JP2015071671A - Propylene-ethylene copolymer resin composition and film or sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene-ethylene copolymer resin composition and a film or the like having excellent extrusion moldability even during extrusion molding at low temperature while maintaining excellent properties such as excellent transparency or flexibility of a soft propylene-ethylene copolymer obtained by a metallocene catalyst.SOLUTION: There is provided a propylene-ethylene copolymer resin composition containing 65 to 95 wt.% of a propylene resin composition (C) obtained by mixing a specific propylene polymer (A) of 0 to 99 wt.% and a specific propylene-ethylene copolymer (B) of 1 to 100 wt. by a method for removing a polymerization blend and 5 to 35 wt.% of a specific propylene-ethylene copolymer (D) and the propylene-ethylene copolymer (D) is a propylene-ethylene copolymer resin composition consisting of a specific propylene polymer component (D1) of 65 to 95 wt.% and a specific propylene-ethylene copolymer component (D2) of 5 to 35 wt.% or the like.

Description

  The present invention relates to a propylene-ethylene copolymer resin composition and a film or sheet, and more specifically, maintains excellent properties such as transparency and flexibility of a soft propylene-ethylene copolymer obtained by a metallocene catalyst. However, the present invention relates to a soft propylene-ethylene copolymer resin composition having excellent extrudability even when extruded at a low temperature, and a film or sheet formed by molding the same.

Olefin-based thermoplastic elastomers have moderate flexibility and strength, have excellent recyclability, low environmental impact that does not produce environmental hormones during incineration, and are lightweight and easy to mold. It is used in a wide range of fields such as films and sheets, fibers and non-woven fabrics, various containers and molded products.
In recent years, with the expansion of usage of such olefinic thermoplastic elastomers, there has been an increasing demand for materials that have flexibility and heat resistance while maintaining the transparency unique to polypropylene. Improvement proposals have been made.
For example, in order to improve flexibility and solve the deterioration of transparency, a polypropylene or propylene-ethylene copolymer having a low ethylene content in the first step and an ethylene content higher than that in the first step in the second step A technique is disclosed in which relatively few propylene-ethylene copolymer elastomers are continuously polymerized using a Ziegler-Natta catalyst (see Patent Documents 1 and 2).
However, because Ziegler-Natta catalysts have multiple types of active sites, the resulting propylene-ethylene copolymer has a wide crystallinity and molecular weight distribution, and produces a large amount of low-crystal and low-molecular weight components, resulting in Stickiness and bleed-out (exudation of low molecular weight components and additives) are strongly observed, and there are disadvantages that problems such as blocking and poor appearance tend to occur.

  In order to improve the appearance defects due to stickiness and bleedout caused by low crystalline and low molecular weight components, which are problems of olefinic thermoplastic elastomers produced using such Ziegler-Natta catalysts, metallocene catalysts are used. The crystalline propylene-ethylene copolymer component having a peak between 65 ° C. and 88 ° C. in the temperature rising elution fractionation by TREF in the first step is used, and the low temperature side peak T is reduced to 40 ° C. or lower in the second step. A propylene-ethylene copolymer obtained by polymerizing a low-crystalline or non-crystalline propylene-ethylene random copolymer component that exhibits (B) or does not exhibit a peak is disclosed, which includes molecular weight distribution and crystallinity. Since the distribution is narrow, stickiness and bleed-out are suppressed (see, for example, Patent Document 3).

Further, as a means for obtaining the aforementioned polymer and resin composition more easily, a polypropylene polymer was blended with at least 40 wt% (wt%) or more of a propylene elastomer polymerized using a metallocene catalyst. A packaging film made of a polypropylene resin composition is disclosed, which is characterized by a good balance between flexibility and extensibility, heat resistance and heat sealability (see Patent Document 4).
Furthermore, a polypropylene resin composition containing 2 to 95 wt% of a polypropylene polymer and 5 to 98 wt% of a propylene elastomer polymerized using a metallocene catalyst is disclosed, which has good compatibility. The tensile strength is improved (see Patent Document 5).
The resin composition obtained by such a technique is widely used because it has good quality such as transparency, flexibility, moderate heat resistance, improved blocking property and no deterioration in appearance over time. However, since the olefinic thermoplastic elastomer has significantly reduced the crystallinity, there is a problem that the solidification time is slow at the time of film molding, sheet molding, and injection molding. By lowering, measures to shorten the solidification time have come to be taken.

However, olefinic thermoplastic elastomers obtained with these metallocene catalysts generally have poor extrusion characteristics because they have a narrow molecular weight distribution as well as a composition distribution. In particular, the industrial problem of extrusion characteristics is that surface roughness called sharkskin and melt fracture occurs on the surface of the film discharged from the die in extrusion molding, and these become phenomena that cannot be put into practical use. It is a problem.
In order to improve the surface roughness, it is possible to increase the temperature of the die and widen the width of the die exit as the molding conditions. However, the increase in temperature increases the solidification time. There arises a problem that winding occurs in the case, neck-in when the roll is wound from the die to the roll becomes large, and variation in thickness is likely to occur. When the width of the die exit is increased, the thickness accuracy in the film width direction decreases (see Non-Patent Document 1).
Thus, many attempts have been made to improve the extrusion characteristics of propylene-ethylene copolymers using these metallocene catalysts.
First, as a proposal to broaden the molecular weight distribution with catalysts and polymerization methods,
(1) Proposal of broadening the molecular weight distribution by using a specific metallocene catalyst (see Patent Documents 6 and 7),
(2) Proposal for performing multistage polymerization in order to obtain two-component propylene-ethylene copolymers having different molecular weights (see Patent Documents 8 to 10),
(3) The proposal (refer patent documents 11-15) which introduce | transduces long-chain branching by copolymerizing a graft modification, a macromonomer, and a diene is made | formed.

Regarding the proposal (1) above, for example, according to Patent Document 6, a propylene copolymer having a Mw / Mn of 4.0 to 7.7 produced by a metallocene catalyst is disclosed, but the extrusion characteristics are improved. Manufactured using a propylene copolymer and metallocene catalyst produced using a Ziegler-Natta catalyst that does not disclose Mz / Mn, which suggests the existence of ultra-high molecular weight components that contribute to When comparing the Mz / Mn of the prepared propylene copolymers, it is well known that the propylene copolymers produced using Ziegler-Natta catalysts have significantly higher Mz / Mn and good extrusion characteristics. Therefore, it is clear that the improvement effect of the extrusion characteristics according to the above proposal is insufficient.
As for the proposal (2), it is necessary to provide a molecular weight difference between a low molecular weight component and a high molecular weight component in order to improve surface roughness while ensuring melt fluidity. However, when a metallocene catalyst is used, it is difficult to produce a high molecular weight component, so it is necessary to increase the molecular weight of the high molecular weight component. As a result, the molecular weight disparity increases, and appearance defects called gels and fish eyes are likely to occur. Therefore, it is not preferable.
Furthermore, the proposal (3) has a problem that it is difficult to control the crosslinking reaction that occurs as a side reaction and induces the formation of a gel, which tends to cause a poor appearance.

In addition, as a proposal to blend materials with excellent extrusion characteristics,
(4) Proposal for blending other resins such as polyethylene (see Patent Document 16),
(5) Proposals for blending propylene-ethylene copolymers having a wide molecular weight distribution (see Patent Documents 17 and 18) have been made.
Regarding the proposal (4), since polypropylene and polyethylene are incompatible with each other, blending until the extrusion characteristics are improved results in significantly inferior transparency, so that there is a problem that the usage is limited. .
With regard to the proposal (5), for example, according to Patent Document 17, the propylene-based random copolymer (A) obtained with a metallocene catalyst is 1 to 70% by weight, and obtained with a conventional Ziegler-Natta catalyst. A copolymer resin composition comprising 30 to 99% by weight of the propylene random copolymer (B) is disclosed. However, since the propylene-based random copolymer (B) used in the present invention has a high MFR of 9.2 g / 10 min and does not have a high molecular weight component necessary for improving the surface roughness, Surface roughness is not improved.
Patent Document 18 discloses a method for improving extrusion characteristics by blending polypropylene produced by a metallocene catalyst with polypropylene having a high melt tension produced by two-stage polymerization using a metallocene catalyst. Yes. However, since the polypropylene having a high melt tension used in the present invention does not contain a comonomer, when extrusion is performed at a relatively low temperature of about 180 ° C., the molecular chain having a long relaxation time in the flow in the die. Causes orientational crystallization and presents an aspect of solid-liquid phase separation at the die outlet, so when the draft ratio (ratio of cooling roll winding speed and resin discharge speed) increases, the liquid layer part cracks and is practical There is a problem that the shape becomes unsuitable for.

Furthermore, (6) a proposal to improve surface roughness by using a specific additive (see Patent Document 19) has been made. Regarding this proposal, it is disclosed that the generation of melt fracture can be suppressed by adding a fluoroelastomer as a processing aid. Generally, by adding fluorine elastomer, when the resin flows in the die, the surface of the die is coated with fluorine elastomer, the resin pressure near the die wall surface is reduced, and as a result, the occurrence of melt fracture is suppressed. It has been known.
However, when such a method is used, if continuous molding is performed for a long time, the fluoroelastomer coated on the die wall surface deteriorates due to heat and becomes burnt, and appears as a black spot in the film. May be a problem.

JP-A 63-159212 JP 63-168414 A JP-A-2005-132979 JP-T-2006-505658 JP-T-2001-512771 Japanese Patent Laid-Open No. 4-110308 JP 2001-288220 A JP 10-338705 A International Publication No. WO94 / 16009 JP 2001-64314 A JP 10-338704 A JP 11-292944 A JP 2001-226497 A JP 2001-253913 A JP 2001-253922 A JP 2000-136274 A Japanese Patent Laid-Open No. 5-112683 International Publication WO02 / 8304 JP 2009-155357 A

Extrusion molding 7th edition revision, Kenkichi Murakami, Plastics Age, 1989

  The object (issue) of the present invention is to provide excellent extrusion molding even at low temperature while maintaining excellent properties such as transparency and flexibility of a soft propylene-ethylene copolymer obtained by a metallocene catalyst. Another object is to provide a soft propylene-ethylene copolymer resin composition having properties and a film or sheet formed by molding the same.

  In view of the state of the prior art represented by the prior art such as the previous patent documents, the present inventors have conducted various studies, and as a result, used a specific propylene-ethylene copolymer obtained by a metallocene catalyst. And it discovered that the resin composition which mix | blended specific amount each of the specific propylene-ethylene copolymer can eliminate the said subject, and came to complete this invention.

That is, according to the first invention of the present invention, the propylene polymer (A) having the following characteristics (Ai) to (A-iv): 0 to 99% by weight, and the following characteristics (Bi) to Propylene-ethylene copolymer (B) having (B-iii) 1 to 100% by weight Propylene-based resin composition (C) obtained by mixing by a method excluding a polymerization blend (C) 65 to 95% %, And a propylene-ethylene copolymer resin composition containing 5 to 35% by weight of a propylene-ethylene copolymer (D) having the following characteristics (Di) to (D-ii),
The propylene-ethylene copolymer (D) is based on a total of 100% by weight of (D1) and (D2), and a propylene-based polymer component (D1) having the following characteristics (D1-i): Propylene-ethylene copolymer resin composition comprising 5 to 35% by weight of propylene-ethylene copolymer component (D2) having the following characteristics (D2-i) and (D2-ii): Is done.
Propylene polymer (A):
(Ai) Obtained by polymerization using a metallocene catalyst.
(A-ii) Melt flow rate [MFR (A)] is 0.1-100 g / 10min.
(A-iii) The ethylene content [E (A)] is 0 to 6.0% by weight.
(A-iv) The molecular weight distribution [Mw / Mn (A)] represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC measurement is 2-4.
Propylene-ethylene copolymer (B):
(Bi) It was obtained by polymerization using a metallocene catalyst.
(B-ii) The ethylene content [E (B)] is 4 to 17% by weight.
(B-iii) The molecular weight distribution [Mw / Mn (B)] represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC is 1 to 4.
Propylene-ethylene copolymer (D):
(Di) The ethylene content [E (D)] in the copolymer (D) is in the range of 0.4 to 13% by weight.
(D-ii) The melt flow rate [MFR (D)] of the copolymer (D) is in the range of 0.5 to 20 g / 10 min.
Propylene polymer component (D1):
(D1-i) The ethylene content [E (D1)] in the polymer component (D1) is in the range of 0 to 6.0% by weight.
Propylene-ethylene copolymer component (D2):
(D2-i) The ethylene content [E (D2)] in the copolymer component (D2) is in the range of 8 to 25% by weight.
(D2-ii) The melt flow rate [MFR (D2)] of the copolymer component (D2) is in the range of 0.0001 to 0.5 g / 10 min.

According to the second invention of the present invention, in the first invention, the propylene-ethylene copolymer (D) comprises a step of producing a propylene-based polymer component (D1) and a propylene-ethylene copolymer component (D2). A propylene-ethylene copolymer resin composition characterized in that it is produced by multi-stage polymerization having a step of producing
According to a third aspect of the present invention, in the first or second aspect, the propylene-ethylene copolymer (D) is produced by a Ziegler-Natta catalyst. A copolymer resin composition is provided.
Furthermore, according to the fourth aspect of the present invention, in any one of the first to third aspects, the propylene-based resin composition (C) is a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement. Propylene-ethylene copolymer resin composition characterized in that a peak of a temperature-loss tangent (tan δ) curve representing a glass transition observed in the range of −60 to 20 ° C. shows a single peak at 0 ° C. or less. Things are provided.

Moreover, according to 5th invention of this invention, the film formed by extrusion-molding the propylene-ethylene copolymer resin composition which concerns on any 1st-4th invention is provided.
Furthermore, according to the sixth aspect of the present invention, there is provided a laminated film formed by laminating the film according to the fifth aspect as a surface layer.

According to the seventh aspect of the present invention, there is provided a sheet formed by extruding the propylene-ethylene copolymer resin composition according to any one of the first to fourth aspects.
Moreover, according to the 8th invention of this invention, the lamination sheet formed by laminating | stacking the sheet | seat concerning 7th invention as a surface layer is provided.
Furthermore, according to the ninth invention of the present invention, the propylene-ethylene copolymer resin composition according to any one of the first to fourth inventions is laminated on the surface layer and is stretched in the biaxial direction. A stretched film is provided.

The propylene-ethylene copolymer resin composition of the present invention has improved extrusion characteristics of the propylene-ethylene copolymer obtained by the metallocene-based catalyst. Even under molding conditions that are superior in productivity and performance, such as narrowing and lowering of the extrusion temperature, molded bodies (films or sheets, laminates thereof) that are suppressed in appearance of surface roughness called melt fracture or shark skin. Body etc.).
Such a film or sheet obtained by the propylene-ethylene copolymer resin composition of the present invention maintains excellent properties such as excellent transparency and flexibility at a high level. Is suitable for use.

FIG. 1 is a perspective view showing an example of surface roughness on the film surface.

The propylene-ethylene copolymer resin composition of the present invention (hereinafter sometimes referred to as a resin composition) includes a propylene-based polymer (A) shown below and a propylene-ethylene copolymer (B described later). And a propylene-based resin composition (C) obtained by mixing by a method excluding a polymerization blend, a specific propylene-ethylene copolymer (D) to be described later is blended in a specific amount. .
Hereinafter, the components and the like will be described for each item.

I. Propylene polymer (A)
The propylene polymer (A) used in the resin composition of the present invention needs to have the following characteristics (Ai) to (A-iv).
(Ai) Obtained by polymerization using a metallocene catalyst.
(A-ii) The melt flow rate [MFR (A)] of the polymer (A) is 0.1 to 100 g / 10 min.
(A-iii) The ethylene content [E (A)] in the polymer (A) is 0 to 6.0% by weight.
(A-iv) The molecular weight distribution [Mw / Mn (A)] represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC measurement of the polymer (A) is 2 to 4. is there.

1. Characteristics (A-i)
The propylene polymer (A) according to the present invention is obtained by polymerization using a metallocene catalyst. By using a metallocene catalyst, it is possible to obtain a propylene polymer having a narrow molecular weight distribution, a narrow crystallinity distribution, and a low amount of low crystalline components.
On the other hand, when a Ziegler-Natta catalyst is used, the molecular weight distribution is wide, the crystallinity distribution is wide, and the amount of low crystalline components generated is large, so that at least one of transparency, flexibility, and blocking performance is deteriorated. It is not preferable.

2. Characteristics (A-ii)
The melt flow rate [MFR (A)] of the propylene polymer (A) according to the present invention is 0.1 to 100 g / 10 minutes, preferably 60 g / 10 minutes or less, more preferably 30 g / 10 minutes or less. More preferably, it is 25 g / 10 min or less, preferably 0.5 g / 10 min or more, more preferably 2 g / 10 min or more, and further preferably 3 g / 10 min or more. When the MFR is smaller than 0.1 g / 10 minutes, it is difficult to adjust the thickness unevenness. On the other hand, when the MFR is larger than 100 g / 10 minutes, the neck at the time of winding from the die to the roll is difficult. In is increased, and the film width is decreased, which is not preferable for practical use.
The method of adjusting the melt flow rate [MFR (MFR (A), MFR (D), etc.]] is well-known, adjusting the temperature and pressure during the polymerization, or adding a chain transfer agent such as hydrogen during the polymerization Adjustment can be easily performed by controlling the amount. Further, a method for controlling the index such as the melt flow rate of the propylene-based polymer (A) will be described in detail later.
The melt flow rate [MFR (A)] is measured at a load of 2.16 kg according to JIS K7210.

3. Characteristics (A-iii)
The ethylene content [E (A)] in the polymer (A) is 0 to 6.0% by weight, preferably 0.5 to 5.0% by weight, more preferably 1.0 to 5.0%. % By weight. When the ethylene content exceeds 6.0 wt%, the crystallinity decreases, and the anti-blocking performance deteriorates.
In addition, about the measuring method of ethylene content used in this invention, the detail is described in an Example.

4). Characteristics (A-iv)
Mw / Mn (A) of the polymer (A) is 2-4. When Mw / Mn is larger than 4, the low molecular weight component increases, which is not preferable because it adversely affects the gloss of the film surface or deteriorates the anti-blocking performance.
In addition, the specific method of GPC measurement is demonstrated in detail in an Example.

5. Method for Preparing Propylene Polymer (A) A preferred embodiment for producing the propylene polymer (A) will be described in detail below.
5-1. Metallocene catalyst The main point of the present invention is to use a propylene-based polymer (A) obtained by polymerization using a metallocene catalyst and a specific propylene-ethylene copolymer (B), and is used for the former production. The kind of metallocene catalyst is not particularly limited.
As a typical example of the metallocene catalyst that can be used in the present invention, a metallocene catalyst comprising the following components (a) and (b) and an optional component (c) can be mentioned.
Component (a): At least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1) Component (b): At least selected from the following (b-1) to (b-4) One solid component (b-1) A particulate carrier on which an organoaluminum compound is supported (b-2) An ionic compound capable of reacting with component (a) to convert component (a) into a cation Or a particulate carrier on which a Lewis acid is supported (b-3) a solid acid particulate (b-4) an ion-exchange layered silicate Component (c): an organoaluminum compound

(1) Component (a)
Component (a) is at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1).

（式中、ＡおよびＡ’は、置換基を有していてもよい共役五員環配位子、Ｑは、二つの共役五員環配位子間を任意の位置で架橋する結合性基、Ｘ及びＹは、成分（ｂ）と反応してオレフィン重合能を発現させるσ共有結合性補助配位子、Ｍは、周期表第４族の遷移金属である。）

(In the formula, A and A ′ are conjugated five-membered ring ligands that may have a substituent, and Q is a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position. , X and Y are σ covalent auxiliary ligands that react with the component (b) to develop olefin polymerization ability, and M is a transition metal of Group 4 of the periodic table.

  In the general formula (1), the conjugated five-membered ring ligand is a cyclopentadienyl group derivative that may have a substituent. When it has a substituent, examples of the substituent include a hydrocarbon group having 1 to 30 carbon atoms (which may contain a heteroatom such as halogen, silicon, oxygen, sulfur, etc.), and this hydrocarbon. The group may be bonded to the cyclopentadienyl group as a monovalent group, or when a plurality of these groups are present, two of them are bonded to each other at the other end (ω-end) to form cyclopentadienyl. A ring may be formed together with a part of Examples of such a conjugated five-membered ring ligand include an indenyl group, a fluorenyl group, or a hydroazurenyl group, and among them, an indenyl group or a hydroazurenyl group is preferable. These groups may further have a substituent.

Q is preferably a methylene group, an ethylene group, a silylene group, a germylene group, a group in which these are substituted with a hydrocarbon group, a silafluorene group, or the like.
The auxiliary ligands X and Y are those which react with a cocatalyst such as component (b) to produce an active metallocene having olefin polymerization ability, and each of them is a hydrogen atom, a halogen atom, a hydrocarbon group, or The hydrocarbon group which may have hetero atoms, such as oxygen, nitrogen, and silicon, can be illustrated. Among these, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom is preferable.
M is preferably titanium, zirconium or hafnium. In particular, zirconium and hafnium are preferable.
Further, among the above transition metal compounds, those in which stereoregular polymerization of propylene proceeds and the obtained propylene polymer has a high molecular weight are preferable. Specifically, JP-A-1-301704, JP-A-4-221694, JP-A-6-1005909, JP-T 2002-535339, JP-A-6-239914, JP-A-10-226712. Preferably, transition metal compounds described in JP-A No. 3-193396 and JP-A No. 2001-504824 are listed.

Non-limiting examples of the transition metal compound include the following.
(1) Dichloro [1,1′-dimethylsilylenebis (2-methylcyclopentadienyl)] zirconium (2) Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-phenylcyclopentadienyl) Zirconium (3) Dichloro [1,1′-dimethylsilylenebis (2,4,5-trimethylcyclopentadienyl)] zirconium (4) Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-) Phenyl-indenyl)] zirconium (5) dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-phenyl-indenyl)] zirconium (6) dichloro [1,1′-dimethylsilylene (2-methyl-4) -Phenyl-indenyl) (2-isopropyl-4-phenyl-indenyl)] zirconium (7) dichloro [1,1'- Dimethylsilylene (2-methyl-4-t-butylphenyl-indenyl) (2-isopropyl-4-t-butylphenyl-indenyl)] zirconium (8) dichloro [1,1′-dimethylsilylenebis {2- (5 -Methyl-2-furyl) -4-phenyl-indenyl}] zirconium (9) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] zirconium (10) Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] zirconium (11) dichloro [1,1′-dimethylsilylene Bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] zirconium (12) dichloro {1,1 '-Dimethylsilylenebis (2-methyl-4-phenyl-4H-azurenyl)} zirconium (13) dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl} ] Zirconium (14) dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4H-azulenyl}] zirconium (15) dichloro [1,1'-dimethylsilylenebis] {2-Ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] zirconium (16) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H -5,6,7,8-tetrahydroazurenyl}] zirconium (17) dichloro {1,1'-dimethylsilylene (2,3-dimethyl) Cyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} zirconium (18) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl- 4-phenyl-4H-azurenyl)} zirconium (19) dichloro {1,1′-dimethylsilylene (2,3,4-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} zirconium (20) dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) fluorenyl) zirconium (21) dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7- Di-t-butylfluorenyl) zirconium (22) dichlorodimethylmethylene (3-t-butyl) 5-methylcyclopentadienyl) (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzofluorene Nyl) zirconium The preferred compounds represented above are only representative exemplary compounds, avoiding many complicated examples. Although a compound whose central metal is zirconium has been described, it goes without saying that similar hafnium compounds can be used, and various conjugated five-membered ring ligands, binding groups, or auxiliary ligands are optionally used. What you can do is self-evident.

(2) Component (b)
As the component (b), at least one solid component selected from the components (b-1) to (b-4) described above is used. Each of these components is a well-known thing, and can be used selecting it suitably from well-known techniques. Specific examples and manufacturing methods thereof are described in detail in JP-A No. 2002-284808, JP-A No. 2002-53609, JP-A No. 2002-69116, and the like.
Examples of the particulate carrier used for the component (b-1) and the component (b-2) include inorganic oxides such as silica, alumina, magnesia, silica alumina, and silica magnesia, magnesium chloride, magnesium oxychloride, aluminum chloride, and chloride. Examples thereof include inorganic halides such as lanthanum, and porous organic carriers such as polypropylene, polyethylene, polystyrene, styrene divinyl benzene copolymer, and acrylic acid copolymer.
Further, as a non-limiting specific example of the component (b), as the component (b-1), a particulate carrier on which methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate tetraisobutyl and the like are supported As component (b-2), triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Silica alumina and pentafluorophenol calcined after treating a particulate carrier carrying anilinium tetrakis (pentafluorophenyl) borate or the like as component (b-3) with alumina, silica alumina, magnesium chloride or fluorine compound And diethyl sub In addition, after reacting with an organometallic compound such as silica, silica, etc., carrying the product after reacting with water, as component (b-4), montmorillonite, zakonite, beidellite, nontronite, saponite, hectorite, steven Smectites such as sites, bentonites, and teniolites, vermiculites, and micas. These may form a mixed layer.
Particularly preferred among the above components (b) is the ion-exchange layered silicate of component (b-4), and more preferred are chemical treatments such as acid treatment, alkali treatment, salt treatment, and organic matter treatment. It is an ion exchange layered silicate applied.

(3) Component (c)
Examples of the organoaluminum compound used as component (c), if necessary, are trialkylaluminum or diethyl such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trioctylaluminum represented by the following general formula Halogen or alkoxy-containing alkylaluminum such as aluminum monochloride or diethylaluminum monomethoxide.
General formula: AlR _a X _3-a
(In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a hydrogen atom, a halogen or an alkoxy group, and a represents a number of 0 <a ≦ 3.)
In addition, aluminoxanes such as methylaluminoxane can also be used.
Of these, trialkylaluminum is particularly preferable as component (c).

(4) Formation of catalyst Component (a), component (b) and, if necessary, component (c) are brought into contact to form a catalyst. Although the contact method is not specifically limited, Contact can be made in the following order. Further, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin.
(I) The component (a) is contacted with the component (b).
(Ii) After contacting the component (a) and the component (b), the component (c) is added.
(Iii) After contacting the component (a) and the component (c), the component (b) is added.
(Iv) Component (b) and component (c) are contacted, and then component (a) is added.
(V) contacting the three components simultaneously.

The amount of components (a), (b) and (c) used in the present invention is arbitrary. For example, the amount of component (a) used relative to component (b) is preferably in the range of 0.1 μmol to 500 μmol, particularly preferably 0.5 μmol to 100 μmol, relative to 1 g of component (b). The amount of component (c) used relative to component (b) is preferably in the range of 0.001 mmol to 100 mmol, particularly preferably 0.005 mmol to 50 mmol, with respect to 1 g of component (b). It is. Accordingly, the amount of component (c) to component (a) is 0.002 to ⁶ in a molar ratio, preferably 0.02 to 10 ^5, particularly preferably in the range of 0.2 to 10 ^4.

The metallocene catalyst is preferably preliminarily subjected to a prepolymerization treatment consisting of a small amount of polymerization by contacting with an olefin.
The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. It is possible to use, and it is particularly preferable to use propylene.
In the prepolymerization treatment, any method can be used for supplying the olefin, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change. . The temperature and time of the prepolymerization are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The prepolymerization amount is preferably 0.01 to 100 g / g, more preferably 0.1 to 50 g / g, based on the component (b). After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst. However, if necessary, drying can be performed.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

5-2. Propylene Polymer (A) Production Method (1) Polymerization Process Any polymerization process can be used.
First, the operation method over time will be described. From this point of view, it is possible to use either a batch method or a continuous method, but it is generally desirable to use a continuous method from the viewpoint of productivity. In any case, the number of polymerization tanks can be arbitrarily set. When using a plurality of polymerization tanks, the connection method of the tanks may be in series or in parallel. Of course, both series and parallel may be used together.
Next, regarding the reaction phase, a method using a liquid medium or a method using a gaseous medium may be used.
Specific examples include a slurry method, a bulk method, and a gas phase method. Although supercritical conditions can be used as intermediate conditions between the bulk method and the gas phase method, they are substantially the same as the gas phase method, and are therefore included in the gas phase method without particular distinction. In the case of a multi-tank continuous polymerization process, a bulk polymerization reactor may be followed by a gas phase polymerization reactor. In this case, it will be referred to as a bulk method in accordance with the practice of the industry. In the case of the batch method, the first step may be performed by a bulk method, and the second step may be performed by a vapor phase method. This case is also referred to as a bulk method. As described above, the reaction phase is not particularly limited, but the slurry method has a problem that the production cost is generally increased because of the use of an organic solvent such as hexane and heptane, because there are many attached facilities. Therefore, it is more desirable to use a bulk method or a gas phase method.
Various processes have been proposed for the bulk method and the gas phase method. Although there is a difference in the stirring (mixing) method and the heat removal method, in this aspect, in the present invention, the special process species is not limited.

(2) General polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within a commonly used temperature range. Specifically, a range of 0 ° C to 200 ° C, preferably 40 ° C to 100 ° C can be used.
Although the polymerization pressure varies depending on the process to be selected, it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 to 200 MPa, preferably 0.1 to 50 MPa can be used. At this time, there is no problem even if an inert gas such as nitrogen coexists.

(3) Organoaluminum compound Unlike a Ziegler catalyst, the metallocene catalyst does not necessarily use an organoaluminum compound as a promoter. Therefore, it is not always necessary to add an organoaluminum compound to the polymerization reactor in terms of forming an activated catalyst. However, the polymerization reaction of olefins is unique in that it has a very large number of catalyst cycles in a very short period of time compared to other catalytic reactions, and therefore has the technical problem of being easily affected by impurities. Exists.
In order to solve this problem, it is a well-known fact that various materials have been devised, such as using raw materials that are much higher in purity than ordinary chemical products, or further purifying and using raw materials. . From this point of view, a method is often used in which a highly reactive organoaluminum compound is added to the polymerization reactor and reacted with the organoaluminum compound before the impurities react with the metallocene catalyst to render them harmless.
Also in the present invention, it is desirable to use an organoaluminum compound from this viewpoint. Although any compound can be used as the organoaluminum compound, examples of suitable compounds are the same as those of component (c), which is an optional component of the metallocene catalyst, and triisobutylaluminum and trioctylaluminum are particularly preferable.
The amount of the organoaluminum compound used can be arbitrarily set according to the level of impurities. Generally, it adds so that it may become in the range of 0.001-1000 mmol-Al / kg as the number-of-moles of aluminum atom with respect to the weight of the propylene-type polymer (A) to manufacture. Preferably, it is added in a range of 0.01 to 100 mmol-Al / kg, more preferably 0.1 to 20 mmol / kg.

6). Next, a method for controlling the index of the propylene polymer (A) will be described in detail.
First, MFR will be described. As described above, the MFR of the propylene-based polymer (A) is 0.1 to 100 g / 10 minutes, preferably 60 g / 10 minutes or less, more preferably 30 g / 10 minutes or less, and still more preferably 25 g / It is 10 minutes or less, preferably 0.5 g / 10 minutes or more, more preferably 2 g / 10 minutes or more, and further preferably 3 g / 10 minutes or more.
The MFR of the propylene polymer (A) can be adjusted by using hydrogen as a chain transfer agent. Specifically, when the concentration of hydrogen which is a chain transfer agent is increased, the MFR of the propylene-based polymer (A) is increased. The reverse is also true. In order to increase the concentration of hydrogen in the polymerization tank, it is sufficient to increase the amount of hydrogen supplied to the polymerization tank, and adjustment is very easy for those skilled in the art.

Next, the ethylene content, as described above, the ethylene content of the propylene polymer (A) is 0 to 6.0 wt%, preferably 0.5 to 5.0 wt%, more preferably. Is 1.0 to 5.0 wt%.
As a means for controlling the ethylene content, it is convenient to use a method for controlling the amount of ethylene supplied to the polymerization tank.
Specifically, if the ratio of ethylene to propylene supplied to the polymerization tank is increased (ethylene supply amount ÷ propylene supply amount), the ethylene content of the resulting propylene polymer (A) is increased. The reverse is also true. The relationship between the amount ratio of propylene and ethylene supplied to the polymerization tank and the ethylene content of the resulting propylene polymer (A) varies depending on the type of metallocene catalyst used, but by adjusting the supply amount ratio as appropriate. It is extremely easy for those skilled in the art to obtain a propylene polymer (A) having the desired ethylene content.

Finally, Mw / Mn, which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in GPC measurement, will be described. As described above, Mw / Mn is 2-4.
By using a metallocene catalyst, the Mw / Mn can be made smaller than when using a Ziegler-Natta catalyst, but when controlling the Mw / Mn, select an appropriate metallocene catalyst for the target value. At the same time, it is also effective to devise polymerization conditions.
For example, if a two-tank continuous polymerization process is adopted and a propylene-ethylene copolymer having a different molecular weight is produced in the first-stage polymerization tank and the second-stage polymerization tank, the value originally given by the metallocene catalyst used is Mw / Mn can be increased. At this time, the relationship between the polymerization conditions to be used, particularly the hydrogen concentration and the molecular weight of the resulting propylene-ethylene copolymer is known in advance, and the Mw / Mn is set to a desired value by appropriately adjusting the hydrogen concentration in each tank. It is easy for those skilled in the art to adjust the value.

II. Propylene-ethylene copolymer (B)
The propylene-ethylene copolymer (B) used in the resin composition of the present invention needs to have the following characteristics (Bi) to (B-iii).
(Bi) It was obtained by polymerization using a metallocene catalyst.
(B-ii) The ethylene content [E (B)] in the copolymer (B) is 4 to 17% by weight.
(B-iii) The molecular weight distribution [Mw / Mn (B)] represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC measurement of the copolymer (B) is 1-4. It is.

1. Characteristics (Bi)
The copolymer (B) according to the present invention is obtained by polymerization using a metallocene catalyst. By using a metallocene-based catalyst, it is possible to obtain a propylene-ethylene copolymer (B) having a narrow molecular weight distribution, a narrow crystallinity distribution, and a small amount of low crystallinity components. When the Ziegler-Natta catalyst is used, the molecular weight distribution is wide and the amount of low crystalline components produced is increased, so that not only the blocking performance is remarkably deteriorated, but also the crystalline distribution is widened, so that the propylene polymer (A ) And the flexibility deteriorates, which is not preferable.

2. Characteristics (B-ii)
The ethylene content [E (B)] in the copolymer (B) is 4 to 17 wt%, preferably 5 to 16 wt%, more preferably 6 to 15 wt%, and still more preferably 7 to 14 wt%. . When E (B) exceeds 17 wt%, the compatibility of the polymer (A) and the copolymer (B) is reduced, and the copolymer (B) is not compatible with the polymer (A), Since it exhibits a separation structure and the transparency is drastically lowered, it is not preferable. When E (B) is less than 4 wt%, it is not preferable because sufficient flexibility cannot be exhibited.
In addition, about the measuring method of ethylene content used in this invention, the detail is described in an Example.

3. Characteristics (B-iii)
Mw / Mn (B) of the copolymer (B) is 1 to 4. When Mw / Mn is larger than 4, the low molecular weight component increases, which is not preferable because it adversely affects the gloss of the film surface or deteriorates the anti-blocking performance.
In addition, the specific method of GPC measurement is demonstrated in detail in an Example.

The polymerization process used for obtaining the copolymer (B) is not particularly limited, and a known polymerization process can be used. For example, a slurry polymerization method, a bulk polymerization method, a solution polymerization method and the like can be used.
In addition, as a copolymer (B), if the said characteristic (Bi)-(B-iii) are satisfy | filled, it can select and use suitably from what is marketed as a propylene-type elastomer. it can.
Examples of commercially available products include Dow Chemical Co., Ltd., trade name “VERSIFY”, ExxonMobil Corporation, trade name “VistaMAXX”, and the like.

III. Propylene resin composition (C)
The propylene-based resin composition (C) (hereinafter also referred to as resin composition (C)) used in the resin composition of the present invention comprises a polymer (A) of 0 to 99 wt% and a copolymer (B). Kneading 1 to 100 wt% using a mixing apparatus such as a ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single-screw, twin-screw or multi-screw extruder, and a kneader, regardless of the polymerization blend method. Need to be manufactured.
The proportion of the copolymer (B) in the resin composition (C) is 1 to 100 wt%, preferably 10 to 90 wt%, more preferably 20 to 80 wt%, and still more preferably 30 to 70 wt%. . If the copolymer (B) is not contained, the effect of improving the flexibility cannot be obtained, so that the copolymer (B) needs to be contained in the resin composition (C).

Furthermore, additives such as an antioxidant that can be added to the propylene-based resin can be appropriately added to the resin composition (C) as long as the effects of the present invention are not hindered.
Specifically, 2,6-di-t-butyl-p-cresol (BHT), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (“IRGANOX 1010 ", trade name manufactured by BASF Japan) or n-octadecyl-3- (4'-hydroxy-3,5'-di-t-butylphenyl) propionate (" IRGANOX 1076 ", trade name manufactured by BASF Japan) Phenol stabilizers typified by representative phenolic stabilizers, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl) phosphite Agents, lubricants represented by higher fatty acid amides and higher fatty acid esters, glycerin esters and sols of fatty acids having 8 to 22 carbon atoms You may add antistatic agents, such as a bittanic acid ester and polyethyleneglycol ester, antiblocking agents represented by silica, calcium carbonate, talc, etc.

  Furthermore, the resin composition (C) needs to show a single peak at −60 to 20 ° C. in the temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement, which is defined as the glass transition point. is there. When the resin composition (C) has a phase separation structure, the glass transition temperature of the amorphous part contained in the polymer (A) and the glass transition temperature of the amorphous part contained in the copolymer (B) are Since each is observed, multiple peaks are observed. When the resin composition (C) has a phase separation structure, the transparency of the molded product is significantly deteriorated. In order for the molded product to exhibit good transparency, the resin composition (C) needs to have a compatible structure. The peak of the tan δ curve is -60 to 20 ° C. This is confirmed by the observation of a single peak.

As described above, whether or not the resin composition (C) exhibits a phase separation structure depends on the compatibility of the polymer (A) and the copolymer (B). In the present invention, the polymer (A) The difference [Egap = E (B) −E (A) ≧ 0 wt%] between the ethylene content [E (A)] and the ethylene content [E (B)] of the copolymer (B) is determined depending on whether it is large or small. . When Egap is large, for example, when the value of E (A) is low and the value of E (B) is high, the compatibility between the polymer (A) and the copolymer (B) becomes small, and the phase separation structure Indicates. On the contrary, when Egap is small, for example, when the value of E (A) is high and the value of E (B) is low, the compatibility between the polymer (A) and the copolymer (B) is improved, The compatible structure is shown.
Therefore, in order to obtain a single peak, a resin composition (C) having a certain value of E (A) and E (B) is manufactured, and the solid viscoelasticity is measured. If it does not become one peak, for example, if E (A) is further increased and the difference (Egap) between E (A) and E (B) is reduced, adjustment is made so that a single peak is obtained. can do. About what value Egap is adjusted to, it can be easily determined by adjusting while measuring solid viscoelasticity, but Egap is usually in the range of 0 to 17 wt%. Preferably, it is desirable to set it in the range of 1 to 16 wt%.
In addition, about the measuring method of the solid viscoelasticity used in this invention, the detail is described in an Example.

IV. Propylene-ethylene copolymer (D)
The propylene-ethylene copolymer (D) used in the present invention needs to have characteristics (Di) to (D-ii).
(Di) The ethylene content [E (D)] in the copolymer (D) is in the range of 0.4 to 13% by weight.
(D-ii) The melt flow rate [MFR (D)] of the copolymer (D) is in the range of 0.5 to 20 g / 10 min.

1. Characteristics (Di)
The ethylene content [E (D)] in the propylene-ethylene copolymer (D) is in the range of 0.4 to 13 wt%, preferably in the range of 0.5 to 12 wt%. When the ethylene content [E (D)] in the copolymer (D) is within this range, a sufficient surface roughness improving effect can be obtained. Further, when the amount is less than 0.4 wt%, oriented crystal may be induced. On the other hand, when the amount exceeds 13 wt%, the effect of improving the surface roughness may not be obtained.

2. Characteristics (D-ii)
The melt flow rate [MFR (D)] of the propylene-ethylene copolymer (D) is 0.5 to 20 g / 10 minutes, and preferably 1.0 to 15 g / 10 minutes. When it is smaller than 0.5 g / 10 min, the dispersibility in the propylene-based resin composition (C) is inferior, and a nonuniformity pattern is generated on the film, resulting in an unusable appearance. On the other hand, when it is larger than 20 g / 10 minutes, the difference in melt flow characteristics between the propylene-based polymer component (D1) and the propylene-ethylene copolymer component (D2) becomes remarkable, and the propylene-ethylene copolymer component (D2 ) Is not preferable because fish eyes and gels are generated due to poor dispersion, resulting in a film that cannot be practically used.

3. Composition (configuration) of propylene-ethylene copolymer (D)
Furthermore, the propylene-ethylene copolymer (D) (hereinafter also referred to as copolymer (D)) is a propylene-based polymer component (D1) (hereinafter also referred to as component (D1)) and propylene-. Component (D1) having the following characteristics (D1-i): 65 to 95 wt%, based on the total of 100% by weight of ethylene copolymer component (D2) (hereinafter also referred to as component (D2)), and the following characteristics: Component (D2) having (D2-i) to (D2-ii): It is necessary to be a propylene-ethylene copolymer comprising 5 to 35 wt%.
(D1-i) The ethylene content [E (D1)] in the component (D1) is in the range of 0 to 6.0% by weight.
(D2-i) The ethylene content [E (D2)] in the component (D2) is in the range of 8 to 25% by weight.
(D2-ii) The melt flow rate [MFR (D2)] of the component (D2) is in the range of 0.0001 to 0.5 g / 10 min.

Here, E (D2) is expressed by the following formula using the weight ratio (% by weight) of component (D1) and component (D2) in E (D), E (D1), and copolymer (D). The defined value.
E (D2) = {E (D) −E (D1) × (W (D1) ÷ 100)} ÷ (W (D2) ÷ 100)
[W (D1) and W (D2) are weight ratios (% by weight) of the component (D1) and the component (D2) in the polymer (D), and W (D1) + W (D2) = 100 Satisfy the relationship. ]
In addition, about the measuring method of ethylene content used in this invention, the detail is described in an Example.

Similarly, MFR (D2) is obtained by adding the logarithm of viscosity using the weight ratio (% by weight) of components (D1) and (D2) in MFR (D), MFR (D1), and copolymer (D). As a rule, the value is defined by the following well-known formula.
MFR (D2) = exp {(log [MFR (D)] − (W (D1) ÷ 100) × log [MFR (D1)]) ÷ (W (D2) ÷ 100)}
[Here, MFR (D1) is the MFR of the propylene polymer component (D1), and W (D1) and W (D2) are defined above. )
The melt flow rate MFR (D) and MFR (D1) are measured at 230 ° C. and a load of 2.16 kg in accordance with JIS K7210.

A component (D1) is a component which has crystallinity, and ethylene content [E (D1)] is 0-6.0 wt%, Preferably it is 0.5-5.0 wt%. When the ethylene content [E (D1)] exceeds 6.0 wt%, the polymer properties are extremely deteriorated, which not only induces blockage in the polymerization equipment but also deteriorates the stickiness of the film. Increases low crystalline content.
Moreover, a component (D2) is a component which suppresses the slip phenomenon in the die wall surface produced in the flow field in a die, and needs to have a very high molecular weight component. Therefore, the component (D2) needs to have an MFR (D2) in the range of 0.0001 to 0.5 g / 10 minutes, and preferably the upper limit is 0.2 g / 10 minutes or less. On the other hand, if the molecular weight is too high, the dispersibility deteriorates and causes the generation of fish eyes and gels.

Furthermore, the component (D2) has crystallinity so that when the extrusion molding is performed at a relatively low temperature of about 180 ° C., orientational crystallization of molecular chains having a long relaxation time does not occur in the flow in the die. Since the crystallinity is controlled by the ethylene content, the ethylene content [E (D2)] needs to be 8 wt% or more, and preferably 10 wt% or more.
On the other hand, if the ethylene content [E (D2)] is too high, the compatibility between the resin composition (C) and the propylene molecular chain of the component (D1) and the molecular chain of the component (D2) is significantly reduced, and shear Since stress propagation in the flow field does not occur and the surface roughness suppressing effect is not exhibited, the ethylene content [E (D2)] needs to be 25 wt% or less, and preferably 20 wt% or less.

  The proportion of the component (D2) in the propylene-ethylene copolymer (D) is that the component (D2) has a remarkably high molecular weight. Therefore, if the proportion of the component (D2) is too large, It is necessary to increase the disparity and cause fish eyes and gels. Therefore, it is necessary to be 35 wt% or less, and preferably 30 wt% or less. On the other hand, if the amount of the component (D2) is too small, it is necessary to contain the component (D) excessively in the composition, which may lead to deterioration of dispersibility and a decrease in transparency of the film. It is necessary to be, and preferably 10 wt% or more.

4). Method for Preparing Propylene-Ethylene Copolymer (D) The propylene-ethylene copolymer (D) according to the present invention has the above-mentioned properties (Di) to (D-ii), and Propylene-based polymer component (D1) having a characteristic (D1-i) 65 to 95 wt%, and propylene-ethylene copolymer component (D2) having a characteristic (D2-i) to (D2-ii) 5 to 35 wt% The production method is not particularly limited as long as it is a propylene-ethylene copolymer characterized by comprising:
Hereinafter, preferred embodiments for producing the propylene-ethylene copolymer (D) according to the present invention will be described with specific examples.

4-1. Catalyst Any catalyst can be used as the catalyst for producing the propylene-ethylene copolymer (D), but the propylene-ethylene copolymer component having the characteristics (D2-i) to (D2-ii) ( From the viewpoint of producing D2) as a constituent component, it is preferable to use a Ziegler-Natta catalyst.
In the case of using a Ziegler-Natta catalyst, a specific method for producing the catalyst is not particularly limited, but as an example, a catalyst disclosed in JP 2007-254671 A can be exemplified.
Specifically, as a typical example of a Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (D) according to the present invention, the following components, titanium, magnesium and halogen are contained as essential components. The catalyst which consists of a solid component (a1), an organoaluminum compound (a2), and an electron donor (a3) can be mentioned.

(1) Solid component (a1)
The solid component (a1), which is a constituent component of the Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (D) according to the present invention, must contain titanium (a1a), magnesium (a1b) and halogen (a1c). As an optional component, an electron donor (a1d) can be used.
Here, “containing as an essential component” indicates that, in addition to the above components, any component may be included in any form as long as the effects of the present invention are not impaired.
This will be described in detail below.

(1-1) Titanium (a1a)
Any titanium compound can be used as the titanium source. Representative examples include compounds disclosed in JP-A-3-234707. With respect to the valence of titanium, a titanium compound having any valence of tetravalent, trivalent, divalent, and zero can be used, preferably tetravalent and trivalent titanium compounds, more preferably tetravalent. It is desirable to use the titanium compound.
Specific examples of tetravalent titanium compounds include titanium halide compounds typified by titanium tetrachloride, alkoxy titanium compounds typified by tetrabutoxy titanium, tetrabutoxy titanium dimer (BuO) ₃ Ti—O—Ti ( Examples thereof include condensation compounds of alkoxy titanium having a Ti—O—Ti bond typified by OBu) ₃ and organometallic titanium compounds typified by dicyclopentadienyl titanium dichloride. Of these, titanium tetrachloride and tetrabutoxy titanium are particularly preferred.
The above titanium compounds can be used not only alone but also in combination with a plurality of compounds. Further, a mixture of the above titanium compounds or a compound whose average composition formula is a mixed formula thereof (for example, a compound such as Ti (OBu) _m Cl _4-m ; 0 <m <4), or a phthalate ester Complexes with other compounds such as Ph (COOBu) ₂ .TiCl ₄ and the like can be used.

(1-2) Magnesium (a1b)
Any magnesium compound can be used as the magnesium source. Representative examples include compounds disclosed in JP-A-3-234707.
In general, magnesium halide compounds represented by magnesium chloride, alkoxymagnesium compounds represented by diethoxymagnesium, metal magnesium, oxymagnesium compounds represented by magnesium oxide, and magnesium hydroxide Hydroxymagnesium compounds, Grignard compounds typified by butylmagnesium chloride, organometallic magnesium compounds typified by butylethylmagnesium, magnesium salts of inorganic and organic acids typified by magnesium carbonate and magnesium stearate, In addition, a compound in which a mixture thereof or an average composition formula thereof is a mixed formula thereof (for example, a compound such as Mg (OEt) _m Cl _2-m ; 0 <m <2) can be used. Of these, magnesium chloride, diethoxymagnesium, metallic magnesium and butylmagnesium chloride are particularly preferred.

(1-3) Halogen (a1c)
As the halogen, fluorine, chlorine, bromine, iodine, and a mixture thereof can be used. Of these, chlorine is particularly preferred.
The halogen is generally supplied from the above titanium compounds and / or magnesium compounds, but can also be supplied from other compounds.
Typical examples include silicon halide compounds typified by silicon tetrachloride, aluminum halide compounds typified by aluminum chloride, halogenated organic compounds typified by 1,2-dichloroethane and benzyl chloride, Halogenated borane compounds represented by trichloroborane, phosphorus halide compounds represented by phosphorus pentachloride, tungsten halide compounds represented by tungsten hexachloride, molybdenum halide compounds represented by molybdenum pentachloride , Etc.
These compounds can be used not only alone but also in combination. Of these, silicon tetrachloride is particularly preferred.

(1-4) Electron donor (a1d)
The solid component (a1) may contain an electron donor (a1d) as an optional component. Representative examples of the electron donor (a1d) include compounds disclosed in JP-A No. 2004-124090.
In general, organic acids and inorganic acids and derivatives thereof (esters, acid anhydrides, acid halides, amides) compounds, ether compounds, ketone compounds, aldehyde compounds, alcohol compounds, amine compounds, etc. It is desirable to use

Examples of organic acid compounds that can be used as the electron donor (a1d) include aromatic polyvalent carboxylic acid compounds represented by phthalic acid, aromatic carboxylic acid compounds represented by benzoic acid, and 2-n-butyl. -Malonic acid having one or two substituents at the 2-position, such as malonic acid, or 2- or 2-substituents such as 2-n-butyl-succinic acid, or 2- and 3-positions, respectively. Aliphatic polycarboxylic acid compounds represented by succinic acid having one or more substituents, aliphatic carboxylic acid compounds represented by propionic acid, aromatics represented by benzenesulfonic acid and methanesulfonic acid, and Examples thereof include aliphatic sulfonic acid compounds. These carboxylic acid compounds and sulfonic acid compounds may have an arbitrary number of unsaturated bonds at arbitrary positions in the molecule like maleic acid, regardless of whether they are aromatic or aliphatic.
Examples of the organic acid derivative compound that can be used as an electron donor include the above-mentioned organic acid esters, acid anhydrides, acid halides, amides, and the like.

Aliphatic and aromatic alcohols can be used as the alcohol that is a constituent of the ester. Among these alcohols, alcohols composed of aliphatic free radicals having 1 to 20 carbon atoms such as ethyl group, butyl group, isobutyl group, heptyl group, octyl group and dodecyl group are preferable. More preferably, an alcohol composed of an aliphatic radical having 2 to 12 carbon atoms is desirable. In addition, an alcohol having an alicyclic free group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group can also be used.
Fluorine, chlorine, bromine, iodine, or the like can be used as the halogen that is a constituent element of the acid halide. Of these, chlorine is most preferred. In the case of polyhalides of polyvalent organic acids, the plurality of halogens may be the same or different.
Examples of inorganic acid compounds that can be used as electron donors include carbonic acid, phosphoric acid, silicic acid, sulfuric acid, and nitric acid. As derivatives of these inorganic acids, it is desirable to use esters. Specific examples include tetraethoxysilane (ethyl silicate), tetrabutoxysilane (butyl silicate), and the like.

Examples of ether compounds that can be used as electron donors include aliphatic ether compounds typified by dibutyl ether, aromatic ether compounds typified by diphenyl ether, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane Aliphatic polyhydric ether compounds represented by 1,3-dimethoxypropane having one or two substituents at the 2-position, such as 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, Examples thereof include polyvalent ether compounds having an aromatic free radical represented by 9-bis (methoxymethyl) fluorene in the molecule.
Examples of alcohol compounds that can be used as an electron donor include aliphatic alcohol compounds typified by butanol and 2-ethylhexanol, phenol derivative compounds typified by phenol and cresol, glycerin and 1,1′-bi- Examples thereof include aliphatic or aromatic polyhydric alcohol compounds represented by 2-naphthol.

  These electron donors can be used not only alone but also in combination with a plurality of compounds. Among these, preferred are dibutyl phthalate, dibutyl phthalate, diisobutyl phthalate, phthalic acid ester compounds typified by diheptyl phthalate, phthalic acid halide compounds typified by phthaloyl dichloride, 2-n- Malonic acid ester compounds having one or two substituents at the 2-position such as butyl-diethyl malonate, one or two substituents at the 2-position such as 2-n-butyl-diethyl succinate, or 2 Succinic acid ester compounds having one or more substituents at each of the 3-position and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane or 2-isopropyl-2-isopentyl-1,3-dimethoxypropane Aliphatic polyhydric ether compounds represented by 1,3-dimethoxypropane having one or two substituents at the 2-position , Polyvalent ether compounds having 9,9-bis radical of aromatic typified by (methoxymethyl) fluorene in the molecule, and the like.

(1-5) Amount ratio of each component constituting the solid component (a1) The amount ratio of each component constituting the solid component (a1) is arbitrary as long as the performance of the catalyst is not impaired. In general, the following range is preferred.
The amount of the titanium compound used is a molar ratio (number of moles of titanium compound / number of moles of magnesium compound) with respect to the amount of magnesium compound used, and is preferably in the range of 0.0001 to 1,000. In particular, the range of 0.01 to 10 is desirable. In the case of using a halogen source compound in addition to the magnesium compound and the titanium compound, the amount of the magnesium compound used depends on whether the magnesium compound and the titanium compound each contain a halogen or not. It is preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100, in terms of molar ratio (number of moles of compound serving as halogen source / number of moles of magnesium compound) to the amount used. The inside is desirable.
When the solid component (a1) is prepared, the amount used when an electron donor is used as an optional component is the molar ratio with respect to the amount of magnesium compound used (number of moles of electron donor / number of moles of magnesium compound). ), Preferably in the range of 0.001 to 10, particularly preferably in the range of 0.01 to 5.

The solid component (a1) is obtained by contacting each component constituting the above in the above quantitative ratio. Although it is necessary for the contact condition of each component not to make oxygen exist, arbitrary conditions can be used in the range which does not impair the effect of this invention. In general, the following conditions are preferred.
The contact temperature is about −50 to 200 ° C., preferably 0 to 100 ° C. Examples of the contact method include a mechanical method using a rotating ball mill and a vibration mill, and a method of contacting by stirring in the presence of an inert diluent.

(2) Organoaluminum compound (a2)
Examples of the organoaluminum compound (a2) that is a constituent of a Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (D) according to the present invention include compounds disclosed in JP-A No. 2004-124090. Can be used.
In general, it is desirable to use a compound represented by the following general formula.
R ⁹ _c AlX _d (OR ¹⁰ ) _e
(In the formula, R ⁹ represents a hydrocarbon group. X represents a halogen atom or a hydrogen atom. R ¹⁰ represents a hydrocarbon group or a bridging group of Al. C ≧ 1, 0 ≦ d ≦ 2, 0 ≦ e ≦ 2, c + d + e = 3)

In the above general formula, R ⁹ is a hydrocarbon group, preferably having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms.
Specific examples of R ⁹ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. Of these, a methyl group, an ethyl group, and an isobutyl group are most preferable.
In the above general formula, X is a halogen atom or a hydrogen atom. Examples of halogen that can be used as X include fluorine, chlorine, bromine, iodine, and the like. Of these, chlorine is particularly preferred.
In the above general formula, R ¹⁰ is a hydrocarbon group or a bridging group by Al. When R ¹⁰ is a hydrocarbon group, R ¹⁰ can be selected from the same group as exemplified for the hydrocarbon group of R ⁹ . Further, as the organoaluminum compound (a2), alumoxane compounds typified by methylalumoxane can be used, in which case R ¹⁰ represents a cross-linking group of Al.

Examples of compounds that can be used as the organoaluminum compound (a2) include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum chloride, diethylaluminum ethoxide, methylalumoxane, and the like. Can be mentioned. Of these, triethylaluminum and triisobutylaluminum are preferable.
As the organoaluminum compound (a2), not only a single compound but also a plurality of compounds can be used in combination.

(3) Electron donor (a3)
As an electron donor (a3) which is a constituent of a Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (D) according to the present invention, it has an organosilicon compound having an alkoxy group or at least two ether bonds Compounds can be exemplified.

(3-1) Organosilicon compound having an alkoxy group The organosilicon compound having an alkoxy group, which is a constituent component of a Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (D) according to the present invention, The compounds disclosed in Japanese Unexamined Patent Publication No. 2004-124090 can be used.
In general, it is desirable to use a compound represented by the following general formula.
R ³ R ⁴ _a Si (OR ⁵ ) _b
(In the formula, R ³ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. R ⁴ represents any free radical selected from the group consisting of a hydrogen atom, a halogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. R ⁵ represents a hydrocarbon group, 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, a + b = 3.)

In the above general formula, R ³ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group.
The hydrocarbon group that can be used as R ³ is generally one having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ³ include a linear aliphatic hydrocarbon group typified by an n-propyl group, a branched chain typified by an i-propyl group and a t-butyl group. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group typified by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group as R ³ , and in particular, i-propyl group, i-butyl group, t-butyl group, texyl group (Me ₂ CHCMe). _2- ), cyclopentyl group, cyclohexyl group, etc. are desirable.
When R ³ is a heteroatom-containing hydrocarbon group, the heteroatom is preferably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon, and particularly preferably nitrogen or oxygen. The skeleton structure of the hetero atom-containing hydrocarbon group R ^3, it is desirable to select from the example of the case where R ³ is a hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.

In the above general formula, R ⁴ represents a hydrogen atom, a halogen, a hydrocarbon group or a heteroatom-containing hydrocarbon group.
Examples of halogen that can be used as R ⁴ include fluorine, chlorine, bromine, iodine, and the like.
When R ⁴ is a hydrocarbon group, it generally has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ⁴ include a linear aliphatic hydrocarbon group represented by a methyl group and an ethyl group, a branch represented by an i-propyl group and a t-butyl group. And an aliphatic hydrocarbon group typified by a cycloaliphatic hydrocarbon group, a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. Among these, it is desirable to use methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, and the like.
In addition, when R ⁴ is a heteroatom-containing hydrocarbon group, it is desirable to select from the examples when R ³ is a heteroatom-containing hydrocarbon group. In particular, N, N-diethylamino group, quinolino group, isoquinolino group and the like are preferable.
When the value of a is 2, two R ⁴ may be the same or different. Regardless of the value of a, R ⁴ and R ³ may be the same or different.

In the above general formula, R ⁵ represents a hydrocarbon group. The hydrocarbon group that can be used as R ⁵ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specific examples of the hydrocarbon group that can be used as R ⁵ include a linear aliphatic hydrocarbon group represented by a methyl group or an ethyl group, a branch represented by an i-propyl group or a t-butyl group. And an aliphatic hydrocarbon group. Of these, a methyl group and an ethyl group are most preferable. When the value of b is 2 or more, a plurality of R ⁵ may be the same or different.

Preferred examples of the organosilicon compound having an alkoxy group include t-Bu (Me) Si (OMe) ₂ , t-Bu (Me) Si (OEt) ₂ , t-Bu (Et) Si (OMe) ₂ , t _{-Bu (n-Pr) Si (} OMe) 2, c-Hex (Me) Si (OMe) 2, c-Hex (Et) Si (OMe) 2, c-Pen 2 Si (OMe) 2, i-Pr ₂ Si (OMe) ₂ , i-Bu ₂ Si (OMe) ₂ , i-Pr (i-Bu) Si (OMe) ₂ , n-Pr (Me) Si (OMe) ₂ , t-BuSi (OEt) _{3 , (Et 2 N) 2 Si} (OMe) 2, Et 2 N-Si (OEt) 3,

And so on.
These organosilicon compounds can be used not only alone but also in combination with a plurality of compounds.

(3-2) Compound having at least two ether bonds As a compound having at least two ether bonds, which is a component of a Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (B) according to the present invention, The compounds disclosed in JP-A-3-294302 and JP-A-8-333413 can be used. In general, it is desirable to use a compound represented by the following general formula.
_{^{R 8 O-C (R 7}} ) 2 -C (R 6) 2 -C (R 7) 2 -OR 8
(Wherein R ⁶ and R ⁷ represent any free radical selected from the group consisting of a hydrogen atom, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon. Represents a group.)

In the above general formula, R ⁶ represents any free radical selected from the group consisting of a hydrogen atom, a hydrocarbon group, and a heteroatom-containing hydrocarbon group.
The hydrocarbon group that can be used as R ⁶ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
Specific examples of the hydrocarbon group that can be used as R ⁶ include a linear aliphatic hydrocarbon group typified by an n-propyl group, a branched chain typified by an i-propyl group and a t-butyl group. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group typified by a cyclopentyl group and a cyclohexyl group, and an aromatic hydrocarbon group typified by a phenyl group. More preferably, it is desirable to use a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group as R ⁶ , and in particular, i-propyl group, i-butyl group, i-pentyl group, cyclopentyl group, cyclohexyl group, Etc. are desirable.
Two R ⁶ may combine to form one or more rings. In this case, a cyclopolyene structure containing 2 or 3 unsaturated bonds in the ring structure can be taken. Further, it may be condensed with other cyclic structures. Regardless of whether monocyclic, polycyclic, or condensed, one or more hydrocarbon groups may be present as substituents on the ring. Substituents on the ring are generally those having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples include linear aliphatic hydrocarbon groups typified by n-propyl groups, branched aliphatic hydrocarbon groups typified by i-propyl groups and t-butyl groups, cyclopentyl groups, and cyclohexyl groups. And alicyclic hydrocarbon groups, and aromatic hydrocarbon groups typified by phenyl groups.

In the above general formula, R ⁷ represents any free radical selected from the group consisting of a hydrogen atom, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. Specifically, R ⁷ can be selected from the examples of R ⁶ . Preferably it is a hydrogen atom.
In the above general formula, R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. Specifically, R ⁸ can be selected from the examples when R ⁶ is a hydrocarbon group. Preferably, it is a C1-C6 hydrocarbon group, and more preferably an alkyl group. Most preferred is a methyl group.
When R ^{6 to} R ⁸ are hetero atom-containing hydrocarbon groups, the hetero atom is preferably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon.
Regardless of whether R ^{6 to} R ⁸ are hydrocarbon groups or heteroatom-containing hydrocarbon groups, they may optionally contain halogen. When R ^{6 to} R ⁸ contain a hetero atom and / or halogen, the skeleton structure is preferably selected from the examples in the case of a hydrocarbon group. Further, the eight substituents of R ^{6 to} R ⁸ may be the same as or different from each other.

Preferred examples of the compound having at least two ether bonds include 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, and 2,2-diisobutyl-1,3- Diethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2, 2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2- Methyl-2-phenyl-1,3-dimethoxypropane, 9,9-bis (meth Cymethyl) fluorene, 9,9-bis (methoxymethyl) -1,8-dichlorofluorene, 9,9-bis (methoxymethyl) -2,7-dicyclopentylfluorene, 9,9-bis (methoxymethyl) -1 , 2,3,4-tetrahydrofluorene, 1,1-bis (1′-butoxyethyl) cyclopentadiene, 1,1-bis (α-methoxybenzyl) indene, 1,1-bis (phenoxymethyl) -3, Examples thereof include 6-dicyclohexylindene, 1,1-bis (methoxymethyl) benzonaphthene, 7,7-bis (methoxymethyl) -2,5-nobornadinene, and the like.
Among them, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl Particularly preferred are -1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, and 9,9-bis (methoxymethyl) fluorene.
These compounds having at least two ether bonds can be used alone or in combination with a plurality of compounds. Moreover, it may be the same as or different from the polyvalent ether compound used as the electron donor (a1d) which is an optional component in the solid component (a1).

(4) Amount of catalyst component used The amount of each component used in the catalyst exemplified above is not particularly limited, but is generally preferably within the following range.
The amount of the organoaluminum compound (a2) used is a molar ratio (the number of moles of the organoaluminum compound (a2) / the number of moles of titanium atoms) to the titanium component constituting the solid component (a1), preferably 1 to 1,000. And particularly preferably within the range of 10 to 500.
The amount used when the organosilicon compound (a3a) is used as the electron donor (a3) is the molar ratio to the titanium component constituting the solid component (a1) (number of moles of organosilicon compound (a3a) / titanium atom). The number of moles) is preferably within the range of 0.01 to 10,000, and particularly preferably within the range of 0.5 to 500.
Further, when the compound (a3b) having at least two ether bonds is used as the electron donor (a3), the amount used is a molar ratio with respect to the titanium component constituting the solid component (a1) (compound having at least two ether bonds). The number of moles of titanium atoms / number of moles of titanium atoms) is preferably within the range of 0.01 to 10,000, and particularly preferably within the range of 0.5 to 500.

(5) Prepolymerization The catalyst exemplified above may be prepolymerized before being used in the main polymerization. Prior to the polymerization process, by generating a small amount of polymer around the catalyst in advance, the catalyst becomes more uniform and the generation amount of fine powder can be suppressed.
As the monomer in the prepolymerization, compounds disclosed in JP-A No. 2004-124090 can be used. Specific examples of the compound include olefins represented by ethylene, propylene, 1-butene, 3-methylbutene-1, 4-methylpentene-1, and the like, styrene, α-methylstyrene, allylbenzene, and chlorostyrene. Styrene-like compounds typified by, etc., and 1,3-butadiene, isoprene, 1,3-pentadiene, 1,5-hexadiene, 2,6-octadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1 , 9-decadiene, divinylbenzenes, and the like, and the like. Of these, ethylene, propylene, 3-methylbutene-1, 4-methylpentene-1, styrene, divinylbenzenes, and the like are particularly preferable.

The reaction conditions for the catalyst exemplified above and the above monomer are not particularly limited, but generally are preferably within the following ranges.
The amount of prepolymerization is in the range of 0.001 to 100 g, preferably 0.1 to 50 g, more preferably 0.5 to 10 g, based on the solid component (a1) per gram.
The reaction temperature at the time of prepolymerization is −150 to 150 ° C., preferably 0 to 100 ° C. And it is desirable to make the reaction temperature at the time of preliminary polymerization lower than the polymerization temperature at the time of main polymerization. In general, the reaction is preferably carried out with stirring, and an inert solvent such as hexane or heptane can also be present.
The prepolymerization may be performed a plurality of times, and the monomers used at this time may be the same or different. In addition, after preliminary polymerization, washing can be performed with an inert solvent such as hexane or heptane.

4-2. Production method of propylene-ethylene copolymer (D) Next, the production method of the propylene-ethylene copolymer (D) according to the present invention will be described in detail.
The propylene-ethylene copolymer (D) in the present invention has a propylene-based polymer component (D1) having a characteristic (D1-i) of 65 to 95 wt% and characteristics (D2-i) to (D2-ii). Propylene-ethylene copolymer component (D2) comprising 5 to 35 wt%, and in the production of propylene-ethylene copolymer (D), a propylene-based polymer component It is necessary to produce two polymer components, (D1) and a propylene-ethylene copolymer component (D2).
Both polymer components can be produced separately and then blended, but the propylene-ethylene copolymer component (D2) having a relatively high molecular weight and low viscosity and MFR can be produced by propylene. From the viewpoint of neatly dispersing in the system polymer component (D1) and expressing the original performance of the propylene-ethylene copolymer (D), both components may be referred to as multistage polymerization (hereinafter referred to as “sequential polymerization”). )) Is preferable.

(1) Sequential polymerization Specifically, it is desirable to polymerize the propylene-ethylene copolymer component (D2) in the second step after polymerizing the propylene-based polymer component (D1) in the first step.
Although it is possible to reverse the production order, the propylene-ethylene copolymer component (D2) has an ethylene content [E (D2)] of 8 to 8 from the definition of (D2-i). Since it is a polymer having a low crystallinity in the range of 25 wt%, when it is produced in the first step, there is a high possibility of causing a production trouble such as adhering inside the polymerization tank or blocking the transfer pipe, Not very good.
When performing sequential polymerization, either a batch method or a continuous method can be used, but it is generally desirable to use a continuous method from the viewpoint of productivity.
In the case of the batch method, the propylene-based polymer component (D1) and the propylene-ethylene copolymer component (D2) are individually polymerized using a single polymerization reactor by changing the polymerization conditions with time. It is possible. As long as the effects of the present invention are not impaired, a plurality of polymerization reactors may be connected in parallel.
In the case of a continuous process, since it is necessary to individually polymerize the propylene polymer component (D1) and the propylene-ethylene copolymer component (D2), a production facility in which two or more polymerization reactors are connected in series. Must be used. The polymerization reactor corresponding to the first step for producing the propylene-based polymer component (D1) and the polymerization reactor corresponding to the second step for producing the propylene-ethylene copolymer component (D2) are in a series relationship. Although it is necessary, a plurality of polymerization reactors may be connected in series and / or in parallel for each of the first step and the second step.

(2) Polymerization process Any polymerization process can be used.
The reaction phase may be a method using a liquid medium or a method using a gas medium.
Specific examples include a slurry method, a bulk method, and a gas phase method. Although it is possible to use supercritical conditions as intermediate conditions between the bulk method and the gas phase method, they are substantially the same as the gas phase method and are therefore included in the gas phase method without any particular distinction.
In the case of a multi-tank continuous polymerization process, a bulk polymerization reactor may be followed by a gas phase polymerization reactor. In this case, it will be referred to as a bulk method in accordance with the practice in the art. In the case of a batch method, the first step may be performed by a bulk method, and the second step may be performed by a vapor phase method. This case is also referred to as a bulk method.
As described above, the reaction phase is not particularly limited, but the slurry method has a problem that the production cost is generally increased because of the use of an organic solvent such as hexane and heptane, because there are many auxiliary equipments. Therefore, it is more desirable to use a bulk method or a gas phase method.
Various processes have been proposed for the bulk method and the gas phase method. Although there are differences in the stirring (mixing) method and the heat removal method, in this respect, the present invention does not limit the special process species.

(3) General polymerization conditions The polymerization temperature can be used without any particular problem as long as it is usually in the temperature range used. Specifically, a range of 0 ° C to 200 ° C, preferably 40 ° C to 100 ° C can be used.
In addition, the polymerization pressure varies depending on the process to be selected, but it can be used without any problem as long as it is usually in the pressure range used. Specifically, a range of greater than 0 to 200 MPa, preferably 0.1 to 50 MPa can be used. At this time, there is no problem even if an inert gas such as nitrogen coexists.
Moreover, in the 2nd process which manufactures a propylene-ethylene copolymer component (D2), polymerization inhibitors, such as ethanol and oxygen, can also be added. When such a polymerization inhibitor is used, not only the polymerization amount in the second step can be easily controlled, but also the properties of the polymer particles can be improved.

5. Next, a method for controlling the index of the propylene-ethylene copolymer (D) will be described in detail.
(1) Index control method of propylene-based polymer component (D1) First, the ethylene content, as described above, the ethylene content of the propylene-based polymer component (D1) is 0 to 6.0 wt%, More preferably, it is 0.5-5.0 wt%.
As a means for controlling the ethylene content, it is convenient to use a method for controlling the amount of ethylene supplied to the polymerization tank. Specifically, if the ratio of ethylene to propylene supplied to the polymerization tank is increased (ethylene supply amount ÷ propylene supply amount), the ethylene content of the resulting propylene polymer component (D1) increases. The reverse is also true.
The relationship between the amount ratio of propylene and ethylene supplied to the polymerization tank and the ethylene content of the resulting propylene polymer component (D1) varies depending on the type of Ziegler-Natta catalyst used, but the supply amount ratio is adjusted appropriately. Thus, it is very easy for those skilled in the art to obtain the propylene polymer component (D1) having the desired ethylene content.

Next, MFR will be described.
The MFR (D1) of the propylene-based polymer component (D1) is not particularly limited, but as described below, propylene-ethylene copolymer (D) as a means for controlling the MFR (D) is propylene. The MFR (D1) of the system polymer component (D1) may be controlled. The MFR (D1) of the propylene-based polymer component (D1) can be adjusted by using hydrogen as a chain transfer agent.
Specifically, when the concentration of hydrogen as a chain transfer agent is increased, the MFR (D1) of the propylene-based polymer component (D1) is increased. The reverse is also true. In order to increase the concentration of hydrogen in the polymerization tank, it is sufficient to increase the amount of hydrogen supplied to the polymerization tank, and adjustment is very easy for those skilled in the art.

(2) Index control method of propylene-ethylene copolymer component (D2) The propylene-ethylene copolymer component (D2), which is a constituent component of the propylene-ethylene copolymer (D), contains ethylene in the copolymer. The amount [E (D2)] is in the range of 8 to 25 wt%, and the MFR (D2) of the copolymer is in the range of 0.0001 to 0.5 g / 10 min. Although it is necessary to control ethylene content and MFR, both can be controlled like the propylene polymer (D1).

(3) Index control method for propylene-ethylene copolymer (D) The propylene-ethylene copolymer (D) has a content of ethylene in the copolymer [E (D)] in the range of 0.4 to 13 wt%. The MFR (D) of the copolymer is in the range of 0.5 to 20 g / 10 min, and the propylene-based polymer component (D1) is 65 to 95 wt% and the propylene-ethylene copolymer component (D2). 5 to 35 wt%.
Therefore, items to be considered in controlling the index of the propylene-ethylene copolymer (D) are the ethylene content E (D), MFR (D), the propylene-based polymer component (D1) and the propylene-ethylene copolymer. The weight ratio of the polymer component (D2) is three.

First, the control method of the weight ratio of the propylene-based polymer component (D1) and the propylene-ethylene copolymer component (D2) will be described.
The weight ratio of the propylene-based polymer component (D1) and the propylene-ethylene copolymer component (D2) is the same as the production amount in the first step for producing the propylene-based polymer component (D1) and the propylene-ethylene copolymer (D2). ) Is controlled by the manufacturing amount in the second step of manufacturing. For example, in order to increase the amount of the propylene polymer component (D1) and reduce the amount of the propylene-ethylene copolymer (D2), the production amount of the second step while maintaining the production amount of the first step. This can be achieved by shortening the residence time of the second step or lowering the polymerization temperature. In addition, it can be controlled by adding a polymerization inhibitor such as ethanol or oxygen or increasing the amount of addition when it is originally added. The reverse is also true.
Usually, the weight ratio of the propylene-based polymer component (D1) and the propylene-ethylene copolymer component (D2) is determined according to the production amount in the first step for producing the propylene-based polymer component (D1) and the propylene-ethylene copolymer. (D2) is defined by the production amount in the second step of producing. The formula is shown below.
Weight of component (D1): Weight of component (D2) = W (D1): W (D2)
W (D1) = Production amount of the first step / (Production amount of the first step + Production amount of the second step) × 100
W (D2) = Production amount of the second step / (Production amount of the first step + Production amount of the second step) × 100
W (D1) + W (D2) = 100
(W (D1) and W (D2) are weight ratios (weight) of the propylene-based polymer component (D1) and the propylene-ethylene copolymer component (D2) in the propylene-ethylene copolymer (D), respectively. %).)

In an industrial production facility, the production amount is usually obtained from the heat balance and material balance of each polymerization tank. If the crystallinity of the propylene polymer component (D1) and the propylene-ethylene copolymer component (D2) are sufficiently different, they are separated using an analytical method such as TREF (temperature rising elution fractionation method). The quantity ratio may be obtained by identification.
A technique for evaluating the crystallinity distribution of polypropylene by TREF measurement is well known to those skilled in the art, and detailed measurement methods are shown in the above-mentioned patent documents.

Next, a method for controlling the ethylene content [E (D)] will be described.
Since the propylene-ethylene copolymer (D) is a mixture of the propylene-based polymer component (D1) and the propylene-ethylene copolymer component (D2), the following relational expression exists between the respective ethylene contents. To establish.
E (D) = E (D1) × W (D1) + E (D2) × W (D2)
This formula shows the material balance regarding ethylene content.
As described above, since the ethylene content [E (D2)] of the propylene-ethylene copolymer component (D2) is defined by the following formula, the above formula is a modification of the formula used for the definition. Only.
E (D2) = {E (D) −E (D1) × (W (D1) ÷ 100)} ÷ (W (D2) ÷ 100)

Therefore, if the weight ratio of the propylene-based polymer component (D1) and the propylene-ethylene copolymer component (D2) is determined, that is, if W (D1) and W (D2) are determined, E (D) becomes E It is uniquely determined by (D1) and E (D2). That is, E (D) is controlled by controlling the weight ratio of propylene-based polymer component (D1) and propylene-ethylene copolymer component (D2), and three factors E (D1) and E (D2). can do.
For example, in order to increase E (D), E (D1) may be increased or E (D2) may be increased. If it is noted that E (D2) is higher than E (D1), it can be easily understood that W (D1) may be reduced and W (D2) may be increased. The reverse control method is the same.
In addition, it is E (D) and E (D1) that the measurement value can be actually obtained directly, and E (D2) is calculated using the measurement value of both. Therefore, if an operation to increase E (D2), that is, an operation to increase the amount of ethylene supplied to the second step is selected as a means when performing an operation to increase E (D), the measured value directly Although it is E (D) and not E (D2) that can be confirmed, it is obvious that the reason why E (D) increases is that E (D2) increases.

Finally, a method for controlling MFR (D) will be described.
Similar to the ethylene content [E (D)], the following relational expression holds for MFR (D).
log [MFR (D)] = (W (D1) ÷ 100) × log [MFR (D1)] + (W (D2) ÷ 100) × log [MFR (D2)]
(Where log is the logarithm with e as the base)

This formula is an empirical formula called the logarithm addition rule of viscosity, and is used routinely in the industry. As described above, since the MFR (D2) of the propylene-ethylene copolymer component (D2) is defined by the following equation, the above equation is merely a modification of the equation used for the definition.
MFR (D2) = exp {(log [MFR (D)] − (W (D1) ÷ 100) × log [MFR (D1)]) ÷ (W (D2) ÷ 100)}

In any case, the weight ratio of the propylene-based polymer component (D1) and the propylene-ethylene copolymer component (D2), MFR (D), MFR (D1), and MFR (D2) are not independent. Therefore, in order to control MFR (D), the weight ratio of propylene-ethylene copolymer component (D2), MFR (D1), and MFR (D2) may be controlled.
For example, in order to increase MFR (D), MFR (D1) may be increased or MFR (D2) may be increased. Moreover, since MFR (D2) is below MFR (D), it can be seen that MFR (D2) is below MFR (D1), but when MFR (D2) is lower than MFR (D1), It can be easily understood that MFR (D) can be increased even if W (D1) is increased and W (D2) is decreased. The reverse control method is the same.
It is to be noted that MFR (D) and MFR (D1) can actually obtain the measured values directly, and MFR (D2) is calculated using the measured values of both. Therefore, if an operation for increasing the MFR (D2), that is, an operation for increasing the amount of hydrogen supplied to the second step is selected as a means when performing an operation for increasing the MFR (D), the measurement value is directly selected. What can be confirmed is MFR (D) and not MFR (D2), but it is obvious that the reason why MFR (D) increases is that MFR (D2) increases.

V. Propylene-ethylene copolymer resin composition The propylene-ethylene copolymer resin composition of the present invention is a resin composition (C) 65 based on a total of 100 wt% of the resin composition (C) and the copolymer (D). -95 wt% and a copolymer (D) 5-35 wt% are contained. When the amount of the resin composition (C) exceeds 95 wt%, the amount of the component (D2) contained in the propylene-ethylene copolymer resin composition is insufficient. As a result, the reforming effect is inferior and surface roughness occurs, and as a result, a molded article having an excellent appearance cannot be obtained. On the other hand, when the amount of the resin composition (C) is less than 65 wt%, the component (D2) contained in the propylene-ethylene copolymer resin composition is excessively contained, and the dispersibility with other components is poor. As a result, the resulting streak-like pattern is scattered, resulting in a molded article having a poor appearance.
From the above viewpoint, it is necessary that the resin composition (C) is 65 to 95 wt% and the copolymer (D) is 5 to 35 wt%, and the resin composition (C) is 70 to 95 wt% and the copolymer (D 5-30 wt% is more preferable.
The propylene-ethylene copolymer resin composition of the present invention is a composition comprising the resin composition (C) and the polymer (D) as essential components described above, but various kinds of materials can be used as long as the object of the present invention is not impaired. These components can be added and used.

1. Various other components other than essential components (1) Additives Additives such as antioxidants that can be added to the propylene-based resin in the propylene-ethylene copolymer resin composition of the present invention as long as the effects of the present invention are not hindered. Can be added as appropriate.
Specifically, 2,6-di-t-butyl-p-cresol (BHT), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (“IRGANOX 1010 ", trade name manufactured by BASF Japan) or n-octadecyl-3- (4'-hydroxy-3,5'-di-t-butylphenyl) propionate (" IRGANOX 1076 ", trade name manufactured by BASF Japan) Phenol stabilizers typified by representative phenolic stabilizers, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl) phosphite Agents, lubricants represented by higher fatty acid amides and higher fatty acid esters, glycerin esters and sols of fatty acids having 8 to 22 carbon atoms You may add antistatic agents, such as a bittanic acid ester and polyethyleneglycol ester, antiblocking agents represented by silica, calcium carbonate, talc, etc.

(2) Other polymers The propylene-ethylene copolymer resin composition of the present invention is provided with a modifier such as an elastomer or an alicyclic hydrocarbon resin that can be added to the propylene-based resin as long as the effects of the present invention are not hindered. It can be added as appropriate.
Specifically, ethylene-α-olefin copolymer, for example, polyethylene resin represented by low density polyethylene, high density polyethylene, etc., binary random copolymer of propylene and α-olefin having 4 to 12 carbon atoms. Examples thereof include a coalescent resin, a ternary random copolymer resin of propylene, ethylene, and an α-olefin having 4 to 12 carbon atoms. Here, as the α-olefin, butene is preferable. In addition, alicyclic hydrocarbon resins represented by petroleum resins, terpene resins, rosin resins, coumarone indene resins, and hydrogenated derivatives thereof may be added.
Furthermore, a styrene-based elastomer can be added, and the styrene-based elastomer can be appropriately selected from commercially available ones. For example, Kraton polymer can be used as a hydrogenated product of a styrene-butadiene block copolymer. “Clayton G” from Japan Co., Ltd., “Tough Tech” from Asahi Kasei Chemicals Co., Ltd., and “Septon” from Kuraray Co., Ltd. as a hydrogenated product of styrene-isoprene block copolymer. As a hydrogenated product of styrene-vinylated polyisoprene block copolymer, Kuraray Co., Ltd. has a trade name of “Hibler”, and as a hydrogenated product of styrene-butadiene random copolymer, “Dynalon” from JSR Corporation. The product is sold under the product name of It may be.

2. Propylene-ethylene copolymer resin composition production method The propylene-ethylene copolymer resin composition of the present invention comprises the above resin composition (C), copolymer (D), and other additives as required. In addition, the elastomer can be obtained by mixing with an Henschel mixer, v blender, ribbon blender, tumbler blender or the like and then kneading with a kneader such as a single screw extruder, multi-screw extruder, kneader, or Banbury mixer.

VI. Film or sheet The propylene-ethylene copolymer resin composition of the present invention has improved extrusion characteristics of the propylene-ethylene copolymer resin composition obtained by a metallocene catalyst, and the amount of extrusion during extrusion molding Molded product with excellent appearance that suppresses the occurrence of surface roughness called melt fracture or shark skin even under molding conditions that are superior in productivity and performance such as increase, narrow die exit width, and decrease in extrusion temperature. Can be obtained.
Since the film or sheet obtained by such a composition maintains the excellent properties of the propylene-ethylene copolymer resin composition by the metallocene catalyst such as transparency and flexibility at a high level, the film or sheet It is suitable for use as a sheet (hereinafter also referred to as “film”).

The film processing apparatus used for manufacturing the film is not particularly limited, and examples thereof include a known T-die film processing apparatus and a known extrusion laminating apparatus, and a T-die film processing apparatus is preferable.
As preferable film forming conditions in the manufacture of the T-die film, conditions of a resin temperature of 160 to 260 ° C and a cooling roll temperature of 20 to 80 ° C can be applied.
The obtained T-die film may be a single layer film or a multilayer film including at least one layer composed of the propylene-ethylene copolymer resin composition.
In particular, a laminated film or laminated sheet obtained by laminating the film or sheet of the present invention as a surface layer can be mentioned as a preferred application taking advantage of the above characteristics.
Although the use which uses this film is not specifically limited, For example, it can use for food packaging uses, such as bread and vegetables, clothing packaging uses, such as a shirt, and industrial parts packaging use.
In addition, the film is made of cellophane, paper, woven fabric, paperboard, aluminum foil, nylon 6, nylon 66, or other polyamide resin, polyethylene terephthalate, polybutylene terephthalate, or the like by a known technique such as a lamination method such as a dry lamination method or a sand lamination method. It can also be used as a film laminated on a base material such as polyester resin or stretched polypropylene.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
The evaluation methods and resins used in the examples and comparative examples are as follows.

1. Propylene polymer (A)
(1) Measuring method of physical properties of propylene polymer (A) (1-1) Ethylene content [E (A)]
The ethylene content [E (A)] is a value determined by analyzing a ¹³ C-NMR spectrum according to the following conditions by a proton complete decoupling method.
Model: JSX Corporation GSX-400 or equivalent device (carbon nuclear resonance frequency 100 MHz or more)
Solvent: o-dichlorobenzene + heavy benzene (4: 1 (volume ratio))
Concentration: 100 mg / mL
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration count: 5,000 times or more The attribution of the spectrum may be performed with reference to, for example, Macromolecules 17, 1950 (1984). The attribution of spectra measured under the above conditions is as shown in Table 1 below. Table 1 Symbols such as S _{alpha alpha} of, in accordance with conventions of Carman et al. (Macromolecules 10,536 (1977)), P represents methyl carbon, S is methylene carbon, T is a methine carbon, respectively.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. . As described in Macromolecules 15, 1150 (1982) and the like, the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (T _ββ ) (1)
[PPE] = k × I (T _βδ ) (2)
[EPE] = k × I (T _δδ ) (3)
[PEP] = k × I (S _ββ ) (4)
[PEE] = k × I (S _βδ ) (5)
[EEE] = k × {I (S _δδ ) / 2 + I (S _γδ ) / 4} (6)
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads. Therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1
... (7)
It is. Further, k is a constant, I indicates the spectral intensity, and for example, I (T _ββ ) means the intensity of the peak at 28.7 ppm attributed to T _ββ . By using the relational expressions (1) to (7) above, the fraction of each triad is obtained, and the ethylene content is obtained from the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
The propylene random copolymer of the present invention contains a small amount of propylene heterogeneous bonds (2,1-bonds and / or 1,3-bonds), thereby producing the minute peaks in Table 2.

In order to obtain an accurate ethylene content, it is necessary to consider these peaks derived from heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from heterogeneous bonds. Therefore, the ethylene content [E (A)] of the propylene polymer (A) is the same as the analysis of the copolymer produced with a Ziegler-Natta catalyst that does not substantially contain a heterogeneous bond. The relational expressions of the above formulas (1) to (7) are used.
The conversion of the ethylene content from mol% to wt% is performed using the following formula.
Ethylene content (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100)} × 100
Here, X is the ethylene content in mol%.

(1-2) MFR (A)
According to JIS K7210 A method condition M, it measured on condition of the following.
Test temperature: 230 ° C
Nominal load: 2.16kg
Die shape: 2.095mm diameter, 8.00mm length

(1-3) GPC measurement and number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn)
It is a value obtained by measurement by a gel permeation chromatography (GPC) method. Specifically, it is obtained as follows.
Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
Standard polystyrenes used are F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000, all of which are manufactured by Tosoh Corporation. A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) to 5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. The following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78
The measurement conditions for GPC are as follows.
Apparatus: Waters GPC (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO Measurement wavelength: 3.42 μm
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve at 140 ° C. for about 1 hour.

(2) Production of propylene polymer (A) [Production Example A-1]
(I) Preparation of prepolymerization catalyst (i-1) Chemical treatment of silicate Into a glass separable flask equipped with a 10-liter stirring blade, 3.75 liters of distilled water, followed by concentrated sulfuric acid (96%) 5 kg was added slowly. At 50 ° C., 1 kg of montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 25 μm, particle size distribution = 10-60 μm) was dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing solution (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.

(I-2) Drying of silicate The silicate chemically treated previously was dried by a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical, inner diameter 50 mm, heating zone 550 mm (electric furnace)
Rotating speed with lifting blade: 2rpm
Tilt angle: 20/520
Silicate supply rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying temperature: 200 ° C. (powder temperature)

(I-3) Preparation of catalyst 20 g of dry silicate was introduced into a glass reactor with an internal volume of 1 liter, and 116 ml of mixed heptane and 84 ml of a heptane solution of triethylaluminum (0.60 M) were added. Stir at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare a silicate slurry to 200 ml.
Next, 0.96 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the silicate slurry prepared above and reacted at 25 ° C. for 1 hour. In parallel, 218 mg (0.3 mM) of [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium] in 87 ml of mixed heptane Then, 3.31 ml of a heptane solution of triisobutylaluminum (0.71 M) was added and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, mixed heptane was added to prepare 500 ml. did.

(I-4) Preliminary polymerization / washing Subsequently, the previously prepared silicate / metallocene complex slurry was introduced into a stirring autoclave having an internal volume of 1.0 liter sufficiently substituted with nitrogen. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours.
After completion of the prepolymerization, the residual monomer was purged, stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted. Subsequently, 0.95 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 560 ml of mixed heptane were further added, stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then 560 ml of the supernatant was removed. Further, this operation was repeated three times.
When the component analysis of the final supernatant was performed, the concentration of the organoaluminum component was 1.23 mmol / liter, the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the presence in the supernatant with respect to the charged amount The amount was 0.016%. Subsequently, 17.0 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. A prepolymerized catalyst A containing 2.0 g of polypropylene per 1.0 g of catalyst was obtained.

(Ii) Production of propylene-ethylene copolymer (A) Using this prepolymerized catalyst A, a propylene-ethylene copolymer (A-1) was produced according to the following procedure.
(Ii-1) Propylene-Ethylene Random Copolymerization After the inside of a 200 liter stirred autoclave was sufficiently substituted with propylene, 470 ml of triisobutylaluminum (50 g / L) heptane solution (23.5 g as triisobutylaluminum) Then, 45 kg of liquefied propylene, 4NL of hydrogen, and 1900 g of ethylene were introduced, and the internal temperature was adjusted to 30 ° C.
Next, 0.6 g of the prepolymerized catalyst A synthesized earlier (0.2 g as the catalyst weight excluding the prepolymerized polymer) was added. Thereafter, the temperature was raised to 65 ° C. to initiate polymerization. Two hours later, 100 ml of ethanol was added to stop the polymerization reaction. Thereafter, unreacted gas was purged and the polymer was dried.
The PP (A-1) thus obtained had a polymer yield of 20 kg and a catalytic activity (a value obtained by dividing the polymer yield by the amount of catalyst) of 100 kg-PP / g-catalyst.
Table 3 shows the results of analyzing the obtained PP (A-1).

[Production Examples A-2 to A-4 and A-6 to A-8]
A propylene-ethylene random copolymerization was carried out in the same manner as in Production Example A-1 except that the polymerization conditions described in Table 3 were used (However, Production Example A-2 is a propylene homopolymer. ).
Table 3 shows the results of analyzing the obtained PP (A-2) to PP (A-4) and PP (A-6) to PP (A-8).

[Production Example A-5]
In preparing the prepolymerization catalyst, instead of [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium], [(r) -Prepolymerization catalyst B obtained using dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] hafnium] and A propylene-ethylene random copolymerization was carried out in the same manner as in Production Example A-1, except that the polymerization conditions described were used.
The results of analyzing the obtained PP (A-5) are shown in Table 3.

2. Propylene-ethylene copolymer (B)
(1) Measuring method of physical properties of propylene-ethylene copolymer (B) (1-1) Ethylene content [E (B)]
The ethylene content [E (B)] in the propylene-ethylene copolymer (B) was measured by ¹³ C-NMR detailed in the section of the propylene polymer (A).
(1-2) MFR (B)
The MFR (B) of the propylene-ethylene copolymer (B) was measured in accordance with the above-described JIS K7210 A method condition M.
(1-3) GPC measurement and number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the propylene-ethylene copolymer (B) were measured by the GPC method described above, and the molecular weight distribution (Mw / Mn) was calculated.

(2) Used propylene-ethylene copolymer (B)
(I) PP (B-1): commercial product, trade name “VISTAMAXX 3000” manufactured by ExxonMobil Chemical Co. (propylene-ethylene copolymer produced by metallocene catalyst)
(Ii) PP (B-2): Commercial product, trade name “VERSIFY3000” manufactured by Dow Chemical Co. (propylene-ethylene copolymer produced by metallocene catalyst)
(Iii) PP (B-3): Commercial product, trade name “ADFLEX X100G” manufactured by Lion Del Basel (propylene-ethylene copolymer produced by Ziegler-Natta catalyst)
Table 4 shows the results of analyzing PP (B-1) to PP (B-3).

3. Propylene resin composition (C)
(1) Method for measuring physical properties of propylene-based resin composition (C) (1-1) MFR (C)
The MFR (C) of the propylene-based resin composition (C) was measured in accordance with JIS K7210A method condition M described above.
(1-2) Solid viscoelasticity measurement (DMA)
The glass transition point (glass transition temperature) (Tg) was calculated from the peak of the obtained temperature-loss tangent (tan δ) curve by solid viscoelasticity measurement.
The sample used was cut into a strip of 10 mm width × 18 mm length from a sheet of 2 mm thickness obtained by press-molding a pellet of the resin composition (C) under the following conditions. As the apparatus, ARES manufactured by Rheometric Scientific was used.
The frequency is 1 Hz. The measurement temperature was raised stepwise from −60 ° C., and measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.
・ Press molding conditions:
Preheat at 230 ° C for 5 minutes, then pressurize at the same temperature for 3 minutes at a pressure of 50 kgf / cm ² and immediately apply a pressure of 100 kgf / cm ² with a press machine adjusted to 30 ° C for cooling and solidification. The press sheet of thickness 2mm was obtained.

(2) Production of Propylene Resin Composition (C) (2-1) Formulation As the propylene polymer (A), the above PP (A-1) to PP (A-8) and a propylene-ethylene copolymer (B ) And PP (B-1) to PP (B-3) are weighed so as to have the blending ratios shown in Table 5 and Table 6 below, and the propylene polymer (A) and the propylene-ethylene copolymer are measured. The following antioxidant and neutralizing agent were added in the following amounts to 100 parts by weight of the polymer (B) mixture, and the mixture was introduced into a Henschel mixer and mixed thoroughly.
(I) Antioxidant:
Tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane (manufactured by BASF Japan, trade name “Irganox 1010”) 500 wtppm
Tris (2,4-di-t-butylphenyl) phosphite (BASF Japan, trade name “Irgaphos 168”) 500 wtppm
(Ii) Neutralizing agent:
・ Calcium stearate 500wtppm

(2-2) Granulation In a “KZW” twin-screw extruder manufactured by Technobel with a screw diameter of 15 mm, the above conditions were performed under the conditions of extruder temperature = 200 ° C., screw rotation speed = 300 rpm, discharge amount = 3.0 kg / h. The mixture is melt-mixed, the molten resin extruded from the strand die is taken out while being cooled and solidified in a cooling water tank, and the strand is cut into a diameter of 3 mm and a length of 2 mm using a strand cutter, whereby the propylene-based resin composition PP ( C-1) to PP (C-15) pellets were obtained.
The results of analyzing the composition (C) are shown in Tables 5 and 6.

4). Propylene-ethylene copolymer (D)
(1) Measuring method of physical properties of propylene-ethylene copolymer (D) (1-1) Ethylene content [E (D1) and E (D)]
Ethylene content [E (D1)] in the propylene polymer component (D1) extracted from the polymerization tank after the first step of sequential polymerization, and in the propylene-ethylene copolymer (D) obtained after the second step The ethylene content [E (D)] was measured by ¹³ C-NMR as described above.
(1-2) MFR (D1) and MFR (D)
The MFR (D1) of the propylene-based polymer component (D1) obtained after the first step and the MFR (D) of the propylene-ethylene copolymer (D) obtained after the second step are JIS K7210 A described above. Measurements were performed according to method condition M.

(1-3) Specification of weight ratio of each component [W (D1) and W (D2)] As described above, the weight ratio of the propylene polymer component (D1) and the propylene-ethylene copolymer component (D2). (% By weight) is defined by the following equation.
W (D1) = Production amount of the first step / (Production amount of the first step + Production amount of the second step) × 100
W (D2) = Production amount of the second step / (Production amount of the first step + Production amount of the second step) × 100
As will be described later in [Production Example D-1], when the copolymer (D) is produced, the polymer obtained after the first step of producing the component (D1) is finished once. The whole volume flask was extracted and the yield of the first step was measured. After separating 10 g of the obtained component (D1) as a sample, the rest was filled in the polymerization tank, and the second step of producing the component (D2) was performed. After the 2nd process was completed, the yield of the obtained copolymer (D) was measured.
From this result, the production amount of the first step and the production amount of the second step were calculated by the following formulas, and W (D1) and W (D2) were calculated by the above formulas using the results.
Production amount of the first step = [Yield of the first step] −10 g (sampling amount)
Production amount of second step = [Yield of copolymer (B)]-[Production amount of first step]

(1-4) Ethylene content [E (D2)] in propylene-ethylene copolymer component (D2)
As the ethylene content [E (D2)] in the component (D2), the ethylene content [E (D1, E (D)] and the component amounts [W (D1) and W (D2)] described above are used. And calculated from the following formula.
E (D2) = {E (D) −E (D1) × (W (D1) ÷ 100)} ÷ (W (D2) ÷
100)

(1-5) Melt flow rate of copolymer component (D2) [MFR (D2)]
The MFR (D2) of the component (D2) was calculated from the following formula using the MFR (D1) and MFR (D) described above and W (D1) and W (D2).
MFR (D2) = exp {(log _e [MFR (D)] − (W (D1) ÷ 100) log _e [MFR (D1)]) ÷ (W (D2) ÷ 100)}
(Where log _e is the logarithm with e as the base)

(2) Production of propylene-ethylene copolymer (D) [Production Example D-1]
(I) Analysis of catalyst composition-Ti content:
The sample was accurately weighed, hydrolyzed, and measured using a colorimetric method. About the sample after prepolymerization, content was calculated using the weight remove | excluding prepolymerized polymer.
・ Silicon compound content:
The sample was accurately weighed and decomposed with methanol. The silicon compound concentration in the obtained methanol solution was determined by comparison with a standard sample using gas chromatography.
The content of the silicon compound contained in the sample was calculated from the concentration of the silicon compound in methanol and the weight of the sample. About the sample after preliminary polymerization, content was calculated using the weight remove | excluding the preliminary polymerization polymer.

(Ii) Preparation of prepolymerization catalyst (ii-1) Preparation of solid component A 10 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 2 L of purified toluene was introduced. Here, 200 g of Mg (OEt) ₂ was added at room temperature, and 1 L of TiCl ₄ was slowly added thereto. The temperature was raised to 90 ° C. and 50 ml of di-n-butyl phthalate was introduced. Thereafter, the temperature was raised to 110 ° C. to carry out a reaction for 3 hours. The reaction product was thoroughly washed with purified toluene.
Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. The reaction product was thoroughly washed with purified toluene. Subsequently, the refined toluene was introduce | transduced and the whole liquid quantity was adjusted to 2L. 1 L of TiCl ₄ was added at room temperature, the temperature was raised to 110 ° C., and the reaction was performed for 2 hours. The reaction product was thoroughly washed with purified toluene. Furthermore, using purified n-heptane, toluene was replaced with n-heptane to obtain a solid component slurry. A portion of this slurry was sampled and dried.
As a result of analysis, the Ti content of the solid component was 2.7% by weight.
Next, a 20 L autoclave equipped with a stirrer was sufficiently replaced with nitrogen, and 100 g of the solid component slurry was introduced as a solid component. Purified n-heptane was introduced to adjust the solid component concentration to 25 g / L. 50 ml of SiCl ₄ was added and a reaction was performed at 90 ° C. for 1 hr. The reaction product was thoroughly washed with purified n-heptane.
Thereafter, purified n-heptane was introduced to adjust the liquid level to 4 L. Here, dimethyl divinyl silane 30 ml, 80 g was added _{t-BuMeSi (OMe) 2 30ml} , the n- heptane dilution of _Et 3 Al as _Et 3 Al, were 2hr reaction at 40 ° C.. The reaction product was thoroughly washed with purified n-heptane to obtain a solid catalyst. A portion of the resulting solid catalyst slurry was sampled and dried for analysis.
The solid catalyst contained 1.2 wt% Ti and 8.9 wt% t-BuMeSi (OMe) ₂ .

(Ii-2) Prepolymerization Prepolymerization was performed by the following procedure using the solid catalyst obtained above.
Purified n-heptane was introduced into the slurry, and the solid catalyst concentration was adjusted to 20 g / L. After cooling the slurry to 10 ° C., 10 g was added n- heptane dilution of _Et 3 Al as _Et 3 Al, were fed over 4hr of propylene 280 g. After the supply of propylene was completed, the reaction was continued for another 30 minutes. Next, the gas phase was sufficiently replaced with nitrogen, and the reaction product was thoroughly washed with purified n-heptane. The obtained slurry was extracted from the autoclave and vacuum-dried to obtain a prepolymerized catalyst B.
This prepolymerized catalyst B contained 2.5 g of polypropylene per 1 g of the solid catalyst. As a result of analysis, the portion of the prepolymerized catalyst B excluding polypropylene contained 1.0% by weight of Ti and 8.3% by weight of t-BuMeSi (OMe) ₂ .
Using this prepolymerized catalyst B, a propylene-ethylene copolymer (D) was produced according to the following procedure.

(Iii) Production of propylene-ethylene copolymer (D) (iii-1) First step: Production of propylene-based polymer component (D1) Autoclave with an internal volume of 3 L having a stirring and temperature control device is sufficiently substituted with propylene After that, 550 mg of Et ₃ Al in an n-heptane dilution as Et ₃ Al was added, 15 NL of hydrogen, 10.5 g of ethylene, and 750 g of liquid propylene were introduced, and the temperature was raised to 60 ° C. and maintained at that temperature. The prepolymerized catalyst B was slurried with n-heptane, and 9 mg (excluding the weight of the prepolymerized polymer) was injected as a solid catalyst to initiate polymerization. Polymerization was continued for 30 minutes while maintaining the temperature in the tank at 60 ° C. Thereafter, the residual monomer was purged to normal pressure and further completely replaced with purified nitrogen. Prepare a 2 L glass flask fully substituted with nitrogen in advance, and prepare the propylene polymer component (D1) polymer obtained in the first step in a tube made of polytetrafluoroethylene resin under a nitrogen stream. Through the flask. As a result of the weighing, the propylene polymer component (D1) obtained in the first step was 252 g. Of these, 10 g was separated and used for analysis.

(Iii-2) Second step: Production of propylene-ethylene copolymer component (D2) After completion of the first step, the autoclave used for the polymerization was opened, and it was confirmed that no polymer remained inside. . After cleaning, it was reassembled, and it was thoroughly dried by flowing nitrogen while heating. After drying, the mixture was cooled to room temperature. After that, among the 252 g of the propylene polymer component (D1) obtained in the first step, the remaining 242 g obtained by separating 10 g for analysis was passed through a polytetrafluoroethylene resin tube under a nitrogen stream into an autoclave. Full amount was filled.
Separately, a mixed gas used in the second step was prepared using an autoclave having an internal volume of 20 L having a stirring and temperature control device. The preparation temperature was 75 ° C., and the composition of the mixed gas was 19 vol% ethylene, 81 vol% propylene, and 320 ppm hydrogen. This mixed gas was supplied to a 3 L autoclave and the pressure was increased to 2.0 MPaG to start polymerization in the second step. The polymerization was continued at 70 ° C. for 14 minutes. Thereafter, 10 ml of ethanol was introduced to terminate the polymerization.
The recovered polymer was sufficiently dried in an oven. As a result of weighing, 302 g of the obtained propylene-ethylene copolymer (D) was obtained. Of these, 242 g was a propylene-based polymer component (D1), so the resulting propylene-ethylene copolymer component (D2) was 60 g.
As a result of calculating the weight ratio of the propylene-based polymer component (D1) and the propylene-ethylene copolymer component (D2) based on these yield values, W (D1) was 80% by weight and W (D2) was 20 It became weight%.
The propylene-based polymer component (D1) prepared for analysis after the end of the first step and the propylene-ethylene copolymer (D) obtained after the end of the second step are analyzed, and E (D1 of ethylene content) is analyzed. ), E (D), melt flow rate MFR (D1), and MFR (D).
The results are shown in Table 7. Further, E (D2) and MFR (D2) were calculated using the values of W (D1), W (D2), E (D1), E (D), MFR (D1), and MFR (D). These values are also shown in Table 7.

[Production Examples D-2 to D-5]
A propylene-ethylene copolymer (D) was produced in the same manner as in Production Example D-1, except that the polymerization conditions described in Table 7 were used.
The results are shown in Table 7.

[Production Examples D-6 to D-10]
A propylene-ethylene copolymer (D) was produced in the same manner as in Production Example D-1, except that the polymerization conditions described in Table 8 were used. The results are shown in Table 8.

[Example 1]
1. Formulation PP (C-1) as the propylene-based resin composition (C) and PP (D-1) obtained in Production Example D-1 as the propylene-ethylene copolymer (D) are each 95% by weight, 5% The following antioxidant, neutralizer, slip agent, anti-blocking agent (AB) are weighed to 100% by weight of this PP (C-1) and PP (D-1) mixture. Agent) was added in the following amount, and the mixture was put into a Henschel mixer and mixed thoroughly.
(I) Antioxidant:
Tetrakis {methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate} methane (manufactured by BASF Japan, trade name “Irganox 1010”) 500 wtppm
Tris (2,4-di-t-butylphenyl) phosphite (BASF Japan, trade name “Irgaphos 168”) 500 wtppm
(Ii) Neutralizing agent:
・ Calcium stearate 500wtppm
(Iii) Slip agent:
-Erucamide (Nippon Seika Co., Ltd., trade name "Nutron S") 1000wtppm
(Iv) Anti-blocking agent:
・ Silicon oxide (trade name “Mizpearl K-300” manufactured by Mizusawa Chemical Co., Ltd.) 1500 wtppm

2. Granulation In a “KZW” twin screw extruder manufactured by Technobel with a screw diameter of 15 mm, melt-mixed under the conditions of extruder temperature = 200 ° C., screw rotation speed = 300 rpm, discharge rate = 3.0 kg / h, and from strand die The extruded molten resin was taken out while being cooled and solidified in a cooling water tank, and the strand was cut into a diameter of 3 mm and a length of 2 mm using a strand cutter to obtain a propylene-ethylene copolymer resin composition raw material pellet.

3. Film forming The obtained propylene-ethylene copolymer resin composition raw material pellets were extruded with a 30 mmφ diameter extruder under conditions of a resin temperature of 180 ° C. and a discharge rate of 8 kg / h, and the die width heated to 180 ° C. It was introduced into a single-layer T die adjusted to 150 mm and a lip opening of 0.8 mm, and melt extrusion was performed. The shear rate at the die wall surface was calculated by the following mathematical formula (1), and was 186 sec ⁻¹ .
The melt-extruded film was cooled and solidified with a cooling roll that was temperature-controlled at 30 ° C. and rotated at 30 m / min to obtain a single-layer unstretched film having a thickness of 40 μm.

  In the mathematical formula (1), each number and the like mean the following.

4). Film Appearance Evaluation (1) Surface Roughness Surface roughness is an appearance defect that occurs on the film surface as shown in FIG. In FIG. 1, the arrow indicates the MD direction.
Ten people visually observed the obtained unstretched film, and evaluated and judged according to the following criteria. ◯ and △ judgments are at a level that causes no problem in practical use.
A: A film judged by 8 or more people that no wave pattern has occurred.
(Triangle | delta): The film from which 5 or more and 7 or less determined that the wave pattern did not arise, and determined that there was no problem practically.
X: A film in which 6 or more people judge that there is a wave pattern, the wave pattern is clear, and the sense of transparency is poor.

(2) Oriented Crystal Oriented crystal is a phenomenon in which lumps of crystal structure (white spots) that can be visually observed are scattered at the die exit, and the entire film becomes cloudy. When orientation crystallization is extremely promoted, the draft ratio (ratio of cooling roll winding speed and resin discharge speed) is 1.5 or more in order to exhibit a solid-liquid phase separation at the die outlet. When enlarged, the liquid phase part is cracked, and the film is perforated and broken.
Ten people visually observed the obtained unstretched film, and evaluated and judged according to the following criteria. ◯ and △ judgments are at a level that causes no problem in practical use. In addition, some of the films with x were perforated or broken.
A: A film judged by 8 or more people that no white spots or cloudiness is generated.
(Triangle | delta): The film from which 5 or more and 7 or less persons judged that the whiteness and the cloudiness were not produced, and determined that there is no problem practically.
X: A film in which 6 or more people have white spots or cloudiness as a whole, or are perforated or broken.

(3) Fish Eye (FE)
The appearance of the obtained unstretched film was visually observed and evaluated according to the following criteria to confirm the presence or absence of fish eyes. ◯ and △ judgments are at a level that causes no problem in practical use.
○: Fish eyes are hardly seen and the appearance is excellent.
Δ: Some fish eyes are confirmed.
X: Many fish eyes are generated and the appearance is remarkably inferior.

(4) Dispersed state When the dispersed state of the resin is inferior, several stripes are generated in the film flow direction.
Ten people visually observed the appearance of the obtained unstretched film, and evaluated and judged according to the following criteria. ◯ and △ judgments are at a level that causes no problem in practical use.
◯: A film judged by 8 or more people that no streaking has occurred.
(Triangle | delta): The film from which 5 or more and 7 or less determined that a stripe did not arise, and determined that there was no problem practically.
X: A film in which 6 or more people judged that streaks are scattered over several lines as a whole.

5. Film properties evaluation (1) HAZE (transparency)
Based on JIS K7136-2000, it measured with the haze meter by one film.
The smaller the value obtained, the better the transparency.
(2) Tensile modulus (Young's modulus)
Based on JIS K7127-1989, the tensile elasticity modulus (Young's modulus) about a film flow direction (MD) was measured on condition of the following.
Sample shape: strip Sample length: 150 mm
Sample width: 15mm
Distance between chucks: 100mm
Crosshead speed: 1mm / min

(3) Blocking The film obtained by the above method is cut into a size of 2 cm (width) × 15 cm (length), and the two films are overlapped in parallel to the length direction so that the overlapping area is 10 cm ² . After leaving for 24 hours in a 40 ° C. gear oven under a load of 15 kg / cm ² (Tabaye Spec Corp./Tabai Gear Oven: GPH-100), a tensile tester (AGS-5KNG manufactured by Shimadzu Corporation) was used. Using the sample, both ends of the sample were pulled at a pulling speed of 500 mm / min, and the force required for peeling and peeling (peeling when a force pulling in the vertical direction was applied to the overlapping portion of the sample) was measured. It shows that blocking resistance is so good that this value is small.

The obtained film evaluation results are shown in Table 9.
The resulting film was extremely excellent in film appearance, transparency, flexibility, and blocking properties because the propylene-based resin composition raw material satisfied all the specific physical properties of the present invention.

[Examples 2 to 5]
Examples 2 to 5 were the same as in Example 1 except that the ratio of the resin composition (C) and the copolymer (D) was changed as shown in Table 9. Evaluation and physical property evaluation were carried out. Table 9 shows the evaluation results.
In Example 5, although some dispersion | distribution defect was seen, it was a level which is satisfactory practically. Otherwise, all the evaluation results were satisfactory.

[Comparative Examples 1-3]
Comparative Examples 1 to 3 were the same as in Example 1 except that the ratio of the resin composition (C) and the copolymer (D) was changed as shown in Table 9. Evaluation and physical property evaluation were carried out. Table 9 shows the evaluation results.
In Comparative Examples 1 and 2, since the blending amount of the copolymer (D) was insufficient, remarkable surface roughness occurred, and thus a film that could withstand evaluation could not be obtained.
Moreover, in Comparative Example 3, the blending amount of the copolymer (D) was excessive, streaks due to the deterioration of the dispersion state were scattered, and a film that could withstand evaluation could not be obtained.

[Examples 6 to 9]
In Examples 6 to 9, the resin composition (C) of Example 1 was changed to PP (C-2) to PP (C-5), respectively, and the resin composition (C) and the copolymer (D) Except that the ratio was 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. Table 10 shows the evaluation results.
In Example 6, all the evaluation results were satisfied.
In Example 7, since the content of the copolymer (B) contained in the resin composition (C) was increased, the blocking property was slightly deteriorated, but the film was wound around a paper tube. Since it had sufficient film peelability after removal, it was at a level with no problem in use.
Further, in Examples 8 and 9, since the content of the copolymer (B) contained in the resin composition (C) is further increased, the adhesiveness was strong and the blocking property was deteriorated. The results were satisfactory in terms of properties, flexibility and film appearance.

[Comparative Examples 4 to 6]
In Comparative Examples 4 to 6, the resin composition (C) of Example 1 was changed to PP (C-6) to PP (C-8), respectively, and the resin composition (C) and copolymer (D) Except for the ratio of 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. Table 10 shows the evaluation results.
In Comparative Example 4, since the copolymer (B) was not included in the resin composition (C), the Young's modulus of the film exceeded 400 MPa, and the result was inferior in flexibility.
In Comparative Example 5, the ethylene content [E (B)] contained in the copolymer (B) contained in the resin composition (C) is as low as 3 wt%, and the resin composition (C) is sufficient. Since the film did not have such flexibility, the Young's modulus of the film exceeded 400 MPa, resulting in poor flexibility.
Furthermore, in Comparative Example 6, the copolymer (B) contained in the resin composition (C) was produced using a Ziegler-Natta catalyst, and the molecular weight distribution [Mw of the copolymer (B)] / Mn (B)] is as wide as 4.3, and since the ethylene content [E (B)] contained in the copolymer (B) is as high as 18 wt%, the glass transition of the resin composition (C) Since the temperature (Tg) became two peaks and the resin composition (C) exhibited a phase separation structure, it became cloudy and the film had a HAZE of 4.2, which was inferior in transparency.

[Examples 10 to 16]
In Examples 10 to 16, the resin composition (C) of Example 1 was changed to PP (C-9) to PP (C-15), respectively, and the resin composition (C) and the copolymer (D) Except that the ratio was 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 11.
All the evaluation results were satisfactory results.

[Examples 17 and 18]
In Examples 17 and 18, the copolymer (D) of Example 1 was changed to PP (D-3) and PP (D-4), respectively, and the resin composition (C) and the copolymer (D) Except that the ratio was 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 12.
All the evaluation results were satisfactory results.

[Comparative Examples 7 and 8]
In Comparative Examples 7 and 8, the copolymer (D) of Example 1 was changed to PP (D-2) and PP (D-5), respectively, and the resin composition (C) and the copolymer (D) Except that the ratio was 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The results are shown in Table 12.
In Comparative Example 7, an extremely oriented crystal was exhibited, and tearing occurred at the die outlet, so that a film could not be obtained.
Moreover, since the comparative example 8 had surface roughness notably produced, the film which can endure evaluation was not able to be obtained.

[Examples 19 to 22]
In Examples 19 to 22, the copolymer (D) of Example 1 was changed to PP (D-6) to PP (D-9), respectively, and the resin composition (C) and the copolymer (D) Except that the ratio was 90:10, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 13.
In Example 19, white spots caused by oriented crystals were slightly observed, but the level was satisfactory for use. Otherwise, all the evaluation results were satisfactory.

[Comparative Example 9]
In Comparative Example 9, the copolymer (D) of Example 1 was changed to PP (D-10), and the ratio of the resin composition (C) and the copolymer (D) was 90:10. In the same manner as in Example 1, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed. The evaluation results are shown in Table 13.
In Comparative Example 9, since the MFR of the component (D2) contained in the copolymer (D) was high, surface roughness occurred remarkably, and a film that could withstand evaluation could not be obtained.

  Comparing each of the above examples and each comparative example, when a new propylene-ethylene copolymer resin composition satisfying the respective regulations in the present invention is used, it is excellent in extrusion characteristics and extruded at a low temperature of about 180 ° C. However, it can be seen that a film that exhibits excellent characteristics such as excellent transparency and flexibility without causing appearance defects such as surface roughness and white spots caused by oriented crystals can be obtained.

  The propylene-ethylene copolymer resin composition of the present invention is useful as a material for molding various films or sheets, and the obtained film or sheet is suitable as a packaging material for various foods. It can be widely used as a package for cartons, tubes, bags, cups, standing packs, trays, and the like.

Claims (9)

Propylene-based copolymer (A) having the following characteristics (Ai) to (A-iv): 0 to 99% by weight, and propylene-ethylene copolymer having the following characteristics (Bi) to (B-iii) (B) 1 to 100% by weight of a propylene-based resin composition (C) obtained by mixing by a method excluding a polymerization blend (C) 65 to 95% by weight;
A propylene-ethylene copolymer resin composition containing 5 to 35% by weight of a propylene-ethylene copolymer (D) having the following characteristics (D-i) to (D-ii),
The propylene-ethylene copolymer (D) is based on a total of 100% by weight of (D1) and (D2) and has a propylene-based polymer component (D1) having the following characteristics (D1-i) of 65 to 95% by weight: A propylene-ethylene copolymer resin composition comprising 5 to 35% by weight of a propylene-ethylene copolymer component (D2) having the following characteristics (D2-i) and (D2-ii):
Propylene polymer (A):
(Ai) Obtained by polymerization using a metallocene catalyst.
(A-ii) Melt flow rate [MFR (A)] is 0.1-100 g / 10min.
(A-iii) The ethylene content [E (A)] is 0 to 6.0% by weight.
(A-iv) The molecular weight distribution [Mw / Mn (A)] represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC measurement is 2-4.
Propylene-ethylene copolymer (B):
(Bi) It was obtained by polymerization using a metallocene catalyst.
(B-ii) The ethylene content [E (B)] is 4 to 17% by weight.
(B-iii) The molecular weight distribution [Mw / Mn (B)] represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC is 1 to 4.
Propylene-ethylene copolymer (D):
(Di) The ethylene content [E (D)] in the copolymer (D) is in the range of 0.4 to 13% by weight.
(D-ii) The melt flow rate [MFR (D)] of the copolymer (D) is in the range of 0.5 to 20 g / 10 min.
Propylene polymer component (D1):
(D1-i) The ethylene content [E (D1)] in the polymer component (D1) is in the range of 0 to 6.0% by weight.
Propylene-ethylene copolymer component (D2):
(D2-i) The ethylene content [E (D2)] in the copolymer component (D2) is in the range of 8 to 25% by weight.
(D2-ii) The melt flow rate [MFR (D2)] of the copolymer component (D2) is in the range of 0.0001 to 0.5 g / 10 min.   The propylene-ethylene copolymer (D) is produced by multistage polymerization having a step of producing a propylene-based polymer component (D1) and a step of producing a propylene-ethylene copolymer component (D2). The propylene-ethylene copolymer resin composition according to claim 1.   The propylene-ethylene copolymer resin composition according to claim 1 or 2, wherein the propylene-ethylene copolymer (D) is produced by a Ziegler-Natta catalyst.   The propylene-based resin composition (C) is a temperature-loss tangent (tan δ) curve representing a glass transition observed in a range of −60 to 20 ° C. in a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement. The propylene-ethylene copolymer resin composition according to any one of claims 1 to 3, wherein the peak of the polymer exhibits a single peak at 0 ° C or lower.   The film formed by extrusion-molding the propylene-ethylene copolymer resin composition of any one of Claims 1-4.   A laminated film obtained by laminating the film according to claim 5 as a surface layer.   The sheet | seat formed by extrusion-molding the propylene-ethylene copolymer resin composition of any one of Claims 1-4.   A laminated sheet obtained by laminating the sheet according to claim 7 as a surface layer.   A propylene-based laminated stretched film obtained by laminating the propylene-ethylene copolymer resin composition according to any one of claims 1 to 4 on a surface layer and stretching in a biaxial direction.

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