraction of the polypropylene resin constituting the film is 96%, and the lower limit of the plane orientation coefficient of the film is 0.0125.   The polypropylene film according to claim 1 or 2, wherein the upper limit of the amount of copolymerization monomer of the polypropylene resin constituting the film is 0.1 mol%.   The polypropylene film according to any one of claims 1 to 3, wherein the polypropylene resin constituting the film has a normal-temperature xylene soluble content of 7% by mass or less.