JP4746211B2 - Propylene resin composition, film using the same, and laminated resin film - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a propylene-based resin composition having high transparency and low blocking properties, a film using the same, and a laminated resin film.
[0002]
[Prior art]
Propylene-based resin produced using a metallocene catalyst has a larger melting point drop with respect to comonomer content than propylene-based resin obtained by a conventional Ziegler catalyst mainly composed of Ti, Mg, Cl, etc. Since the obtained film is small in blocking and excellent in low-temperature heat sealability, great expectations are placed on development for sealant film applications.
[0003]
However, as a result of investigations by the present inventors, a propylene-based resin based on a metallocene catalyst is formed by taking a sufficient time for heat removal of the film, such as lowering the take-off speed when formed into a film using a T-die. In this case, it has been found that, while excellent transparency is obtained, transparency is lowered when cooling becomes insufficient due to a high molding speed or the like.
[0004]
The reason for this is that polypropylene resins based on metallocene catalysts generally have a narrow molecular weight distribution and small orientational crystals when forming a film, so crystallization slows down, and depending on the cooling conditions, the spherulites in the film grow large, It is presumed that unevenness is formed on the surface and film transparency is lowered.
[0005]
In order to sufficiently cool the film, it is desirable to reduce the molding speed. However, since productivity is important in commercial production lines, it is not desirable to reduce the molding speed. Although it is conceivable to lower the cooling temperature, a large cooling device is required to lower the cooling temperature, and there is a problem that the manufacturing cost increases. Therefore, it is necessary to develop a resin that can ensure quality without depending on molding conditions.
[0006]
For this purpose, it is conceivable to add a nucleating agent to generate crystal nuclei. However, when adding a nucleating agent, it is important to effectively disperse the nucleating agent in the resin, which leads to poor dispersion. There is a problem that the quality of the base film is likely to deteriorate. Moreover, there is a problem that a sufficient transparency improving effect cannot be obtained by adding a nucleating agent.
[0007]
For this reason, there is a demand for the development of a propylene-based resin capable of obtaining a film having excellent transparency even when the production rate is increased.
[0008]
[Problems to be solved by the invention]
The present invention is a propylene-based resin composition with reduced film-transparency dependency on cooling conditions, good surface smoothness, and a film with excellent transparency, and excellent moldability in T-die molding, A propylene-based resin film and a laminated resin film are provided.
[0009]
[Means for Solving the Problems]
As a result of intensive studies by the present inventors, a film having excellent transparency can be obtained by adding a small amount of polyethylene wax having specific physical properties to a specific propylene / α-olefin copolymer polymerized by a metallocene catalyst. Thus, the present invention has been found.
[0010]
Specifically, with respect to 100 parts by weight of the resin composition, 95.0 to 99.999 parts by weight of propylene / α-olefin copolymer polymerized by the component (A) metallocene catalyst, and component (B) polyethylene. 0.001 to 5.0 parts by weight of wax (provided that the total amount of components (A) and (B) is 100 parts by weight), and component (A) and component (B) satisfy the following conditions, respectively. The present invention provides a propylene-based resin composition characterized by being satisfied.
[0011]
Component (A): Propylene / α-olefin copolymer
1) Melt index MI_P(230 ° C) is 2-30g / 10min
2) The main melting peak temperature (Tm) determined by DSC is 110 to 145 ° C.
[0012]
Component (B): Polyethylene wax
1) Density is 0.94-0.98 g / cm^Three
2) The viscosity at 140 ° C. is 10 cps or more
[0013]
The present invention also provides a propylene-based resin composition in which a compound represented by the following general formula (1) or a partial hydrogenated product thereof is used as the metallocene catalyst of the component (A).
[0014]
[Chemical 2]
[0015]
[Wherein Q is a bonding group that bridges two conjugated five-membered ring ligands, M is a metal atom selected from titanium, zirconium, and hafnium, and X and Y are hydrogen atoms and halogen atoms bonded to M. , Hydrocarbon group, alkoxy group, amino group, nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group, R¹, R^ThreeAre hydrogen, hydrocarbon group having 1 to 20 carbon atoms, halogen, halogenated hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing carbon group, respectively. A hydrogen group or a phosphorus-containing hydrocarbon group, and R²Are hydrogen, hydrocarbon group having 1 to 20 carbon atoms, halogen, halogenated hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing carbon group, respectively. A hydrogen group or a phosphorus-containing hydrocarbon group is shown. ]
Furthermore, the present invention provides a propylene-based resin film formed by molding the propylene-based resin composition using a T die, and a resin laminated film including the propylene-based resin film.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The propylene resin composition of the present invention comprises a specific propylene / α-olefin copolymer polymerized with a metallocene catalyst and a polyethylene wax.
[0017]
In the present invention, “consisting of” does not exclude the addition of an appropriate third component in addition to the above two components.
[0018]
<Component (A): Propylene / α-olefin copolymer>
The component (A) propylene / α-olefin copolymer of the present invention is composed of propylene as a main component and α-olefin unit as a subsidiary component (comonomer unit), and may be a block copolymer. It may be a random copolymer, but a random copolymer is particularly preferable.
[0019]
The α-olefin used as a comonomer includes ethylene, and generally ethylene and 1-olefin having 4 to 18 carbon atoms are used. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene are used. 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene-1, etc., among which ethylene, 1-butene, 1-hexene, particularly preferably ethylene.
[0020]
The proportion of propylene units in the copolymer is preferably 80 to 99.9 mol%, more preferably 85 to 99.5 mol%, particularly preferably 90 to 99 mol% or more, and the comonomer is preferably 20 to 9 mol%. It is 0.1 mol%, More preferably, it is 15-0.5 mol%, Most preferably, it is 10-1 mol% or less. As the comonomer, the α-olefin is not limited to one type, and a multi-component copolymer using two or more types such as a terpolymer may be used.
[0021]
As the copolymer of component (A), a propylene / α-olefin copolymer satisfying the following conditions 1) and 2) is used. Desirably, a propylene / α-olefin copolymer satisfying the following condition 3) simultaneously with conditions 1) and 2) is used.
[0022]
1) Melt index (MI_P)
230 ° C. (2.16 Kg) melt index (MI_P) Is a propylene / α-olefin copolymer of 2 to 30 g / 10 min, preferably 3 to 15 g / 10 min, more preferably 5 to 10 g / 10 min. When the melt index is less than 2 g / 10 minutes, the dischargeability is poor and the T-die moldability is lowered, and when it is more than 30 g / 10 minutes, the film strength is lowered, which is not preferable.
[0023]
2) Main melting peak temperature (Tm) determined by DSC
A propylene / α-olefin copolymer having a main melting peak temperature (Tm) determined by DSC of 110 to 145 ° C, preferably 115 to 140 ° C is used. When the melting peak temperature (Tm) is lower than 110 ° C., it is not preferable because the films tend to be blocked at high temperatures even in a practical environment as a film, and when it exceeds 145 ° C., the low temperature heat sealability is impaired. As well as undesirable.
[0024]
3) When a propylene-based resin composition (component (A) and component (B)) was formed into a film having a thickness of 25 μm at a cooling temperature of 25 ° C. and 45 ° C. using a T-die, an atomic force microscope on the surface thereof was used. Measured average surface roughness [Ra (A + B)_{twenty five}], [Ra (A + B)₄₅And an average surface roughness [Ra (A) measured by an atomic force microscope of the surface when only a component (A) is formed into a film of 25 μm at a cooling temperature of 25 ° C. and 45 ° C. using a T-die]_{twenty five}], [Ra (A)₄₅] Satisfies the following relational expressions (1), (2), (3), and (4).
[0025]
[Ra (A)₄₅]-[Ra (A)_{twenty five}] ≧ 10 Formula (1)
[Ra (A)₄₅] ≧ 15 Formula (2)
[Ra (A + B)₄₅]-[Ra (A + B)_{twenty five}] <10 Formula (3)
[Ra (A + B)₄₅] <15 Formula (4)
[0026]
Further, the average surface roughness [Ra (A + B) of the film surface by an atomic force microscope_{twenty five}], [Ra (A + B)₄₅], [Ra (A)_{twenty five}], [Ra (A)₄₅] Can be measured by using an atomic force microscope cyclic contact mode, and the average surface roughness Ra, that is, the degree of unevenness in the three-dimensional direction, is quantified by calculating according to the following formula (5). Can know.
[0027]
[Expression 1]
[0028]
Here, in Equation (5), F (X, Y) is the measurement surface, So is the measurement area, Y_T~ Y_BIs the Y direction measurement range, X_L~ X_RIs the X direction measurement range, and Zo is the reference plane. Zo is represented by the following formula (6).
[0029]
[Expression 2]
[0030]
The propylene / α-olefin copolymer in the present invention is polymerized using a metallocene catalyst. The metallocene catalyst may be any as long as the above-mentioned polypropylene resin is obtained. Generally, it is a group 4-6 transition metal compound such as Zr, Ti, Hf, etc., particularly a group 4 transition metal compound. An organic transition metal compound having a cyclopentadienyl group or a cyclopentadienyl derivative group can be used.
[0031]
As the group of the cyclopentadienyl derivative, an alkyl substituent such as pentamethylcyclopentadienyl or a group in which two or more substituents are combined to form a saturated or unsaturated cyclic substituent may be used. Typically, an indenyl group, a fluorenyl group, an azulenyl group, or a partial hydrogenated product thereof can be given.
[0032]
Further, it is desirable that a plurality of cyclopentadienyl groups be bonded by an alkylene group, a silylene group, a germylene group, or the like.
[0033]
As a preferable metallocene catalyst for producing the propylene-based resin according to the present invention, a transition metal compound represented by the following general formula (1) can be used.
[0034]
[Chemical Formula 3]
[0035]
[Wherein Q is a bonding group that bridges two conjugated five-membered ring ligands, M is a metal atom selected from titanium, zirconium, and hafnium, and X and Y are hydrogen atoms and halogen atoms bonded to M. , Hydrocarbon group, alkoxy group, amino group, nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group, R¹, R^ThreeAre hydrogen, hydrocarbon group having 1 to 20 carbon atoms, halogen, halogenated hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing carbon group, respectively. A hydrogen group or a phosphorus-containing hydrocarbon group, and R²Are hydrogen, hydrocarbon group having 1 to 20 carbon atoms, halogen, halogenated hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing carbon group, respectively. A hydrogen group or a phosphorus-containing hydrocarbon group is shown. ]
[0036]
Q represents a divalent linking group that bridges two conjugated 5-membered ring ligands. For example, (i) a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, ) Silylene group or oligosilylene group, (c) Silylene or oligosilylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms as a substituent, (d) Germylene group, or (e) 1 carbon number. Examples thereof include a germylene group having a hydrocarbon group of ˜20 as a substituent. Among these, a silylene group having an alkylene group or a hydrocarbon group as a substituent is preferable.
[0037]
X and Y may be each independently, that is, the same or different, and (a) hydrogen, (b) halogen, (c) a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or (2) A hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms containing oxygen, nitrogen or silicon. Of these, preferred are hydrogen, chlorine, methyl, isobutyl, phenyl, dimethylamide, diethylamide groups and the like.
[0038]
R¹, R^ThreeIs a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, Alternatively, it represents a phosphorus-containing hydrocarbon group, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, and a butadienyl group. In addition to hydrocarbon groups, methoxy group, ethoxy group, phenoxy group, trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, dimethyl group containing halogen, silicon, nitrogen, oxygen, boron, phosphorus, etc. Typical examples include phosphino groups, diphenylphosphino groups, diphenylboron groups, dimethoxyboron groups, and the like. Of these, a hydrocarbon group is preferable, and methyl, ethyl, propyl, and butyl are particularly preferable.
[0039]
R²Are hydrogen, hydrocarbon group having 1 to 20 carbon atoms, halogen, halogenated hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing carbon group, respectively. A hydrogen group and a phosphorus-containing hydrocarbon group, and among them, preferably an aryl group having 6 to 16 carbon atoms, specifically phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, And phenalenyl, aseantrirenyl, and the like. In addition, these aryl groups are halogen, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group. , May be substituted with a phosphorus-containing hydrocarbon group. Of these, phenyl, naphthyl, halogenated phenyl, and halogenated naphthyl are preferable.
[0040]
M is a metal selected from titanium, zirconium and hafnium, preferably zirconium and hafnium.
[0041]
Non-limiting examples of the transition metal compound include the following.
(1) Methylenebis {1,1 '-(2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(2) Methylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride
(3) Methylenebis [1,1 '-{2-methyl-4- (4-chloro-2-naphthyl) -4H-azulenyl}] zirconium dichloride
(4) Methylenebis {1,1 '-(2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(5) Methylenebis [1,1 '-{2-ethyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride
(6) Methylenebis [1,1 '-{2-ethyl-4- (4-chloro-2-naphthyl) -4H-azulenyl}] zirconium dichloride
(7) Ethylene bis {1,1 '-(2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(8) Ethylene bis [1,1 '-{2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride
(9) Ethylene bis [1,1 '-{2-methyl-4- (4-chloro-2-naphthyl) -4H-azulenyl}] zirconium dichloride
(10) Ethylene bis {1,1 '-(2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(11) Ethylene bis [1,1 '-{2-ethyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride
(12) Ethylene bis [1,1 '-{2-ethyl-4- (4-chloro-2-naphthyl) -4H-azulenyl}] zirconium dichloride
(13) Isopropylidenebis {1,1 '-(2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(14) Isopropylidenebis {1,1 '-(2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(15) Dimethylsilylenebis {1,1 '-(2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(16) Dimethylsilylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride
(17) Dimethylsilylenebis [1,1 '-{2-methyl-4- (4-chloro-2-naphthyl) -4H-azulenyl}] zirconium dichloride
(18) Dimethylsilylenebis {1,1 '-(2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(19) Dimethylsilylenebis [1,1 '-{2-ethyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride
(20) Dimethylsilylenebis [1,1 '-{2-ethyl-4- (4-chloro-2-naphthyl) -4H-azulenyl}] zirconium dichloride
(21) Phenylmethylsilylenebis {1,1 '-(2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(22) Phenylmethylsilylenebis [1,1 ′-{2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride
(23) Phenylmethylsilylenebis [1,1 '-{2-methyl-4- (4-chloro-2-naphthyl) -4H-azurenyl}] zirconium dichloride
(24) Phenylmethylsilylenebis {1,1 '-(2-ethyl-4-phenyl-4H-azulenyl)} zirconium dichloride
(25) Phenylmethylsilylenebis [1,1 '-{2-ethyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride
(26) Phenylmethylsilylenebis [1,1 '-{2-ethyl-4- (4-chloro-2-naphthyl) -4H-azulenyl}] zirconium dichloride
(27) Diphenylsilylenebis {1,1 '-(2-methyl-4-phenyl-4H-azulenyl)} zirconium dichloride
(28) Dimethylgermylenebis {1,1 '-(2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(29) Dimethylgermylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride
(30) Dimethylgermylenebis [1,1 '-{2-methyl-4- (4-chloro-2-naphthyl) -4H-azurenyl}] zirconium dichloride
(31) Dimethylgermylenebis {1,1 '-(2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride
(32) Dimethylgermylenebis [1,1 '-{2-ethyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride
(33) Dimethylgermylenebis [1,1 ′-{2-ethyl-4- (4-chloro-2-naphthyl) -4H-azurenyl}] zirconium dichloride and the like are exemplified.
[0042]
Among these, dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4H-azulenyl)} zirconium dichloride, dimethylsilylenebis [1,1 ′-{2-methyl-4- (4 -Chlorophenyl) -4H-azurenyl}] zirconium dichloride, dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-chloro-2-naphthyl) -4H-azurenyl}] zirconium dichloride, dimethylgermylenebis {1,1 ′-(2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride, dimethylgermylenebis [1,1 ′-{2-methyl-4- (4-chlorophenyl) -4H-azurenyl} ] Zirconium dichloride, dimethylgermylenebis {1,1 '-(2-ethyl-4-phenyl-4H-azule) Le)} zirconium dichloride are preferred.
[0043]
In addition, as a hydrogenated product,
(1) Methylenebis {1,1 '-(2-methyl-4-phenylhexahydroazulenyl)} zirconium dichloride
(2) Methylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) hexahydroazulenyl}] zirconium dichloride
(3) Methylenebis [1,1 '-{2-methyl-4- (4-chloro-2-naphthyl) hexahydroazulenyl}] zirconium dichloride
(4) Methylenebis {1,1 '-(2-ethyl-4-phenylhexahydroazulenyl)} zirconium dichloride
(5) Methylenebis [1,1 '-{2-ethyl-4- (4-chlorophenyl) hexahydroazulenyl}] zirconium dichloride
(6) Methylenebis [1,1 '-{2-ethyl-4- (4-chloro-2-naphthyl) hexahydroazulenyl}] zirconium dichloride
(7) Ethylene bis {1,1 '-(2-methyl-4-phenylhexahydroazulenyl)} zirconium dichloride
(8) Ethylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) hexahydroazulenyl}] zirconium dichloride
(9) Ethylene bis [1,1 '-{2-methyl-4- (4-chloro-2-naphthyl) hexahydroazulenyl}] zirconium dichloride
(10) Isopropylidenebis {1,1 '-(2-methyl-4-phenylhexahydroazulenyl)} zirconium dichloride
(11) Dimethylsilylenebis {1,1 '-(2-methyl-4-phenylhexahydroazulenyl)} zirconium dichloride
(12) Dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-chlorophenyl) hexahydroazulenyl}] zirconium dichloride
(13) Dimethylsilylenebis [1,1 '-{2-methyl-4- (4-chloro-2-naphthyl) hexahydroazulenyl}] zirconium dichloride
(14) Phenylmethylsilylenebis {1,1 '-(2-methyl-4-phenylhexahydroazurenyl)} zirconium dichloride
(15) Phenylmethylsilylenebis [1,1 ′-{2-methyl-4- (4-chlorophenyl) hexahydroazulenyl}] zirconium dichloride
(16) Diphenylsilylenebis {1,1 '-(2-methyl-4-phenylhexahydroazulenyl)} zirconium dichloride
(17) Dimethylgermylenebis {1,1 '-(2-methyl-4-phenylhexahydroazulenyl)} zirconium dichloride
(18) Dimethylgermylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) hexahydroazulenyl}] zirconium dichloride
(19) Dimethylgermylenebis [1,1 ′-{2-methyl-4- (4-chloro-2-naphthyl) hexahydroazulenyl}] zirconium dichloride and the like are exemplified.
[0044]
In addition, compounds in which one or both of the chlorides of these compounds are replaced with bromine, iodine, hydrogen, methylphenyl, benzyl, alkoxy, dimethylamide, diethylamide and the like can also be exemplified. Furthermore, instead of the above-mentioned zirconium, compounds in place of titanium, hafnium and the like can be exemplified.
[0045]
The co-catalyst is selected from the group consisting of an ionic compound capable of reacting with an aluminum oxy compound, a metallocene compound to convert a metallocene compound component into a cation, or a Lewis acid, a solid acid, or an ion-exchange layered silicate. At least one compound. Moreover, an organoaluminum compound can be added with these compounds as needed.
[0046]
Specifically as said aluminum oxy compound, the compound represented by following General formula (2), (3) or (4) is mentioned.
[0047]
[Formula 4]
[0048]
In each of the above general formulas, R^FourRepresents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. Also, multiple R^FourMay be the same or different. P represents an integer of 0 to 40, preferably 2 to 30.
[0049]
The compounds represented by the general formulas (2) and (3) are also called alumoxanes, and are obtained by reaction of one type of trialkylaluminum or two or more types of trialkylaluminum with water. Specifically, (a) methyl alumoxane, ethyl alumoxane, propyl alumoxane, butyl alumoxane, isobutyl alumoxane obtained from one type of trialkylaluminum and water, (b) two types of trialkylaluminum and Examples thereof include methylethylalumoxane, methylbutylalumoxane, methylisobutylalumoxane and the like obtained from water. Of these, methylalumoxane or methylisobutylalumoxane is preferred.
[0050]
The compound represented by the general formula (4) is 10: 1 to 1: 1 of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and the alkylboronic acid represented by the following general formula (5). It can be obtained by a (molar ratio) reaction. In general formula (5), R^FiveRepresents a hydrocarbon residue or halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
[0051]
R^FiveB (OH)₂              (5)
[0052]
Specifically, the following reaction products can be exemplified.
(A) 2: 1 reaction product of trimethylaluminum and methylboronic acid
(B) 2: 1 reaction product of triisobutylaluminum and methylboronic acid
(C) 1: 1: 1 reaction product of trimethylaluminum, triisobutylaluminum and methylboronic acid
(D) 2: 1 reaction product of trimethylaluminum and ethylboronic acid
(E) 2: 1 reaction product of triethylaluminum and butylboronic acid
[0053]
Among ionic compounds and Lewis acids capable of reacting with component (A) to convert component (A) to cations, certain Lewis acids react with component (A) to form component (A ) Can also be understood as an ionic compound that can be converted into a cation. Therefore, the compounds belonging to both the Lewis acid and the ionic compound belong to either one.
[0054]
Examples of the ionic compound that can react with the component (A) to convert the component (A) into a cation include a compound represented by the general formula (6).
[0055]
[K]^{e +}[Z]^e-                  (6)
[0056]
In the general formula (6), K is a cation component, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. Moreover, the cation of the metal which is easy to reduce itself, the cation of an organic metal, etc. are mentioned.
[0057]
Specific examples of the cation include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, Triphenylphosphonium, trimethylphosphonium, tris (dimethylphenyl) phosphonium, tris (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, copper ion, palladium ion , Mercury ions, ferrocenium ions and the like.
[0058]
In the above general formula (6), Z is an anion component, which is a component (generally a non-coordinating component) that becomes a counter anion with respect to the cationic species into which the component (A) has been converted. Examples of Z include an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound anion, an organic arsenic compound anion, and an organic antimony compound anion.
[0059]
Examples of the solid acid include solid acids such as alumina and silica-alumina.
[0060]
The layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with each other with a weak binding force. In the present invention, the layered silicate is preferably ion-exchangeable. Here, ion exchange means that the interlayer cation of the layered silicate can be exchanged.
[0061]
Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to natural ones, and may be artificial synthetics. Specific examples of the layered silicate are known layered silicates described in, for example, Haruo Shiramizu, “Clay Mineralogy”, Asakura Shoten (1995), and include dickite, nacrite, kaolinite, anoxite. , Kaolins such as metahalloysite, halloysite, serpentine such as chrysotile, lizardite, antigolite, montmorillonite, zauconite, beidellite, nontronite, saponite, teniolite, hectorite, stemite, vermiculite, etc. Examples include vermiculites, mica, illite, sericite, sea chlorite and other mica, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite. These may form a mixed layer.
[0062]
Among these, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, teniolite and the like, smectite group, vermiculite group and mica group are preferable.
[0063]
Typical examples of the smectite group include montmorillonite, beidellite, saponite, nontrite, hectorite, and soconite. "Ben Clay SL" (manufactured by Mizusawa Chemical Co., Ltd.), "Kunipia", "Smecton" (all manufactured by Kunimine Kogyo Co., Ltd.), "Montmorillonite K10" (manufactured by Aldrich, Jutehemy), "K-Catalysts series" (Jutehemy It is also possible to use a commercial product such as a product made by the company.
[0064]
Typical examples of the mica group include muscovite, paragonite, phlogopite, biotite, and lipidite. Commercially available products such as “synthetic mica somasif” (manufactured by Corp Chemical Co., Ltd.), “fluorine phlogopite mica”, “fluorine tetrasilicon mica”, “teniolite” (all manufactured by Topy Industries, Ltd.) and the like can also be used.
[0065]
These silicates are preferably subjected to chemical treatment. Here, as the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure and chemical composition of the layered silicate can be used. Specific examples include (i) acid treatment, (b) alkali treatment, (c) salt treatment, and (d) organic matter treatment. These treatments remove impurities on the surface, exchange cations between layers, elute cations such as Al, Fe, and Mg in the crystal structure, resulting in ion complexes, molecular complexes, organic derivatives, etc. The surface area, interlayer distance, solid acidity, etc. can be changed. These processes may be performed independently or two or more processes may be combined.
[0066]
Examples of the (a) acid used in the chemical treatment include a purposeful inorganic acid or organic acid, preferably hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, and the like. (B) Alkali includes NaOH, KOH, NH_ThreeEtc. (C) The salt was selected from the group consisting of a cation containing at least one atom selected from the group consisting of Group 2 to Group 14 atoms, and a halogen atom or an anion derived from an inorganic or organic acid. A compound consisting of at least one anion is preferred. (D) As the organic substance, alcohol (C1-C4 aliphatic alcohol, preferably methanol, ethanol, propanol, ethylene glycol, glycerin, C6-C8 aromatic alcohol, preferably phenol, for example), higher Examples thereof include hydrocarbons (having 5 to 10, preferably 5 to 8 carbon atoms, preferably hexane, heptane, etc.). In addition, formamide, hydrazine, dimethyl sulfoxide, N-methylformamide, N, N-dimethylaniline and the like are preferable compounds.
[0067]
Two or more salts and acids may be used. In the case of combining salt treatment and acid treatment, there are a method of performing acid treatment after performing salt treatment, a method of performing salt treatment after performing acid treatment, and a method of simultaneously performing salt treatment and acid treatment.
[0068]
Examples of the polymerization method include a slurry method using an inert solvent in the presence of these catalysts, a gas phase method or a solution method using substantially no solvent, or a bulk polymerization method using a polymerization monomer as a solvent.
[0069]
As a method for obtaining the propylene / α-olefin copolymer specified by the present invention, for example, by adjusting the polymerization temperature and the comonomer amount and appropriately controlling the molecular weight and the distribution of crystallinity, a desired polymer can be obtained. Can do.
[0070]
<Component (B) Polyethylene wax>
In the present invention, the polyethylene wax used as component (B) is —CH₂The polymer of-is designated, and polyethylene, a copolymer of ethylene and α-olefin, or a polymer into which a polar group is introduced by acid-modifying them is used. The number average molecular weight is generally about 500 to 15,000, preferably about 1,000 to 10,000.
[0071]
Polyethylene wax is produced by various methods. In the present invention, any wax produced by any method can be used. As a method for producing the polyethylene wax, for example, there is a method of producing by polymerization of ethylene. In this case, there are a method of polymerizing at a high temperature and a high pressure by radical polymerization and a method of polymerizing at a low pressure by a Ziegler catalyst. Also, a method for lowering the molecular weight of general molding polyethylene by pyrolysis, a method for separating and purifying low molecular weight polyethylene produced as a by-product when producing general molding polyethylene, or a method for oxidizing general molding polyethylene Etc.
[0072]
The polyethylene wax used in the present invention must satisfy the following conditions 1) and 2).
[0073]
1) Density
Density is 0.94-0.98 g / cm^Three, Preferably 0.95 to 0.98 g / cm^ThreeMore preferably, 0.96-0.98 g / cm^Three, Is used. When it is higher than this range, the dispersion diameter of the polyethylene wax is not sufficiently reduced, and the dispersed particles are reflected as unevenness on the film surface, resulting in a decrease in transparency.
[0074]
2) The melt viscosity at 140 ° C. is 10 cps or more, preferably 15 to 30000 cps. When the melt viscosity is lower than 10 cps, the effect of improving the transparency is reduced, which is not preferable.
[0075]
In the present invention, polyethylene wax, acid-modified polyethylene wax, and oxidized polyethylene wax can be used alone, or a mixture thereof or a mixture of these and polypropylene wax can be used.
[0076]
[Combination]
The blending ratio of the component (A) propylene / α-olefin copolymer and the component (B) polyethylene wax is 100 parts by weight of the total amount of the component (A) and the component (B). α-olefin copolymer 95.0 to 99.999 parts by weight, preferably 96.5 to 99.99, more preferably 98.0 to 99.9 parts by weight, and component (B) polyethylene wax is 0.001 to 0.001. 5.0 parts by weight, preferably 0.01 to 3.5 parts, more preferably 0.1 to 2.0 parts by weight.
[0077]
If the component (B) is less than 0.001 part by weight, the effect of improving the film transparency is not sufficient. On the other hand, if it exceeds 5.0 parts by weight, the dispersed diameter of the polyethylene wax is not sufficiently reduced, and the dispersed particles are uneven on the film surface. As a result, transparency is impaired.
[0078]
Since the propylene-based resin of the present invention has the above characteristics, it is excellent in transparency and anti-blocking property. Therefore, it is effective when high transparency is required and the addition of the anti-blocking agent is limited. However, in the present invention, the addition of an antiblocking agent is not excluded, and an antiblocking agent can be added depending on the purpose.
[0079]
As the antiblocking agent, an inorganic fine powder having an average particle size of 1.0 to 7.0 μm and a pore volume of 0.4 to 1.6 ml / g is preferable.
[0080]
Specific examples of the anti-blocking agent include inorganic or synthetic silica (silicon dioxide), magnesium silicate, aluminosilicate, talc, zeolite, aluminum borate, calcium carbonate, calcium sulfate, barium sulfate, calcium phosphate. Etc. are used.
[0081]
Moreover, as an organic type, polymethyl methacrylate, polymethylsilsesquioxane (silicone), polyamide, polytetrafluoroethylene, epoxy resin, polyester resin, benzoguanamine / formaldehyde (urea resin), phenol resin, and the like can be used. . When these antiblocking average particle diameters are within such a range, a polypropylene film having good transparency and scratch resistance can be obtained.
[0082]
The antiblocking agent is preferably 0.01 to 0.7 parts by weight, more preferably 0.05 to 0.5, particularly preferably 100 parts by weight of the total amount of the component (A) and the component (B). It is used at a ratio of 0.05 to 0.3 parts by weight.
[0083]
The anti-blocking agent is preferably surface-treated, and as the surface treating agent, surfactant, metal soap, acrylic acid, oxalic acid, citric acid, tartaric acid and other organic acids, higher alcohols, esters, silicones, fluorine Resins, silane coupling agents, hexametaphosphate soda, pyrophosphate soda, tripolyphosphate soda, trimetaphosphate soda, etc. can be used, especially those that have been treated with citric acid among organic acids. is there.
[0084]
The treatment method is not particularly limited, and a known method such as surface spraying or dipping can be employed. The anti-blocking agent may have any shape, and can be any shape such as a spherical shape, a square shape, a columnar shape, a needle shape, a plate shape, and an indefinite shape.
[0085]
In the present invention, it is preferable to add a lubricant, and as the lubricant, for example, a linear monocarboxylic acid monoamide compound or a linear monocarboxylic acid bisamide compound can be used alone or in combination. . Examples of the linear monocarboxylic acid monoamide compound include oleic acid amide, stearic acid amide, erucic acid amide, palmitic acid amide, behenic acid amide, and lauric acid amide.
[0086]
Examples of the linear monocarboxylic acid bisamide compound include ethylene bisoleic acid amide, ethylene bis stearic acid amide, and methylene bis stearic acid amide.
[0087]
The addition amount of the lubricant is preferably 0.01 to 1.0 part by weight, more preferably 0.02 to 0.5 part by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B). Particularly preferred is 0.04 to 0.25 parts by weight.
[0088]
In particular, an unsaturated fatty acid amide having a melting point of 70 to 90 ° C. and a saturated fatty acid amide having a melting point of 100 to 125 ° C. are preferable. The blending ratio of unsaturated fatty acid amide and saturated fatty acid amide is (unsaturated fatty acid amide / saturated fatty acid amide) on a weight basis, 1/99 to 99/1, preferably 2/98 to 98/2, more preferably A range of 10/90 to 90/10 is used. By using such a blending system, good performance is exhibited with a smaller amount of lubricant than in the case of a single system.
[0089]
Examples of unsaturated fatty acid amides having a melting point in the range of 70 ° C. to 90 ° C. include C₁₈~ C_{twenty two}The unsaturated fatty acid amide can be used. Specifically, for example, oleic acid amide, erucic acid amide, brandic acid amide, elaidic acid amide, N-stearyl erucic acid amide, lauric acid amide, N- (2-hydroxyethyl) lauric acid amide and the like are the main components. Are illustrated. Unsaturated fatty acid amides having a melting point of less than 70 ° C. are not preferred because the slipperiness at high temperatures of 45 ° C. or higher is deteriorated, and those having a melting point of more than 90 ° C. are not effective. Since it is small, it is not preferable.
[0090]
Saturated fatty acid amides having a melting point of 100 to 125 ° C. include C₁₆~ C_{twenty two}Saturated fatty acid amides and derivatives thereof can be used. Specifically, for example, stearic acid amide, palmitic acid amide, behenic acid amide, N- (2-hydroxymethyl) stearic acid amide, hexamethylene bisoleic acid amide, hexamethylene biserucic acid amide, octamethylene biserucic acid The thing which has amide etc. as a main component is illustrated. When the saturated fatty acid amide has a melting point of less than 100 ° C., the initial slip property is often good, but is not preferred because the effect of slip property at a high temperature of 45 ° C. or higher is low, and the melting point exceeds 125 ° C. However, it is not preferable because initial slipperiness itself does not appear. Saturated fatty acid amides having a melting point of 107 ° C. to 120 ° C. are more preferable from the viewpoint of roll stain resistance during film formation.
[0091]
(Additional ingredients)
Additional components include, for example, antioxidants (phenolic, phosphorous, sulfur, etc.), light stabilizers, UV absorbers, neutralizers, lubricants (silicone oil, etc.), antistatic agents, fluidity improvers. , Molecular weight modifier (peroxide), anti-adhesive agent, impact modifier, foam inhibitor, dispersant, metal deactivator, antibacterial agent, fluorescent brightener, colorant (titanium oxide, titanium yellow, Inorganic pigments such as zinc white, petal, ultramarine blue, compounding agents such as condensed azo, isoindolinone, quinacridone, perinone, perylene, quinophthalone, anthraquinone, phthalocyanine, and the like, Or resin and elastomer components other than the above can be mentioned.
[0092]
(mixture)
The above component (A) propylene / α-olefin copolymer and component (B) polyethylene wax are blended with various compounding ingredients as required. First, Henschel mixer, super mixer, V blender, tumbler mixer, ribbon mixer , Mixing or melt-kneading in a conventional mixing or kneading machine such as a Banbury mixer, kneader blender, uniaxial or biaxial extruder, etc., preferably melt-kneading at a temperature of 160 to 300 ° C., preferably 180 to 280 ° C. The material for molding can be obtained by pelletizing.
[0093]
The propylene-based resin composition of the present invention has a small temperature dependency of transparency, and can provide a film having excellent transparency even when molded at high speed.
[0094]
[Film forming]
The film can be produced using the propylene-based resin composition as a raw material resin. Specifically, a sheet or a film (unstretched film) is produced by a known technique such as a casting method or an inflation method. Can do.
[0095]
As a casting method for producing extruded products such as sheets and films (unstretched films), a resin melt-kneaded by an extruder is extruded from a T-die and brought into contact with a roll through which a coolant such as water is passed. When cooled, it is generally possible to produce a film with good transparency and good thickness accuracy. Such a method is a preferable manufacturing method for the film.
[0096]
In the film of the present invention, when it is formed and used as a single layer film, the thickness is usually 5 to 500 μm, preferably 10 to 200 μm. If the thickness is too thinner than this range, processing becomes difficult. On the other hand, if it is too thick, it is difficult to process and heat sealability is not exhibited.
[0097]
Moreover, when setting it as a stretched film, it can manufacture with a well-known stretching apparatus using the sheet | seat or film which consists of a propylene-type polymer of this invention. Examples of these stretching apparatuses include a tenter method, a simultaneous biaxial stretching method, and a uniaxial stretching method. In the case of a biaxially stretched film, the stretch ratio of the stretched film is desirably 10 to 70 times. In the case of a uniaxially stretched film, it is desirably 2 to 10 times. Moreover, it is desirable that the thickness of the stretched film is usually 5 to 200 μm.
[0098]
(Characteristics of film)
The film of the present invention has characteristics such as transparency, rigidity, and impact resistance, which are features of the propylene-based polymer, and can improve the low-temperature heat-sealability that has been a drawback. It is a film made of a propylene-based resin composition that has never existed.
[0099]
In addition, the film of the present invention can be used for a composite film with another substrate in order to sufficiently exhibit its excellent transparency, rigidity, impact resistance, heat seal and the like. The substrate can be selected from, for example, any polymer capable of film forming, cellophane, paper, fiber structure, aluminum foil, and the like.
[0100]
Examples of the polymer that can be formed into a film include polyamide resin, polyester resin, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, polyolefin resin such as ethylene / methacrylic acid copolymer, polyvinyl chloride, and polychlorinated resin. It can be selected from vinylidene, vinyl alcohol copolymer and the like according to the purpose of making the composite film in consideration of transparency, rigidity, adhesiveness, printability, gas barrier property and the like.
[0101]
When the substrate is stretchable, it may be stretched uniaxially or biaxially. The composite film can be produced by a known technique such as a coextrusion method, a dry lamination method, an extrusion lamination method, or a combination thereof. In the case of the coextrusion method, the dry lamination method, and the extrusion lamination method, the thickness of the film of the present invention in the composite film constituting layer is preferably 0.5 to 200 μm.
[0102]
The thickness of the film is not particularly limited, but is generally 0.5 to 200 μm, preferably 1 to 150 μm, and more preferably 3 to 100 μm.
[0103]
【The invention's effect】
In the present invention, since the polyethylene wax functions as a crystal nucleus, the crystallization temperature Tc determined by DSC is higher than that of a single polypropylene resin obtained using a metallocene catalyst. By increasing the crystallization temperature, it is possible to prevent a decrease in transparency due to crystal growth, and it is possible to improve roll trace transfer due to insufficient heat removal, which becomes a problem when T-die molding is performed at high speed. For this reason, the transparency of a polypropylene resin film can be remarkably improved. Polypropylene resins obtained using a metallocene catalyst have a narrow molecular weight distribution, and those having a low melting point have a problem that the nip roll marks during the T-die film molding process are easily transferred, but a small amount of polyethylene wax is added. As a result, the crystallization temperature rises, and an improvement effect on roll transfer can be obtained without impairing the low-temperature heat sealability.
[0104]
【Example】
(Physical property evaluation method)
The evaluation methods used in Examples and Comparative Examples are (1) to (11), and the physical properties of the film were measured after heat treatment (aging) in a 40 ° C. oven for 24 hours.
[0105]
(1) Melt index (MI)
Measured according to JIS K6758 (conditions: 230 ° C., load 2.16 kgf) (unit: g / 10 minutes).
[0106]
(2) Viscosity of polyethylene wax
The viscosity at 140 ° C. was measured based on JIS Z8803 (viscosity measurement with a single cylindrical rotational viscometer).
[0107]
(3) Melting peak temperature (Tm) and crystallization peak temperature (Tc) by differential scanning calorimeter (DSC)
Using a Seiko DSC, take a sample amount of 5.0 mg, hold at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a cooling rate of 10 ° C./min, and further melt at a heating rate of 10 ° C./min. The crystallization peak temperature (Tc) and the melting peak temperature (Tm) were evaluated (unit: ° C.).
[0108]
(4) Density
The measurement was performed according to JIS K6760.
[0109]
(5) Transparency (HAZE)
In accordance with ASTM-D1003, the obtained film was measured with a haze meter (unit:%). It means that transparency is excellent, so that this value is small.
[0110]
(6) Blocking property
A sample film of 2 cm (width) x 15 cm (length) is taken from the film obtained under the condition of a cooling roll temperature of 35 ° C., and the corona-treated surfaces and the untreated surfaces are overlapped for a length of 5 cm (contact area 10 cm).²), 50 g / cm²After adjusting the conditions for 1 day and 7 days in an atmosphere of 40 ° C. under a load of 40 ° C., after adjusting the temperature to 23 ° C. after removing each load and using a shopper type tensile tester, the speed is 200 mm / min. To determine the force required for shear peeling of the sample (unit: g / 10 cm)²). The smaller this value, the better the blocking resistance.
[0111]
(7) Slip (slip)
A sample obtained by conditioning a film obtained under the condition of a cooling roll temperature of 35 ° C. for 1 day in an atmosphere at a temperature of 23 ° C. and a sample prepared by conditioning the film for 7 days in an atmosphere at a temperature of 40 ° C. are in accordance with ASTM-D1894. The friction between the corona-treated surface and the untreated surface of the sample film was evaluated by the coefficient of static friction by the slip tester method. The smaller this value, the better the slipperiness.
[0112]
(8) Heat sealability (HS temperature)
Using a heat seal bar of 5 mm × 200 mm, the untreated surfaces of the film obtained under the condition of a cooling roll temperature of 35 ° C. were subjected to heat seal pressure of 2 kg / cm at each temperature setting²A sample having a width of 15 mm is taken from a sample sealed so as to be perpendicular to the melt-extrusion direction (MD) of the film under the condition of a heat sealing time of 1 second, and a tensile rate of 500 mm / min is used using a shopper type tester It pulled away in MD direction and the load was read. The heat sealability was evaluated at the sealing temperature when the load reached 300 g (unit: ° C.). It means that heat sealability is excellent, so that this value is small.
[0113]
(9) Tensile strength at break
Dumbbell specimens were collected from the film obtained under the condition of a cooling roll temperature of 35 ° C. in accordance with JIS K6781, and in accordance with JIS K6781 (tensile speed 500 mm / min, gripping interval 80 mm, marked line interval 40 mm), tensile breaking point The strength was determined.
[0114]
(10) Extrusion load
The resin pressure at the time of forming the film was measured. The higher the resin pressure, the more extrusion load is applied and the extrudability is worse.
[0115]
(11) Measurement of average surface roughness of film with atomic force microscope
A cantilever DF-40 is mounted on an SPI3700 (SPA300 unit) manufactured by Seiko Denshi Kogyo Co., Ltd., and irregularities are measured in a cyclic contact mode in a 20 μm × 20 μm range, and then the average surface roughness (Ra ) Was calculated.
[0116]
(Synthesis of metallocene catalyst)
(1) Synthesis of racemic dimethylsilylene bis [1,1 '-{2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride
[0117]
(A) Synthesis of racemic / meso mixture: A solution of 1.84 g (9.6 mmol) of 1-bromo-4-chlorobenzene in n-hexane (10 ml) and diethyl ether (10 ml) at −78 ° C. at t-butyllithium 11.7 ml (19.2 mmol) of a pentane solution (1.64 M) was added dropwise.
[0118]
The resulting solution was stirred at −5 ° C. for 1.5 hours, and then 1.2 g (8.6 mmol) of 2-methylazulene was added to the solution for 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. The reaction solution was stirred at room temperature for 1.5 hours, the reaction was stopped by adding dilute hydrochloric acid, the separated organic phase was concentrated under reduced pressure, dichloromethane was added, and the mixture was dried over magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to obtain 2.1 g of an amorphous solid.
[0119]
Next, 1.27 g of the above reaction product was dissolved in 15 ml of diethyl ether, and 2.8 ml (4.5 mmol) of an n-butyllithium solution (1.66M) in n-butyllithium was added dropwise thereto at −78 ° C. 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 cooled to −78 ° C., and 0.53 g (2.3 mmol) of zirconium tetrachloride was added thereto. . Then, it returned to room temperature immediately and stirred at room temperature for 4 hours and reacted. The resulting reaction solution was filtered on celite, and the solid separated by filtration was washed with 3 ml of toluene and collected. The recovered solid was extracted with dichloromethane, the solvent was distilled off from the extract, and dimethylsilylene bis [1,1 ′-{2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride racemic. -906 mg (56% yield) of meso mixture was obtained.
[0120]
(B) Purification of racemate
Furthermore, 900 mg of the above racemic / meso mixture was dissolved in 20 ml of dichloromethane, and the ratio of the racemic body was increased by irradiation with a 100 W high-pressure mercury lamp for 40 minutes. Thereafter, the insoluble matter was filtered off, and the collected filtrate was concentrated to dryness. did. Next, the obtained solid component was stirred together with 22 ml of toluene, and after standing, the supernatant was removed. This purification operation was repeated four times, and the remaining solid component was dried, and dimethylsilylene bis [1,1 ′-{ 2-Methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium dichloride 275 mg was obtained.
[0121]
(2) Production of chemically treated clay
In an aqueous solution in which 218.1 g of sulfuric acid (96%) and 130.4 g of magnesium sulfate were mixed with 909 ml of demineralized water, 200.03 g of commercially available montmorillonite (Kunimine Industries, Ltd., Kunipia F) was dispersed and stirred at 100 ° C. for 2 hours. This water slurry of montmorillonite was prepared to a solid content concentration of 12%, and spray granulation was performed with a spray dryer to obtain particles. Thereafter, the particles were dried under reduced pressure at 200 ° C. for 2 hours.
[0122]
(3) Adjustment of solid catalyst components
After the inside of the stirring type autoclave having an internal volume of 1 liter was sufficiently substituted with propylene, 230 ml of dehydrated and deoxygenated heptane was introduced, and the system temperature was maintained at 40 ° C. To this, 10 g of chemically treated clay slurried with toluene was added. Furthermore, 0.15 mmol of racemic dimethylsilylene bis [1,1 ′-{2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride mixed with toluene in another container and triisobutylaluminum 1.5 mmol was added.
[0123]
Here, propylene was introduced at a rate of 10 g / hr for 120 minutes, and then 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 1 g of the solid component.
[0124]
(Polymerization 1)
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, 2.25 kg of ethylene and 8.0 NL of hydrogen were added, and the internal temperature was maintained at 30 ° C.
[0125]
Next, 1.2 g of the above solid catalyst component (as a solid component excluding polypropylene) was injected with argon to initiate polymerization, and the temperature was raised to 70 ° C. over 30 minutes, and the temperature was maintained for 1 hour. Here, 100 ml of ethanol was added to stop the reaction. The remaining gas was purged to obtain 21 kg of a propylene-ethylene copolymer (A1) having MI = 7.2 g / 10 min, Tm = 12.4 ° C., Tc = 88.5 ° C., and ethylene content = 3.7 wt%. It was.
[0126]
(Polymerization 2)
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, 2.25 kg of ethylene and 2.5 NL of hydrogen were added, and the internal temperature was maintained at 30 ° C.
[0127]
Next, 1.5 g of the solid catalyst component (as a solid component excluding polypropylene) was injected with argon to initiate polymerization, and the temperature was raised to 70 ° C. over 30 minutes, and the temperature was maintained for 1 hour. Here, 100 ml of ethanol was added to stop the reaction. The residual gas was purged to obtain 18 kg of a propylene-ethylene copolymer (A2) having MI = 1.5 g / 10 minutes, Tm = 124.9 ° C., Tc = 88.9 ° C., and ethylene content = 3.7 wt%. It was.
[0128]
(Polymerization 3)
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, 2.25 kg of ethylene and 14 NL of hydrogen were added, and the internal temperature was maintained at 30 ° C.
[0129]
Next, 0.8 g of the above solid catalyst component (as a solid component excluding polypropylene) was injected with argon to initiate polymerization, and the temperature was raised to 70 ° C. over 30 minutes, and the temperature was maintained for 1 hour. Here, 100 ml of ethanol was added to stop the reaction. The residual gas was purged to obtain 23 kg of a propylene-ethylene copolymer (A3) having MI = 35 g / 10 min, Tm = 15.3 ° C., Tc = 89.4 ° C., and ethylene content = 3.6% by weight.
[0130]
(Polymerization 4)
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, 0.27 kg of ethylene and 0.5 NL of hydrogen were added, and the internal temperature was maintained at 30 ° C.
[0131]
Next, 2.7 g of the above solid catalyst component (as a solid component excluding polypropylene) was injected with argon to initiate polymerization, and the temperature was raised to 70 ° C. over 30 minutes, and the temperature was maintained for 1 hour. Here, 100 ml of ethanol was added to stop the reaction. The residual gas was purged to obtain 16 kg of a propylene-ethylene copolymer (A4) having MI = 7.0 g / 10 min, Tm = 146.0 ° C., Tc = 110.3 ° C., and ethylene content = 0.5 wt%. It was.
[0132]
[0133]
(Example 1)
100 parts by weight of propylene-based resin composition obtained by adding 0.3 parts by weight of polyethylene wax (Mitsui High Wax 400P, 140 ° C. viscosity 650 cps) to 99.7 parts by weight of propylene / ethylene copolymer (A1) is oxidized. As an inhibitor, Irganox 1010 (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane) 0.05 parts by weight, Irgafos 168 (Tris- (2, 4-di-t-butylphenyl) phosphite) and 0.05 part by weight of calcium stearate as a neutralizing agent were mixed at 750 rpm for 1 minute at room temperature with a Henschel mixer, and then mixed at a high speed. Melted, kneaded, cooled and cut at 230 ° C. with a shaft extruder (Ikegai PCM30) to obtain a pellet-shaped resin composition .
[0134]
Using this resin composition as a raw material, an extrusion resin temperature of 230 ° C., a cooling roll temperature of 25 ° C., 35 ° C., using a T-die method film manufacturing apparatus equipped with an extruder having a diameter of 35 mmφ, a width of 300 mm T die, an air knife, and a cooling roll, Three types of unstretched films having a thickness of 25 μm were obtained by molding at a film forming take-up speed of 21 m / min at three levels of 45 ° C. The results of evaluating the physical properties are shown in Table 2.
[0135]
(Example 2)
Using a propylene-based resin composition in which 1.0 part by weight of polyethylene wax (Mitsui High Wax 400P, 140 ° C. viscosity 650 cps) was added to 99.0 parts by weight of the propylene / ethylene copolymer (A1), Example 1 and A similar experiment was conducted. The results are shown in Table 2.
[0136]
Example 3
A propylene-based resin composition in which 0.3 part by weight of polyethylene wax (Mitsui High Wax 800P, 140 ° C. viscosity 8,000 cps) was added to 99.7 parts by weight of the propylene / ethylene copolymer (A1) was used as an example. The same experiment as 1 was performed. The results are shown in Table 2.
[0137]
Example 4
Example 1 Using a propylene resin composition in which 1.0 part by weight of polyethylene wax (Sanyo Sun Wax LEL800, 140 ° C. viscosity 22000 cps) was added to 99.0 parts by weight of the propylene / ethylene random copolymer (A1). The same experiment was conducted. The results are shown in Table 2.
[0138]
(Comparative Example 1)
The same experiment as in Example 1 was performed except that the polyethylene wax was not added using the propylene / ethylene random copolymer (A1). The results of evaluating the physical properties are shown in Table 3. It can be seen that the temperature dependency of the cooling roll is seen as compared with that to which polyethylene wax is added, and the transparency tends to deteriorate if the cooling is not sufficient.
[0139]
(Comparative Example 2)
The same experiment as in Example 1 was performed using a propylene-based resin composition in which 10 parts by weight of polyethylene wax (Sanyo Sun Wax LEL800) was added to 90 parts by weight of the propylene / ethylene random copolymer (A1). The results are shown in Table 3. It can be seen that the transparency tends to deteriorate if the cooling is not sufficient.
[0140]
(Comparative Example 3)
Example 1 Using a propylene-based resin composition obtained by adding 1.0 part by weight of polyethylene wax (Mitsui High Wax 400P, 140 ° C. viscosity 650 cps) to 99.0 parts by weight of propylene / ethylene random copolymer (A2), Example 1 The same experiment was conducted. The results are shown in Table 4. It can be seen that the transparency tends to deteriorate if the cooling is not sufficient.
[0141]
(Comparative Example 4)
Example 1 Using a propylene-based resin composition obtained by adding 1.0 part by weight of polyethylene wax (Mitsui High Wax 400P, 140 ° C. viscosity 650 cps) to 99.0 parts by weight of propylene / ethylene random copolymer (A3), Example 1 The same experiment was conducted. The results are shown in Table 4. It can be seen that the transparency tends to deteriorate if the cooling is not sufficient.
[0142]
(Comparative Example 5)
Example 1 Using a propylene-based resin composition in which 1.0 part by weight of polyethylene wax (Mitsui High Wax 400P, 140 ° C. viscosity 650 cps) was added to 99.0 parts by weight of the propylene / ethylene random copolymer (A4). The same experiment was conducted. The results are shown in Table 4. It can be seen that the transparency tends to deteriorate if the cooling is not sufficient.
[0143]
(Comparative Example 6)
Example 1 Using a propylene-based resin composition in which 1.0 part by weight of polyethylene wax (Mitsui High Wax 720P, 140 ° C. viscosity 6000 cps) was added to 99.0 parts by weight of the propylene / ethylene random copolymer (A1). The same experiment was conducted. The results are shown in Table 4. It can be seen that the transparency tends to deteriorate if the cooling is not sufficient.
[0144]
(Examples 5 to 10)
As an antioxidant, Irganox 1010 (tetrakis [methylene-3- (3 ′, 5′-diene) was used as an antioxidant with respect to 100 parts by weight of each of the propylene-based resin compositions shown in Example 1, Example 3, and Example 4. -T-butyl-4-hydroxyphenyl) propionate] methane) 0.05 parts by weight, Irgafos 168 (Tris- (2,4-di-t-butylphenyl) phosphite) 0.05 parts by weight, neutralized 0.05 parts by weight of calcium stearate as an agent, synthetic silica and magnesium silicate as shown in Table 4, erucic acid amide (EA) as a lubricant [A], and behenic acid amide (B) as a lubricant [B] After adding BA) at a high speed at 750 rpm for 1 minute at room temperature with a Henschel mixer, 2) using a twin screw extruder (Ikegai PCM30) Melting at 0 ° C., kneaded to cool, to obtain a pellet-like resin composition was cut.
[0145]
Using this resin composition as a raw material, an extrusion resin temperature of 230 ° C., cooling roll temperatures of 35 ° C. and 45 ° C. using an extruder with a diameter of 35 mmφ, a 300 mm T die, an air knife, and a T die method film manufacturing apparatus equipped with a cooling roll An unstretched film having a thickness of 25 μm was obtained by molding at a film forming speed of 21 m / min and applying a corona treatment of 40 dyne / cm on one side. The physical properties were evaluated by using films formed at 35 ° C. and 45 ° C. HAZE, and other physical properties at 35 ° C. The results are shown in Table 5.
[0146]
(Comparative Example 7)
In Example 6, polyethylene wax was removed (Comparative Example 1) The same experiment as in Example 6 was performed, except that a propylene-based resin composition was used. The results are shown in Table 6. It can be seen that if the polyethylene wax is added, the transparency tends to deteriorate if the cooling is not sufficient.
[0147]
(Examples 11 and 12)
Each of the single-layer films obtained by applying a 40 dyne / cm corona treatment to one side of the propylene-based resin film obtained under the conditions of the cooling roll temperature of 35 ° C. in Example 6 and Example 10 was performed in an atmosphere of 40 ° C. Aging was performed for 2 days. Next, a 40 μm biaxially stretched polypropylene film was used as the base film, and after applying a urethane two-component reactive adhesive, dry lamination was performed on the corona discharge treated surface of the single layer film to obtain a laminated film. About the obtained film, it hold | maintained for 6 days in the atmosphere of temperature 45 degreeC, and measured slip property, blocking property, and heat seal property. The results are shown in Table 7.
[0148]
(Examples 13 to 17)
Irganox 1010 (tetrakis [methylene-3- (3 ′, 5′-di-t) is used as an antioxidant with respect to 100 parts by weight of the propylene-based resin composition shown in Example 1, Example 3, and Example 4. -Butyl-4-hydroxyphenyl) propionate] methane) 0.05 parts by weight, irgaphos 168 (tris- (2,4-di-t-butylphenyl) phosphite) 0.05 parts by weight, as neutralizing agent 0.05 parts by weight of calcium stearate, as shown in Table 8, synthetic silica, magnesium silicate, erucic acid amide (EA) as lubricant [A], and behenic acid amide (BA) as lubricant [B] After mixing with a Henschel mixer at 750 rpm for 1 minute at room temperature, the mixture was melted at 230 ° C. with a twin screw extruder (Ikegai PCM30). , Kneaded to cool, to obtain a pellet-like resin composition was cut.
[0149]
This resin composition was used as a sealing layer, and a homopolypropylene (manufactured by Nippon Polychem Co., Ltd., trade name FB3GT) having a melting point of 163 ° C. and MFR (230 ° C.) = 7.0 g / 10 min was used as an intermediate layer, and a melting point of 140 ° C. MFR (230 ° C.) = 7.0 g / 10 min random polypropylene (manufactured by Nippon Polychem Co., Ltd., trade name: FW3E) was used for the surface layer, and the surface layer / intermediate layer / seal layer was 1/4 / 1, three extruders each having three layers (surface layer / intermediate layer / seal = extruder of 20 mmφ / 35 mmφ / 20 mmφ), a three-layer T die having a width of 300 mm, an air knife and Using a three-layer T-die method film manufacturing apparatus equipped with a cooling roll, after melt co-extrusion at an extrusion resin temperature of 230 ° C., a cooling roll temperature of 35 ° C., a film forming speed of 17 m / min, and a thickness of 30 μm To obtain a coextruded unstretched film. The results of evaluating the physical properties are shown in Table 8. In addition, evaluation was performed about the slip property between sealing surfaces, blocking property, and heat-sealing property.
[0150]
[Table 2]
[0151]
[Table 3]
[0152]
[Table 4]
[0153]
[Table 5]
[0154]
[Table 6]
[0155]
[Table 7]
[0156]
[Table 8]

Claims (12)

Component (A) A propylene / α-olefin copolymer polymerized by using a compound represented by the following general formula (1) or a metallocene catalyst that is a partial hydrogenated product thereof using an ion-exchange layered silicate as a co-catalyst. 95.0 to 99.999 parts by weight of polymer and 0.001 to 5.0 parts by weight of component (B) polyethylene wax (provided that the total amount of components (A) and (B) is 100 parts by weight) And a component (A) and a component (B) satisfy the following conditions, respectively.
Component (A): Propylene / α-olefin copolymer 1) Melt index MI _P (230 ° C.) is 2 to 30 g / 10 min 2) Main melting peak temperature (Tm) determined by DSC is 110 to 145 ° C.
Component (B): Polyethylene wax 1) Density of 0.94 to 0.98 g / cm ³
2) Viscosity at 140 ° C. is 10 cps or more
[Wherein Q is a bonding group that bridges two conjugated five-membered ring ligands, M is a metal atom selected from titanium, zirconium, and hafnium, and X and Y are hydrogen atoms and halogen atoms bonded to M. , A hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group, R ¹ and R ³ are each hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, A halogen, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group; R ² is hydrogen, hydrocarbon group having 1 to 20 carbon atoms, halogen, halogenated hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron Contains A hydrocarbon group or a phosphorus-containing hydrocarbon group is shown. ] The propylene-type resin composition of Claim 1 which contains 0.01-1.0 weight part of fatty acid amide as a lubricant with respect to 100 weight part of total amounts of component (A) and (B). As a lubricant, an unsaturated fatty acid amide having a melting point of 70 to 90 ° C. and / or a saturated fatty acid amide having a melting point of 100 to 125 ° C. The propylene-based resin composition according to claim 1, containing 0.0 part by weight. An anti-blocking agent having an average particle diameter of 1.0 to 7.0 μm and a pore volume of 0.4 to 1.6 ml / g is 0.01% with respect to 100 parts by weight of the total amount of components (A) and (B). The propylene-type resin composition in any one of Claims 1-3 containing -0.7 weight part. The propylene-based resin composition according to claim 4 , wherein the antiblocking agent is surface-treated with an organic substance. The propylene-based resin composition according to claim 5 , wherein the antiblocking agent is surface-treated with citric acid. A propylene-based resin film obtained by molding the propylene-based resin composition according to claim 1 using a T-die. A propylene-based resin film obtained by molding the propylene-based resin composition according to claim 2 or 3 using a T-die. Propylene resin film comprising a propylene resin composition according to any one of claims 4-6 by molding using a T-die. A laminated resin film comprising at least one layer comprising the propylene-based resin film according to claim 7 . A laminated resin film comprising at least one layer comprising the propylene-based resin film according to claim 8 . A laminated resin film comprising at least one layer comprising the propylene-based resin film according to claim 9 .