JP2009185237A - Laminate film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film with the excellent balance of transparency, low temperature sealing property, anti-blocking property, lot temperature impact strength and heat sealing property. <P>SOLUTION: The film has the melt flow rate (MFR; ASTM D1238, 230°C, load 2.16 kg) in a range of 1-20 g/10 minutes, and the melting point measured by a differential scanning calorimeter (DSC) in a range of 145-170°C. It contains a propylene-ethylene block copolymer (A) including 90-80 wt% of a component satisfying specific requirements, insoluble to n-decane at a room temperature (D<SB>insol</SB>) and 10-20 wt% of a component satisfying specific requirements and being soluble to n-decane at a room temperature (D<SB>sol</SB>). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a film having excellent balance of transparency, low temperature sealability, blocking resistance, low temperature impact strength, and heat seal strength.

  Polypropylene films, in particular homopropylene homopolymer films and propylene random copolymer films, are excellent in rigidity and heat resistance, but have a drawback of low low-temperature impact strength. In order to eliminate this drawback, it is well known to add an elastomer component composed of an ethylene / α-olefin copolymer or to use a propylene-based block copolymer. However, when an elastomer component is added, the heat seal strength is lowered, and when a propylene-based block copolymer is used, there is a problem that transparency is lowered.

In addition, with the increase in packaging speed, there is a demand for low-temperature heat sealability of polypropylene-based films, and it is known to add an elastomer component composed of an ethylene / α-olefin copolymer as well as an improvement in low-temperature impact strength. Yes. However, there is a problem in terms of heat seal strength and cost, and a film excellent in low temperature sealability and low temperature impact strength is demanded from the market. Various films have been proposed so far to obtain films that satisfy these requirements (see, for example, Patent Documents 1 to 3). However, transparency, seal strength, blocking resistance, heat resistance, and impact resistance have been proposed. An excellent film with a good balance has not been obtained for all requirements.
JP 2004-358683 A JP 2004-51675 A JP 2007-45049 A

  An object of the present invention is to provide a film having excellent balance of transparency, low temperature sealing properties, blocking resistance, low temperature impact strength, and heat seal strength.

  As a result of diligent research to solve the above problems, the present inventors have used a specific propylene / ethylene block copolymer (A) and / or (B) for a laminated film, so that transparency, low temperature sealing properties, The inventors have found that the balance of blocking resistance, low temperature impact strength, and heat seal strength is excellent, and have completed the present invention.

That is, this invention is specified by the matter described below.
The film of the present invention has a melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) in a range of 1 to 20 g / 10 min, and a melting point measured by a differential scanning calorimeter (DSC), The room temperature n satisfying the following (1) to (3) in the range of 145 to 170 ° C. and satisfying the following (1) to (3): 90 to 80% by weight of the insoluble portion (D _insol ) and the following (4) to (6) _-Propylene- composed of 10-20% by weight of decane soluble part (D _sol )
An ethylene block copolymer (A) is included.
(1) D _insol molecular weight distribution determined from the GPC (gel permeation chromatography) of molecular weight distribution (Mw / Mn) of 3.5 or less (2) the content of skeletons derived from ethylene in D _insol is less than 3 mol% ( 3) The sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene in D _insol is 0.
2 mol% or less (4) Molecular weight distribution (Mw / Mn) determined from GPC of D _sol is 3.5 or less (5) Intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 3.0 dl / G
(6) Content of skeleton derived from ethylene in D _sol is 15 to 25 mol%
The film of the present invention has a heat seal layer containing the propylene / ethylene copolymer (A) described above, and a melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) of 1 to 20 g / A portion insoluble in room temperature n-decane that has a melting point measured by a differential scanning calorimeter (DSC) in the range of 10 minutes and in the range of 145 to 170 ° C. and satisfies the following (i) to (iii) (D _insol ) 90 to 70% by weight and room temperature n satisfying the following (iv) to (vi)
_-At least one intermediate layer containing a propylene / ethylene block copolymer (B) composed of 10 to 30% by weight of a decane-soluble part ( _Dsol ) is laminated. .
(I) D molecular weight distribution determined from the GPC (gel permeation chromatography) of _insol (Mw / Mn) is 3.5 or less (ii) the content of skeletons derived from ethylene in D _insol is less than 3 mol% ( iii) The sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene in D _insol is 0.2 mol% or less. (iv) Molecular weight distribution (Mw / Mn) determined from GPC of D _sol Is 3.5 or less (v) Intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 2.0 to 3.5 dl / g
(Vi) The content of the skeleton derived from ethylene in D _sol is more than 25 mol% and 60 mol% or less.

  Moreover, the laminated film of the present invention includes a heat seal layer containing the propylene / ethylene block copolymer (A) described above, and at least one intermediate layer containing the propylene / ethylene block copolymer (B) described above. The laminate layer containing the propylene / ethylene block copolymer (A) described above is preferably laminated. Further, the layer ratio of each layer is 10-30% of the heat seal layer, 40-80% of the intermediate layer, and 10-30% of the laminate layer (however, the total of the heat seal layer, the intermediate layer, and the laminate layer is 100%) Is preferred.

  The film of the present invention is preferably formed by polymerizing the propylene / ethylene block copolymer (A) and / or (B) in the presence of a metallocene catalyst.

  The film of the present invention uses a specific propylene / ethylene block copolymer (A) and / or (B), so that the balance of transparency, sealability, blocking resistance, low temperature impact strength, and heat seal strength is achieved. Therefore, it is suitably used for food packaging that can be stored frozen from room temperature, such as frozen food packaging, sanitary refill pouch packaging, or heavy goods packaging such as grains and vegetables.

  In addition, since the film of the present invention has a narrow molecular weight distribution, it has few low molecular weight components and is excellent in hygiene, so that the taste of the packaged food becomes good.

Hereinafter, the film of the present invention will be described in detail.
Specific propylene / ethylene block copolymers (A) and (B) used in the film of the present invention will be described.

<Propylene / ethylene block copolymer (A)>
The propylene / ethylene block copolymer (A) used in the present invention has a melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) of 1 to 20 g / 10 minutes, preferably 3 to 10 g / 10 minutes. , Melting point 145-170 ° C., preferably 15
90 to 80% by weight of a portion in the range of 6 to 165 ° C. and insoluble in room temperature n-decane (D _insol )
And 10 to 20% by weight of a portion soluble in room temperature n-decane (D _sol ). Here, the melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg), melting point, and the weight fraction of the portion insoluble in n-decane (D _insol ) in the propylene / ethylene block copolymer (A) The weight fraction of the portion soluble in n-decane at room temperature (D _sol ) can be appropriately changed. In the present invention, the melting point was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer).

In the propylene / ethylene block copolymer (A), the D _insol satisfies the requirements (1) to (3), and the D _sol satisfies the requirements (4) to (6).
(1) The molecular weight distribution (Mw / Mn) obtained from GPC of D _insol is 3.5 or less, preferably 1.5 to 3.3.
(2) The content of the skeleton derived from ethylene in D _insol is less than 3 mol%. (3) The sum of the 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in D _insol is 0. 2 mol% or less (4) Molecular weight distribution (Mw / Mn) determined from GPC of D _sol is 3.5 or less, preferably 1.5 to 3.3
(5) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 3.0 dl / g
, Preferably 1.8 to 2.8 dl / g
(6) Content of skeleton derived from ethylene in D _sol is 15 to 25 mol%
<Propylene / Ethylene Block Copolymer (B)>
The propylene / ethylene block copolymer (B) used in the present invention has a melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) of 1 to 20 g / 10 minutes, preferably 3 to 10 g / 10 minutes. The melting point is in the range of 145 to 170 ° C., preferably 145 to 170 ° C., more preferably 156 to 165 ° C., and the insoluble portion (D _insol ) of 90 to 70% by weight at room temperature n-decane, and room temperature n-decane. The soluble part ( _Dsol ) is comprised from 10 to 30 weight%. Here, the melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg), melting point, and the weight fraction of the portion insoluble in n-decane (D _insol ) in the propylene / ethylene block copolymer (B) The weight fraction of the portion soluble in n-decane at room temperature (D _sol ) can be appropriately changed.

In the propylene / ethylene block copolymer (B), the D _insol satisfies the requirements (i) to (iii), and the D _sol satisfies the requirements (iv) to (vi).
(I) The molecular weight distribution (Mw / Mn) determined from GPC of D _insol is 3.5 or less, preferably 1.5 to 3.3.
(Ii) The content of the skeleton derived from ethylene in D _insol is less than 3 mol%. (Iii) The sum of the 2,1-insertion bond amount and the 1,3-insertion bond amount of propylene in D _insol is 0. 2 mol% or less (iv) Molecular weight distribution (Mw / Mn) determined from GPC of D _sol is 3.5 or less, preferably 1.5 to 3.3
(V) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 2.0 to 3.5 dl / g, preferably 2.0 to 3.0 dl / g.
(Vi) The content of the skeleton derived from ethylene in D _sol exceeds 25 mol% and is 60 mol% or less, preferably 30 to 55 mol%.

Hereinafter, the requirements (1) to (6) and (i) to (vi) included in the propylene / ethylene block copolymers (A) and (B) will be described in detail.
[Requirements (1) and (i)]
Molecular weight distribution (Mw / Mn) determined from GPC (gel permeation chromatography) of a portion (D _insol ) insoluble in room temperature n-decane of the propylene / ethylene block copolymer (A) or (B) used in the present invention ) Is 3.5 or less, preferably 1.5 to 3.3, and more preferably 1.8 to 2.8. Thus, about the part (D _insol ) insoluble in room temperature n-decane contained in the copolymer, the molecular weight distribution (Mw / Mn) determined from GPC
) Within the above range, it is preferable to use a metallocene catalyst as described below as a catalyst. And when Mw / Mn is larger than 3.5, the low molecular weight component increases, so that bleed out from the laminated film of the present invention may occur.

[Requirements (2) and (ii)]
The content of the skeleton derived from ethylene in the portion (D _insol ) insoluble in room temperature n-decane of the propylene / ethylene block copolymer (A) or (B) used in the present invention is less than 3 mol%, preferably It is less than 1.5 mol%, more preferably less than 0.5 mol%. If the content of the skeleton derived from ethylene in D _insol is 3 mol% or more, the transparency of the film may be lowered.

[Requirements (3) and (iii)]
The propylene / ethylene block copolymer (A) or (B) used in the present invention has 1,2-insertion amount of propylene in a portion (D _insol ) insoluble in room temperature n-decane and 1,
The sum with 3-insertion bond amount is 0.2 mol% or less, preferably 0.1 mol% or less. When the sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene in D _insol is more than 0.2 mol%, the copolymerizability of propylene and ethylene is reduced, and as a result, Since the composition distribution of the propylene / ethylene copolymer rubber in the portion soluble in n-decane at room temperature (D _sol ) becomes wide,
Problems such as reduced impact resistance at low temperatures may occur.

The intrinsic viscosity [η] of the propylene / ethylene block copolymer (A) or (B) insoluble in room temperature n-decane (D _insol ) 135 ° C. decalin is usually 1.5-3.
. 5 dl / g, preferably 1.8 to 3.0 dl / g.

[Requirements (4) and (iv)]
Molecular weight distribution (Mw / Mn) obtained from GPC of a portion soluble in room temperature n-decane (D _sol ) of the propylene / ethylene block copolymer (A) or (B) used in the present invention
Is 3.5 or less, preferably 1.5 to 3.3. In order to narrow the molecular weight distribution (Mw / Mn) obtained from GPC as described above for the portion soluble in room temperature n-decane of the copolymer (D _sol ) as described above, it will be described later as a catalyst. A suitable metallocene catalyst is preferably used. And if Mw / Mn is larger than 3.5, low molecular weight propylene / ethylene copolymer rubber increases in D _sol , resulting in a decrease in impact resistance, deterioration in transparency after heat treatment, and blocking during storage of laminated films. Such a problem may occur.

[Requirements (5) and (v)]
The intrinsic viscosity [η] in 135 ° C. decalin of the portion soluble in room temperature n-decane (D _sol ) of the propylene / ethylene block copolymer (A) used in the present invention is 1.5 to
3.0 dl / g, preferably 1.8 to 2.8 dl / g. A portion soluble in room temperature n-decane (D _sol ) of the propylene / ethylene block copolymer (B) used in the present invention.
The intrinsic viscosity [η] in 135 ° C. decalin is 2.0 to 3.5 dl / g, preferably 2.0 to 3.0 dl / g. When the intrinsic viscosity [η] of the portion soluble in room temperature n-decane (D _sol ) of the propylene / ethylene block copolymer (A) or (B) is within the above range,
It is preferable in terms of transparency and impact. Moreover, 135 _degreeC of the part soluble in room temperature n-decane ( _Dsol )
A propylene / ethylene block copolymer having an intrinsic viscosity [η] in decalin higher than 3.5 dl / g may contain a very small amount of ultrahigh molecular weight or high ethylene amount propylene / ethylene copolymer rubber. Appearance defects such as a reduction in impact resistance of the film and fish eyes may occur.

[Requirements (6) and (vi)]
The content of the skeleton derived from ethylene in the room temperature n-decane soluble portion (D _sol ) of the propylene / ethylene block copolymer (A) used in the present invention is 15 to 25 mol%. Further, the content of the skeleton derived from ethylene in the portion soluble in room temperature n-decane (D _sol ) of the propylene / ethylene block copolymer (B) used in the present invention exceeds 25 mol% and 60 mol%. Hereinafter, it is preferably 30 to 55 mol%. When the content of the skeleton derived from ethylene in the portion soluble in room temperature n-decane (D _sol ) of the propylene / ethylene block copolymer (B) is lower than 25 mol%, the propylene / ethylene block copolymer The impact resistance of the is reduced. Further, when the content of the skeleton derived from ethylene in the portion (D _sol ) soluble in room temperature n-decane of the propylene / ethylene block copolymer (B) is higher than 60 mol%, the transparency is lowered. .

In the laminated film of the present invention, the propylene / ethylene block copolymers (A) and (B) have an appropriate skeleton content derived from ethylene in the portion soluble in room temperature n-decane (D _sol ). By making it within the range, the transparency is hardly lowered and the impact resistance is hardly lowered.

  The propylene / ethylene block copolymer (A) or (B) used in the present invention is preferably a propylene homopolymer or a small amount of propylene in the first polymerization step ([Step 1]) in the presence of a metallocene catalyst. A propylene / ethylene block obtained by producing a propylene / ethylene copolymer rubber by copolymerizing propylene and ethylene in the second polymerization step ([Step 2]) after producing a propylene copolymer comprising A copolymer is preferred.

  The metallocene catalyst used in the present invention includes a metallocene compound and at least one compound selected from compounds capable of reacting with an organometallic compound, an organoaluminum oxy compound and a metallocene compound to form an ion pair, A metallocene catalyst comprising a particulate carrier as required, preferably a metallocene catalyst capable of performing stereoregular polymerization such as isotactic or syndiotactic structure. Among the metallocene compounds, the following crosslinkable metallocene compounds exemplified in the international application (WO01 / 27124 pamphlet) by the applicant of the present application are used.

In the general formula [I], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and may be the same or different. Such hydrocarbon groups include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n -Linear hydrocarbon group such as nonyl group and n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, Branched hydrocarbon groups such as 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group A cyclic saturated hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group; a phenyl group, a tolyl group, a naphthyl group, a biphenyl group; Cyclic unsaturated hydrocarbon groups such as enyl, phenanthryl and anthracenyl groups; saturated hydrocarbon groups substituted with cyclic unsaturated hydrocarbon groups such as benzyl, cumyl, 1,1-diphenylethyl and triphenylmethyl A hetero atom-containing hydrocarbon group such as methoxy group, ethoxy group, phenoxy group, furyl group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, pyryl group, thienyl group, etc. Can do. Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group.

In the general formula [I], the substituents R ^{5 to} R ¹² may be bonded to adjacent substituents to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

In the general formula [I], R ¹ , R ² , R ³ , and R ⁴ substituted on the cyclopentadienyl ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-described hydrocarbon groups. More preferably, R ³ is a hydrocarbon group having 1 to 20 carbon atoms.

In the above general formula [I], R ^{5 to} R ¹² substituted on the fluorene ring have 1 to 20 carbon atoms.
The hydrocarbon group is preferably. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups listed above. Substituents R ⁵ to R ¹² are substituents adjacent may form a ring bonded to each other.

In the general formula [I], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a group 14 element of the periodic table, more preferably carbon, silicon, or germanium, and still more preferably a carbon atom. It is. R ¹³ and R ¹⁴ substituted on Y are preferably a hydrocarbon group having 1 to 20 carbon atoms. These may be the same as or different from each other, and may be bonded to each other to form a ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups listed above. More preferably, R ¹⁴ is aryl having 6 to 20 carbon atoms (a
ryl) group. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, and a heteroatom-containing cyclic unsaturated hydrocarbon group. R ¹³ and R ¹⁴ may be the same or different, and may be bonded to each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthracenylidene group, a dibenzocycloheptadienylidene group, and the like are preferable.

In the metallocene compound represented by the above general formula [I], the substituent selected from R ¹ , R ⁴ , R ⁵ or R ¹² and R ¹³ or R ^{14 at the} bridging part are bonded to each other to form a ring. May be.
In the above general formula [I], M is preferably a Group 4 transition metal of the periodic table, more preferably Ti, Zr, or Hf. Q is selected from the same or different combinations from a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. And ethers such as ethane. It is preferable that at least one Q is a halogen atom or an alkyl group.

Such bridged metallocene compounds include diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl). ) (2,
7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (methyl) (Phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrobenzofluorenyl) zirconium dichloride, [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene) Zirconium dichloride (see the following formula [II]) and the like are preferred.

  In the metallocene catalyst used in the present invention, an ion pair reacts with an organometallic compound, an organoaluminum oxy compound, and a transition metal compound used together with the Group 4 transition metal compound represented by the general formula [I]. At least one compound selected from the compounds that form, and a particulate carrier that is used as necessary. These are disclosed in the above-mentioned publication (WO01 / 27124 pamphlet) or JP-A-11-315109. The compounds disclosed in the publication can be used without limitation.

The propylene / ethylene block copolymer (A) or (B) according to the present invention uses a polymerization apparatus in which two or more reaction apparatuses are connected in series, and the following two steps ([Step 1] and [Step 2]). ) Is carried out continuously.

In [Step 1], propylene is homopolymerized or copolymerized with propylene and a small amount of ethylene at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 1], by containing propylene homopolymerized or containing a skeleton derived from ethylene in D _insol in the propylene-based polymer produced in [Step 1] by reducing the amount of ethylene fed to propylene by a small amount. The amount can be less than 3 mol%, preferably less than 1.5 mol%, more preferably less than 0.5 mol%.

In [Step 2], propylene and ethylene are copolymerized at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 2], the propylene / ethylene copolymer rubber produced in [Step 2] is made the main component of D _sol by increasing the amount of ethylene fed to propylene.

By doing in this way, requirements (1) to (3) and (i) to (iii) related to D _insol
Can satisfy the requirements (4) to (6) and (iv) to (vi) relating to D _sol by adjusting the polymerization conditions in [Step 2]. It becomes possible.

In addition, the physical properties to be satisfied by the propylene / ethylene block copolymer (A) or (B) used in the present invention are often determined by the chemical structure of the metallocene catalyst used. Specifically, requirements (1) and (i) molecular weight distribution (Mw / Mn) determined from GPC of D _insol , requirements (3) and (iii) 2,1-insertion bond amount of propylene in D _insol Sum of 1,3-insertion bond amount, requirements (4) and (iv) molecular weight distribution (Mw / Mn) determined from GPC of D _sol , and propylene / ethylene block copolymer (A) or (B) About melting | fusing point, it can adjust so that the requirements in this invention may be satisfy | filled mainly by selecting appropriately the metallocene catalyst to be used. The metallocene catalyst preferably used in the present invention is as described above.

Furthermore, to _satisfy the requirements (2) and (ii) the content of the skeleton derived from ethylene in D _insol is less than 3 mol%, preferably less than 1.5 mol%, more preferably less than 0.5 mol%. In [Step 1], propylene is preferably homopolymerized, and when propylene and ethylene are copolymerized, the amount of ethylene fed is preferably small. Requirements (5) and (v) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol can be adjusted by the feed amount of a molecular weight regulator such as hydrogen in [Step 2]. Requirements (6) and (vi) The content of skeleton derived from ethylene in D _sol can be adjusted by the amount of ethylene feed in [Step 2]. Further, by adjusting the amount ratio of the polymer produced in [Step 1] and [Step 2], the composition ratio of D _insol and D _sol , and the propylene / ethylene block copolymer (A) or (B ) Melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) can be appropriately adjusted.

  In addition, the propylene / ethylene block copolymer (A) or (B) used in the present invention is produced in the [Step 1] of the above method and the propylene polymer produced in the [Step 1] of the method. The propylene / ethylene copolymer rubber may be produced individually in the presence of a metallocene compound-containing catalyst and then blended using these physical means.

<Elastomer (E)>
An elastomer (E) can be added to the film of the present invention for the purpose of imparting properties such as impact resistance, transparency and flexibility.

  As the elastomer (E), ethylene / α-olefin random copolymer (Ea), ethylene / α-olefin / nonconjugated polyene random copolymer (Eb), hydrogenated block copolymer (Ec) ), Propylene / α-olefin copolymer (E-d), other elastic polymers, and mixtures thereof.

The content of the elastomer (E) in the laminated film of the present invention varies depending on the properties to be imparted, but is usually 0 to 20% by weight, preferably 1 to 10% by weight.
The ethylene / α-olefin random copolymer rubber (Ea) is a random copolymer rubber of ethylene and an α-olefin having 3 to 20 carbon atoms. In the ethylene / α-olefin random copolymer rubber (Ea), the molar ratio between the structural unit derived from ethylene and the structural unit derived from α-olefin (the structural unit derived from ethylene / α- The structural unit derived from olefin) is usually 95/5 to 15/85, preferably 80/20 to 25/75. The melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) of the ethylene / α-olefin random copolymer (Ea) is usually 0.1 g / 10 min or more, preferably It exists in the range of 0.5-30 g / 10min.

The ethylene / α-olefin / non-conjugated polyene random copolymer (Eb) is a random copolymer rubber of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene. As said C3-C20 alpha-olefin, the same thing as the above is mentioned. Non-conjugated polyethylenes include 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene Acyclic dienes such as norbornadiene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1, Chain non-conjugated dienes such as 5-heptadiene, 6-methyl-1,7-octadiene, 7-methyl-1,6-octadiene; and trienes such as 2,3-diisopropylidene-5-norbornene . Of these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferably used. In the ethylene / α-olefin / non-conjugated polyene random copolymer (Eb), the structural unit derived from ethylene is usually 94.9 to 30 mol%, preferably 89.5 to 40 mol%, The structural unit derived from an α-olefin is usually 5 to 45 mol%, preferably 10 to 40 mol%, and the structural unit derived from a non-conjugated polyene is usually 0.1 to 25 mol%, preferably 0.5 to 20 mol%. However, in the present invention, the total of the structural unit derived from ethylene, the structural unit derived from α-olefin, and the structural unit derived from non-conjugated polyene is 100 mol%. The melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) for the ethylene / α-olefin / non-conjugated polyene random copolymer (Eb) is 0.05 g / 10 min or more, preferably 0. Within the range of 1-30 g / 10 min. Specific examples of the ethylene / α-olefin / non-conjugated polyene random copolymer (Eb) include an ethylene / propylene / diene terpolymer (EPDM).

  The hydrogenated block copolymer (Ec) is a hydrogenated product of a block copolymer whose block form is represented by the following formula (a) or (b), and the hydrogenation rate is usually 90 mol%. More preferably, the hydrogenated block copolymer is 95 mol% or more.

Examples of the monovinyl-substituted aromatic hydrocarbon constituting the polymerization block represented by X in the above formula (a) or formula (b) include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, and lower alkyl-substituted styrene. And styrene such as vinyl naphthalene or derivatives thereof. These can be used alone or in a combination of two or more. Examples of the conjugated diene constituting the polymer block represented by Y in the formula (a) or (b) include butadiene, isoprene, chloroprene and the like. These can be used alone or in a combination of two or more. n is usually an integer of 1 to 5, preferably 1 or 2. Specific examples of the hydrogenated block copolymer (E-c) include styrene / ethylene / butene / styrene block copolymer (SEBS), styrene / ethylene / propylene / styrene block copolymer (SEPS), and styrene. -Styrene-type block copolymers, such as ethylene propylene block copolymer (SEP), etc. are mentioned. The block copolymer before hydrogenation can be produced, for example, by a method in which block copolymerization is performed in an inert solvent in the presence of a lithium catalyst or a Ziegler catalyst. A detailed manufacturing method is described in, for example, Japanese Patent Publication No. 40-23798. The hydrogenation treatment can be performed in an inert solvent in the presence of a known hydrogenation catalyst. Detailed methods are described in, for example, Japanese Patent Publication Nos. 42-8704, 43-6636, and 46-20814. When butadiene is used as the conjugated diene monomer, the ratio of the 1,2-bond amount in the polybutadiene block is usually 20 to 80% by weight, preferably 30 to 60% by weight. A commercial item can also be used as a hydrogenated block copolymer (Ec). Specific examples include Clayton G1657 (registered trademark) (manufactured by Shell Chemical Co., Ltd.), Septon 2004 (registered trademark) (manufactured by Kuraray Co., Ltd.),
And Tuftec H1052 (registered trademark) (manufactured by Asahi Kasei Corporation).

The propylene / α-olefin copolymer rubber (Ed) is a random copolymer rubber of propylene and an α-olefin having 4 to 20 carbon atoms. In the propylene / α-olefin random copolymer (Ed), the molar ratio between the structural unit derived from propylene and the structural unit derived from α-olefin (the structural unit derived from propylene / α-olefin). The structural unit derived from is usually 95/5 to 5/95, preferably 80/15 to 20/80. In the propylene / α-olefin random copolymer rubber (Ed), two or more α-olefins may be used, one of which may be ethylene. The melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) for the propylene / α-olefin random copolymer rubber (Ed) is usually 0.1 g / 10 min or more, preferably 0.5 Within the range of ~ 30 g / 10 min.

Elastomer (E) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
In the present invention, the elastomer (E) is usually in the range of 0 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the propylene / ethylene block copolymer (A) or (B). Use in quantity.

<Polyethylene resin (C)>
A polyethylene resin (C) may be added to the film of the present invention together with the elastomer (E) or in place of the elastomer (E) for the purpose of imparting functions such as impact resistance, transparency and flexibility. .

For example, when imparting impact resistance while suppressing a decrease in transparency, a density of 0.900 to 0.930 kg / manufactured by copolymerizing ethylene and a C4 or higher α-olefin in the presence of a metallocene catalyst. It is preferred to add m ³ linear low density polyethylene.

As another example, when improving high-speed extrusion moldability, it is desirable to add high-pressure polyethylene. Here, the high pressure polyethylene is a polyethylene having a long chain branch obtained by radical polymerization of ethylene in the presence of peroxide at a pressure of 100 kg / cm ² or more. Preferred melt flow rate of high pressure polyethylene (ASTMD1
238, 190 ° C. and load 2.16 kg) is usually in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 10 g / 10 min. The density (ASTM D1505) is
Usually, it is in the range of 0.900 to 0.940 g / cm ³ , preferably 0.910 to 0.930 g / cm ³ .

Propylene / ethylene block copolymer (A) or (B) and polyethylene resin (C
The content of the polyethylene resin (C) in the film containing) varies depending on the properties to be imparted, but is usually 0 to 20% by weight, preferably 3 to 10 parts by weight. A polyethylene resin (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type.

In the case of a film comprising a propylene / ethylene block copolymer (A) or (B), an elastomer (E) and a polyethylene resin (C), the amount of the propylene / ethylene block copolymer (A) or (B) Although it varies depending on the properties to be imparted, it is usually in the range of 80 to 99% by weight, preferably 90 to 99% by weight. Further, the total amount of the elastomer (E) and the polyethylene resin (C) is determined based on the propylene-based block random copolymer (A) or (B
) It is usually 1 to 10% by weight, preferably 3 to 7% by weight, based on 100 parts by weight. In addition, the ratio of an elastomer and polyethylene can be arbitrarily adjusted according to the objective.

<Crystal nucleating agent (D)>
If necessary, a crystal nucleating agent (D) may be added to the film of the present invention to improve transparency, heat resistance, moldability, and the like.

  Examples of the crystal nucleating agent (D) used in the present invention include sorbitol compounds such as dibenzylidene sorbitol, organophosphate compounds, rosinate compounds, C4-C12 aliphatic dicarboxylic acids and metal salts thereof, and the like. Can be mentioned.

  Of these, organophosphate compounds are preferred. The organic phosphate ester compound is a compound represented by the following general formula [III] and / or [IV].

In the above formulas [III] and [IV], R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are hydrogen atoms or hydrocarbons having 1 to 10 carbon atoms. R ² and R ³ may be the same or different, M is a 1 to 3 valent metal atom, n is an integer of 1 to 3, and m is 1 or 2.

Specific examples of the organic phosphate ester compound represented by the general formula [III] include sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-
Bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene- Bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'- Methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene- Bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t -Octylmethylene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) Enyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6 -Di-t-butylphenyl) phosphate], sodium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4- Ethyl-6-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis ( 4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6- Di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate ], Magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6-di-t -Butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylfell) phosphate], aluminum-tris [2,2'-ethylidene-bis (4, 6-di-t-butylphenyl) phosphate], and a mixture of two or more thereof.

A hydroxyaluminum phosphate compound represented by the general formula [IV] is also usable as an organic phosphate compound, particularly represented by the general formula [V], in which R ² and R ³ are both tert-butyl groups. Compounds are preferred.

In the formula [V], R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and m is 1 or 2. A particularly preferred organophosphate compound is a compound represented by the general formula [VI].

In the formula [VI], R ¹ is a methylene group or an ethylidene group. Specifically, hydroxyaluminum-bis [2,2-methylene-bis (4,6-di-t-butyl) phosphate] or hydroxyaluminum-bis [2,2-ethylidene-bis (4,6- Di-t-butyl) phosphate]. Specific examples of the sorbitol compounds include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4- p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4 -p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4 -Di (p-ethylbenzylidene) sorbitol, 1,3,2,4-
Di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (p-i-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1 , 3,2,4-di (ps-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxy) Benzylidene) sorbitol, 1,3,2,4-di (
p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidenesorbitol, 1,3-p-
Chlorbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol or 1,3,2,4-di (p-chlorobenzylidene) sorbitol. In particular, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol or 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol preferable.

Specific examples of C4-C12 aliphatic dicarboxylic acids and metal salts thereof that can be used as the crystal nucleating agent (D) in the present invention include succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, and the like. Li salt, Na salt, Mg salt, Ca salt, Ba salt, Al salt and the like can be mentioned. In addition, the aromatic carboxylic acid and its metal salt that can be used as the crystal nucleating agent (D) in the present invention include benzoic acid, aryl-substituted acetic acid, aromatic dicarboxylic acid, and group 1 to 3 metal salts of these periodic tables. Specifically, benzoic acid, p-isopropylbenzoic acid, o-tertiary butyl benzoic acid, p-tertiary butyl benzoic acid, monophenylacetic acid, diphenylacetic acid, phenyldimethylacetic acid, phthalic acid, and These Li salt, Na salt, Mg salt, Ca salt, Ba salt, Al salt etc. can be mentioned.

  The crystal nucleating agent (D) used in the present invention is usually from 0.05 to 0.5 parts by weight, preferably from 0.00 to 100 parts by weight, based on 100 parts by weight of the propylene / ethylene block copolymer (A) or (B). It is added at a ratio of 1 to 0.3 parts by weight.

<Others>
If necessary, a propylene resin (P) may be added to the film of the present invention. The propylene resin (P) used here is a propylene homopolymer, propylene / ethylene copolymer, propylene / α-olefin copolymer different from the propylene / ethylene block copolymer (A) or (B). It refers to a polymer, a propylene / ethylene block copolymer, and a propylene / α-olefin block copolymer. Here, as the α-olefin, an α-olefin having 4 to 20 carbon atoms can be used.

  The film of the present invention is a range that does not impair the purpose of the present invention, such as vitamins, antioxidants, heat stabilizers, weather stabilizers, slip agents, antiblocking agents, petroleum resins, mineral oils, etc. An additive may be included.

  After blending each of the above components and, if necessary, various additives using a mixer such as a Henschel mixer, Banbury mixer, tumbler mixer, etc. It can be obtained by film formation using a pellet.

  Examples of the method for producing the laminated film of the present invention include a multilayer inflation film molding method, a multilayer T die cast film molding method, a press molding method, an extrusion laminating method, and a dry laminating method, and preferably a multilayer T die casting. It is a film forming method.

The laminated film of the present invention may be a composite film. Examples of the composite film include a film in which the laminated film of the present invention is laminated on a base material. Examples of the base material include cellophane, paper, paperboard, woven fabric, aluminum foil, polyamide resin such as nylon 6 and nylon 66, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, and stretched polypropylene. And as a method of laminating the laminated film of this invention on a base material, the dry laminating method, the wet laminating method, the sand laminating method, the hot-melt laminating method etc. are mentioned, for example.

<Heat-fusion film>
In the present invention, by using the propylene / ethylene block copolymer (A) and / or (B) for the film, the transparency, the low temperature sealability, the blocking resistance, the low temperature impact strength, and the heat seal strength are balanced. Can get. Therefore, the film of the present invention is suitably used for a heat-fusible film.

Moreover, the thickness of a heat-fusible film is 10-200 micrometers normally, Preferably it is 20-100 micrometers.
The heat-sealable film requires high-speed bag-making properties (low-temperature sealability) in order to improve the productivity of the package, so the melting point of the propylene / ethylene block copolymer (A) or (B) Is 145 to 170 ° C, preferably 156 to 165 ° C. In particular, a heat-fusible film having a melting point in the range of 146 to 156 ° C. is preferable because it has a high-speed bag-making property while having high low-temperature impact strength and heat seal strength. Moreover, when melting | fusing point exceeds 170 degreeC, it is unpreferable from a viewpoint of low temperature sealing property, and less than 145 degreeC is unpreferable from a heat resistant viewpoint.

  In the heat-fusible film, the melt flow rate is 0.1 to 20 g / 10 minutes, preferably 3 to 10 g / 10 minutes. When the melt flow rate is in this range, it is preferable from the viewpoint of film forming processability.

  The laminated film of the present invention includes a heat seal layer containing the propylene / ethylene block copolymer (A), at least one intermediate layer containing the propylene / ethylene block copolymer (B), and the propylene / ethylene block. It is preferable that a laminate layer containing the copolymer (A) is laminated. The layer ratio of the laminated film is 10 to 30%, preferably 20 to 30% for the heat seal layer, 40 to 80%, preferably 50 to 70% for the intermediate layer, and 10 to 30%, preferably 15 for the laminate layer. -20% (however, the total of the heat seal layer, the intermediate layer and the laminate layer is 100%). Such a laminated film is preferable because it can impart excellent low temperature sealing properties, blocking resistance, low temperature impact strength and heat seal strength while maintaining transparency. Therefore, such a laminated film is also suitably used for a heat-fusible film.

  The melting point of the layer containing the propylene / ethylene block copolymer (A) or (B) is 145 to 170 ° C, preferably 156 to 165 ° C. In particular, those having a melting point in the range of 146 to 156 ° C. are preferable because they have high low temperature impact strength and low temperature sealing properties.

Further, as other laminated films, a film in which three or more layers containing the propylene / ethylene block copolymer (A) and / or (B) used in the present invention are laminated is suitably used. In the case of these films, it is desirable to use the layer containing the propylene / ethylene block copolymer (A) used in the present invention as a heat seal layer. In addition, for example, in the case of a film having a three-layer structure in which a propylene / ethylene block copolymer (A) is used as a heat seal layer and a laminate layer, and a propylene / ethylene block copolymer (B) is used as an intermediate layer, As long as the propylene / ethylene block copolymer (A) used as the seal layer and the laminate layer satisfies the requirements of the present invention, the heat seal layer and the laminate layer may be the same or different. . Further, for example, in the case of a film having a three-layer structure in which the propylene / ethylene block copolymer (A) is used as a heat seal layer and the propylene / ethylene block copolymer (B) is used as an intermediate layer and a laminate layer, As long as the propylene / ethylene block copolymer (B) used as the layer and the laminate layer satisfies the requirements of the present invention, the intermediate layer and the laminate layer may be the same or different. Furthermore, such a laminated film is also suitably used for a heat-fusible film. Moreover, you may use the homopolypropylene or random polypropylene polymerized in presence of a metallocene catalyst as a laminate layer.

  The laminated film of the present invention is excellent in balance of transparency, sealing properties, blocking resistance, low temperature impact strength, and heat seal strength, and therefore a food packaging such as frozen food packaging stored at room temperature, such as frozen food packaging, It is suitably used for sanitary refill pouch packaging or heavy goods packaging such as grains and vegetables. Moreover, since the laminated film of the present invention has a narrow molecular weight distribution and is excellent in hygiene, the taste of the packaged food is good.

EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to the Example which concerns. In addition, the measuring method of the physical property in an Example and a comparative example is as follows.
(m1) Melt flow rate (MFR)
The melt flow rate (MFR) was measured according to ASTM D1238 (230 ° C., load 2.16 kg).

(m2) Melting point (Tm)
The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). The endothermic peak in the third step measured here was defined as the melting point (Tm).

(Measurement condition)
First step: Increase the temperature to 240 ° C at 10 ° C / min and hold for 10 min.
Second step: Decrease the temperature to 60 ° C at 10 ° C / min.

Third step: Increase the temperature to 240 ° C at 10 ° C / min.
(m3) Room temperature n-decane soluble part (D _sol )
200 ml of n-decane was added to 5 g of the final product sample and dissolved by heating at 145 ° C. for 30 minutes. It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (hereinafter, n-decane insoluble part: D _insol ) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane (precipitate (A)). The precipitate (A) and acetone were separated by filtration, and the precipitate was dried. Even when the filtrate side was concentrated to dryness, no residue was observed.

The amount of n-decane soluble part was determined by the following formula.
n-decane soluble part amount (wt%) = [precipitate (A) weight / sample weight] × 100.
(M4) Mw / Mn measurement [weight average molecular weight (Mw), number average molecular weight (Mn)]
Measurement was performed as follows using GPC-150C Plus manufactured by Waters. The separation columns are TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size is 7.5 mm in inner diameter and 600 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) Co., Ltd.) and 0.025 wt% BHT (Wako Pure Chemical Industries, Ltd.) as an antioxidant, moved at 1.0 ml / min, the sample concentration was 0.1 wt%, and the sample injection amount was 500 micron A differential refractometer was used as a detector. Standard polystyrene used for the molecular weight Mw <1000 and Mw> 4 × 10 ⁶ is manufactured by Tosoh Corporation, and 1000 ≦ Mw
For ≦ 4 × 10 ⁶ , those manufactured by Pressure Chemical Co., Ltd. were used.

(m5) Content of skeleton derived from ethylene
To measure the skeleton concentration derived from ethylene in D _insol and D _sol , 20-30 mg of sample was dissolved in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution, and then carbon nuclear magnetism. Resonance analysis ( ¹³ C-NMR) was performed. Propylene, ethylene, and α-olefin were quantitatively determined from the dyad chain distribution. For example, in the case of propylene-ethylene copolymer,

Was obtained by the following calculation formulas (Eq-1) and (Eq-2).

(M6) Intrinsic viscosity [η]
Measurement was performed at 135 ° C. using a decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. Repeat this dilution operation two more times,
The value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.

[Η] = lim (ηsp / C) (C → 0).
(m7) Measurement of 2,1-insertion bond and 1,3-insertion bond
^{Using 13} C-NMR, the amount of 2,1-insertion bond and the amount of 1,3-insertion bond of propylene were measured according to the method described in JP-A-7-152212.

(M8) Heat seal strength of film (sealing start temperature / maximum heat seal strength)
The heat seal strength of the film was measured according to JIS K 6781. The tensile speed is 200 mm / min, and the distance between chucks is 80 mm.

For the heat seal sample, the film was sampled into strips of 15 mm width.
Sealing was performed under the conditions of heat sealing, sealing time 1 second, pressure 0.2 MPa · G (MPa · G means gauge pressure, hereinafter the same), and seal width 5 mm. The upper temperature of the seal bar was varied, both ends of the film heat-sealed at 70 ° C. were pulled at 200 mm / min, the maximum strength was measured, and a graph plotting the relationship between the upper temperature and the heat seal strength was created. From this plot, the seal temperature at which the heat seal strength was 2.94N was measured as the seal start temperature, and the strength at which the heat seal strength was maximized was measured as the maximum heat seal strength.

(M9) Film Impact Test A film was sampled to 5 cm × 5 cm, and surface impact strength was measured with an impact tester (a method of pushing a hammer from the bottom to the top) at a predetermined temperature (hammer condition: tip 1 inch, 3 .0J).

(M10) Haze of film (HAZE)
Measured according to ASTM D-1003.
(M11) Blocking property of film The chill roll surfaces of the film of 10 cm in the MD direction × 10 cm in the TD direction are overlapped and held in a thermostatic bath at 50 ° C. under a load of 200 g / cm ² for 3 days. Then, after conditioning for 24 hours or more in a room at 23 ° C. and 50% humidity, the peel strength when peeled at a tensile rate of 200 mm / min was measured, and the value obtained by dividing the peel strength by the width of the test piece was the blocking coefficient. And blocking resistance was evaluated. Here, the smaller the blocking coefficient, the better the blocking resistance.

[Production Example 1] Production of propylene / ethylene block copolymer (A1)
(1) Production of solid catalyst support 300 g of SiO ₂ was sampled in a 1-liter branch flask, and 800 mL of toluene was added to make a slurry, followed by transfer to a 5-liter 4-neck flask, and 260 mL of toluene was added. 2830 mL of a toluene solution (10 wt% solution) of methylaluminoxane (hereinafter also referred to as “MAO”) was added and stirred at room temperature for 30 minutes. The temperature was raised to 110 ° C. over 1 hour and reacted for 4 hours. After completion of the reaction, the temperature was lowered to room temperature. After cooling, the supernatant toluene solution was removed, toluene was added again, and substitution was performed until the substitution rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on support)
[3- (1 ', 1', 4 ', 4', 7 ', 7] in a 5 liter four-necked flask in the glove box
', 10', 10'-Octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride Was weighed 2.0 g. The flask was taken out, 0.46 liters of toluene and 1.4 liters of the MAO / SiO ₂ / toluene slurry prepared in the above (1) were added under nitrogen, and the mixture was stirred for 30 minutes to carry. The resulting [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3- Trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% substituted with n-heptane to give a final slurry volume of 4 .5 liters. This operation was performed at room temperature.

(3) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (2) above, 218 mL of triethylaluminum, and 100 liters of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 liters, and the internal temperature was maintained at 15 to 20 ° C. 1212 g was inserted and reacted with stirring for 180 minutes. After completion of the polymerization, the solid component was settled, the supernatant was removed, and washed twice with heptane. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 4 g / liter. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, 30 kg / hour of propylene, 1 NL / hour of hydrogen, 6.2 g / hour of the catalyst slurry produced in the above (3) as a solid catalyst component, 2. 3 ml / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerizer with a stirrer having an internal volume of 100 liters and further polymerized. Propylene was supplied to the polymerization vessel at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 liters, gasified, gas-solid separated, and then propylene homopolymer powder was sent to a 480 liter gas phase polymerization vessel to produce an ethylene / propylene block Copolymerization was performed. Propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerizer would be ethylene / (ethylene + propylene) = 0.10 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.1 MPa / G. After the polymerization, it was vacuum dried at 80 ° C. to obtain a propylene / ethylene block copolymer (A1). Table 1 shows the physical properties of the resulting propylene / ethylene block copolymer (A1).

[Production Example 2] Production of propylene / ethylene block copolymer (A2) A propylene / ethylene block copolymer (A2) was produced in the same manner as in Production Example 1 except that the polymerization method was changed as follows. .

(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 30 kg / hour, hydrogen is 1 NL / hour, the catalyst slurry produced in Production Example 1 (3) is 6.2 g / hour, and triethylaluminum. 2.3 ml / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerizer with a stirrer having an internal volume of 100 liters and further polymerized. Propylene was supplied at 15 kg / hour, and hydrogen was supplied to the polymerization reactor so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 liters, gasified, gas-solid separated, and then propylene homopolymer powder was sent to a 480 liter gas phase polymerization vessel to produce an ethylene / propylene block Copolymerization was performed. Propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerizer would be ethylene / (ethylene + propylene) = 0.10 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.9 MPa / G. After the polymerization, it was vacuum dried at 80 ° C. to obtain a propylene / ethylene block copolymer (A2). Table 1 shows the physical properties of the resulting propylene / ethylene block copolymer (A2).

[Production Example 3] Production of propylene-based block copolymer (B1) A propylene-based block copolymer (B1) was produced in the same manner as in Production Example 1 except that the polymerization method was changed as follows.

(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 30 kg / hour, hydrogen is 1 NL / hour, the catalyst slurry produced in Production Example 1 (3) is 6.2 g / hour, and triethylaluminum. 2.3 ml / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerizer with a stirrer having an internal volume of 100 liters and further polymerized. Propylene was supplied to the polymerization vessel at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.09 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 liters, gasified, gas-solid separated, and then propylene homopolymer powder was sent to a 480 liter gas phase polymerization vessel to produce an ethylene / propylene block Copolymerization was performed. Propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerization reactor was ethylene / (ethylene + propylene) = 0.20 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.0 MPa / G. After the polymerization, vacuum drying was performed at 80 ° C. to obtain a propylene-based block copolymer (B1). Table 1 shows the physical properties of the resulting propylene-based block copolymer (B1).

[Production Example 4] Production of propylene / ethylene block copolymer (A3)
(1) Production of solid catalyst support 300 g of SiO ₂ was sampled in a 1-liter branch flask, and 800 mL of toluene was added to make a slurry, followed by transfer to a 5-liter 4-neck flask, and 260 mL of toluene was added. 2830 mL of a toluene solution (10 wt% solution) of methylaluminoxane (hereinafter also referred to as “MAO”) was added and stirred at room temperature for 30 minutes. The temperature was raised to 110 ° C. over 1 hour and reacted for 4 hours. After completion of the reaction, the temperature was lowered to room temperature. After cooling, the supernatant toluene solution was removed, toluene was added again, and substitution was performed until the substitution rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, weigh 2.0 g of diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-t-butylfluorenyl) zirconium dichloride into a 5-liter four-necked flask. It was. The flask was taken out, 0.46 liters of toluene and 1.4 liters of the MAO / SiO ₂ / toluene slurry prepared in (1) above were added under nitrogen.
The mixture was stirred for 0 minutes. The resulting diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-tert-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% in n-heptane. Substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.

(3) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (2) above, 218 mL of triethylaluminum, and 100 liters of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 liters, and the internal temperature was maintained at 15 to 20 ° C. 606 g was inserted and reacted with stirring for 180 minutes. After completion of the polymerization, the solid component was settled, the supernatant was removed, and washed twice with heptane. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 4 g / liter. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, 30 kg / hour of propylene, 1 NL / hour of hydrogen, 10.0 g / hour of the catalyst slurry produced in the above (3) as a solid catalyst component, 2. Polymerization was carried out in a full liquid state where 3 ml / hour was continuously supplied and no gas phase was present. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerizer with a stirrer having an internal volume of 100 liters, and further polymerization was performed. Propylene was supplied at 15 kg / hour, and hydrogen was supplied to the polymerization reactor so that the hydrogen concentration in the gas phase was 0.05 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 liters, gasified, gas-solid separated, and then propylene homopolymer powder was sent to a 480 liter gas phase polymerization vessel to produce an ethylene / propylene block Copolymerization was performed. Propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerizer would be ethylene / (ethylene + propylene) = 0.10 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 1.1 MPa / G. After the polymerization, it was vacuum dried at 80 ° C. to obtain a propylene / ethylene block copolymer (A3). Table 1 shows the physical properties of the resulting propylene / ethylene block copolymer (A3).

[Production Example 5] Production of propylene-based block copolymer (B2)
(1) Production of solid catalyst support 300 g of SiO ₂ was sampled in a 1-liter branch flask, and 800 mL of toluene was added to make a slurry, followed by transfer to a 5-liter 4-neck flask, and 260 mL of toluene was added. 2830 mL of a toluene solution (10 wt% solution) of methylaluminoxane (hereinafter also referred to as “MAO”) was added and stirred at room temperature for 30 minutes. The temperature was raised to 110 ° C. over 1 hour and reacted for 4 hours. After completion of the reaction, the temperature was lowered to room temperature. After cooling, the supernatant toluene solution was removed, toluene was added again, and substitution was performed until the substitution rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, 2.0 g of diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-t-butylfluorenyl) zirconium dichloride was weighed in a 5-liter four-necked flask. . The flask was taken out, 0.46 liters of toluene and 1.4 liters of the MAO / SiO ₂ / toluene slurry prepared in the above (1) were added under nitrogen and stirred for 30 minutes to carry. The obtained diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-tert-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% in n-heptane. Substituting and the final slurry volume is 4.
It was 5 liters. This operation was performed at room temperature.

(3) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (2) above, 218 mL of triethylaluminum, and 100 liters of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 liters, and the internal temperature was maintained at 15 to 20 ° C. After inserting 606 g, the reaction was carried out with stirring for 180 minutes. After completion of the polymerization, the solid component was settled, the supernatant was removed, and washed twice with heptane. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 6 g / liter. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization 30 kg / hour of propylene, 2 NL / hour of hydrogen in a jacketed circulating tubular polymerizer with an internal volume of 58 liters, and 11.0 g of the catalyst slurry produced in (3) above as a solid catalyst component
Per hour, 2.5 ml / hour of triethylaluminum was continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerizer with a stirrer having an internal volume of 100 liters and further polymerized. Propylene was supplied at 15 kg / hour, and hydrogen was supplied to the polymerization reactor so that the hydrogen concentration in the gas phase was 0.02 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was transferred to a transfer tube having an internal volume of 2.4 liters, gasified and subjected to gas-solid separation, and then propylene homopolymer powder was put into a gas phase polymerizer having an internal volume of 480 liters. And ethylene / propylene block copolymerization was performed. Propylene, ethylene, and hydrogen were continuously supplied so that the gas composition in the gas phase polymerization reactor was ethylene / (ethylene + propylene) = 0.50 (molar ratio) and hydrogen / ethylene≈0 (molar ratio). . Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 0.7 MPa / G. After the polymerization, it was vacuum dried at 80 ° C. to obtain a propylene-based block copolymer (B2). Table 1 shows the physical properties of the resulting propylene-based block copolymer (B2).

[Production Example 6]
(1) Preparation of solid titanium catalyst component 952 g of anhydrous magnesium chloride, 4420 ml of n-decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. Add phthalic anhydride 2 to this solution
13 g was added, heated to 130 ° C. and stirred for 1 hour to dissolve phthalic anhydride.

  The homogeneous solution thus obtained was cooled to 23 ° C., and then 750 ml of this homogeneous solvent was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (hereinafter referred to as “DIBP”) was added, and this temperature was maintained. The stirring was continued for 2 hours.

The solid part was then collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride and then heated again at a temperature of 110 ° C. for 2 hours.
After the heating, the solid part was again collected by hot filtration and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.

The solid titanium catalyst component prepared as described above was stored as a hexane slurry. A part of the catalyst was dried to examine the catalyst composition.
The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.

(2) Production of prepolymerized catalyst 56 g of the solid titanium catalyst component obtained in the above (1), 8.0 g of triethylaluminum
80 liters of heptane was introduced into an autoclave equipped with a stirrer having an internal volume of 200 liters, and 560 g of propylene was introduced while maintaining the internal temperature at 5 ° C., and the reaction was allowed to proceed for 60 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice.

  The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted by adding heptane so that the solid titanium catalyst component concentration was 0.7 g / liter. This prepolymerized catalyst contained 10 g of polypropylene per 1 g of the solid titanium catalyst component.

(3) Main polymerization In a vessel polymerization vessel with an internal volume of 100 liters and equipped with a stirrer, 1.1 g / hour, triethylaluminum 4.5 g / hour, cyclohexyl as the prepolymerized catalyst slurry obtained in (2) above as a solid catalyst component 12.5 g / hour of methyldimethoxysilane was continuously fed, 110 kg / hour of propylene, ethylene concentration in the gas phase was 0.8 mol%, and hydrogen in the gas phase was 0.65 mol%. Supplied to be. Polymerization temperature 65 ° C, pressure 2.7M
Polymerization was performed at Pa · G. The catalyst in this reaction is a ZN catalyst.

  The obtained slurry was sent to a vessel polymerization vessel with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization reactor, propylene was supplied at 18 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 2.4 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 1.4 mol%. Polymerization was performed at a polymerization temperature of 65 ° C. and a pressure of 2.5 MPa · G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random copolymer (R1). The resulting propylene random copolymer (R1) was vacuum dried at 80 ° C. The properties of the resulting propylene random copolymer (R1) are shown in Table 1.

[Example 1]
100 parts by weight of the propylene / ethylene block copolymer (A1) produced in Production Example 1 is 0.1 parts by weight of thermal stabilizer IRGANOX 1010 (registered trademark of Ciba-Geigy Corp.), heat stabilizer IRGAFOS168 (Ciba-Geigy Corp.) ) Registered trademark) 0.1 part by weight, 0.1 part by weight of calcium stearate, 0.2 part by weight of synthetic silica having an average particle diameter of 3 μm, and 0.15 part by weight of erucic acid amide were mixed with a tumbler. Thereafter, a polypropylene resin composition (A-1) in the form of pellets was prepared by melting and kneading at 230 ° C. using a twin screw extruder (same direction twin screw kneader) manufactured by Nakatani Machinery Co., Ltd. for heat seal layer A resin composition was obtained.

Thermal stabilizer IRGANOX 1010 (registered trademark of Ciba Geigy Co., Ltd.) 0.1 part by weight, thermal stabilizer IRGAFOS168 (Ciba Geigy Co., Ltd.) per 100 parts by weight of the propylene-based block copolymer (B1) produced in Production Example 3 (Registered trademark) 0.1 parts by weight, calcium stearate 0.1 parts by weight, erucic acid amide 0.15 parts by weight were mixed with a tumbler. Thereafter, a pellet-shaped polypropylene resin composition (C-2) was prepared by melting and kneading at 230 ° C. using a biaxial extruder (same direction biaxial kneader) manufactured by Nakatani Machinery Co., Ltd. It was set as the composition.

100 parts by weight of the propylene / ethylene block copolymer (A1) produced in Production Example 1 is 0.1 parts by weight of thermal stabilizer IRGANOX 1010 (registered trademark of Ciba-Geigy Corp.), heat stabilizer IRGAFOS168 (Ciba-Geigy Corp.) ) Registered trademark) 0.1 part by weight, calcium stearate 0.1 part by weight, erucic acid amide 0.15 part by weight were mixed with a tumbler. Thereafter, a polypropylene resin composition (A-2) in the form of a pellet is prepared by melt-kneading at 230 ° C. using a twin screw extruder (same direction twin screw kneader) manufactured by Nakatani Machinery Co., Ltd. It was set as the composition.

Using these pellet-shaped polypropylene resin compositions, a three-layer three-layer cast extruder (65 mmφ × 3) equipped with a feed block type T die (die width 800 mm, lip opening 1.7 mm) manufactured by SHI Modern Machinery Co., Ltd. And extruded. Extrusion conditions were a die set temperature of 250 ° C., a chill roll temperature of 30 ° C., and a processing speed of 50 m / min. As described above, a three-layer film was produced using A-1 as a heat seal layer, C-2 as an intermediate layer, and A-2 as a laminate layer. The thickness ratio of the heat seal layer, the intermediate layer, and the laminate layer was 20%, 60%, and 20% in this order. The total thickness of the three-layer film was 40 μm. The obtained film was measured for haze (HAZE), impact strength, maximum seal strength, seal start temperature, and blocking coefficient. The measurement results are shown in Table 2.

[Example 2]
A three-layer film was prepared in the same manner as in Example 1 except that the propylene / ethylene block copolymer (A1) included in the heat seal layer was changed to the propylene / ethylene block copolymer (A2) produced in Production Example 2. Manufactured. The haze (HAZE), impact strength, maximum seal strength, seal start temperature, and blocking coefficient of the obtained film were measured. The measurement results are shown in Table 2.

[Example 3]
A three-layer film was produced in the same manner as in Example 1 except that the propylene-based block copolymer (B1) included in the intermediate layer was changed to the propylene-based block copolymer (B2) produced in Production Example 5. The haze (HAZE), impact strength, maximum seal strength, seal start temperature, and blocking coefficient of the obtained film were measured. The measurement results are shown in Table 2.

[Example 4]
The propylene / ethylene block copolymer (A1) included in the heat seal layer and the laminate layer is changed to the propylene / ethylene block copolymer (A3) produced in Production Example 4, and the propylene block copolymer contained in the intermediate layer A three-layer film was produced in the same manner as in Example 1 except that (B1) was changed to the propylene-based block copolymer (B2) produced in Production Example 5. The haze (HAZE), impact strength, maximum seal strength, seal start temperature, and blocking coefficient of the obtained film were measured. The measurement results are shown in Table 2.

[Example 5]
A three-layer film was produced in the same manner as in Example 4 except that the thickness ratios of the heat seal layer, the intermediate layer and the laminate layer were changed to 10%, 80% and 10% in this order. The haze (HAZE), impact strength, maximum seal strength, seal start temperature, and blocking coefficient of the obtained film were measured. The measurement results are shown in Table 2.

[Comparative Example 1]
A three-layer film was produced in the same manner as in Example 1 except that the propylene-based block copolymer (B1) included in the intermediate layer was changed to the propylene / ethylene block copolymer (A1) produced in Production Example 1. . The haze (HAZE), impact strength, maximum seal strength, seal start temperature, and blocking coefficient of the obtained film were measured. Table 3 shows the measurement results.

[Comparative Example 2]
The propylene / ethylene block copolymer (A1) included in the heat seal layer, the intermediate layer and the laminate layer was changed to the propylene-based block copolymer (B2) produced in Production Example 5 in the same manner as in Comparative Example 1. A three-layer film was produced. The resulting film was measured for haze (HAZE), impact strength, maximum seal strength, and blocking resistance. Table 3 shows the measurement results.

[Comparative Example 3]
100 parts by weight of the propylene / ethylene block copolymer (A1) to be included in the heat seal layer, the intermediate layer and the laminate layer, 80 parts by weight of the propylene random copolymer (R1) produced in Production Example 6 and the ethylene elastomer ( Tuffmer A-40 manufactured by Mitsui Chemicals, Inc.
85) A three-layer film was produced in the same manner as in Comparative Example 1 except that the amount was changed to 20 parts by weight. The resulting film was measured for haze (HAZE), impact strength, maximum seal strength, and blocking resistance. Table 3 shows the measurement results.

[Comparative Example 4]
100 parts by weight of the propylene / ethylene block copolymer (A1) to be included in the heat seal layer, the intermediate layer and the laminate layer was added to a commercially available retort brand (manufactured by Prime Polymer Co., Ltd .: F-274NP (melting point: 161 ° C., MFR). ; 3 g / 10 min)) A three-layer film was produced in the same manner as in Comparative Example 1 except that 90 parts by weight and ethylene elastomer (Tuffmer A-4085 manufactured by Mitsui Chemicals, Inc.) were changed to 10 parts by weight. The resulting film was measured for haze (HAZE), impact strength, maximum seal strength, and blocking resistance. Table 3 shows the measurement results.

[Comparative Example 5]
80 parts by weight of a propylene random copolymer (R1) and 20 parts by weight of an ethylene elastomer (Tuffmer A-4085 manufactured by Mitsui Chemicals, Inc.) to be included in the intermediate layer are commercially available retort brand (manufactured by Prime Polymer Co., Ltd.). : F-274NP) A three-layer film was produced in the same manner as in Comparative Example 3 except that 90 parts by weight and ethylene-based elastomer (Tuffmer A-4085 manufactured by Mitsui Chemicals, Inc.) were changed to 10 parts by weight. The resulting film was measured for haze (HAZE), impact strength, maximum seal strength, and blocking resistance. Table 3 shows the measurement results.

  Since the laminated film of the present invention is excellent in balance of transparency, low-temperature sealability, blocking resistance, low-temperature impact strength, and heat seal strength, it is particularly suitably used as a heat-fusible film.

Claims (5)

Melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) is in the range of 1-20 g / 10 min,
The melting point measured with a differential scanning calorimeter (DSC) is in the range of 145-170 ° C.,
A portion insoluble in room temperature n-decane (D _insol ) satisfying the following (1) to (3) (D _insol ) and a portion soluble in room temperature n-decane (D _sol ) satisfying the following (4) to (6) 10-20% by weight
A film comprising a propylene / ethylene block copolymer (A) composed of:
(1) D _insol molecular weight distribution determined from the GPC (gel permeation chromatography) of molecular weight distribution (Mw / Mn) of 3.5 or less (2) the content of skeletons derived from ethylene in D _insol is less than 3 mol% ( 3) Sum of 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in D _insol is 0.2 mol% or less. (4) Molecular weight distribution (Mw / Mn) obtained from GPC of D _sol Is 3.5 or less. (5) The intrinsic viscosity [η] of D _sol in 135 ° C. decalin is 1.5 to 3.0 dl / g.
(6) Content of the skeleton derived from ethylene in D _sol is 15 to 25 mol%. In the heat seal layer containing the propylene / ethylene copolymer (A) according to claim 1,
Melt flow rate (MFR; ASTM D1238, 230 ° C., load 2.16 kg) is in the range of 1-20 g / 10 min,
The melting point measured with a differential scanning calorimeter (DSC) is in the range of 145-170 ° C.,
A portion insoluble in room temperature n-decane satisfying the following (i) to (iii) (D _insol ): 90 to 70% by weight and a portion soluble in room temperature n-decane satisfying the following (iv) to (vi) (D _sol 10-30% by weight
A laminated film comprising at least one intermediate layer comprising a propylene / ethylene block copolymer (B) comprising:
(I) D molecular weight distribution determined from the GPC (gel permeation chromatography) of _insol (Mw / Mn) is 3.5 or less (ii) the content of skeletons derived from ethylene in D _insol is less than 3 mol% ( iii) The sum of the amount of 2,1-insertion bonds and the amount of 1,3-insertion bonds of propylene in D _insol is 0.2 mol% or less. (iv) Molecular weight distribution determined from GPC of D _sol (Mw / Mn) Is 3.5 or less. (V) The intrinsic viscosity [η] of D _sol in 135 ° C. decalin is 2.0 to 3.5 dl / g.
(Vi) The content of the skeleton derived from ethylene in D _sol is more than 25 mol% and 60 mol% or less. A heat seal layer comprising the propylene / ethylene block copolymer (A) according to claim 1,
A laminate comprising at least one intermediate layer comprising the propylene / ethylene block copolymer (B) according to claim 2 and a laminate layer comprising the propylene / ethylene block copolymer (A) according to claim 1 are laminated. A laminated film characterized.   The layer ratio of each layer is 10-30% of the heat seal layer, 40-80% of the intermediate layer and 10-30% of the laminate layer (however, the total of the heat seal layer, the intermediate layer and the laminate layer is 100%) The laminated film according to claim 3.   The film according to any one of claims 1 to 4, wherein the propylene / ethylene block copolymer (A) and / or (B) is polymerized in the presence of a metallocene catalyst.