JP2002020502A - Polypropylene resin film improved in gas barrier property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene resin film improved in gas barrier properties, formed by giving the gas barrier properties to crystalline polypropylene itself without deteriorating characteristics of the crystalline polypropylene. SOLUTION: This propylene resin film improved in the gas barrier properties is formed by using the crystalline polypropylene having the following characteristics (1) to (4):(1) a melt flow rate(MFR) of 0.5-200 g/10 min; (2) a melting point [Tm( deg.C)] of 110-160 deg.C; (3) a ratio of the weight average molecular weight to the number average molecular weight (Q-value) of 2.0-4.0; and (4) a growth rate of spherulite radius [S (μm/sec)] at an isothermal crystallization temperature [Tt( deg.C) which is specified by the formula: Tt=Tm-30] satisfying the following inequity: S>0.140, wherein a relationship between Tm of the crystalline polypropylene and the oxygen permeability [D (cc/m2.24 Hr.atm)] of the formed film satisfies the following inequality: D<=-60×Tm+10,300.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a crystalline polypropylene film. More specifically, the present invention relates to a polypropylene resin film having excellent transparency and rigidity, and having improved gas barrier properties having excellent water vapor transmission resistance and gas transmission resistance.

[0002]

2. Description of the Related Art A film made of crystalline polypropylene has excellent rigidity, mechanical properties such as heat resistance, transparency, and the like.
It is widely used as a packaging film and the like, taking advantage of its optical properties such as gloss and hygiene properties such as non-toxicity and odorlessness.

[0003] However, packaging films in the fields of foods and pharmaceuticals have a problem that gas-gas barrier properties such as moisture-proof properties and oxygen-blocking properties are not sufficient. As a method of improving gas barrier properties, a method of forming a composite film with a film made of polyvinyl alcohol or polyethylene vinyl alcohol copolymer having high gas barrier properties or a polyvinylidene chloride resin, a method of evaporating a metal such as aluminum, a method of A method of blending a resin or a cyclic olefin polymer has been proposed. However, the above method is not desirable because the improvement effect is not sufficient or the excellent properties of crystalline polypropylene such as a decrease in heat resistance due to the use of additional components other than crystalline polypropylene are impaired. In some cases, it is desirable to impart gas barrier properties to the crystalline polypropylene itself.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a film having a high gas barrier property in which a gaseous barrier property is imparted to the crystalline polypropylene itself without impairing the properties of the crystalline polypropylene under such circumstances. It is in.

[0005]

Means for Solving the Problems The present invention has been made as a result of intensive studies in order to achieve the above object, and a film made of a specific crystalline polypropylene has a high gas barrier property not found in a conventional polypropylene film. The inventors have found that the present invention has the above and completed the present invention.

Specifically, the present invention provides the following requirements (1) to
A film formed by molding crystalline polypropylene satisfying (4), wherein the melting point Tm of the crystalline polypropylene is
(° C.) and the oxygen permeability D (cc / m ² · 24) of the film.
(Hr.atm) which satisfies the formula (A).

(1) MFR is 0.5 to 200 g / 10 min. (2) the melting point Tm is 110 to 160 ° C .; (3) the Q value is 2.0 to 4.0; (4) the isothermal crystallization temperature Tt (° C., where Tt = Tm-30) that the spherulite radius growth rate S (μm / sec) satisfies the formula (Ia), S> 0.140 (μm / sec) (Ia) (5) Film D / (cc / m) ⁽² · 24Hr · atm) ≦ −60 × Tm / ° C. + 10300 (A)

The present invention also provides a polypropylene resin film having improved gas barrier properties, wherein the crystalline polypropylene is a polymer obtained by polymerization using a metallocene catalyst, and a method in which the crystalline polypropylene is a propylene / α-olefin random copolymer. An object of the present invention is to provide a polypropylene resin film which is a polymer and has an improved gas barrier property.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polypropylene resin film having improved gas barrier properties of the present invention has a melting point Tm and an oxygen permeability D (cc / m) of the crystalline polypropylene constituting the film.
⁽² · 24Hr · atm) satisfies the expression (A).

D / (cc / m ² · 24Hr · atm) ≦ −60 × Tm / ° C. + 10300 (A)

Preferably, (A ₂ ) is satisfied, and more preferably, (A ₃ ) is satisfied.

D / (cc / m ² · 24Hr · atm) ≦ −60 × Tm / ° C. + 10100 (A ₂ ) D / (cc / m ² · 24Hr · atm) ≦ −60 × Tm / ° C. + 9900 (( A ₃₎

A film that does not satisfy this relational expression cannot be said to be a film having the desired gas barrier properties, and is not an object of the present invention.

The crystalline polypropylene used to obtain the polypropylene resin film having improved gas barrier properties of the present invention has an MFR of 0.5 to 200 g / 1.
0 min. , Preferably 1 to 100 g / 10 min. ,
More preferably, 2 to 50 g / 10 min. It is said. M
When the FR is lower than the above-mentioned range, the surface properties of the film are poor, so that suitable productivity cannot be obtained. When the FR is higher than the above-mentioned range, continuous film production becomes difficult.

The crystalline polypropylene used to obtain the polypropylene resin film having improved gas barrier properties of the present invention has a Tm (° C.) of 110 to 160.
° C, preferably 115-150 ° C, more preferably 12 ° C.
0-140 ° C. When Tm is lower than the above range, a suitable blocking resistance cannot be obtained in the present invention,
If it is higher than the above range, a suitable low-temperature heat sealability cannot be obtained.

The Q value of the crystalline polypropylene is as follows:
2.0 to 4.0, preferably 2.3 to 3.8, more preferably 2.6 to 3.6. When the Q value is lower than the above range, the moldability of the film decreases, and when the Q value is higher than the above range, the surface state of the film deteriorates and the blocking resistance deteriorates.

Further, the crystalline polypropylene used in the present invention has an isothermal crystallization temperature Tt (° C., where Tt = T
m-30), the spherulite radius growth rate S (μm / sec) satisfies the formula (Ia). Preferably, the following formula (I)
b), and more preferably those satisfying the following formula (Ic). If S is less than this range, the blocking property is undesirably reduced.

S> 0.140 (μm / sec) (Ia) S> 0.160 (μm / sec) (Ib) S> 0.180 (μm / sec) (Ic) )

The crystalline polypropylene that satisfies the above requirements (1) to (4) exhibits the above-mentioned respective properties and gives some effect to the crystal form when formed into a film.
A higher gas barrier property than expected from Tm is exhibited.

In the present specification, the spherulite radius growth rate S is:
It can be determined by the following method. That is, the sample resin is sandwiched between two glass plates provided with aluminum foil having a thickness of 20 μm as spacers, and heated on a hot plate at 200 ° C. for 5 minutes to form a sufficiently molten state. After a while, the temperature control tank (TC-600Ph manufactured by Linkham)
And kept at 200 ° C. for 1 minute under a nitrogen atmosphere. The temperature of the tank is adjusted to the isothermal crystallization temperature Tt (the melting point of the resin minus 30).
(C) at a rate of 75 ° C./min, and observe the state change. As an observation device, for example, Olympus microscope B
The company's CCD camera FDC-725 can be used for H-2. In addition, the temperature error of the tank is maintained at ± 0.1 ° C. The obtained image data is translated into National in
Analysis is performed using freeware software NIM image provided by the university of health, and S is obtained from the slope of a straight line obtained by plotting spherulite with respect to elapsed time. S is the number of trials 20
The average value shall be the number of times or more.

The crystalline polypropylene used in the present invention is not particularly limited as long as it satisfies the above requirements. For example, the crystalline polypropylene used in the present invention may be a propylene homopolymer. It may be a propylene-α-olefin random copolymer or a mixture thereof. The α-olefin in the propylene-α-olefin copolymer includes α-olefins having 2 to 20 carbon atoms excluding propylene, and examples thereof include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-octene. Heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene-1 and the like can be exemplified. One or two or more α-olefins copolymerized with propylene may be used. Of these, ethylene and butene-1 are preferred.

The content of α-olefin in the crystalline polypropylene is generally about 0.1 to 20% by weight, preferably about 0.3 to 15% by weight.

The method for producing the crystalline polypropylene used to obtain the polypropylene resin film having improved gas barrier properties of the present invention is not particularly limited, but it is preferable to carry out the polymerization in the presence of a so-called metallocene catalyst,
In particular, using a metallocene catalyst comprising the following components (A) and (B) and optionally component (C), propylene or α containing propylene as a main component is used.
-It is desirable to produce it by polymerizing an olefin.

<Component (A)> A desirable compound as the component (A) is a compound represented by the following general formula (1).

[0025] _{Q (C 5 H 4-a} R 1 a) (C 5 H 4-b R 2 b) MeXY (1)

[0026] _{[wherein, C 5 H 4-a R} 1 a and C ₅ H _4-b R
² _b represents a conjugated five-membered ring ligand, and Q represents a binding group bridging two conjugated five-membered ring ligands, and has 1 carbon atom.
A divalent hydrocarbon group having a hydrocarbon group of 1 to 20; a silylene group having a hydrocarbon group having 1 to 20 carbon atoms; or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms; Me represents zirconium or hafnium; Y is each independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms,
A C1-20 alkoxy group, a C1-20 alkylamide group, a trifluoromethanesulfonic acid group, a C1-20 phosphorus-containing hydrocarbon group or a C1-20
Represents a silicon-containing hydrocarbon group. R ¹ and R ² are substituents on a conjugated five-membered ring ligand, each independently
It represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group. Two adjacent R ¹ or two R ² may be bonded to each other to form a ring. a and b are 0 ≦ a ≦ 4, 0 ≦
It is an integer satisfying b ≦ 4. However, the two five-membered ring ligands having R ¹ and R ² are asymmetric with respect to the plane containing Me in terms of their relative positions via the group Q. ]

[0027] Q is as described above, a bonding group for cross-linking two conjugated five-membered ring ligand ^{_{C 5 H 4-a R 1}} a and ^{_{C 5 H 4-b R 2}} b, specifically Specifically, for example, (A) carbon number 1-2
0, preferably 1 to 6 divalent hydrocarbon group, specifically, for example, an alkylene group, a cycloalkylene group, an arylene group and the like, (b) having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.
A silylene group having a hydrocarbon group of (c) having 1 to 2 carbon atoms
There are 0, preferably 1 to 12, germylene groups having hydrocarbon groups. The distance between the two bonds of the divalent Q group is about 4 atoms or less, especially 3 atoms or less when Q is chain-like, regardless of the number of carbon atoms. In the case of having a cyclic group, it is preferred that the cyclic group is not more than about +2 atoms, particularly, the cyclic group alone.

Therefore, when Q is alkylene, ethylene and isopropylidene (the distance between bonds is 2 atoms and 1 atom), and when Q is cycloalkylene, cyclohexylene (the distance between bonds is only cyclohexylene)
However, in the case of alkylsilylene, dimethylsilylene (the distance between bonds is 1 atom) is preferable. Me
Is zirconium or hafnium.

X and Y may be each independently, that is, they may be the same or different, and (A) hydrogen, (B) halogen (fluorine, chlorine, bromine or iodine, preferably chlorine), (C) C 1 -C 1 20 hydrocarbon groups, (d) an alkoxy group having 1 to 20 carbon atoms, (e) an alkylamide group having 1 to 20 carbon atoms, (f) a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, (g) carbon It represents a silicon-containing hydrocarbon group or a (thi) trifluoromethanesulfonic acid group represented by Formulas 1 to 20.

R ¹ and R ² are substituents on the conjugated five-membered ring ligand, and each independently represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or an alkoxy group having 1 to 20 carbon atoms. A silicon-containing hydrocarbon group having 3 to 20 carbon atoms, 2 to 20 carbon atoms
And a nitrogen-containing hydrocarbon group having 2 to 20 carbon atoms or a boron-containing hydrocarbon group having 2 to 20 carbon atoms. Further, two adjacent R ¹ or two R ² may be bonded at the ω-terminal to form a ring together with a part of the cyclopentadienyl group.

In such a case, a typical example is two adjacent R ¹ (or R ² ) on a cyclopentadienyl group.
Are those which share a double bond of the cyclopentadienyl group to form a fused six-membered ring (ie, an indenyl group and a fluorenyl group) and those which form a fused seven-membered ring (ie, an azulenyl group) is there. a and b are 0
It is an integer satisfying ≦ a ≦ 4 and 0 ≦ b ≦ 4.

Non-limiting examples of the above metallocene compounds include the following. In addition, these compounds are indicated by only chemical names, but needless to say, the three-dimensional structure has the asymmetry referred to in the present invention.

(A1) A transition metal compound having two silylene-bridged five-membered ring ligands, for example, (1) dimethylsilylenebis (1-indenyl) zirconium dichloride,
(2) dimethylsilylenebis {1- (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride,
(3) dimethylsilylenebis {1- (2,4-dimethylindenyl)} zirconium dichloride, (4) dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, (5) dimethyl Silylene bis {1- (2-methyl-4-phenyl-4H-)
Azulenyl) {zirconium dichloride, (6) dimethylsilylenebis} 1- (2-methyl-4-phenyl-4)
H-5,6,7,8-tetrahydroazulenyl) {zirconium dichloride, (7) dimethylsilylenebis} 1
-(2-methyl-4- (4-chlorophenyl) -4H-
Azulenyl) {zirconium dichloride, (8) dimethylsilylenebis {1- (2-methyl-4- (4-chlorophenyl) -4H-5,6,7,8-tetrahydroazulenyl)} zirconium dichloride, (9) dimethyl Silylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, (10) dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl)]
Indenyl}] zirconium dichloride, (11) dimethylsilylene bis [1- {2-methyl-4- (1-naphthyl) -4H-azulenyl}] zirconium dichloride, (12) dimethylsilylenebis [1- {2-methyl- 4- (1-naphthyl) -4H-5,6,7,8-tetrahydroazulenyl}] zirconium dichloride, (1
3) methylphenylsilylenebis (1-indenyl) zirconium dichloride, (14) methylphenylsilylenebis {1- (4,5,6,7-tetrahydroindenyl)} zirconium dichloride, (15) methylphenylsilylenebis} 1 -(2,4-dimethylindenyl) zirconium dichloride, (16) methylphenylsilylene bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, (17) methylphenylsilylene bis} 1- ( 2-methyl-4-phenyl-4H-azulenyl) zirconium dichloride, (1
8) Methylphenylsilylenebis {1- (2-methyl-)
4-phenyl-4H-5,6,7,8, -tetrahydroazulenyl) {zirconium dichloride, (19) methylphenylsilylenebis} 1- (2-methyl-4,5-
Benzoindenyl) zirconium dichloride, (2
0) methylphenylsilylenebis [1- {2-methyl-
4- (1-naphthyl) indenyl}] zirconium dichloride, (21) methylphenylsilylenebis [1-
{2-Methyl-4- (1-naphthyl) -4H-azulenyl}] zirconium dichloride, (22) methylphenylsilylenebis [1- {2-methyl-4- (1-naphthyl) -4H-5,6, 7,8-tetrahydroazulenyl}] zirconium dichloride, (23) dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconiumdimethyl, (24) dimethylsilylenebis {1- (2- Methyl-4,5-benzoindenyl) zirconium methyl chloride, (25) dimethylsilylene bis {1- (2-methyl-4-phenylindenyl)} zirconium dimethyl, (26) dimethylsilylene bis} 1- (2 -Methyl-4-phenyl-4H-azulenyl) {zirconium dimethyl, (27) dimethylsilylenebis} 1- ( - methyl-4-phenyl indenyl)} zirconium chloro dimethylamide, (28)
Dimethylsilylenebis {1- (2-ethyl-4,5-benzoindenyl)} zirconium dichloride, (29)
(30) Dimethylsilylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, (30) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azulenyl)} zirconium dichloride, (3
1) dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-5,6,7,8-tetrahydroazulenyl)} zirconium dichloride, (32) dimethylsilylenebis {1- (2-ethyl-4) -(4-chlorophenyl) -4H-azulenyl)｝ zirconium dichloride,
(33) dimethylsilylenebis {1- (2-ethyl-4)
-(4-chlorophenyl) -4H-4,5,6,7-tetrahydroazulenyl) zirconium dichloride,
(34) dimethylsilylene {1- (2-ethyl-4-phenylindenyl)} 1- (2,3,5-trimethylcyclopentadienyl)} zirconium dichloride;
(35) Dimethylsilylene {1- (2-ethyl-4-phenyl-4H-5,6,7,8-tetrahydroazulenyl)} 1- (2,3,5-trimethylcyclopentadienyl)} zirconium Dichloride, (36) dimethylsilylenebis {1- (2-methyl-4,4-dimethyl-)
4,5,6,7-tetrahydroindenyl) {zirconium dichloride, (37) dimethylsilylenebis} 1-
(2-ethyl-4-phenylindenyl) {zirconium bis (trifluoromethanesulfonic acid), (38) dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azulenyl)} zirconium bis (trifluoromethanesulfone) Acid), (39) dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-5,6,6)
7,8-tetrahydroazulenyl) {zirconium bis (trifluoromethanesulfonic acid), (40) dimethylsilylenebis {1- (2-ethyl-4- (pentafluorophenyl) indenyl)} zirconium dichloride,
(41) dimethylsilylenebis {1- (2-ethyl-4)
-Phenyl-7-fluoroindenyl) {zirconium dichloride, (42) dimethylsilylenebis} 1- (2
-Ethyl-4-indolylindenyl) {zirconium dichloride, (43) dimethylsilylenebis} 1- (2
-Dimethylborano-4-indolylindenyl) zirconium dichloride and the like

(A2) Transition metal compounds having two 5-membered ring ligands bridged by an alkylene group, for example, (1) ethylene-1,2-bis (1-indenyl) zirconium dichloride, (2) ethylene- 1,2-bis ｛1- (4,
(5,6,7-tetrahydroindenyl)} zirconium dichloride, (3) ethylene-1,2-bis {1-
(2,4-dimethylindenyl) {zirconium dichloride, (4) ethylene-1,2-bis} 1- (2,4-
Dimethyl-4H-azulenyl) {zirconium dichloride, (5) ethylene-1,2-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, (6) ethylene-1,2-bis} 1 -(2-methyl-4-phenyl-4H-azulenyl) {zirconium dichloride, (7) ethylene-1,2-bis} 1- (2-
Methyl-8,5-benzoindenyl) zirconium dichloride, (8) ethylene-1,2-bis [1- {2-
Methyl-4- (1-naphthyl) indenyl}] zirconium dichloride, (9) ethylene-1,2-bis [1-
{2-methyl-4- (1-naphthyl) -4H-azulenyl}] zirconium dichloride (10) ethylene-1,
2-bis [1- {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride and the like.

(A3) A transition metal compound having a five-membered ring ligand bridged by a hydrocarbon residue containing germanium, aluminum, boron, phosphorus or nitrogen, for example, (1)
Dimethylgermylenebis (1-indenyl) zirconium dichloride, (2) dimethylgermylenebis {1-
(2-methyl-4-phenylindenyl) {zirconium dichloride, (3) dimethylgermylene bis} 1-
(2-methyl-4-phenyl-4H-azulenyl) zirconium dichloride, (4) dimethylgermylene bis [1- {2-methyl-4- (4-chlorophenyl) -4]
H-azulenyl}] zirconium dichloride (5) dimethylgermylene bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, (6) methylaluminum bis (1-indenyl) zirconium dichloride, (7 ) Phenylphosphinobis (1-indenyl) zirconium dichloride, (8) ethylholanobis (1-indenyl) zirconium dichloride, (9)
Examples thereof include phenylaminobis (1-indenyl) zirconium dichloride.

Particularly preferred among these complexes are:
It is a complex having an azulene skeleton.

<Component (B)> As the component (B), an ion-exchange layered silicate is desirable. The ion-exchangeable phyllosilicate is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and refers to a contained ion-exchangeable silicate.

Most ion-exchangeable phyllosilicates naturally occur mainly as a main component of clay minerals.
In particular, the ion-exchange layered silicate is not limited to a natural product, and may be an artificially synthesized product. Specific examples of the ion-exchangeable layered silicate include known layered silicates described in, for example, "Clay Mineralogy" written by Haruo Shimizu, Asakura Shoten (1995), and include dickite, nacrite, kaolinite, and the like. Kaolin group such as anoxite, metahalloysite, halloysite, serpentine group such as chrysotile, lizardite, antigorite, montmorillonite, zauconite, beidellite, nontronite, saponite,
Smectites such as hectorite, stevensite, bentonite, and teniolite; vermiculites such as vermiculite; mica such as mica, illite, sericite, chlorite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, green mud Stone group. These may form a mixed layer.

Among these, montmorillonite, zauconite, beidellite, nontronite, saponite,
Smectites such as hectorite, stevensite, bentonite and teniolite, vermiculites and mica are preferred. When a compound having a pore volume of 20 Å or more and a pore volume of less than 0.1 cc / g measured by a mercury intrusion method is used as the component (B), a high polymerization activity tends to be hardly obtained. , 0.1cc / g
As described above, those having 0.3 to 5 cc / g are particularly preferable.

Although component (B) can be used without any particular treatment, it is also a preferred embodiment to subject component (B) to chemical treatment. Here, as the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment for affecting the structure of the clay can be used. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned.

The acid treatment not only removes impurities on the surface but also increases the surface area by eluting cations such as Al, Fe and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay.
In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative, and the like are formed, and the surface area and the interlayer distance can be changed. By using the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, it is also possible to obtain a layered material in which the layers are expanded. That is, the bulky ions play a pillar-like role to support the layered structure, and are called pillars. Introducing another substance between layered substance layers is called intercalation.

Examples of the guest compound to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ ,
Metal alcoholates such as B (OR) ₃ [R is alkyl, aryl, etc.], [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (O
H) ₁₄ ] ²⁺ , and metal hydroxide ions such as [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ . These compounds may be used alone or in combination of two or more.
When intercalating these compounds, Si
A polymer obtained by hydrolyzing a metal alcoholate such as (OR) ₄ , Al (OR) ₃ , Ge (OR) _{4, and} a colloidal inorganic compound such as SiO ₂ can also be present. Examples of pillars include oxides formed by intercalating the hydroxide ions between layers and then heating and dehydrating. Component (B) may be used as it is, or may be used after heat dehydration treatment. Further, they may be used alone or as a mixture of two or more of the above solids.

The ion-exchangeable phyllosilicate used in the present invention is preferably at least 40% of the exchangeable Group 1 metal cation contained in the ion-exchange phyllosilicate before being treated with salts, preferably Preferably, 60% or more is ion-exchanged with a cation dissociated from the following salts.

The salt used in the salt treatment for the purpose of ion exchange is a compound containing a cation containing at least one kind of atom selected from the group consisting of Group 2 to 14 atoms, preferably A compound comprising a cation containing at least one atom selected from the group consisting of Group 2 to 14 atoms and at least one anion selected from the group consisting of halogen atoms, inorganic acids and organic acids; Preferably, a cation containing at least one atom selected from the group consisting of Group 2-14 atoms,
l, Br, I, F, PO 4, SO 4, NO 3, CO 3, C 2
O ₄ , OCOCH ₃ , CH ₃ COCHCOCH ₃ , OC
l ₃ , O (NO ₃ ), O (ClO ₄ ) ₂ , O (SO ₄ ), O
H, O ₂ , Cl ₂ , OCl ₃ , OCOH, OCOCH ₂ CH
₃ , a compound comprising at least one anion selected from the group consisting of C ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ .

Specifically, CaCl_Two, CaSO_Four, Ca
C_TwoO_Four, Ca (NO_Three)_Two, Ca_Three(C₆H_FiveO₇)_Two, Mg
Cl_Two, MgBr_Two, MgSO_Four, Mg (PO_Four)_Two, Mg
(ClO_Four)_Two, MgC_TwoO_Four, Mg (NO_Three)_Two, Mg (O
COCH_Three)_Two, MgC_FourH_FourO _Four, Sc (OCOC
H_Three)_Two, Sc_Two(CO_Three)_Three, Sc_Two(C_TwoO_Four)_Three, Sc
(NO_Three)_Three, Sc_Two(SO_Four)_Three, ScF_Three, ScCl_Three,
ScBr_Three, ScI_Three, Y (OCOCH_Three)_Three, Y (CH_Three
COCHCOCH_Three)_Three, Y_Two(CO_Three)_Three, Y_Two(C_TwoO_Four)
_Three, Y (NO_Three)_Three, Y (ClO_Four)_Three, YPO_Four, Y_Two(S
O_Four)_Three, YF_Three, YCl_Three, La (OOCH_Three)_Three, La
(CH_ThreeCOCHCOCH_Three)_Three, La_Two(CO_Three)_Three, La
(NO_Three)_Three, La (ClO_Four)_Three, La_Two(C_TwoO_Four)_Three, L
aPO_Four, La_Two(SO_Four)_Three, LaF_Three, LaCl_Three, La
Br_Three, LaI_Three, Sm (OCOCH_Three)_Three, Sm (CH_Three
COCHCOCH_Three)_Three, Sm_Two(CO_Three)_Three, Sm (N
O_Three)_Three, Sm (ClCO_Four)_Three, Sm_Two(C_TwoO_Four)_Three, Sm
PO_Four, Sm_Two(SO_Four)_Three, SmF_Three, SmCl_Three, SmB
r_Three, Sml_Three, Yb (OCOCH_Three)_Three, Yb (N
O_Three)_Three, Yb (ClO_Four)_Three, Yb (C_TwoO_Four)_Three, Yb
(SO_Four)_Three, YbF_Three, YbCl_Three, Ti (OCOC
H_Three)_Four, Ti (CO_Three)_Two, Ti (NO_Three)_Four, Ti (SO
_Four)_Two, TiF_Four, TiCl_Four, TiBr_Four, TiI_Four, Zr
(OCOCH_Three)_Four, Zr (CO_Three)_Two, Zr (NO_Three)_Four,
Zr (SO_Four)_Two, ZrF_Four, ZrCl_Four, ZrBr_Four, Z
rI_Four, ZrOCl_Two, ZrO (NO_Three)_Two, ZrO (Cl
O_Four)_Two, ZrO (SO_Four), Hf (OCOCH_Three)_Four, H
f (CO_Three)_Two, Hf (NO_Three)_Four, Hf (SO_Four)_Two, Hf
OCI_Two, HfF_Four, HfCl_Four, HfBr_Four, HfI_Four,
V (CH_ThreeCOCHCOCH_Three)_Three, VOSO_Four, VOCl
_Three, VCl_Three, VCl_Four, VBr_Three, Nb (CH_ThreeCOCH
COCH_Three)_Five, Nb_Two(CO_Three)_Five, Nb (NO_Three)_Five, N
b_Two(SO_Four)_Five, ZrF _Five, ZrCl_Five, NbBr_Five, Nb
I_Five, Ta (OCOCH_Three)_Five, Ta_Two(CO_Three)_Five, Ta
(NO_Three)_Five, Ta_Two(SO_Four)_Five, TaF_Five, TaCl_Five,
TaBr_Five, TaI _Five, Cr (OOCH_Three)_TwoOH, Cr
(CH_ThreeCOCHCOCH_Three)_Three, Cr (NO_Three)_Three, Cr
(ClO_Four)_Three, CrPO_Four, Cr_Two(SO_Four)_Three, CrO_Two
Cl_Two, CrF_Three, CrCl_Three, CrBr_Three, CrL_Three, M
oCl_Four, MoCl_Three, MoCl_Four, MoCl_Five, Mo
F₆, MoI_Two, WCl_Four, WCl₆, WF₆, WBr_Five, M
n (OOCH_Three)_Two, Mn (CH_ThreeCOCHCOC
H_Three)_Two, MnCO_Three, Mn (NO_Three)_Two, MnO, Mn
(ClO_Four)_Two, MnF_Two, MnCl_Two, MnBr_Two, Mn
I_Two, Fe (OCOCH_Three)_Two, Fe (CH_ThreeCOCHCO
CH_Three)_Three, FeCO_Three, Fe (NO_Three)_Three, Fe (Cl
O_Four)_Three, FePO_Four, FeSO_Four, Fe_Two(SO_Four)_Three, F
eF_Three, FeCl _Three, FeBr_Three, FeI_Two, FeC₆H_FiveO
₇, Co (OCOCH_Three)_Two, Co (CH_ThreeCOCHCOC
H_Three)_Three, CoCO_Three, Co (NO_Three)_Two, CoC_TwoO_Four, C
o (CLO_Four)_Two, Co_Three(PO_Four)_Two, CoSO_Four, CoF
_Two, CoCl_Two, CoBr_Two, CoI_Two, NiCO_Three, Ni
(NO_Three)_Two, NiC_TwoO_Four, Ni (ClO_Four)_Two, NiSO
_Four, NiCl_Two, NiBr_Two, Pb (OCOCH_Three)_Four, P
b (OOCH_Three)_Two, PbCO_Three, Pb (NO_Three)_Two, Pb
SO_Four, PbHPO_Four, Pb (ClO_Four)_Two, PbF_Two, P
bCl_Two, PbBr_Two, PbI_Two, CuI_Two, CuBr_Two,
Cu (NO_Three)_Two, CuC_TwoO_Four, Cu (ClO_Four)_Two, Cu
SO_Four, Cu (OCOCH_Three)_Two, Zn (OOCH_Three)_Two,
Zn (CH_ThreeCOCHCOCH_Three)_Two, ZnCO_Three, Zn
(NO_Three)_Two, Zn (ClO_Four)_Two, Zn_Three(PO_Four)_Two, Z
nSO_Four, ZnF_Two, ZnCl_Two, ZnBr_Two, ZnI_Two,
Cd (OCOCH_Three)_Two, Cd (CH_ThreeCOCHCOC
H_Three)_Two, Cd (OCOCH_TwoCH_Three)_Two, Cd (N
O_Three)_Two, Cd (ClO_Four)_Two, CdSO_Four, CdF _Two, Cd
Cl_Two, CdBr_Two, CdI_Two, AlF_Three, AlCI_Three, A
lBr_Three, AlI_Three, Al_Two(SO_Four)_Three, Al_Two(C_TwoO_Four)
_Three, Al (CH_ThreeCOCHCOCH_Three)_Three, Al (N
O_Three)_Three, AlPO_Four, GeCl_Four, GeBr_Four, GeI_Four,
Sn (OCOCH _Three)_Four, Sn (SO_Four)_Two, SnF_Four, S
nCl_Four, SnBr_Four, SnI_FourAnd the like. Acid treatment
Is the crystal structure of Al, Fe, M
It can elute some or all of the cations such as g
Wear.

The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, phosphoric acid and acetic acid. Two or more salts and acids may be used for the treatment. When combining salt treatment and acid treatment,
There are a method of performing an acid treatment after performing a salt treatment, a method of performing a salt treatment after performing an acid treatment, and a method of simultaneously performing the salt treatment and the acid treatment.

The conditions for treatment with salts and acids are not particularly limited, but usually the concentration of salts and acids is 0.1 to 30.
Wt%, treatment temperature is from room temperature to boiling point, treatment time is from 5 minutes to 24
It is preferable to select a time condition so as to elute at least a part of at least one compound contained in the ion-exchange layered silicate. Further, salts and acids are generally used in an aqueous solution.

In the present invention, the above-mentioned salt treatment and / or acid treatment is preferably performed, but shape control may be performed by pulverization, granulation or the like before, during, or after the treatment. Further, a chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination.
These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water to use as component (B).

Here, the adsorbed water is water adsorbed on the surface of the ion-exchange layered silicate compound particles or the crystal fracture surface, and the interlayer water is water existing between the layers of the crystal. In the present invention, these adsorbed water and / or interlayer water can be removed by heat treatment before use.

The method of heat-treating the ion-exchanged layered silicate for adsorbed water and interlayer water is not particularly limited.
Methods such as heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The temperature at the time of heating cannot be specified unconditionally because it depends on the type of ion-exchangeable layered silicate and interlayer ions. However, the heating is performed at 100 ° C. or higher, preferably 150 ° C. or higher so that interlayer water does not remain. High temperature conditions that cause breakage (for example, 800 ° C. or higher, depending on the heating time) are not preferable. Further, a heat dehydration method for forming a crosslinked structure such as heating under air flow is not preferable because the polymerization activity of the catalyst may be reduced. The heating time is at least 0.5 hour, preferably at least 1 hour. At this time, the water content of the component (B) after the removal was 200 ° C. at a pressure of 1 mmHg.
0% by weight when dehydrated for 2 hours under the above conditions
It is preferably 3% by weight or less, preferably 1% by weight or less.

As described above, in the present invention, particularly preferred as the component (B) is a salt treatment and / or
Or, the water content obtained by performing the acid treatment is 1% by weight.
The following ion-exchange layered silicates.

As the component (B), it is preferable to use spherical particles having an average particle size of 5 μm or more. More preferably,
Spherical particles having an average particle size of 10 μm or more are used. More preferably, spherical particles having an average particle diameter of 10 μm or more and 100 μm or less are used. The average particle diameter here is represented by a number average particle diameter calculated by image processing an optical microscope photograph (100 times magnification) of the particles. As the component (B), a natural product or a commercially available product may be used as it is as long as the shape of the particle is spherical, or a component in which the shape and particle size of the particle are controlled by pulverization, granulation, classification, or the like may be used. Is also good.

The granulation methods used here include, for example, stirring granulation, spray granulation, tumbling granulation, briquetting, compacting, extrusion granulation, fluidized bed granulation, and emulsion granulation. The method is not particularly limited as long as it is a method capable of granulating the component (B), including a submerged granulation method and a compression molding granulation method. The granulation method is preferably a stirring granulation method, a spray granulation method, a tumbling granulation method, or a fluidized bed granulation method, and particularly preferably a stirring granulation method or a spray granulation method. When the spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene is used as a dispersion medium of the raw material slurry. Preferably, water is used as the dispersion medium.

The concentration of the component (B) in the raw slurry liquid for spray granulation to obtain spherical particles is 0.1 to 70%, preferably 1 to 50%, particularly preferably 5 to 30%. The temperature at the inlet of the hot air for spray granulation to obtain spherical particles varies depending on the dispersion medium, but is preferably 80 to 260 ° C, preferably 100 to 220 ° C when taking water as an example.

At the time of granulation, an organic substance, an inorganic solvent, an inorganic salt, and various binders may be used. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcellulose, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein,
Latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel,
Gum arabic, sodium alginate and the like can be mentioned.

The spherical particles obtained as described above have a particle size of 0.2 MPa to suppress crushing and generation of fine powder in the polymerization step.
It preferably has a compressive breaking strength of at least a. In the case of such particle strength, especially when performing pre-polymerization,
The particle property improving effect is effectively exhibited.

<Component (C)> The component (C) is an organoaluminum compound. The organoaluminum compound used as the component (C) in the present invention has a general formula (AlR)
Compounds represented by ⁴ _n X _{3-n) m} is appropriate. In the present invention, it goes without saying that the compounds represented by this formula can be used alone, in combination of two or more or in combination. Further, not only at the time of preparing the catalyst to be used, but also at the time of preliminary polymerization or polymerization.

In this formula, R^FourIs a hydrocarbon having 1 to 20 carbon atoms
X represents a halogen, hydrogen, an alkoxy group,
Shows a mino group. n is an integer of 1-3 and m is an integer of 1-2
You. R ^FourIs preferably an alkyl group, and X is
When it is a halogen, chlorine; when it is an alkoxy group,
Is when the alkoxy group having 1 to 8 carbon atoms is an amino group
An amino group having 1 to 8 carbon atoms is preferred. Therefore, preferred
A specific example of a new compound is trimethylaluminum.
System, triethylaluminum, trinormal propyl alcohol
Luminium, tri-n-butyl aluminum, tri-butyl
Sobutyl aluminum, tri-normal hexyl aluminum
, Trinormal octyl aluminum, trinorma
Rudecyl aluminum, diethyl aluminum chloride
, Diethylaluminum sesquichloride, diethyl
Aluminum hydride, diethyl aluminum ethoxy
, Diethylaluminum dimethylamide, diisobuty
Aluminum hydride, diisobutylaluminum
Loride and the like. Of these, preferably,
m = 1, n = 3 trialkylaluminum and dia
Lucyl aluminum hydride. More preferably
R^FourIs a trialkyl aluminum having 1 to 8 carbon atoms
is there.

<Preparation of Catalyst> As the catalyst used for producing the above-mentioned crystalline polypropylene, a catalyst comprising the above-mentioned component (A), component (B) and optionally component (C) is used. It can be prepared by contacting in a polymerization vessel or outside a polymerization vessel in the presence or absence of a monomer to be polymerized.

The above catalyst may be one obtained by pre-polymerization in the presence of an olefin. As the olefin used for the prepolymerization, propylene, ethylene,
-Butene, 3-methylbutene-1, styrene, divinylbenzene and the like are used, but a mixture of these with other olefins may be used.

The components (A), (B) and (C) used in the preparation of the above catalyst can be used in any ratio.

<Polymerization> The polymerization of the crystalline polypropylene used in the present invention is carried out by a catalyst comprising the components (A) and (B) and, if necessary, a component (C) and propylene and ethylene or ethylene or carbon having 4 to 20 carbon atoms. It is carried out by mixing and contacting with an α-olefin. The amount ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio, and to change the mixing ratio of the supplied monomers over time. Is also possible. Further, any of the monomers can be dividedly added in consideration of the copolymerization reaction ratio.

As for the polymerization mode, any method can be adopted as long as the catalyst component and each monomer come into efficient contact with each other. Specifically, a slurry method using an inert solvent, a bulk method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a method in which each monomer is substantially gaseous without substantially using a liquid solvent Can be employed.

The present invention is also applicable to continuous polymerization and batch polymerization. In the case of the slurry method, hexane, heptane, pentane, cyclohexane, benzene,
A single or mixture of a saturated aliphatic or aromatic hydrocarbon such as toluene can be used.

The polymerization conditions are as follows.
160 ° C., preferably 0 ° C. to 150 ° C. Hydrogen can be supplementarily used as a molecular weight regulator at the time of polymerization.

The polymerization pressure is 0 to 90 kg / cm ² ···
G, preferably 0 to 60 kg / cm ² · G, particularly preferably 1 to 50 kg / cm ² · G.

The crystalline polypropylene used in the present invention may contain various additives such as a nucleating agent, a heat stabilizer, an antioxidant, a weather stabilizer, and an antistatic agent as long as the object of the present invention is not impaired. , Slip agent, anti-blocking agent,
An antifogging agent, a coloring agent, a filler, an elastomer and the like can be blended.

In particular, the properties of the crystalline polypropylene resin film can be improved by adding the following additives.

(Polyethylene) The rigidity of the film is improved by adding polyethylene satisfying the following conditions 1) and 2).

1) Density: The density is 0.94 to 0.98 g /
cm ³ 2) Melt index (MI _E ) at 190 ° C. is 10 g / 10 min or more, preferably 10 to 500 g / 10
Minute

The compounding amount was 95.0 crystalline polypropylene.
To 99.999 parts by weight, polyethylene
It is about 01 to 5.0 parts by weight.

(Polyethylene Wax) The addition of polyethylene wax improves the rigidity of the film, similarly to polyethylene. It is desirable that the polyethylene wax satisfy the following conditions 1) and 2).

1) Density: 0.94 to 0.98 g / cm ³ 2) Melt viscosity at 140 ° C. is 10 cps or more, preferably 15 to 30000 cps.

The mixing ratio of the polyethylene wax is from 0.009 to 95.0 parts by weight, preferably from 99.99 to 97.0 parts by weight, of the crystalline polypropylene, and from 0.001 to 5.0 parts by weight of the polyethylene wax. , Preferably 0.01 to 3.0 parts by weight.

(Elastomer) The heat sealability can be improved by adding an elastomer. As the elastomer, a propylene-based elastomer or an ethylene-based elastomer is desirable.

The compounding ratio of the elastomer is such that the elastomer is 2.0 to 50.0 parts by weight, preferably the crystalline polypropylene is 70.0 to 95.0 parts by weight based on 50.0 to 98.0 parts by weight of the crystalline polypropylene. To 30.0 parts by weight of elastomer.

(Anti-blocking agent) Examples of the anti-blocking agent include inorganic or synthetic silica (silicon dioxide), magnesium silicate, aluminosilicate, talc, zeolite, aluminum borate, calcium carbonate, calcium sulfate, and the like. Barium sulfate, calcium phosphate and the like are used.

Examples of the organic type include polymethyl methacrylate, polymethylsilyl sesquioxane (silicone), polyamide, polytetrafluoroethylene, epoxy resin, polyester resin, benzoguanamine / formaldehyde (urea resin), and phenol resin. Can be used. When the average particle size of these antiblocking agents is in such a range, a polypropylene film having good transparency and scratch resistance can be obtained.

The anti-blocking agent is preferably surface-treated. Examples of the surface-treating agent include surfactants, organic acids such as metal soap, acrylic acid, oxalic acid, citric acid and tartaric acid, higher alcohols, esters, and the like. Condensed phosphates such as silicone, fluorine resin, silane coupling agent, sodium hexametaphosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium trimetaphosphate, and the like can be used, and especially those treated with citric acid among organic acid treatments Is preferred.

The antiblocking agent is used in an amount of 0.01 to 0.7 part by weight, more preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the crystalline polypropylene.

(Lubricant) In the present invention, it is preferable to add a lubricant. As the lubricant, for example, one or more linear monocarboxylic acid monoamide compounds or linear monocarboxylic acid bisamide compounds are used. They can be used in combination. Examples of the linear monocarboxylic acid monoamide compound include oleic amide, stearic amide, erucic amide, palmitic amide, behenic amide, lauric amide and the like.

Examples of the linear monocarboxylic acid bisamide compound include ethylene bisoleic acid amide, ethylene bis stearic acid amide, and methylene bis stearic acid amide.

The amount of the lubricant to be added is as follows.
The amount is preferably 0.01 to 1.0 part by weight, more preferably 0.02 to 0.5 part by weight, based on 00 parts by weight.

In particular, unsaturated fatty acid amides having a melting point of 70 to 90 ° C. and / or saturated fatty acid amides having a melting point of 100 to 125 ° C. can be used.

The above components are usually blended by heating and melting at 190 ° C. to 350 ° C. using a melt kneader and provided as a film forming material in the form of pellets cut into granules.

The polypropylene resin film having improved gas barrier properties of the present invention can be formed from the above-mentioned crystalline polypropylene by a melt extrusion molding method such as a casting method or an inflation molding method. The thickness of the film is usually about 5 to 500 μm. The film can be suitably used not only for a single layer but also for a multilayer film by a co-extrusion method. Further, the obtained film can be biaxially stretched and used. In the case of a multilayer film, the film of the present invention is preferably used for a surface layer.

[0087]

DESCRIPTION OF THE PREFERRED EMBODIMENTS a. Measurement of MFR Measured according to JIS-K6758 (condition: temperature / 2
30 ° C, load 2.16 kgf).

B. Measurement of melting point Tm Using a Seiko DSC, take a sample amount of 5 mg,
After holding at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a rate of 10 ° C./min and further melt at a rate of 10 ° C./min.

C. Measurement of Q value The ratio between the weight average molecular weight and the number average molecular weight measured by GPC was defined as the Q value. The measurement conditions are as follows.

Apparatus: GPC 150C type manufactured by Waters Co., Ltd. Column: 3 AD80M / S manufactured by Showa Denko KK Measurement temperature: 140 ° C. Concentration: 20 mg / 10 ml Solvent: orthodichlorobenzene

D. Measurement of spherulite radius growth rate S Aluminum foil having a thickness of 20 μm was installed as a spacer 2
The sample resin was sandwiched between two glass plates and heated on a hot plate at 200 ° C. for 5 minutes to form a sufficiently molten state. After a while, the temperature control tank (TC-600P manufactured by Linkham)
h) and kept at 200 ° C. for 1 minute under a nitrogen atmosphere. The temperature of the tank is adjusted to the isothermal crystallization temperature (the melting point (T
m) The temperature was lowered to -30 ° C) at a rate of 75 ° C / minute, and the Olympus microscope BH-2 was used to mount the CCD camera FDC-7.
25 was used to observe a change in state. The temperature error of the tank was kept at ± 0.1 ° C. The obtained image data is
national institute of hair
Analysis was performed using the freeware software NIM image provided by lth, and S was determined from the slope of a straight line obtained by plotting the spherulites against the elapsed time. S is an average value of 20 trials.

(Film production conditions) Resin powder 1
To 100 parts by weight, Ir1010 / Ir168 / CaSt was added in a ratio of 0.05 / 0.05 / 0.05 [parts by weight], and an antiblocking agent, slip agent, polyethylene, or polyethylene wax shown in Table 1 was further added. , And granulation was performed using a twin screw extruder PCM (screw diameter 30 mm) manufactured by Ikegai Seisakusho. Using the obtained pellets, a T-die molding machine (35 mm
(φ) was used to obtain a single-layer film having a thickness of 25 μm. In this case, the surface temperature of the cooling roll was 34 ° C.
One surface of the obtained film was subjected to a corona treatment of 40 dyne / cm.

E. Measurement of Transparency (Haze) The obtained film was measured with a haze meter according to ASTM-D1003 (unit:%). The smaller the value, the better the transparency.

F. Measuring method of Young's modulus (tensile elastic modulus) It was measured according to ISO-R1184.

G. Measurement of puncture impact Measured according to JIS-P8134.

H. Measurement of Slip Property (SLIP Property) The obtained film was placed in an atmosphere at a temperature of 40 ° C. for 7 days,
Next, the sample, which had been conditioned for 7 days in an atmosphere at a temperature of 23 ° C. and 50% RH, was subjected to a slip tester to measure the static friction coefficient between treated surfaces in accordance with ASTM-D1894.

I. Measurement of blocking property Measured according to ASTM-D1893 (CT method).

From the obtained film, width 2 cm, length 1
Take a 5cm sample and make the corona treated surfaces 5cm long
At a temperature of 40 ° C. under a load of 50 g / cm ^2.
After standing for 7 days in an atmosphere of
After sufficiently adjusting the temperature to 50 ° C. and a humidity of 50% RH, the force required for peeling when the overlapped portion was opened at a speed of 500 mm / min was determined using a tensile tester. The smaller this value is, the better the blocking resistance is.

J. Measurement of water vapor permeability Measured in accordance with JIS K-7129. The measurement conditions are
The test was performed at a transmission area of 50 cm ² , a temperature of 40 ° C., and a humidity of 90% RH.

K. Measurement of Oxygen Permeability Using the above-mentioned film as a test piece, with the test piece as a boundary, flowing a carrier gas (He) on one side, and flowing air on the other side, measure oxygen permeating the test piece by gas chromatography, and obtain oxygen permeability. Was. The measurement was performed with a transmission area of 50 cm ² , a temperature of 23 ° C., and a humidity of 5
Performed at 0% RH. Apparatus: GPM-200 mixed gas permeability measuring device manufactured by Lissi

L. Measurement of Heat Sealing Property (HS Property) Using a heat sealing bar of 5 mm × 200 mm, the untreated surfaces of the obtained films were heated at a temperature of 2 kg / cm ² and a heat sealing time of 1 second at each temperature setting. A sample having a width of 15 mm was taken from a sample heat-sealed so as to be perpendicular to the direction in which the film was melt-extruded (MD), and was subjected to a pulling speed of 50 using a Shopper type tester.
It was separated in the MD direction at 0 mm / min, and the load was read. The sealing temperature at which the load became 300 g was defined as the heat sealing temperature (unit: ° C.). The smaller the value, the better the heat sealing property.

Examples 1 to 6 (i) Dimethylsilylenebis [1- {2-methyl-4-
(4-Chlorophenyl) -4H-azulenyl}] Synthesis of Racemic Form of Zirconium Dichloride (a) Synthesis of Racemic / Meso Mixture 1.84 g of 1-bromo-4-chlorobenzene (9.6 m
mol) of n-hexane (10 ml) and diethyl ether (10 ml) at -78 ° C in 11.7 ml of a pentane solution of t-butyllithium (1.64 M) (19.
2 mmol) was added dropwise. The resulting solution was treated at -5 ° C with 1.
After stirring for 5 hours, 1.2 g of 2-methylazulene was added to the solution.
(8.6 mmol) was added to carry out the reaction. The reaction solution was stirred for 1.5 hours while gradually returning to room temperature.
Thereafter, the reaction solution was cooled to 0 ° C., 15 μl (0.19 mmol) of 1-methylimidazole was added, and 0.52 ml (4.3 mmol) of dichlorodimethylsilane was further added.
Was added. After stirring the reaction solution at room temperature for 1.5 hours, dilute hydrochloric acid was added to stop the reaction, the separated organic phase was concentrated under reduced pressure, dichloromethane was added, and the mixture was dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 2.1 g of an amorphous solid.

Next, 1.27 g of the above reaction product was dissolved in 15 ml of diethyl ether.
1. n-hexane solution of butyllithium (1.66 M)
8 ml (4.5 mmol) were added dropwise. After completion of the dropwise addition, the reaction solution was stirred for 12 hours while gradually returning to room temperature.
After distilling off the solvent under reduced pressure, 5 ml of a mixed solvent of toluene and diethyl ether (40: 1) was added, and the mixture was cooled to -78 ° C, and 0.53 g of zirconium tetrachloride (2.3 g) was added thereto.
mmol) was added.

Thereafter, the temperature was immediately returned to room temperature, and the reaction was carried out by stirring at room temperature for 4 hours. The obtained reaction solution was filtered over celite, and the solid separated by filtration was washed with 3 ml of toluene and collected. The collected solid was extracted with dichloromethane, the solvent was distilled off from the extract, and dimethylsilylenebis [1-
{2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] 906 mg (56% yield) of a racemic / meso mixture of zirconium dichloride was obtained.

(B) Purification of the racemic body Further, 900 mg of the above-mentioned racemic / meso mixture was dissolved in 20 ml of dichloromethane, and a high-pressure mercury lamp of 100 W was used for 40 minutes.
Increase the proportion of the racemate by irradiating
The insolubles were removed by filtration, and the collected filtrate was concentrated to dryness. Then, the obtained solid component was stirred with 22 ml of toluene, and after standing, the supernatant was removed.
This was repeated twice, and the remaining solid component was dried to obtain 275 mg of a racemic dimethylsilylenebis [1- {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride.

(Ii) Chemical treatment of clay mineral 218.1 g of sulfuric acid (96%) and magnesium sulfate 13
200.03 g of commercially available montmorillonite (Kunimine Kogyo, Knipia F) was dispersed in an aqueous solution obtained by mixing 0.4 g of 909 ml of deionized water, and the mixture was stirred at 100 ° C. for 2 hours. This aqueous slurry of montmorillonite was adjusted to a solid concentration of 12%, and subjected to spray granulation with a spray drier to obtain particles. Thereafter, the particles were dried under reduced pressure at 200 ° C. for 2 hours.

(Iii) Preparation of a solid catalyst component A 1 l internal volume stirred autoclave was sufficiently replaced with propylene, and then dehydrated and deoxygenated heptane 23 was prepared.
0 ml was introduced, and the temperature in the system was maintained at 40 ° C. Here, 10 g of chemically treated clay slurried with toluene was added. Further, dimethylsilylenebis [1- {2-methyl-4- (4
-Chlorophenyl) -4H-azulenyl}] 0.15 mmol of racemic zirconium dichloride and 1.5 mmol of triisobutylaluminum were added. Here, propylene was introduced at a rate of 10 g / hr for 120 minutes, and thereafter polymerization was continued for 120 minutes. Further, the solvent was removed and dried under nitrogen to obtain a solid catalyst component. This solid catalyst component contained 1.9 g of polypropylene per gram of solid component.

(Iv) Polymerization After thoroughly replacing the inside of a stirred autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. 500 ml (0.12 mol) of triisobutylaluminum / n-heptane solution
l), 2.25 kg of ethylene and 7.8 liters of hydrogen (as a standard volume) were added, and the internal temperature was maintained at 30 ° C. Next, 1.2 g of the above solid catalyst component was injected with argon to start polymerization, and the temperature was raised to 70 ° C. over 30 minutes.
The temperature was maintained for one hour. Here 100m ethanol
The reaction was stopped by adding 1. The residual gas was purged to obtain 20 kg of a propylene-ethylene copolymer A.

(V) Evaluation A resin composition shown in Table 1 was prepared using propylene-ethylene copolymer A, and a film was formed. The results of evaluating the film are shown in Examples 1 to 6 in Table 2.

Examples 7 and 8 The amounts of ethylene and hydrogen introduced and the amount of catalyst used were changed, and propylene having the properties shown in Example 7 (A) of Example 1 in Table 1 was prepared according to the production example of propylene-ethylene copolymer A. -An ethylene copolymer B was produced, and a resin composition shown in the same table was prepared to form a film. Table 2 shows the evaluation results of the film.
Examples 7 and 8

Comparative Examples 1 to 3 After sufficiently replacing a stirred autoclave having an internal volume of 200 liters with propylene, dehydration and deoxygenation of n-heptane 6
0 L was introduced, and diethyl aluminum chloride 45 g,
Titanium trichloride catalyst (manufactured by M & S) 16g
(Comparative Examples 1 and 3) or supported titanium trichloride catalyst 1.8
g (Comparative Example 2) was introduced at 55 ° C. under a propylene atmosphere. Hydrogen, propylene and ethylene (Comparative Example 1) or ethylene and butene (Comparative Examples 2 and 3) were introduced, and 55
The polymerization is carried out at a temperature of ° C., after which the residual gas is purged,
The product was filtered and dried to obtain three propylene-ethylene copolymers as shown in component (A) in Table 3. Using the obtained polymer, a resin composition shown in Table 3 was prepared to form a film. Table 4 shows the evaluation results of the film.

[0112]

[Table 1]

[0113]

[Table 2]

[0114]

[Table 3]

[0115]

[Table 4]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takao Tagano 1-toho-cho, Yokkaichi-shi, Mie Japan F-term in the Process Development Center of Polychem Corporation (reference) 4F071 AA15X AA20 AA20X AA21X AA81 AA84 AA88 AA89 AF08 AF09 AF20 AF23 AF30 AF58 AF59 AH04 BA01 BB06 BC01

Claims (3)

[Claims] 1. A film formed by molding a crystalline polypropylene satisfying the following requirements (1) to (4), wherein the melting point Tm (° C.) of the crystalline polypropylene and the oxygen permeability D (cc) / M ² · 24Hr · atm), which satisfies the formula (A). (1) MFR is 0.5 to 200 g / 10 min. (2) the melting point Tm is 110 to 160 ° C .; (3) the Q value is 2.0 to 4.0; (4) the isothermal crystallization temperature Tt (° C., where Tt = Tm-30) that the spherulite radius growth rate S (μm / sec) satisfies the formula (Ia), S> 0.140 (μm / sec) (Ia) (5) Film D / (cc / m) ⁽² · 24Hr · atm) ≦ −60 × Tm / ° C. + 10300 (A) 2. The polypropylene resin film having improved gas barrier properties according to claim 1, wherein the crystalline polypropylene is a polymer polymerized using a metallocene catalyst. 3. The method according to claim 1, wherein the crystalline polypropylene is propylene α-
The polypropylene resin film having improved gas barrier properties according to claim 1 or 2, which is an olefin random copolymer.