JP3210040B2 - Polypropylene composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a propylene random copolymer composition. More specifically, the invention relates to a propylene polymer composition suitable for a heat seal film of a packaging film such as tobacco and caramel, and is obtained by blending a propylene polymer having a specific property and a propylene random copolymer in an appropriate ratio. It relates to a composition.

[0002]

2. Description of the Related Art Propylene homopolymers or copolymers (hereinafter sometimes collectively referred to as propylene polymers) are being developed for use in a wide range of fields because of their excellent properties. Is well known. For example, polypropylene is widely used as a packaging film, but since polypropylene has a relatively high melting point, propylene is generally used to improve heat sealability at low temperatures in this type of application. A propylene random copolymer obtained by copolymerizing an α-olefin is used.

[0003] Such a conventional packaging film made of a propylene random copolymer is excellent in transparency and scratch resistance as compared with a film made of low-density polyethylene, but still has a heat sealing property at a low temperature. Is not enough. For the purpose of improving this, a copolymer in which the copolymerization amount of ethylene or an α-olefin having 4 to 20 carbon atoms is increased is known. Since stickiness (blocking resistance) is deteriorated and the rigidity of the film is lowered, further improvement is required. In order to improve the heat sealability and the blocking resistance at low temperatures as described above, it is desired to develop a propylene random copolymer having a low melting point and a small amount of components that cause stickiness.

[0004] Conventionally, an olefin polymerization catalyst comprising a titanium compound and an organoaluminum compound has been generally used for the production of a propylene polymer. In recent years, however, a new Ziegler-type olefin catalyst comprising a metallocene compound and an alumoxane (Japanese Patent Laid-Open 1958-1930
No. 9, No. 60-3500, No. 61-130314,
JP-A-63-295607, JP-A-1-275609,
JP-A-1-301704 and JP-A-2-41303), a propylene random copolymer using these olefin polymerization catalysts, and a method for producing the same (JP-A-62-1).
19215, JP-A-1-266116 and 2-17
No. 3014, No. 2-173015, No. 2-24720
No. 7, No. 7, and the use of the obtained copolymer as a heat sealant (Japanese Patent Application Laid-Open No. 2-173016) has been proposed. According to these proposals, a propylene random copolymer having a low melting point and a small amount of components causing stickiness has been obtained, but on the other hand, since the molecular weight distribution is narrow, film formation cannot be performed practically or However, there is a problem that it cannot be used because it causes surface roughness.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems.

[0006]

SUMMARY OF THE INVENTION Means for Solving the Problems] <Summary> The present invention, propylene polymer following the (A) 1
It is a polypropylene composition containing about 70% by weight and 99 to 30% by weight of the propylene random copolymer (B). Propylene polymer (A) : A propylene polymer having the following characteristics (a) to (c). (A) a propylene homopolymer or a propylene polymer containing less than 0.5 mol% of ethylene or an α-olefin having 4 to 20 carbon atoms, and (b) a molecular weight distribution (Mw / Mn) of 3 or less. (C) the average elution temperature (T ₅₀ ) is 4
It is in the range of 0 to 100 ° C, and the dissolution degree (σ value) is 10
Must be: Propylene random copolymer (B) : a propylene random copolymer composed of propylene, ethylene and / or an α-olefin having 4 to 20 carbon atoms and having the following characteristics (d) to (e). (D) 90 to 99.5 mol% of a structural unit obtained from propylene, ethylene and / or
Alternatively, 0.5 to 10 mol% of structural units obtained from an α-olefin having 4 to 20 carbon atoms are present, and (e) the molecular weight distribution (Mw / Mn) is in the range of 3.5 to 10.

The molecular weight distribution (Mw / M
n) is gel permeation chromatography (G
PC) and the average elution temperature (T ₅₀ )
Is temperature rising elution fractionation using o-dichlorobenzene as a solvent (Temperature Rising Elution Fraction:
F ”) based on the elution curve of the polymer. Details of them will be described later.

<Effect> According to the present invention, it is possible to provide a heat seal film having excellent low temperature heat sealability and blocking resistance.

[0009] DETAILED DESCRIPTION <Propylene polymer (A)> The propylene polymer of the present invention the invention (A) is a propylene homopolymer, or less than 0.5 mol% of ethylene or 4 to 20 carbon atoms α- It is a propylene polymer containing olefin. As the α-olefin having 4 to 20 carbon atoms, 1-butene, 1-pentene,
3-methylbutene-1, 1-hexene, 4-methylpentene-1, 1-heptene, 1-octene, 1-nonene,
Examples thereof include 1-decene and 1-hexadecene. Although the preferred proportion of the structural unit differs somewhat depending on the type of the monomer other than propylene, generally, the propylene structural unit has 9
2 to 99 mol%.

The molecular weight distribution (Mw / M) of the copolymer (A)
n) is in the range of 3 or less. It is preferably in the range of 1 to 2.8. In general, a polymer obtained with a catalyst comprising a metallocene compound and an alumoxane can obtain only those having Mw / Mn of 3 or less, but those having a Mw / Mn of more than 3 deteriorate the blocking resistance because the catalyst also has non-uniformity. Therefore, it is not preferable. The molecular weight of the copolymer of gel permeation chromatography (GPC) was measured according to "Gel Permeation Chromatography" published by Maruzen by Takeuchi. That is, using standard polystyrene having a known molecular weight (monodisperse polystyrene manufactured by Tosoh Corporation), it was converted into a number average molecular weight (Mn) and a weight average molecular weight (Mw) by a universal method, and the value of Mw / Mn was obtained. The measurement is 150C-ALC / GPC manufactured by Waters.
And three columns of AD80M / S manufactured by Showa Denko KK were used. The sample is 0.2-wt% in 0-dichlorobenzene
The reaction was carried out at 140 ° C. at a flow rate of 1 ml / min.

The average elution temperature (T ₅₀ ) by TREF is 4
It is in the range of 0 to 90 ° C, and the dissolution degree (σ value) is 10 or less. The average dissolution temperature (T ₅₀ ) indicates the temperature at which the cumulative weight of the dissolution polymer becomes 50% by weight. The elution dispersity (σ value) is calculated by assuming that the elution amount by TREF follows a normal probability distribution with respect to the elution temperature.
(T) is the following formula:

[0012]

(Equation 1)

Is the σ value defined as expressed by
Specifically defined _{σ = T 84. 1 -T 50} . T _{84. 1} shows the temperature at which the cumulative weight becomes 84.1 wt%. still,
Measurement of TREF is based on the Journal of Applied Polymer S
cience 26, 4217-4231 (1981). The average dissolution temperature and dispersibility are preferably 50 to 95 ° C. and the σ value is 9 or less. More preferably, it is 50 to 90 ° C. and the σ value is 8 or less. If the average dissolution temperature is less than 40 ° C, the molecular weight is too low or the melting point is too low, which causes blocking. If it exceeds 100 ° C, the molecular weight is too high to be molded or the melting point is too high, so Does not have heat sealability. If the dissolution degree is 10 or more, the components causing blocking increase, so that both of the heat sealing property at low temperature and the blocking resistance cannot be satisfied.

The propylene polymer (A) can be produced using a polymerization catalyst comprising the following components (C) and (D). <Component (C)> component C, the following general _{formula: Qa (C 5 H 5-} ab R 1 b) (C 5 H 5-ac R 2 c) MeXY or the following general formula: Sa (C ₅ H _{5 -ad} R ³ _d ) is a transition metal compound represented by ZMeXY. Here, Q represents a binding group bridging the two conjugated five-membered ring ligands, and S represents a binding group bridging the conjugated five-membered ligand and the Z group. Specifically, (a) an alkylene group such as a methylene group, an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, and a cyclohexylene group; (b) a silylene group, a dimethylsilylene group, a phenylmethylsilylene group, and a diphenylsilylene Group, disilylene group,
(C) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum [specifically, (CH ₃ ) ₂ Ge
Group, (C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group, (C ₆ H ₅ ) P
Group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group, (CH ₃ ) B
Group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group, (C ₆ H ₅ ) Al
Group, (CH ₃ O) Al group, etc.]. Preferred are an alkylene group and a silylene group. a is 0 or 1;

In the above general formula, (C ₅ H
_5-ab R ¹ _b ), (C ₅ H _5-ac R ² _c ) and (C ₅ H _5-ad
The conjugated five-membered ring ligands represented by R ³ _d ) are each independently defined, but are b, c and d, and R
^Since the definitions of ¹ , R ² and R ³ are the same (details described later), it goes without saying that these three conjugated five-membered ring groups may be the same or different. One specific example of the conjugated five-membered ring group is a cyclopentadienyl group of b = 0 (or c = 0, d = 0) (no substituent other than the crosslinking group Q or S). When the conjugated five-membered ring group has b ≠ 0 (or c ≠ 0, d ≠ 0) and has a substituent, one specific example of R ¹ (or R ² , R ³ ) is hydrogen group (C ₁ -C _20, preferably C ₁ -C ₁₂₎ is a,
This hydrocarbon group may be bonded to a cyclopentadienyl group as a monovalent group, or may be bonded to a cyclopentadienyl group as a divalent group. A typical example of the latter is R
¹ (or R ² , R ³ ) sharing a double bond of the cyclopentadienyl group to form a fused six-membered ring,
That is, the conjugated five-membered ring group is an indenyl group or a fluorenyl group. That is, typical examples of the conjugated five-membered ring group are a substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group.

R ¹ , R ² and R ³ each represent, in addition to the above-mentioned C ₁ -C ₂₀ , preferably C ₁ -C ₁₂ hydrocarbon group,
Halogen group (for example, fluorine, chlorine, bromine), alkoxy group (for example, _one of C _{1 to} C ₁₂ ), silicon-containing hydrocarbon group (for example, when a silicon atom is -Si (R ¹ )
(R ² ) a group having about 1 to 24 carbon atoms contained in the form of (R ³ )),
A phosphorus-containing hydrocarbon group (for example, a phosphorus atom is -P (R)
A group having about 1 to 18 carbon atoms in the form of (R)), a nitrogen-containing hydrocarbon group (for example, a group having about 1 to 18 carbon atoms in which a nitrogen atom is included in the form of -N (R) (R ')) Alternatively, a boron-containing hydrocarbon group (for example, when a boron atom is -B (R) (R)
A group having about 1 to 18 carbon atoms). b (or c, d) is 2 or more and R ¹ (or R ² ,
When a plurality of R ³ ) are present, they may be the same or different. b, c and d are 0 when a is 0
≦ b ≦ 5, 0 ≦ c ≦ 5, 0 ≦ d ≦ 5, and when a is 1, it is an integer satisfying 0 ≦ b ≦ 4, 0 ≦ c ≦ 4, and 0 ≦ d ≦ 4.

Me is a transition metal from Groups IVB to VIB of the Periodic Table, preferably titanium, zirconium, and hafnium. Z is oxygen (-O-), sulfur (-S-) having 1 to 1 carbon atoms.
20, preferably 1 to 10 alkoxy groups, 1 to 1 carbon atoms
20, preferably 1 to 12 thioalkoxy groups, 1 to 40 carbon atoms, preferably 1 to 18 silicon-containing hydrocarbon groups, 1 to 40 carbon atoms, preferably 1 to 18 nitrogen-containing hydrocarbon groups, 1 to 40, preferably 1 to 18 phosphorus-containing hydrocarbon groups. X and Y each represent hydrogen, a halogen group, a hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, and 1 carbon atom. ~ 20, preferably 1 ~
A phosphorus-containing hydrocarbon group (specifically, for example, diphenylphosphine group) or a silicon-containing hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms (specifically, for example, trimethylsilyl group) is there. X and Y may be the same or different. Of these, a halogen group and a hydrocarbon group are preferred.

Specific examples of the transition metal compound when Me is zirconium are as follows. (A) Transition metals having no bridging linking group and having two conjugated five-membered ring ligands, such as (1) bis (cyclopentadienyl) zirconium dichloride and (2) bis (methylcyclopentadienyl) Zirconium dichloride, (3) bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (trimethylcyclopentadienyl) zirconium dichloride, (5) bis (tetramethylcyclopentadienyl) zirconium dichloride,

(6) bis (pentamethylcyclopentadienyl) zirconium dichloride, (7) bis (indenyl) zirconium dichloride, (8) bis (fluorenyl) zirconium dichloride, (9) bis (cyclopentadienyl) zirconium monochloride Chloride monohydride, (10) bis (cyclopentadienyl) methylzirconium monochloride,

(11) bis (cyclopentadienyl) ethyl zirconium monochloride, (12) bis (cyclopentadienyl) phenyl zirconium monochloride, (13)
Bis (cyclopentadienyl) zirconium dimethyl, (14) bis (cyclopentadienyl) zirconium diphenyl, (15) bis (cyclopentadienyl) zirconium dineopentyl,

(16) bis (cyclopentadienyl) zirconium dihydride, (17) (cyclopentadienyl) (indenyl) zirconium dichloride, (18)
(Cyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

(B) Transition metal compounds having two 5-membered ring ligands bridged by an alkylene group, such as (1) methylenebis (indenyl) zirconium dichloride, (2) ethylenebis (indenyl) zirconium dichloride, (3) Ethylene bis (indenyl) zirconium monohydride monochloride, (4) ethylene bis (indenyl) methyl zirconium monochloride,
(5) ethylenebis (indenyl) zirconium monomethoxymonochloride,

(6) Ethylene bis (indenyl) zirconium diethoxide, (7) ethylene bis (indenyl) zirconium dimethyl, (8) ethylene bis (4
5,6,7-tetrahydroindenyl) zirconium dichloride, (9) ethylenebis (2-methylindenyl) zirconium dichloride, (10) ethylene (2,4
-Dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride;

(11) Ethylene (2-methyl-4-tertbutylcyclopentadienyl) (3'-tertbutyl-5 '
-Methylcyclopentadienyl) zirconium dichloride, (12) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, (13) isopropyl Ridenebis (indenyl) zirconium dichloride, (14) isopropylidenebis (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, (15) isopropylidenebis (2- Methyl-4-tertbutylcyclopentadienyl) (3′-tertbutyl-5-methylcyclopentadienyl) zirconium dichloride,

(16) Methylene (cyclopentadienyl)
(3,4-dimethylcyclopentadienyl) zirconium dichloride, (17) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium chloride hydride, (18) methylene (cyclopentadienyl) ( 3,4-dimethylcyclopentadienyl) zirconium dimethyl, (19) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium diphenyl, (20) methylene (cyclopentadienyl) (trimethylcyclo Pentadienyl)
Zirconium dichloride,

(21) Methylene (cyclopentadienyl)
(Tetramethylcyclopentadienyl) zirconium dichloride, (22) isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (23) isopropylidene (cyclopentadienyl) (2, 3,4,5-tetramethylcyclopentadienyl) zirconium dichloride, (24) isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, (25) isopropylidene (cyclopentadienyl) (fluorenyl ) Zirconium dichloride,

(26) isopropylidene (2-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (27) isopropylidene (2,5-dimethylcyclopentadienyl) (3,4-dimethylcyclopentadienyl) Zirconium dichloride, (28) isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (29) ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, 30) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

(31) ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (32) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride,
(33) Diphenylmethylene (cyclopentadienyl)
(3,4-diethylcyclopentadienyl) zirconium dichloride, (34) diphenylmethylene (cyclopentadienyl) 3,4-diethylcyclopentadienyl)
Zirconium dichloride, (35) cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (36) cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ′, 4′-dimethyldimethylcyclopentadiene) Enyl) zirconium dichloride and the like.

(C) Transition metal compounds having a silylene group-bridged five-membered ligand, such as (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylene (4,5,6)
7-tetrahydroindenyl) zirconium dichloride, (3) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, (4) phenylmethylsilylenebis (indenyl) ) Zirconium dichloride, (5) phenylmethylsilylenebis (4, 5, 6,
7-tetrahydroindenyl) zirconium dichloride,

(6) Phenylmethylsilylene (2,4-
Dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride,
(7) phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, (8)
Phenylmethylsilylenebis (tetramethylcyclopentadienyl) zirconium dichloride, (9) diphenylsilylenebis (indenyl) zirconium dichloride, (10) tetramethyldisilylenebis (indenyl)
Zirconium dichloride,

(11) tetramethyldisilylenebis (cyclopentadienyl) zirconium dichloride, (12) tetramethyldisilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, (13) dimethylsilylene (cyclopentane Dienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (14) dimethylsilylene (cyclopentadienyl)
(Trimethylcyclopentadienyl) zirconium dichloride, (15) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride,

(16) dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (17) dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, 18) dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride, (19) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (20) dimethylsilylene (cyclopentadienyl) (2) , 7-Di-t-butyl fluorenyl) zirconium dichloride,

(21) Dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (22) Dimethylsilylene (2-methylcyclopentadienyl-fluorenyl) zirconium dichloride, (23) Dimethylsilylene (2 , 5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (24) dimethylsilylene (2-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (25) dimethylsilylene (2,5-diethylcyclopentadienyl) ) (Fluorenyl) zirconium dichloride,

(26) Diethylsilylene (2-methylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (27) Dimethylsilylene (2,5-dimethylcyclopentadienyl) (2,7
-Di-t-butylfluorenyl) zirconium dichloride, (28) dimethylsilylene (2-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, (29) dimethylsilylene ( Diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (30) dimethylsilylene (methylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (31) dimethylsilylene (Dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (3
2) Dimethylsilylene (ethylcyclopentadienyl)
(Octahydrofluorenyl) zirconium dichloride, (33) dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride and the like.

(D) Transition metal compounds having a five-membered ring ligand bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, such as (1) dimethylgermanium bis (indenyl) zirconium dichloride, 2) Dimethylgermanium (cyclopentadienyl) (fluorenyl) zirconium dichloride, (3) methylaluminum bis (indenyl)
Zirconium dichloride, (4) phenylaluminum bis (indenyl) zirconium dichloride, (5) phenylphosphinobis (indenyl) zirconium dichloride, (6) ethylholanobis (indenyl) zirconium dichloride, (7) phenylaminobis (indenyl) zirconium dichloride, (8) Phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

(E) Transition metal compounds having one 5-membered ring ligand, such as (1) pentamethylcyclopentadienyl-bis (phenyl) aminozirconium dichloride (2) indenyl-bis (phenyl) aminozirconium dichloride (3) pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride (4) pentamethylcyclopentadienylphenoxyzirconium dichloride (5) dimethylsilylene (tetramethylcyclopentadienyl) phenylaminozirconium dichloride (6) dimethyl Silylene (tetrahydroindenyl) decylaminozirconium dichloride (7) Dimethylsilylene (tetrahydroindenyl)
(Bis (trimethylsilyl) amino) zirconium dichloride (8) dimethylgermane (9) tetramethylcyclopentadienyl (phenyl)
Examples include amino zirconium dichloride.

(F) Further, compounds obtained by replacing chlorine in the compounds (a) to (e) with bromine, iodine, hydride, methyl, phenyl and the like can also be used. Further, in the present invention, a compound in which the central metal of the zirconium compounds exemplified in the above (a) to (e) is changed from zirconium to titanium, hafnium, niobium, molybdenum or tungsten can be used as the component (C). Of these, preferred are zirconium compounds, hafnium compounds and titanium compounds. More preferred are zirconium compounds and hafnium compounds cross-linked with an alkylene group or a silylene group.

<Component D> Component (D) is alumoxane. Alumoxanes are products obtained by the reaction of one trialkylaluminum or two or more trialkylaluminums with water. Specifically, methylalumoxane, ethylalumoxane, butylalumoxane, isobutylalumoxane, etc. obtained from one type of trialkylaluminum, and methylethylalumoxane, methylbutylalumoxane obtained from two types of trialkylaluminum and water Xan, methyl isobutylalumoxane and the like are exemplified. These alumoxanes may be used in combination of two or more, and may be used in combination with other alkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and dimethylaluminum chloride. It is also possible to use a modified alumoxane by reacting two kinds of alumoxanes or one kind of alumoxane with another organoaluminum compound. Of these, preferred are methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, and a mixture of these alumoxane and trialkylaluminum. Particularly preferred are methylalumoxane and methylisobutylalumoxane.

These alumoxanes can be prepared under various known conditions. Specifically, the following method can be exemplified. (A) a method in which a trialkylaluminum is directly reacted with water using an appropriate organic solvent such as toluene, benzene or ether; (b) a salt hydrate having a trialkylaluminum and water of crystallization such as copper sulfate or aluminum sulfate A method of reacting a trialkylaluminum with water impregnated in silica gel or the like; (d) mixing trimethylaluminum with triisobutylaluminum;
(E) a method of mixing trimethylaluminum and triisobutylaluminum directly with water using an appropriate organic solvent such as benzene or ether, and a salt hydrate having water of crystallization such as copper sulfate and aluminum sulfate hydrate (F) a method of impregnating silica gel or the like with water, treating with triisobutylaluminum, and then additionally treating with trimethylaluminum. (G) Synthesizing methylalumoxane and isobutylalumoxane by a known method. A method in which a predetermined amount of these two components are mixed and reacted by heating.

<Formation of Catalyst> The catalyst used in the present invention is prepared by subjecting the above-mentioned components (C) and (D) in a polymerization vessel or outside the polymerization vessel in the presence or absence of a monomer to be polymerized. It can be prepared by contact. The amounts of the components (C) and (D) used in the present invention are arbitrary, but generally, the atomic ratio (Al / Me) between the aluminum atom in the component (D) and the transition metal in the component (C).
0.01 to 100,000, preferably 0.1 to 30,0
00. The contacting method is optional and may be introduced separately during the polymerization and brought into contact, or may be brought into contact in advance.

The catalyst of the present invention comprises the components (C) and (D)
In addition to the above, it is possible to include other components as described above. However, as the third component (optional component) that can be added to the components (C) and (D), for example, water, methanol, Active hydrogen-containing compounds such as ethanol and butanol; electron-donating compounds such as ethers, esters and amines; phenyl borate, dimethylmethoxyaluminum,
Examples thereof include alkoxy-containing compounds such as phenyl phosphite, tetraethoxysilane, and diphenyldimethoxysilane; and organic boron compounds such as triphenylboron and tributylboron.

<Production Method of Propylene Polymer (A)> The production of the propylene polymer (A) using the polymerization catalyst comprising the components (C) and (D) is carried out by using propylene alone or propylene and ethylene or carbon number. It is carried out by mixing and contacting 4 to 20 α-olefins. In the case of copolymerization, the quantitative 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. It is also possible to change over time. Further, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio.

The polymerization mode may be any mode as long as the catalyst component and each monomer are in efficient contact with each other. Specifically, a slurry method using an inert solvent, a slurry method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or each monomer is substantially gaseous without using a substantially liquid solvent. Gas phase method or the like can be adopted. Further, the present invention is also applicable to a method of performing continuous polymerization, batch polymerization or preliminary polymerization. In the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene is used as a polymerization solvent. The polymerization temperature is about −78 ° C., preferably 0 ° C. to 150 ° C. At that time, hydrogen can be used as an auxiliary as a molecular weight regulator. At the time of slurry polymerization, the amount of component (C) used is
A range of 0.001-1. 0 g component (C) / liter solvent is preferred. 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.
m ² G is appropriate.

It is preferable to use a catalyst in which propylene is previously polymerized alone before copolymerization for the purpose of improving the activity, eliminating the solvent-soluble by-product polymer or preventing the melting point from lowering. The molecular weight of the polymer is
It can be controlled by adding hydrogen into the polymerization system.

<Propylene random copolymer (B)>
The propylene random copolymer (B) of the present invention has a structural unit obtained from propylene of 90 to 99.5 mol%,
0.5 to 10 mol% of structural units obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms. As an α-olefin having 4 to 20 carbon atoms, 1
-Butene, 1-pentene, 3-methylbutene-1,1-
Hexene, 4-methylpentene-1, 1-heptene, 1
-Octene, 1-nonene, 1-tesene, 1-hexadecene and the like are exemplified. Although the preferred proportion of the structural unit varies somewhat depending on the type of the monomer other than propylene, the proportion of the propylene structural unit is generally 92 to 99 mol%.

The ratio of Mw / Mn measured by gel permeation chromatography (GPC) is 3.5 to 10
, Preferably in the range of 4-9. Mw / Mn> 1
If it is 0, it is difficult to mix the copolymer (A) and the blend uniformly, and the transparency is deteriorated and the surface is roughened. on the other hand,
When Mw / Mn <3.5, the film formability of the whole polymer is deteriorated, and the effect of improving the formability of the composition of the present invention cannot be obtained.

<Production of Propylene-Based Random Copolymer (B)> The present polymer can be polymerized using a generally known Ziegler-type catalyst comprising a titanium compound and an organoaluminum. Non-limiting examples include a catalyst consisting of a TiCl ₃ composition manufactured by Marubeni Solvay and diethylaluminum chloride, or a highly active catalyst component containing titanium, magnesium, and halogen, and triethylaluminum, and A catalyst comprising an electron donating compound to be used accordingly can be mentioned.

<Production of Propylene Polymer Composition> The composition of the present invention can be obtained by blending a propylene polymer (A) and a propylene random copolymer (B). The compounding ratio of the polymer (A) is 1 to 70% by weight,
Preferably 3 to 50% by weight, more preferably 5 to 50% by weight.
% By weight. If the amount is less than 1% by weight, the effect of improving the low-temperature heat sealability and the blocking resistance cannot be obtained. If the amount is more than 70% by weight, the moldability cannot be improved, and the film cannot be formed substantially. In the composition of the present invention, in addition to the above essential components, additional components can be further added as long as the effects of the present invention are not significantly impaired. These additional components include antioxidants, neutralizers, UV absorbers, and the like used for ordinary polyolefins.
Examples thereof include an air bubble inhibitor, a dispersant, an antistatic agent, a lubricant, a molecular weight regulator (peroxide), various auxiliaries such as a nucleating agent, a rubber component, and a coloring agent.

The method of producing the composition of the present invention includes a commonly used Henschel mixer, super mixer, V
Blender, tumbler mixer, ribbon blender,
It is preferable that the mixture is mixed for a predetermined time using a mixer or kneader such as a Banbury mixer, a kneader blender, or an extruder, and the mixture is formed into pellets using a normal extruder. This composition is processed into various molded articles through extrusion molding, hollow molding, film molding, injection molding, compression molding and the like. In particular, the effect of the present invention is greatly exerted on an extruded product.

[0050]

【Example】

Experimental Example Production of Propylene Polymer (A) : [ Production of Catalyst Component (C) -1] 50 sufficiently purged with nitrogen.
After introducing 200 ml of THF and 5 g of fluorene into a 0 ml flask and cooling the mixture to -50 ° C or lower, 67 ml of a diluted solution of methyllithium diethyl ether (1.4 M) was added dropwise over 30 minutes, and the temperature was gradually raised to room temperature. Allowed to react for hours. Then, after cooling again to -50 ° C or lower, 10 g of 6,6-dimethylfulvene was added dropwise over 30 minutes. After the completion of the dropwise addition, the temperature was slowly raised to room temperature, and the reaction was carried out for two days and nights. After completion of the reaction, the reaction was stopped by adding 60 ml of H ₂ O, the ether layer was separated, dehydrated with anhydrous MgSO ₄ , and the ether was evaporated to dryness to give 2-cyclopentadienyl 2-fluorene. Nilpropane crude crystal 17.6
g was obtained.

Next, 10 g of the above crude crystals were added to THF 100
The mixture was diluted to -50 ml and cooled to -50 ° C or lower, and 46.0 ml (0.0736 mol) of n-butyllithium was added dropwise over 10 minutes.
The temperature was returned to room temperature over 1 hour and reacted at room temperature for 2 hours.
Next, under a nitrogen stream, after evaporating and drying the solvent,
100 ml of dichloromethane was added, and the mixture was cooled to -50 ° C or lower. Next, a solution prepared by previously mixing 8.16 g of zirconium tetrachloride in 50 ml of dichloromethane at a low temperature was fed at once. After mixing, the temperature was slowly raised over 3 hours, and the reaction was carried out at room temperature for one day. After completion of the reaction, the solid matter was removed by filtration, and the filtrate was concentrated and recrystallized to obtain 4.6.
8 g of red isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride component (C) -1 was obtained.

[Production of Catalyst Component (C) -2] All reactions were carried out under an inert gas atmosphere. The reaction solvent used was previously dried. 5.0 g (33 mmol) of 2-methylindene in a 500 ml glass reaction vessel
Was dissolved in 80 ml of tetrahydrofuran, and n-
21 ml of a 1.6M hexane solution of butyllithium was slowly dropped into the reaction vessel. After stirring at room temperature for 1 hour, the mixture was cooled again, 3.1 g of 1,2-dibromine was slowly added dropwise, and after stirring at room temperature for 12 hours, 50 ml of water was added, and the organic phase was separated and dried. After further washing with heptane several times and drying, bis- (2-methylindenyl) ethane 2.9 was obtained.
g was obtained.

2.1 g (7.3 mmol) of bis- (2-methylindenyl) ethane obtained by the above method was dissolved in 70 ml of tetrahydrofuran, and cooled under cooling with 1.
5.2 ml of a 6M hexane solution was slowly added dropwise. After stirring at room temperature for 3 hours, 1.6 g of zirconium tetrachloride (7.0 mm
ol) / 60 ml of tetrahydrofuran solution, slowly stirred for 5 hours, then blown with hydrogen chloride gas and dried. Subsequently, soluble portions were separated by adding toluene and crystallized at a low temperature to obtain 0.95 g of a yellow powder. The obtained compound is ethylenebis- (2-methylindenyl)
It was confirmed by ¹ H-NMR that zirconium dichloride and both 2-methylindenyl groups were asymmetric, that is, they were not in a mirror image with the substance in the plane containing the zirconium atom.

[Production of catalyst component (D)] In a reaction vessel, 48.2 g of trimethylaluminum was added to 565 m of a toluene solution.
of copper sulfate pentahydrate at 0 ° C.
It was thrown into the container at minute intervals. After finishing, slowly cool down to 25 ℃
To 25 ° C. for 2 hours, and further to 35 ° C. for 2 hours.
Allowed to react for days. The remaining copper sulfate solid was separated by filtration to obtain a toluene solution of alumoxane. The concentration of methylalumoxane was 27.3 mg / ml (2.7 w / v%).

Production of Propylene Polymer (A) -1 After sufficiently replacing the inside of a 15-liter stirred autoclave with propylene, the mixture was sufficiently dehydrated and deoxygenated.
-5 liters of heptane were introduced, 100 mmol of methylalumoxane as component (D) in terms of alumino atom, and 100 mmol of isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride of component (C) -1 were introduced. At 15 ° C at 20 ° C.
Polymerized for minutes. Further, propylene was introduced, and polymerization was carried out at 40 ° C. for 2 hours at an internal pressure of 7 kg / cm ² G of the autoclave. After the completion of the reaction, 500 ml of butanol was added, and the mixture was detouched at 50 ° C. for 1 hour. Then, the mixture was gradually fed into a steam stripping tank over 30 minutes to evaporate the solvent, and the polymer was separated and recovered. Polymer (A) -1 was obtained. As a result of GPC measurement, the number average molecular weight was 64,000, Mw / Mn = 2.21, the MFR was 7.93,
As a result of DSC measurement, two peaks were obtained at 141.0 ° C. and 135.7 ° C. As a result of TREF measurement, the average elution temperature was 81 ° C., and the elution dispersion degree was 3.5.

Production of Propylene Polymer (A) -2 Except that the polymerization temperature was changed to 50 ° C., all the procedures were carried out under the same conditions as in the production of the propylene polymer (A) -1. As a result, 490 g of a propylene polymer (A) -2 was obtained. The number average molecular weight of the polymer was 51,000, Mw / Mn = 2.10,
MFR = 13.5 g / 10 min, and melting points showed peaks at 134.2 ° C. and 127.0 ° C. As a result of TREF measurement, the average dissolution temperature (T ₅₀ ) was 63 ° C. and the dissolution degree was 4.7.

Production of Propylene Polymer (A) -3 After sufficiently replacing the inside of a 15-liter stirred autoclave with propylene, n was sufficiently dehydrated and deoxygenated.
5 liters of heptane was introduced, and 100 mmol of methylalumoxane as Al atom was converted as the component (D).
After introducing 10.0 mmol of (2-methylindenyl) zirconium dichloride component (C) -2, propylene was introduced and polymerization was carried out at 20 ° C. for 15 minutes. When propylene was further introduced and the internal pressure of the autoclave was 7 kg / cm ² G, 4
It polymerized at 0 degreeC for 2 hours. After completion of the reaction, butanol 500
After the mixture was desorbed at 50 ° C. for 1 hour, the solution was gradually fed into a steam stripping tank over 30 minutes to evaporate the solvent, and the polymer was separated and recovered. As a result, 860 g of a propylene polymer (A)- 3 was obtained. Its number average molecular weight is 23,500 Mw / Mn = 2.05. Melting point is 135.2 ° C.
Met. As a result of TREF measurement, the average elution temperature was 87.
The elution dispersity at ℃ was 3.6.

Production of propylene-based random copolymer (B)
Using granulated copolymer (B) an ethylene content of 2.5 wt% of a propylene random copolymer as -1. MFR is 9.
2. The molecular weight distribution (Mw / Mn) was 6.50. The melting point was 147.7 ° C., the average elution temperature (T ₅₀ ) was 95 ° C., and the elution dispersity was 7.2.

Comparative Propylene Polymer (A) -4 A propylene polymer having an MFR of 7.6 and containing no ethylene was used. Mw / Mn = 6.2 Melting point: 169.6 ° C. Average elution temperature (T ₅₀ ): 120 ° C. Elution dispersity was 5.1.

Example 1 As a substrate layer, MFR 2.3 g / 10 min and II9
100 parts of 8% polypropylene [FL6S (trade name) manufactured by Mitsubishi Yuka Co., Ltd.] was mixed with 0.6 parts by weight of glycerin monostearate and 0.1 part by weight of N, N'bis (2-hydroxyethyl) alkylamine. Was used. As the surface layer, the propylene polymer (A) -1, 10
0.1 part by weight of 2,6-di-tert-butyl-p-cresol as an antioxidant and 0.05 part by weight of calcium stearate as a catching agent for hydrochloric acid were added to 90 parts by weight of copolymer (B) -1 and 90 parts by weight of copolymer (B) 0.1 parts by weight of silica having an average particle size of 3 μm
5 parts by weight were added, and after mixing, pelletized was used.

Using these compositions, they were laminated under the following conditions and sequentially biaxially stretched to obtain a biaxially stretched polypropylene multilayer film. The polypropylene as the base material layer and the composition of the present invention as the surface layer are each formed into a three-layer structure of surface layer composition / polypropylene / surface layer composition using a three-layer die from a 115 mm diameter and 35 mm diameter extruder. In the same manner, a sheet was formed by co-extrusion at 250 ° C. Subsequently, the film was stretched 5 times in the radial direction at 115 ° C. using a difference in roll peripheral speed. Next, the film was stretched 10 times in the transverse direction in a tenter oven at 168 ° C., heat-set at 155 ° C., and subsequently subjected to a corona discharge treatment on one side of the film to obtain a biaxially stretched multilayer film. The thickness configuration was 1 μ / 23 μ / 1 μ.

The heat sealing temperature and the blocking resistance of this film were measured under the following conditions. Table 1 shows the results. Heat seal temperature : Using a heat seal bar of 5 mm x 200 mm, at each set temperature, a heat seal pressure of 1 kg /
A sample having a width of 20 mm was cut out from a sample sealed under heat sealing conditions of 0.5 cm ² and a heat sealing time of 0.5 second, and separated at a tensile speed of 500 mm / min using a Shopper type tester. The heat sealing temperature was used. Blocking resistance : Two films (corona discharge treated surfaces) are stacked so that the contact area is 10 cm ² , sandwiched between two glass plates, and applied with a load of 50 g / cm ² under an atmosphere of 40 ° C. , And the maximum load at the time of peeling was measured with a shopper type testing machine.

Examples 2 and 3 and Comparative Example 1 The mixing ratio of the propylene polymer (A) -1 and the propylene ethylene random copolymer (B) -1 of Example 1 is shown in Table 1.
The evaluation was performed in the same manner as in Example 1 except that the evaluation was changed as shown in (1).

Examples 4 and 5 and Comparative Example 2 Except that (A) -2, (A) -3 and (A) -4 were used instead of the propylene polymer (A) -1 of Example 1,
All were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 Evaluation was performed in the same manner as in Example 1 except that only 100 parts by weight of the propylene ethylene random copolymer (B) -1 was used as the surface layer. Table 1 shows the above results.
As shown in Table 1, the film of Comparative Example 1 had a severe surface roughness and was not practically used, so that the heat seal temperature and the blocking resistance could not be measured.

[0066]

[Table 1]

──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Eiji Uchino 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Yuka Co., Ltd. In Yokkaichi Research Institute, Inc. (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 23 / 12-23/16

Claims (1)

(57) [Claims] 1. The method according to claim 1, wherein the propylene polymer (A) is
0% by weight, and a propylene random copolymer (B)
Is a polypropylene composition containing 99 to 30% by weight. Propylene polymer (A) : A propylene polymer having the following characteristics (a) to (c). (A) a propylene homopolymer or a propylene polymer containing less than 0.5 mol% of ethylene or an α-olefin having 4 to 20 carbon atoms; (b) a molecular weight distribution (Mw / Mn) of 3 or less (C) The average dissolution temperature (T ₅₀ ) is in the range of 40 to 100 ° C. and the dissolution degree (σ value) is 10 or less. Propylene random copolymer (B) : a propylene random copolymer composed of propylene, ethylene and / or an α-olefin having 4 to 20 carbon atoms and having the following characteristics (d) to (e). (D) When the structural unit obtained from propylene is 90 to 99.
5 to 10 mol% of structural units obtained from 5 mol%, ethylene and / or an α-olefin having 4 to 20 carbon atoms, (e) a molecular weight distribution (Mw / Mn) of 3.5 to 10 Range.