JPH11245351A - Polyolefin laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyolefin laminated film which is good at surface printability and the melt-cut seal strength of a gusset part and free from the coloring of the end face of a film-wound product, the deterioration of transparency after the passage of time, and offensive odors. SOLUTION: A polyolefin laminated film is the laminate of a resin composition layer A consisting of 50-99 wt.% of a crystalline propylene polymer in which a molecular weight distribution (Mw/Mn) expressed by the ratio of weight average molecular weight(Mw) to number average molecular weight(Mn) is 1.8-4.0, a temperature increase elution fraction elution curve with a measurement starting temperature made 10 deg.C exhibits one eluted component peak at 30 deg.C or above, a peak temperature is 70-120 deg.C or below, and an elution temperature width of a half peak height is 2.5-6 deg.C and 50-1 wt.% of a low crystalline or noncrystalline olefin polymer whose crystallinity measured by X-ray diffraction is 0-30% and a polyolefin layer B, and the layer A is a surface layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin laminate film having excellent surface printability and fusing seal strength at a gusset portion.

[0002]

2. Description of the Related Art Conventionally, polyolefin films have been used for packaging foods, clothing, sundries, etc., and the film surface is subjected to a printing treatment as required.

However, polyolefin-based films are known to have poor printability due to non-polarity.
Usually, in order to improve this, a corona discharge treatment is performed on the film surface. On the other hand, it is also known that the film subjected to the corona discharge treatment has reduced fusing seal strength when fusing and sealing. In particular, when the corona discharge treated polyolefin film is used for a gusset-filled packaging bag whose corona discharge treated surface is the outer surface of the bag, the corona discharge treated surfaces will be fused and sealed, There is a problem that the fusing seal strength of the gusset portion is reduced and cannot be put to practical use.

For this reason, when printing using a polyolefin-based film for a gusset-containing packaging bag, special printing is performed without performing corona discharge treatment on the film surface in order to prevent a decrease in the fusing seal strength at the gusset portion. Ink was used. However, since the film surface is not subjected to corona discharge treatment, even if a special ink is used, the adhesiveness between the film and the printing ink is insufficient, and ink drops due to oil or friction between the film surfaces during transportation. There was a problem.

[0005] For this reason, Japanese Patent Application Laid-Open No. 8-281885 discloses a method for imparting printability to a film and obtaining a polyolefin-based film having a small decrease in the strength of a fusing seal at a gusset portion. Molecular weight distribution (Mw / M) represented by the ratio of average molecular weight (Mn)
n) a polyolefin-based laminated film having at least one surface layer of a resin composition layer composed of a crystalline propylene-based polymer of 2.5 to 4.0 and a low-crystalline or non-crystalline olefin-based copolymer, It has been disclosed.

[0006] However, this method can improve the above-mentioned problem to some extent, but the improvement effect is not yet sufficient, and further improvement has been desired.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a film having excellent printability on the gusset portion while imparting printability on the surface and printability to the film.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been proposed in order to achieve the above-mentioned object, and a polyolefin-based laminated film using a specific resin composition for a surface layer to be subjected to corona discharge treatment has a high printability. The present invention has been completed based on a new finding, confirmed by the present inventors, that the gusset portion is excellent in fusing seal strength as well as excellent in fusing seal strength.

That is, the present invention provides a weight average molecular weight (hereinafter, referred to as "weight average molecular weight")
Mw) and a number average molecular weight (hereinafter abbreviated as Mn) have a molecular weight distribution (Mw / Mn) of 1.8 to 4.
In a temperature rise elution fractionation (hereinafter abbreviated as TREF) elution curve with 0 and 10 ° C. as a measurement start temperature, one elution component peak at 30 ° C. or more is present, and the peak temperature is 70 to 1
50 to 99% by weight of a crystalline propylene polymer having an elution temperature width (hereinafter, abbreviated as a half width) of not more than 2.5 to 6 ° C. A layer (A) of a resin composition comprising 50 to 1% by weight of a low-crystalline or non-crystalline olefin polymer having a crystallinity of 0 to 30% by a line diffraction measurement, and a layer (B) comprising a polyolefin. Wherein the layer (A) is a surface layer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The crystalline propylene polymer as a raw material of the layer (A) used in the present invention must have the following properties.

That is, the crystalline propylene-based polymer 1
In the TREF elution curve with 0 ° C. as the measurement starting temperature, 3
It is necessary that there is one peak of the eluted component at 0 ° C. or higher. When the peak temperature is two or more, the effect of improving the fusing seal strength, which is the original object of the present invention, is not recognized, which is not preferable.

Further, T is defined as a temperature at which measurement is started at 10 ° C.
In the REF elution curve, the half width of the peak of the eluted component at 30 ° C. or more needs to be 2.5 to 6.0 ° C.,
Preferably it is 2.5-5.0 degreeC, More preferably, it is 2.5-4.0 degreeC. The half width is 6 ° C
In the case where it exceeds, the effect of improving the fusing seal strength which is the original object of the present invention is not recognized, which is not preferable. On the other hand, when the half width of the TREF elution curve is 2.5 ° C. or less, the production becomes extremely difficult, which is not preferable.

Further, TR having 10 ° C. as a measurement starting temperature.
In the EF elution curve, the peak temperature of the eluted component at 30 ° C. or higher needs to be 70 to 120 ° C., preferably 75 to 115 ° C., and more preferably 80 to 11 ° C.
0 ° C. When the peak temperature is higher than 120 ° C., the effect of improving the fusing seal strength, which is the original object of the present invention, is not recognized, which is not preferable. On the other hand, when the peak temperature is lower than 70 ° C., it is not preferable because film formation becomes difficult.

In the present invention, it is particularly necessary to set the half width and the peak temperature in the TREF elution curve in the above ranges in order to improve the printability and the fusing seal strength, which are the objects of the present invention.

Further, the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to Mn needs to be 1.8 to 4.0, preferably 1.8 to 3.5, and more preferably 1.8 to 3.5. Preferably it is 2.0-3.0. The molecular weight distribution is 4.0
When the value exceeds, the effect of improving the fusing seal strength, which is the original object of the present invention, is not recognized, which is not preferable. On the other hand, if the molecular weight distribution is less than 1.8, it is not preferable because the production becomes difficult.

FIG. 1 shows a typical TREF chart of the crystalline propylene-based polymer of the present invention. As shown in FIG. 1, the crystalline propylene-based polymer of the present invention has one peak at 30 ° C. or higher. The half width is the elution temperature width at half the height of the peak in the elution peak as shown in FIG.

The crystalline propylene polymer used in the present invention is not particularly limited as long as it has the above characteristics, but preferably has the following characteristics.

The crystalline propylene polymer used in the present invention may be propylene homopolymer or propylene and another α-polymer.
It is preferably a random copolymer obtained by copolymerizing an olefin. Structural units derived from propylene in the crystalline propylene-based polymer are 93 to 100 mol%, preferably 95 to 100 mol%, and structural units derived from a copolymerized monomer are 0 to 7 mol%, preferably 0 to 0 mol%.
Preferably it is 5 mol%. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene. Specific examples of the polymer include a propylene homopolymer, a propylene / ethylene copolymer, a propylene / 1-butene copolymer, a propylene / ethylene / 1-butene copolymer, a propylene / 1-hexene copolymer, propylene·
3-methyl-1-butene, propylene-4-methyl-1
-Pentene copolymer and the like.

The crystallinity of the crystalline propylene polymer used in the present invention is preferably 30% or more, more preferably 35% or more, and further preferably 40% or more. When the crystallinity is lower than 30%, the film formation becomes difficult, and the effect of improving the fusing seal strength is insufficient, which is not preferable.

The melting point of the crystalline propylene polymer used in the present invention is preferably 110 to 160 ° C, more preferably 120 to 155 ° C.

The melt flow index of the crystalline propylene polymer used in the present invention (230 ° C., 2.1
6 kg load, 10 minutes, hereinafter abbreviated as MI. ) Is from 1 to 50 g / g from the viewpoint of extrusion characteristics or film forming properties.
10 minutes, preferably 5 to 40 g /
More preferably, the range is 10 minutes.

The method for producing the crystalline propylene polymer used in the present invention can be used without any particular limitation as long as a resin satisfying the above requirements can be obtained. The method used is not preferred, even if the above requirements are satisfied, because coloring of the end face of the film wound product and unpleasant odor occur.

Therefore, it can be suitably produced by, for example, the following method other than the method using the above-mentioned decomposing means using an organic peroxide or the like.

That is, a metallocene compound (hereinafter abbreviated as component A) and an aluminoxane compound or a non-coordinating ionic compound (hereinafter abbreviated as component B) are essential components, and an organic aluminum compound (hereinafter abbreviated as component C) is optional. Propylene) or propylene and ethylene and / or C 4 to C 1 using a catalyst comprising
And a method of random copolymerizing the α-olefin of No. 6.

As the component A, known components can be used without any limitation, and among them, the following formula (1)

[0026]

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(Wherein, M represents a transition metal atom belonging to Group IVb of the periodic table. (C ₅ H _{4 -m} R ¹ _m ), (C ₅ H _{4 -n} R ² _n )
Represents a substituted cyclopentadienyl group, m and n are
R ¹ and R ² may be the same or different from each other, and each of R ¹ and R ² may be a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, or a cyclopentadienyl ring. A hydrocarbon group bonded to two carbon atoms to form one or more hydrocarbon rings which may be substituted with a hydrocarbon. Q represents (C ₅ H _{4 -m} R ¹ _m ) and (C ₅ H
_4-n R ² _n ) is a crosslinkable group, which is a divalent hydrocarbon group, unsubstituted silylene group or hydrocarbon-substituted silylene group. X ¹ and X ² represent a hydrogen, halogen or hydrocarbon group which may be the same or different. )) Can be suitably used. More preferably, in the formula (1), M is a zirconium or hafnium atom, R ¹ and R ² are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and X ¹ and X ² are the same or different halogen atoms. Alternatively, a chiral compound in which the hydrocarbon group Q is a hydrocarbon-substituted silylene group is preferable.

Specific examples of the component A include rac-dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride and rac-dimethylsilylene (2,4 -Dimethylcyclopentadienyl) (3 ′,
5′-dimethylcyclopentadienyl) zirconium dimethyl, rac-dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′trimethylcyclopentadienyl) zirconium dichloride, rac-dimethyl Silylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4′5 ′, 5′-trimethylcyclopentadienyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-indenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-
Methyl-indenyl) zirconium dimethyl, rac-
Diphenylsilylenebis (2-methyl-indenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4, 5,6,7-tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, rac
-Diphenylsilylenebis (2-methyl-4,5,6,
7-tetrahydroindenyl) zirconium dimethyl,
rac-dimethylsilylenebis (2,4-dimethyl-indenyl) zirconium dichloride, rac-diphenylsilylenebis (2,4-dimethyl-indenyl) zirconium dichloride, rac-dimethylsilylenebis (2,4-dimethyl-indenyl) zirconium dimethyl Rac-diphenylsilylenebis (2,4-dimethyl-indenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-isopropyl) Indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-isopropylindenyl) zirconiumdimethyl, rac-diphenylsilylenebis (2-methyl -4-isopropylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium Dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl, rac-dimethylsilylenebis ( 2-methyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-t-butylindenyl) zirconium dichloride, rac-dimethylsilyl Renbisu (2
-Methyl-4-t-butylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4-t-butylindenyl) zirconium dimethyl,
rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-
Diphenylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4-phenylindene) Nil) zirconium dimethyl, rac-dimethylsilylenebis (2-
Methyl-4-naphthylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-
Naphthylindenyl) zirconium dimethyl, rac-
Diphenylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-benzindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-benzindenyl) zirconium dichloride, rac-dimethyl Silylene bis (2-methyl-
Benzindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-benzindenyl) zirconium dimethyl, and the like. Further, a compound in which zirconium is replaced with hafnium is also preferably used.

As the component B, known components can be used without any limitation. Among them, the following components can be preferably used.

As the aluminoxane compound, an aluminum compound represented by the following formula (2) or (3) is preferable.

[0031]

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[0032]

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In the formula (2) or (3), R ³ and R ⁴ each have 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
And a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. Of these, a methyl group is particularly preferred. p and q are each an integer of 4 to 100, preferably 6 to 8
0, particularly preferably 10 to 60.

As the method for producing the aluminoxane compound, various known methods may be employed, for example, a method in which a trialkylaluminum is directly reacted with water in a hydrocarbon solvent, a method for producing copper sulfate hydrate having water of crystallization. , Aluminum sulfate hydrate, a method of reacting adsorbed water with a trialkylaluminum in a hydrocarbon solvent using a hydrous silica gel or the like.

The non-coordinating ionic compound has the following formula (4)
The compound represented by is suitable.

[0036]

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(Where M is the 3Bth term shown in the periodic table)
X ³ , X ⁴ , X ⁵ , and X ⁶ each represent a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , An alkylaryl group, an arylalkyl group, a substituted alkyl group, a halogen-substituted aryl group, an organic metalloid group, or a halogen atom. C represents a counter cation such as carbonium and ammonium.
r is a valence of M and is an integer of 1 to 7, and s is an integer of 2 to 8. Specific examples of these compounds include triethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, and methylanilinium tetrakis ( Pentafluorophenyl)
Borate, dimethyl anilium tetrakis (pentafluorophenyl) borate, trimethyl anilium tetrakis (pentafluorophenyl) borate, tri-n-butyl borane, triphenyl borane, triphenyl carbonium tetrakis (pentafluorophenyl) borane,
Tris (pentafluorophenyl) borane and the like can be mentioned. Among them, triphenylcarbonium tetrakis (pentafluorophenyl) borane, tris (pentafluorophenyl) borane, and dimethylaninium tetrakis (pentafluorophenyl) borate are preferably used.

The component (A) and / or (B) can be used by being supported on an inorganic oxide such as silica gel or alumina, or an organic polymer such as polyethylene, polypropylene or polystyrene. When these catalyst components are supported on these carriers, the particle properties of the resulting polymer are improved, and the process suitability in resin production such as prevention of polymerization scale in a reactor can be significantly improved. The particle size of these carriers is generally 0.1 to 500 μm, preferably 1 to 500 μm.
It is 200 μm, more preferably 10 to 100 μm.
If the particle size is small, the resulting particles will be a finely powdered polymer, and if too large, they will be coarse particles, making it difficult to handle the powder. The pore volume of these carriers is usually 0.1 to 5c.
m ³ / g, preferably 0.3 to ³ cm ³ / g. The pore volume can be measured by a BET method, a mercury intrusion method, or the like.

The component A and / or the component B can be used by being supported on an inorganic oxide such as silica gel or alumina, or an organic polymer such as polyethylene, polypropylene or polystyrene. When these catalyst components are supported on these carriers, the particle properties of the resulting polymer are improved, and the process suitability in resin production such as prevention of polymerization scale in a reactor can be significantly improved. The particle size of these carriers is generally 0.1 to 500 μm, preferably 1 to 20 μm.
0 μm, more preferably 10 to 100 μm. If the particle size is small, the resulting particles will be a finely powdered polymer, and if too large, they will be coarse particles, making it difficult to handle the powder. The pore volume of these carriers is usually 0.1 to ⁵ cm ³
/ G, preferably 0.3 to ³ cm ³ / g.
The pore volume can be measured by a BET method, a mercury intrusion method, or the like.

The amounts of the components A and B are arbitrary. However, when the aluminoxane is used as the component B, the amount of the component B used (molar amount of Al atoms in the component B) is 0.1-100,000 mol is preferable with respect to 1 mol of transition metals, More preferably, it is 1-50,000 mol,
More preferably, 10 to 30,000 mol is suitable. Further, the use amount of the B component when a non-coordinating ionic compound is used as the B component (molar amount of the third group B atom in the B component)
Is 0.01 to 1 with respect to 1 mol of the transition metal in the component A.
000 mol is preferred, and more preferably 0.1 to
5,000 mol, more preferably 1-3000 mol, is suitable.

The compound represented by the following formula (5) is preferably used as the component C if necessary in the present invention.

[0042]

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(In the formula, R ⁷ represents a hydrocarbon group such as an alkyl group or an aryl group having 1 to 10 carbon atoms or an alkoxy group. X ⁷ represents a halogen atom. T is 1 to 3.) Specific examples of the compound represented by the above general formula include trimethylaluminum, triethylaluminum, trin-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum trin-hexylaluminum, trin-octylaluminum , Trialkylaluminums such as tri-n-decylaluminum, diethylaluminum monochloride, diethylaluminum monobromide,
Dialkylaluminum monohalides such as diethylaluminum monofluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride,
Alkyl aluminum halides such as ethylaluminum dichlorides, alkoxyaluminums such as diethylaluminum monoethoxide and ethylaluminum diethoxide are exemplified. Among them, trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferably used.

The amount of the component C used as required is not particularly limited, but is generally preferably 1 to 50,000 mol per 1 mol of the transition metal in the component A.
More preferably, it is 5 to 10,000 mol, and still more preferably 10 to 5,000 mol.

In the production of the polypropylene resin for an unstretched film of the present invention, known methods can be used without any limitation.
For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and isooctane; aliphatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; gasoline fractions and hydrogenation Any of the well-known polymerization processes such as slurry polymerization in which polymerization is performed in an inert solvent such as diesel oil fraction, bulk polymerization in which propylene itself is used as a solvent, and gas phase polymerization in which propylene is used in a gas phase are preferably used.

The polymerization temperature of the above polymerization is preferably -10
-200 ° C, more preferably 20-150 ° C.

In the polymerization, the above-mentioned catalyst component A
The component, the component B, and / or the component C may be mixed in an inert solvent in advance and then supplied into the polymerization system, or each component may be supplied separately. The order of supplying these catalyst components is not limited at all. Further, hydrogen can be allowed to coexist as a molecular weight regulator.

Prior to the main polymerization, a small amount of α-olefin is added to a catalyst obtained by combining the catalyst components A, B and / or C in an inert solvent in an amount of 1 g per mole of transition metal in the component A. After preliminarily polymerizing 10 to 10 kg, the main polymerization can also be carried out. Examples of the α-olefin that can be used for the prepolymerization include an α-olefin having 2 to 12 carbon atoms. Specifically, ethylene, propylene,
Examples thereof include 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene, and ethylene, propylene and 4-methyl-1-pentene are particularly preferably used.

The polypropylene resin for a non-stretched film of the present invention may be any of various commonly used additives such as an antioxidant and a chlorine scavenger, as long as the object of the present invention is not impaired.
An antistatic agent, a lubricant, an anti-blocking agent and the like can be blended, and a low-crystalline or amorphous olefin polymer such as an ethylene / 1-butene copolymer, a propylene / 1-butene copolymer, Propylene-1
Butene copolymers and the like can also be added.

The low-crystalline or non-crystalline olefin polymer which is a raw material of the layer (A) used in the present invention includes X
As long as it is an α-olefin polymer having a crystallinity of less than 30% as measured by X-ray diffraction, a known olefin polymer can be used. Such olefin polymers include ethylene / 1-butene copolymer and propylene / 1-
Butene copolymers and ethylene / propylene / 1-butene copolymers can be exemplified.

The MI of the low-crystalline or amorphous olefin polymer used in the present invention (230 ° C., 2.16 kg load,
(10 minutes) is preferably 0.5 to 40 g / min, and more preferably 1 to 20 g / 10 min.

The mixing ratio of the crystalline propylene polymer and the low-crystalline or amorphous olefin polymer used in the present invention is 50 to 99 when the total amount of both is 100% by weight. % By weight, the latter being 50 to 1
It is necessary that the content be in the range of 70 to 97% by weight, and the latter be in the range of 30 to 3% by weight in consideration of the effect of improving the strength of the fusing seal and the surface roughness of the film. When the mixing ratio of the crystalline propylene-based polymer is less than 50% by weight, the original effect of improving the fusing seal strength is insufficient, which is not preferable.
On the other hand, when the content exceeds 99% by weight, the fusing seal strength is reduced and the surface of the film is roughened, and the bleeding to the surface of the lubricant, antistatic agent, antifogging agent, etc. added to the resin is slow, which is not practical. Therefore, it is not preferable.

As a method for producing a resin composition of a crystalline propylene-based polymer and a low-crystalline or amorphous olefin-based polymer, a conventionally known method may be used. For example, a method of mixing with a tumbler blender, a Henschel mixer, or the like, a method of melt-kneading and granulating using a single-screw extruder or a multi-screw extruder after mixing, or melt-kneading and granulating with a kneader, a Banbury mixer, or the like. A method or the like can be adopted.

The T of the resin composition of the crystalline propylene polymer and the low crystalline or amorphous olefin polymer
In the REF elution curve, an elution component peak derived from a low-crystalline or amorphous olefin-based polymer and a peak of an elution component derived from a crystalline propylene-based polymer are separately observed,
The peak of the eluting component derived from the low-crystalline or amorphous olefin polymer is less than 70 ° C., and the peak of the eluting component derived from the crystalline propylene polymer alone is 70 to 12
Preferably it is observed between 0 ° C.

As the material for the layer (B) used in the present invention, known polyolefins can be used without any limitation. However, it is preferable to use a crystalline polyolefin from the viewpoint of the compatibility with the material for the layer (A).

As the above-mentioned crystalline polyolefin, similar to the above-mentioned crystalline propylene-based polymer, any known polyolefin, for example, propylene homopolymer, may be used as long as it has a crystallinity of more than 30% as measured by X-ray diffraction. Propylene / ethylene copolymer, propylene / ethylene / 1-
Propylene polymers such as butene copolymers; ethylene homopolymers such as ethylene homopolymers such as high-density polyethylene, low-density polyethylene, and medium-density polyethylene, and ethylene / α-olefin copolymers such as linear low-density polyethylene Polymer; butene-based polymers such as 1-butene homopolymer and the like can be used. These polymers can be used alone or in combination of two or more. Of course, the crystalline propylene-based polymer which is one component of the resin composition as the raw material of the layer (A) can be used without any limitation.

Among the above-mentioned various polymers, a propylene-based polymer or a linear low-density polyethylene is preferable as the crystalline polyolefin. Further, as the propylene-based polymer, in particular, a propylene homopolymer and a propylene / ethylene copolymer having a structural unit derived from ethylene or 1-butene copolymerized with propylene of 10 mol% or less, Butene-1 copolymer is preferred. Further, the MI (230 ° C., 2.16 kg load, 10 minutes) of the propylene polymer is
It is preferably 0.5 to 30 g / 10 min, and more preferably 5 to 20 g / 10 min.

The linear low-density polyethylene particularly has 4 to 1 carbon atoms copolymerized with ethylene.
Ethylene / α-olefin copolymers having 0.1 to 10 mol% of structural units derived from 0 α-olefin are preferred. The linear low-density polyethylene preferably has a density of 0.880 to 0.940 g / cm ³ and an MI (190 ° C., 2.16 kg load, 10 minutes) of 0.5 to 10 g / 10 minutes. Is preferred.

The polyolefin-based laminated film of the present invention comprises a layer (A) made from a resin composition of the above-mentioned crystalline propylene polymer and a low-crystalline or amorphous olefin-based polymer, and the above-mentioned polyolefin. And a layer (B), and the layer (A) needs to be a surface layer. When the layer (A) is used alone, the transparency deteriorates, which is not preferable. When the layer (B) is used alone or when the layer (A) is not the surface layer, the object of the present invention is to improve the fusing seal strength of the gusset seal portion. This is not preferable because no effect is exhibited.

In the present invention, the layer structure of the laminate is not particularly limited as long as the layer (A) is a surface layer, and is not limited to the two-layer structure of the layer (A) and the layer (B). , A layer (B) or a layer (A), and may be appropriately configured in consideration of physical properties such as film rigidity, flexibility, and heat sealability.

Further, other layers may be laminated for imparting other properties as long as the effects of the present invention are not impaired. The raw material of the other layer is not particularly limited, and various resins may be used according to the purpose. Needless to say, the above-mentioned crystalline polyolefin may be used. For example, considering the strength of the fusing seal other than the gusset part, propylene-based random copolymers such as propylene / ethylene random copolymer, propylene / 1-butene random copolymer, propylene / ethylene / 1-butene random copolymer, etc. Coalescence may be selected as the layer (C) raw material.

Among the above-mentioned layer configurations, a particularly preferable layer configuration is as follows: when the other layer is a layer (C), (1) layer (A) / layer (B) (2) layer (A) / layer (B) / layer (A) (3) layer (A) / layer (B) / layer (C).

The total thickness of the polyolefin-based laminated film of the present invention is preferably 10 to 100 μm.
In particular, the thickness is more preferably in the range of 20 to 60 μm.

The thickness of each of the laminated layers is the same as that of the layer (A).
Preferably has a thickness of 2 to 30 μm.
It is more preferably from 10 to 10 μm.

The layer (B) has a thickness of 5 to 70 μm
And more preferably from 10 to 50 μm.

The thickness of the other layers is not particularly limited, but is preferably 3 to 30 μm.

The raw material of each layer of the polyolefin-based laminated film of the present invention may optionally contain additives such as an antioxidant, a lubricant, an antiblocking agent, an antistatic agent, an antifogging agent, etc. It can be added within a range that does not inhibit.

The polyolefin-based laminated film of the present invention may be an unstretched film simply extruded or a uniaxially or biaxially stretched film, but the effect of the present invention is remarkably exhibited when it is an unstretched film. Therefore, it is particularly preferable.

The method for producing the polyolefin-based laminated film of the present invention is not particularly limited, but a co-extrusion T-die method, a co-extrusion inflation method, an extrusion lamination method, a dry lamination method, a sand lamination method and the like are used.
Among them, the co-extrusion T-die method is particularly preferably used.

When manufacturing by the above-mentioned co-extrusion T-die method,
For example, when the crystalline polyolefin is used for the layer (B), the resin composition specified in the present invention for the layer (A), and if necessary, the crystalline polyolefin for the layer (C), the layer (A) ) / Layer (B) / Layer (C) can be produced by melt extrusion using a plurality of extruders and a co-extrusion lamination method of laminating before and after a die or inside a die.

The molding conditions for the polyolefin-based laminated film of the present invention are not particularly limited, but generally, the resin temperature is 190 to 300 ° C., the air gap is 60 to 200 mm, the cooling roll temperature is 10 to 70 ° C., and the film forming speed is 50 to 200 ° C. 300m /
It is preferably performed in minutes.

The polyolefin-based laminated film of the present invention may be used as it is, but is preferably subjected to a corona discharge treatment in order to improve the adhesion to printing ink. The corona discharge treatment is performed on the surface of the layer (A) in consideration of the effects of the present invention. The conditions of the corona discharge treatment are not particularly limited.However, from the viewpoint of the adhesion of the obtained polyolefin-based laminated film to the printing ink, or the prevention of the generation of offensive odor due to the damage of the corona discharge treatment, the wetting tension of the film surface is reduced. 31 to 43 dynes / cm,
Preferably, it is performed so as to be 33 to 38 dynes / cm.

The method for printing the polyolefin-based laminated film of the present invention is not particularly limited, and includes gravure printing, offset printing, silk screen printing and the like, and gravure printing and offset printing are preferably used.

The printing ink used for the above printing is aqueous,
Any oil type can be used, and a method of drying at 20 to 100 ° C. after printing with ink is generally performed.

The polyolefin-based laminated film of the present invention is not particularly limited, and is used for packaging of foods, clothing, stationery, miscellaneous goods, etc. Among them, the gusset portion has excellent fusing seal strength and transparency after aging. Since it does not cause deterioration or unpleasant odor, it is suitably used especially for food applications.

[0076]

According to the present invention, the use of a crystalline propylene polymer having a narrow molecular weight distribution as well as a narrow molecular weight distribution as a raw material provides a polyolefin-based laminated film which is extremely excellent in fusing sealability. it can. Therefore, in the production of a packaging bag having a gusset form, even if corona treatment for improving the printability of the surface is performed, the fusing seal strength of the gusset portion is excellent, and further, the coloring of the end face color of the film wound product, after aging It is suitable as a packaging film, especially a food packaging film, because it has no deterioration in transparency and no unpleasant odor.

[0077]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

The measuring methods used in Examples and Comparative Examples will be described.

1) Wetting tension This was carried out according to JIS K6768.

2) According to MI JIS K7210, linear low density polyethylene was measured at a load of 2.16 kg and a temperature of 190 ° C., and other raw materials were measured at a load of 2.16 kg and a temperature of 23 ° C.
It was measured at 0 ° C.

3) Measurement of Crystallinity Using an X-ray diffractometer manufactured by JEOL Ltd., an X-ray output of 16
kw (tube voltage: 40 kV, tube current: 400 mA), target: Cu, measurement angle: 2 ° = 9 to 31 degrees. The crystal peak was waveform-separated from the obtained X-ray diffraction pattern, and the crystallinity was determined from the area intensity ratio. The sample is
What was previously melted at 230 ° C. and then gradually cooled to 50 ° C. was used.

4) Measurement of molecular weight distribution Using a water permeation 150C type gel permeation chromatography (GPC), orthodichlorobenzene (ODCB) as an eluent, and a column GMH6H
T (manufactured by Tosoh Corporation). The molecular weight distribution (Mw / Mn) was determined from the ratio between the obtained weight average molecular weight (Mw) and number average molecular weight (Mn).

5) Measurement of TREF (Temperature Rise Elution Fractionation) Elution Curve An automatic TREF device (SSC-73, manufactured by Senshu Kagaku)
00, ATREF) under the following conditions.

Solvent: orthodichlorobenzene Flow rate: 150 ml / hour Heating rate: 4 ° C./hour Detector: Infrared detector Measurement wave number: 3.41 μm Column: “Packed column 30” manufactured by Senshu Kagaku
Φ ”, 30 mm Φ × 300 mm Concentration: 1 g / 120 ml Injection volume: 100 ml In this case, the sample solution is introduced into the column at 145 ° C., and then cooled to 10 ° C. at a rate of 2 ° C./hour to fill the sample polymer. After the adsorption on the surface of the agent, the column temperature was raised under the above conditions, and the concentration of the polymer eluted at each temperature was measured with an infrared detector to obtain an elution temperature-elution amount curve.

6) Measurement of Fusing Seal Strength A gusset-containing package was formed using a PP500 bag making machine manufactured by Kyoei Printing Machinery. A gusset seal portion at the time of bag making at a sealing temperature of 320 ° C. and a bag making speed of 140 sheets / minute was cut out, and a tensile speed of 100 mm / min. The seal strength (indicated by g / 15 mm width) when peeled off was determined.

7) Evaluation of printability A gravure ink "Alpha RG" (manufactured by Toka Dye Chemical Co., Ltd.) was applied to the corona discharge treated surface of the film with a bar coater # 10.
After coating using No. 0, it was dried at 80 ° C. for 1 minute. A cellophane tape (Nichiban cellophane tape) was adhered to the printed surface, and a five-point evaluation was performed based on the remaining area of the printing ink when the film was rapidly peeled off.

[0087] 8) Color of the end face The rolled original film of the laminated film obtained by film formation (width: 500 m)
m, the length of the end face of 1000 m) was visually observed. Light yellow is normal. Reddish brown indicates discoloration.

9) Odor A test piece (100 mm × 5) of a laminated film obtained by film formation.
(0 mm) 20 pieces were placed in a bottle with a lid, and a sensory test for odor in the bottle was performed to determine the presence or absence of odor.

[0089] 10) Haze difference after lapse of time When the haze immediately after aging of the laminated film obtained by film formation was H ₁ , and the haze after being left in a thermostat at 23 ° C. for one month after aging was H ₂ , ₂ -H ₁₎
Is the haze difference after aging.

Preparation Example 1 of Crystalline Propylene Polymer [Preparation of supported metallocene catalyst] 10 g of silica gel-supported methylaluminoxane (MAO on SiO2, manufactured by Witco, 25 wt% Al product) was added to rac-dimethylsilylenebis-1- (2 -Methylindenyl) zirconium dichloride in 100 ml of toluene solution (0.005 m
(mol / ml toluene solution) and stirred at room temperature for 30 minutes. Next, the reaction mixture was filtered, and the obtained solid was washed twice with 50 ml of toluene, and dried under reduced pressure to obtain a metallocene catalyst supported on silica gel.
0.045 mmol of metallocene was supported per 1 g of the catalyst.

[Polymerization] 600 kg of propylene was inserted into a polymerization tank having an internal volume of 2 m3, and triisobutylaluminum 6
12 mmol were introduced. After the introduction of hydrogen gas, the internal temperature of the polymerization tank was raised to 55 ° C. Then, ethylene was introduced, and 20 g of the metallocene catalyst supported on the silica gel was charged. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was carried out for 2 hours while supplying the ethylene gas and the hydrogen gas at a constant concentration. After the completion of the polymerization, unreacted propylene was purged and dried at 70 ° C. for 1 hour to obtain 200 kg of a white granular polymer. The ethylene content was 1.0% by weight.

[Granulation] To 100 parts by weight of the obtained polymer,
0.1 part by weight of 2,6-di-t-butyl-p-cresol as an antioxidant, 0.05 part by weight of calcium stearate as a chlorine scavenger, thyroid 55 as an antiblocking agent, and an average particle size of 2.73 μm) 0 .15 parts by weight,
After adding 0.06 parts by weight of erucamide as a lubricant and mixing with a Henschel mixer for 5 minutes, a screw diameter of 6
It was extruded at 230 ° C. using a 5 mmφ extrusion granulator to obtain raw material pellets. Melting point of pellets after granulation, MFR,
Table 1 shows the molecular weight distribution (Mw / Mn), the peak temperature and the half width of the TREF elution curve.

Crystalline propylene-based polymer production example 2 A crystalline propylene-based polymer was obtained except that the amount of hydrogen gas introduced during polymerization was changed to 7.0 g / 10 minutes in Production example 1 of a crystalline propylene-based polymer. Performed in the same manner as in Production Example 1.
The amount of polymer produced was 150 kg and the ethylene content was
0.95% by weight. Melting point of pellet after granulation, M
Table 1 shows the FR, molecular weight distribution (Mw / Mn), peak temperature and half width of the TREF elution curve.

Production Example 3 of Crystalline Propylene Polymer The same procedure was carried out as in Production Example 1 of the crystalline propylene polymer except that the amount of ethylene gas introduced during the polymerization was changed. . The amount of polymer produced is 1
60 kg and an ethylene content of 1.5% by weight. Melting point, MFR, molecular weight distribution (M
w / Mn), the peak temperature and the half width of the TREF elution curve are shown in Table 1.

Production Example 4 of Crystalline Propylene Polymer Production was carried out in the same manner as in Production Example 1 of the crystalline propylene polymer, except that ethylene was not introduced in the polymerization of Production Example 1 of the crystalline propylene polymer. 140 kg of polymer produced
Met. Table 1 shows the melting point, MFR, molecular weight distribution (Mw / Mn), peak temperature and half width of the TREF elution curve of the pellet after granulation.

Preparation Example 5 of Crystalline Propylene Polymer [Preparation of Titanium Catalyst Supported on Magnesium Chloride]
A titanium catalyst supported on magnesium chloride was obtained according to the method of Example 1 of JP-A-83006.

The composition of the titanium catalyst supported on magnesium chloride was 2.1% by weight of titanium, 57% by weight of chlorine, 18.0% of magnesium, and 21.9% by weight of diisobutyl phthalate.

[Polymerization] 600 kg of propylene was inserted into a polymerization tank having an internal volume of 2 m 3, and triethyl aluminum 612 was added.
mmol, diphenyldimethoxysilane 306mmo
1 After further introducing hydrogen gas, the internal temperature of the polymerization tank was raised to 55 ° C. Then, ethylene was introduced, and 6 g of a magnesium chloride-supported titanium catalyst was charged. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was carried out for 2 hours while supplying the ethylene gas and the hydrogen gas at a constant concentration. After completion of the polymerization, unreacted propylene was purged to obtain a white granular polymer. The resulting polymer is 1
Drying was performed for hours. The amount of polymer produced was 180 kg,
The ethylene content was 4.0% by weight.

[Granulation] Granulation was carried out in the same manner as in Production Example 1 of the crystalline propylene polymer. Melting point of pellets after granulation,
Table 1 shows the MI, molecular weight distribution (Mw / Mn), peak temperature and half width of the TREF elution curve.

Crystalline Propylene Polymer Production Example 6 [Polymerization] Crystalline propylene polymer production example 5 was changed except that the amount of hydrogen gas introduced in the polymerization of polymerization propylene polymer production example 5 was changed. Polymerization].
150 kg of a polymer of 4 g / 10 min was obtained. The ethylene content was 4.0% by weight.

[Determination and Granulation by Organic Peroxide] In the granulation of Production Example 1 of the crystalline propylene polymer, 2,5-dimethyl-2,5-di (t
-Butylperoxy) hexane was performed in the same manner as in the granulation of Production Example 1 of the crystalline propylene polymer except that 0.02 parts by weight of hexane was added. Table 1 shows the melting point, MI, molecular weight distribution (Mw / Mn), peak temperature and half width of the TREF elution curve of the pellet after granulation.

Production Example 7 of Crystalline Propylene Polymer [Polymerization] A toluene solution of 25 L of hexane and methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.)
Product name: MMAO, concentration 2 mol-Al / L) 1.5 mol in terms of Al atom, rac-dimethylsilylenebis-1- (2-methyl-4-naphthylindenyl) zirconium dichloride toluene solution 1 as metallocene 1
After further introducing 00 ml (0.005 mmol / ml) of hydrogen gas, the temperature of the polymerization tank was raised to 30 ° C. Then, propylene gas was introduced so that the pressure in the polymerization vessel became 8 kg / cm2G, and polymerization was carried out for 2 hours while supplying propylene so as to keep the pressure in the polymerization tank constant during the polymerization. After completion of the polymerization, unreacted propylene was purged from the polymerization tank, and then 1 L of isopropanol was introduced into the polymerization tank to stop the polymerization. Subsequently, 0.4 L of 6 N hydrochloric acid was added, and
For 15 minutes. After the treatment, the produced polymer was filtered, the polymer was washed three times with 25 L of methanol, and dried at 70 ° C. under reduced pressure to obtain 5 k of polymer as a white powder.
g was obtained.

[Granulation] Granulation was carried out in the same manner as in Production Example 1 of crystalline propylene-based polymer. Melting point of pellets after granulation,
Table 1 shows the MI, molecular weight distribution (Mw / Mn), peak temperature and half width of the TREF elution curve.

Crystalline Propylene Polymer Production Example 8 3 kg of pellets obtained from Crystalline Polypropylene Polymer Production Example 3 and 3 kg of pellets obtained from Crystalline Polypropylene Polymer 7 were blended.

Table 1 shows the melting point, MI, molecular weight distribution (Mw / Mn), peak temperature and half width of the TREF elution curve of the blended pellets. The TREF elution curve had two peaks at 30 ° C. or higher.

Production Example 9 of Crystalline Propylene Polymer [Polymerization] 25 L of hexane and a toluene solution of methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.)
Product name: MMAO, concentration 2 mol-Al / L) 1.5 mol in terms of Al atom, rac-dimethylsilylenebis-1- (2-methyl-4-naphthylindenyl) zirconium dichloride toluene solution 1 as metallocene 1
After further introducing 00 ml (0.005 mmol / ml) of hydrogen gas, the temperature of the polymerization tank was raised to 30 ° C. Next, a propylene / ethylene mixed gas was fed to the polymerization vessel at a pressure of 8 kg.
/ Cm ² G, and the polymerization was carried out for 2 hours while supplying a propylene / ethylene mixed gas so as to keep the pressure inside the polymerization tank constant during the polymerization. After completion of the polymerization, unreacted propylene was purged from the polymerization tank, and then 1 L of isopropanol was introduced into the polymerization tank to stop the polymerization. Subsequently, 0.4 L of 6N hydrochloric acid was added, and the mixture was treated at 30 ° C. for 15 minutes. After the treatment, the produced polymer was filtered, the polymer was washed three times with 25 L of methanol, and then dried under reduced pressure at 70 ° C. to obtain a white solid having an ethylene content of 8.0% by weight.
Was obtained in an amount of 5 kg.

[Granulation] Granulation was carried out in the same manner as in Production Example 1 of the crystalline propylene polymer. Melting point of pellets after granulation,
Table 1 shows the MI, the molecular weight distribution (Mw / Mn), the peak temperature and the half width of the TREF elution curve.

[0108]

[Table 1]

Example 1 [Preparation and Evaluation of Film] 90 parts by weight of the pellets obtained in Production Example 1 of a crystalline propylene polymer were mixed with a low-crystalline ethylene / 1-butene copolymer (1-butene content = 1
2 mol%, crystallinity = about 5%, MI = 7 g / 10 min) 1
And 0 parts by weight to prepare a resin composition. Using three extruders, the above resin composition as a surface layer raw material (A),
A crystalline propylene homopolymer (crystallinity = 66.7%, MI = 8.5 g / 10 min) as a base material (B);
As another surface layer raw material (C), a crystalline propylene / ethylene / 1-butene copolymer (crystallinity = 57.2%,
MI = 7 g / 10 min, ethylene content = 3.7 mol%,
1-butene content = 3.5 mol%) and the composition ratio A:
Extruded so that B: C becomes 1: 2: 1, thickness 30μ
m was obtained.

Further, the surface of the obtained laminated film on the surface layer raw material (A) side was subjected to corona discharge treatment so that the wetting index was 35 dynes / cm, and aged at 40 ° C. for 24 hours. The test was performed. The results are shown in Table 2.

Example 2 Low-crystalline ethylene / 1-butene copolymer (1-butene content = 12 mol%, crystallinity = about 5)
%, MI = 7 g / 10 min) except that 30 parts by weight was used. The results are shown in Table 2.

Example 3 The procedure of Example 1 was repeated except that 5 parts by weight of a low-crystalline ethylene / 1-butene copolymer was used as a raw material for the surface layer. The results are shown in Table 2.

Example 4 An amorphous ethylene / propylene copolymer (crystallinity 0%, MI = 5, propylene content = 18 mol) was prepared in place of the low-crystalline ethylene / 1-butene copolymer in Example 1. %)
The procedure was performed in the same manner as in Example 1, except that was used. Table 2 shows the results
It was shown to.

Example 5 A low-crystalline propylene-butene-1 copolymer (crystallinity = about 20%, MI = 7, butene- 1 content =
(23 mol%) was used in the same manner as in Example 1. The results are shown in Table 2.

Example 6 The procedure of Example 1 was repeated, except that the pellets obtained in Example 2 for producing a crystalline propylene polymer were used instead of the pellets obtained in Example 1 for producing a crystalline propylene polymer. . The results are shown in Table 2.

Example 7 The same procedure as in Example 1 was carried out except that the pellets obtained in Example 3 for producing a crystalline propylene polymer were used instead of the pellets obtained in Example 1 for producing a crystalline propylene polymer. . The results are shown in Table 2.

Example 8 The procedure of Example 1 was repeated, except that the pellets obtained in Example 4 for producing a crystalline propylene polymer were used instead of the pellets obtained in Example 1 for producing a crystalline propylene polymer. . The results are shown in Table 2.

Comparative Examples 1 to 4 Instead of the pellets obtained in the crystalline propylene polymer production example 1, the crystalline propylene polymer production example 5 (comparative example 1) and the crystalline propylene polymer production example 6 ( Comparative Example 2), Crystalline Propylene Polymer Production Example 7 (Comparative Example 3), Crystalline Propylene Polymer Production Example 8 (Comparative Example 4)
The procedure was performed in the same manner as in Example 1 except that the pellet obtained in the above was used. The results are shown in Table 2.

Comparative Example 5 The same procedure as in Example 1 was carried out except that the ethylene / 1-butene copolymer was not used. The results are shown in Table 2.

Comparative Example 6 In Example 1, the ethylene / 1-butene copolymer was replaced with 60
The procedure was performed in the same manner as in Example 1 except that parts by weight were used. The results are shown in Table 2.

Comparative Example 7 In Example 1, the ethylene / 1-butene copolymer (1-
Butene content = 8 mol%, crystallinity = about 40%, MI =
(7 g / 10 min) The same procedure as in Example 1 was carried out except that 10 parts by weight was used. The fusing seal strength of the gusset seal is 1
The weight was 380 g / 15 mm, and no remarkable improvement effect was observed.

Comparative Example 8 The same procedure was performed as in Example 1 except that the pellets obtained in the crystalline propylene polymer production example 9 were used instead of the pellets obtained in the crystalline propylene polymer production example 1. . A laminated film could not be obtained.

[0123]

[Table 2]

Example 9 A linear low-density polyethylene (density 0.912 g / cm 3, 1-hexene content of a copolymer component of 4.5 mol%, MI = 2.0 g / 10 Propylene / ethylene copolymer (MI = 7.5 g / 10 min, ethylene content 3.6 mol%) as the other surface layer resin (C), and the layer composition ratio A: B: C 1: 1
1, except that the thickness was 40 μm. The results are shown in Table 3.

Example 10 A propylene / ethylene copolymer (MI = 7.5 g / 10 min, ethylene content: 3.6 mol%) was used as the base layer resin (B), and the layer composition ratio A: B: C Of 1: 4: 1 and the thickness of 50 μm. The results are shown in Table 3.

Example 11 As a base layer resin (B), a 1-butene homopolymer (MI =
3.3 g / 10 min) and a propylene / ethylene copolymer (MI = 7.5 g / 1) as another surface layer resin (C).
0 minutes, ethylene content 3.6 mol%), and the same procedure as in Example 1 was performed except that the layer composition ratio A: B: C was 1: 3: 1 and the thickness was 20 μm. The results are shown in Table 3.

[0127]

[Table 3]

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a TREF elution curve pattern of a crystalline propylene-based polymer, a peak temperature and a half width.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23:00)

Claims (2)

[Claims] 1. A temperature at which a molecular weight distribution (Mw / Mn) represented by a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) is 1.8 to 4.0, and 10 ° C. is a measurement start temperature. In the rising elution fractionation elution curve, there is one peak of the elution component at 30 ° C. or higher, the peak temperature is 70 to 120 ° C., and the elution temperature width of １ ／ of the peak height is 2.5 to 6
Resin consisting of 50 to 99% by weight of a crystalline propylene polymer at a temperature of 50 ° C. and 50 to 1% by weight of a low crystalline or non-crystalline olefin polymer having a crystallinity of 0 to 30% by X-ray diffraction measurement. A polyolefin laminate film comprising a laminate of a layer (A) of the composition and a layer (B) composed of polyolefin, wherein the layer (A) is a surface layer. 2. The polyolefin-based laminated film according to claim 1, wherein the surface of the layer (A) on the surface layer side is subjected to a corona discharge treatment.