JP2013199642A - Propylene-based polymer resin composition and film and sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene-based polymer resin composition excellent in transparency, stiffness and heat seal properties, and having excellent extrusion processability even extrusion molded at low temperature; and a film and sheet.SOLUTION: A propylene-based polymer resin composition includes 97-65 pts.wt. of a propylene-based polymer (A) having characteristics (A-i) to (A-iii) produced with a metallocene-based catalyst, and 3-35 pts.wt. of a propylene-ethylene copolymer (B) having characteristics (B-i) to (B-ii), wherein the copolymer (B) is composed of 65-95 wt.% of a propylene-based polymer component (B1) having a characteristic (B1-i) and 5-35 wt.% of propylene-ethylene copolymer component (B2) having characteristics (B2-i) and (B2-ii). (A-i) The ethylene content in polymer (A) is 0-6.0 wt.%. (A-ii) The MFR of the polymer (A) is 0.1-100 g/10 min. (A-iii) Mw/Mn is 2-4. (B-i) The ethylene content in the copolymer (B) is 0.4-13 wt.%. (B-ii) The MFR of the copolymer (B) is 0.5-20/10 min. (B1-i) The ethylene content of the polymer component (B1) is 0-6.0 wt.%. (B2-i) The ethylene content of the copolymer component (B2) is 8-25 wt.%. (B2-ii) MFR of the copolymer component (B2) is 0.0001-0.5 g/10 min.

Description

  The present invention relates to a propylene-based polymer resin composition and a film and sheet, and more specifically, a propylene-ethylene copolymer obtained by a metallocene-based catalyst has excellent transparency, high rigidity, and excellent heat seal characteristics. The present invention relates to a propylene-based polymer resin composition having excellent extrudability even if it is extruded at a low temperature while maintaining such excellent characteristics, and a film and sheet formed by molding the same.

Polypropylene films and sheets (hereinafter also referred to as “films”) are widely used in packaging fields such as food packaging and fiber packaging because of their excellent optical properties, mechanical properties, and packaging suitability. . In recent years, there has been a demand for a reduction in molding temperature for the purpose of improving thickness accuracy in the width direction of the film and reducing manufacturing costs.
Propylene-ethylene copolymers produced with metallocene catalysts have a narrow composition distribution and do not contain low molecular weight substances or low crystallinity components that cause stickiness or reduced rigidity. It is known that a film can be obtained (see Patent Document 1).

On the other hand, however, these metallocene copolymers are generally poor in extrusion characteristics because of not only the composition distribution but also the narrow molecular weight distribution. In particular, an industrial problem in terms of extrusion characteristics is a phenomenon in which surface roughness called shark skin or melt fracture occurs on the surface of a film discharged from a die in extrusion molding, resulting in an unusable appearance.
These surface roughness improvements can be made by increasing the temperature of the die and expanding the width of the die exit as the molding conditions. Or a neck-in at the time of being wound from a die to a roll becomes large, or a thickness variation is likely to occur. When the width of the die exit is increased, problems other than thermal degradation are not easily solved, and thickness accuracy in the film width direction is reduced (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 by a catalyst or a polymerization method, (1) a proposal to widen the molecular weight distribution by using a specific metallocene catalyst (Patent Documents 2 to 4), (2) two-component propylene having different molecular weights Proposals for performing multistage polymerization to obtain an ethylene copolymer (Patent Documents 5 to 7), (3) Proposals for introducing long chain branching by copolymerization of graft modification or macromonomer or diene (Patent Documents 8 to 8) 12) has been made.

Regarding the proposal (1), for example, according to Patent Document 2, a propylene copolymer having a Mw / Mn of 4.0 to 7.7 produced by a metallocene catalyst is disclosed. There is no disclosure of Mz / Mn that suggests the existence of a contributing ultra high molecular weight component, and a propylene copolymer and metallocene catalyst produced using a Ziegler-Natta catalyst with the same weight average molecular weight. When the Mz / Mn of the propylene copolymer produced by the above method is compared, the propylene copolymer produced using the Ziegler-Natta catalyst is clearly high in Mz / Mn and has good extrusion characteristics. Since it is known, it is clear that the effect of improving the extrusion characteristics by the above proposal is insufficient.
In the proposal (2), in order to improve surface roughness while ensuring melt fluidity, it is necessary to provide a molecular weight difference between a low molecular weight component and a high molecular weight component. 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, resulting in a large molecular weight disparity, and a poor appearance called gel or fish eye is likely to occur. It is not preferable.
In the proposal (3), it is difficult to control the cross-linking reaction that occurs as a side reaction, and there is a problem that appearance defects are likely to occur because the formation of gel is induced.

In addition, as proposals for blending materials with excellent extrusion characteristics, (4) proposals for blending other resins such as polyethylene (Patent Document 13), (5) proposals for blending propylene-ethylene copolymers having a wide molecular weight distribution (patent References 14 and 15) have been made.
In the proposal (4), since polypropylene and polyethylene are incompatible with each other, blending until the extrusion characteristics are improved results in extremely poor transparency.
In the proposal (5), for example, according to Patent Document 14, 1 to 70% by weight of the propylene-based random copolymer (A) obtained by the metallocene catalyst and propylene obtained by the conventional Ziegler-Natta catalyst. A copolymer resin composition comprising 30 to 99% by weight of a random copolymer (B) is disclosed. However, the propylene-based random copolymer (B) used in the present invention has a high MFR of 9.2 and does not have a high molecular weight component necessary for improving the surface roughness, so the surface roughness is improved. Not.

  Patent Document 15 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. . 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., molecular chains with a long relaxation time are oriented in the flow in the die. Since crystallization occurs and a solid-liquid phase separation appears at the die outlet, cracking occurs in the liquid layer when the draft ratio (ratio between the cooling roll winding speed and the resin discharge speed) increases, which is not suitable for practical use. There is a problem of becoming a shape.

  Further, (6) a proposal (Patent Document 16) for improving surface roughness by using a specific additive has been made. In this proposal, it is disclosed that the generation of melt fracture is suppressed by adding a fluoroelastomer as a processing aid. In general, by adding a fluorine elastomer, when the resin flows into the die, the surface of the die is coated with the fluorine elastomer, the resin pressure near the die wall surface is reduced, and as a result, the occurrence of melt fracture can be suppressed. Are 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 burns and appears as black spots in the film. It may become.

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

JP-A-11-302470 JP-A-11-92515 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

  In view of the above-mentioned problems, the present invention provides a propylene-based polymer obtained by a metallocene-based catalyst, having excellent transparency such as excellent transparency, high rigidity, and excellent heat seal characteristics, while maintaining low temperature. It is an object of the present invention to obtain a propylene-based polymer resin composition having excellent extrusion characteristics even if extrusion molding is performed, and a film or sheet excellent in quality formed by molding the same.

As a result of various investigations in the conventional state of the art represented by the prior art in the previous patent documents and the like, the present inventors have identified a specific propylene-ethylene copolymer obtained by a metallocene catalyst. It was found that a composition containing a specific amount of a specific propylene-ethylene copolymer was able to solve the above-mentioned problems.
According to the present invention, the following propylene polymer resin composition, film or sheet, and laminated film or laminated sheet are provided.

[1] Propylene polymer (A) 97 having the following characteristics (Ai) to (A-iii) produced by a metallocene catalyst based on a total of 100 parts by weight of the following (A) and (B) A propylene-based polymer resin composition containing 65 parts by weight and 3 to 35 parts by weight of a propylene-ethylene copolymer (B) having the following characteristics (Bi) to (B-ii),
The propylene-ethylene copolymer (B) is based on a total of 100% by weight of (B1) and (B2), and a propylene-based polymer component (B1) having the following characteristics (B1-i): A propylene-based polymer resin composition comprising 5 to 35% by weight of a propylene-ethylene copolymer component (B2) having the following characteristics (B2-i) and (B2-ii):
(A-i) The ethylene content E (A) in the polymer (A) is in the range of 0 to 6.0 wt%. (A-ii) The melt flow rate MFR (A) of the polymer (A) is 0. (A-iii) The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn in the GPC measurement of the polymer (A) in the range of 1 to 100 g / 10 min is in the range of 2 to 4 (B-i ) The ethylene content E (B) in the copolymer (B) is in the range of 0.4 to 13 wt%. (B-ii) The melt flow rate MFR (B) of the copolymer (B) is 0.5. (B2-i) copolymer component (B2) in which ethylene content E (B1) in the polymer component (B1) in the range of ˜20 g / 10 min is in the range of 0 to 6.0 wt% ) In which ethylene content E (B2) is in the range of 8 to 25 wt% (B2-ii) The melt flow rate MFR of the body component (B2) (B2) is in the range of 0.0001~0.5g / 10min

[2] The propylene-ethylene copolymer (B) is produced by multistage polymerization of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2). The propylene-based polymer resin composition described.
[3] The propylene-based polymer resin composition according to the above [1] or [2], wherein the propylene-ethylene copolymer (B) is produced by a Ziegler-Natta catalyst.
[4] A film or sheet obtained by extruding the propylene polymer resin composition according to any one of [1] to [3].
[5] A laminated film or laminated sheet obtained by laminating the film or sheet according to [4] as a surface layer.

The propylene-based polymer resin composition of the present invention has an improved extrusion characteristic of the propylene-based copolymer obtained by the metallocene-based catalyst. Even under molding conditions that are advantageous in terms of productivity and performance, such as a decrease in extrusion temperature, the occurrence of surface roughness called melt fracture or shark skin can be suppressed.
Such a film / sheet obtained by the propylene-based polymer resin composition of the present invention has a good appearance, is excellent in transparency, has high rigidity, and does not deteriorate in blocking. The excellent properties of the propylene-ethylene copolymer are maintained at a high level.

It is a perspective view which shows an example of the surface roughness on the film surface.

  The resin composition of the present invention is a resin composition in which a specific amount of a specific propylene-ethylene copolymer (B) described later is blended with the following propylene polymer (A) produced by a metallocene catalyst.

[Propylene polymer (A)]
The propylene polymer (A) used in the resin composition of the present invention is produced by a metallocene catalyst and needs to have the following characteristics (Ai) to (A-iii).
(A-i) The ethylene content E (A) in the polymer (A) is in the range of 0 to 6.0 wt%. (A-ii) The melt flow rate MFR (A) of the polymer (A) is 0. Mw / Mn, which is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn in the GPC measurement of the polymer (A) in the range of 1 to 100 g / 10 min, is in the range of 2 to 4.

(Ai) The ethylene content E (A) in the polymer (A) is 0 to 6.0 wt%, more preferably 0.5 to 5.0 wt%, more preferably 1.0 to 5 wt%. 0.0 wt%. When the ethylene content exceeds 6.0 wt%, the crystallinity decreases, and thus the anti-blocking performance deteriorates. (A-ii) The melt flow rate MFR (A) of the polymer (A) is 0.1 to 0.1%. 100 g / 10 min, preferably 60 g / 10 min or less, more preferably 30 g / 10 min or less, still more preferably 25 g / 10 min or less, preferably 0.5 g / 10 min or more, more preferably 2 g / 10 min. As mentioned above, More preferably, it is 3 g / 10min or more. When the MFR is smaller than 0.1 g / 10 min, it is difficult to adjust the thickness deviation, and when the MFR is larger than 100 g / 10 min, the neck-in when winding from the die to the roll increases. Since the film width becomes narrow, it is not preferable for practical use.
The melt flow rate MFR (A) is measured at a load of 2.16 kg according to JIS K7210.
(A-iii) Mw / Mn of the polymer (A) is 2-4. When Mw / Mn is greater 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.

  As the propylene polymer (A), a polymer obtained by polymerization using a metallocene catalyst is used. The metallocene catalyst uses a narrower molecular weight distribution, the crystallinity distribution is narrower, and the amount of low crystalline components produced is less than the Ziegler-Natta catalyst. An excellent propylene-ethylene random copolymer can be produced.

An appropriate form for producing the propylene polymer (A) will be described in detail below.
1. Metallocene catalyst The gist 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 the metallocene catalyst used for the former production. The type 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 the transition metal compounds represented by the general formula (1) Component (b): At least one selected from the following (b-1) to (b-4) (B-1) an ionic compound capable of reacting with component (a) to convert component (a) into a cation or (B-3) Solid acid fine particles (b-4) Ion exchange layered silicate Component (c): Organoaluminum compound

・ Ingredient (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、周期律表第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 bond 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 which 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. Even if the group is bonded to the cyclopentadienyl group as a monovalent group, when two or more of them are present, two of them are bonded at the other end (ω-end) to form a cyclopentadienyl group. A ring may be formed together with a part. 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

  For the preferred compounds represented above, only representative exemplary compounds are described avoiding many complicated examples. Although a compound in which the central metal is zirconium has been described, it goes without saying that the same hafnium compound can also be used, and various conjugated five-membered ring ligands, binding groups or auxiliary ligands are optionally used. It is self-evident.

・ Ingredient (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 known component, and can be appropriately selected from known technologies and used. 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 After reacting with an organometallic compound such as, and further reacting with water, silica or the like carrying the product is used as component (b-4) as montmorillonite, zakonite, beidellite, nontronite, saponite, hectorite, stevensite. , Bentonite, teniolite and other smectites, vermiculite, mica and the like. 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.

・ Ingredient (c)
Examples of organoaluminum compounds used as component (c) as needed are:
General formula AlR _a X _3-a
(Wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is hydrogen, halogen, alkoxy group, a is a number of 0 <a ≦ 3)
Or a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, or trioctylaluminum, or a halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride or diethylaluminum monomethoxide.
In addition, aluminoxanes such as methylaluminoxane can also be used.
Of these, trialkylaluminum is particularly preferable as component (c).

-Formation of a catalyst A component (a), a component (b), and the component (c) as needed are made to contact, and it is set as a catalyst. The contact method is not particularly limited, but the 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.
1) Contact component (a) and component (b) 2) Add component (c) after contacting component (a) and component (b) 3) Contact component (a) and component (c) 4) Add component (a) after contacting component (b) and component (c) 5) Contact 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.

It is preferable to subject the metallocene catalyst to a prepolymerization treatment consisting of preliminarily contacting an olefin and polymerizing a small amount.
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 amount of prepolymerization 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.

-Manufacturing method-Polymerization process Any polymerization process can be used.
First, the operation method over time will be described. From this viewpoint, 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, the bulk polymerization method will be referred to as a bulk method according to the practice in the art. In the case of the batch method, the first step may be performed by the bulk method and the second step may be performed by the vapor phase method. This case is also referred to as the bulk method. As described above, the reaction phase is not particularly limited, but the slurry method has a problem that the production cost increases in general because there are many auxiliary facilities because an organic solvent such as hexane and heptane is used. 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, the particular process type is not limited in the present invention from this viewpoint.

..General polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within the usual temperature range. Specifically, a range of 0 ° C to 200 ° C, preferably 40 ° C to 100 ° C can be used.
The polymerization pressure varies depending on the process to be selected, but 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.

-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 an extremely large number of catalyst cycles rotate in a very short time compared to other catalyst reactions, and therefore there is a technical problem that it is easily affected by impurities. In order to solve this problem, it is a well-known fact that various contrivances have been made, 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 technique is often used in which a highly reactive organoaluminum compound is added to a polymerization reactor and reacted with the organoaluminum compound before the impurities react with the metallocene catalyst to render it harmless.
Also in the present invention, it is desirable to use the organoaluminum compound (C) from this viewpoint. Although any compound can be used as the organoaluminum compound (C), examples of suitable compounds are the same as those of the component (c) which is an optional component of the metallocene catalyst, and triisobutylaluminum and trioctylaluminum are particularly preferable. .

  The amount of the organoaluminum compound (C) 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.

-Index control method Next, the index control method of a propylene polymer (A) is explained in full detail.

First, regarding ethylene content, as described above, the ethylene content of the propylene polymer (A) is 0 to 6.0 wt%, more preferably 0.5 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) 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-based polymer (A) varies depending on the type of metallocene catalyst used. Obtaining a propylene polymer (A) having an ethylene content is very easy for those skilled in the art.

Next, MFR will be described. As described above, the MFR of the propylene polymer (A) is 0.1 to 100 g / 10 min.
The MFR of the propylene polymer (A) 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 of the propylene 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.

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 already described, Mw / Mn is 2-4.
By using a metallocene catalyst, the Mw / Mn can be made smaller than when using a Ziegler-Natta catalyst. However, when controlling the Mw / Mn, an appropriate metallocene catalyst is selected at the same time as the target value. It is also effective to devise polymerization conditions. For example, if a two-tank continuous polymerization process is employed to produce propylene-ethylene copolymers having different molecular weights in the first and second polymerization tanks, the Mw is higher than the value originally given by the metallocene catalyst used. / Mn can be increased. At this time, the polymerization conditions to be used, in particular, the relationship between 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 make adjustments.

[Propylene-ethylene copolymer (B)]
The propylene-ethylene copolymer (B) used in the present invention needs to have the characteristics (Bi) to (B-ii).
(B-i) The ethylene content E (B) in the copolymer is in the range of 0.4 to 13 wt%. (B-ii) The melt flow rate MFR (B) of the copolymer is 0.5 to 20 g. In the range of / 10 min

(Bi) The ethylene content E (B) in the copolymer is in the range of 0.4 to 13 wt%, preferably in the range of 0.5 to 12 wt%. By setting the ethylene content E (B) in the copolymer within this range, a sufficient surface roughness improving effect can be obtained. Moreover, when it is less than 0.4 wt%, the heat seal characteristics may be deteriorated and induced orientation crystals may occur. When it exceeds 13 wt%, the effect of improving the surface roughness may not be obtained.
The melt flow rate MFR (B) of (B-ii) is 0.5 to 20 g / 10 min, and preferably 1.0 to 15 g / 10 min. When it is smaller than 0.5 g / 10 min, the dispersibility in the propylene polymer (A) is poor, streaks occur in the film, and the appearance is not practical. If it is larger than 20 g / 10 min, the thickness accuracy of the film may be inferior, or the difference between the MFR of the propylene-based polymer component (B1) and the MFR of the propylene-ethylene copolymer component (B2) becomes large, This is not preferable because fish eyes and gel are generated due to poor dispersion of the propylene-ethylene copolymer component (B2), and the film cannot be practically used.

Further, the propylene-ethylene copolymer (B) is a propylene-based polymer component (B1) having the following characteristics (B1-i) based on a total of 100% by weight of (B1) and (B2): 65 to 95 wt%. And propylene-ethylene copolymer component (B2) having the following properties (B2-i) to (B2-ii): 5 to 35 wt%, and a propylene-ethylene copolymer.
(B1-i) The ethylene content E (B1) in the polymer component (B1) is in the range of 0 to 6.0 wt% (B2-i) The ethylene content E ( B2) is in the range of 8 to 25 wt% (B2-ii) The melt flow rate MFR (B2) of the copolymer component (B2) is in the range of 0.0001 to 0.5 g / 10 min.

Here, E (B2) is the weight of E (B), E (B1), propylene-based polymer component (B1) and propylene-ethylene copolymer component (B2) in the propylene-ethylene copolymer (B). The value is defined by the following formula using the ratio.
E (B2) =
{E (B) −E (B1) × (W (B1) ÷ 100)} ÷ (W (B2) ÷ 100)
(W (B1) and W (B2) are weight ratios of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) in the propylene-ethylene copolymer (B), respectively. , W (B1) + W (B2) = 100 is satisfied.)

Similarly, MFR (B2) is the weight of MFR (B), MFR (B1), propylene-based polymer component (B1) and propylene-ethylene copolymer component (B2) in propylene-ethylene copolymer (B). Using the ratio, the value is defined by the following formula, which is well known as a logarithmic additivity rule.
MFR (B2) = exp {(log _e [MFR (B)] − (W (B1) ÷ 100) × log _e [MFR (B1)]) ÷ (W (B2) ÷ 100)}
(Here, MFR (B1) is the MFR of the propylene polymer component (B1), and W (B1) and W (B2) are defined above.)

  A component (B1) is a component which has crystallinity, and ethylene content E (B1) is 0-6.0 wt%, Preferably it is 0.5-5.0 wt%. When the ethylene content E (B1) exceeds 6.0 wt%, the polymer properties are extremely deteriorated, which not only induces blockage in the polymerization equipment, but also causes low film crystallinity. Sexual component increases.

  The component (B2) is a component that suppresses the slip phenomenon on the die wall surface caused by the flow field in the die, and is also a component that stabilizes the lamination interface in multilayer molding, and needs to have a very high molecular weight component. Therefore, the component (B2) needs to have an MFR (B2) in the range of 0.0001 to 0.5 g / 10 min, and preferably the upper limit is 0.2 g / 10 min. On the other hand, if the molecular weight is too high, the dispersibility is deteriorated, causing fish eyes and gel generation, and is 0.0001 g / 10 min or more, preferably 0.001 g / 10 min or more.

In addition, the component (B2) has low crystallinity or crystallinity so that when the extrusion molding is performed at a relatively low temperature of about 180 ° C., orientational crystallization of molecular chains with 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 (B2) needs to be 8 wt% or more, preferably 10 wt% or more, more preferably 10. 5 wt% or more, more preferably 11 wt% or more.
On the other hand, if the ethylene content E (B2) is too high, the compatibility between the component (A) and the propylene molecular chain of the component (B1) and the molecular chain of the component (B2) is remarkably reduced. Since stress propagation does not occur and the surface roughness suppressing effect is not exhibited, the ethylene content E (B2) needs to be 25 wt% or less, and preferably 20 wt% or less.

  The proportion of the component (B2) in the propylene-ethylene copolymer (B) is significantly different from the MFR of the component (B1) when the proportion of the component (B2) is excessive because the component (B2) has a remarkably high molecular weight. Needs to be large, and causes fish eyes and gels. Therefore, it is necessary to be 35 wt% or less, preferably 30 wt% or less. On the other hand, if the amount of the component (B2) is too small, it is necessary to contain an excessive amount of the propylene-ethylene copolymer (B) in the composition, which may cause a decrease in transparency of the film. It is necessary to be, and preferably 10 wt% or more.

The propylene-ethylene copolymer (B) of the present invention has the above-mentioned characteristics (Bi) to (B-ii) and has the characteristics (B1-i). Propylene-ethylene copolymer comprising (B1) 65-95 wt% and propylene-ethylene copolymer component (B2) 5-35 wt% having characteristics (B2-i)-(B2-ii) If it is a coalescence and has this requirement, the production method is not particularly limited.
Hereinafter, an appropriate form for producing the propylene-ethylene copolymer (B) of the present invention will be described with specific examples.

1. Catalyst Any catalyst can be used for producing the propylene-ethylene copolymer (B), but the propylene-ethylene copolymer component (B2) having the characteristics (B2-i) to (B2-ii). ) As a constituent component, it is preferable to use a Ziegler-Natta catalyst. In the case of using a Ziegler-Natta catalyst, the specific method for producing the catalyst is not particularly limited, but the catalyst disclosed in JP 2007-254671 A can be exemplified.
Specifically, as representative examples of Ziegler-Natta catalysts suitable for the production of the propylene-ethylene copolymer (B) of the present invention, the following components, (a1) titanium, magnesium, and halogen as essential components: Examples thereof include a catalyst comprising a solid component to be contained, (a2) an organoaluminum compound, and (a3) an electron donor.

Solid component (a1)
The solid component (a1), which is a constituent component of the Ziegler-Natta catalyst suitable for producing the propylene-ethylene copolymer (B) of the present invention, is composed of titanium (a1a), magnesium (a1b), and halogen (a1c) as essential components. As an optional component, an electron donor (a1d) can be used. Here, “contained as an essential component” indicates that, in addition to the listed three components, any component may be included in any form within a range that does not impair the effects of the present invention. This will be described in detail below.

..Titanium (a1a)
Arbitrary things can be used as a titanium compound used as a 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.

..Magnesium (a1b)
Any magnesium compound can be used as the magnesium source. Representative examples include compounds disclosed in JP-A-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.

..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-described 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.

..Electron donor (a1d)
The solid component (a1) may contain an electron donor 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 the organic acid compound that can be used as an electron donor include aromatic polyvalent carboxylic acid compounds represented by phthalic acid, aromatic carboxylic acid compounds represented by benzoic acid, and 2-n-butyl-malonic acid. One or two substituents such as malonic acid or 2-n-butyl-succinic acid having one or two substituents at the 2-position as shown above or one or more at the 2-position and 3-position respectively Aliphatic carboxylic acid compounds typified by succinic acid having the above-mentioned substituents, aliphatic carboxylic acid compounds typified by propionic acid, aromatic and aliphatic typified by benzenesulfonic acid and methanesulfonic acid Examples thereof include 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, etc. 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 the inorganic acid compound that can be used as the electron donor 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 electron donors 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 alone or 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.

..Quantity ratio of each component constituting the solid component The amount ratio of each component constituting the solid component (a1) can be any as long as it does not impair the performance of the catalyst. The following range is preferable.
The amount of 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. The molar ratio with respect to the amount used (number of moles of the halogen source compound / number of moles of the magnesium compound) is preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.1 to 100. The inside is desirable.
The amount used when an electron donor is used as an optional component in preparing the solid component (a1) is a molar ratio (number of moles of electron donor / number of moles of magnesium compound) to the amount of magnesium compound used. , 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. As the contact condition of each component, it is necessary that oxygen does not exist, but any condition can be used as long as the effect of the present invention is not impaired. 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 or a vibration mill, and a method of contacting by stirring in the presence of an inert diluent.

-Organoaluminum compound (a2)
As the organoaluminum compound (a2) which is a constituent of the Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (B) of the present invention, compounds disclosed in JP-A No. 2004-124090 are used. I can do it. 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 or hydrogen. R ¹⁰ represents a hydrocarbon group or a crosslinking group by 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, and particularly preferably 1 to 6 carbon atoms. Specific examples of R ⁹ include methyl group, ethyl group, propyl group, butyl group, isobutyl group, hexyl group, octyl group, and the like. Of these, a methyl group, an ethyl group, and an isobutyl group are most preferable.
In the above formula, X is halogen or hydrogen. 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 formula, R ¹⁰ is a hydrocarbon group or a cross-linking 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 . Moreover, it is also possible to use alumoxane compounds represented by methylalumoxane as the organoaluminum compound (a2), 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. I can list them. 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.

・ 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 (B) of the present invention, an organosilicon compound having an alkoxy group, or at least two ether bonds The compound which has can be illustrated.

.. Organosilicon compound having an alkoxy group As an organosilicon compound having an alkoxy group that is a constituent of a Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (B) of the present invention, JP-A-2004-124090 The compound etc. which were indicated by the gazette 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 hetero atom-containing hydrocarbon group. R ⁴ represents an arbitrary radical selected from hydrogen, halogen, a hydrocarbon group, and a hetero atom-containing hydrocarbon group. R ⁵ represents Represents a hydrocarbon group, 0 ≦ a ≦ 2, 1 ≦ b ≦ 3, a + b = 3)

In the above 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, cyclopentyl group, It is desirable to use a cyclohexyl group or the like.
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 formula, R ⁴ represents hydrogen, 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.
When R ⁴ is a heteroatom-containing hydrocarbon group, it is desirable to select from the examples in the case where 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 formula, R ⁵ represents a hydrocarbon group. The hydrocarbon groups that can be used as R ⁵ are generally those 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 and an ethyl group, a branch represented by an i-propyl group and a t-butyl group. And the like, and the like. 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.

などを挙げることが出来る。
これらの有機ケイ素化合物類は単独で用いるだけでなく、複数の化合物を併用することも出来る。 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 alone or in combination with a plurality of compounds.

..Compound having at least two ether bonds As a compound having at least two ether bonds, which is a component of the Ziegler-Natta catalyst suitable for the production of the propylene-ethylene copolymer (B) of the present invention, The compounds disclosed in Japanese Patent No. -294302 and Japanese Patent Laid-Open No. 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
(In the formula, R ⁶ and R ⁷ represent any free radical selected from hydrogen, a hydrocarbon group, and a hetero atom-containing hydrocarbon group. R ⁸ represents a hydrocarbon group or a hetero atom-containing hydrocarbon group.)

In the above formula, R ⁶ represents any free radical selected from hydrogen, 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 alicyclic hydrocarbon group as R ⁶ , and in particular, i-propyl group, i-butyl group, i-pentyl group, cyclopentyl group, cyclohexyl group, It is desirable to use etc.
Two R ⁶ may combine to form one or more rings. In this case, a cyclopolyene structure having 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 formula, R ⁷ represents any free radical selected from hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. Specifically, R ⁷ can be selected from the examples of R ⁶ . Preferably it is hydrogen.
In the 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 hydrocarbon group having 1 to 6 carbon atoms, 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. Further, regardless of whether R ⁶ to R ⁸ are a hydrocarbon group or a heteroatom-containing hydrocarbon group, they may optionally contain a 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 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 include 6-dicyclohexylindene, 1,1-bis (methoxymethyl) benzonaphthene, 7,7-bis (methoxymethyl) -2,5-nobornazene. 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 not only alone but also in combination with a plurality of compounds. Moreover, it may be the same as or different from the polyvalent ether compound used as the optional component (A1d) in the solid component (A1).

-Amount of catalyst constituent used The amount of each constituent 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) (mole number of the organosilicon compound (a3a) / mole number of titanium atoms). ), Preferably in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 500.
When the compound (a3b) having at least two ether bonds is used as the electron donor (a3), the amount used is the molar ratio with respect to the titanium component constituting the solid component (a1) (mole of the compound having at least two ether bonds). Number / number of moles of titanium atoms), preferably in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 500.

-Prepolymerization The catalyst illustrated above may be prepolymerized before using it by this superposition | polymerization. Prior to the polymerization process, a small amount of polymer is generated around the catalyst in advance, so that 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, divinyl benzenes, 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-mentioned monomer are not particularly limited, but are generally preferably within the following ranges.
The amount of prepolymerization is within 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 during the 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. Moreover, it can wash | clean with inert solvents, such as hexane and heptane, after preliminary polymerization.

2. Production method of propylene-ethylene copolymer (B) Next, the production method of the propylene-ethylene copolymer (B) of the present invention will be described in detail.
The propylene-ethylene copolymer (B) in the present invention has a propylene-based polymer component (B1) having a characteristic (B1-i) of 65 to 95 wt% and characteristics (B2-i) to (B2-ii). Propylene-ethylene copolymer component (B2) comprising 5 to 35 wt%, and in the production of propylene-ethylene copolymer (B), a propylene-based polymer component It is necessary to produce two polymer components, (B1) and a propylene-ethylene copolymer component (B2). Both polymer components can be produced separately and then blended, but the propylene-ethylene copolymer component (B2) having a relatively high molecular weight and low viscosity and MFR can be used as a propylene-based polymer. Produced by multi-stage polymerization (hereinafter also referred to as “sequential polymerization”) from the viewpoint of neatly dispersing in the combined component (B1) to express the original performance of the propylene-ethylene copolymer (B). It is better to do.

-Multistage polymerization The multistage polymerization as a desirable method for producing the propylene-ethylene copolymer (B) is a process for producing the component (B1) (hereinafter referred to as B1 production process) and a process for producing the component (B2) ( Hereafter, if it is multistage polymerization which has B2 manufacturing process), the front and back of B1 manufacturing process and B2 manufacturing process will not ask | require.
It is desirable to polymerize the propylene-ethylene copolymer component (B2) in the B2 production step after polymerizing the propylene-based polymer component (B1) in the B1 production step. Although it is possible to reverse the production order, the propylene-ethylene copolymer component (B2) has an ethylene content E (B2) in the copolymer of 8 to 25 wt% from the definition of (B2-i). Because it is a polymer with low crystallinity or no crystallinity, if it is manufactured in the first step, it may cause manufacturing troubles such as adhering inside the polymerization tank or clogging the transfer pipe. There is.
When performing multistage 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 polymer component (B1) and the propylene-ethylene copolymer component (B2) are individually polymerized using a single polymerization reactor by changing the polymerization conditions with time. 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 the continuous method, it is necessary to use a production facility in which two or more polymerization reactors are connected in series because the propylene polymer component (B1) and the propylene-ethylene copolymer component (B2) need to be individually polymerized. is there. The polymerization reactor corresponding to the step of producing the propylene-based polymer component (B1) and the polymerization reactor corresponding to the step of producing the propylene-ethylene copolymer component (B2) must be in series. A plurality of polymerization reactors may be connected in series and / or in parallel for each of the B1 production process and the B2 production process.

.. 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 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, the bulk polymerization method will be referred to as a bulk method according to the practice in the art. In the case of the batch method, the first step may be performed by the bulk method and the second step may be performed by the vapor phase method. This case is also referred to as the bulk method. As described above, the reaction phase is not particularly limited, but the slurry method has a problem that the production cost increases in general because there are many auxiliary facilities because an organic solvent such as hexane and heptane is used. 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, the present invention does not limit the particular process species in this respect.

..General polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within the usual temperature range. Specifically, a range of 0 ° C to 200 ° C, preferably 40 ° C to 100 ° C can be used.
The polymerization pressure varies depending on the process to be selected, but 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.
In the step of producing the propylene-ethylene copolymer component (B2), a polymerization inhibitor such as ethanol or oxygen can be added. When such a polymerization inhibitor is used, not only the polymerization amount in the B2 production process can be easily controlled, but also the properties of the polymer particles can be improved.

3. Next, a method for controlling the index of the propylene-ethylene copolymer (B) will be described in detail.

-Index control method of propylene-based polymer component (B1) First, the ethylene content, but as described above, the ethylene content of the propylene-based polymer component (B1) is 0 to 6.0 wt%, more preferably 0.5 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 component (B1) 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 (B1) varies depending on the type of catalyst used, but the desired amount can be adjusted by adjusting the supply amount ratio. Obtaining a propylene-based polymer component (B1) having an ethylene content is very easy for those skilled in the art.

  Next, MFR will be described. The MFR (B1) of the propylene-based polymer component (B1) is not particularly limited, but as a means for controlling the MFR (B) of the propylene-ethylene copolymer (B) as described later, The MFR (B1) of the combined component (B1) may be controlled. The MFR (B1) of the propylene polymer component (B1) 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 (B1) of the propylene polymer component (B1) 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.

-Index control method for propylene-ethylene copolymer component (B2) The propylene-ethylene copolymer component (B2), which is a constituent component of the propylene-ethylene copolymer (B), has an ethylene content E in the copolymer. (B2) is in the range of 8 to 25 wt%, and the MFR (B2) 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 similarly to the propylene polymer component (B1).

-Index control method for propylene-ethylene copolymer (B) The propylene-ethylene copolymer (B) has an ethylene content E (B) in the copolymer in the range of 0.4 to 13 wt%. The MFR (B) of the polymer is in the range of 0.5 to 20 g / 10 min, and the propylene-based polymer component (B1) is 65 to 95 wt% and the propylene-ethylene copolymer component (B2) is 5 to 35 wt%. It consists of Accordingly, items to be considered in controlling the index of the propylene-ethylene copolymer (B) are the ethylene content E (B), MFR (B), the propylene-based polymer component (B1) and the propylene-ethylene copolymer. There are three weight ratios of the polymer component (B2).

First, the control method of the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) will be described.
The weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) is the production amount in the first step for producing the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2). ) Is controlled by the manufacturing amount in the second step of manufacturing. For example, in order to increase the amount of the propylene-based polymer component (B1) and decrease the amount of the propylene-ethylene copolymer component (B2), the production amount of the second step is maintained while maintaining the production amount of the first step. What is necessary is just to reduce the residence time of a 2nd process, or just to reduce polymerization temperature. It can also 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 (B1) and the propylene-ethylene copolymer component (B2) is the production amount in the first step for producing the propylene-based polymer component (B1) and propylene-ethylene. It is defined by the production amount in the second step for producing the copolymer component (B2). The formula is shown below.
Weight of component (B1): Weight of component (B2) = W (B1): W (B2)
W (B1) = Production amount of the first step / (Production amount of the first step + Production amount of the second step) × 100
W (B2) = Production amount of the second step / (Production amount of the first step + Production amount of the second step) × 100
W (B1) + W (B2) = 100
(W (B1) and W (B2) are weight ratios of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) in the propylene-ethylene copolymer (B), respectively. )

In an industrial production facility, the production amount is usually obtained from the heat balance and material balance of each polymerization tank. In addition, when the crystallinity of the propylene polymer component (B1) and the propylene-ethylene copolymer component (B2) 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. Glokner, J. et al. Appl. Polym. Sci: Appl. Poly. Symp. 45, 1-24 (1990), L .; Wild, Adv. Polym. Sci. 98, 1-47 (1990), J .; B. P. Soares, A .; E. Detailed measurement methods are shown in documents such as Hamielec, Polymer; 36, 8, 1639-1654 (1995).

Next, a method for controlling the ethylene content E (B) will be described. Since the propylene-ethylene copolymer (B) is a mixture of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2), the following relational expression is established between the respective ethylene contents. To do.
E (B) = E (B1) × (W (B1) ÷ 100) + E (B2) × (W (B2) ÷ 100)
This formula shows the material balance regarding ethylene content. As described above, since the ethylene content E (B2) of the propylene-ethylene copolymer component (B2) is defined by the following formula, the above formula is merely a modification of the formula used for the definition. .
E (B2) =
{E (B) −E (B1) × (W (B1) ÷ 100)} ÷ (W (B2) ÷ 100)
Therefore, if the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) is determined, that is, if W (B1) and W (B2) are determined, E (B) is E (B It is uniquely determined by B1) and E (B2). That is, E (B) is controlled by controlling the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2), and the three factors E (B1) and E (B2). I can do it. For example, in order to increase E (B), E (B1) may be increased or E (B2) may be increased. If it is noted that E (B2) is higher than E (B1), it can be easily understood that W (B1) may be reduced and W (B2) may be increased. The reverse control method is the same.

  It is to be noted that E (B) and E (B1) can actually obtain the measured values directly, and E (B2) is calculated using the measured values of both. Therefore, if an operation to increase E (B2), 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 (B), it is directly confirmed as a measured value. What can be done is E (B), not E (B2), but it is obvious that the reason why E (B) increases is that E (B2) increases.

Finally, a method for controlling MFR (B) will be described. Similar to the ethylene content E (B), the following relational expression holds for MFR (B).
log _e [MFR (B)] = (W (B1) ÷ 100) × log _e [MFR (B1)] + (W (B2) ÷ 100) × log _e [MFR (B2)]
(Where log _e is the logarithm with e as the base)
This formula is an empirical formula called the logarithm addition law of viscosity, and is used routinely in the industry. As described above, since the MFR (B2) of the propylene-ethylene copolymer component (B2) is defined by the following formula, the above formula is merely a modification of the formula used for the definition.
MFR (B2) = exp {(log _e [MFR (B)] − (W (B1) ÷ 100) × log _e [MFR (B1)]) ÷ (W (B2) ÷ 100)

  In any case, the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2), MFR (B), MFR (B1), and MFR (B2) are not independent. Therefore, in order to control MFR (B), the weight ratio of propylene-ethylene copolymer component (B2), MFR (B1), and MFR (B2) may be controlled. For example, in order to increase MFR (B), MFR (B1) may be increased or MFR (B2) may be increased. Further, since MFR (B2) is equal to or less than MFR (B), it is understood that MFR (B2) is equal to or less than MFR (B1). However, when MFR (B2) is lower than MFR (B1), W ( It can be easily understood that MFR (B) can be increased even if B1) is increased and W (B2) is decreased. The reverse control method is the same.

  It is to be noted that MFR (B) and MFR (B1) can actually obtain the measured values directly, and MFR (B2) is calculated using the measured values of both. Therefore, if an operation to increase MFR (B2), that is, an operation to increase the amount of hydrogen supplied to the second step is selected as a means when performing an operation to increase MFR (B), it is directly confirmed as a measured value. What can be done is MFR (B) and not MFR (B2), but it is obvious that the reason why MFR (B) increases is that MFR (B2) increases.

3. Propylene Polymer Resin Composition The propylene polymer resin composition of the present invention is based on a total of 100 parts by weight of (A) and (B), and 97 to 65 parts by weight of propylene polymer (A) and propylene-ethylene. It contains 3 to 35 parts by weight of copolymer (B). When the amount is outside this range, that is, when the amount of the propylene polymer (A) exceeds 97 parts by weight, the high molecular weight component (B2) contained in the propylene polymer resin composition is insufficient, so that the extrusion characteristics are reduced. As a result, the surface becomes rough, and as a result, a molded article having an excellent appearance cannot be obtained. On the other hand, when the amount of the propylene polymer (A) is less than 65 parts by weight, the high molecular weight component (B2) contained in the propylene polymer resin composition is excessively contained and dispersibility with other components is increased. As a result, a streak-like pattern caused by inferiority is scattered, resulting in a molded article having an inferior appearance.
From the above viewpoints, it is necessary that the propylene polymer (A) is 97 to 65 parts by weight and the propylene-ethylene copolymer (B) is 3 to 35 parts by weight, and the propylene polymer (A) 95 to 70. More preferred are 5 parts by weight and 5 to 30 parts by weight of the propylene-ethylene copolymer (B).

  The propylene polymer resin composition of the present invention is a composition comprising the above-mentioned propylene polymer (A) and propylene-ethylene copolymer (B) as essential components, but does not impair the effects of the present invention. Thus, various components can be added and used.

(1) Other Additives To the propylene polymer resin composition of the present invention, additives such as an antioxidant that can be added to the propylene resin can be appropriately added 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 (BASF Japan) And trade name “IRGANOX 1010”) and n-octadecyl-3- (4′-hydroxy-3,5′-di-t-butylphenyl) propionate (trade name “IRGANOX 1076” manufactured by BASF Japan). Phenol stabilizers such as bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl) phosphite, Lubricants represented by higher fatty acid amides and higher fatty acid esters, glycerin esters and sorbita of fatty acids having 8 to 22 carbon atoms Antistatic agents such as acid esters and polyethylene glycol esters, antiblocking agents represented by silica, calcium carbonate, talc and the like may be added.

(2) Other polymers As long as the effects of the present invention are not hindered, modifiers such as elastomers and alicyclic hydrocarbon resins that can be added to the propylene resin are appropriately added to the propylene polymer resin composition of the present invention. be able to.
Specifically, ethylene-α-olefin copolymers, for example, polyethylene resins represented by low density polyethylene, high density polyethylene, and the like, binary random copolymers of propylene and α-olefins having 4 to 12 carbon atoms. Examples thereof include a 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. For example, a binary random copolymer resin of propylene and butene is sold under the trade name “Toughmer XM” by Mitsui Chemicals, and may be used as appropriate. 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. “Kuraton G” from Japan Co., Ltd., “Tough Tech” from Asahi Chemicals Co., Ltd., “Septon” from Kuraray Co., Ltd. as a hydrogenated styrene-isoprene block copolymer. From Kuraray Co., Ltd. as a hydrogenated product of styrene-vinylated polyisoprene block copolymer, and from JSR Co., Ltd. as a hydrogenated product of styrene-butadiene random copolymer. It is sold under the trade name “Dynaron” and is used by appropriately selecting from these product groups. It may be.

(3) Production method of composition The propylene-based polymer resin composition of the present invention comprises the above-mentioned propylene-based polymer (A), propylene-ethylene copolymer (B) and other additives and / or as required. Alternatively, the elastomer is obtained by mixing the elastomer with a Henschel mixer, a v-blender, a ribbon blender, a tumbler blender or the like and then kneading the elastomer with a kneader such as a single-screw extruder, a multi-screw extruder, a kneader, or a Banbury mixer.

4). Molded body The propylene polymer resin composition of the present invention is molded into various molded bodies. The molding method is not particularly limited, and includes known molding methods such as extrusion molding, injection molding, blow molding, extrusion blow molding, injection blow molding, inflation molding, mold stamping molding, and the like. Thus, an extrusion molded body, an injection molded body, a blow molded body, an extrusion blow molded body, an injection blow molded body, an inflation molded body, a mold stamping molded body, and the like are obtained.
The shape and product type of the molded body are not particularly limited, and examples include a sheet, a film, a pipe, a hose, a wire coating, a filament, and the like, preferably a sheet and a film, and more preferably a sheet.

5. Film or sheet The propylene-based polymer resin composition of the present invention has improved extrusion characteristics of the propylene-ethylene copolymer obtained by the metallocene-based catalyst, and increases the amount of extrusion during extrusion and the die exit width. It is possible to suppress the occurrence of surface roughness called melt fracture or shark skin even under molding conditions that are superior in productivity and performance such as narrowing of the extrusion and lowering of the extrusion temperature.
A film or sheet obtained from such a composition (hereinafter, also referred to as “film”) has a good appearance and excellent transparency, high rigidity, and blocking does not deteriorate. The excellent properties of the propylene-ethylene copolymer by the metallocene catalyst are maintained at a high level.

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 made of the propylene-based polymer 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 be used 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 a cellophane, paper, woven fabric, paperboard, aluminum foil, nylon 6, nylon 66, or other polyamide resin film, 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 substrate such as a polyester resin film or a stretched polypropylene film.

  EXAMPLES The present invention will be specifically described below 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) Methods for measuring 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: GSX-400 manufactured by JEOL Ltd. or equivalent device (carbon nuclear resonance frequency of 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 spectrum may be assigned with reference to Macromolecules 17, 1950 (1984), for example. The attribution of spectra measured under the above conditions is as shown in Table 1 below. Table 1 Symbols such as S _{alpha alpha} in accordance with notation Carman et al (Macromolecules 10,536 (1977)), P represents respectively the methyl carbon, S is methylene carbon, T is a methine carbon.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six kinds of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. As described in Macromolecules 15, 1150 (1982), 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 include these peaks derived from heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from heterogeneous bonds, and the amount of heterogeneous bonds is small. Therefore, the ethylene content E (A) of the propylene-based polymer (A) is the same as in the analysis of the copolymer produced with a Ziegler-Natta catalyst substantially free of heterogeneous bonds. It is determined using the relational expression (7).
Conversion from mol% to wt% of ethylene content is performed using the following formula.
Ethylene content (wt%) =
(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, number average molecular weight Mn, and weight average molecular weight Mw
It is a value obtained by measurement by gel permeation chromatography (GPC) method, and is specifically determined as follows.
Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
The standard polystyrene used is 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 viscosity equation [η] = K × M ^α used for conversion to molecular weight uses the following numerical values.
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]
Preparation of pre-polymerization catalyst (chemical treatment of silicate)
To a 10-liter glass separable flask with a stirring blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). 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.

(Drying silicate)
The silicate previously chemically treated was dried with a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical inner diameter 50mm Heating zone 550mm (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)

(Preparation of catalyst)
20 g of dry silicate was introduced into a glass reactor equipped with a stirring blade with an internal volume of 1 liter, 116 ml of mixed heptane and 84 ml of a heptane solution of triethylaluminum (0.60 M) were added, and the mixture was stirred 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.

(Prepolymerization / 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 by 240 ml. Subsequently, 0.95 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 560 ml of mixed heptane were further added, stirred for 30 minutes at 40 ° C., allowed to stand for 10 minutes, and then 560 ml of the supernatant was removed. This operation was further repeated 3 times. When the component analysis of the final supernatant was performed, the concentration of the organoaluminum component was 1.23 mmol / liter and the Zr concentration was 8.6 × 10 ⁻⁶ g / L. 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.

Using this prepolymerized catalyst A, a propylene-ethylene copolymer (A) was produced according to the following procedure.
Propylene-ethylene random copolymer After the inside of the stirring autoclave with an internal volume of 200 liters is sufficiently substituted with propylene, 470 ml of triisobutylaluminum (50 g / L) heptane solution (23.5 g as triisobutylaluminum), 45 kg of liquefied propylene, Hydrogen 4NL and ethylene 1900g 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 polymer yield of PP (A-1) thus obtained was 20 kg, and the catalyst activity (value obtained by dividing the polymer yield by the amount of catalyst) was 100 kg-PP / g-catalyst.
Table 3 shows the results of analyzing the obtained PP (A-1).

[Production Examples A-2 to A-5 and A-7 to A-9]
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).
The results are shown in Table 3.

[Production Example A-6]
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 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.
Table 3 shows the results of analyzing the obtained PP (A-1) to PP (A-9).

2. Propylene-ethylene copolymer (B)
(1) Measuring method of physical properties of propylene-ethylene copolymer (B) (1-1) Ethylene content E (B1), E (B)
Ethylene content E (B1) in the polymer component (B1) extracted from the polymerization tank after the first step of sequential polymerization, and ethylene content in the propylene-ethylene copolymer (B) obtained after the second step The amount E (B) was measured by ¹³ C-NMR as described above.

(1-2) MFR (B1), MFR (B)
The MFR (B1) of the propylene-ethylene copolymer (B1) obtained after the first step and the MFR (B) of the propylene-ethylene copolymer (B) obtained after the second step are the propylene described above. It measured by the same method as the measuring method of MFR of a system polymer (A).

(1-3) Specification of Weight Ratio W (B1) and W (B2) of Each Component As described above, the weight ratio (%) of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2). ) Is defined by the following equation.
W (B1) = Production amount of the first step / (Production amount of the first step + Production amount of the second step) × 100
W (B2) = Production amount of the second step / (Production amount of the first step + Production amount of the second step) × 100

As described in [Production Example B-1] described later, when the propylene-ethylene copolymer (B) is produced, after the first step of producing the propylene-based polymer component (B1) is completed. The polymer obtained in (1) was once withdrawn into a flask, and the yield in the first step was measured. After separating 10 g of the obtained propylene polymer component (B1) as a sample, the rest was filled in the polymerization tank, and the second step of producing the propylene-ethylene copolymer component (B2) was performed. . After the second step was finished, the yield of the resulting propylene-ethylene copolymer (B) was measured. From this result, the manufacturing amount of the first step and the manufacturing amount of the second step were calculated by the following formulas, and W (B1) and W (B2) 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 the second step =
[Yield of propylene-ethylene copolymer (B)]-[Production amount of first step]

(1-4) Ethylene content E (B2) in propylene-ethylene copolymer component (B2)
The ethylene content E (B2) in the copolymer component (B2) is obtained by using the above-described ethylene contents E (B1) and E (B) and the respective component amounts W (B1) and W (B2). It was calculated from the following formula.
E (B2) =
{E (B) −E (B1) × (W (B1) ÷ 100)} ÷ (W (B2) ÷ 100)

(1-5) Melt flow rate MFR (B2) of copolymer component (B2)
The MFR (B2) of the copolymer component (B2) was calculated from the following formula using the above-described MFR (B1) and MFR (B), and W (B1) and W (B2).
MFR (B2) = exp {(log _e [MFR (B)] − (W (B1) ÷ 100) × log _e [MFR (B1)]) ÷ (W (B2) ÷ 100)}
(Where log _e is the logarithm with e as the base)

(2) Production of propylene-ethylene copolymer (B) [Production Example B-1]
Analysis of catalyst composition-Ti content:
The sample was accurately weighed, hydrolyzed, and measured using a colorimetric method. About the sample after preliminary polymerization, content was calculated using the weight remove | excluding the preliminary polymerization 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 comparing 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.

Preparation of prepolymerization catalyst (1) Preparation of solid component A 10 L autoclave equipped with a stirrer was sufficiently substituted 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 wt%.

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 .

(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 further continued for 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 C. This prepolymerized catalyst C contained 2.5 g of polypropylene per 1 g of the solid catalyst. As a result of analysis, the portion of the prepolymerization catalyst C excluding polypropylene contained 1.0 wt% Ti and 8.3 wt% t-BuMeSi (OMe) ₂ .
Using this prepolymerized catalyst C, a propylene-ethylene copolymer (B) was produced according to the following procedure.

Production of Propylene-Ethylene Copolymer (B) First Step: Production of Propylene Polymer Component (B1) After fully substituting an autoclave with an internal volume of 3 L having a stirring and temperature control device with propylene, n of Et ₃ Al -550 mg of a heptane dilution as Et ₃ Al was added, 15 NL of hydrogen, 10.5 g of ethylene, and then 750 g of liquid propylene were introduced, and the temperature was raised to 60 ° C and maintained at that temperature. The above prepolymerized catalyst C was slurried with n-heptane, and 9 mg of a solid catalyst (excluding the weight of the prepolymerized polymer) was injected 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 2L glass flask fully substituted with nitrogen in advance, and extract the entire amount of the propylene polymer component (B1) polymer obtained in the first step into this flask through a Teflon tube under a nitrogen stream. It was. As a result of weighing, 252 g of the propylene polymer component (B1) obtained in the first step was obtained. Of these, 10 g was separated and used for analysis.

Second step: Production of propylene-ethylene copolymer component (B2) After the first step was completed, 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. Thereafter, of the 252 g of the propylene polymer component (B1) obtained in the first step, the remaining 242 g obtained by separating 10 g for analysis was filled in an autoclave through a Teflon tube under a nitrogen stream.
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 (B) was obtained. Of these, 242 g was the propylene-based polymer component (B1), so the obtained propylene-ethylene copolymer component (B2) was 60 g. As a result of calculating the weight ratio of the propylene-based polymer component (B1) and the propylene-ethylene copolymer component (B2) based on these yield values, W (B1) was 80 wt% and W (B2) was 20 wt%. It became.
The propylene-based polymer component (B1) separated for analysis after the end of the first step and the propylene-ethylene copolymer (B) obtained after the end of the second step are analyzed, and the ethylene content E (B1) , E (B), MFR (B1), MFR (B) values were obtained.
The results are shown in Table 4. Further, E (B2) and MFR (B2) were calculated using the values of W (B1), W (B2), E (B1), E (B), MFR (B1), and MFR (B). These values are also shown in Table 4.

[Production Examples B-2 to B-6]
A propylene-ethylene copolymer (B) was produced in the same manner as in Production Example B-1, except that the polymerization conditions described in Table 4 were used. The results are shown in Table 4.

[Production Example B-7]
Propylene-ethylene copolymer (B) in the same manner as in Production Example B-1, except that hydrogen is 25 NL, ethylene is 20 g, and the prepolymerized catalyst C is a solid catalyst (excluding the weight of the prepolymerized polymer) and is 8 mg. However, after the first step, the propylene-based polymer component (B1) could not be extracted with a Teflon tube, and the propylene-ethylene copolymer (B) could not be produced. When the autoclave was opened, most of the propylene polymer component (B1) formed a lump inside. When a part of the lump was sampled and analyzed, the ethylene content was 7 wt% and the MFR was 20 g / 10 min.

[Production Examples B-8 to B-13]
A propylene-ethylene copolymer (B) was produced in the same manner as in Production Example B-1, except that the polymerization conditions shown in Table 5 were used.
The results are shown in Table 5.

[Production Examples B-14 to B-20]
A propylene-ethylene copolymer (B) was produced in the same manner as in Production Example B-1, except that the polymerization conditions shown in Table 6 were used. The results are shown in Table 6.

[Production Examples B-21 to B-24]
A propylene-ethylene copolymer (B) was produced in the same manner as in Production Example B-1, except that the polymerization conditions described in Table 7 were used. At this time, in Production Example B-21, only the first step was performed and the second step was not performed.
The results are shown in Table 7.

[Production Examples B-25 to B-31]
A propylene-ethylene copolymer (B) was produced in the same manner as in Production Example B-1, except that the polymerization conditions shown in Table 8 were used.
The results are shown in Table 8.

Example 1
1. Formulation PP (A-1) obtained in Production Example A-1 as a propylene polymer (A), PP (B-1) obtained in Production Example B-1 as a propylene-ethylene copolymer (B) Are weighed to be 95 wt% and 5 wt%, respectively, and put into a Henschel mixer. Then, with respect to 100 parts by weight of the mixture of propylene polymer (A) and propylene-ethylene copolymer (B), Antioxidants and neutralizers were added in the following amounts and mixed thoroughly.
·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 (manufactured by BASF Japan, trade name “Irgaphos 168”) 500 wtppm
・ Neutralizing agent: Calcium stearate 500wtppm

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-based polymer resin composition raw material pellet.

3. Film molding The resulting propylene-based polymer 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 was raised to 180 ° C. and the lip width was 150 mm. It was introduced into a single-layer T die adjusted to an opening of 0.8 mm and melt extrusion was performed. The shear rate at the die wall surface was calculated by the following 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.

式（１）中、それぞれ以下を意味する。

In formula (1), the following are meant respectively.

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.
Film obtained by 10 persons visually observing the obtained unstretched film and judged by 8 or more people as not having a wave pattern. △, and the film which 6 or more determined to have a wave pattern was determined to be ×. ○ and △ are at a level where there is no practical problem. In addition, the film of X was inferior in a see-through feeling.

(2) Oriented crystal Oriented crystal is a phenomenon in which a lump of crystal structure (white spots) visible at the exit of a die is scattered and the entire film becomes cloudy. When orientation crystallization is extremely promoted, the draft ratio (ratio between the cooling roll winding speed and the resin discharge speed) is increased to 1.5 or more because a solid-liquid phase separation state is exhibited at the die outlet. Then, a crack occurs in the liquid phase portion, and the film is perforated or broken.
10 people visually observe the obtained unstretched film, and 8 or more people judge that no white spots or cloudiness is generated. ○ 5 to 7 people have white spots or cloudiness. The film judged not to be Δ, and the film judged that 6 or more people had white spots or cloudiness were judged as x. ○ and △ are at a level where there is no practical problem. In addition, some of the X films were perforated or broken.

(3) Fish Eye (FE)
The appearance of the obtained unstretched film was visually observed to confirm the presence or absence of fish eyes. A product having almost no fish eye and excellent in appearance was evaluated as ◯, a product in which some fish eyes were confirmed was evaluated as Δ, and a product having a large number of fish eyes and extremely in appearance was determined as ×.

(4) Dispersed state When the dispersed state of the resin is inferior, several stripes are generated in the film flow direction.
A film in which the appearance of the obtained unstretched film was visually observed by 10 people, and 8 or more people determined that no streaks occurred. △, and the film which 6 or more people judged to have a streak as a whole was judged as x. ○ and △ are at a level where there is no practical problem.

5. Film physical property evaluation (1) HAZE (transparency) measurement Based on JIS K7136-2000, it measured with the haze meter by 1 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) Heat seal temperature (HS temperature)
Using a heat seal bar of 10 mm × 200 mm, the obtained unstretched films were melt-extruded in a range of 80 ° C. to 170 ° C. under a heat seal condition of pressure 1 kg / cm ² and time 1 second (MD). A sample having a width of 15 mm was cut out from the sample sealed so as to be vertical, and separated by a tensile tester at a pulling speed of 500 mm / min, and a temperature at which a strength of 300 g was obtained was obtained.

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

(Examples 2 to 5)
Except for changing the ratio of the propylene polymer (A) and the propylene-ethylene copolymer (B) as shown in Table 9, blending, granulation, molding, appearance evaluation, and physical properties were performed in the same manner as in Example 1. Evaluation was performed. The results are shown in Table 9.
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)
Except for changing the ratio of the propylene polymer (A) and the propylene-ethylene copolymer (B) as shown in Table 9, blending, granulation, molding, appearance evaluation, and physical properties were performed in the same manner as in Example 1. Evaluation was performed. The results are shown in Table 9.
In Comparative Examples 1 and 2, since the blending amount of the propylene-ethylene copolymer (B) was insufficient, remarkable surface roughness occurred, and thus a film that could withstand evaluation could not be obtained. In Comparative Example 3, the blending amount of the propylene-ethylene copolymer (B) 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 13)
The propylene polymer (A) of Example 1 was changed to PP (A-2) to PP (A-9) obtained in Production Examples A-2 to 9, and the propylene polymer (A), propylene- Except that the ratio of the ethylene copolymer (B) 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 10.
All the evaluation results were satisfactory results.

(Examples 14 to 18)
The propylene-ethylene copolymer (B) of Example 1 was changed to PP (B-2) to PP (B-6) obtained in Production Examples B-2 to 6, and the propylene-based polymer (A), Compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1 except that the ratio of the propylene-ethylene copolymer (B) was 90:10. The results are shown in Table 11.
All the evaluation results were satisfactory results.

(Examples 19 to 22)
The propylene-ethylene copolymer (B) of Example 1 was changed to PP (B-9) to PP (B-12) obtained in Production Examples B-9 to 12, and the propylene-based polymer (A), Compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1 except that the ratio of the propylene-ethylene copolymer (B) was 90:10. The results are shown in Table 12.
In Example 19, white spots caused by oriented crystals were slightly observed, but the level was satisfactory for use. In Example 22, the surface was slightly rough, but it was at a level where there was no problem in use. Otherwise, all the evaluation results were satisfactory.

(Comparative Examples 4-5)
The propylene-ethylene copolymer (B) of Example 1 was changed to PP (B-8) and PP (B-13) obtained in Production Examples B-8 and B-13, and a propylene polymer (A ), Propylene-ethylene copolymer (B), except that the ratio was 90:10, the same as in Example 1, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed.
In Comparative Example 4, an extremely oriented crystal was exhibited, and tearing occurred at the die outlet, so that a film could not be obtained. In Comparative Example 5, since the surface roughness was remarkably generated, a film that could withstand the evaluation could not be obtained. The results are shown in Table 12.

(Examples 23 to 28)
The propylene-ethylene copolymer (B) of Example 1 was changed to PP (B-14) to PP (B-19) obtained in Production Examples B-14 to 19, and the propylene-based polymer (A), Compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1 except that the ratio of the propylene-ethylene copolymer (B) was 90:10. The results are shown in Table 13.
In Example 23, white spots caused by oriented crystals were slightly observed, but the level was not problematic in use. In Example 28, although the surface was slightly roughened, it was at a level that does not cause a problem in use. Otherwise, all the evaluation results were satisfactory.

(Comparative Example 6)
Propylene-ethylene copolymer (B) of Example 1 was changed to PP (B-20) obtained by B-20, and the ratio of propylene-based polymer (A) and propylene-ethylene copolymer (B) The composition, granulation, molding, appearance evaluation, and physical property evaluation were carried out in the same manner as in Example 1 except that the ratio was 90:10.
Since the surface roughness was remarkable, a film that could withstand the evaluation could not be obtained.
The results are shown in Table 13.

(Examples 29 to 30)
The propylene-ethylene copolymer (B) of Example 1 was changed to PP (B-22) to PP (B-23) obtained in Production Examples B-22 to 23, and the propylene-based polymer (A), Compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1 except that the ratio of the propylene-ethylene copolymer (B) was 90:10. The results are shown in Table 14.
All the evaluation results were satisfactory results.

(Comparative Examples 7-8)
The propylene-ethylene copolymer (B) of Example 1 was changed to PP (B-21) and PP (B-24) obtained in Production Examples B-21 and B-24, and a propylene polymer (A ), Propylene-ethylene copolymer (B), except that the ratio was 90:10, the same as in Example 1, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed. The results are shown in Table 14.
In Comparative Example 7, since the surface roughness was remarkable, a film that could withstand the evaluation could not be obtained. In Comparative Example 8, the copolymer component (B2) contained in the propylene-ethylene copolymer (B) is excessive, streaks due to the deterioration of the dispersion state are scattered, and a film that can withstand evaluation cannot be obtained. It was.

(Examples 31-35)
The propylene-ethylene copolymer (B) of Example 1 was changed to PP (B-26) to PP (B-30) obtained in Production Examples B-26 to 30, and the propylene-based polymer (A), Compounding, granulation, molding, appearance evaluation, and physical property evaluation were performed in the same manner as in Example 1 except that the ratio of the propylene-ethylene copolymer (B) was 90:10. The results are shown in Table 15.
In Example 35, a slight amount of fine fish eyes due to poor dispersion of the high molecular weight component was observed, but the level was satisfactory for use. Otherwise, all the evaluation results were satisfactory.

(Comparative Examples 9 to 10)
The propylene-ethylene copolymer (B) of Example 1 was changed to PP (B-25) and PP (B-31) obtained in Production Examples B-25 and B-31, and a propylene polymer (A ), Propylene-ethylene copolymer (B), except that the ratio was 90:10, the same as in Example 1, blending, granulation, molding, appearance evaluation, and physical property evaluation were performed. The results are shown in Table 15.
In Comparative Example 9, since the MFR (B) of the propylene-ethylene copolymer (B) is low, the dispersibility with the propylene-based polymer (A) is inferior. A film that could withstand the evaluation could not be obtained. Comparative Example 10 is a film that can withstand evaluation because fish eyes caused by high molecular weight gel are remarkably generated due to a large difference between MFR (B1) and MFR (B2) in propylene-ethylene copolymer (B). Could not get.

  Comparing each of the above examples and comparative examples in comparison, the use of a novel propylene polymer resin composition satisfying the respective regulations in the present invention results in excellent extrusion characteristics and extrusion molding at a low temperature of about 180 ° C. However, it is possible to obtain a film that exhibits excellent characteristics such as surface roughness and white defects caused by oriented crystals, excellent transparency, high rigidity, and excellent heat seal characteristics. I understand that.

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

式（１）中、それぞれ以下を意味する。

In formula (1), the following are meant respectively.

Claims (5)

97 to 65 parts by weight of a propylene-based polymer (A) having the following characteristics (Ai) to (A-iii) produced by a metallocene catalyst, based on a total of 100 parts by weight of the following (A) and (B) And a propylene-based polymer resin composition containing 3 to 35 parts by weight of a propylene-ethylene copolymer (B) having the following characteristics (Bi) to (B-ii):
The propylene-ethylene copolymer (B) is based on a total of 100% by weight of (B1) and (B2), and a propylene-based polymer component (B1) having the following characteristics (B1-i): A propylene-based polymer resin composition comprising 5 to 35% by weight of a propylene-ethylene copolymer component (B2) having the following characteristics (B2-i) and (B2-ii):
(A-i) The ethylene content E (A) in the polymer (A) is in the range of 0 to 6.0 wt%. (A-ii) The melt flow rate MFR (A) of the polymer (A) is 0. (A-iii) The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn in the GPC measurement of the polymer (A) in the range of 1 to 100 g / 10 min is in the range of 2 to 4 (B-i ) The ethylene content E (B) in the copolymer (B) is in the range of 0.4 to 13 wt%. (B-ii) The melt flow rate MFR (B) of the copolymer (B) is 0.5. (B2-i) copolymer component (B2) in which ethylene content E (B1) in the polymer component (B1) in the range of ˜20 g / 10 min is in the range of 0 to 6.0 wt% ) In which ethylene content E (B2) is in the range of 8 to 25 wt% (B2-ii) The melt flow rate MFR of the body component (B2) (B2) is in the range of 0.0001~0.5g / 10min   The propylene-ethylene copolymer (B) is produced by multistage polymerization of a propylene-based polymer component (B1) and a propylene-ethylene copolymer component (B2). Polymer resin composition.   The propylene-based polymer resin composition according to claim 1 or 2, wherein the propylene-ethylene copolymer (B) is produced by a Ziegler-Natta catalyst.   The film or sheet formed by extrusion-molding the propylene-type polymer resin composition in any one of Claims 1-3.   A laminated film or laminated sheet obtained by laminating the film or sheet according to claim 4 as a surface layer.

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