JP5832098B2 - Application to ethylene polymers and molded products - Google Patents

Description

  The present invention relates to an ethylene polymer that provides a molded article having excellent moldability and excellent mechanical strength and appearance, and a molded article obtained therefrom.

  High-density polyethylene used in a wide range of applications such as films, pipes, and bottle containers has been conventionally produced using Ziegler-Natta catalysts and chromium catalysts. However, due to the properties of these catalysts, there is a limit to the control of the molecular weight distribution and composition distribution of the polymer.

  In recent years, ethylene homopolymers or ethylene / α-olefin copolymers with a relatively low molecular weight have been used with a single-site catalyst or a catalyst with a single-site catalyst supported on a carrier that can easily control the composition distribution. Have disclosed several methods for producing an ethylene polymer having excellent moldability and mechanical strength, including a large ethylene homopolymer or ethylene / α-olefin copolymer, by a continuous polymerization method.

  JP-A-11-106432 discloses a low molecular weight polyethylene and a high molecular weight ethylene / α-olefin copolymer obtained by polymerization using a supported geometrically constrained single site catalyst (CGC / Borate catalyst). A composition prepared by melt blending is disclosed. However, since the molecular weight distribution of the composition is not wide, the fluidity of the composition may be inferior. Further, in the claims of the above publication, the preferred carbon number range of the α-olefin copolymerized with ethylene is not disclosed, but if the carbon number is less than 6, the mechanical strength may not be sufficiently developed. is expected. Furthermore, since the molecular weight distribution (Mw / Mn) of the single-stage polymer is wide, it is expected that the mechanical properties such as impact strength are not sufficient as compared with the narrow molecular weight distribution of the single-stage product. The forecast that the above-mentioned strength is inferior when the composition distribution of the single-stage polymer is wide is that of CMC Publishing Co., Ltd., “Functional Materials”, Cross Separation (CFC) data described on page 50 of the March 2001 issue. This is also clear from the cross fractionation (CFC) data described in FIG. 2 of the Kaihei 11-106432 publication.

WO01 / 25328 discloses an ethylene polymer obtained by solution polymerization using a catalyst system comprising CpTiNP ( ^t Bu) ₃ Cl ₂ and borate or alumoxane. In this ethylene-based polymer, since the component having a low molecular weight is branched, the crystal structure is weak, and therefore, it is expected that the mechanical strength is inferior. Further, since the molecular weight of the low molecular weight component is relatively large, it is expected that the fluidity is inferior. Further, in the claims of the publication, the preferred carbon number range of the α-olefin copolymerized with ethylene is not disclosed, but if the carbon number is less than 6, the mechanical strength may not be sufficiently developed. It is done.

  EP1201711A1 discloses ethylene obtained by slurry polymerization in the presence of a catalyst system consisting of ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and methylalumoxane supported on silica. System polymers are disclosed. Among these ethylene polymers, the single-stage polymer has a wide molecular weight distribution (Mw / Mn), and therefore, it is expected that the impact strength and the like are inferior to those of the single-stage product having a narrow molecular weight distribution. In addition, when the molecular weight distribution is wide, it is presumed that the active species are non-uniform. As a result, there is a concern that the composition distribution is widened and the fatigue strength is lowered. In addition, in some examples of the publication, a single-stage polymer product having a low molecular weight and a single-stage polymer product having a high molecular weight are melt-kneaded. In such a kneading method, a continuous crystal structure exceeding 10 μm is often generated, and it is expected that sufficient strength may not be exhibited.

  JP 2002-53615 discloses an ethylene polymer obtained by slurry polymerization using a catalyst system comprising a zirconium compound having a specific salicylaldimine ligand supported on silica and methylalumoxane. ing. Although the preferred carbon number range of the α-olefin copolymerized with ethylene is not disclosed in the claims of the publication, 1-butene (the number of carbon atoms) used as the α-olefin in the examples of the publication = 4) It is assumed that the ethylene polymer obtained in 4) has a small number of carbon atoms and does not exhibit sufficient mechanical strength.

  In general, an ethylene polymer exhibits a multimodal molecular weight distribution. When the molecular weight difference between the multimodal peaks is large, it is difficult to mix them by melt-kneading, so that multistage polymerization is usually employed. In general, multistage polymerization is often performed continuously. In such a continuous multistage polymerization, the residence time in the polymerization vessel in a polymerization environment that produces a low molecular weight product and the residence time in the polymerization environment in a polymerization environment that produces a high molecular weight product. In general, there is a difference in the molecular weight between particles in the case of a polymerization method in which the polymer takes a particle shape, such as a gas phase method or a slurry method. . Such a difference in molecular weight was recognized even when using a Ziegler catalyst described in Japanese Patent No. 821037, etc., but because the catalyst is multi-site, the molecular weight distribution is wide, and therefore normal melt-kneading. Even in the pelletization by, the polymer particles were well mixed. On the other hand, when a single site catalyst is used, since the molecular weight distribution is narrow, pelletization by ordinary melt-kneading often does not sufficiently mix the polymer particles. Therefore, a history of the shape of the polymer particles remains, which may cause flow disturbance and deteriorate the appearance, or may not exhibit sufficient mechanical strength. Moreover, in such an ethylene polymer, the smoothness coefficient calculated | required from the surface roughness of an extrusion strand tends to become large.

  The ethylene (co) polymer using a Ziegler catalyst described in Japanese Patent No. 821037 and the like has methyl branches in the molecular chain because methyl branches are by-produced during the polymerization. Methyl branching is known to be incorporated into crystals and weaken the crystals (see, for example, Polymer, Vol. 31, page 1999, 1990), which causes the mechanical strength of ethylene (co) polymers. Was lowering. In addition, in the copolymerization of ethylene and α-olefin, a hard and brittle component is formed when almost no α-olefin is contained, whereas when α-olefin is excessively copolymerized, it is soft and has a crystal structure. As a result of generation of weak components, stickiness may be caused. Furthermore, since the molecular weight distribution is wide, there has been a problem that a low molecular weight body exhibits a phenomenon of adhering to the surface of the molded product as a powdery substance.

  In an ethylene polymer obtained by polymerization using a metallocene catalyst described in JP-A-9-183816 and the like, methyl branches are present in the molecular chain as a result of by-production of methyl branches during the polymerization. The methyl branch is incorporated into the crystal and weakens the crystal structure. This has been a cause of lowering the mechanical strength. Further, an ethylene polymer having an extremely large molecular weight has not been disclosed so far.

  The ethylene-based polymer obtained by polymerization using a chromium-based catalyst has long chain branching and thus has a small molecular spread, and therefore has poor mechanical strength. Further, methyl branching was present in the molecular chain because methyl branching was by-produced during the polymerization. The methyl branch is incorporated into the crystal and weakens the crystal structure. This has been a cause of lowering the mechanical strength. In addition, in the case of a copolymer of ethylene and α-olefin, a hard and brittle component is formed when almost no α-olefin is contained, whereas when α-olefin is excessively copolymerized, stickiness may be caused. Or a soft component with a weak crystal structure was formed.

  The ethylene polymer obtained by polymerization using a constrained geometric catalyst (CGC) described in WO 93/08221 and the like has a methyl branch as a by-product during the polymerization, and therefore has a methyl branch in the molecular chain. It was. The methyl branch is incorporated into the crystal and weakens the crystal structure. This has caused a decrease in mechanical strength. Moreover, since the long-chain branching is contained, the molecular spread is small, so that the mechanical strength is insufficient.

  The ethylene polymer obtained by the high-pressure radical polymerization method has methyl branches and long chain branches in the molecular chain because methyl branches and long chain branches are by-produced during the polymerization. The methyl branch is incorporated into the crystal and weakens the crystal strength. This has been a cause of lowering the mechanical strength. In addition, since it contains long-chain branches, the molecular spread is small and the molecular weight distribution is wide, so that the mechanical strength is poor.

  An ethylene-based polymer obtained by low-temperature polymerization using a catalyst containing Ta or Nb complex described in JP-A-6-323323 and the like has a weight average molecular weight (Mw) and a number average molecular weight (Mn) measured by GPC. Since the ratio of (Mw / Mn) is small, the moldability may not be sufficient.

Japanese Patent Laid-Open No. 11-106432 Japanese Patent Laid-Open No. 11-106432 WO01 / 25328 EP1201711A1 Publication JP 2002-53615 A Japanese Patent No. 821037 JP-A-9-183816 WO93 / 08221 Publication Japanese Unexamined Patent Publication No. 6-23723

CMC Publishing Co., Ltd., “Functional Materials”, March 2001, page 50 Polymer, Vol. 31, 1999, 1990

  To provide an ethylene polymer having excellent moldability, particularly excellent mechanical strength, and excellent appearance, particularly a blow molded article, a pipe and a pipe joint.

In view of the prior art, the present inventors have conducted intensive research on an ethylene polymer that can provide a molded article having excellent moldability and excellent mechanical strength. -An ethylene polymer containing 0.01 to 1.20 mol% of structural units derived from olefin, and satisfying at least one of the following (1) or (2) in cross fractionation (CFC) It has been found that (E) provides a molded article having excellent moldability, particularly excellent mechanical strength, and excellent appearance, in particular, a blow molded article, a pipe and a pipe joint, thereby completing the present invention.
(1) The weight average molecular weight (Mw) of the component eluted at 73 to 76 ° C does not exceed 4,000.
(2) The following relational expression (Eq-1) is satisfied.

（Eq-1中、S_xは70〜85℃で溶出する成分に基づく全ピークの面積合計値であり、S_totalは0〜145℃で溶出する成分に基づく全ピークの面積合計値である。）
本発明に係わるエチレン系重合体（E）は、上記要件に加えて、下記(1')〜(7')の要件を全て満たすことが好ましい。
(1') 炭素原子数6〜10のα-オレフィンから導かれる構成単位を0.02〜1.00mol%含む。
(2') 密度（d）が945〜970kg/m³の範囲にある。
(3') 135℃、デカリン中で測定した極限粘度（［η］）が1.6〜4.0（dl/g）の範囲にある。
(4') GPCで測定した重量平均分子量（Mw）と数平均分子量（Mn）の比（Mw/Mn）が5 〜70の範囲にある。
(5') クロス分別（CFC）において、分子量が100,000未満で最も強いピークの頂点の溶出温度をT₁（℃）、分子量が100,000以上で最も強いピークの頂点の溶出温度をT₂（℃）とした場合、（T₁−T₂）（℃）が0〜11℃の範囲にある。
(6') [（T₂−1）〜T₂]（℃）で溶出した画分のGPC曲線の中で、分子量が100,000以上で最も強いピークの頂点の分子量が200,000〜800,000の範囲にある。
(7') 95〜96℃で溶出する成分のGPC曲線のうち分子量が100,000以下の領域において最も強いピークの頂点の分子量が28,000を超えない。

(In Eq-1, S _x is the total area value of all peaks based on the components eluting at 70 to 85 ° C, and S _total is the _total area value of all peaks based on the components eluting at 0 to 145 ° C. )
The ethylene polymer (E) according to the present invention preferably satisfies all the following requirements (1 ′) to (7 ′) in addition to the above requirements.
(1 ′) Containing 0.02 to 1.00 mol% of a structural unit derived from an α-olefin having 6 to 10 carbon atoms.
(2 ′) The density (d) is in the range of 945 to 970 kg / m ³ .
(3 ′) Intrinsic viscosity ([η]) measured in decalin at 135 ° C. is in the range of 1.6 to 4.0 (dl / g).
(4 ′) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC is in the range of 5 to 70.
(5 ') In cross fractionation (CFC), the elution temperature at the peak of the strongest peak with a molecular weight of less than 100,000 is T ₁ (° C), and the elution temperature at the peak of the strongest peak with a molecular weight of 100,000 or more is T ₂ (° C). (T ₁ −T ₂ ) (° C.) is in the range of 0 to 11 ° C.
(6 ') at _{[(T 2 -1) ~T 2} ] (℃) in the eluted fractions by GPC curve, the molecular weight of the apex of the strongest peak at a molecular weight of 100,000 or more is in the range of 200,000～800,000 .
(7 ') The molecular weight of the peak of the strongest peak does not exceed 28,000 in the region where the molecular weight is 100,000 or less in the GPC curve of the component eluted at 95 to 96 ° C.

In the following description, this ethylene polymer may be referred to as an ethylene polymer (E ′).
In addition to the above-mentioned requirements, a more preferred ethylene polymer according to the present invention has the requirement that the number of methyl branches measured by ¹³ C-NMR is less than 0.1 per 1000 carbon atoms (in the following description, (Sometimes called (1 '')). In the following description, such an ethylene polymer may be referred to as an ethylene polymer (E ″).

The particularly preferred ethylene polymer according to the present invention satisfies the following requirements (1 ′ ″) and (2 ″ ′) simultaneously in addition to all the above-mentioned requirements.
(1 ''') When the GPC curve is separated into two lognormal distribution curves, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) of each curve is 1.5 to 3.5, high The weight average molecular weight (Mw ₂ ) of the curve separated on the molecular weight side is 200,000 to 800,000,
(2 ''') The smoothness coefficient R obtained from the surface roughness of the extruded strand does not exceed 20 μm.
In the following description, this ethylene polymer may be referred to as an ethylene polymer (E ′ ″).

When the ethylene polymer (E) of the present invention is applied to a blow molded article, the following requirements (1 _B ) to (3 _B ) must be satisfied at the same time in addition to the above requirements that the ethylene polymer (E) should satisfy. Is preferred.
(1 _B ) 0.02 to 0.20 mol% of structural units derived from an α-olefin having 6 to 10 carbon atoms.
The ratio of (2 _B) weight average molecular weight measured by GPC (Mw) to the number average molecular weight (Mn) (Mw / Mn) is in the range of 5-30.
(3 _B ) In cross fractionation (CFC), the elution temperature at the peak of the strongest peak with a molecular weight of less than 100,000 is T ₁ (° C), and the elution temperature at the peak of the strongest peak with a molecular weight of 100,000 or more is T ₂ (° C). In such a case, (T ₁ −T ₂ ) (° C.) is in the range of 0 to 5 ° C.

In the following description, this ethylene polymer may be referred to as an ethylene polymer (E _B ).
Further, a more preferable ethylene-based polymer for blow molded articles preferably satisfies the following requirements (1 _B ′) and (2 _B ′) in addition to the above requirements (1 _B ) to (3 _B ) [this The ethylene polymer may be referred to as an ethylene polymer (E _B ') in the following description. It is particularly preferable that the following requirement (1 _B ″) is satisfied [this ethylene polymer may be referred to as an ethylene polymer (E _B ″) in the following description. ].
According to (1 _B ′) ASTM-D-790, the flexural modulus measured at 23 ° C. is in the range of 1,500 to 1,800 MPa.
Is a non-destructive _{(2 B ') ASTM-D} -1693 environmental stress cracking resistance ESCR at 50 ° C. were measured according to (hr) is 10 hours or more.
(1 _B ″) tan δ (= loss elastic modulus G ″ / storage elastic modulus G ′) at 190 ° C. and an angular frequency of 100 rad / sec measured using a dynamic viscoelastic device is 0.7 to 0.9.

Further, in the ethylene polymer (E _B ), (E _B ′) and (E _B ″) for blow molded products, the ethylene polymer (E) satisfies the requirements (1) to (7). It is preferable that the ethylene polymer (E ′) satisfies the above-mentioned requirements, and the ethylene polymer (E ′) is an ethylene polymer (E ″) that also satisfies the above requirement (1 ″). Further, it is particularly preferable that the ethylene polymer (E ″) is an ethylene polymer (E ′ ″) that also satisfies the requirements (1 ′ ″) and (2 ′ ″).

When the ethylene polymer (E) according to the present invention is applied to pipe applications, the following requirements (1 _P ) and (2 _P ) must be satisfied at the same time in addition to the above requirements that the ethylene polymer (E) should satisfy. Is preferred.
(1 _P ) Containing 0.10 to 1.00 mol% of structural units derived from an α-olefin having 6 to 10 carbon atoms.
The ratio of (2 _P) weight average molecular weight measured by GPC (Mw) to the number average molecular weight (Mn) (Mw / Mn) is in the range of 11-70.

In the following description, this ethylene polymer may be referred to as an ethylene polymer (E _P ').
Further, a more preferable ethylene polymer for pipes preferably satisfies the following requirement (1 _P ′) in addition to the above requirements (1 _P ) and (2 _P ) [this ethylene polymer is described below. Then, it may be called an ethylene polymer (E _P ''). ].
(1 _P ') Based on JIS K-6744, the tensile stress characteristics measured at 80 ° C, the actual stress when the number of times to break is 10,000 times is 13MPa to 17MPa, and the number of times to break is 100,000 times The stress is 12-16 MPa.

In the ethylene polymer of the pipe (E _P ') and (E _P' '), the ethylene polymer (E) is, the requirement (1) satisfies also to (7) the ethylene polymer ( E ′) is preferred, and the ethylene polymer (E ′) is more preferably an ethylene polymer (E ″) that also satisfies the requirement (1 ″). The polymer (E ″) is particularly preferably an ethylene polymer (E ′ ″) that also satisfies the requirements (1 ′ ″) and (2 ′ ″).

  The ethylene polymer according to the present invention can be molded into blow molded products, inflation molded products, cast molded products, extruded laminated molded products, extruded molded products such as pipes and irregular shapes, foam molded products, injection molded products, and the like. . Furthermore, it can be used for fibers, monofilaments, nonwoven fabrics and the like. These molded products include molded products (laminates and the like) including a part made of an ethylene polymer and a part made of another resin. The ethylene polymer may be one that has been crosslinked in the molding process. When the ethylene-based polymer according to the present invention is used in blow molded products and extruded molded products such as pipes and irregular shapes among the above molded products, excellent characteristics are given.

  The ethylene-based polymer of the present invention is excellent in moldability, particularly excellent in mechanical strength, and provides a molded body excellent in appearance, particularly a blow molded body, a pipe and a pipe joint.

2 is a CFC contour diagram of the ethylene polymer obtained in Example 1. FIG. 3 is a three-dimensional GPC chart (bird's eye view) and T _{2 as} viewed from the low temperature side of the ethylene polymer obtained in Example 1. FIG. 3 is a three-dimensional GPC chart (bird's eye view) and T ₁ viewed from the high temperature side of the ethylene polymer obtained in Example 1. ₂ is a GPC curve of an elution component of the ethylene polymer obtained in Example 1 at a peak temperature [(T ₂ −1) to T ₂ ] (° C.). 2 is a GPC curve of components eluted at 73 to 76 (° C.) of the ethylene polymer obtained in Example 1. FIG. 2 is a GPC curve of components eluted at 95 to 96 (° C.) of the ethylene polymer obtained in Example 1. FIG. 2 is a CFC contour diagram of the ethylene polymer obtained in Comparative Example 1. FIG. 3 is a three-dimensional GPC chart (bird's eye view) and T _{2 as} seen from the low temperature side of the ethylene polymer obtained in Comparative Example 1. 3 is a three-dimensional GPC chart (bird's eye view) and T ₁ viewed from the high temperature side of the ethylene polymer obtained in Comparative Example 1. 3 is a GPC curve of an elution component at the peak temperature [(T ₂ −1) to T ₂ ] (° C.) of the ethylene polymer obtained in Comparative Example 1. FIG. 3 is a GPC curve of components eluted at 73 to 76 (° C.) of the ethylene polymer obtained in Comparative Example 1. FIG. 3 is a GPC curve of a component eluted at 95 to 96 (° C.) of the ethylene polymer obtained in Comparative Example 1. FIG. 4 is a graph showing an elution curve of components eluted at 0 to 145 (° C.) of the ethylene polymer obtained in Comparative Example 1 and an integrated value of component amounts. 6 is a CFC contour diagram of the ethylene polymer obtained in Comparative Example 5. FIG. 3 is a three-dimensional GPC chart (bird's eye view) and T _{2 as} seen from the low temperature side of the ethylene polymer obtained in Comparative Example 5. 3 is a three-dimensional GPC chart (bird's eye view) and T _{1 as} seen from the high temperature side of the ethylene-based polymer obtained in Comparative Example 5. 6 is a GPC curve of an elution component at the peak temperature [(T ₂ −1) to T ₂ ] (° C.) of the ethylene polymer obtained in Comparative Example 5. 6 is a GPC curve of components eluted at 73 to 76 (° C.) of the ethylene polymer obtained in Comparative Example 5. 6 is a GPC curve of a component eluted at 95 to 96 (° C.) of the ethylene-based polymer obtained in Comparative Example 5. 4 is a CFC contour diagram of the ethylene polymer obtained in Example 3. FIG. 3 is a three-dimensional GPC chart (bird's eye view) and T _{2 as} seen from the low temperature side of the ethylene polymer obtained in Example 3. 3 is a three-dimensional GPC chart (bird's eye view) and T _{1 as} seen from the high temperature side of the ethylene polymer obtained in Example 3. 4 is a GPC curve of an elution component at a peak temperature [(T ₂ −1) to T ₂ ] (° C.) of the ethylene polymer obtained in Example 3. FIG. 4 is a GPC curve of components eluted at 73 to 76 (° C.) of the ethylene polymer obtained in Example 3. FIG. 4 is a GPC curve of components eluted at 95 to 96 (° C.) of the ethylene polymer obtained in Example 3. FIG. 4 is a graph showing an elution curve of components eluted at 0 to 145 (° C.) of the ethylene polymer obtained in Example 3 and an integrated value of component amounts. It is the figure which showed the density | concentration integration | accumulation (whole = 100%) of the amount of elution components obtained by CFC measurement about several Examples and comparative examples. It is a GPC chart which showed an example of GPC separation analysis. It is an example of the measurement result (75 times) of the crystal structure of an ethylene polymer. It is an example of the measurement result (150 times) of the crystal structure of an ethylene polymer. It is a schematic diagram of a pinch-off part. It is the figure which showed the comparison of the 80 degreeC tension fatigue test result of an Example and a comparative example.

Hereinafter, an ethylene polymer (E) according to the present invention, an ethylene polymer (E _B ) suitably used for a blow molded article, a blow molded article comprising the same, and an ethylene polymer suitably used for a pipe (E _P ) and the pipe or pipe joint comprising the same, the best mode for carrying out the invention will be sequentially described, and then a typical production method of an ethylene polymer according to the present invention and various measurements according to the present invention The method is described, and finally the examples are described.

Ethylene polymer (E)
The ethylene polymer (E) according to the present invention is an ethylene polymer containing 0.01 to 1.20 mol% of a structural unit derived from an α-olefin having 6 to 10 carbon atoms, and is usually an ethylene homopolymer and It consists of a copolymer of ethylene / α-olefin having 6 to 10 carbon atoms.

  Here, examples of the α-olefin having 6 to 10 carbon atoms (hereinafter sometimes simply referred to as “α-olefin”) include 1-hexene, 4-methyl-1-pentene, 3-methyl- Examples include 1-pentene, 1-octene, 1-decene and the like. In the present invention, among these α-olefins, it is preferable to use at least one selected from 1-hexene, 4-methyl-1-pentene, and 1-octene.

The ethylene polymer (E) according to the present invention is characterized by satisfying either of the following requirements (1) or (2) in cross fractionation (CFC).
(1) The weight average molecular weight (Mw) of the component eluted at 73 to 76 ° C does not exceed 4,000.
(2) The following relational expression (Eq-1) is satisfied.

（Eq-1中、S_xはCFCにおいて70〜85℃で溶出する成分に基づく全ピークの面積合計値であり、S_totalは0〜145℃で溶出する成分に基づく全ピークの面積合計値である。）
このようなエチレン系重合体（E）は、成形体に応用した場合、疲労特性などの長期物性などに優れる。以下、要件(1)および(2)について具体的に説明する。

(In Eq-1, S _x is the total area value of all peaks based on components eluting at 70 to 85 ° C in CFC, and S _total is the _total area value of all peaks based on components eluting at 0 to 145 ° C. is there.)
Such an ethylene polymer (E) is excellent in long-term physical properties such as fatigue properties when applied to a molded body. The requirements (1) and (2) will be specifically described below.

[Requirement (1)]
In the ethylene polymer (E) according to the present invention, the weight average molecular weight (Mw) measured by GPC of the component eluted at 73 to 76 ° C. does not exceed 4,000 in the cross fractionation (CFC). More specifically, the weight average molecular weight (Mw) for the GPC peak detected in the region where the molecular weight is 10 ⁸ or less does not exceed 4,000. The preferred range of the weight average molecular weight (Mw) is 2,000 to 4,000, more preferably 2,500 to 3,500. Such an ethylene polymer means that the high molecular weight component copolymerized with α-olefin is low in content, or does not contain a component having a relatively low molecular weight and having a short chain branch. In this case, the molded article has excellent long-term physical properties such as fatigue strength. The ethylene / α-olefin copolymer described in JP-A-11-106432 does not satisfy this range because of the wide composition distribution, and the ethylene-based polymer described in WO01 / 25328 also has a relatively low molecular weight. This range is not satisfied due to the presence of short chain branching due to the copolymerization of α-olefin. Conventional ethylene polymers such as Ziegler catalysts and chromium catalysts also do not satisfy this range because of the wide composition distribution.

  An ethylene polymer in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later. Specifically, when polymerized under the conditions described in Example 3 of the present application, the weight average molecular weight (Mw) of the component eluted at 73 to 76 ° C. in the temperature rising elution fractionation using a cross fractionation (CFC) apparatus is 2,900. Yes, unless the catalyst and polymerization temperature are changed, unless α-olefin is supplied to the first polymerizer, and α-olefin supplied to the second polymerizer, in this case, unless 1-hexene is increased to 900 g / hr or more The weight average molecular weight (Mw) is less than 4,000.

[Requirement (2)]
The ethylene-based polymer (E) according to the present invention is a cross-fractionated CFC. The total area of all peaks based on components eluting at 70 to 85 ° C. is Sx, and all peaks based on components eluting at 0 to 145 ° C. When the total area value is S _total , the relationship represented by the following formula (Eq-1) is satisfied.

要件(2)を満たすこのようなエチレン系重合体は、要件(1)の項で述べた内容と同じく、α-オレフィンが共重合した高分子量成分を含有量が少ないこと、または比較的分子量が低くかつ短鎖分岐を有するような成分を含有しないことを意味し、その場合成形体としての疲労強度などの長期物性に優れる。特開平11-106432号公報記載のエチレン・α-オレフィン共重合体は組成分布が広いために上記式(Eq-1)の関係を満たさず、WO01/25328号公報記載のエチレン系重合体は比較的分子量が小さい成分にもα-オレフィンが共重合したことによる短鎖分岐が存在するために上記式(Eq-1)の関係を満たさない。従来のチーグラー触媒やクロム触媒などからなるエチレン系重合体も組成分布が広いので上記式(Eq-1)の関係を満たさない。なお、上記式（Eq-1）におけるS_xおよびS_totalはC-H結合の伸縮振動の赤外分析に基づく値であることから、S_x/S_totalの値は、原則として70〜85℃で溶出する成分の、0〜145℃で溶出する成分量に占める重量%に等しい。通常、本発明のエチレン系重合体については0〜145℃の領域のスキャンで全成分が溶出してしまうため、S_x/S_totalの値は、エチレン系重合体の単位重量に占める70〜85℃での溶出成分量の重量%と言い換えることもできる。

Such an ethylene polymer satisfying the requirement (2) has a low molecular weight or a relatively high molecular weight, as described in the requirement (1). This means that it does not contain a component that is low and has short chain branching, and in that case, it is excellent in long-term physical properties such as fatigue strength as a molded article. The ethylene / α-olefin copolymer described in JP-A-11-106432 does not satisfy the relationship of the above formula (Eq-1) because the composition distribution is wide, and the ethylene-based polymer described in WO01 / 25328 is a comparison. Since the short chain branching due to the copolymerization of α-olefin is present even in a component having a low molecular weight, the relationship of the above formula (Eq-1) is not satisfied. Conventional ethylene polymers such as Ziegler catalysts and chromium catalysts also do not satisfy the relationship of the above formula (Eq-1) because of the wide composition distribution. In addition, since S _x and S _total in the above formula (Eq-1) are values based on infrared analysis of the stretching vibration of CH bond, the value of S _x / S _total is eluted at 70 to 85 ° C in principle. It is equal to the weight% of the component eluting at 0 to 145 ° C. Usually, for the ethylene polymer of the present invention, all components are eluted in a scan in the range of 0 to 145 ° C., so the value of S _x / S _total is 70 to 85 occupying the unit weight of the ethylene polymer. In other words, it can be paraphrased as% by weight of the amount of the eluted component at ° C.

An ethylene polymer in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later. Specifically, when polymerized under the conditions described in Example 3 of the present application, in the cross fractionation (CFC) of the obtained ethylene polymer, the left side of the above formula (Eq-1), that is, (S _x / S _total ) Value of 0.042, unless the catalyst and polymerization temperature are changed, and unless α-olefin is supplied to the first polymerization vessel, α-olefin supplied to the second polymerization vessel, in this case 1-hexene is 900 g / Unless it is not less than hr, the value of (S _x / S _total ) satisfies the above relational expression (Eq-1).

Among the ethylene polymers (E), a more preferable form is an ethylene copolymer (E ′) that satisfies the following requirements (1 ′) to (7 ′).
(1 ′) Containing 0.02 to 1.00 mol% of a structural unit derived from an α-olefin having 6 to 10 carbon atoms. (2 ′) The density (d) is in the range of 945 to 970 kg / m ³ .
(3 ′) Intrinsic viscosity ([η]) measured in decalin at 135 ° C. is in the range of 1.6 to 4.0 (dl / g).
(4 ′) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC is in the range of 5 to 70.
(5 ') In cross fractionation (CFC), the peak peak elution temperature is less than 100,000 and the peak peak elution temperature is T ₁ (° C), and the peak peak elution temperature is 100,000 and the strongest peak peak elution temperature is T ₂ ( (T ₁ -T ₂ ) (° C.) is in the range of 0 to 11 ° C.
(6 ') Among the GPC curves of fractions eluted from [(T ₂ -1) to T ₂ ] (° C) in cross fractionation (CFC), the molecular weight at the peak of the strongest peak with a molecular weight of 100,000 or more is 200,000. It is in the range of ~ 800,000.
(7 ') The molecular weight at the peak of the strongest peak does not exceed 28,000 in the region where the molecular weight is 100,000 or less in the GPC curve of the component eluted at 95 to 96 ° C in cross fractionation (CFC).
Hereinafter, the requirements (1 ′) to (7 ′) will be specifically described sequentially.

[Requirement (1 ')]
The ethylene polymer (E ′) according to the present invention usually contains 0.02 to 1.00 mol% of structural units derived from an α-olefin having 6 to 10 carbon atoms. When the ethylene-based polymer (E ′) does not contain an ethylene homopolymer, that is, only a copolymer of ethylene and an α-olefin having 6 to 10 carbon atoms, the structural unit derived from ethylene is , Usually 99 to 99.98 mol%, preferably 99.5 to 99.98 mol%, more preferably 99.6 to 99.98 mol%, and the repeating unit derived from α-olefin is usually 0.02 to 1 mol%, preferably 0.02 to It is preferably present at a ratio of 0.5 mol%, more preferably 0.02 to 0.4 mol%. In addition, the ethylene polymer (E ′) may contain an ethylene homopolymer, in which case the structural unit derived from ethylene in the ethylene / α-olefin copolymer portion is usually 95 to 99.96 mol%. , Preferably 97.5 to 99.96 mol%, more preferably 98 to 99.96 mol%, and the repeating unit derived from α-olefin is 0.04 to 5 mol%, preferably 0.04 to 2.5 mol%, more preferably 0.04. It is preferably present at a rate of ˜2.0 mol%. The repeating unit derived from the α-olefin, even if it contains an ethylene homopolymer, is usually 0.02 to 1 mol%, preferably 0.02 to 0.5 mol%, more preferably 0.02 to 0.4. mol%. When the number of carbon atoms of the α-olefin is 5 or less, the probability that the α-olefin is incorporated into the crystal is high (see Polymer, Vol. 31, page 1999, 1990). . If the α-olefin has more than 10 carbon atoms, the activation energy of the flow increases, and the viscosity change during molding is large, which is not preferable. Moreover, when the number of carbon atoms of the α-olefin exceeds 10, the side chain (branch caused by the α-olefin copolymerized with ethylene) may be crystallized, which is not preferable because the amorphous part becomes weak. .

[Requirement (2 ') and Requirement (3')]
Density (d) are 945~970kg / m ³ of ethylene polymer according to the present invention (E '), preferably 947~969 kg / m ^3, more preferably 950~969 kg / m ^3, 135 ℃ decalin The intrinsic viscosity ([η]) measured in (1) is in the range of 1.6 to 4.0 dl / g, preferably 1.7 to 3.8 dl / g, more preferably 1.8 to 3.7 dl / g. An ethylene polymer having a density and an intrinsic viscosity in these ranges is excellent in the balance between hardness and moldability. For example, by changing the supply amount ratio of hydrogen, ethylene, α-olefin to the polymerization vessel, the polymerization amount ratio of ethylene homopolymer and ethylene / α-olefin copolymer, etc., the value falls within the above numerical range. It can be increased or decreased. Specifically, in the slurry polymerization of Example 3 using hexane as the solvent, when the polymerization is performed while stirring the system uniformly, the density becomes 953 kg / m ³ and [η] becomes 3.10 dl / g. When the ethylene supplied to the second polymerization tank is 6.0 kg / hr, hydrogen is 0.45 N-liter / hr, and 1-hexene is 300 g / hr, the density is 944 kg / m ³ and [η] is 3.6 dl / g. The ethylene supplied to the first polymerization tank is 7.0 kg / hr, the hydrogen is 125 N-liter / hr, the ethylene supplied to the second polymerization tank is 3.0 kg / hr, the hydrogen is 0.07 N-liter / hr, and 1-hexene is supplied. If it is 30 g / hr, the density is 968 kg / m ³ and [η] is 2.10 dl / g.

[Requirement (4 ')]
The ethylene polymer (E ′) according to the present invention has an Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) measured by gel permeation chromatography (GPC) of usually 5 to 70, preferably 5 In the range of ~ 50. An ethylene polymer in this range can be produced by controlling the molecular weight and the polymerization amount ratio of each component when performing a multistage polymerization described later using a catalyst system described later.

  For example, Mw / Mn can be increased by widening the molecular weight difference between the components. A polymer having Mw / Mn in the above range is excellent in balance between mechanical strength and moldability. Specifically, when polymerized under the conditions described in Example 3 of the present application, Mw / Mn is 14.8. Here, when ethylene supplied to the first polymerization tank is changed from 5.0 kg / hr to 7.0 kg / hr and hydrogen is changed from 57 N-liter / hr to 125 N-liter / hr, the ethylene polymer produced in the first polymerization tank As the molecular weight decreases, Mw / Mn is about 18, while ethylene is supplied to the second polymerization tank from 4.0 kg / hr to 3.3 kg / hr and hydrogen from 0.2 N-liter / hr to 0.07 N-liter / hr. When the molecular weight of the ethylene polymer produced in the second polymerization tank is increased, the Mw / Mn becomes about 22. Alternatively, if the hydrogen supplied to the first polymerization tank is 52 N-liter / hr, the ethylene supplied to the second polymerization tank is 6.0 kg / hr, hydrogen is 0.45 N-liter / hr, and 1-hexene is 200 g / hr, then Mw / Mn is about 12.

[Requirement (5 ')]
In the temperature rising elution fractionation of the ethylene polymer according to the present invention using a cross fractionation (CFC) apparatus, the molecular weight is less than 100,000, the elution temperature at the peak of the strongest peak is T ₁ (° C.), and the molecular weight is 100,000 or more. When the elution temperature at the peak of the strongest peak is T ₂ (° C.), (T ₁ −T ₂ ) (° C.) is in the range of 0 to 11 ° C., preferably in the range of 0 to 10 ° C. More preferably, it is in the range of 0 to 9 ° C. In the CFC analysis according to the present invention, for example, referring to FIG. 2, the “peak” indicates the distribution of solute (chromatogram), that is, the entire shape of the mountain, and “the strongest (or the highest peak). “Strength is strong” means that the height of the mountain is the highest, and “peak vertex” means the point where the differential value becomes zero (that is, the peak of the mountain). In addition, when the peak of a mountain does not exist, the point (namely, shoulder) part with a differential value nearest to zero is pointed out.

Such an ethylene polymer can produce an ethylene polymer in this range by using a catalyst system described later and setting the polymerization conditions described later.
By increasing or decreasing the copolymerization amount of α-olefin within a specific range, (T ₁ -T ₂ ) can be increased or decreased within this range. Specifically, when polymerized under the conditions described in Example 3, there are two peaks with different molecular weights in the temperature rising elution fractionation using a cross fractionation (CFC) apparatus, and the peak molecular weight of the elution component is lower than 100,000. The temperature difference between the peak temperature (T ₁ ) with the strongest peak intensity and the peak molecular weight (T ₂ ) with the peak molecular weight of the elution component of 100,000 or more is (T ₁ −T ₂ ) ( ℃) becomes 6 ℃. By changing the amount of 1-hexene supplied to the second polymerization vessel from 130 g / hr to 50 g / hr, (T ₁ -T ₂ ) (° C.) becomes 1 ° C., and by changing to 200 g / hr, ( T ₁ −T ₂ ) (° C.) is 11 ° C.

[Requirement (6 ')]
In the cross fractionation (CFC) of the ethylene-based polymer (E ′) according to the present invention, the molecular weight of the peak of the strongest peak at a molecular weight of 100,000 or more in the fraction eluted at T ₂ (° C.) is It is in the range of 200,000 to 800,000. The fraction eluted at T ₂ (° C.) refers to the component eluted at [(T ₂ −1) to T ₂ ] (° C.). Such an ethylene polymer is excellent in a balance between long-term physical properties such as fatigue properties and moldability. An ethylene polymer in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later. The highest molecular weight peak in the GPC curve of the fraction eluted at T ₂ (° C) by increasing or decreasing the amount of α-olefin, hydrogen, ethylene, etc. supplied to the polymerization environment for producing the copolymer The molecular weight at the apex of can be increased or decreased within a specific range. Specifically, when polymerized under the conditions described in Example 3, the fraction eluted at [(T ₂ −1) to T ₂ ] (° C.) in the temperature rising elution fractionation using a cross fractionation (CFC) apparatus. Of the GPC curve in minutes, the molecular weight at the peak of the strongest peak is 493,000 when the molecular weight is 100,000 or more. When the amount of 1-hexene supplied to the second polymerization vessel is changed from 130 g / hr to 200 g / hr, ethylene 4.0 kg / hr is changed to 6.0 kg / hr, hydrogen 0.2 N-liter / hr is changed to 0.45 N-liter / hr Among the GPC curves of fractions eluted at [(T ₂ −1) to T ₂ ] (° C.) in the temperature rising elution fractionation using a cross fractionation (CFC) apparatus, the strongest peak with a molecular weight of 100,000 or more The molecular weight at the apex becomes 361,000. When the hydrogen supplied to the second polymerization vessel is changed from 0.2 N-liter / hr to 0.1 N-liter / hr, the above [(T ₂ −1) to T ₂ ] (° C.), the peak molecular weight of the peak with the highest molecular weight is 680,000. In the conventionally known metallocene catalysts, an ethylene copolymer having a narrow molecular weight distribution and such a high molecular weight could not be obtained.

[Requirement (7 ')]
The molecular weight of the peak of the strongest peak does not exceed 28,000 among the GPC curves of the components eluted at 95 to 96 ° C. in the cross fractionation (CFC) of the ethylene polymer according to the present invention. Usually it is in the range of 15,000-27,000. Such an ethylene polymer means that it does not contain a component having a low molecular weight and short chain branching, and in that case, it is excellent in long-term physical properties such as fatigue strength.

  An ethylene polymer in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later. Specifically, when polymerized under the conditions described in Example 3, the peak of the strongest peak among the GPC curves of the components that elute at 95 to 96 ° C. in the temperature rising elution fractionation using a cross fractionation (CFC) apparatus The molecular weight is 22,000, unless the catalyst and polymerization temperature are changed, unless α-olefin is supplied to the first polymerizer, and the amount of hydrogen supplied to the second polymerizer is not more than 10 N-liter / hr. The Mw falls within this range. When branching also exists in the low molecular weight component as in WO01 / 25328, the crystallinity of the low molecular weight component is lowered, so that a component having a higher molecular weight is eluted even at the same elution temperature, and this requirement is satisfied. Absent.

Among the ethylene polymers (E ′) described above, a more preferred form is an ethylene polymer (E) in which the number of methyl branches measured by ¹³ C-NMR is less than 0.1 per 1000 carbon atoms, preferably less than 0.08. ''). Since such a polymer has a strong crystal structure, it has excellent mechanical strength. Since the ethylene polymer produced using a catalyst system as exemplified below has a detection limit (0.08 per 1000 carbon atoms) or less, methyl branching is not detected.

Among the ethylene-based polymers (E ″) described above, a particularly preferred form is an ethylene-based copolymer (E ′ ″) that simultaneously satisfies the following requirements (1 ′ ″) to (2 ′ ″). is there.
(1 ''') When the GPC curve is separated into two lognormal distribution curves, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) of each curve is in the range of 1.5 to 3.5 The weight average molecular weight (Mw ₂ ) of the curve separated on the high molecular weight side is in the range of 200,000 to 800,000.
(2 ''') The smoothness coefficient R obtained from the surface roughness of the extruded strand does not exceed 20 μm.
The requirements (1 ′ ″) and (2 ′ ″) will be specifically described below.

[Requirement (1 ''')]
When the molecular weight curve (GPC curve) measured by gel permeation chromatography (GPC) is separated into two lognormal distribution curves, the ethylene polymer (E ′ ″) according to the present invention has a weight of each curve. Average molecular weight (Mw) / number average molecular weight (Mn) is usually in the range of 1.5 to 3.5, preferably 1.5 to 3.2. By using a catalyst system as described later, multistage polymerization as described later is performed, and by controlling the type of catalyst compound selected at that time, the number of stages when performing multistage polymerization, and the molecular weight of each component, An ethylene polymer in the range can be produced. When polymerized in the gas phase, Mw / Mn is increased. On the other hand, when polymerized in the slurry phase, heat removal and monomer diffusion become more uniform, so that Mw / Mn can be decreased. Further, when the catalyst component is used without being supported on the carrier, the Mw / Mn becomes small because it approaches a homogeneous system. In the case of slurry polymerization using a supported geometrically constrained single site catalyst (CGC / Borate) described in JP-A-11-106432, or ethylene bis (4,5,4) supported on silica described in EP1201711A1 When slurry polymerization is carried out using a catalyst system comprising 6,7-tetrahydro-1-indenyl) zirconium dichloride and methylalumoxane, the Mw / Mn of single-stage polymerization is 4 or more, which does not satisfy the claims of this application. The Mw / Mn of the ethylene polymer obtained by single-stage polymerization at 80 ° C. using the catalyst described in Example 1 of the present application is about 2.3.

Further, when the GPC curve of the ethylene polymer (E ′ ″) according to the present invention is separated into two lognormal distribution curves, the weight average molecular weight (Mw ₂ ) of the curve separated on the high molecular weight side is 200,000 to It is in the range of 800,000. By selecting the amount ratio of hydrogen, ethylene, and α-olefin at the time of producing the ethylene polymer, an ethylene polymer having Mw ₂ in this range can be produced. Specifically, when polymerized under the conditions described in Example 3, when the GPC curve was separated into two lognormal distribution curves, the weight average molecular weight (Mw ₂ ) of the curve separated on the high molecular weight side was 416,000. Become. If ethylene supplied to the second polymerization tank is 6.0 kg / hr, hydrogen is 0.35 N-liter / hr, and 1-hexene is 200 g / hr, Mw ₂ will be 312,000, and ethylene supplied to the second polymerization tank will be 3.0 kg. / W, hydrogen is 0.07 N-liter / hr, and 1-hexene supplied to the second polymerization tank is 30 g / hr, Mw ₂ is 539,000. An ethylene polymer having Mw ₂ in this range has an excellent balance between strength and moldability.

[Requirement (2 ''')]
In the ethylene polymer (E ′ ″) according to the present invention, the smoothness coefficient R obtained from the surface roughness of the extruded strand does not exceed 20 μm, preferably does not exceed 15 μm. When the ethylene polymer obtained by polymerization is in the form of particles, as in the gas phase polymerization method or slurry polymerization method, the polymer particles are not completely mixed and dispersed even after post-treatment such as melt kneading. In some cases, the portions having different viscosities may remain on the surface. In that case, when the molten resin is extruded in the form of a tube or a strand, the surface becomes rough. In that case, the same rough skin occurs when the product is molded. The degree is obtained by the smoothness coefficient R obtained from the surface roughness measurement. Usually, the size of ethylene polymer particles produced by gas phase polymerization method or slurry polymerization method is about several tens of μm to 2 mm, and if the history of the shape of the polymer particles remains, the surface of the extrudate becomes rough. Thus, R becomes larger than 20 μm. For example, when a polymerization method as described below is selected, an ethylene polymer in which R does not exceed 20 μm, usually does not exceed 15 μm can be produced. If R does not exceed 20 μm, fluctuations in the range of 0 to 20 μm can occur where there is no relation to the essence of foreign matter contamination, die scratches, measurement errors, etc. during film formation. Therefore, it is meaningful that R does not exceed 20 μm. For the ethylene polymer having a value of R exceeding 20 μm, for example, the ethylene polymer powder obtained in Example 3 was used using a lab plast mill (batch type opposite direction rotating twin screw kneader) manufactured by Toyo Seiki Co., Ltd. If melt-kneaded for a very long time such as 190 ° C., 25 rpm, 15 minutes, an ethylene polymer having an R of less than 20 μm can be obtained. It is possible to make R smaller by further lengthening the kneading time. However, there may be a structural change accompanying decomposition or crosslinking. Further, an ethylene polymer having an R value exceeding 20 μm is dissolved at a rate of about 5 g in 500 ml of a good solvent such as para-xylene, and then cooled with ice and cooled to about 5 times as much as acetone. When precipitated in a solvent at a rate of about 10 ml / min, dried and then melt-kneaded, an ethylene polymer having an R value of 10 μm or less can be obtained. A polymer in which R does not exceed the above-mentioned value is particularly excellent in mechanical strength because it has no history of polymer particles and is uniform in flow, so that the surface of the molded body is smooth and excellent in appearance. As shown in Example 1 of the present application, when two-stage polymerization is carried out in a batch mode, R does not exceed 20 μm even if long-time melt kneading is not performed. Further, among the ethylene polymers obtained in Example 3, the ethylene homopolymer was extracted from the first polymerizer, and melt-kneaded with the ethylene polymer obtained by single-stage slurry polymerization under the conditions of the second polymerizer separately. Even in this case, an ethylene polymer in which R does not exceed 20 μm may be obtained.

  The ethylene-based polymers (E), (E ′), (E ″) and (E ′ ″) according to the present invention were melted at 190 ° C. and cooled at 20 ° C., and a microtome section of a 0.5 mm thick press sheet. When observed with a polarizing microscope, a continuous crystal structure exceeding 10 μm is not observed.

  Specifically, when a microtome section of a 0.5 mm thick press sheet melted at 190 ° C. and cooled at 20 ° C. is observed with a polarizing microscope, a continuous crystal structure exceeding 10 μm is not observed. Such an ethylene polymer is excellent in mechanical strength. For example, the ethylene polymer powder obtained in Example 3 of the present application was melt kneaded for a long time such as 190 ° C., 25 rpm, 10 minutes or more using a lab plast mill (batch type different direction rotating twin screw kneader) manufactured by Toyo Seiki Co., Ltd. Then, an ethylene polymer in which a continuous crystal structure exceeding 10 μm is not observed can be obtained. In addition, as shown in Example 1, when the two-stage polymerization was carried out in batch mode, an ethylene-based polymer in which a continuous crystal structure exceeding 10 μm was not observed only by performing melt-kneading for a very short time. Can be obtained. On the other hand, among the ethylene polymers obtained in Example 3, the ethylene homopolymer was extracted from the first polymerizer and melt-kneaded with the ethylene polymer obtained by single-stage slurry polymerization under the conditions of the second polymerizer separately. In this case, a continuous crystal structure exceeding 10 μm is observed even if the kneading time is increased.

  The polymerization for obtaining the ethylene polymers (E) to (E ′ ″) of the present invention is preferably carried out in a slurry phase or a gas phase. When polymerized in the slurry phase or gas phase, preferably multistage polymerization, two kinds of ethylene polymers with different molecular weights in the primary particle order (nanometer order) corresponding to one active point of the catalyst are mixed during the polymerization. preferable.

Ethylene polymer (E _B ) suitable for blow molding
Among the ethylene-based polymers (E) according to the present invention, preferably (E ′), more preferably (E ″), and particularly preferably (E ′ ″), it is suitably used for blow molded products. The ethylene-based polymer (E _B ) has a constitutional unit concentration derived from an α-olefin having 6 to 10 carbon atoms, Mw / Mn value, and (T ₁ -T ₂ ) value in cross fractionation (CFC), respectively. It is preferable to be limited as (1 _B ), (2 _B ) and (3 _B ).
(1 _B ) 0.02 to 0.20 mol% of structural units derived from an α-olefin having 6 to 10 carbon atoms.
The ratio of (2 _B) weight average molecular weight measured by GPC (Mw) to the number average molecular weight (Mn) (Mw / Mn) is in the range of 5-30.
(3 _B ) In cross fractionation (CFC), the peak peak elution temperature is less than 100,000 and the peak peak elution temperature is T ₁ (° C), and the peak peak elution temperature is 100,000 and the strongest peak peak elution temperature is T ₂ ( (T ₁ -T ₂ ) (° C.) is in the range of 0 to 5 ° C.
Hereinafter, only the requirement (1 _B ) and the requirement (3 _B ) will be supplementarily explained.

[Requirement ( _1B )]
The ethylene polymer (E _B ) suitably used for the blow molded article according to the present invention usually contains 0.02 to 0.2 mol% of structural units derived from an α-olefin having 6 to 10 carbon atoms. When the ethylene polymer (E _B ) of the present invention does not contain an ethylene homopolymer, that is, when it is only a copolymer of ethylene and an α-olefin having 6 to 10 carbon atoms, it is derived from ethylene. The structural unit is usually present at a ratio of 99.80 to 99.98 mol%, and the repeating unit derived from the α-olefin is preferably present at a ratio of 0.02 to 0.20 mol%. The ethylene polymer (E _B ) may contain an ethylene homopolymer. In that case, the structural unit derived from ethylene in the ethylene / α-olefin copolymer portion is usually 99.00 to 99.96 mol%. The repeating unit derived from the α-olefin is preferably present in a proportion of 0.04 to 1.00 mol%. Even when an ethylene homopolymer is included, the repeating unit derived from α-olefin in the entire polymer is usually 0.02 to 0.20 mol%.

[Requirements ( _3B )]
The ethylene polymer (E _B ) suitably used for blow molded products according to the present invention has a molecular peak of less than 100,000 and the peak of the strongest peak in temperature rising elution fractionation using a cross fractionation (CFC) apparatus. the elution temperature T ₁ of the (° C.), a molecular weight of 100,000 or more, if the elution temperature of the strongest peak apex of the _{T 2 (℃), (T} 1 -T 2) (℃) is 0 to 5 ° C. It is in the range, preferably in the range of 0 to 4 ° C, more preferably in the range of 0 to 3 ° C. Here, the vertex of the strongest peak indicates a point (ie, shoulder) where the differential value is zero (that is, the peak of the mountain), and when the peak of the peak does not exist, the differential value is closest to zero. Such an ethylene-based polymer has high rigidity and excellent environmental stress fracture resistance. An ethylene polymer in this range can be produced by setting a polymerization condition as described later using a catalyst system as described later. By increasing or decreasing the copolymerization amount of α-olefin within a specific range, (T ₁ -T ₂ ) can be increased or decreased within this range. Specifically, when polymerization was performed under the conditions described in Example 14 using hexane as a solvent, two peaks with different molecular weights were present in the temperature rising elution fractionation using a cross fractionation (CFC) apparatus, and the molecular weight of the eluted component was 100,000. The difference in temperature between the peak temperature (T ₁ ), which is lower than the highest peak intensity, and the peak temperature (T2) where the molecular weight of the eluted component is 100,000 or more and the strongest peak intensity is (T ₁ -T ₂ ) (℃) becomes 1 ℃. By changing the amount of 1-hexene supplied to the second polymerization vessel from 50 g / hr to 130 g / hr, (T ₁ -T ₂ ) (° C.) can be set to 5 ° C.

The ethylene polymer (E _B ) according to the present invention preferably satisfies the following requirements (1 _B ′) and (2 _B ′) in addition to the above requirements (1 _B ) to (3 _B ). The polymer may be referred to as an ethylene polymer (E _B ′)], more preferably the following requirement (1 _B ″) is satisfied [this ethylene polymer is referred to as an ethylene polymer in the following description. (Sometimes called (E _B ″)).
(1 _B ′) The flexural modulus measured at 23 ° C. is in the range of 1,500 to 1,800 MPa in accordance with ASTM-D-790.
Is a non-destructive _{(2 B ') ASTM-D} -1693 environmental stress cracking resistance ESCR at 50 ° C. were measured according to (hr) is 10 hours or more.
(1 _B ″) tan δ (= loss elastic modulus G ″ / storage elastic modulus G ′) at 190 ° C. and an angular frequency of 100 rad / sec measured using a dynamic viscoelastic device is 0.7 to 0.9.
The requirements (1 _B ′), (2 _B ′) and (1 _B ″) are described in detail below.

[Requirements (1 _B ') and (2 _B ')]
The ethylene polymer (E _B ′) according to the present invention has a flexural modulus measured at 23 ° C. in the range of 1,500 to 1,800 MPa, and has an environmental stress fracture resistance ESCR (hr) at 50 ° C. of 10 hours or more. Non-destructive, preferably non-destructive after 50 hours. Ethylene polymers with a flexural modulus and ESCR in this range are hard and strong, so the molded product can be made thinner than before. Control the molecular weight and polymerization amount ratio of each component by changing the supply ratio of hydrogen, ethylene, α-olefin, etc. Thus, an ethylene polymer having [η] in this range can be produced. Specifically, what was polymerized under the conditions described in Example 14 using hexane as a solvent was kneaded at a setting of 190 ° C. and 50 rpm for 10 minutes in a laboratory plast mill (equipment batch volume = 60 cm ³ ) manufactured by Toyo Seiki Co., Ltd. The elastic modulus is 1,650 MPa, ESCR becomes nondestructive after 600 hours, 1-hexene supplied to the second polymerization tank is changed from 50 g / hr to 30 g / hr, and the amount of ethylene supplied to the second polymerization tank is 4.0 kg / When lowered from hr to 3.0 kg / hr, the flexural modulus was 1,780 MPa, ESCR was 50% broken in 233 hours, and 1-hexene supplied to the second polymerization tank was changed from 50 g / hr to 65 g / hr. Flexural modulus is 1,520 MPa, ESCR is nondestructive after 600 hours.

[Requirements (1 _B '')]
The ethylene-based polymer (E _B ′) according to the present invention is tan δ (loss elastic modulus G ″ / storage elastic modulus G) at 190 ° C. and an angular frequency of 100 rad / sec measured using a dynamic viscoelastic device. It is preferable that ') is 0.7 to 0.9. When tan δ is within this range, the pinch fusion property when blow molding is excellent. As the molecular weight of the low molecular weight ethylene polymer is increased and the molecular weight of the high molecular weight ethylene / α-olefin copolymer is decreased, tan δ tends to increase. The pinch fusion property indicates that the resin is raised and well adhered to the fusion part when the cylindrical molten resin extruded from the extruder is fused with a mold. It means that the larger tan δ is, the stronger the viscosity is, and in this case, the resin is likely to rise.

Furthermore, the ethylene polymers (E _B ), (E _B ′) and (E _B ″) for blow molded products according to the present invention are preferably soluble in 140 ° C. decane. This means that the crosslinking step has not been performed. If the crosslinking step has not been performed, it can be remelted and reused, and the production process of the molded product is simpler and preferable.

Further, in the ethylene polymer (E _B ), (E _B ′) and (E _B ″) for blow molded products, the ethylene polymer (E) is the above-mentioned requirements (1 ′) to (7 It is preferable that it is an ethylene polymer (E ') that satisfies'), and the ethylene polymer (E') is an ethylene polymer (E '') that also satisfies the above requirement (1 ''). It is more preferable that the ethylene polymer (E ″) is an ethylene polymer (E ′ ″) that also satisfies the above requirements (1 ′ ″) and (2 ′ ″). preferable. In other words, as the ethylene-based polymer for the blow molded article of the present invention, the ethylene-based polymer (E ′ ″) is the requirements (1 _B ′), (2 _B ′) and (1 _B ″). Those satisfying both are most preferably used.

Ethylene polymer (E _P ) suitable for pipe applications
Among the ethylene-based polymers (E) according to the present invention, preferably (E ′), more preferably (E ″), particularly preferably (E ′ ″), ethylene which is suitably used for pipe applications The system polymer preferably has a concentration of constituent units derived from an α-olefin having 6 to 10 carbon atoms and an Mw / Mn value limited as follows (1 _P ) and (2 _P ), respectively. The ethylene polymer thus limited may be referred to as an ethylene polymer (E _P ) in the following description.
(1 _P ) Containing 0.10 to 1.00 mol% of structural units derived from an α-olefin having 6 to 10 carbon atoms.
The ratio of (2 _P) weight average molecular weight measured by GPC (Mw) to the number average molecular weight (Mn) (Mw / Mn) is in the range of 11-70.
The requirement ( _1P ) and requirement ( _2P ) will be described below.

[Requirements ( _1P )]
The ethylene polymer (E _P ) suitably used for the pipe according to the present invention usually contains 0.10 to 1.00 mol% of structural units derived from an α-olefin having 6 to 10 carbon atoms. When the ethylene polymer (E _P ) of the present invention does not contain an ethylene homopolymer, that is, when it is only a copolymer of ethylene and an α-olefin having 6 to 10 carbon atoms, it is derived from ethylene. The structural unit is usually present in a ratio of 99.00 to 99.90 mol%, and the repeating unit derived from the α-olefin is preferably present in a ratio of 0.10 to 1.00 mol%. The ethylene polymer (E _P ) may contain an ethylene homopolymer. In that case, the structural unit derived from ethylene in the ethylene / α-olefin copolymer portion is usually 95.00 to 99.80 mol%. The repeating unit derived from the α-olefin is preferably present in a proportion of 0.20 to 5.00 mol%. Even when an ethylene homopolymer is included, the repeating unit derived from α-olefin in the entire polymer is usually 0.10 to 1.00 mol%.

[Requirements ( _2P )]
In the ethylene polymer (E _P ) according to the present invention, Mw / Mn (Mw: weight average molecular weight, Mn: number average molecular weight) measured by gel permeation chromatography (GPC) is usually 11 to 70, preferably 11 It is in the range of ~ 50. When a multistage polymerization as described later is carried out using a catalyst system as described later, an ethylene polymer within this range can be produced by controlling the molecular weight and the polymerization amount ratio of each component. For example, Mw / Mn increases as the molecular weight difference between the components increases. A polymer having Mw / Mn in the above range is excellent in balance between mechanical strength and moldability. Specifically, when polymerized under the conditions described in Example 1 using hexane as the solvent, Mw / Mn is 14.8. Here, when the ethylene supplied to the first polymerization tank is changed from 5.0 kg / hr to 7.0 kg / hr and the hydrogen is changed from 57 N-liter / hr to 125 N-liter / hr, the ethylene polymer produced in the first polymerization tank Mw / Mn is reduced to about 18 by decreasing the molecular weight, while ethylene supplied to the second polymerization tank is from 4.0 kg / hr to 3.3 kg / hr, and hydrogen is from 0.2 N-liter / hr to 0.07 N-liter / hr. If the molecular weight of the ethylene polymer produced in the second polymerization tank is increased, the Mw / Mn becomes about 22. Also, assuming that hydrogen supplied to the first polymerization tank is 52 N-liter / hr, ethylene supplied to the second polymerization tank is 6.0 kg / hr, hydrogen is 0.45 N-liter / hr, and 1-hexene is 200 g / hr. Mw / Mn is about 12.

The ethylene polymer (E _P ) of the present invention preferably satisfies the following requirement (1 _P ′) in addition to the above requirements (1 _P ) and (2 _P ). Sometimes called polymer (E _P ').
(1 _P ') Based on JIS K-6744, the tensile stress characteristics measured at 80 ° C, the actual stress when the number of times to break is 10,000 times is 13MPa to 17MPa, and the number of times to break is 100,000 times The stress is 12-16 MPa.
The requirement (1 _P ') is described in detail below.

[Requirements (1 _P ')]
The ethylene-based polymer (E _P ') according to the present invention has an actual stress of 13 MPa to 17 MPa, preferably 14 MPa when the number of times to break is 10,000 with a tensile fatigue property measured at 80 ° C. with a notch in the sample. The actual stress when the number of times to break is 100,000 times is in the range of 12 MPa to 17 MPa, preferably 13 MPa to 16 MPa. An ethylene polymer having a tensile fatigue strength measured at 80 ° C. with a notch in the sample in this range is excellent in long-term life characteristics in which the fracture mode is brittle. When carrying out multistage polymerization as described later using a catalyst system as described later, the molecular weight of each component, the amount of α-olefin copolymerized with ethylene, the composition distribution, the polymerization amount ratio, and the compatibility are controlled. Thus, an ethylene polymer in this range can be produced.

  For example, a specific single site catalyst is used, [η] is increased within the scope of the claims, an α-olefin having 6 to 10 carbon atoms is selected as the α-olefin to be copolymerized, and the α-olefin in the copolymer By selecting the polymerization conditions such that the composition distribution is narrow within the range of 0.1 to 5.0 mol%, the fatigue strength can be further increased within the scope of the claims.

  Specifically, polymerization was carried out under the conditions described in Example 3 using hexane as the solvent, and granulation was performed under the conditions described in Example 3. When the tensile fatigue characteristics measured at 80 ° C. were used, the number of times to break was 10,000. The actual stress is 13.7 MPa, and the actual stress when the number of times to fracture is 100,000 is 13.1 MPa. When granulation is carried out at 20 ° φ single screw extruder (L / D = 28, compression ratio = 3), 230 ° C setting, 100 rpm, full flight screw, discharge rate 50 g / min, granulated at 80 ° C The actual stress when the number of times to fracture is 10,000 is 12.3 MPa, and the actual stress when the number of times to fracture is 100,000 is 11.3 MPa, which does not satisfy the claim. This is presumed to be due to the poor compatibility of the polymer particles. Further, during the polymerization, ethylene supplied to the second polymerization tank was 3.3 kg / hr, hydrogen was 0.07 N-liter / hr, and granulated under the conditions described in Example 3, tensile fatigue characteristics measured at 80 ° C. Thus, the actual stress when the number of times of breaking is 10,000 is 13.9 MPa, and the actual stress when the number of times of breaking is 100,000 is 13.4 MPa. In addition, when the polymerization conditions as in Comparative Example 1 are adopted, the tensile stress characteristics measured at 80 ° C., the actual stress when the number of times to break is 10,000 times is 12.1 MPa, and the number of times to break is 100,000 times The actual stress of 11.2MPa is not fulfilling the claims. On the contrary, by reducing the amount of hydrogen when copolymerizing the comonomer with the same comonomer amount as in Example 1, the number of times to break becomes 10,000 as the [η] of the resin approaches the upper limit of 3.7 dl / g. The actual stress at the time of 100,000 times and 100,000 times becomes high. In addition, even when the molecular structure is the same, when a low molecular weight ethylene homopolymer polymerized in a single stage and a high molecular weight ethylene / α-olefin copolymer polymerized in a single stage are melt blended, 10 μm is reduced. There is a continuous crystal structure that exceeds, that is, a continuous structure that exceeds 10 μm made of a low molecular weight ethylene homopolymer that is easy to break, so that the tensile fatigue strength measured at 80 ° C with a notch is developed. do not do.

  Furthermore, if the component that weakens the crystal part as a molecular structure, that is, if the low molecular weight component contains short chain branches or the high molecular weight component contains too many short chain branches, the crystals are connected to each other. Since it becomes difficult to form strong tie molecules, the amorphous material becomes weak, so the tensile fatigue strength measured at 80 ° C for a notched sample does not appear. In addition, when the continuous crystal structure exceeding 10 μm is not observed, the microtome section of a 0.5 mm thick press sheet melted at 190 ° C. and cooled at 20 ° C. was observed with a polarizing microscope. By not observing a continuous crystal structure that exceeds, the ethylene-based polymer was melted at 190 ° C using a hydraulic press molding machine manufactured by Shinto Metal Industry Co., Ltd. Create a 0.5mm thick press sheet with the set cooling press, then cut to 0.5mm (press sheet thickness) x 10-20μm using a microtome etc., and then apply a small amount of glycerin to the cut piece Adhere to the slide and place a cover glass on top of it to make a sample for observation. Set this sample between the crossed Nicol polarizing plates and observe it with an optical microscope magnified about 75 times and 150 times. It is seen in the. 29 and 30 show an example in which there is no continuous crystal structure exceeding 10 μm when the crystal structure is observed only in a part of the field of view, and 10 μm when the crystal structure is observed in the entire field of view. An example of what is said to be a continuous crystal structure exceeding is shown. The scale bar has a total length of 0.5 mm. 29 is a photograph observed at about 75 times and FIG. 30 at about 150 times.

Furthermore, it is preferable that the ethylene polymers (E _P ), (E _P ′) and (E _P ″) for pipes according to the present invention are soluble in 140 ° C. decane. This means that the crosslinking step has not been performed. If the crosslinking step has not been performed, it can be remelted and reused, and the production process of the molded product is simpler and preferable.

The ethylene-based polymer of the pipe (E _P), the in (E _P ') and (E _P' '), the ethylene polymer (E) is above requirements (1') to (7 ') It is preferably an ethylene polymer (E ′) that satisfies, more preferably an ethylene polymer (E ″) that satisfies the above requirement (1 ″). Further, the ethylene polymer (E ″) is particularly preferably an ethylene polymer (E ′ ″) that also satisfies the above requirements (1 ′ ″) and (2 ′ ″). In other words, as the ethylene polymer for the pipe of the present invention, the one in which the ethylene polymer (E ′ ″) satisfies both the above requirements (1 _P ′) and (2 _P ′) is most preferably used. Is done.

Production method of ethylene polymer The ethylene polymer according to the present invention is, for example,
(A) a transition metal compound in which a cyclopentadienyl group and a fluorenyl group are bonded by a covalent bridge containing a Group 14 atom;
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) Is ethylene homopolymerized using an olefin polymerization catalyst formed from a carrier (C) and at least one compound selected from compounds that react with transition metal compounds to form ion pairs? Alternatively, it can be obtained by copolymerizing ethylene and an α-olefin having 6 to 10 carbon atoms. More specifically, the components (A), (B), and (C) used in the examples of the present application are as follows.

* (A) Transition metal compound The transition metal compound (A) is a compound represented by the following general formulas (1) and (2).

（上記一般式（1）、（2）中、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸、R¹⁹およびR²⁰は水素原子、炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、R⁷〜R¹⁸までの隣接した置換基は互いに結合して環を形成してもよく、Aは一部不飽和結合および／または芳香族環を含んでいてもよい炭素原子数2〜20の2価の炭化水素基であり、Yとともに環構造を形成しており、AはYと共に形成する環を含めて2つ以上の環構造を含んでいてもよく、Yは炭素またはケイ素であり、Mは周期律表第4族から選ばれた金属であり、Qはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、jは1〜4の整数である。）

(In the above general formulas (1) and (2), R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different, and adjacent substituents from R ^{7 to} R ¹⁸ are bonded to each other to form a ring. A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and forms a ring structure with Y. May contain two or more ring structures including a ring formed with Y, Y is carbon or silicon, M is a metal selected from Group 4 of the periodic table, Q is halogen, The hydrocarbon group, the anionic ligand, or a neutral ligand that can coordinate with a lone pair may be selected in the same or different combination, and j is an integer of 1 to 4.)

Specifically, R ^{7 to} R ¹⁰ are hydrogen, Y is carbon, M is Zr, and j is 2.
The transition metal compound (A) used in Examples of the present application described later is specifically represented by the following formulas (3) and (4), but is not limited to the transition metal compound in the present invention.

なお、上記式（3）および（4）で表わされる遷移金属化合物は、270MHz¹H-NMR（日本電子 GSH-270）およびFD-質量分析（日本電子 SX-102A）を用いて構造決定した。

The structure of the transition metal compound represented by the above formulas (3) and (4) was determined using 270 MHz ¹ H-NMR (JEOL GSH-270) and FD-mass spectrometry (JEOL SX-102A).

★ (B-1) Organometallic compound (B-1) Organometallic compound used as necessary in the present invention, specifically, the following periodic table groups 1, 2 and 12, 13 These organometallic compounds are mentioned.

General formula R ^a _m Al (OR ^b ) _n H _p X _q
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3). .
The aluminum compound used in the Examples described later is triisobutylaluminum or triethylaluminum.

★ (B-2) Organoaluminum Oxy Compound The organoaluminum oxy compound (B-2) used as necessary in the present invention may be a conventionally known aluminoxane or exemplified in JP-A-2-78687. It may be a benzene insoluble organoaluminum oxy compound.
The organoaluminum oxy compound used in Examples described later is a commercially available MAO (= methylalumoxane) / toluene solution manufactured by Nippon Alkyl Aluminum Co., Ltd.

★ (B-3) A compound that reacts with a transition metal compound to form an ion pair A compound that reacts with the bridged metallocene compound (A) of the present invention to form an ion pair (B-3) (hereinafter referred to as “ionized ionicity”) Compound "), for example, JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207703. Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207704 and US-5321106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such ionized ionic compounds (B-3) are used singly or in combination of two or more. In addition, as (B) component used in this-application Example mentioned later, the above-mentioned (B-1) and (B-2) shown above are used.

★ (C) Fine particle carrier The (C) fine particle carrier used as necessary in the present invention is an inorganic or organic compound and is a granular or fine particle solid. Among these, as the inorganic compound, a porous oxide, an inorganic halide, clay, clay mineral, or an ion-exchange layered compound is preferable. Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 1 to 300 μm, preferably 3 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 800 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after being calcined at 80 to 1000 ° C., preferably 100 to 800 ° C., if necessary. The carrier used in the examples of the present application described later is manufactured by Asahi Glass Co., Ltd., which has an average particle size of 12 μm, a specific surface area of 800 m ² / g, and a pore volume of 1.0 cm ³ / g unless otherwise specified. SiO ₂ was used.

  The olefin polymerization catalyst according to the present invention comprises the bridged metallocene compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound according to the present invention. A specific organic compound component (D) as described later may be included as necessary together with at least one selected compound (B) and, if necessary, the particulate carrier (C).

★ (D) Organic Compound Component In the present invention, the (D) organic compound component is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

★ Polymerization The ethylene-based polymer according to the present invention is obtained by homopolymerizing ethylene as described above or using ethylene and an α-olefin having 6 to 10 carbon atoms. Can be obtained by copolymerization.

In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods (P1) to (P10) are exemplified.
(P1) Component (A) and at least one component (B) selected from (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound (hereinafter referred to as “P1”) And simply adding “component (B)”) to the polymerization vessel in any order.
(P2) A method in which a catalyst in which the component (A) and the component (B) are previously contacted is added to the polymerization vessel.
(P3) A method in which component (A) and component (B) are contacted in advance, and component (B) is added to the polymerization vessel in any order. In this case, each component (B) may be the same or different.
(P4) A method in which the catalyst component having the component (A) supported on the particulate carrier (C) and the component (B) are added to the polymerization vessel in an arbitrary order.
(P5) A method in which a catalyst in which component (A) and component (B) are supported on a particulate carrier (C) is added to a polymerization vessel.
(P6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the particulate carrier (C), and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, each component (B) may be the same or different.
(P7) A method in which the component (B) is supported on the particulate carrier (C) and the component (A) is added to the polymerization vessel in any order.
(P8) A method of adding the catalyst component having component (B) supported on fine particle carrier (C), component (A), and component (B) to the polymerization vessel in any order. In this case, each component (B) may be the same or different.
(P9) A method in which a catalyst in which a component (A) and a component (B) are supported on a particulate carrier (C) and a catalyst component that has been brought into contact with the component (B) in advance are added to a polymerization vessel. In this case, each component (B) may be the same or different.
(P10) A catalyst in which the component (A) and the component (B) are supported on the fine particle carrier (C), the catalyst component previously contacted with the component (B), and the component (B) in any order How to add to. In this case, each component (B) may be the same or different.

In each of the above methods (P1) to (P10), at least two of the catalyst components may be contacted in advance.
The solid catalyst component in which the component (A) and the component (B) are supported on the particulate carrier (C) may be prepolymerized with olefin. This prepolymerized solid catalyst component is usually prepolymerized at a ratio of 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g of polyolefin per 1 g of the solid catalyst component.

Further, for the purpose of allowing the polymerization to proceed smoothly, an antistatic agent, an anti-fouling agent, or the like may be used in combination or supported on a carrier.
The polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, and gas phase polymerization methods, and suspension polymerization and gas phase polymerization methods are particularly preferred.

  Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene, etc., aromatic hydrocarbons, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane or mixtures thereof, and the olefin itself as a solvent. It can also be used.

When (co) polymerization is performed using the above olefin polymerization catalyst, the component (A) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻ , per liter of reaction volume. It is used in such an amount that it becomes ³ mol.

  The component (B-1) used as necessary has a molar ratio [(B-1) / M] of the component (B-1) and the transition metal atom (M) in the component (A) is usually It is used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000.

  The component (B-2) used as necessary is a molar ratio of the aluminum atom in the component (B-2) and the transition metal atom (M) in the component (A) [(B-2) / M ] Is usually used in an amount of 10 to 500,000, preferably 20 to 100,000.

  The component (B-3) used as necessary has a molar ratio [(B-3) / M] of the component (B-3) and the transition metal atom (M) in the component (A) is usually The amount used is 1 to 10, preferably 1 to 5.

  When the component (B) is the component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1. When the component (B) is the component (B-2), the molar ratio [(D) / (B-2)] is usually 0.001 to 2, preferably 0.005 to 1. When the component (B) is the component (B-3), the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5. Used in quantity.

The polymerization temperature using such an olefin polymerization catalyst is usually in the range of -50 to + 250 ° C, preferably 0 to 200 ° C, particularly preferably 60 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction is carried out in any of batch, batch, semi-continuous and continuous methods. Can also be done. The polymerization is usually performed in a gas phase or a slurry phase in which polymer particles are precipitated in a solvent. Furthermore, the polymerization is carried out in two or more stages with different reaction conditions. Among these, it is preferable to carry out by a batch type. In the case of slurry polymerization or gas phase polymerization, the polymerization temperature is preferably 60 to 90 ° C, more preferably 65 to 85 ° C. By polymerizing in this temperature range, an ethylene polymer having a narrower composition distribution can be obtained. The obtained polymer is in the form of particles of about several tens to several thousand μmφ. When the polymerization is carried out in a continuous system comprising two or more polymerization vessels, it is necessary to perform operations such as dissolution in a good solvent and precipitation in a poor solvent, or sufficient melting and kneading with a specific kneader.

  For example, when the ethylene polymer according to the present invention is produced in two stages, an ethylene homopolymer having an intrinsic viscosity of 0.3 to 1.8 dl / g is produced in the previous stage, and the intrinsic viscosity is 3.0 to 10.0 dl / g in the latter stage. The (co) polymer is produced. This order may be reversed.

  Since such an olefin polymerization catalyst has extremely high polymerization performance for α-olefins (for example, 1-hexene) copolymerized with ethylene, an α-olefin content that is too high after a predetermined polymerization is completed. It is necessary to devise such that no copolymer is formed. For example, [1] a method of separating a polymer, a solvent, and unreacted α-olefin with a solvent separation device simultaneously or as soon as possible after the contents of the polymerization vessel are extracted from the polymerization vessel; [2] A method of forcibly discharging the solvent and unreacted α-olefin out of the system by adding an inert gas such as nitrogen, [3] Forcing the solvent and unreacted α-olefin to be controlled by controlling the pressure applied to the contents [4] A method of diluting unreacted α-olefin to a concentration at which it is considered that substantially no polymerization occurs by adding a large amount of solvent to the contents, [5] Methanol, etc. Examples include a method of adding a substance that deactivates the polymerization catalyst, and [6] a method of cooling the contents to a temperature at which polymerization is considered not to occur. These methods may be carried out singly or in combination.

  The molecular weight of the resulting ethylene polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. Furthermore, it can also adjust by the difference in the component (B) to be used.

The polymer particles obtained by the polymerization reaction may be pelletized by the following method.
(1) A method of mechanically blending ethylene-based polymer particles and other components added as required using an extruder, a kneader, etc., and cutting them into a predetermined size.
(2) Dissolve the ethylene polymer and other components added as required in a suitable good solvent (for example, a hydrocarbon solvent such as hexane, heptane, decane, cyclohexane, benzene, toluene and xylene), and then remove the solvent. Removal and then mechanically blending using an extruder, kneader, etc., and cutting to a predetermined size.

  The ethylene polymer according to the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an anti-fogging agent, a lubricant, a dye, as long as the object of the present invention is not impaired. Additives such as nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbents, antioxidants, carbon black, titanium oxide, titanium yellow, phthalocyanine, isoindolinone, quinacridone compounds, condensed azo compounds, ultramarine, cobalt blue, etc. A pigment may be blended as necessary.

  The ethylene polymer according to the present invention can be molded into blow molded products, inflation molded products, cast molded products, extruded laminated molded products, extruded molded products such as pipes and irregular shapes, foam molded products, injection molded products, and the like. . Furthermore, it can be used for fibers, monofilaments, nonwoven fabrics and the like. These molded products include molded products (laminates and the like) including a part made of an ethylene polymer and a part made of another resin. The ethylene polymer may be one that has been crosslinked in the molding process. It is preferable to use the ethylene-based polymer according to the present invention for blow molded products and extruded molded products such as pipes and irregular shapes in the above molded products.

The ethylene polymer (E _B ) for blow molded articles according to the present invention can be molded into a bottle container, an industrial chemical can, a gasoline tank, or the like by blow molding. These molded products include molded products (laminates and the like) including a portion made of an ethylene polymer (E _B ) and a portion made of another resin. When the ethylene polymer (E _B ) contains a pigment, the concentration is usually 0.01 to 3.00% by weight.

The ethylene-based polymer (E _P ) for pipes according to the present invention can be formed into a pipe or a pipe joint formed by injection molding. These molded bodies include molded bodies (laminates and the like) including a portion made of an ethylene (co) polymer and a portion made of another resin. When the ethylene polymer (E _B ) contains a pigment, the concentration is usually 0.01 to 3.00% by weight.

Measurement method of various physical properties ★ Preparation of sample for measurement 0.1 weight of tri (2,4-di-t-butylphenyl) phosphate as secondary antioxidant to 100 parts by weight of particulate ethylene polymer 1 part by weight of n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propinate as heat stabilizer and 0.05 part by weight of calcium stearate as hydrochloric acid absorbent To do. Thereafter, using a lab plast mill (two-axis batch type melt kneader) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 190 ° C., an ethylene polymer charge amount of 40 g (apparatus batch volume = 60 cm ³ ), 50 rpm, 5 minutes or 50 rpm, After melt-kneading for 10 minutes, the sample was taken out and formed into a sheet with a cooling press set at 20 ° C., and this was cut into an appropriate size to obtain a sample for measurement. In addition, you may granulate using a normal extruder. However, when granulating the particulate ethylene polymer obtained by continuous two-stage polymerization, ingenuity such as using a twin screw extruder with a long L / D to sufficiently homogenize the polymer particles is necessary.

★ Measurement of ethylene content and α-olefin content
^The number of methyl branches per 1,000 carbons in the molecular chain of the ethylene polymer was measured by ¹³ C-NMR. Measurement was performed using a Lambda 500 type nuclear magnetic resonance apparatus ( ¹ H: 500 MHz) manufactured by JEOL Ltd. Measurement was performed at 10,000 to 30,000 integrations. The main chain methylene peak (29.97 ppm) was used as the chemical shift standard. Mixing of 250 to 400 mg of sample and Wako Pure Chemical Industries, Ltd. special grade o-dichlorobenzene: ISOTEC benzene-d ₆ = 5: 1 (volume ratio) in a commercially available NMR measuring quartz glass tube with a diameter of 10 mm 2 ml of the solution was added, and the NMR measurement was performed on the solution which was heated and uniformly dispersed at 120 ° C. Assignment of each absorption in the NMR spectrum was carried out in accordance with Chemistry Special Issue 141 NMR-Review and Experiment Guide [I], pages 132-133. The composition of the ethylene / α-olefin copolymer is usually ¹³ C-NMR of a sample in which 250 to 400 mg of copolymer is uniformly dissolved in 2 ml of hexachlorobutadiene in a 10 mmφ sample tube. The spectrum is determined by measurement under measurement conditions of a measurement temperature of 120 ° C., a measurement frequency of 125.7 MHz, a spectrum width of 250,000 Hz, a pulse repetition time of 4.5 seconds, and a 45 ° pulse.

★ Cross separation (CFC)
Measurement was carried out as follows using a Mitsubishi CFC T-150A model. The separation column is three Shodex AT-806MS, the eluent is o-dichlorobenzene, the sample concentration is 0.1-0.3wt / vol%, the injection volume is 0.5ml, the flow rate is 1.0ml / min. It is. The sample was heated at 145 ° C. for 2 hours, then cooled to 0 ° C. at 10 ° C./hr, and further maintained at 0 ° C. for 60 minutes to coat the sample. The temperature elution column capacity is 0.86 ml and the pipe capacity is 0.06 ml. The detector used an infrared spectrometer MIRAN 1A CVF type (CaF ₂ cell) manufactured by FOXBORO, and infrared light of 3.42 μm (2924 cm ⁻¹ ) was detected by setting the absorbance mode with a response time of 10 seconds. The elution temperature was divided into 35 to 55 fractions from 0 ° C. to 145 ° C., particularly in the vicinity of the elution peak. All temperature indications are integers. For example, the elution fraction at 90 ° C. indicates a component eluted at 89 ° C. to 90 ° C. The molecular weight of the components that were not coated even at 0 ° C. and the molecular weight of the fraction eluted at each temperature were measured, and the molecular weight in terms of PE was determined using a general-purpose calibration curve. The SEC temperature is 145 ° C., the internal standard injection volume is 0.5 ml, the injection position is 3.0 ml, and the data sampling time is 0.50 seconds. In addition, when there are too many components to elute in a narrow temperature range and a pressure abnormality occurs, the sample concentration may be less than 0.1 wt / vol%. Data processing was performed with the analysis program “CFC data processing (version 1.50)” included with the device. Cross fractionation (CFC) itself is said to be an analytical method that reproduces the results with high analytical accuracy if the measurement conditions are exactly the same. Is more preferable.

* Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight curve It measured as follows using GPC-150C by Waters. The separation columns are TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size is 7.5 mm in inner diameter and 600 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) ) And 0.025 wt% BHT (Takeda Pharmaceutical) as the antioxidant, moved at 1.0 ml / min, the sample concentration was 0.1 wt%, the sample injection amount was 500 μl, and a differential refractometer was used as the detector. Standard polystyrene for molecular weight Mw <1,000 and Mw> 4 × 10 ⁶ Using Tosoh Corp., for 1,000 ≦ Mw ≦ 4 × 10 ⁶ was used Pressure Chemical Corporation. The molecular weight calculation is a value obtained by universal calibration and conversion into polyethylene.

* Separation of molecular weight curve A program was created using Visual Basic of Excel (registered trademark) 97 manufactured by Microsoft Corporation. The two curves to be separated were log-normal distributions, and the molecular weight distribution curve was separated into two curves with different molecular weights by convergence calculation. The curve obtained by re-synthesizing the two separated curves and the molecular weight curve measured by GPC are compared, and the calculation is executed while changing the initial values so that the two are almost the same. Calculation is performed by dividing Log (molecular weight) into 0.02 intervals. Normalize the intensity so that the area of the measured molecular weight curve and the area of the curve obtained by recombining the two separated curves are 1, and the measured intensity (height) at each molecular weight and the strength of the recombined curve (high The value obtained by dividing the absolute value of the difference by the measured strength (height) is 0.4 or less, preferably 0.2 or less, more preferably 0.1 or less in the molecular weight range of 10,000 to 1,000,000. The curve separation calculation is repeated until the maximum peak position is 0.2 or less, preferably 0.1 or less. At this time, the difference between the Mw / Mn of the peak separated on the low molecular weight side and the Mw / Mn of the peak separated on the high molecular weight side is set to 1.5 or less. A calculation example is shown in FIG.

★ Smoothness coefficient R
The resin is extruded at a resin temperature of 200 ° C and a speed of 50 mm / min (3.6 cm ³ / min) using a capillary flow characteristic tester Capillograph 1B manufactured by Toyo Seiki Co., Ltd. A nozzle with a length L = 60mm and a diameter D = 1mm, or a cylindrical die (outer diameter 4mmφ, slit = 1mm, length 10mm) that can extrude a tube-shaped object is attached instead of a capillary die. Even if the polymer is pelletized, if the polymer particles polymerized in the gas phase or slurry phase are not sufficiently mixed together, the surface of the melt-extruded product becomes rough. The surface roughness is measured using the strand or tube thus obtained as the measurement surface. For measurement, Surfcom 1400D manufactured by Tokyo Seimitsu Co., Ltd. was used. Measurement length = 10 mm, measurement speed = 0.06 mm / sec, sampling time = 0.01 sec, sampling pitch = 0.6 μm, measuring needle material is diamond, measuring needle tip = 5 μmφ, and is calculated according to the calculation standard JIS B0601-1982. Let the point average roughness be Rz. Rz is the value of the difference between the average value of the altitude at the top of the peak from the highest to the fifth and the average value of the altitude at the bottom of the valley from the deepest to the fifth with respect to the average line of the measurement length of 10 mm. The measurement is performed three times at different locations, and the average value is the dispersion coefficient R. Here, the standard deviation is obtained for Rz measured three times. If the value of the standard deviation is larger than 1/2 of the value of R, which is the average value of Rz measured three times, remeasurement is performed. When R exceeds 20 μm, the polymer particles are not sufficiently mixed, and therefore, even when forming a thick molded body such as a pipe or blow bottle, flow failure occurs and the surface skin is not smooth. Or stress concentration occurs between the polymer particles, and the mechanical strength is not sufficiently developed. On the other hand, if R is 20 μm or less, it can be said that no history of polymer particles remains.

★ Measurement of continuous crystal structure exceeding 10μm Ethylene polymer was melted at 190 ° C using a hydraulic press molding machine manufactured by Shinto Metal Industry Co., Ltd. A press sheet having a thickness of 0.5 mm was prepared by pressing. Then, it cuts to about 0.5 mm (press sheet thickness) × 10 to 20 μm using a microtome or the like. Thereafter, a small amount of glycerin was applied to the cut piece and brought into close contact with the preparation, and a cover glass was placed thereon to form an observation sample. This sample was set between crossed Nicols polarizing plates and observed with an optical microscope magnified about 75 times and 150 times. 29 and 30 show an example in which there is no continuous crystal structure exceeding 10 μm when the crystal structure is observed only in a part of the field of view, and 10 μm when the crystal structure is observed in the entire field of view. An example of what is said to be a continuous crystal structure exceeding is shown. The scale bar has a total length of 0.5 mm.

★ Measurement of the number of methyl branches
^The number of methyl branches per 1,000 carbon atoms in the polyethylene molecular chain was measured by ¹³ C-NMR. For the measurement, an EPC500 type nuclear magnetic resonance apparatus ( ¹ H; 500 MHz) manufactured by JEOL Ltd. was used. Measurement was performed at 10,000 to 30,000 integrations. The main chain methylene peak (29.97 ppm) was used as the chemical shift standard. Mixing of 250 to 400 mg of sample and special grade o-dichlorobenzene manufactured by Wako Pure Chemical Industries, Ltd .: benzene-d ₆ = 5: 1 manufactured by ISOTEC (volume ratio) into a commercially available quartz glass tube with a diameter of 10 mm 3 ml of the liquid was added, heated at 120 ° C. and uniformly dispersed, and measured. Assignment of each absorption in the NMR spectrum was performed in accordance with Chemistry Special Issue 141 NMR-Review and Experiment Guide [I], pages 132-133. The number of methyl branches per 1,000 carbons was calculated from the integrated intensity ratio of the absorption of methyl groups derived from methyl branches (19.9 ppm) to the integrated sum of absorptions appearing in the range of 5 to 45 ppm. When the number of methyl branches per 1,000 carbon atoms is less than 0.08, it is not detected below the measurement limit.

★ Intrinsic viscosity ([η])
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of granulated pellets are dissolved in 15 ml of decalin, and the specific viscosity η _sp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity η _sp is measured in the same manner. This dilution operation is repeated two more times, and the value of η _sp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity (see the following formula).

★密度（d）
190℃に設定した神藤金属工業社製油圧式熱プレス機を用い、100kg／cm²の圧力で0.5mm厚のシートを成形し（スペーサー形状; 240×240×0.5mm厚の板に45×45×0.5mm、9個取り）、20℃に設定した別の神藤金属工業社製油圧式熱プレス機を用い、100kg／cm²の圧力で圧縮することで冷却して測定用試料を作成した。熱板は5mm厚のSUS板を用いた。このプレスシートを120℃で１時間熱処理し、1時間かけて直線的に室温まで徐冷したのち、密度勾配管で測定した。

★ Density (d)
Using a hydraulic heat press manufactured by Shinfuji Metal Industry Co., Ltd., set at 190 ° C, a 0.5mm thick sheet was formed at a pressure of 100kg / cm ² (spacer shape; 45x45x on a 240x240x0.5mm thick plate) Samples for measurement were prepared by cooling by compressing at a pressure of 100 kg / cm ² using another hydraulic heat press machine manufactured by Shinfuji Metal Industry Co., Ltd., set to 20 ° C., which was set to 20 ° C. The hot plate was a 5 mm thick SUS plate. The press sheet was heat-treated at 120 ° C. for 1 hour, linearly cooled to room temperature over 1 hour, and then measured with a density gradient tube.

★ Soluble in decane According to JIS K 6796, except that decane controlled at 140 ° C is used as the solvent, and the sample is cut from a 0.5 mm thick press sheet or granulated pellets and the concentration is 1 mg / ml. The gel content is measured, and if the gel fraction is 1 wt% or less, it is soluble in 140 ° C decane.

-Environmental stress cracking test for press sheets: ESCR (hr)
Using a hydraulic heat press manufactured by Shinfuji Metal Industry Co., Ltd. set at 190 ° C, a 2mm thick sheet was formed at a pressure of 100kg / cm ² (spacer shape; 80x80x2mm on a 240x240x2mm thick plate, A sample for measurement was prepared by cooling by compressing at a pressure of 100 kg / cm ² using another hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set at 20 ° C. The hot plate was a 5 mm thick SUS plate. From the above 80 × 80 × 2 mm thick press sheet, a 13 mm × 38 mm test piece was punched out using an ordered bell and used as an evaluation sample.

Environmental stress fracture resistance (ESCR) resistance was measured according to ASTM D1693. The outline of the evaluation conditions (vent strip method) is shown below.
Sample shape: Press molding C method specie 38x13mm Thickness 2mm (HDPE)
Notch length 19mm, depth 0.35mm
Test temperature: 50 ° C Constant temperature water bath Controllable to 50.0 ± 0.5 ° C Sample holding: 11.75mm inner dimension 165mm length holder set with special bending jig Surfactant: Nonylphenyl polyoxyethylene ethanol ( AntaroxCO-630 (commercially available) is diluted with water and used at a concentration of 10%.
Evaluation method: F50 destruction time (50% destruction time) is obtained using logarithmic probability paper.

★ Bending elastic modulus of press sheet A test piece with a width of 12.7mm and a length of 63.5mm is punched from the 80 × 80 × 2mm thick press sheet for ESCR property measurement, and the test temperature is 23 ° C in accordance with ASTM-D-790. The measurement was performed at a bending speed of 5.0 mm / min and a distance between bending spans of 32.0 mm.

★ tanδ (= loss modulus G '' / storage modulus G ')
Details of tan δ are described in, for example, Polymer publications, “Lectures / Rheology”, pages 20-23 of the Japanese Society of Rheology. The measurement was performed using a rheometer RS-II manufactured by Rheometrics, Inc., and measuring the angular frequency (ω (rad / sec)) dispersion of the storage elastic modulus G ′ (Pa) and the loss elastic modulus G ″ (Pa). The sample holder was a 25 mmφ parallel plate, and the sample thickness was about 2 mm. The measurement temperature was 190 ° C., and G ′ and G ″ were measured in the range of 0.04 ≦ ω ≦ 400. The number of measurement points was 5 per ω digit. The amount of strain was appropriately selected in the range of 2 to 25% so that the torque in the measurement range could be detected and the torque was not exceeded.

★ Bottle buckling strength, environmental stress fracture resistance (ESCR) measurement, and bottle creation to check pinch-off property Using Plako's extrusion blow molding machine (model name: 3B 50-40-40), set temperature Blow molding under the conditions of 180 ° C, die diameter 23mmφ, core diameter 21mmφ, extrusion rate 12kg / hr, mold temperature 25 ° C, clamping speed 1.4 seconds, clamping pressure 5.5t, blowing air pressure 5kg / cm ² A cylindrical bottle with an amount of 1,000 cc and a basis weight of 50 g was obtained.

★ Buckling strength of the bottle The buckling strength of the bottle created as described above was measured with a universal testing machine manufactured by Instron at a crosshead speed of 20 mm / min.

★ Environmental stress fracture resistance (ESCR) of bottles After filling 100 cc of Kao's kitchen hitter into the bottle created as above, the mouth is sealed with resin and held in an oven at 65 ° C to reduce the breakage time. Observed and determined F50 destruction time using logarithmic probability paper.

★ Pinch-off property of bottle (measurement of pinch thickness ratio)
When the bottom of the bottle obtained by blow molding as described above is cut in a direction perpendicular to the mating surface of the mold, the thickness of the center of the bottle is a, and the thickness of the thickest part is b. Then, the pinch thickness ratio is represented by (a / b). The larger the value, the better the pinch shape (see FIG. 31).

★ 80 ℃ tensile fatigue strength
Using a hydraulic heat press manufactured by Shinfuji Metal Industry Co., Ltd. set at 190 ° C, sheets of 2mm and 6mm thickness were formed at a pressure of 100kg / cm ² (spacer shape: 80 × on a 240 × 240 × 2mm thick plate) 80 x 2 mm, 4 pieces, and 30 x 60 x 6 mm on a 200 x 200 x 6 mm thick plate, 4 pieces), using another Kamito Metal Industries hydraulic heat press set at 20 ° C, 100 kg / The sample was cooled by compressing at a pressure of cm ² to prepare a sample for measuring 80 ° C. tensile fatigue strength. A 30 × 60 × 6 mm thick press sheet was cut into a 5-5 mm vertical × 6 mm wide × 60 mm long prism and used as an evaluation sample for actual measurement.

  Tensile fatigue strength (test specimen shape) conforms to JIS K-6774 using Shimadzu servo pulsar EHF-ER1KN × 4-40L. (All-around notch type, notch depth 1 mm) The outline of the evaluation conditions is as follows; Test piece shape (with 5-6 x 6 x 60 mm prismatic notch), test waveform and test frequency (rectangular wave 0.5 Hz), test temperature (80 ° C.), several points were measured in the range of 10 to 18 MPa of actual stress, and the number of vibrations when the sample broke was defined as fatigue strength. Measure at least 3 points with different actual stresses, measure at 3 digits or more in the number of fractures or 3MPa or more in actual stress, create an approximate expression by logarithmic least squares method, The actual stress corresponding to the number of times and 100,000 times is obtained.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[Synthesis Example 1]
[Preparation of solid catalyst component (α)]
After 8.5 kg of silica dried at 200 ° C. for 3 hours was suspended in 33 liters of toluene, 82.7 liters of methylaluminoxane solution (Al = 1.42 mol / liter) was added dropwise over 30 minutes. Next, the temperature was raised to 115 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The obtained solid catalyst component was washed with toluene three times and then resuspended with toluene to obtain a solid catalyst component (α) (total volume 150 liters).

[Preparation of supported catalyst]
In a 100 ml two-necked flask thoroughly purged with nitrogen, 20.39 mmol of the solid catalyst component (α) suspended in 20 ml of toluene was placed in an aluminum equivalent, and the suspension was stirred at room temperature (23 ° C.). Then, 45.2 ml (0.09 mmol) of a toluene solution of diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride having a concentration of 2 mmol / liter was added, followed by stirring for 60 minutes. After stopping the stirring, the supernatant liquid was removed by decantation, washing was performed 4 times with 50 ml of n-decane, and the obtained supported catalyst was reslurried in 100 ml of n-decane to form a catalyst suspension as a solid catalyst component ( β) was obtained.

[Example 1]
[polymerization]
Put 500 ml of n-heptane in a 1000 ml autoclave thoroughly purged with nitrogen, 0.25 ml (0.25 mmol) of triisobutylaluminum with a concentration of 1 mol / liter, 3.85 ml of the solid catalyst component (β) obtained in Synthesis Example 1 (0.003 as Zr atoms) mmol equivalent) was added, pressurized to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 2.53 vol%, and polymerization was started at 80 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and polymerization was performed for 70 minutes. After the polymerization, the pressure was released and nitrogen substitution was performed to remove the ethylene / hydrogen mixed gas.

The autoclave was charged with 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1 mol / liter and 2.7 ml of 1-hexene, and pressurized to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 0.10 vol%. Polymerization was started again at 0 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and the polymerization was carried out for 20.5 minutes. After completion of the polymerization, the pressure was released and methanol was added to deactivate the catalyst. Then, the polymer was filtered, washed, and dried under vacuum at 80 ° C. for 12 hours. The obtained polymer was 84.50 g.

0.1 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl-3- (4 & apos) as a heat stabilizer for 100 parts by weight of the polymer particles 0.1 parts by weight of; -hydroxy-3 ', 5'-di-t-butylphenyl) propinate and 0.05 parts by weight of calcium stearate as a hydrochloric acid absorbent. Thereafter, using a lab plast mill manufactured by Toyo Seiki Co., Ltd. (biaxial batch type melt kneader), set temperature 190 ° C, resin charge 40g (device batch volume = 60cm ³ ), 50rpm, 5 minutes after melt kneading and taking out, 20 It was made into a sheet with a cooling press set at 0 ° C., and cut into an appropriate size to obtain a sample for measurement. The results are shown in Tables 1 to 3 and Table 6. Fig. 1 shows the contour line of CFC separation, Fig. 2 shows a 3D chart (bird's eye view) viewed from the low temperature side, Fig. 3 shows a 3D chart (bird's eye view) viewed from the high temperature side, and peak temperature (T ₂ ) (℃) FIG. 4 shows the GPC curve of the eluted component in FIG. 4, FIG. 5 shows the GPC curve of the component eluted at 73 to 76 (° C.), and FIG. 6 shows the GPC curve of the component eluted at 95 to 96 (° C.). In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. It can also be seen that this sample has an extremely high tensile fatigue strength at 80 ° C. compared to the sample used in the comparative example (see FIG. 32).

[Example 2]
[polymerization]
500 ml of n-heptane is put into a 1000 ml autoclave sufficiently purged with nitrogen, 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1 mol / liter, 3.90 ml of the solid catalyst component (β) obtained in Synthesis Example 1 (0.00304 as Zr atoms) mmol equivalent) was added, pressurized to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 2.53 vol%, and polymerization was started at 80 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and polymerization was performed for 63 minutes. After the polymerization, the pressure was released and nitrogen substitution was performed to remove the ethylene / hydrogen mixed gas.

The autoclave was charged with 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1 mol / liter and 2.7 ml of 1-hexene, and pressurized to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 0.15 vol%. Polymerization was started again at 0 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and polymerization was performed for 20.5 minutes. After completion of the polymerization, the pressure was released and methanol was added to deactivate the catalyst. Then, the polymer was filtered, washed, and dried under vacuum at 80 ° C. for 12 hours. The obtained polymer was 84.50 g.

  The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were added to 100 parts by weight of the polymer particles. After that, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., melt-kneaded at the same setting temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, and then taken out to form a sheet with a cooling press set at 20 ° C. Then, this was cut into an appropriate size to obtain a measurement sample. Moreover, a press sheet was prepared using the sample and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. It can be seen that this sample has a higher tensile fatigue strength at 80 ° C. than the sample used in the comparative example (see FIG. 32).

[Synthesis Example 2]
[Preparation of supported catalyst]
In a fully nitrogen-substituted reactor, 19.60 mol of the solid catalyst component (α) synthesized in Synthesis Example 1 suspended in toluene was added in terms of aluminum, and the suspension was stirred at room temperature ( At 20 to 25 ° C., 2 liters (74.76 mmol) of a 37.38 mmol / liter solution of diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride was added, followed by stirring for 60 minutes. . After the stirring is stopped, the supernatant liquid is removed by decantation, washing is performed twice with 40 liters of n-hexane, and the obtained supported catalyst is reslurried in n-hexane to form a 25 liter catalyst suspension as a solid catalyst. Component (γ) was obtained.

[Preparation of Solid Catalyst Component (δ) by Prepolymerization of Solid Catalyst Component (γ)]
Into a reactor equipped with a stirrer, 15.8 liters of purified n-hexane and the above solid catalyst component (γ) were added in a nitrogen atmosphere, then 5 mol of triisobutylaluminum was added and 3 g of polyethylene per 1 g of the solid component was added while stirring. Was pre-polymerized with an equivalent amount of ethylene. The polymerization temperature was kept at 20-25 ° C. After completion of the polymerization, the stirring was stopped, the supernatant was removed by decantation, washing was performed 4 times with 35 liters of n-hexane, and the obtained supported catalyst was made into a catalyst suspension with 20 liters of n-hexane. A solid catalyst component (δ) was obtained.

[Comparative Example 1]
[polymerization]
In the first polymerization tank, hexane is 50 liters / hr, the solid catalyst component (δ) obtained in Synthesis Example 2 is 0.15 mmol / hr in terms of Zr equivalent atoms, triethylaluminum is 20 mmol / hr, ethylene is 5.0 kg / hr. hr, hydrogen is continuously supplied at 65 N-liter / hr, and the polymerization tank contents are continuously withdrawn so that the liquid level in the polymerization tank becomes constant, while the polymerization temperature is 85 ° C., the reaction pressure is 8.5 kg / Polymerization was carried out under conditions of cm ² G and an average residence time of 2.5 hours. In the contents continuously extracted from the first polymerization tank, unreacted ethylene and hydrogen were substantially removed by a flash drum maintained at 65 ° C. under an internal pressure of 0.2 kg / cm ² G.

Thereafter, the contents are continuously fed to the second polymerization tank together with hexane 20 liter / hr, ethylene 4.0 kg / hr, hydrogen 0.2 N-liter / hr, 1-hexene 450 g / hr, polymerization temperature 70 ° C., Polymerization was continued under the conditions of a reaction pressure of 7 kg / cm ² G and an average residence time of 1.5 hours.

  In the second polymerization tank, the contents of the polymerization tank are continuously withdrawn so that the liquid level in the polymerization tank is constant, and hexane and unreacted monomers in the contents are removed with a solvent separator and dried to remove the polymer. Obtained. In Comparative Example 1, methanol was not supplied to the contents as in Example 3 described later.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. After that, using Thermoplastics 20mmφ single screw extruder (L / D = 28, full flight screw, compression ratio = 3, mesh 60/100/60), set temperature 230 ° C, resin extrusion rate 60g / min And granulated at 100 rpm to obtain a sample for measurement. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm.

Fig. 7 shows the contour line of CFC separation, Fig. 8 shows the 3D chart (bird's eye view) viewed from the low temperature side, Fig. 9 shows the 3D chart (bird's eye view) viewed from the high temperature side, and peak temperature (T ₂ ) (℃) FIG. 10 shows the GPC curve of the eluted component in FIG. 10, FIG. 11 shows the GPC curve of the component eluted at 73 to 76 (° C.), and FIG. 12 shows the GPC curve of the component eluted at 95 to 96 (° C.). FIG. 13 is a bird's-eye view (FIG. 8 or FIG. 9), where Log (M) is the x axis, Temp (° C.) is the y axis, and the vertical axis is the z axis. The projection figure (elution curve) and the integrated value of the eluted components (100 area% overall) are shown.
As shown in FIG. 32, the tensile fatigue strength at 80 ° C. of this sample is not so high.

[Comparative Example 2]
The same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles obtained in Comparative Example 1. After that, it was made at a set temperature of 240 ° C, a resin extrusion rate of 22g / min, and 100rpm using a Plavo twin screw extruder BT-30 (30mmφ, L / D = 46, rotating in the same direction, 4 needing zones). It was granulated and used as a sample for measurement. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. The smoothness is higher than that of Comparative Example 1 and the 80 ° C. tensile fatigue strength is slightly higher, but the 80 ° C. tensile fatigue strength is lower than that of Example 1 (see FIG. 32).

[Comparative Example 3]
The sample for measurement was Mitsui Chemicals Hi-Zex 7700M product pellets. The comonomer is 1-butene. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In observation with a polarizing microscope observed with a 100 × field, there is no continuous crystal structure exceeding 10 μm. As shown in FIG. 32, it can be seen that the 80 ° C. tensile fatigue measurement of this sample has a lower fatigue strength than the example.

[Comparative Example 4]
[Η] = 0.72 dl / g ethylene homopolymer and [η] = 5.2 dl / g by 80 ° C. slurry polymerization using the catalyst used in Example 1 described in JP-A-2002-53615 As a result, an ethylene / butene-1 copolymer having a butene-1 content of 1.7 mol% was obtained. These were mixed at a ratio of 49/51 (weight ratio), dissolved in paraxylene at 130 ° C at a concentration of 10 g / 1000 ml, stirred for 3 hours and then 1 hour to precipitate in 3000 ml of acetone at 20 ° C. After filtration, vacuum drying was performed at 60 ° C. all day and night, and then melt-kneaded using a lab plast mill to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Table 1 and Table 6.

[Comparative Example 5]
A product pellet of HDPE (trade name: Hostalen, brand name: CRP100) manufactured by Basel was used as a measurement sample. The comonomer is 1-butene. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. Fig. 14 shows the contour line by CFC separation, Fig. 15 shows the 3D chart (bird's eye view) viewed from the low temperature side, Fig. 16 shows the 3D chart (bird's eye view) viewed from the high temperature side, and peak temperature (T ₂ ) (℃) FIG. 17 shows the GPC curve of the eluted component in FIG. 17, FIG. 18 shows the GPC curve of the component eluted at 73 to 76 (° C.), and FIG. 19 shows the GPC curve of the component eluted at 95 to 96 (° C.). Here, T ₁ = T ₂ . In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. As shown in FIG. 32, it can be seen that the 80 ° C. tensile fatigue measurement test of this sample has a lower fatigue strength than the example.

[Example 3]
[polymerization]
In the first polymerization tank, hexane is 45 liters / hr, the solid catalyst component (δ) obtained in Synthesis Example 2 is converted to Zr atoms, 0.11 mmol / hr, triethylaluminum is 20 mmol / hr, and ethylene is 5.0 kg / hr. While continuously supplying hydrogen at 57 N-liter / hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank becomes constant, the polymerization temperature is 85 ° C., the reaction pressure is 8.5 kg / cm. Polymerization was carried out under the conditions of ² G and an average residence time of 2.5 hours.

In the contents continuously extracted from the first polymerization tank, unreacted ethylene and hydrogen were substantially removed by a flash drum maintained at 65 ° C. under an internal pressure of 0.2 kg / cm ² G.
Thereafter, the contents were continuously fed to the second polymerization tank together with hexane 35 liter / hr, ethylene 4.0 kg / hr, hydrogen 0.2 N-liter / hr, 1-hexene 130 g / hr, polymerization temperature 80 ° C., Polymerization was continued under the conditions of a reaction pressure of 4.5 kg / cm ² G and an average residence time of 1.2 hours.

  In the second polymerization tank, the contents of the polymerization tank were continuously withdrawn so that the liquid level in the polymerization tank was constant. In order to prevent unintended polymerization such as the production of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2 liter / hr to deactivate the polymerization catalyst. Thereafter, hexane and unreacted monomers in the contents were removed with a solvent separator and dried to obtain a polymer.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. Thereafter, granulation was carried out using a Plavo twin screw extruder BT-30 under the same conditions as in Comparative Example 2, such as the set temperature, the amount of resin extrusion, and the number of rotations to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6.

Fig. 20 shows the contour line of CFC separation, Fig. 21 shows the 3D chart (bird's eye view) seen from the low temperature side, Fig. 22 shows the 3D chart (bird's eye view) seen from the high temperature side, and peak temperature (T ₂ ) (℃) FIG. 23 shows the GPC curve of the eluted component in FIG. 23, FIG. 24 shows the GPC curve of the component eluted at 73 to 76 (° C.), and FIG. 25 shows the GPC curve of the component eluted at 95 to 96 (° C.). FIG. 26 is a bird's-eye view (FIG. 21 or FIG. 22), where Log (M) is the x axis, Temp (° C.) is the y axis, and the vertical axis is the z axis. The projection figure (elution curve) and the integrated value of the eluted components (100 area% overall) are shown. FIG. 27 shows only the integrated value of the eluted component amount (100 area% as a whole). In FIG. 27, the ethylene polymers obtained (or used) in Comparative Examples 1, 3 and 5 and Examples 12 and 13 described later are also shown.

  In the observation of the ethylene polymer obtained in Example 3 with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. As shown in FIG. 32, it can be seen that the 80 ° C. tensile fatigue measurement test of this sample has higher fatigue strength than the polymer used in the comparative example.

[Example 4]
[polymerization]
In the first polymerization tank, hexane is 45 liters / hr, the solid catalyst component (δ) obtained in Synthesis Example 2 is converted to Zr atoms, 0.11 mmol / hr, triethylaluminum is 20 mmol / hr, and ethylene is 7.0 kg / hr. , While continuously supplying hydrogen at 125 N-liter / hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank is constant, the polymerization temperature is 85 ° C., the reaction pressure is 8.5 kg / cm. Polymerization was carried out under conditions of ² G and an average residence time of 2.5 hours.

The contents continuously extracted from the first polymerization tank are substantially free of unreacted ethylene and hydrogen by a flash drum maintained at 65 ° C. with an internal pressure of 0.2 kg / cm ² G.
Thereafter, the contents were continuously fed to the second polymerization tank together with hexane 35 liter / hr, ethylene 3.0 kg / hr, hydrogen 0.07 N-liter / hr, 1-hexene 30 g / hr, polymerization temperature 80 ° C., Polymerization was continued under the conditions of a reaction pressure of 4.5 kg / cm ² G and an average residence time of 0.8 hr.

  In the second polymerization tank, the contents of the polymerization tank were continuously withdrawn so that the liquid level in the polymerization tank was constant. In order to prevent unintended polymerization such as the production of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2 liter / hr to deactivate the polymerization catalyst. Thereafter, hexane and unreacted monomers in the contents were removed with a solvent separator and dried to obtain a polymer.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. After that, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., melt-kneaded at the same setting temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, and then taken out to form a sheet with a cooling press set at 20 ° C. Then, this was cut into an appropriate size to obtain a measurement sample. Moreover, a press sheet was prepared using the sample and the physical properties were measured. The results are shown in Tables 1-4. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm.

[Comparative Example 6]
The sample for measurement was Mitsui Chemicals Hi-Zex 6200B product pellets. The comonomer is 1-butene. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-5. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. As compared with Example 4, it was found that the balance between rigidity and ESCR property was inferior.

[Synthesis Example 3]
[Preparation of supported catalyst]
In a reactor sufficiently purged with nitrogen, 9.50 mol of the solid catalyst component (α) synthesized in Synthesis Example 1 suspended in toluene was added in terms of aluminum, and the suspension was stirred at room temperature ( 12.6 ml (0.038 mmol) of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride 3 mmol / liter solution was added at 20 to 25 ° C., followed by stirring for 60 minutes . After stopping the stirring, the supernatant liquid was removed by decantation, washing was performed 4 times with 50 ml of n-pentane, and the obtained supported catalyst was reslurried in 50 ml of n-pentane to form a catalyst suspension as a solid catalyst component ( θ) was obtained.

[Preparation of solid catalyst component (φ) by prepolymerization of solid catalyst component (θ)]
Into a reactor equipped with a stirrer, the solid catalyst component (θ) was charged in a nitrogen atmosphere, and then 1.92 mmol of triisobutylaluminum was added, and 3 g of polyethylene was produced per 1 g of the solid component with stirring in an equivalent amount of ethylene. Prepolymerization was performed. The polymerization temperature was kept at 25 ° C. After completion of the polymerization, the stirring is stopped, the supernatant liquid is removed by decantation, washing is performed 4 times with 50 ml of n-pentane, and the obtained supported catalyst is solid as a catalyst suspension in 100 ml of n-pentane. A catalyst component (φ) was obtained.

[Example 5]
[polymerization]
Put 500 ml of n-heptane in a 1000 ml autoclave thoroughly purged with nitrogen, 0.25 ml (0.25 mmol) of triisobutylaluminum with a concentration of 1 mol / liter, 6.50 ml of solid catalyst component (φ) obtained in Synthesis Example 3 (0.0018 mmol of Zr atom) The pressure was increased to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 2.50 vol%, and polymerization was started at 80 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and polymerization was performed for 70.5 minutes. After the polymerization, the pressure was released and nitrogen substitution was performed to remove the ethylene / hydrogen mixed gas.

This autoclave was charged with 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1 mol / liter and 20.0 ml of 1-octene, and pressurized to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 0.021 vol%. Polymerization was started again at ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and polymerization was performed for 19.5 minutes. After completion of the polymerization, the pressure was released and methanol was added to deactivate the catalyst. Then, the polymer was filtered, washed, and dried under vacuum at 80 ° C. for 12 hours. The obtained polymer was 104.9 g.

  The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were added to 100 parts by weight of the polymer particles. Thereafter, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., after melt-kneading at the same set temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, take out with a cooling press set at 20 ° C. It was set as the sheet | seat and the sample for a measurement was cut | disconnected to a suitable magnitude | size. Moreover, a press sheet was prepared using the sample and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm.

[Example 6]
[polymerization]
In the first polymerization tank, hexane is 45 l / hr, the solid catalyst component (δ) obtained in Synthesis Example 2 is 0.13 mmol / hr in terms of Zr atoms, triethylaluminum is 20 mmol / hr, ethylene is 5.0 kg / hr. While continuously supplying hydrogen at 57 N-liter / hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank becomes constant, the polymerization temperature is 85 ° C., the reaction pressure is 8.3 kg / cm. Polymerization was carried out under the conditions of ² G and an average residence time of 2.6 hours. The contents continuously extracted from the first polymerization tank are substantially free of unreacted ethylene and hydrogen by a flash drum maintained at 60 ° C. with an internal pressure of 0.35 kg / cm ² G.

Thereafter, the contents were continuously supplied to the second polymerization tank together with hexane 35 liter / hr, ethylene 3.5 kg / hr, hydrogen 0.5 N-liter / hr, 1-hexene 220 g / hr, polymerization temperature 80 ° C., Polymerization was continued under the conditions of a reaction pressure of 3.8 kg / cm ² G and an average residence time of 1.2 hours.

  In the second polymerization tank, the contents of the polymerization tank were continuously withdrawn so that the liquid level in the polymerization tank was constant. In order to prevent unintended polymerization such as the production of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2 liter / hr to deactivate the polymerization catalyst. Thereafter, hexane and unreacted monomers in the contents were removed with a solvent separator and dried to obtain a polymer.

  The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were added to 100 parts by weight of the polymer particles. After that, using a Placo single screw extruder (screw diameter: 65 mm, L / D = 28, screen mesh 40/60/300 × 4/60/40), making at a set temperature of 200 ° C and a resin extrusion rate of 25 kg / hr. It was granulated and used as a sample for measurement. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. As shown in FIG. 32, in the 80 ° C. tensile fatigue measurement of this sample, the fatigue strength is higher than that of the sample used in the comparative example.

[Example 7]
[polymerization]
In the first polymerization tank, hexane is 45 liters / hr, the solid catalyst component (δ) obtained in Synthesis Example 2 is converted to Zr atoms, 0.13 mmol / hr, triethylaluminum is 20 mmol / hr, and ethylene is 5.0 kg / hr. While continuously supplying hydrogen at 55 N-liter / hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank becomes constant, the polymerization temperature is 85 ° C., the reaction pressure is 8.1 kg / cm. Polymerization was carried out under the conditions of ² G and an average residence time of 2.6 hours.

The contents continuously extracted from the first polymerization tank are substantially free of unreacted ethylene and hydrogen by a flash drum maintained at 60 ° C. with an internal pressure of 0.35 kg / cm 2 G.
Thereafter, the contents were continuously fed to the second polymerization tank together with hexane 35 liter / hr, ethylene 3.0 kg / hr, hydrogen 0.5 N-liter / hr, 1-hexene 130 g / hr, polymerization temperature 80 ° C., Polymerization was continued under the conditions of a reaction pressure of 3.9 kg / cm ² G and an average residence time of 1.2 hours.

  In the second polymerization tank, the contents of the polymerization tank were continuously withdrawn so that the liquid level in the polymerization tank was constant. In order to prevent unintended polymerization such as the production of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2 liter / hr to deactivate the polymerization catalyst. Thereafter, hexane and unreacted monomers in the contents were removed with a solvent separator and dried to obtain a polymer.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. Thereafter, a single screw extruder manufactured by Plako Corporation was used to granulate at the same set temperature and resin extrusion amount as in Example 6 to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. As can be seen from the 80 ° C. tensile fatigue measurement results shown in FIG. 32, this sample has higher fatigue strength than the sample used in the comparative example.

[Synthesis Example 4]
[Preparation of solid catalyst component]
Only in Synthesis Example 4, SiO ₂ manufactured by Asahi Glass Co., Ltd. having an average particle diameter of 3 μm, a specific surface area of 800 m ² / g, and a pore volume of 1.0 cm ³ / g was used as silica.

  After 9.0 kg of silica dried at 200 ° C. for 3 hours was suspended in 60.7 liters of toluene, 61.8 liters of methylaluminoxane solution (3.03 mol / liter as Al) was added dropwise over 30 minutes. Next, the temperature was raised to 115 ° C. over 1.5 hours, and the reaction was carried out at the same temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The obtained solid catalyst component was washed with toluene three times and then resuspended with toluene to obtain a solid catalyst component (ε) (total volume 150 liters).

[Preparation of supported catalyst]
In a reactor sufficiently purged with nitrogen, 9.58 mol of the solid catalyst component (ε) in terms of aluminum is added, and the suspension is stirred and di (p-tolyl) methylene at room temperature (20 to 25 ° C.). After adding 2 liters (24.84 mmol) of (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride 12.42 mmol / liter solution, the mixture was stirred for 60 minutes. After stopping the stirring, the supernatant liquid is removed by decantation, washing is performed twice with 40 liters of n-hexane, and the obtained supported catalyst is reslurried in n-hexane to form a 25 liter catalyst suspension as a solid catalyst. Component (κ) was obtained.

[Preparation of Solid Catalyst Component (λ) by Prepolymerization of Solid Catalyst Component (κ)]
Into a reactor equipped with a stirrer, 21.9 liters of purified n-hexane and the above solid catalyst component (κ) were charged under a nitrogen atmosphere, and then 1.7 mol of triisobutylaluminum was added, and 3 g of 2 g per 1 g of the solid component was added while stirring. Polyethylene was produced and prepolymerized with a considerable amount of ethylene. The polymerization temperature was kept at 20-25 ° C. After completion of the polymerization, stirring was stopped, the supernatant was removed by decantation, washing was performed 3 times with 40 liters of n-hexane, and the obtained supported catalyst was made into a catalyst suspension with 20 liters of n-hexane. A solid catalyst component (λ) was obtained.

[Example 8]
[polymerization]
In the first polymerization tank, hexane is 45 liters / hr, the solid catalyst component (λ) obtained in Synthesis Example 4 is 0.11 mmol / hr in terms of Zr atoms, triethylaluminum is 15 mmol / hr, and ethylene is 7.0 kg / hr. While continuously supplying hydrogen at 105 N-liter / hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank becomes constant, the polymerization temperature is 85 ° C., the reaction pressure is 7.9 kg / cm. Polymerization was carried out under the conditions of ² G and an average residence time of 2.5 hours.

Unreacted ethylene and hydrogen are substantially removed from the contents continuously extracted from the first polymerization tank by a flash drum maintained at an internal pressure of 0.30 kg / cm ² G and 60 ° C.
Thereafter, the contents were continuously fed to the second polymerization tank together with hexane 35 liter / hr, ethylene 4.0 kg / hr, hydrogen 2.0 N-liter / hr, 1-hexene 80 g / hr, polymerization temperature 80 ° C., Polymerization was continued under the conditions of a reaction pressure of 2.5 kg / cm ² G and an average residence time of 1.1 hours.

  In the second polymerization tank, the contents of the polymerization tank were continuously withdrawn so that the liquid level in the polymerization tank was constant. In order to prevent unintended polymerization such as the production of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2 liter / hr to deactivate the polymerization catalyst. Thereafter, hexane and unreacted monomers in the contents were removed with a solvent separator and dried to obtain a polymer.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. Thereafter, a single screw extruder manufactured by Plako Corporation was used to granulate at the same set temperature and resin extrusion amount as in Example 6 to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. As can be seen from the 80 ° C. tensile fatigue measurement results shown in FIG. 32, this sample has higher fatigue strength than the sample of the comparative example.

[Synthesis Example 5]
[Preparation of supported catalyst]
In a fully nitrogen-substituted reactor, 19.60 mol of the solid catalyst component (α) synthesized in Synthesis Example 1 suspended in toluene was added in terms of aluminum, and the suspension was stirred at room temperature ( 20 ~ 25 ° C) di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride 31.06mmol / L solution was added 2L (62.12mmol) and stirred for 60 minutes did. After stopping the stirring, the supernatant liquid is removed by decantation, washing is performed twice with 40 liters of n-hexane, and the obtained supported catalyst is reslurried in n-hexane to form a 25 liter catalyst suspension as a solid catalyst. Component (τ) was obtained.

[Preparation of solid catalyst component (ω) by prepolymerization of solid catalyst component (τ)]
Into a reactor equipped with a stirrer, 15.8 liters of purified n-hexane and the above solid catalyst component (τ) were added in a nitrogen atmosphere, and then 5 mol of triisobutylaluminum was added and 3 g of polyethylene per 1 g of the solid component was added while stirring. Was pre-polymerized with an equivalent amount of ethylene. The polymerization temperature was kept at 20-25 ° C. After completion of the polymerization, the stirring was stopped, the supernatant was removed by decantation, washing was performed 4 times with 35 liters of n-hexane, and the obtained supported catalyst was made into a catalyst suspension with 20 liters of n-hexane. A solid catalyst component (ω) was obtained.

[Example 9]
[polymerization]
In the first polymerization tank, hexane is 45 liters / hr, the solid catalyst component (ω) obtained in Synthesis Example 5 is 0.14 mmol / hr in terms of Zr atoms, triethylaluminum is 20 mmol / hr, and ethylene is 7.0 kg / hr. While continuously supplying hydrogen at 120 N-liter / hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank becomes constant, the polymerization temperature is 85 ° C., the reaction pressure is 7.9 kg / cm. Polymerization was carried out under the conditions of ² G and an average residence time of 2.6 hours.

Unreacted ethylene and hydrogen are substantially removed from the contents continuously extracted from the first polymerization tank by a flash drum maintained at an internal pressure of 0.30 kg / cm ² G and 60 ° C.
Thereafter, the contents were continuously fed to the second polymerization tank together with hexane 35 liter / hr, ethylene 7.0 kg / hr, hydrogen 3.0 N-liter / hr, 1-hexene 100 g / hr, polymerization temperature 80 ° C., Polymerization was continued under the conditions of a reaction pressure of 3.8 kg / cm ² G and an average residence time of 1.1 hours.

  In the second polymerization tank, the contents of the polymerization tank were continuously withdrawn so that the liquid level in the polymerization tank was constant. In order to prevent unintended polymerization such as the production of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2 liter / hr to deactivate the polymerization catalyst. Thereafter, hexane and unreacted monomers in the contents were removed with a solvent separator and dried to obtain a polymer.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. Thereafter, a single screw extruder manufactured by Plako Corporation was used to granulate at the same set temperature and resin extrusion amount as in Example 6 to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. As can be seen from the 80 ° C. tensile fatigue measurement results shown in FIG. 32, this sample has higher fatigue strength than the sample of the comparative example.

[Example 10]
[polymerization]
500 ml of n-heptane is put into a 1000 ml autoclave thoroughly purged with nitrogen, 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1 mol / liter, 4.87 ml of the solid catalyst component (β) obtained in Synthesis Example 1 (0.0038 mmol of Zr atom) The pressure was increased to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 2.50 vol%, and polymerization was started at 80 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and the polymerization was carried out for 54.5 minutes. After the polymerization, the pressure was released and nitrogen substitution was performed to remove the ethylene / hydrogen mixed gas.

This autoclave was charged with 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1 mol / liter and 1.0 ml of 1-hexene, and pressurized to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 0.10 vol%. Polymerization was started again at 0 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and the polymerization was carried out for 15.75 minutes. After completion of the polymerization, the pressure was released and methanol was added to deactivate the catalyst. Then, the polymer was filtered, washed, and dried under vacuum at 80 ° C. for 12 hours. The obtained polymer was 102.50 g.

  The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were added to 100 parts by weight of the polymer particles. After that, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., melt-kneaded at the same setting temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, and then taken out to form a sheet with a cooling press set at 20 ° C. Then, this was cut into an appropriate size to obtain a measurement sample. Moreover, a press sheet was prepared using the sample and the physical properties were measured. The results are shown in Tables 1-4. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Excellent rigidity and ESCR compared to the comparative example.

[Example 11]
[polymerization]
In the first polymerization tank, hexane is 45 liters / hr, the solid catalyst component (δ) obtained in Synthesis Example 2 is converted to Zr atoms, 0.11 mmol / hr, triethylaluminum is 20 mmol / hr, ethylene is 6.0 kg / hr. While continuously supplying hydrogen at 100 N-liter / hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank is constant, the polymerization temperature is 85 ° C., the reaction pressure is 8.5 kg / cm. Polymerization was carried out under the conditions of ² G and an average residence time of 2.5 hours.

The contents continuously extracted from the first polymerization tank are substantially free of unreacted ethylene and hydrogen by a flash drum maintained at 65 ° C. with an internal pressure of 0.2 kg / cm ² G.
Thereafter, the contents were continuously fed to the second polymerization tank together with hexane 35 liter / hr, ethylene 5.0 kg / hr, hydrogen 1.5 N-liter / hr, 1-hexene 55 g / hr, polymerization temperature 70 ° C., Polymerization was continued under the conditions of a reaction pressure of 6.5 kg / cm ² G and an average residence time of 1.2 hours.

  In the second polymerization tank, the contents of the polymerization tank were continuously withdrawn so that the liquid level in the polymerization tank was constant. In order to prevent unintended polymerization such as the production of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2 liter / hr to deactivate the polymerization catalyst. Thereafter, hexane and unreacted monomers in the contents were removed with a solvent separator and dried to obtain a polymer.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of polymer particles. Thereafter, it was granulated at a set temperature of 190 ° C. and a resin extrusion rate of 20 g / min at 100 rpm using a Plavo twin screw extruder to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-5. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Excellent rigidity and ESCR compared to the comparative example. It was also found that the physical properties of the bottle molded body were superior to the comparative example.

[Example 12]
[polymerization]
In the first polymerization tank, hexane was 45 liters / hr, the solid catalyst component (ω) obtained in Synthesis Example 5 was converted to Zr atoms, 0.08 mmol / hr, triethylaluminum 20 mmol / hr, and ethylene 7.0 kg / hr. While continuously supplying hydrogen at 52 N-liter / hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank becomes constant, the polymerization temperature is 85 ° C., the reaction pressure is 7.3 kg / cm. Polymerization was carried out under the conditions of ² G and an average residence time of 2.6 hours.

The contents continuously extracted from the first polymerization tank were substantially free from unreacted ethylene and hydrogen by a flash drum maintained at 60 ° C. with an internal pressure of 0.30 kg / cm ² G.
Thereafter, the contents were continuously fed to the second polymerization tank together with hexane 43 liter / hr, ethylene 3.8 kg / hr, hydrogen 14.0 N-liter / hr, 1-hexene 20 g / hr, polymerization temperature 75 ° C., Polymerization was continued under the conditions of a reaction pressure of 4.2 kg / cm ² G and an average residence time of 1.0 hr.

  In the second polymerization tank, the contents of the polymerization tank were continuously withdrawn so that the liquid level in the polymerization tank was constant. In order to prevent unintended polymerization such as the production of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2 liter / hr to deactivate the polymerization catalyst. Thereafter, hexane and unreacted monomers in the contents were removed with a solvent separator and dried to obtain a polymer.

  0.20 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and n-octadecyl-3- (4 & apos) as a heat stabilizer for 100 parts by weight of the polymer particles ; -Hydroxy-3 ', 5'-di-t-butylphenyl) propinate is mixed with 0.20 parts by weight, and calcium stearate as a hydrochloric acid absorbent is mixed with 0.15 parts by weight. Thereafter, a single screw extruder manufactured by Plako Corporation was used to granulate at the same set temperature and resin extrusion amount as in Example 6 to obtain a measurement sample. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. In addition, Table 5 shows the results of measuring the physical properties of bottles formed using the samples. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. The bottle molded body is excellent in rigidity as compared with the comparative example, and is excellent in moldability as compared with other examples.

[Example 13]
[polymerization]
In the first polymerization tank, hexane is 45 liters / hr, the solid catalyst component (ω) obtained in Synthesis Example 5 is converted to Zr atoms, 0.13 mmol / hr, triethylaluminum is 20 mmol / hr, and ethylene is 5.0 kg / hr. While continuously supplying hydrogen at 67 N-liter / hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank is constant, the polymerization temperature is 85 ° C., the reaction pressure is 7.4 kg / cm. Polymerization was carried out under the conditions of ² G and an average residence time of 2.7 hours.

Unreacted ethylene and hydrogen are substantially removed from the contents continuously extracted from the first polymerization tank by a flash drum maintained at an internal pressure of 0.30 kg / cm ² G and 60 ° C.
Thereafter, the content was continuously fed to the second polymerization tank together with hexane 43 liter / hr, ethylene 3.9 kg / hr, hydrogen 10.0 N liter / hr, 1-hexene 110 g / hr, polymerization temperature 75 ° C., Polymerization was then continued under the conditions of a reaction pressure of 4.5 kg / cm ² G and an average residence time of 1.1 hours.

  In the second polymerization tank, the contents of the polymerization tank were continuously withdrawn so that the liquid level in the polymerization tank was constant. In order to prevent unintended polymerization such as the production of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2 liter / hr to deactivate the polymerization catalyst. Thereafter, hexane and unreacted monomers in the contents were removed with a solvent separator and dried to obtain a polymer.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. Thereafter, a single screw extruder manufactured by Plako Corporation was used to granulate at the same set temperature and resin extrusion amount as in Example 6 to obtain a measurement sample. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. As can be seen from the 80 ° C. tensile fatigue measurement results shown in FIG. 32, this sample has higher fatigue strength than the comparative example.

[Example 14]
In the first polymerization tank, hexane is 45 liters / hr, the solid catalyst component (δ) obtained in Synthesis Example 2 is 0.24 mmol / hr in terms of Zr atoms, triethylaluminum is 20 mmol / hr, and ethylene is 7.0 kg / hr. While continuously supplying hydrogen at 125 N-liter / hr and continuously withdrawing the contents of the polymerization tank so that the liquid level in the polymerization tank becomes constant, the polymerization temperature is 85 ° C., the reaction pressure is 8.5 kg / cm. Polymerization was carried out under the conditions of ² G and an average residence time of 2.5 hours.

The contents continuously extracted from the first polymerization tank are substantially free of unreacted ethylene and hydrogen by a flash drum maintained at 65 ° C. with an internal pressure of 0.2 kg / cm ² G.
Thereafter, the content was continuously fed to the second polymerization tank together with hexane 35 liter / hr, ethylene 4.0 kg / hr, hydrogen 1.0 N-liter / hr, 1-hexene 50 g / hr, polymerization temperature 80 ° C., Polymerization was continued under the conditions of a reaction pressure of 2.8 kg / cm ² G and an average residence time of 1.2 hours.

  In the second polymerization tank, the contents of the polymerization tank were continuously withdrawn so that the liquid level in the polymerization tank was constant. In order to prevent unintended polymerization such as the production of a polymer containing a large amount of 1-hexene, methanol was supplied to the contents extracted from the second polymerization tank at 2 liter / hr to deactivate the polymerization catalyst. Thereafter, hexane and unreacted monomers in the contents were removed with a solvent separator and dried to obtain a polymer.

  Next, the same amount of the same secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 was blended with 100 parts by weight of the particulate ethylene polymer. After that, a measurement sample was granulated using Plato's twin screw extruder BT-30 under the same conditions of set temperature, resin extrusion amount and rotation speed as in Example 11. In observation with a polarizing microscope observed with a 100 × field, there is no continuous crystal structure exceeding 10 μm. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. In addition, Table 5 shows the results of measuring the physical properties of bottles formed using the samples.

[Example 15]
The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were added to 100 parts by weight of the polymer particles obtained in Example 4. After that, a measurement sample was granulated using Plato's twin screw extruder BT-30 under the same conditions of set temperature, resin extrusion amount and rotation speed as in Example 11. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. In observation with a polarizing microscope observed with a 100 × field, there is no continuous crystal structure exceeding 10 μm. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. In addition, Table 5 shows the results of measuring the physical properties of bottles formed using the samples.

[Example 16]
500 ml of n-heptane is placed in a 1000 ml autoclave thoroughly purged with nitrogen, 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1 mol / liter, 6.70 ml of the solid catalyst component (β) obtained in Synthesis Example 1 (0.0038 mmol of Zr atom) Was added to a pressure of 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 2.50 vol%, and polymerization was started at 80 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and polymerization was performed for 65 minutes. After the polymerization, the pressure was released and nitrogen substitution was performed to remove the ethylene / hydrogen mixed gas.

This autoclave was charged with 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1 mol / liter and 1.5 ml of 1-hexene, and pressurized to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 0.10 vol%. Polymerization was started again at 0 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and the polymerization was carried out for 10.5 minutes. After completion of the polymerization, the pressure was released and methanol was added to deactivate the catalyst. Then, the polymer was filtered, washed, and dried under vacuum at 80 ° C. for 12 hours. The obtained polymer was 97.80 g.

  The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were added to 100 parts by weight of the polymer particles. After that, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., melt-kneaded at the same setting temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, and then taken out to form a sheet with a cooling press set at 20 ° C. Then, this was cut into an appropriate size to obtain a measurement sample. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. Excellent rigidity and ESCR compared to the comparative example.

[Example 17]
The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were added to 100 parts by weight of the polymer particles obtained in Example 14. After that, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., melt-kneaded at the same setting temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, and then taken out to form a sheet with a cooling press set at 20 ° C. Then, this was cut into an appropriate size to obtain a measurement sample. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. Excellent rigidity and ESCR compared to comparative examples.

[Comparative Example 7]
A press sheet was prepared using the Hi-Zex 3000B product pellets manufactured by Mitsui Chemicals, and the physical properties were measured. The results are shown in Tables 1-4. Compared to the examples, the rigidity is inferior and the ESCR property is not so good.

[Example 18]
500 ml of n-heptane was put into a 1000 ml autoclave sufficiently purged with nitrogen, 0.25 (0.25 mmol) of triisobutylaluminum having a concentration of 1 mol / liter, 8.00 ml of the solid catalyst component (β) obtained in Synthesis Example 1 (0.0045 mmol of Zr atom) The pressure was increased to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 2.53 vol%, and polymerization was started at 80 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and polymerization was performed for 80 minutes. After the polymerization, the pressure was released and nitrogen substitution was performed to remove the ethylene / hydrogen mixed gas.

This autoclave was charged with 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1 mol / liter and 0.4 ml of 1-hexene, and pressurized to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 0.10 vol%. Polymerization was started again at 0 ° C. During the polymerization, an ethylene / hydrogen mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and polymerization was performed for 12.75 minutes. After completion of the polymerization, the pressure was released and methanol was added to deactivate the catalyst. Then, the polymer was filtered, washed, and dried under vacuum at 80 ° C. for 12 hours. The obtained polymer was 110.70 g.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. After that, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., melt-kneaded at the same setting temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, and then taken out to form a sheet with a cooling press set at 20 ° C. Then, this was cut into an appropriate size to obtain a measurement sample. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. Excellent rigidity compared to the comparative example.

[Example 19]
The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were added to 100 parts by weight of the polymer particles obtained in Example 4. Thereafter, a 20 mmφ single screw extruder manufactured by Thermo Plastics Co., Ltd. was used, and granulated at a set temperature of 190 ° C. with a resin extrusion rate of 60 g / min and 100 rpm to obtain a measurement sample. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. Since the smoothness is lower than that of Example 4, the ESCR property is also low.

[Comparative Example 8]
A press sheet was prepared using Novatec HD HB332R product pellets manufactured by Nippon Polyethylene Co., Ltd., and the physical properties were measured. The results are shown in Tables 1-4. Compared to the examples, the rigidity and the ESCR property are inferior.

[ Example 26 ]
The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles obtained in Example 3. Thereafter, a 20 mmφ single screw extruder manufactured by Thermoplastics was used, and granulated under the same conditions of set temperature, resin extrusion amount and rotation speed as in Comparative Example 1 to obtain a measurement sample. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. The smoothness is low compared to Example 3, and the 80 ° C. tensile fatigue measurement results shown in FIG. 32 show that the fatigue strength is lower than that of the comparative example. In addition, the fracture surface of the sample after tensile fatigue measurement broke without substantially extending.

[Synthesis Example 6]
[Preparation of Solid Catalyst Component (π) by Prepolymerization of Solid Catalyst Component (β)]
Into a 200 ml three-necked glass reactor equipped with a stirrer was charged 28 ml of purified hexane under nitrogen atmosphere, 2 ml (2 mmol) of triisobutylaluminum, and the solid catalyst component (β) synthesized in Synthesis Example 1 (equivalent to 0.03 mmol of Zr atom). Then, 3 g of polyethylene was produced in 1 hour per 1 g of the solid component, and prepolymerization was carried out with a considerable amount of ethylene. The polymerization temperature was kept at 20 ° C. After completion of the polymerization, the reactor was replaced with nitrogen, the prepolymerized catalyst was filtered under a nitrogen atmosphere with a glass filter sufficiently substituted with nitrogen, washed three times with purified hexane, suspended in about 100 ml of purified decane and the catalyst. The whole liquid was transferred to a bottle to obtain a solid catalyst component (π).

[Comparative Example 10]
[polymerization]
Put 100 ml of n-heptane in a 1000 ml autoclave thoroughly purged with nitrogen, 0.5 ml (0.5 mmol) of triisobutylaluminum with a concentration of 1 mol / liter, 3.5 ml of solid catalyst component (π) obtained in Synthesis Example 6 (0.003 mmol of Zr atom) 1 ml of Epan 720 (100 mg) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. and 2 mg / ml solution prepared by adding 25 ml of toluene and 25 ml of hexane (Epan 720 manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; equivalent to 2 mg) the charged was initiated hydrogen at 1.6 kg / cm ² polymerized in G pressurized then pressurized with 80 ° C. to 8.0 kg / cm ² G with ethylene. During the polymerization, ethylene was added so as to maintain 8.0 kg / cm ² G, and polymerization was performed for 40 minutes. After polymerization, depressurization and nitrogen substitution were performed to remove ethylene and hydrogen.

This autoclave was charged with 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1.0 mol / liter and 1.5 ml of 1-hexene, and pressurized to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 0.0990 vol%. Polymerization was started again at 80 ° C. During the polymerization, ethylene / mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and polymerization was performed for 50 minutes. After completion of the polymerization, the mixture was deheated and methanol was added to deactivate the catalyst. Then, the polymer was filtered, washed, and dried under vacuum at 80 ° C. for 12 hours. The obtained polymer was 150.2 g.

  The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were added to 100 parts by weight of the polymer particles. After that, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., melt-kneaded at the same setting temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, and then taken out to form a sheet with a cooling press set at 20 ° C. Then, this was cut into an appropriate size to obtain a measurement sample. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. As can be seen from the 80 ° C. tensile fatigue measurement results shown in FIG. 32, this polymer has lower fatigue strength than the polymers described in the examples. In addition, the fracture surface of the sample after tensile fatigue measurement broke without substantially extending.

[Example 20]
[polymerization]
500 ml of n-heptane was put into a 1000 ml autoclave sufficiently purged with nitrogen, 0.5 ml (0.5 mmol) of triisobutylaluminum having a concentration of 1 mol / liter, 5.0 ml of the solid catalyst component (π) obtained in Synthesis Example 6 (0.00214 mmol of Zr atoms) Equivalent), Epan 720 (100 mg) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. used in Comparative Example 10, and 1 ml (equivalent to 2 mg) of a 2 mg / ml solution prepared by adding 25 ml of toluene and 25 ml of hexane was added. the polymerization was initiated at under pressure and then ethylene 1.6 kg / cm ² G to 8.0 kg / cm ² G under pressure 80 ° C.. During polymerization, ethylene was added so as to maintain 8.0 kg / cm ² G, and polymerization was performed for 50 minutes. After polymerization, depressurization and nitrogen substitution were performed to remove ethylene and hydrogen.

This autoclave was charged with 0.25 ml (0.25 mmol) of triisobutylaluminum having a concentration of 1.0 mol / liter and 2.7 ml of 1-hexene, and pressurized to 8.0 kg / cm ² G with an ethylene / hydrogen mixed gas having a hydrogen content of 0.0994 vol%. Polymerization was started again at 80 ° C. During the polymerization, ethylene / mixed gas was added so as to keep the pressure at 8.0 kg / cm ² G, and polymerization was performed for 70 minutes. After completion of the polymerization, the mixture was deheated and methanol was added to deactivate the catalyst. Then, the polymer was filtered, washed, and dried under vacuum at 80 ° C. for 12 hours. The obtained polymer was 90.2 g.

  The same amount of secondary antioxidant, heat stabilizer and hydrochloric acid absorbent as those used in Example 1 were added to 100 parts by weight of the polymer particles. After that, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., melt-kneaded at the same setting temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, and then taken out to form a sheet with a cooling press set at 20 ° C. Then, this was cut into an appropriate size to obtain a measurement sample. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1 to 3 and Table 6. As is apparent from the 80 ° C. tensile fatigue measurement shown in FIG. 32, this sample has higher fatigue strength than the sample described in the comparative example. In addition, the fracture surface of the sample after tensile fatigue measurement broke without substantially extending.

[Example 21]
In order to remove nitrogen in the polymerizer after putting 1200 liters of hexane into the polymerizer sufficiently dried and purged with nitrogen, introducing 650 mmol of triisobutylaluminum and 1.3 g of Epan 720 from Daiichi Kogyo Seiyaku Co., Ltd. Then, pressurization and depressurization with ethylene were repeated three times. When the temperature in the polymerization reactor was heated to 70 ° C., the pressure was increased to 0.50 MPa with ethylene, and further, with hydrogen, the hydrogen concentration in the gas phase was 29 mol%. The solid catalyst component obtained in Synthesis Example 5 (omega) and simultaneously introducing 1.6mmol in terms of Zr atom, ethylene 30 Nm ³ / hr, the hydrogen was fed at a rate of 0.2 Nm ³ / hr, polymerization at 80 ° C. Started. After the ethylene supply integrated amount after starting ethylene supply reaches 52 Nm ³ , the supply of ethylene and hydrogen is stopped and the pressure in the system is released while depressurizing and removing ethylene and hydrogen with nitrogen. The temperature was lowered to 55 ° C. After removing ethylene and hydrogen in the system, the system was again heated to 70 ° C., 1.95 liters of 1-hexene was added, and the pressure was increased to 0.35 MPa with ethylene. Ethylene was fed at a rate of 24 Nm ³ / hr and hydrogen was fed at a rate of 1.0 N-liter / hr, and polymerization was resumed at 80 ° C. After the ethylene supply cumulative amount after starting ethylene supply reaches 28 Nm ³ , the supply of ethylene and hydrogen is stopped, and the polymerization slurry is quickly transferred to another container, depressurized, and supplied with nitrogen. Then, while removing ethylene and hydrogen, methanol was fed at 20 N-liter / hr for 1 hour to deactivate the catalyst. At this time, the temperature in the system was kept at 60 ° C.

The polymer was separated from hexane by filtration, washed with excess hexane, and then dried for 3 hours. The obtained polymer was 102.5 kg.
Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. After that, using a Placo single screw extruder (screw diameter 65 mm, L / D = 28, screen mesh # 300 × 4 sheets), granulate at a set temperature of 200 ° C. and a resin extrusion rate of 25 kg / hr, and a measurement sample. It was. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-3.

[Example 22]
In order to remove nitrogen in the polymerizer after putting 1200 liters of hexane into the polymerizer sufficiently dried and purged with nitrogen, introducing 650 mmol of triisobutylaluminum and 1.3 g of Epan 720 from Daiichi Kogyo Seiyaku Co., Ltd. Then, pressurization and depressurization with ethylene were repeated three times. When the temperature in the polymerization vessel was heated to 70 ° C., the pressure was increased to 0.50 MPa with ethylene, and further, with hydrogen, the hydrogen concentration in the gas phase was 28 mol%. The solid catalyst component (ω) obtained in Synthesis Example 5 was converted to Zr atoms and 1.6 mmol was added. At the same time, ethylene was fed at a rate of 32 Nm ³ / hr and hydrogen was fed at a rate of 0.2 Nm ³ / hr, and polymerized at 80 ° C. Started. After the ethylene supply integrated amount after starting ethylene supply reaches 52 Nm ³ , the supply of ethylene and hydrogen is stopped and the pressure in the system is released while depressurizing and removing ethylene and hydrogen with nitrogen. The temperature was lowered to 55 ° C. After removing ethylene and hydrogen in the system, the system was again heated to 70 ° C., 1.95 liters of 1-hexene was added, and the pressure was increased to 0.35 MPa with ethylene. Ethylene was fed at a rate of 26 Nm ³ / hr and hydrogen was fed at a rate of 1.1 N-liter / hr, and polymerization was resumed at 80 ° C. After the ethylene supply cumulative amount after starting ethylene supply reaches 23 Nm ³ , the supply of ethylene and hydrogen is stopped and the polymerization slurry is quickly transferred to another container, depressurized and supplied with nitrogen. Then, while removing ethylene and hydrogen, methanol was fed at 20 N-liter / hr for 1 hour to deactivate the catalyst. At this time, the temperature in the system was kept at 60 ° C.

The polymer was separated from hexane by filtration, washed with excess hexane, and then dried for 3 hours. The obtained polymer was 99.5 kg.
Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. After that, using a Placo single screw extruder (screw diameter 65 mm, L / D = 28, screen mesh # 300 × 4 sheets), granulate at a set temperature of 200 ° C. and a resin extrusion rate of 25 kg / hr, and a measurement sample. It was. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-3.

[Example 23]
In order to remove nitrogen in the polymerizer after putting 1200 liters of hexane into the polymerizer sufficiently dried and purged with nitrogen, introducing 650 mmol of triisobutylaluminum and 1.3 g of Epan 720 from Daiichi Kogyo Seiyaku Co., Ltd. Then, pressurization and depressurization with ethylene were repeated three times. When the temperature in the polymerization reactor was heated to 70 ° C., the pressure was increased to 0.50 MPa with ethylene, and further, with hydrogen, the hydrogen concentration in the gas phase was 29 mol%. The solid catalyst component (ω) obtained in Synthesis Example 5 was converted to Zr atoms and 1.6 mmol was added. At the same time, ethylene was fed at a rate of 32 Nm ³ / hr and hydrogen was fed at a rate of 0.1 Nm ³ / hr, and polymerization was performed at 80 ° C. Started. After the ethylene supply integration amount after starting ethylene supply reaches 40 Nm ³ , the supply of ethylene and hydrogen is stopped and the pressure in the system is released while removing the ethylene and hydrogen with nitrogen. The temperature was lowered to 55 ° C. After removing ethylene and hydrogen in the system, the system was heated again to 70 ° C., 1.39 liters of 1-hexene was added, and then pressurized to 0.35 MPa with ethylene. Ethylene was fed at a rate of 26 Nm ³ / hr and hydrogen was fed at a rate of 3.2 N-liter / hr, and polymerization was resumed at 80 ° C. After the ethylene supply cumulative amount after starting ethylene supply reaches 33 Nm ³ , the supply of ethylene and hydrogen is stopped, the polymerization slurry is quickly transferred to another container, depressurized, and supplied to nitrogen. Then, while removing ethylene and hydrogen, methanol was fed at 20 N-liter / hr for 1 hour to deactivate the catalyst. At this time, the temperature in the system was kept at 60 ° C.

The polymer was separated from hexane by filtration, washed with excess hexane, and then dried for 3 hours. The obtained polymer was 91.0 kg.
Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. After that, using a Placo single screw extruder (screw diameter 65 mm, L / D = 28, screen mesh # 300 × 4 sheets), granulate at a set temperature of 200 ° C. and a resin extrusion rate of 25 kg / hr, and a measurement sample. It was. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-3.

[Synthesis Example 7]
[Preparation of supported catalyst]
In a glove box, 0.18 g of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was weighed into a 1 liter four-necked flask. The flask was taken out of the glove box, 46 ml of toluene and 140 ml of a MAO / SiO ₂ toluene slurry (a solid amount of 8.82 g) were added under nitrogen, and the mixture was stirred for 30 minutes to carry. The resulting di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was replaced with 99% n-heptane, and finally The amount of slurry was 450 ml, and a solid catalyst component (σ) was prepared. This operation was performed at room temperature.

[Example 24]
[Ethylene polymerization]
An autoclave equipped with a stirrer with an internal volume of 200 liters was charged with 86.5 liters of heptane, 90 mmol of triisobutylaluminum, and 9 g of the solid catalyst component (σ) prepared above. The internal temperature was kept at 80 ° C., ethylene and hydrogen were charged, and the internal pressure was kept at 0.6 MPa / G for polymerization. The amount of ethylene charged was 13.7 kg.

Subsequently, the pressure in the polymerization tank was depressurized to 0 MPa / G and replaced with nitrogen to remove hydrogen in the polymerization tank.
Subsequently, 340 ml of 1-hexene was charged. The internal temperature was kept at 65 ° C., ethylene and hydrogen were charged, and the internal pressure was kept at 0.5 MPa / G for polymerization. The amount of ethylene charged was 9.0 kg.

  The total amount of the obtained polyethylene slurry was transferred to an autoclave with a stirrer having an internal volume of 500 liters, and 10.7 ml of methanol was charged to deactivate the catalyst. This slurry was transferred to a filter dryer equipped with a stirrer, filtered, and then vacuum dried at 85 ° C. for 6 hours to obtain polyethylene powder.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. After that, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., melt-kneaded at the same setting temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, and then taken out to form a sheet with a cooling press set at 20 ° C. Then, this was cut into an appropriate size to obtain a measurement sample. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. It was soluble in 140 ° C decane. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-3.

[Example 25]
[Ethylene polymerization]
An autoclave equipped with a stirrer with an internal volume of 200 liters was charged with 86.5 liters of heptane, 90 mmol of triisobutylaluminum, and 9 g of the solid catalyst component (σ) prepared in Synthesis Example 7. The internal temperature was kept at 80 ° C., ethylene and hydrogen were charged, and the internal pressure was kept at 0.6 MPa / G for polymerization. The amount of ethylene charged was 13.7 kg.

Subsequently, the pressure in the polymerization tank was reduced to 0 MPa / G and replaced with nitrogen to remove hydrogen in the polymerization tank.
Next, 473 ml of 1-hexene was charged. The internal temperature was kept at 65 ° C., ethylene and hydrogen were charged, and the internal pressure was kept at 0.5 MPa / G for polymerization. The amount of ethylene charged was 9.0 kg.

  The total amount of the obtained polyethylene slurry was transferred to an autoclave with a stirrer having an internal volume of 500 liters, and 10.7 ml of methanol was charged to deactivate the catalyst. This slurry was transferred to a filter dryer equipped with a stirrer, filtered, and then vacuum dried at 85 ° C. for 6 hours to obtain polyethylene powder.

  Next, the same amount of secondary antioxidant, heat resistance stabilizer and hydrochloric acid absorbent as those used in Example 1 were blended with 100 parts by weight of the polymer particles. After that, using a lab plast mill manufactured by Toyo Seiki Co., Ltd., melt-kneaded at the same setting temperature, resin charge amount, rotation speed and melting time conditions as used in Example 1, and then taken out to form a sheet with a cooling press set at 20 ° C. Then, this was cut into an appropriate size to obtain a measurement sample. In the observation with a polarizing microscope, there is no continuous crystal structure exceeding 10 μm. Soluble in decane at 140 ° C. Further, a press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-3.

  The ethylene-based polymer of the present invention provides a molded product having excellent moldability and excellent mechanical strength and appearance. When used in an ethylene-based polymer blow-molded product according to the present invention and an extrusion-molded product such as a pipe or an irregular shape, excellent characteristics are given.

Claims (13)

An ethylene polymer containing a structural unit derived from an α-olefin having 6 to 10 carbon atoms, which satisfies the following (1) and (2) in cross fractionation (CFC), and satisfies the following requirements (1 Ethylene polymer satisfying ') to (7').
(1) The weight average molecular weight (Mw) of the component eluted at 73 to 76 ° C does not exceed 4,000.
(2) The following relational expression (Eq-1) is satisfied.

(In Eq-1, S _x is the total area value of all peaks based on the components eluting at 70 to 85 ° C, and S _total is the _total area value of all peaks based on the components eluting at 0 to 145 ° C. )
(1 ′) Containing 0.02 to 1.0 mol% of a structural unit derived from an α-olefin having 6 to 10 carbon atoms.
(2 ′) The density (d) is in the range of 945 to 970 kg / m ³ .
(3 ′) The intrinsic viscosity ([η]) measured in decalin at 135 ° C. is in the range of 1.6 to 4.0 (dl / g).
(4 ′) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC is in the range of 5 to 70.
(5 ') In cross fractionation (CFC), the elution temperature at the peak of the strongest peak with molecular weight less than 100,000 is T ₁ (° C), and the elution temperature at the peak of the strongest peak with molecular weight of 100,000 or more is T ₂ (° C). In such a case, (T ₁ −T ₂ ) (° C.) is in the range of 0 to 11 ° C.
(6 ') Among the GPC curves of fractions eluted from [(T ₂ -1) to T ₂ ] (° C) in cross fractionation (CFC), the molecular weight at the peak of the strongest peak with a molecular weight of 100,000 or more is 200,000. It is in the range of ~ 800,000.
(7 ') The molecular weight of the peak of the strongest peak does not exceed 28,000 in the region where the molecular weight is 100,000 or less in the GPC curve of the component eluted at 95 to 96 ° C in cross fractionation (CFC).   The ethylene-based polymer according to claim 1, wherein the intrinsic viscosity ([η]) measured in decalin at 135 ° C is in the range of 1.92 to 3.47 (dl / g). The ethylene polymer according to claim 1, wherein the number of methyl branches measured by ¹³ C-NMR is less than 0.1 per 1000 carbon atoms. The ethylene polymer according to any one of claims 1 to 3, wherein the following requirements (1 _B ) to (3 _B ) are simultaneously satisfied.
(1 _B ) 0.02 to 0.20 mol% of structural units derived from an α-olefin having 6 to 10 carbon atoms are contained.
The ratio of (2 _B) weight average molecular weight measured by GPC (Mw) to the number average molecular weight (Mn) (Mw / Mn) is in the range of 5-30.
_{(3 B) T 1 (℃} ) elution temperature of the strongest peak apex of the molecular weight of the peak apex in cross fractionation (CFC) is less than 100,000, the dissolution temperature of the molecular weight of the strongest peak apex at 100,000 T ₂ ( (T ₁ -T ₂ ) (° C.) is in the range of 0 to 5 ° C. (1 _B ') The flexural modulus measured at 23 ° C in accordance with ASTM-D-790 is in the range of 1,500 to 1,800 MPa, 50 measured according to (2 _B ') ASTM-D-1693 5. The ethylene-based polymer according to claim 4, which has a non-destructive ESCR (hr) resistance to environmental stress fracture at 10 ° C. for 10 hours or more.   The ethylene system according to claim 5, wherein tan δ (= loss elastic modulus G ″ / storage elastic modulus G ′) at 190 ° C. and an angular frequency of 100 rad / sec measured using a dynamic viscoelastic device is 0.7 to 0.9. Polymer. The ethylene polymer according to any one of claims 1 to 3, which satisfies the following requirement (1 _P ).
(1 _P ) Containing 0.10 to 1.0 mol% of a structural unit derived from an α-olefin having 6 to 10 carbon atoms.
(2 _P) weight average molecular weight measured by GPC (Mw) to the number average molecular weight ratio (Mn) (Mw / Mn) is in the range of 11-70. The ethylene polymer according to claim 7, which satisfies the following requirement (1 _P ').
(1 _P ') Based on JIS K-6744, the tensile fatigue characteristics measured at 80 ° C, the actual stress when the number of times of breaking is 10,000 times is 13MPa to 17MPa, the actual number of times when breaking is 100,000 times The stress is 12-16 MPa.   A blow molded article comprising the ethylene polymer according to any one of claims 4 to 6.   The blow molded article according to claim 9, wherein the blow molded article is a gasoline tank, an industrial chemical can or a bottle container.   A pipe or pipe joint comprising the ethylene-based polymer according to claim 7 or 8.   The pipe or pipe joint according to claim 11 used for water supply.   The molded object containing the ethylene-type polymer in any one of Claims 1-8.

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