JP5842397B2 - Polyolefin resin composition, film, packaging material, multi-chamber container and lid material - Google Patents

Description

  The present invention relates to a polyolefin-based resin composition, a film obtained by using the resin composition, a packaging material, a multi-chamber container, and a lid material.

  From the viewpoint of protecting the contents, packaging bags and packaging containers are required to have a high peel strength and high sealing performance so that the contents do not leak due to the seal part being peeled off during transportation or handling. . On the other hand, if the peel strength is too high, it may be difficult to open the seal portion by hand, and the contents may pop out at the time of opening, resulting in a decrease in easy peelability (openability). In this way, packaging materials used for packaging bags and packaging containers are required to have a trade-off between sealing performance and easy peelability (openability). Various packaging films have been studied and proposed so far. Has been. For example, as a packaging material film using a polyolefin-based polymer, Patent Document 1 discloses, as a sealing layer, ethylene / α- having a monomer unit content of 75 to 95 mol% based on a polypropylene resin and ethylene. A package comprising a composition with an olefin random copolymer is described. Patent Document 2 discloses that an ethylene / α-olefin random copolymer having an ethylene-based monomer unit content of 70 to 90 mol% and a propylene-based monomer unit content of 80 to 99%. A laminated film comprising a composition of mol% of a propylene / α-olefin random copolymer and polyethylene is described.

Japanese Patent Laid-Open No. 61-246061 JP-A-10-264332

  Usually, a film composed of a composition of a linear ethylene-α-olefin random copolymer having a monomer unit based on ethylene of 95 to 99 mol% and a polypropylene resin has a high peel strength, It is difficult to use as an easily peelable film. Therefore, in patent document 1 and patent document 2, easy peelability is expressed using the ethylene-alpha-olefin random copolymer with few monomer unit content based on ethylene. However, the easily peelable film described in Patent Document 1 and Patent Document 2 uses an ethylene-α-olefin random copolymer with a small content of monomer units based on ethylene, and therefore has a low melting point and heat resistance. Further improvements are required in terms of sex. Under such circumstances, the problem to be solved by the present invention consists of a polyolefin-based resin composition suitable for producing a film having an excellent balance between easy peeling and sealing properties and excellent heat resistance, and the resin composition. It is providing the film which has a sealing layer, a packaging material, and a lid | cover material.

That is, the first of the present invention is a polyolefin resin composition containing the following component (A) and component (B), wherein the total amount of component (A) and component (B) is 100% by weight: The polyolefin resin composition wherein the content of the component (A) is more than 20% by weight and 95% by weight or less, and the content of the component (B) is 5% by weight or more and less than 80% by weight.
(A): Polyethylene resin satisfying the following requirements (a1), (a2) and (a3) (a1): The content of monomer units based on ethylene is 95 mol% or more (however, it constitutes a polyethylene resin) (A2): The number of branches having 5 carbon atoms (N _C5 ) measured by ¹³ C-NMR is less than 0.1 per 1000 carbon atoms. (A3): Flow activation energy (Ea) is 40 kJ / mol or more (B): Polypropylene resin The second aspect of the present invention is that the component (A) is a monomer based on ethylene. It is the said polyolefin resin composition which is an ethylene-alpha-olefin copolymer which has a unit and the monomer unit based on a C3-C20 alpha olefin, and satisfies the following requirements (a4).
(A4): Molecular weight distribution (Mw / Mn) is 5 to 25 In the third aspect of the present invention, the component (B) is a propylene homopolymer or a propylene-based monomer unit of 90% by weight or more. It is a polyolefin-type resin composition which is a propylene-type random copolymer containing.
A fourth aspect of the present invention is a polyolefin resin composition containing a polyethylene resin (X) and a polypropylene resin (Y), wherein the content of the polyethylene resin (X) is more than 20% by weight and 95% by weight. %, And the content of the polypropylene resin (Y) is 5% by weight or more and less than 80% by weight (provided that the total amount of the polyethylene resin (X) and the polypropylene resin (Y) is 100% by weight) The polyolefin resin composition satisfies the following requirements (x1) and (x2).
(X1): The number of branches having 6 or more carbon atoms (N _LCB ) measured by ¹³ C-NMR is 0.01 or more per 1000 carbon atoms, and the number of branches having 5 carbon atoms (N _C5 ) is a carbon atom. Less than 0.1 per 1000 pieces (x2): Melt tension at 230 ° C. (MT; unit is cN) is 1.5 cN or more The fifth aspect of the present invention is the polyolefin system described above It is a film made of a resin composition.
6th of this invention is a multilayer film which has a sealing layer which consists of a polyolefin resin composition as described above, 7th of this invention is the said film which is a packaging material.
The eighth aspect of the present invention is a multi-chamber container comprising the film described above.
The ninth of the present invention is the film as a lid material.
A tenth aspect of the present invention is a container formed by sealing the lid member and a polyolefin resin container main body.
An eleventh aspect of the present invention is a container in which the polyolefin resin container body described above is made of a polyethylene resin or a polypropylene resin.
The twelfth aspect of the present invention includes two different regions constituted by a heat seal temperature range of 15 ° C. or higher and a peel strength range in which the difference between the maximum value and the minimum value of the peel strength is less than 1.5 N / 15 mm width. Have
The difference in average peel strength between the respective regions is a film having a width of 2.0 N / 15 mm or more.

  According to the present invention, there is provided a polyolefin-based resin composition suitable for producing a film having an excellent balance between easy peelability and sealing property and excellent heat resistance, a film having a sealing layer made of the resin composition, a packaging material, and a lid material. Can be provided.

Schematic showing one embodiment of a multi-chamber container according to the present invention

One aspect of the present invention is a polyolefin resin composition containing the following component (A) and component (B), wherein the total amount of component (A) and component (B) is 100% by weight: The polyolefin resin composition wherein the content of the component (A) is more than 20% by weight and 95% by weight or less, and the content of the component (B) is 5% by weight or more and less than 80% by weight.
(A): Polyethylene resin satisfying the following requirements (a1), (a2) and (a3) (a1): The content of monomer units based on ethylene is 95 mol% or more (however, it constitutes a polyethylene resin) (A2): The number of branches having 5 carbon atoms (N _C5 ) measured by ¹³ C-NMR is less than 0.1 per 1000 carbon atoms. (A3): Flow activation energy (Ea) is 40 kJ / mol or more (B): Polypropylene resin

  The component (A) polyethylene resin is a polymer having a monomer unit based on ethylene as a main unit, and is produced by a high-pressure low-density polyethylene produced by a high-pressure radical polymerization method, a coordination polymerization method, or the like. Examples thereof include an ethylene-α-olefin copolymer. Component (A) is preferably an ethylene-α-olefin copolymer. The ethylene-α-olefin copolymer is an ethylene-α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms, and is a monomer unit based on ethylene and carbon. It is a copolymer having a monomer unit based on an α-olefin having 3 to 20 atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4 -Methyl-1-pentene, 4-methyl-1-hexene and the like are mentioned, and 1-hexene and 1-octene are preferable. Moreover, the said C3-C20 alpha olefin may be used independently and may use 2 or more types together.

  Examples of the ethylene-α-olefin copolymer include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, and an ethylene-1 -Butene-1-hexene copolymer, ethylene-1-butene-1-octene copolymer and the like, preferably ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1 -Butene-1-hexene copolymer and ethylene-1-butene-1-octene copolymer.

  From the viewpoint of suppressing stickiness of the film and heat resistance, the content of monomer units based on ethylene in the polyethylene resin of component (A) is 100 mol of the total of all monomer units constituting the polyethylene resin. %, It is 95 mol% or more, preferably 96 mol% or more. Therefore, the content of the monomer unit based on the α-olefin having 3 to 20 carbon atoms is 5 mol% or less, preferably 4 mol% or less, more preferably 3 mol% or less. From the viewpoint of the flexibility of the film, when the total of all the monomer units constituting the polyethylene resin is 100 mol%, it is preferably 99 mol% or less. Therefore, the content of the monomer unit based on the α-olefin having 3 to 20 carbon atoms is preferably 1 mol% or more.

The polyethylene-based resin of the component (A) has a branch number of 5 carbon atoms (hereinafter sometimes referred to as “N _C5 ”) measured by ¹³ C-NMR of less than 0.1 per 1000 carbon atoms. It is. N _C5 is preferably less than 0.05 per 1000 carbon atoms, more preferably less than 0.01 and most preferably zero.

The polyethylene-based resin of the component (A) has a branch number of 6 or more carbon atoms (hereinafter sometimes referred to as “N _LCB ”) measured by ¹³ C-NMR of 0.01 per 1000 carbon atoms. The above is preferable. N _LCB of 0.01 or more is preferable because the peelability is good. N _LCB is preferably at least 0.1 per 1000 carbon atoms. From the viewpoint of enhancing the sealing performance, N _LCB is preferably 1 or less per 1000 carbon atoms, more preferably 0.7 or less.

N _LCB and N _C5 of component (A) are adjusted according to polymerization conditions such as selection of a production method such as gas phase polymerization and slurry polymerization, selection of a polymerization catalyst, polymerization temperature, polymerization pressure, comonomer type and addition amount. be able to. For example, when the hydrogen concentration or the ethylene pressure is lowered, the N _{LCB of the} ethylene-α-olefin copolymer is increased. Moreover, _NLCB can be increased by carrying out prepolymerization.

N _LCB can be obtained by the following method. From a ¹³ C-NMR spectrum using a 600 MHz, cryoprobe with an exponential applied to the window function, the sum of all peaks observed at 5 to 50 ppm is 1000, and a peak near 38.09 to 38.27 ppm. Let A be the peak area of a peak having a top. This A is a value corresponding to the number of branched methine carbons having 4 or more carbon atoms. In the ¹³ C-NMR spectrum in which Gaussian was applied to the window function in order to separate the peaks of branched methine carbon having 5 or less carbon atoms and branched methine carbon having 6 or more carbon atoms, and 38.2 to 38. The peak observed at 27 ppm is B, and the peak observed at 38.21 to 38.09 ppm is C. N _LCB was determined from the following equation.
N _LCB = A × B / (B + C)
N _C5 can be obtained by the following method. In a ¹³ C-NMR spectrum in which an exponential is applied to the window function, the sum of all peaks observed at 5 to 50 ppm is 1000, and the peak area of a peak having a peak top near 32.5 to 32.7 ppm Asked. The peak area is a value corresponding to the number of branched methylene carbons having 5 carbon atoms (C ^** in the following structural formula).
・ ・ ・ ・ CH ₂ -CH-CH ₂ -...
└CH ₂ -CH ₂ -C ^** H ₂ -CH ₂ -CH ₃
In addition, since the position of the peak derived from the methine carbon to which the branch having 5 or more carbon atoms is bonded may be deviated depending on the measurement apparatus and measurement conditions, the standard is usually measured for each measurement apparatus and measurement conditions. To decide. In the spectrum analysis, it is preferable to use a negative exponential function as the window function.

  From the viewpoint of easy releasability, the flow activation energy (Ea) of the polyethylene-based resin of the component (A) is 40 kJ / mol or more, preferably 50 kJ / mol or more, more preferably 55 kJ / mol or more. Yes, more preferably 60 kJ / mol or more. From the viewpoint of hermeticity, Ea is preferably 100 kJ / mol or less, and more preferably 90 kJ / mol or less. The Ea can be changed, for example, by the hydrogen concentration or ethylene pressure during polymerization. When the hydrogen concentration or ethylene pressure is lowered, the Ea of the ethylene-α-olefin copolymer increases.

The flow activation energy (Ea) is a master curve showing the dependence of the melt complex viscosity (unit: Pa · sec) at 190 ° C. on the angular frequency (unit: rad / sec) based on the temperature-time superposition principle. Is a numerical value calculated by the Arrhenius equation from the shift factor (a _T ) at the time of creating the value, and is a value obtained by the following method. That is, the melt complex viscosity-angular frequency curve of the ethylene-α-olefin copolymer at temperatures of 130 ° C., 150 ° C., 170 ° C. and 190 ° C. (T, unit: ° C.) (the unit of melt complex viscosity is Pa · sec. The unit of the angular frequency is rad / sec.), Based on the temperature-time superposition principle, for each melt complex viscosity-angular frequency curve at each temperature (T), The shift factor (a _T ) at each temperature (T) obtained when superposed on the melt complex viscosity-angular frequency curve of the coalescence is obtained, and each temperature (T) and the shift factor at each temperature ( _T ) are obtained. From (a _T ), a first-order approximate expression (formula (I) below) of [ln (a _T )] and [1 / (T + 273.16)] is calculated by the method of least squares. Next, Ea is obtained from the slope m of the linear expression and the following expression (II).
ln (a _T ) = m (1 / (T + 273.16)) + n (I)
Ea = | 0.008314 × m | (II)
a _T : Shift factor Ea: Activation energy of flow (unit: kJ / mol)
T: Temperature (unit: ° C)
For the calculation, commercially available calculation software may be used. As the calculation software, Rheos V. manufactured by Rheometrics is used. 4.4.4.
The shift factor (a _T ) is obtained by moving the logarithmic curve of the melt complex viscosity-angular frequency at each temperature (T) in the log (Y) = − log (X) axis direction (however, the Y axis Is the complex viscosity of the melt, and the X axis is the angular frequency.), And the amount of movement when superposed on the melt complex viscosity-angular frequency curve at 190 ° C., in the superposition, melting at each temperature (T) The logarithmic curve of complex viscosity-angular frequency shifts the angular frequency by a _T times and the melt complex viscosity by 1 / a _T times for each curve. Moreover, the correlation coefficient when calculating | requiring (I) Formula by the least squares method from the value of four points | pieces, 130 degreeC, 150 degreeC, 170 degreeC, and 190 degreeC is usually 0.99 or more.

  The melt complex viscosity-angular frequency curve is measured using a viscoelasticity measuring apparatus (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), and usually geometry: parallel plate, plate diameter: 25 mm, plate interval: 1. It is performed under the conditions of 5 to 2 mm, strain: 5%, angular frequency: 0.1 to 100 rad / sec. The measurement is performed in a nitrogen atmosphere, and it is preferable that an appropriate amount (for example, 1000 ppm) of an antioxidant is added to the measurement sample in advance.

The density of the polyethylene resin as the component (A) is usually 900 to 950 kg / m ³ . Said seal degree of heat resistance, blocking, from the viewpoint of the stability of the peel strength, preferably from ^{910kg / m 3 ~940kg / m 3} , more preferably ^{920kg / m 3 ~930kg / m 3} . In addition, a density is measured in accordance with the underwater substitution method prescribed | regulated to JISK7112-1995 using the sample which annealed as described in JISK6760-1995.

  The melt flow rate (MFR) of the polyethylene-based resin of the component (A) is usually 0.01 to 50 g / 10 minutes, and preferably 5 g / 10 minutes or less, more preferably from the viewpoint of improving the sealing performance. 3 g / 10 min or less. MFR is measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N by the method defined in JIS K7210-1995.

  From the viewpoint of film processability, the molecular weight distribution (Mw / Mn) of the polyethylene resin of component (A) is preferably 5 or more, more preferably 6 or more, still more preferably 7 or more, particularly preferably. Is 8 or more. Further, from the viewpoint of the mechanical strength of the film, the molecular weight distribution of the component (A) polyethylene resin is preferably 25 or less, more preferably 20 or less. The molecular weight distribution (Mw / Mn) is a value obtained by calculating a polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) by gel permeation chromatography, and dividing Mw by Mn. (Mw / Mn). The Mw / Mn can be changed, for example, depending on the hydrogen concentration or polymerization temperature during polymerization. When the hydrogen concentration or polymerization temperature is increased, the Mw / Mn of the ethylene-α-olefin copolymer increases.

It is preferable that g * defined by following formula (II) is 0.70-0.95 about the polyethylene-type resin of a component (A).
g * = [η] / ([η] _GPC × g _SCB *) (II)
[Wherein [η] represents the intrinsic viscosity (unit: dl / g) of the polyethylene resin, and is defined by the following formula (II-I). It was defined by the following formula (II-II). g _SCB * is defined by the following formula (II-III).
[Η] = 23.3 × log (ηrel) (II-I)
(In the formula, ηrel represents the relative viscosity of the polyethylene resin.)
[Η] _GPC = 0.00046 × Mv ^0.725 (II-II)
(In the formula, Mv represents the viscosity average molecular weight of the polyethylene resin.)
g _SCB * = (1-A) ^1.725 (II-III)
(In formula, A measures the content of the short chain branch in a polyethylene-type resin, and is defined by following formula (II-V).
A = ((12 * n + 2n + 1) * y) / ((1000-2y-2) * 14 + (y + 2) * 15 + y * 13) (II-V)
In the formula, n represents the number of short-chain branched carbon atoms (for example, n = 2 when butene is used as the α-olefin, n = 4 when hexene is used), and y is from NMR or infrared spectroscopy. It represents the number of short chain branches per 1000 carbon atoms required. ]]
Regarding g *, the following literature was referred to: Developments in Polymer Characterisation-4, JV. Dawkins, Ed., Applied Science, London, 1983, Chapter. I, “Characterization. Long Chain Branching in Polymers, "by Th. G. Scholte

[Η] _GPC represents the intrinsic viscosity (unit: dl / g) of a polymer that is assumed to have the same molecular weight distribution as that of the polyethylene-based resin and that the molecular chain is linear.
g _SCB * represents a contribution to g * caused by introducing a short chain branch into a polyethylene resin.
As the formula (II-II), the formula described in Journal of Polymer Science, 36, 130 (1959) pp. 287-294 by LH Tung was used.

  The relative viscosity (ηrel) of the polyethylene resin can be measured by the following method. A sample solution is prepared by dissolving 100 mg of a polyethylene-based resin at 135 ° C. in 100 ml of tetralin containing 0.5% by weight of butylhydroxytoluene (BHT) as a thermal deterioration preventing agent, and using the Ubbelohde viscometer, BHT is calculated from the falling time of the blank solution composed of tetralin containing only 0.5% by weight as a thermal deterioration inhibitor.

で定義され、a＝０．７２５とした。 The viscosity-average molecular weight (Mv) of the polyethylene resin is the following formula (II-IV)

And a = 0.725.

  g * is an index representing the degree of contraction of a molecule in a solution caused by long chain branching. When the amount of long chain branching per molecular chain is large, the contraction of the molecular chain increases. Get smaller. The g * of the polyethylene resin is preferably 0.70 to 0.95, more preferably 0.75 to 0.90, and still more preferably 0.75 to 0.85, from the viewpoint of easy peelability. It is. When g * is 0.95 or less, long-chain branching is sufficiently contained, so that the peel strength does not become too high, and the easy peelability is excellent, which is preferable. In addition, when g * is 0.70 or more, the molecular chain spreads sufficiently when a crystal is formed, so that the probability of tie molecule formation is high, the relaxation time of the molecular chain is short, and the sealing property is improved. Excellent and preferred.

  Examples of the polyethylene resin preferably used as the component (A) include polyethylene resins described in JP-A-2008-106264.

  The polypropylene resin of component (B) can be produced by a method of homopolymerizing propylene, a method of copolymerizing propylene and another copolymerizable comonomer, or the like. As the polymerization catalyst, for example, (a) a Ti—Mg-based catalyst comprising a solid catalyst component containing magnesium, titanium and halogen as essential components, and (b) a solid catalyst component comprising magnesium, titanium and halogen as essential components, Examples thereof include a catalyst system in which an organoaluminum compound is combined with a third component such as an electron donating compound as required, and (c) a metallocene catalyst.

The polypropylene resin of component (B) may be a homopolymer of propylene (homopolypropylene), and is mainly composed of propylene and a small amount of a comonomer copolymerizable therewith, for example, 20% by weight or less, preferably 10% by weight. It may be copolymerized at the following ratio. When the polypropylene resin is a copolymer, the amount of comonomer is preferably 2% by weight or more, more preferably 3% by weight or more.
Moreover, when using the film which has a sealing layer which consists of polyolefin resin compositions of this invention, and heat-seals it to a homo polypropylene resin sheet, it is preferable that a component (B) is a homo polypropylene.
Furthermore, when the film having a sealing layer made of the polyolefin resin composition of the present invention is used by heat sealing to a polyethylene resin sheet, the component (B) is preferably a propylene copolymer containing a small amount of a comonomer.

  When the component (B) polypropylene resin is a copolymer, examples of the comonomer include ethylene and an α-olefin having 4 to 20 carbon atoms. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene and 4-methyl. Examples include -1-pentene and 4-methyl-1-hexene. From the viewpoint of copolymerization, the comonomer is preferably ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene, and more preferably ethylene, 1-butene and 1-hexene. Moreover, the said ethylene and C4-C20 alpha olefin may be used independently, and may use 2 or more types together.

  When the polypropylene resin as the component (B) is a copolymer, the copolymer may be a random copolymer or a block copolymer. A preferable copolymer is a random copolymer, and specific examples include a propylene / ethylene random copolymer and a propylene / 1-butene random copolymer. In the propylene / ethylene random copolymer and propylene / 1-butene random copolymer, the content of the monomer unit based on ethylene and the content of the monomer unit based on 1-butene are, for example, “Polymer Analysis Handbook” "(1995, published by Kinokuniya Shoten), page 616, can be obtained by measuring infrared (IR) spectrum.

  The polypropylene resin of component (B) has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 21.18 N in accordance with JIS K 7210 within a range of 0.1 to 200 g / 10 minutes. It is preferable that it exists in the range of 0.5-50 g / 10min, and it is more preferable from the point of a moldability.

  The stereoregularity of the component (B) polypropylene resin may be any of isotactic, syndiotactic and atactic. In the present invention, a syndiotactic or isotactic polypropylene resin is preferably used from the viewpoint of heat resistance.

  The polypropylene resin of component (B) is, for example, a solution polymerization method using an inert solvent typified by a hydrocarbon compound such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, It can be produced by a bulk polymerization method using a monomer as a solvent or a gas phase polymerization method in which a gaseous monomer is polymerized as it is. Polymerization by these methods may be carried out batchwise or continuously.

The polyolefin resin composition of the present invention contains the polyethylene resin as the component (A) and the polypropylene resin as the component (B). The content of component (A) and component (B) in the resin composition is such that when the total amount of component (A) and component (B) is 100% by weight, the content of component (A) is 20% by weight. More than 95% by weight and the content of component (B) is 5% by weight or more and less than 80% by weight.
In order to obtain a better balance between easy peeling and sealing properties, the content of the component (A) is preferably 25% by weight or more and 80% by weight or less, and the content of the component (B) is 20% by weight or more and 75%. % By weight or less. A large content of component (A) is advantageous from the viewpoint of flexibility or molding processability, and a high content of component (B) is advantageous from the viewpoint of heat resistance.

In the polyolefin resin composition of the present invention, when the content of the component (A) is 40 wt% or more and 80 wt% or less, and the content of the component (B) is 20 wt% or more and 60 wt% or less, the above A film having a sealing layer made of a resin composition has a heat sealing temperature range of 15 ° C. or higher, and a difference between the maximum value and the minimum value of peel strength is less than 1.5 N / 15 mm width in applications where the sealing layers are heat-sealed. Having two different regions composed of a range of peel strengths that are
Since the difference of the average peel strength of each area | region becomes a film which is 2.0 N / 15mm width or more, it is preferable. More preferably, the content of component (A) is 50 wt% or more and 75 wt% or less, and the content of component (B) is 25 wt% or more and 50 wt% or less.

Having two different regions composed of a heat seal temperature range of 15 ° C. or higher and a peel strength range where the difference between the maximum and minimum peel strength is less than 1.5 N / 15 mm width,
A film having a difference in average peel strength in each region of 2.0 N / 15 mm width or more is preferable because it is a single film and different peel strengths can be obtained by changing the heat seal temperature.
As a method for determining the region, for example, heat sealing is performed by changing the temperature by 5 ° C., the peel strength is measured at each heat seal temperature, and the difference between the maximum value and the minimum value of the peel strength is 1.5 N / 15 mm width. Identify the maximum and minimum heat seal temperatures that will be less than A case where the difference between the maximum value and the minimum value of the heat seal temperature is 15 ° C. or more is defined as one region.
When sealing the sealing layers of the film, it is preferable to have the two different regions, and the difference in average peel strength between the regions is 2.0 N / 15 mm width or more.
Further, when the sealing layers are heat-sealed, it is preferable that the average peel strength of each region is 3 N / 15 mm width to 15 N / 15 mm width.
In applications where a film having a sealing layer made of the polyolefin resin composition of the present invention is heat-sealed between sealing layers, the difference between the heat seal temperature range of 15 ° C. or higher and the maximum and minimum peel strength is 1.5 N. / Has two different regions composed of a range of peel strengths that are less than 15 mm wide,
In order to obtain a film having a difference in average peel strength in each region of 2.0 N / 15 mm width or more, preferably a difference in melting point between the polyethylene resin of component (A) and the polypropylene resin of component (B) Is less than 30 ° C.
From the same viewpoint, preferably, the density of the polyethylene-based resin of the component (A) is 915 kg / m ³ or more.
From the same point of view, the component (B) polypropylene resin is preferably a propylene random copolymer.

Moreover, the film which has a sealing layer which consists of a polyolefin resin composition of this invention can be used for a multi-chamber container. A multi-chamber container has two or more spaces (accommodating chambers) separated from each other in one container. The storage chambers are separated by a heat-sealed part (seal part).
As shown in FIG. 1, the multi-chamber container is overlapped so that the sealing layers of the film are heat-sealed, and heat-seal the outer peripheral part 2 forming the container and the part 3 separating the storage chambers. Manufactured.
A multi-chamber container, for example, contains a plurality of substances (drugs, etc.) that cause interaction when mixed in separate storage chambers, so that a plurality of substances are not mixed during storage in one container. Can be saved. At the time of use, the substances accommodated in the different accommodating chambers are mixed by communicating the seal portions separating the accommodating chambers. Therefore, the seal part that separates the storage chambers of the multi-chamber container has a sealing property that allows the storage chambers to be isolated without being connected to each other during storage. By applying a strong pressure to the chamber, it is required that at least a part of the seal portion is peeled off and has easy peelability (openability) that allows communication between the storage chambers, and the balance between sealing performance and easy peelability is excellent. Is required.
In addition, even when a strong pressure is applied to any of the storage chambers during use, the outer peripheral seal portion that forms the container is required to maintain a sealed state.
This multi-chamber container is expected to spread mainly in the pharmaceutical field.

When a film having a seal layer made of the polyolefin resin composition of the present invention is used in a multi-chamber container, the content of the component (A) in the resin composition is preferably more than 20% by weight and 40% by weight or less. The content of the component (B) is preferably 60% by weight or more and less than 80% by weight, more preferably the content of the component (A) is more than 20% by weight and 30% by weight or less. ) Content is 70% by weight or more and less than 80% by weight. When manufacturing a multi-chamber container using a film having a sealing layer made of the above resin composition, the outer periphery forming the container is heat-sealed at a high temperature, so that a strong pressure is applied to the storage chamber when the multi-chamber container is used Even if added, the seal part of the outer peripheral part does not peel, the sealed state is maintained, and the seal part that separates the storage chambers is heat-sealed at a low temperature, so that the balance between sealability and easy peelability is excellent Since it can be used, it is preferable.
When a film having a sealing layer made of the polyolefin resin composition of the present invention is used for a multi-chamber container, from the same viewpoint, preferably, the melting point of the polyethylene resin of component (A) and the polypropylene resin of component (B) Is less than 30 ° C.
From the same viewpoint, when the film having the sealing layer made of the polyolefin resin composition of the present invention is used for a multi-chamber container, the density of the polyethylene resin of the component (A) is preferably 915 kg / m ³ or more.
From the same point of view, the component (B) polypropylene resin is preferably a propylene random copolymer.

The film suitable for the multi-chamber container of the present invention has a heat seal temperature range of 15 ° C. or higher and a difference between the maximum value and the minimum value of the peel strength of less than 4 N / 15 mm width when the seal layers are heat sealed. Having a first region comprised of a range of peel strength;
The average peel strength of the first region is 3 N / 15 mm width or more and 15 N / 15 mm width or less,
When heat-sealed at a temperature higher than that of the first region, the film has a peel strength of 30 N / 15 mm width or more. At this time, the peel strength when heat-sealing at a temperature higher than that of the first region and at least one temperature may be 30 N / 15 mm width or more.
As a film which shows such a property, the film which has a sealing layer which consists of the above polyolefin resin compositions is mentioned, for example.
When a multi-chamber container is manufactured using such a film, the outer peripheral portion forming the container is heat-sealed at a temperature higher than that of the first region and a peel strength of 30 N / 15 mm width or more. Thus, even when a strong pressure is applied to the storage chamber when the multi-chamber container is used, the seal portion of the outer peripheral portion does not peel off, and the seal portion that maintains the sealed state and isolates the storage chamber is the first region. Heat sealing in the temperature range is preferable because the balance between sealing property and easy peelability can be improved.

The amount of polyethylene resin and polypropylene resin contained in the resin composition can be determined by ¹³ C-NMR when the amount at the time of blending is unknown.
In the ¹³ C-NMR spectrum in which the exponential was applied to the window function, the peak derived from polypropylene was methyl at 19.6-22.2 ppm, methine at 28.4-29.2 ppm, and 45.8-47.3 ppm. A methylene peak is observed. The content of monomer units based on propylene contained in the composition is 1000, where the integrated value of 5 to 50 ppm is 1000.
Propylene content (% by weight) = P × 3/1000 × 100
P: It can be determined with an integrated intensity of 19.6-22.2 ppm.

Another aspect of the present invention is a polyolefin resin composition containing a polyethylene resin (X) and a polypropylene resin (Y), wherein the content of the polyethylene resin (X) is more than 20% by weight and 95. The content of polypropylene resin (Y) is 5% by weight or more and less than 80% by weight (provided that the total amount of polyethylene resin (X) and polypropylene resin (Y) is 100% by weight) ), A polyolefin-based resin composition that satisfies the following requirements (x1) and (x2).
(X1): The number of branches having 6 or more carbon atoms (N _LCB ) measured by ¹³ C-NMR is 0.01 or more per 1000 carbon atoms, and the number of branches having 5 carbon atoms (N _C5 ) is a carbon atom. Less than 0.1 per 1000 pieces (x2): Melt tension at 230 ° C. (MT; unit is cN) is 1.5 cN or more

When the N _LCB of the polyolefin resin composition of the present invention is 0.1 or more per 1000 carbon atoms, it becomes a composition more suitable for film forming processing that requires melt tension, such as inflation processing, preferable. N _LCB and N _C5 of the polyolefin resin composition are values measured with a composition in which the total amount of the polyethylene resin (X) and the polypropylene resin (Y) is 100% by weight.

  The melt tension (MT) at a temperature of 190 ° C. of the polyolefin-based resin composition of the present invention is preferably 1.7 cN to 10 cN because it becomes a composition more suitable for film forming processing requiring melt tension. More preferably, it is 2.0 cN-10 cN. In addition, MT of the said polyolefin resin composition is the value measured with the composition whose total amount of polyethylene resin (X) and polypropylene resin (Y) is 100 weight%.

  The melt tension (MT; unit is cN) is obtained by using a melt tension tester sold by Toyo Seiki Seisakusho Co., Ltd. and a molten resin filled in a 9.5 mmφ barrel at a temperature of 230 ° C. At a piston lowering speed of 5.5 mm / min, a molten resin strand is formed by melting and extruding from an orifice having a diameter of 2.09 mmφ and a length of 8 mm, and the rotation speed is increased by 40 rpm / min using a roller having a diameter of 150 mm. It is the tension value immediately before the strand breaks when it is wound up.

[Polyethylene resin (X)]
Examples of the polyethylene resin (X) include an ethylene-α-olefin copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms. From the viewpoint of stickiness suppression and heat resistance, the content of the monomer units based on ethylene in the polyethylene resin (X) is 100 mol% of the total of all monomer units constituting the polyethylene resin (X). When it is, it is preferable that it is 95 mol% or more, and it is preferable that content of the monomer unit based on a C3-C20 alpha olefin is 5 mol% or less.

The polyethylene-based resin (X) preferably has a branch number of 5 carbon atoms (N _C5 ) measured by ¹³ C-NMR of less than 0.1 per 1000 carbon atoms. N _C5 is more preferably less than 0.05 per 1000 carbon atoms, still more preferably less than 0.01, and particularly preferably zero.

In the polyethylene resin (X), the number of branches having 6 or more carbon atoms (N _LCB ) is preferably 0 or more and 1 or less per 1000 carbon atoms. For example, the polyethylene resin (A) is exemplified as the polyethylene resin having an N _LCB of 0.01 or more, and the linear low density polyethylene is exemplified as the polyethylene resin having an N _LCB of 0 or more and less than 0.01. Can be mentioned.
6 or more branch number of carbon atoms in the polyolefin resin composition (N _LCB) are formed so that 0.01 or more per 1000 carbon atoms, and N _LCB of the polyethylene resin (X) contained in the resin composition, the polypropylene N _LCB of the resin based resin (Y), and the contents of the polyethylene based resin (X) and the polypropylene based resin (Y) are adjusted. When a polyethylene resin having an N _LCB of 0 or more and less than 0.01 is used as the polyethylene resin (X), a polypropylene resin having an N _LCB of 0.01 or more is used as the polypropylene resin (Y).

  The activation energy (Ea) of the polyethylene resin (X) is preferably 10 kJ / mol or more and 100 kJ / mol or less. For example, as the polyethylene resin having an Ea of 10 kJ / mol or more and less than 40 kJ / mol, linear low density polyethylene can be mentioned, and as the polyethylene resin having an Ea of 40 kJ / mol or more but less than 100 kJ / mol, the polyethylene resin (A) is mentioned.

  The melt flow rate (MFR) of the polyethylene resin (X) is 0.01 to 50 g / 10 minutes, and preferably 5 g / 10 minutes or less from the viewpoint of improving the sealing performance. MFR is measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N by the method defined in JIS K7210-1995.

  As the polyethylene resin (X), the polyethylene resin of the component (A) is preferable.

[Polypropylene resin (Y)]
Examples of the polypropylene resin (Y) include propylene homopolymer (homopolypropylene) and a small amount of a comonomer mainly composed of propylene and copolymerizable therewith, for example, 20% by weight or less, preferably 10% by weight or less. What was polymerized is mentioned.

In the polypropylene resin (Y), the number of branches having 6 or more carbon atoms (N _LCB ) is preferably 0 or more and 1 or less per 1000 carbon atoms.

  The melt flow rate (MFR) of the polypropylene resin (Y) is usually 0.01 to 200 g / 10 minutes, and the polyolefin resin composition containing the polyethylene resin (X) and the polypropylene resin (Y). In order to set the melt tension (MT) at 230 ° C. to 1.5 cN or more, the MFR of the polypropylene resin (Y) is preferably 10 g / 10 minutes or less. The MFR of the polypropylene resin is measured under the conditions of a temperature of 230 ° C. and a load of 21.18 N by the method defined in JIS K7210-1995.

  As the polypropylene resin (Y), the polypropylene resin of the component (B) is preferable.

  It is obtained using the polyolefin resin composition containing the component (A) and the component (B) and the polyolefin resin composition containing the polyethylene resin (X) and the polypropylene resin (Y). The film has an excellent balance between easy peelability and sealing properties, and also has excellent heat resistance. The film obtained using the polyolefin resin composition may be a single layer or a laminated film in which a layer made of the resin composition and one or more other layers are laminated. In the case of a laminated film, the layer made of the resin composition is at least one surface layer, and it is preferable to use the layer as a sealing layer. Examples of other layers in the laminated film include other synthetic resin layers, paper layers, ink layers, vapor deposition layers, and aluminum foil layers. Other synthetic resin layers include, for example, polyethylene resin, polypropylene resin, polystyrene resin, polyester resin, polyvinyl chloride resin, polyamide resin, methacrylic resin, polyvinylidene chloride, saponified ethylene / vinyl acetate copolymer, Examples include a layer containing a polyvinyl alcohol resin or the like as a resin component. Examples of the polyethylene resin include low density polyethylene, linear low density polyethylene, high pressure method low density polyethylene, and ethylene-vinyl acetate copolymer. Examples of polystyrene resins include styrene-butadiene-styrene copolymers.

The thickness of the film made of the polyolefin resin composition of the present invention is usually 5 to 500 μm.
The thickness of the seal layer in the film having the seal layer made of the polyolefin resin composition of the present invention (in the case of a single layer film, the film thickness) is usually from 5 to 150 μm, preferably from 10 to 100 μm. When setting it as a laminated | multilayer film, the thickness of a sealing layer makes film thickness 100%, Preferably it is 3-70%, More preferably, it is 5-50%.

  The film obtained using the polyolefin-based resin composition of the present invention may contain other components, for example, an antioxidant, a lubricant, an antiblocking agent, an antistatic agent, a pigment, a colorant, and a processability improver, as necessary. One or more kinds of additives such as the above and other resins may be included.

  Examples of the antioxidant include hindered phenol compounds and phosphorus ester compounds. Examples of hindered phenol compounds include 2,6-dialkylphenol derivatives and 2-alkylphenol derivatives. Examples of the phosphorus ester compound include a phosphorus ester compound containing a trivalent phosphorus atom, and examples thereof include a phosphite compound and a phosphonite compound. These antioxidants may be used alone or in combination of two or more. In particular, from the viewpoint of stabilizing the hue, it is preferable to use a hindered phenol compound and a phosphorus ester compound in combination. The antioxidant is preferably contained in an amount of 0.01 to 1% by weight, preferably 0.03 to 0.5% by weight, when the weight of a film obtained using the polyolefin resin composition is 100% by weight. More preferably contained

  Examples of the lubricant include fatty acids, fatty acid amides, fatty acid esters, and glycerin esters of higher fatty acids. Examples of fatty acids include stearic acid, oleic acid, lauric acid and the like. Examples of fatty acid amides include oleylamide, erucylamide, ricinolamide, and behenamide. Examples of the fatty acid ester include sorbitan ester and n-butyl stearate.

  Examples of the anti-blocking agent include synthetic silica, natural silica, silicon resin, polymethyl methacrylate and the like. Examples of the synthetic silica include dry silica and wet silica. Examples of natural silica include diatomaceous earth.

  Examples of the antistatic agent include glycerin esters and sorbitan acid esters of fatty acids having 8 to 22 carbon atoms, alkyl dialkanolamides of fatty acids having 8 to 22 carbon atoms, polyethylene glycol esters, and alkyldiethanolamines. .

  Examples of the pigment include white pigment and carbon black.

  Examples of the other resins include polyolefin resins, and examples include high-density polyethylene, high-pressure low-density polyethylene, polypropylene, polybutene, and elastomer.

  When producing a film using the polyolefin resin composition of the present invention, the component (A) and the component (B), or the polyethylene resin (X) and the polypropylene resin (Y), and further if necessary. Components to be blended (such as the additives and other resins) may be mixed with a tumbler blender, a Henschel mixer, etc., and then formed into a film. After mixing the above components with a tumbler blender, Henschel mixer, etc., further kneaded with a single screw extruder or a multi-screw extruder, or kneaded product obtained by melt kneading with a kneader or Banbury mixer, You may shape | mold into a film.

  Examples of a method for producing a single layer film using the polyolefin resin composition of the present invention include an inflation molding method and a T die cast molding method. The laminated film can be produced by a coextrusion inflation molding method, a coextrusion T-die casting method, a coextrusion lamination molding method, or the like. Further, there are a coextrusion lamination molding method; a method of pasting a previously molded film by a dry lamination method; a method of laminating a preformed film and then hot pressing.

Since the film of the present invention has an excellent balance between easy peelability and sealability and is excellent in heat resistance, it is suitable as an easily peelable film and suitable as a packaging material. Moreover, the film of the present invention can be used as a lid and sealed with a polyolefin resin container body to obtain a container. In particular, it is suitable as a lid material for a polyolefin resin container body made of polyethylene resin or polypropylene resin.
Moreover, since the film of the present invention can exhibit hermeticity and easy peelability even when the films are sealed, it is suitable for three-sided seal bags and pillow packages represented by bread packaging, livestock meat packaging, confectionery bags, etc. It can be used for various applications such as films that require easy peelability. It can also be suitably used as a sealant material for a multi-chamber container.

Hereinafter, the present invention will be described with reference to examples and comparative examples.
The physical properties of Examples and Comparative Examples were measured according to the following methods.

(1) Melt flow rate of polyethylene resin and polypropylene resin (MFR, unit: g / 10 min)
According to the method defined in JIS K 7210-1995, the measurement was performed under the conditions of a load of 21.18 N, a polyethylene resin at a temperature of 190 ° C., and a polypropylene resin at a temperature of 230 ° C.

(2) Density of polyethylene resin (unit: kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-11995. In addition, the measurement sample piece was annealed according to the method of low density polyethylene described in JIS K6760-1995 and used for measurement.

(3) Molecular weight distribution of polyethylene resin (Mw / Mn, unit:-)
Using a gel permeation chromatograph (GPC) method, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured under the following conditions (1) to (9), and the molecular weight distribution (Mw / Mn) was determined.
Measurement condition
(1) Equipment: 150CV ALC / GPC manufactured by Waters
(2) Separation column: Shodex GPC AT-806MS manufactured by Showa Denko KK
(3) Temperature: 140 ° C
(4) Solvent: o-dichlorobenzene
(5) Elution solvent flow rate: 1.0 ml / min
(6) Sample concentration: 1 mg / ml
(7) Measurement injection volume: 400 μl
(8) Molecular weight standard substance: Standard polystyrene (manufactured by Tosoh Corporation; molecular weight = 6000000 to 500)
(9) Detector: Differential refraction

(4) Flow activation energy of polyethylene resin (Ea, unit: kJ / mol)
Using a viscoelasticity measuring device (Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics), a melt complex viscosity-angular frequency curve at 130 ° C., 150 ° C., 170 ° C. and 190 ° C. was measured under the following measurement conditions. From the obtained melt complex viscosity-angular frequency curve, calculation software Rhios V. The activation energy (Ea) was determined using 4.4.4.
<Measurement conditions>
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.5-2mm
Strain: 5%
Angular frequency: 0.1-100 rad / sec Measurement atmosphere: Under nitrogen

(5) Melting point (Tm, unit: ° C)
(5-1) Melting point of polyethylene-based resin A differential scanning calorimeter (DSC manufactured by Perkin Elmer Co., Ltd.) was prepared by measuring about 10 mg of a specimen cut from a sheet having a thickness of about 0.5 mm prepared by hot pressing. -7). In the measurement, the measurement sample was held at 150 ° C. for 5 minutes, then cooled to 40 ° C. at 1 ° C./minute, then held at 40 ° C. for 5 minutes, and then increased to 150 ° C. at a rate of 10 ° C./minute. Warm up. The melting point was determined from the melting peak of the melting curve obtained when the temperature was raised from 40 ° C. to 150 ° C. at a rate of 10 ° C./min.
(5-2) Melting point of polypropylene-based resin A sample obtained by cutting out a specimen of about 10 mg from a sheet having a thickness of about 0.5 mm produced by hot pressing was used as a measurement sample, and a differential scanning calorimeter (Diamond, manufactured by PerkinElmer Co., Ltd.) DSC). In the measurement, the measurement sample was held at 220 ° C. for 5 minutes, then rapidly cooled to 150 ° C., held at 150 ° C. for 1 minute, and then cooled to 50 ° C. at a rate of 5 ° C./min. Then, after holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at 5 ° C./min, and the temperature of the maximum peak of the obtained melting endotherm curve was defined as the melting point (Tm).

(6) g * of polyethylene resin
g * = [η] / ([η] _GPC × g _SCB *) (II)
G * was determined by the formula (II).
[Η] was determined by the following method. First, a sample solution is prepared by dissolving 100 mg of polyethylene resin at 135 ° C. in 100 ml of tetralin containing 0.5% by weight of butylhydroxytoluene (BHT) as a thermal degradation inhibitor with a relative viscosity (ηrel) of the polyethylene resin. Then, using an Ubbelohde viscometer, the sample solution was calculated from the falling time of the blank solution made of tetralin containing only 0.5% by weight of BHT as a thermal degradation inhibitor. The calculated relative viscosity (ηrel) was substituted into the formula (II-I) to obtain [η].
[Η] _GPC was determined by the following method. The viscosity average molecular weight (Mv) was calculated from the measurement result of (3) molecular weight distribution. The calculated Mv was substituted into the formula (II-II) to obtain [η] _GPC .
g _SCB * was obtained by substituting A obtained by the formula (II-V) into the formula (II-III).
In addition, the measurement and calculation of the short chain branch number n of the short chain branch and the short chain branch number y per 1000 carbon atoms of the polyethylene-based resin are described in the literature (Die Makromoleculare Chemie, 177, 449 (1976) McRae, MA, According to the method described in Madams, WF), the characteristic absorption derived from α-olefin was used. The infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation).

(7) Calculation method of various branch numbers of polyethylene resin and resin composition The carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR) is measured by the carbon nuclear magnetic resonance method under the following measurement conditions, and obtained from the following calculation method. It was.
<Measurement conditions>
Equipment: AVANCE 600 (600 MHz) manufactured by Bruker
Measurement probe: 10 mm cryoprobe Measurement solvent: 1,2-dichlorobenzene / 1,2-dichlorobenzene-d4 = 75/25 (volume ratio) mixture Measurement temperature: 130 ° C.
Measurement method: proton decoupling method Pulse width: 45 degrees Pulse repetition time: 4 seconds Measurement standard: Tetramethylsilane Window function: Exponential or Gaussian Integration count: 2500 times <Branch degree calculation method>
Calculation method of carbon number 5 (N _C5 , unit: 1 / 1000C)
In a ¹³ C-NMR spectrum in which an exponential is applied to the window function, a peak area of a peak having a peak top in the vicinity of 32.5 to 32.7 ppm, assuming that the sum of all peaks observed at 5 to 50 ppm is 1000 Asked.
Number of branches having 6 or more carbon atoms (N _LCB , unit: 1 / 1000C)
In a ¹³ C-NMR spectrum in which exponential is applied to the window function, the peak area of a peak having a peak top in the vicinity of 38.09 to 38.27 ppm, where the sum of all peaks observed at 5 to 50 ppm is 1000 Is A. This A is a value corresponding to a branched methine carbon having 4 or more carbon atoms. In the ¹³ C-NMR spectrum in which Gaussian was applied to the window function in order to separate the peaks of branched methine carbon having 5 or less carbon atoms and branched methine carbon having 6 or more carbon atoms, and 38.2 to 38. The peak observed at 27 ppm is B, and the peak observed at 38.21 to 38.09 ppm is C. Then, N _LCB was obtained from the following equation.
N _LCB = A × B / (B + C)

(8) Melt tension of resin composition (MT, unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, a molten resin filled in a 9.5 mmφ barrel at a temperature of 230 ° C., a piston descending speed of 5.5 mm / min, a diameter of 2.09 mmφ, and a length of 8 mm The extruded molten resin was extruded at a winding speed of 40 rpm / minute using a winding roll having a diameter of 150 mm, and the tension value immediately before the molten resin was broken was measured. It shows that melt tension is so large that this value is large.

[Physical properties of film]
(9) Easy peelability of heat seal part between seal layers <heat seal>
After the sealing layers of the laminated films obtained in the examples were overlapped, heat sealing was performed using a heat sealer (manufactured by Tester Sangyo Co., Ltd.) under the following heat sealing conditions.
Heat sealing temperature: 110 ° C to 180 ° C (in increments of 10 ° C, partly in increments of 5 ° C)
Heat sealing time: 1 second Heat sealing pressure: 0.3 MPa
Heat seal width: 20mm
<Peel strength>
The peel strength was measured according to JIS K6854-2. The peeling speed was 300 mm / min. If the peel strength is 3 N / 15 mm width to 15 N / 15 mm width, it can be said that the peel strength is moderate with both sealing properties and easy peelability.
When the heat seal temperature at which the difference between the maximum value and the minimum value of the peel strength is less than 5 N / 15 mm width is 15 ° C. or more, the peel strength stability with respect to the heat seal temperature is excellent.

(10) Easy peelability of heat seal part from homopolypropylene plate <Heat seal>
After laminating the sealing layer of the laminated film obtained in Examples and a homopolypropylene plate (thickness 0.4 mm), heat sealing was performed using a heat sealer (manufactured by Tester Sangyo Co., Ltd.) under the following heat sealing conditions.
Heat sealing temperature: 120 ° C to 200 ° C (in increments of 10 ° C, in increments of 5 ° C)
Heat sealing time: 1 second Heat sealing pressure: 3.1 MPa
Heat seal width: 20mm
<Peel strength>
The peel strength was measured according to JIS K6854-2. The peeling speed was 300 mm / min. If the peel strength is 3 N / 15 mm width to 15 N / 15 mm width, it can be said that the peel strength is moderate with both sealing properties and easy peelability.
When the heat seal temperature at which the difference between the maximum value and the minimum value of the peel strength is less than 5 N / 15 mm width is 15 ° C. or more, the peel strength stability with respect to the heat seal temperature is excellent.

(11) Easy peelability of heat seal part with polyethylene plate <Heat seal>
After laminating the sealing layer of the laminated film obtained in Examples and a polyethylene plate (thickness 0.25 mm) made of high-pressure low-density polyethylene, using a heat sealer (manufactured by Tester Sangyo Co., Ltd.) under the following heat sealing conditions. Heat sealing was performed.
Heat sealing temperature: 110 ° C to 180 ° C (in increments of 10 ° C, partly in increments of 5 ° C)
Heat sealing time: 1 second Heat sealing pressure: 3.1 MPa
Heat seal width: 20mm
<Peel strength>
The peel strength was measured according to JIS K6854-2. The peeling speed was 300 mm / min. If the peel strength is 3 N / 15 mm width to 15 N / 15 mm width, it can be said that the peel strength is moderate with both sealing properties and easy peelability.
When the heat seal temperature at which the difference between the maximum value and the minimum value of the peel strength is less than 5 N / 15 mm width is 15 ° C. or more, the peel strength stability with respect to the heat seal temperature is excellent.

[Example 1]
(1) Preparation of co-catalyst support Silica (Sypolol 948 manufactured by Devison Corp .; 50% volume average particle size = 55 μm; pore capacity = 1.67 ml / g; specific surface area = 325 m ² / g) 2.8 kg and 24 kg of toluene were added and stirred. Thereafter, after cooling to 5 ° C., a mixed solution of 0.9 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.4 kg of toluene was maintained for 30 minutes while maintaining the reactor temperature at 5 ° C. It was dripped at. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 95 ° C., stirred at 95 ° C. for 3 hours, and filtered. The obtained solid product was washed 6 times with 20.8 kg of toluene. Thereafter, 7.1 kg of toluene was added to form a slurry, which was allowed to stand overnight.

To the slurry obtained above, 3.46 kg of diethylzinc in hexane (diethylzinc concentration: 50% by weight) and 2.05 kg of hexane were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 1.54 kg of 3,4,5-trifluorophenol and 2.88 kg of toluene was added dropwise over 60 minutes while maintaining the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour, then heated to 40 ° C. and stirred at 40 ° C. for 1 hour. Then cooled to 5 ° C., was added dropwise for 1.5 hours while maintaining the H ₂ O0.221kg the temperature of the reactor to 5 ° C.. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, then heated to 40 ° C, stirred at 40 ° C for 2 hours, further heated to 80 ° C, and stirred at 80 ° C for 2 hours. After stirring, at room temperature, the supernatant was withdrawn to a residual amount of 16 L, charged with 11.6 kg of toluene, then heated to 95 ° C. and stirred for 4 hours. After stirring, the supernatant liquid was extracted at room temperature to obtain a solid product. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Thereafter, drying was performed to obtain a solid component (hereinafter referred to as a promoter support (a)).

(2) Preparation of pre-polymerization catalyst component (1) After 80 liters of butane was charged into an autoclave with a stirrer having an internal volume of 210 liters that had been previously purged with nitrogen, 91.8 mmol of racemic-ethylenebis (1-indenyl) zirconium diphenoxide The autoclave was heated to 50 ° C. and stirred for 2 hours. Next, 0.7 kg of the cocatalyst carrier (a) is added, the autoclave is cooled to 31 ° C. and the system is stabilized, and then 0.1 kg of ethylene and 0.1 liter of hydrogen (room temperature and normal pressure volume) are charged. Subsequently, 267 mmol of triisobutylaluminum was added to initiate polymerization. After 30 minutes passed while continuously supplying ethylene and hydrogen at 0.6 kg / Hr and 0.5 liter (normal temperature and normal pressure volume), respectively, the temperature was raised to 50 ° C., and ethylene and hydrogen were each 3.6 kg / hour. And 10.9 liters (room temperature and normal pressure volume) / hour were continuously fed for a total of 6 hours of prepolymerization. After the polymerization was completed, ethylene, butane, hydrogen and the like were purged and the remaining solid was vacuum dried at room temperature to obtain a prepolymerized catalyst component (1) containing 37 g of polyethylene per 1 g of the promoter support (a).

(3) Production of ethylene-1-hexene copolymer Using the pre-polymerization catalyst component (1), copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. The polymerization conditions were a temperature of 85 ° C., a total pressure of 2 MPa, a molar ratio of hydrogen to ethylene of 1.22%, and a molar ratio of 1-hexene to ethylene of 1.31% to maintain a constant gas composition during the polymerization. Ethylene, 1-hexene and hydrogen were continuously fed to the reactor. Further, the pre-polymerization catalyst component and triisobutylaluminum were continuously supplied at a constant ratio so that the total powder weight of the fluidized bed was maintained at 80 kg and the average polymerization time was 4 hours. By polymerization, a powder of an ethylene-1-hexene copolymer (hereinafter referred to as PE-1) was obtained with a polymerization efficiency of 20.5 kg / hr.

(4) Granulation of ethylene-1-hexene copolymer powder The PE-1 powder obtained above was fed at a feed rate of 50 kg / hr, a screw rotation speed of 450 rpm, and a gate using an extruder (LCM50 manufactured by Kobe Steel). Pelletizing PE-1 was obtained by granulation under conditions of an opening degree of 4.2 mm, a suction pressure of 0.2 MPa, and a resin temperature of 200 to 230 ° C. The evaluation results of PE-1 pellets are shown in Table 1.

(5) Film processing The propylene-ethylene random copolymer (hereinafter referred to as PP-1) in which the pellet of PE-1 obtained above is 75% by weight and the content of monomer units based on ethylene is 5% by weight. The basic physical properties of PP-1 are shown in Table 1.) Polyolefin having a thickness of 30 μm was processed by a film made at 210 ° C. using a 50 mmφ inflation machine manufactured by Plako Co., Ltd. so that the pellets would be 25% by weight. A monolayer film was obtained.

(6) Manufacture of laminated film Two-component curable polyurethane adhesive using the above-mentioned polyolefin-based single-layer film and a biaxially stretched nylon film (thickness 15 μm) using a test coater (manufactured by Yasui Seiki Co., Ltd.) (Lay Takeda Pharmaceutical Co., Ltd. Takelac A310 / Takenate A-3) was subjected to dry laminating to obtain a laminated film having a structure of polyolefin-based single layer film / adhesive layer / biaxially stretched nylon film. Moreover, in the dry laminating process, it aged at 40 degreeC after bonding for 48 hours. The physical property evaluation results of the obtained laminated film are shown in Table 2 and Table 7.
The obtained laminated film has a heat seal temperature of 130 ° C. to 180 ° C. indicating a suitable peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width in a peel test between seal layers. The heat seal temperature range showing the strength was continuously over 50 ° C., and the difference between the maximum value and the minimum value of the peel strength in this heat seal temperature range was 4.3 N / 15 mm width.
This laminated film has a heat seal temperature range of 15 ° C. or higher when the sealing layers are sealed, and a peel strength range in which the difference between the maximum value and the minimum value of the peel strength is less than 1.5 N / 15 mm width. The film had two different regions, and the difference in average peel strength between the regions was 2.0 N / 15 mm width or more. That is, the obtained laminated film has a heat seal temperature range of 120 ° C. to 140 ° C. and a peel strength range in which the difference between the maximum value and the minimum value of the peel strength is 0.6 N / 15 mm width. A second region having one region S1 and having a heat seal temperature range of 160 ° C. to 180 ° C. and a peel strength range in which the difference between the maximum value and the minimum value of the peel strength is 1.1 N / 15 mm width. The average peel strength P _(S1) of the first region S1 is 3.0 N / 15 mm width, and the average peel strength P _(S2) of the second region S2 is 6.6 N / 15 mm width. The difference between the average peel strength P _(S1) of _S1 and the average peel strength P _(S2) of _S2 was 3.6 N / 15 mm width. The difference between the maximum value and the minimum value of the heat seal temperature in S1 was 20 ° C., and the difference between the maximum value and the minimum value of the heat seal temperature in S2 was 20 ° C.
Further, in a peel test with a homopolypropylene plate, a heat seal temperature exhibiting an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width is 135 ° C. to 200 ° C., and a heat exhibiting an appropriate peel strength The sealing temperature range was continuously over 65 ° C. Of the heat seal temperature range showing an appropriate peel strength, the heat seal temperature range where the difference between the maximum value and the minimum value of the peel strength is less than 5 N / 15 mm width is 160 ° C to 200 ° C, and the peel strength is continuous. It was stable over 40 ° C.

[Example 2]
Inflation film processing was performed in the same manner as in Example 1 except that the pellets of PE-1 were 50% by weight and the pellets of PP-1 were 50% by weight. The evaluation results of the obtained laminated film are shown in Table 2 and Table 9.
The obtained laminated film has a heat seal temperature of 120 ° C. to 180 ° C. indicating a suitable peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width in a peel test between seal layers, and a suitable peel strength. The heat seal temperature range showing the strength was continuously over 60 ° C., and the difference between the maximum value and the minimum value of the peel strength in this heat seal temperature range was 5.4 N / 15 mm width.
This laminated film has a heat seal temperature range of 15 ° C. or higher when the sealing layers are sealed, and a peel strength range in which the difference between the maximum value and the minimum value of the peel strength is less than 1.5 N / 15 mm width. The film had two different regions, and the difference in average peel strength between the regions was 2.0 N / 15 mm width or more. That is, the obtained laminated film has a heat seal temperature range of 120 ° C. to 135 ° C. and a peel strength range in which the difference between the maximum value and the minimum value of the peel strength is 0.7 N / 15 mm width. A second region having a region S1 and having a heat seal temperature range of 160 ° C. to 180 ° C. and a peel strength range in which the difference between the maximum value and the minimum value of the peel strength is 0.2 N / 15 mm width. The average peel strength P _(S1) of the first region S1 is 3.3 N / 15 mm width, and the average peel strength P _(S2) of the second region S2 is 8.3 N / 15 mm width. The difference between the average peel strength P _(S1) of _S1 and the average peel strength P _(S2) of _S2 was 5.0 N / 15 mm width. The difference between the maximum value and the minimum value of the heat seal temperature in S1 was 15 ° C., and the difference between the maximum value and the minimum value of the heat seal temperature in S2 was 20 ° C.
Further, in a peel test with a polyethylene plate, a heat seal temperature having a peel strength of 3 N / 15 mm width to 15 N / 15 mm width showing an appropriate peel strength is 130 ° C. to 180 ° C., and showing an appropriate peel strength The temperature range was continuously over 50 ° C. Among heat seal temperature ranges showing moderate peel strength, the heat seal temperature range where the difference between the maximum value and the minimum value of peel strength is less than 5 N / 15 mm width is 135 ° C to 180 ° C, and the peel strength is continuous. It was stable over 45 ° C.

[Example 3]
Inflation film processing was performed in the same manner as in Example 1 except that the pellets of PE-1 were 25% by weight and the pellets of PP-1 were 75% by weight. The evaluation results of the obtained laminated film are shown in Table 2 and Table 9.
In the peel test between the sealing layers, the obtained laminated film has a heat seal temperature of 125 ° C. to 140 ° C. indicating a suitable peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width, and a suitable peel strength. The heat seal temperature range showing the strength was continuously over 15 ° C., and the difference between the maximum value and the minimum value of the peel strength in this heat seal temperature range was 3.7 N / 15 mm width.
This laminated film has a first region constituted by a heat seal temperature range of 125 ° C. to 140 ° C. and a peel strength range in which the difference between the maximum value and the minimum value of the peel strength is 3.7 N / 15 mm width. The average peel strength of this first region is 5.2 N / 15 mm width, and the peel strength when heat sealed at 160 ° C., which is a higher temperature than the first region, is 32 N / 15 mm width This laminated film is preferably used as a film for producing a multi-chamber container.
Further, in a peel test with a polyethylene plate, a heat seal temperature having a peel strength of 3 N / 15 mm width to 15 N / 15 mm width showing an appropriate peel strength is 160 ° C. to 180 ° C., and showing an appropriate peel strength The temperature range was continuously over 20 ° C., and the difference between the maximum value and the minimum value of the peel strength in this heat seal temperature range was 0.3 N / 15 mm width.

[Comparative Example 1]
(1) Film processing 75 pellets of commercially available metallocene linear low-density polyethylene (Sumitomo Chemical Co., Ltd., Sumikasen E FV205: hereinafter referred to as LL-1, the basic physical properties of LL-1 are shown in Table 1). What was mixed so that it might become 25 weight% of PP% and PP-1 was film-processed at 210 degreeC with the 50 mm diameter inflation processing machine by Plako Co., Ltd., and obtained the polyethylene-type single layer film of thickness 30 micrometers.

(2) Manufacture of laminated film Using the test coater (manufactured by Yasui Seiki Co., Ltd.), the two-component curable polyurethane adhesive with the polyolefin single layer film and the biaxially stretched nylon film (thickness 15 μm). (Lay Takeda Pharmaceutical Co., Ltd. Takelac A310 / Takenate A-3) was subjected to dry laminating to obtain a laminated film having a structure of polyolefin-based single layer film / adhesive layer / biaxially stretched nylon film. Moreover, in the dry laminating process, it aged at 40 degreeC after bonding for 48 hours. The physical property evaluation results of the obtained laminated film are shown in Table 3, Table 8, and Table 9.
The obtained laminated film did not have a heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width in a peel test between seal layers. Further, in a peel test with a homopolypropylene plate, a heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width is 135 ° C. to 150 ° C., and a heat showing an appropriate peel strength The sealing temperature range was continuously over 15 ° C. Among the heat seal temperature range showing an appropriate peel strength, the heat seal temperature range in which the difference between the maximum value and the minimum value of the peel strength is less than 5 N / 15 mm width is 140 ° C. to 150 ° C., and the peel to the heat seal temperature It was inferior in strength stability.
Further, in a peel test with a polyethylene plate, the heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width is only 125 ° C., and a heat seal temperature range showing an appropriate peel strength Is not suitable as an easily peelable film.

[Comparative Example 2]
Inflation film processing was performed in the same manner as in Comparative Example 1 except that the pellets of LL-1 were 50% by weight and the pellets of PP-1 were 50% by weight. The evaluation results of the obtained laminated film are shown in Table 3, Table 8, and Table 9.
In the peel test between the sealing layers, the obtained laminated film had a heat seal temperature of only 125 ° C. showing an appropriate peel strength having a peel strength of 3 N / 15 mm width to 15 N / 15 mm width. Further, in a peel test with a homopolypropylene plate, a heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width is 135 ° C. to 150 ° C., and a heat showing an appropriate peel strength The sealing temperature range was continuously over 15 ° C. Among the heat seal temperature range showing an appropriate peel strength, the heat seal temperature range in which the difference between the maximum value and the minimum value of the peel strength is less than 5 N / 15 mm width is 140 ° C. to 150 ° C., and the peel to the heat seal temperature It was inferior in strength stability. Further, in a peel test with a polyethylene plate, the heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width is only 125 ° C., and a heat seal temperature range showing an appropriate peel strength Is not suitable as an easily peelable film.

[Comparative Example 3]
Inflation film processing was performed in the same manner as in Comparative Example 1 except that the LL-1 pellets were 25 wt% and the PP-1 pellets were 75 wt%. As a result, since the melt tension of the polyolefin-based resin composition was low, film breakage occurred during film formation, and the film could not be formed.

[Comparative Example 4]
Inflation film processing was carried out in the same manner as in Example 1 except that PE-1 pellets were not used and only PP-1 pellets were used. Table 3 shows the evaluation results of the obtained laminated film.
In the peel test between the sealing layers, the obtained laminated film had a heat seal temperature of only 140 ° C. showing an appropriate peel strength having a peel strength of 3 N / 15 mm width to 15 N / 15 mm width.

[Comparative Example 5]
(1) Film processing 75 weight of pellets of commercially available high pressure method low density polyethylene (Sumitomo Chemical Co., Ltd. Sumikasen F200-0: hereinafter referred to as LD-1; basic physical properties of LD-1 are shown in Table 1). %, PP-1 was mixed at 25% by weight, and the film was processed at 210 ° C. with a Plako Co., Ltd. 50 mmφ inflation machine to obtain a polyethylene-based single layer film having a thickness of 30 μm.

(2) Manufacture of laminated film Using the test coater (manufactured by Yasui Seiki Co., Ltd.), the two-component curable polyurethane adhesive with the polyolefin single layer film and the biaxially stretched nylon film (thickness 15 μm). (Lay Takeda Pharmaceutical Co., Ltd. Takelac A310 / Takenate A-3) was subjected to dry laminating to obtain a laminated film having a structure of polyolefin-based single layer film / adhesive layer / biaxially stretched nylon film. Moreover, in the dry laminating process, it aged at 40 degreeC after bonding for 48 hours. Table 4 shows the physical property evaluation results of the obtained laminated film.
The obtained laminated film did not have a heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width in a peel test between seal layers.

[Comparative Example 6]
Inflation film processing was performed in the same manner as in Comparative Example 5, except that the LD-1 pellets were 50 wt% and the PP-1 pellets were 50 wt%. The evaluation results of the obtained laminated film are shown in Table 4 and Table 9.
The obtained laminated film did not have a heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width in a peel test between seal layers.
Further, in a peel test with a polyethylene plate, the heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width is only 120 ° C., and a heat seal temperature range showing an appropriate peel strength Is not suitable as an easily peelable film.

[Comparative Example 7]
Inflation film processing was performed in the same manner as in Example 1 except that only PP-1 pellets were used without using PP-1 pellets. Table 4 shows the evaluation results of the obtained laminated film.
In the peel test between the sealing layers, the obtained laminated film had a heat seal temperature of only 120 ° C. showing an appropriate peel strength having a peel strength of 3 N / 15 mm width to 15 N / 15 mm width.

[Example 4]
(1) Production of ethylene-1-hexene copolymer Using the above prepolymerization catalyst component (1), copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. The polymerization conditions were a temperature of 80 ° C., a total pressure of 2 MPa, a molar ratio of hydrogen to ethylene of 1.48%, and a molar ratio of 1-hexene to ethylene of 1.70% to maintain a constant gas composition during the polymerization. Ethylene, 1-hexene and hydrogen were continuously fed to the reactor. Furthermore, the pre-polymerization catalyst component and triisobutylaluminum were continuously supplied at a constant ratio so that the total powder weight of the fluidized bed was maintained at 80 kg and the average polymerization time was 4 hours. By polymerization, a powder of an ethylene-1-hexene copolymer (hereinafter referred to as PE-2) was obtained at a polymerization efficiency of 20.3 kg / hour.

(2) Granulation of ethylene-1-hexene copolymer powder The PE-2 powder obtained above was fed at a feed rate of 50 kg / hour, a screw rotation speed of 450 rpm, and a gate using an extruder (LCM50 manufactured by Kobe Steel). PE-2 pellets were obtained by granulation under conditions of an opening degree of 4.2 mm, a suction pressure of 0.2 MPa, and a resin temperature of 200 to 230 ° C. The evaluation results of PE-2 pellets are shown in Table 1.

(3) Film processing What was mixed so that the pellet of PE-2 obtained above was 50% by weight and the pellet of PP-1 was 50% by weight was obtained at 210 ° C. with a 50 mmφ inflation processing machine manufactured by Plako Co., Ltd. The film was processed to obtain a polyolefin-based single layer film having a thickness of 30 μm.

(4) Manufacture of laminated film Two-component curable polyurethane adhesive using the above-mentioned polyolefin-based single-layer film and a biaxially stretched nylon film (thickness 15 μm) using a test coater (manufactured by Yasui Seiki Co., Ltd.). (Lay Takeda Pharmaceutical Co., Ltd. Takelac A310 / Takenate A-3) was subjected to dry laminating to obtain a laminated film having a structure of polyolefin-based single layer film / adhesive layer / biaxially stretched nylon film. Moreover, in the dry laminating process, it aged at 40 degreeC after bonding for 48 hours. Table 4 shows the physical property evaluation results of the obtained laminated film.
In the peel test between the sealing layers, the obtained laminated film has a heat seal temperature of 125 ° C. to 140 ° C. indicating a suitable peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width, and a suitable peel strength. The heat seal temperature range indicating the strength was continuously over 15 ° C., and the difference between the maximum value and the minimum value of the peel strength in this heat seal temperature range was 4.3 N / 15 mm width.

[Example 5]
(1) Production of ethylene-1-hexene copolymer Using the above prepolymerization catalyst component (1), copolymerization of ethylene and 1-hexene was carried out in a continuous fluidized bed gas phase polymerization apparatus. The polymerization conditions were a temperature of 85 ° C., a total pressure of 2 MPa, a molar ratio of hydrogen to ethylene of 1.59%, and a molar ratio of 1-hexene to ethylene of 1.25% to maintain a constant gas composition during the polymerization. Ethylene, 1-hexene and hydrogen were continuously fed to the reactor. Furthermore, the pre-polymerization catalyst component and triisobutylaluminum were continuously supplied at a constant ratio so that the total powder weight of the fluidized bed was maintained at 80 kg and the average polymerization time was 4 hours. By polymerization, a powder of an ethylene-1-hexene copolymer (hereinafter referred to as PE-3) was obtained.

(2) Granulation of ethylene-1-hexene copolymer powder The PE-3 powder obtained above was fed at a feed rate of 50 kg / hour, a screw rotation speed of 450 rpm, and a gate using an extruder (LCM50 manufactured by Kobe Steel). PE-3 pellets were obtained by granulation under conditions of an opening degree of 4.2 mm, a suction pressure of 0.2 MPa, and a resin temperature of 200 to 230 ° C. Table 5 shows the evaluation results of the PE-3 pellets.

(3) Film processing The pellet of PE-3 obtained above was 50% by weight and homopolypropylene (hereinafter referred to as PP-2. The basic physical properties of PP-2 are shown in Table 5). The pellet was 50% by weight. The mixed material was processed with a 50 mmφT die processing machine manufactured by Sumitomo Heavy Industries Modern Co., Ltd. at a processing temperature of 250 ° C. and a chill roll temperature of 70 ° C. to obtain a polyolefin-based single layer film having a thickness of 30 μm.

(4) Manufacture of laminated film Two-component curable polyurethane adhesive using the above-mentioned polyolefin-based single-layer film and a biaxially stretched nylon film (thickness 15 μm) using a test coater (manufactured by Yasui Seiki Co., Ltd.). (Lay Takeda Pharmaceutical Co., Ltd. Takelac A310 / Takenate A-3) was subjected to dry laminating to obtain a laminated film having a structure of polyolefin-based single layer film / adhesive layer / biaxially stretched nylon film. Moreover, in the dry laminating process, it aged at 40 degreeC after bonding for 48 hours. The physical property evaluation results of the obtained laminated film are shown in Table 6 and Table 7.
The obtained laminated film has a heat seal temperature of 180 ° C. to 200 ° C. indicating a suitable peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width in a peel test between seal layers, and a suitable peel strength. The heat seal temperature range showing the strength was continuously over 20 ° C., and the difference between the maximum value and the minimum value of the peel strength in this heat seal temperature range was 1.0 N / 15 mm width. Further, in a peel test with a homopolypropylene plate, a heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width is 160 ° C. to 200 ° C., and a heat showing an appropriate peel strength The sealing temperature range was continuously over 40 ° C., and the difference between the maximum value and the minimum value of the peel strength in this heat sealing temperature range was 2.8 N / 15 mm width.

[Example 6]
T-die film processing was performed in the same manner as in Example 5 except that the pellets of PE-3 were 25% by weight and the pellets of PP-2 were 75% by weight. The evaluation results of the obtained laminated film are shown in Table 6 and Table 7.
The obtained laminated film has a heat seal temperature of 160 ° C. to 200 ° C. indicating a suitable peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width in a peel test between seal layers, and a suitable peel strength. The heat seal temperature range showing the strength was continuously over 40 ° C. Among the heat seal temperature range showing an appropriate peel strength, the heat seal temperature range where the difference between the maximum value and the minimum value of the peel strength is less than 5 N / 15 mm width is 170 ° C. to 200 ° C., and the peel strength is continuous. It was stable over 30 ° C.
Further, in a peel test with a homopolypropylene plate, a heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width is 170 ° C. to 200 ° C., and a heat showing an appropriate peel strength The sealing temperature range was continuously over 30 ° C., and the difference between the maximum value and the minimum value of the peel strength in this heat sealing temperature range was 1.6 N / 15 mm width.

[Comparative Example 8]
Pellets of commercially available metallocene linear low density polyethylene (hereinafter referred to as LL-2. The basic physical properties of LL-2 are shown in Table 5) having a MFR = 3.7 g / 10 min and a density of 918 kg / m ³ . Was mixed with 50% by weight of PP-2 and 50% by weight of PP-2, and the film was processed at a processing temperature of 250 ° C. and a chill roll temperature of 70 ° C. using a 50 mmφT die processing machine manufactured by Sumitomo Heavy Industries Modern Co., Ltd. As a result, the film was cut during film formation and could not be formed.

[Comparative Example 9]
T-die film processing was performed in the same manner as in Comparative Example 8 except that LL-2 pellets were 25 wt% and PP-2 pellets were 75 wt%. As a result, the film was cut during film formation and could not be formed.

[Comparative Example 10]
T-die film processing was performed in the same manner as in Example 5 except that only the pellets of PP-2 were used without using the pellets of PE-3. The evaluation results of the obtained laminated film are shown in Table 6 and Table 8.
In the peel test between the seal layers, the obtained laminated film had a heat seal temperature of only 160 ° C. showing an appropriate peel strength having a peel strength of 3 N / 15 mm width to 15 N / 15 mm width. Moreover, in the peel test with a homopolypropylene plate, there was no heat seal temperature showing an appropriate peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width.

[Example 7]
T-die film processing was performed in the same manner as in Example 5 except that PE-3 pellets were 75 wt% and PP-2 pellets were 25 wt%. Table 7 shows the evaluation results of the obtained laminated film.
In the peel test with the homopolypropylene plate, the obtained laminated film had a heat seal temperature of 180 ° C. to 200 ° C. indicating a suitable peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width. The heat seal temperature range showing the peel strength was continuously over 20 ° C., and the difference between the maximum value and the minimum value of the peel strength in this heat seal temperature range was 0.2 N / 15 mm width.

[Comparative Example 11]
Inflation film processing was performed in the same manner as in Comparative Example 5 except that the LD-1 pellets were 25% by weight and the PP-1 pellets were 75% by weight. Table 10 shows the evaluation results of the obtained laminated film.
In the peel test with the polyethylene plate, the obtained laminated film had a heat seal temperature of 140 ° C. to 150 ° C. indicating a suitable peel strength with a peel strength of 3 N / 15 mm width to 15 N / 15 mm width, and a suitable peel strength. The heat-sealing temperature range showing strength is narrow, making it unsuitable as an easily peelable film.

ＮＧ：母材切れ（剥離中にシール層が切れ、剥離不可。）

NG: Out of base material (Seal layer is cut during peeling and cannot be peeled)

ＮＧ：母材切れ（剥離中にシール層が切れ、剥離不可。）

NG: Out of base material (Seal layer is cut during peeling and cannot be peeled)

DESCRIPTION OF SYMBOLS 1 Storage chamber 2 Peripheral part 3 Isolation part (part which isolates between storage rooms)
4 Extraction port

Claims (9)

As a resin, a polyolefin resin composition containing only the following component (A) and component (B), and when the total amount of component (A) and component (B) is 100% by weight, component (A ) Is more than 20% by weight and 95% by weight or less, and the content of component (B) is 5% by weight or more and less than 80% by weight.
(A): having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, the following requirements (a1), (a2), (a3) and (a4) -Α-olefin copolymer (a1) satisfying the formula: content of monomer units based on ethylene is 95 mol% or more (however, the total of all monomer units constituting the polyethylene resin is 100 mol%) (A2): the number of carbon 5 branches (N _C5 ) measured by ¹³ C-NMR is less than 0.1 per 1000 carbon atoms (a3): flow activation energy (Ea) is 40 kJ / mol or more (a4): Molecular weight distribution (Mw / Mn) is 5 to 25 (B): Polypropylene resin The polyolefin resin composition according to claim 1, wherein the component (B) is a propylene homopolymer or a propylene random copolymer containing 90% by weight or more of a monomer unit based on propylene. A film comprising the polyolefin resin composition according to claim 1. The multilayer film which has a sealing layer which consists of a polyolefin-type resin composition of Claim 1 or 2. The film according to claim 3, which is a packaging material. A multi-chamber container comprising the film according to claim 3. The film according to claim 3, which is a lid material. A container formed by sealing the film according to claim 7 and a polyolefin resin container main body. A container in which the polyolefin resin container body according to claim 8 is made of a polyethylene resin or a polypropylene resin.

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