JP2006083370A - Ethylene-based polymer and application for blow-molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene-based polymer excellent in moldability, and mechanical strength and environmental breaking stress resistance, and capable of giving a molded article excellent in appearance, especially a blow-molded article. <P>SOLUTION: This ethylene-based polymer containing 0.02-0.50 mol% constituting unit introduced from a 6-10C α-olefin is provided by satisfying any one or more of the following (1) and (2) in its cross fractionation chromatography (CFC). (1) The amount of eluted components at ≤80°C is ≤5% based on the total eluted amount in the CFC. (2) A relational formula (Eq-1) [wherein, S<SB>x</SB>is the total value of areas of total peaks based on the components eluted between 70-85°C; S<SB>total</SB>is the total value of areas of total peaks based on the components eluted between 0-145°C] is satisfied. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ethylene polymer that provides a molded article having excellent moldability and particularly excellent mechanical strength and environmental stress fracture resistance (ESCR), 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, in the claims of the above publication, the preferred carbon number range of the α-olefin copolymerized with ethylene is not disclosed, but when 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 composed of CpTiNP (tBu) 3Cl2 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, in the claims of this 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. .

  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, the broad molecular weight distribution is presumed that the active species are non-uniform, and as a result, there is a concern that the composition distribution is widened and long-term physical properties such as environmental stress fracture resistance (ESCR) are lowered.

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) does not exhibit sufficient mechanical strength.

  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, while a soft and weak component is formed when α-olefin is excessively copolymerized. In addition to the generation, there are cases where components that cause stickiness are generated due to the wide composition distribution. In addition, 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 or the like, methyl branching is present in the molecular chain as a result of by-production of methyl branching 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 expansion, and therefore has poor mechanical strength and environmental stress fracture resistance (ESCR). 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.

  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. In addition, since it contains long chain branches, the molecular spread is small, and therefore mechanical strength and environmental stress fracture resistance (ESCR) are 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, and therefore it is inferior in environmental stress fracture resistance (ESCR).
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 CMC Publishing Co., Ltd., “Functional Materials”, March 2001, page 50 Polymer, Vol. 31, 1999, 1990

  Disclosed is an ethylene polymer that provides a molded article having excellent moldability and particularly excellent mechanical strength and environmental stress fracture resistance (ESCR), particularly a blow molded article.

In view of the above prior art, the present inventors have conducted intensive research on an ethylene-based polymer capable of obtaining a molded article having excellent moldability and excellent mechanical strength and environmental stress fracture resistance. An ethylene-based polymer containing 0.02 to 0.50 mol% of structural units derived from α-olefin of several 6 to 10, and in cross fractionation (CFC), at least one of the following (1) or (2) The present invention has been completed by finding that an ethylene polymer (E) satisfying the requirements provides a molded product having excellent moldability and excellent mechanical strength and environmental stress fracture resistance (ESCR), particularly a blow molded product. It was.
(1) The elution component at 80 ° C. or less is 5% or less with respect to the total elution amount of CFC.
(2) The following relational expression (Eq-1) is satisfied.

(In Eq-1, Sx is the total area value of all peaks based on components eluting at 70 to 85 ° C., and Stotal is the total area value of all peaks based on components eluting at 0 to 145 ° C.)
The ethylene polymer (E) according to the present invention preferably satisfies all the following requirements (1 ′) to (5 ′) in addition to the above requirements.
(1 ') Density (d) is in the range of 945-975kg / m3.
(2 ′) The intrinsic viscosity ([η]) measured in decalin at 135 ° C. is in the range of 1.6 to 2.8 (dL / g).
(3 ′) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC is in the range of 5-30.
(4 ') When the GPC curve is separated into two lognormal distribution curves, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of each curve is 1.5 to 3.5, high molecular weight side The weight-average molecular weight (Mw2) of the curve separated into two is 200,000 to 800,000.
(5 ') When the elution temperature at the peak of the strongest peak with a molecular weight of 100,000 or more in cross fractionation (CFC) is Th (° C), the fraction eluted with [(Th-1) to Th] (° C) In the GPC curve, the molecular weight of the strongest peak at a molecular weight of 100,000 or more is in the range of 200,000 to 800,000.

  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, it is preferable to satisfy the following requirement (1B) in addition to the above-mentioned requirement that the ethylene polymer (E) should satisfy [the ethylene polymer May be referred to as an ethylene polymer (EB) in the following description], particularly preferably satisfying the following requirement (1B ′) [this ethylene polymer is referred to as an ethylene polymer in the following description ( EB '). (1B) Environmental stress fracture resistance ESCR (hr at 50 ° C measured in accordance with ASTM-D-790, measured at 23 ° C as M, and measured in accordance with ASTM-D-1693 ) Is T
When 1,500 ≦ M ≦ 1,800 (MPa), T ≧ 10 (hr) and
When 600 ≦ M <1500 (MPa), the relationship between M and T satisfies the following formula (Eq-2).

(1B ') tanδ measured at 190 ° C and angular frequency 100 rad / sec measured using a dynamic viscoelastic device
(= Loss elastic modulus G ″ / storage elastic modulus G ′) is 0.6 to 0.9.

  In the ethylene polymers (EB) and (EB ′) for blow molded products, the ethylene polymer (E) satisfies the requirements (1 ′) to (5 ′) ( E ′) is preferred.

  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 an extrusion-molded product such as a blow-molded product among the above-mentioned molded products, excellent characteristics are given.

  The ethylene-based polymer of the present invention provides a blow molded article having excellent moldability and particularly excellent mechanical strength and environmental stress fracture resistance (ESCR).

  BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the invention will be sequentially described for an ethylene polymer (E) according to the present invention, an ethylene polymer (EB) suitably used for a blow molded product, and a blow molded product comprising the same. Then, a typical method for producing an ethylene polymer according to the present invention and various measuring methods according to the present invention will be described, and finally examples will be described.

Ethylene polymer (E)
The ethylene polymer (E) according to the present invention is an ethylene polymer containing 0.02 to 0.50 mol% of a structural unit derived from an α-olefin having 6 to 10 carbon atoms, and 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) usually contains 0.02 to 0.50 mol% of structural units derived from α-olefin. When the ethylene polymer (E) 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, the structural unit derived from ethylene is: Usually, it is present in a proportion of 99.50 to 99.98 mol%, preferably 99.80 to 99.98 mol%, and the repeating unit derived from α-olefin is usually present in a proportion of 0.02 to 0.50 mol%, preferably 0.02 to 0.20 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 97.50 to 99.96 mol%, Preferably it exists in the ratio of 99-99.96 mol%, and the repeating unit derived | led-out from an alpha olefin exists in the ratio of 0.04-2.50 mol%, Preferably it is 0.04-1.00 mol%. Even when the ethylene homopolymer is included, the repeating unit derived from the α-olefin in the entire polymer is usually 0.02 to 0.50 mol%, preferably 0.02 to 0.20 mol%. If the number of carbon atoms of the α-olefin is 5 or less, the probability that the α-olefin will be incorporated into the crystal increases (see Polymer, Vol.31, 1999, 1999), and as a result, the strength decreases, which is not preferable. . 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. The α-olefin has 1 carbon atom
If the number exceeds 0, the side chain (branch caused by the α-olefin copolymerized with ethylene) may crystallize, which is not preferable because the amorphous part becomes weak.

The ethylene-based polymer (E) according to the present invention is characterized by satisfying at least one of the following requirements (1) and (2) in cross fractionation (CFC).
(1) The elution component at 80 ° C. or less is 5% or less with respect to the total elution amount of CFC.
(2) The following relational expression (Eq-1) is satisfied.

(In Eq-1, Sx is the total area value of all peaks based on components eluted at 70 to 85 ° C in CFC, and Stotal is the total area value of all peaks based on components eluted at 0 to 145 ° C. )
Such an ethylene-based polymer (E) is excellent in long-term physical properties such as mechanical strength and environmental stress fracture resistance (ESCR) when applied to a molded body. The requirements (1) and (2) will be specifically described below.

[Requirement (1)]
The ethylene-based polymer (E) of the present invention is characterized in that an elution component at 80 ° C. or less with respect to the total elution amount of CFC is 5% or less. ("%" Is the percentage of the total peak area attributed to the elution component of 80 ° C or less in the total peak area of all the elution components.) Requirement [2] taking the results described in the examples as an example [2] Is described in detail. In the CFC analysis of the ethylene polymer used in Example 2, which will be described later, the proportion of the elution component at 80 ° C. or lower is 1.9%, which satisfies the requirement [1]. As shown in Table 5, the blow molded product made of this ethylene polymer exhibits a good balance between stiffness (buckling strength) and environmental stress fracture resistance (ESCR). On the other hand, the proportion of the elution component of 80 ° C. or lower is 7.1% in the ethylene-based polymer used in Comparative Example 1, and does not satisfy the requirement [1]. As can be easily understood from Table 5, the blow molded body made of this ethylene polymer has a balance of rigidity (buckling strength) and environmental stress fracture resistance (ESCR) compared to the ethylene polymer of Example 2. Inferior.

  Such an ethylene polymer has a low α-olefin content of a high molecular weight component copolymerized with α-olefin and a uniform α-olefin composition, or a relatively low molecular weight and short chain branching. It means that such a component is not contained, and in that case, it is excellent in long-term physical properties such as mechanical strength and environmental stress fracture resistance (ESCR) as a molded body. 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 5 of the present application, the elution component of 80 ° C. or less with respect to the total elution amount of CFC is 3.2%, and unless the catalyst and polymerization temperature are changed, the first polymerizer Unless the α-olefin is supplied to the second polymerizer, the amount is 5.0% or less unless the α-olefin supplied to the second polymerization vessel is excessively increased.

[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 Stotal, the relationship represented by the following formula (Eq-1) is satisfied.

  Such an ethylene polymer satisfying the requirement (2) is the same as the content described in the requirement (1), and the α-olefin content of the high molecular weight component copolymerized with the α-olefin is small and the α-olefin Means that the composition is uniform or does not contain a component having a relatively low molecular weight and short chain branching, in which case the mechanical strength and environmental stress fracture resistance (ESCR) etc. Excellent long-term physical properties. 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 Sx and Stotal in the above formula (Eq-1) are values based on infrared analysis of the stretching vibration of CH bond, the value of Sx / Stotal is 0 of the component eluted in principle at 70 to 85 ° C. It is equal to the weight% of the amount of components eluted at ˜145 ° C. Usually, for the ethylene polymer of the present invention, all components are eluted by scanning in the region of 0 to 145 ° C, so the value of Sx / Stotal is 70 to 85 ° C 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.

  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 5 of the present application, the left side of the above formula (Eq-1) in the cross fractionation (CFC) of the obtained ethylene polymer, that is, the value of (Sx / Stotal) Unless the catalyst and polymerization temperature are changed, α-olefin is not supplied to the first polymerization vessel, and α-olefin supplied to the second polymerization vessel is not excessively increased (Sx / Stotal ) 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 (5 ′).
(1 ') Density (d) is in the range of 945-975kg / m3.
(2 ′) The intrinsic viscosity ([η]) measured in decalin at 135 ° C. is in the range of 1.6 to 2.8 (dL / g).
(3 ′) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC is in the range of 5-30.
(4 ') When the GPC curve is separated into two lognormal distribution curves, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of each curve is 1.5 to 3.5, high molecular weight side The weight-average molecular weight (Mw2) of the curve separated into two is 200,000 to 800,000.
(5 ') When the elution temperature at the peak of the strongest peak with a molecular weight of 100,000 or more in cross fractionation (CFC) is Th (° C), the fraction eluted with [(Th-1) to Th] (° C) In the GPC curve, the molecular weight of the strongest peak at a molecular weight of 100,000 or more is in the range of 200,000 to 800,000.

[Requirement (1 ') and Requirement (2')]
The density (d) of the ethylene polymer (E ′) according to the present invention is 945 to 975 kg / m 3, preferably 950 to 970 kg / m 3, and the intrinsic viscosity ([η]) measured in decalin at 135 ° C. is 1.6 to It is in the range of 2.8 dl / g, preferably 1.8 to 2.5 dl / g. An ethylene polymer having a density and an intrinsic viscosity within these ranges is excellent in mechanical strength, moldability, and resistance to environmental stress destruction. 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 2 in which the solvent was hexane, the polymerization was performed while stirring so that the inside of the system was uniform, and the density was 962 kg / m3 and [η] was 2.15 dl / g. When ethylene supplied to the second polymerization tank is 4.3 kg / hr, hydrogen is 3.0 N-liter / hr and 1-hexene is 26 g / hr, the density is 967 kg / m3 and [η] is 2.10 dl / g. Ethylene supplied to one polymerization tank is 7.0 kg / hr, hydrogen is 40 N-liter / hr, ethylene supplied to the second polymerization tank is 3.8 kg / hr, hydrogen is 4.5 N-liter / hr, 1-hexene is 180 g / hr If hr, the density is 954 kg / m3 and [η] is 2.43 dl / g.

[Requirement (3 ')]
The ethylene-based 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 30, preferably 5 It is in the range of ~ 20. 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 moldability, mechanical strength, and environmental stress fracture resistance. Specifically, when polymerized under the conditions described in Example 1, Mw / Mn is 6.6. Here, when hydrogen supplied to the first polymerization tank is changed from 40 N-liter / hr to 70 N-liter / hr, and hydrogen supplied to the second polymerization tank is changed from 5.5 N-liter / hr to 2.0 N-liter / hr, The molecular weight of the ethylene polymer produced in the first polymerization tank is small, and the molecular weight of the ethylene polymer produced in the second polymerization tank is increased, so that Mw / Mn is about 11.5. When polymerized under the conditions described in Example 2 of the present application, Mw / Mn is 8.6.

[Requirement (4 ')]
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 average molecular weight of each curve. (Mw) and number average molecular weight (Mn) ratio (Mw / Mn) is in the range of 1.5 to 3.5, preferably 1.5 to 3.2, and the weight average molecular weight (Mw2) of the curve separated on the high molecular weight side is 200,000 to It is in the range of 800,000.

  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 the catalyst component is used without being supported on the carrier, the Mw / Mn becomes small in order to approach 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 this application is about 2.2.

When the GPC curve of the ethylene polymer (E ′) according to the present invention is separated into two logarithmic normal distribution curves, the weight average molecular weight (Mw2) of the curve separated on the high molecular weight side is in the range of 200,000 to 800,000. It is in. By selecting the amount ratio of hydrogen, ethylene, and α-olefin when the ethylene polymer is produced, an ethylene polymer having an Mw2 in this range can be produced. Specifically, when polymerized under the conditions described in Example 2, when the GPC curve was separated into two lognormal distribution curves, the weight average molecular weight (Mw2) of the curve separated on the high molecular weight side was 319,000. . Here, when the hydrogen supplied to the second polymerization tank is 3.4 N-liter / hr and 1-hexene is 66 g / hr, Mw2
When the ethylene supplied to the second polymerization tank is 4.3 kg / hr, hydrogen is 3.0 N-liter / hr, and 1-hexene supplied to the second polymerization tank is 26 g / hr, the Mw2 is 411,000. An ethylene polymer having Mw2 in this range is excellent in mechanical strength, moldability, and environmental stress fracture resistance.

[Requirement (5 ')]
The ethylene polymer (E ') according to the present invention has a molecular weight of 100,000 or more and a peak elution temperature of Th (° C) as the highest peak in temperature rising elution fractionation using a cross fractionation (CFC) apparatus. In this case, the peak of the strongest peak means 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. Among the GPC curves of the fraction eluted at Th (° C.), the molecular weight of the peak of the strongest peak with a molecular weight of 100,000 or more is in the range of 200,000 to 800,000. The fraction eluted at Th (° C.) refers to the component eluted at [(Th-1) to Th] (° C.). Such an ethylene polymer is excellent in long-term physical properties such as environmental stress fracture resistance 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. Among the GPC curves of fractions eluted at Th (° C) by increasing or decreasing the amount of α-olefin, hydrogen, ethylene, etc. supplied to the polymerization environment for producing α-olefin copolymer, the molecular weight is the most. The molecular weight at the peak of a high peak can be increased or decreased within a specific range.

  Specifically, when polymerized under the conditions described in Example 5, the fraction eluted at [(Th-1) to Th] (° C.) in the temperature rising elution fractionation using a cross fractionation (CFC) apparatus. Among the GPC curves, the molecular weight at the peak of the strongest peak with a molecular weight of 100,000 or more is 250,000, and when polymerized under the conditions described in Example 2, the above [(Th- Among the GPC curves of fractions eluted at 1) to Th] (° C.), the molecular weight at the peak of the strongest peak is 264,000 when the molecular weight is 100,000 or more. 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.

Ethylene-based polymer (EB) suitably used for blow molded article Among the ethylene-based polymer (E), preferably (E ') according to the present invention, ethylene-based polymer suitably used for blow molded article The union (EB) preferably satisfies the following requirement (1B), and more preferably satisfies the following requirement (1B ′) [when this ethylene polymer is referred to as an ethylene-based polymer (EB ′) in the following description] There are].
(1B) Environmental stress fracture resistance ESCR (hr at 50 ° C measured in accordance with ASTM-D-790, measured at 23 ° C as M, and measured in accordance with ASTM-D-1693 ) Is T
When 1,500 ≦ M ≦ 1,800 (MPa), T ≧ 10 (hr) and
When 600 ≦ M <1500 (MPa), the relationship between M and T satisfies the following formula (Eq-2).

[Requirement (1B)]
The ethylene-based polymer (EB) according to the present invention has a flexural modulus M measured at 23 ° C. according to ASTM-D-790 and 50 ° C. measured according to ASTM-D-1693. Assuming that the environmental stress fracture resistance ESCR (hr) in T is 1,500 ≦ M ≦ 1,800 (MPa), T ≧ 10 (hr) and 600 ≦ M <1500 (MPa) The relationship with T satisfies the following formula (Eq-2). 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. When performing multistage polymerization as described later using a catalyst system as described later, the ratio of the amount of hydrogen, ethylene, α-olefin supplied to the polymerization vessel is changed, and the molecular weight and polymerization ratio of each component are changed. By controlling, an ethylene polymer in this range can be produced.

  More specifically, when polymerized under the conditions described in Example 5, the flexural modulus is 1,500 MPa, and ESCR breaks 50% in 14 hours. Further, when polymerized under the conditions described in Example 4, the flexural modulus was 1,490 MPa, ESCR broke 50% in 177 hours, and the hydrogen supplied to the first polymerization tank under the conditions of Example 4 was increased from 75 N-liter / hr. 70N-liter / hr, hydrogen supplied to the second polymerization tank from 3.0N-liter / hr to 4.0N-liter / hr, 1-hexene supplied to the second polymerization tank from 52g / hr to 65g / hr When changed, the flexural modulus is 1,410 MPa and the ESCR is 50% fractured in 188 hours.

[Requirements (1B ')]
The ethylene polymer (EB ′) according to the present invention is tan δ (loss elastic modulus G ″ / storage elastic modulus G ′) measured at 190 ° C. and angular frequency of 100 rad / sec using a dynamic viscoelastic device. ) Is preferably 0.6 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 or the total molecular weight 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.

  In the ethylene polymers (EB) and (EB ′) for blow molded products, the ethylene polymer (E) satisfies the above-mentioned requirements (1 ′) to (5 ′) ( E ′) is preferred. In other words, as the ethylene polymer for the blow molded article of the present invention, one in which the ethylene polymer (E ′) satisfies both the above requirements (1B) and (1B ′) is most preferably used.

Production method of ethylene polymer Hereinafter, a preferred production method of the ethylene polymer of the present invention will be described. However, as long as the above-described requirements for the ethylene polymer of the present invention are satisfied, the production method is not limited. Other manufacturing methods can be arbitrarily used instead of those.

The ethylene polymer according to the present invention is preferably
(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. Hereinafter, preferred embodiments of the components (A), (B), and (C) will be described.

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

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 is selected from a hydrogen atom, a hydrocarbon group, a halogen-containing 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. 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 A may include two or more ring structures including a ring formed with Y, Y is carbon or silicon, and M is a metal selected from group 4 of the periodic table. , Q may be selected from the same or different combinations from halogens, hydrocarbon groups, anionic ligands, or neutral ligands capable of coordinating with lone pairs, and j is 1 to 4 It is an integer.

Among the transition metal compounds (A) represented by the above general formula (1) or (2), the compound preferably used is that R ^{7 to} R ¹⁰ are hydrogen, Y is carbon, and M is Zr And j is a compound of 2.

Among the transition metal compounds (A) represented by the general formula (1), compounds in which R ¹² , R ¹³ , R ¹⁶ and R ¹⁷ are all hydrocarbon groups are preferably used.

Among the transition metal compounds (A) represented by the general formula (1), compounds having an aryl group in which the bridging atoms Y of the covalent bond bridging portions may be the same or different from each other (that is, R ^A compound in which ¹⁹ and R ²⁰ are aryl groups which may be the same or different from each other is preferably used. Examples of the aryl group include a phenyl group, a naphthyl group, anthracenyl group and can be one or more of these aromatic hydrogen (sp ² type hydrogen) illustrate been substituted with a substituent. Examples of the substituent include a hydrocarbon group having 1 to 20 carbon atoms (f1), a silicon-containing group having 1 to 20 carbon atoms (f2), and a halogen atom. In addition to alkyl, alkenyl, alkynyl, and aryl groups composed only of carbon and hydrogen, a hydrocarbon group having 1 to 20 carbon atoms in total (f1) includes a part of hydrogen atoms directly connected to these carbon atoms as halogen atoms, oxygen A hetero atom-containing hydrocarbon group substituted with a containing group, a nitrogen-containing group, or a silicon-containing group, or a group in which any two adjacent hydrogen atoms form an alicyclic group are also included. Examples of such a group (f1) include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Group, n-nonyl group, linear hydrocarbon group such as n-decanyl group; isopropyl group, t-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethyl group Branched butyl, 1-methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl, etc. Hydrocarbon group: Cyclic saturated hydrocarbon group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; cyclic unsaturated group such as phenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group Hydrocarbon groups and these Alkyl-substituted product; saturated hydrocarbon group substituted with aryl group such as benzyl group, cumyl group; methoxy group, ethoxy group, phenoxy group N-methylamino group, trifluoromethyl group, tribromomethyl group, pentafluoroethyl group, A hetero atom-containing hydrocarbon group such as a pentafluorophenyl group can be exemplified.

  The silicon-containing group (f2) is, for example, a group in which a ring carbon of a cyclopentadienyl group is directly covalently bonded to a silicon atom, and specifically an alkylsilyl group or an arylsilyl group. Examples of the silicon-containing group (f2) having a total carbon number of 1 to 20 include a trimethylsilyl group and a triphenylsilyl group.

  Specific examples of the aryl group that may be the same as or different from each other and bonded to the bridging atom Y of the covalent bridging moiety in the general formula (1) include a phenyl group, tolyl group, t-butylphenyl group, and dimethylphenyl group , Biphenyl group, cyclohexylphenyl group, (trifluoromethyl) phenyl group, bis (trifluoromethyl) phenyl group, chlorophenyl group, and dichlorophenyl group.

  The transition metal compound (A) used in Examples of the present application described later is specifically a compound represented by the following formulas (3) and (4), but in the present invention, it is not limited to this transition metal compound. It is not a thing.

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 group 1, 2 and group 12, 13 An organometallic compound is 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 0 ≦ p <3, q is a number of 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 used as necessary in the present invention may be a conventionally known aluminoxane, and is 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) Compound that reacts with transition metal compound to form ion pair Compound (B-3) that reacts with bridged metallocene compound (A) of the present invention to form ion pair (hereinafter referred to as “ionized ionic compound”) Are referred to as JP-A-1-501950, JP-A-1-502036, JP-A-3-17905, JP-A-3-179006, JP-A-3-207703, JP-A-3. And Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent No. -207704 and US5321106. 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) Particulate carrier The (C) particulate carrier used as necessary in the present invention is an inorganic or organic compound, and is a granular or particulate 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 invention described later has an average particle diameter 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. Asahi Glass Co., Ltd. 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. Such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, sulfonates, and the like.

  The ethylene polymer according to the present invention is obtained by homopolymerizing ethylene as described above or copolymerizing ethylene and an α-olefin having 6 to 10 carbon atoms using the olefin polymerization catalyst as described above. Is obtained.

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 contacted in advance is added to the polymerization reactor.
(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.

  Component (B-2) used as necessary is a molar ratio of the aluminum atom in component (B-2) to the transition metal atom (M) in 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 100, preferably 2 to 80.

  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) in such an amount that it becomes ˜5, 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 batch type (batch type), semi-continuous type, continuous. This can be done in any way of the formula. 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 in the latter stage. (dl / g) (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.

Molded body made of an ethylene polymer The ethylene polymer of the present invention is a blow molded body, an inflation molded body, a cast molded body, an extruded laminated body, an extruded molded body such as a pipe or a deformed body, a foam molded body, an injection molded body. It can be formed into a vacuum formed body or 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. Among the above molded products, blow molded products, extrusion molded products, and injection molded products are preferable because they give excellent characteristics.

  Preferred embodiments of the blow molded article of the present invention are a bottle container, an industrial chemical can and a bottle container. The hollow molded body prepared as described above is suitable for use in bleach containers, detergent containers, softener containers, etc., for example, cosmetics, clothing detergents, residential detergents, softeners, shampoos, rinses, Used for containers such as conditioners.

  It can also be used for kerosene cans, generators, lawn mowers, motorcycles, gasoline tanks for automobiles, agricultural chemicals, chemical canisters for storing chemicals, drum cans, and the like. It is also used as a hollow molded article for storing mayonnaise, food applications for storing edible oil, and medical products.

  Moreover, in these uses, it is used suitably also as a multilayer molded object for the purpose of protecting the foodstuff from oxidation, and suppressing the permeation | transmission of the contents, such as gasoline.

  A preferred embodiment of the extruded product of the present invention is a pipe, a wire coating material, or a steel pipe / steel wire coating material. Extrudates prepared as described above are miscellaneous including gas pipes, water and sewage pipes, pipes used for transportation of agricultural water, industrial water, etc., and applications for storing information communication equipment such as optical fibers. Also used for pipes to protect the contents. Moreover, it is used suitably also as a steel pipe coating | covering material used for protection of the steel pipe coating | coated material which corrodes the inside of a cast iron pipe, and the wire which supports a building. It is demanded that these extruded molded products and the short-term and long-term destruction do not occur, and the use of the resin of the present invention is effective for extending the product life.

  A preferred embodiment of the injection molded article of the present invention is a pipe joint or an automotive part. Pipe joints and automotive parts are also preferably used because they are fused to hollow molded bodies or extruded molded bodies. There are various types of pipe joints depending on the attachment method such as electron fusion joint, heat fusion joint, etc., and pipe connection / branch method depending on the purpose. Can be suitably used because it does not break for a long time. In particular, it is effective to use the product of the present invention in terms of enhancing the reliability of the welded portion with the pipe body produced by fracture of the weld portion and extrusion molding for a long period of time.

Many automotive parts are often used as fusion parts for enhancing the functionality of gasoline tanks, which are hollow molded articles. By using the product of the present invention, it is possible to improve the long-term reliability of the welded portion and the fused portion.
Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, the measurement method of various physical properties described in the present invention and the preparation method of the measurement sample are as follows.

  The ethylene-based polymer (EB) for blow molded products according to the present invention can be formed into a bottle container, an industrial chemical can, a gasoline tank, or the like by blow molding. These molded bodies include molded bodies (laminates and the like) including a portion made of an ethylene polymer (EB) and a portion made of another resin. When the ethylene polymer (EB) 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 0.20 weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant for 100 parts by weight of particulate ethylene polymer N-octadecyl-3- as a heat-resistant stabilizer
0.24 parts by weight of (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate and 0.15 parts by weight of calcium stearate as a hydrochloric acid absorbent were blended. After that, using a Placo single screw extruder (screw diameter 65mm, L / D = 28, screen mesh # 40 / # 60 / # 300 × 4 / # 60 / # 40), set temperature 200 ° C, resin extrusion rate The sample was granulated at 25 kg / hr to obtain a measurement sample.

★ Measurement of ethylene content and α-olefin content
The ethylene content and α-olefin content in the molecular chain of the ethylene polymer were measured by 13C-NMR. Measurement was performed using a Lambda 500 type nuclear magnetic resonance apparatus (1H: 500 MHz) manufactured by JEOL Ltd. Measurement was performed at 10,000 to 30,000 integrations. In a commercially available quartz glass tube having a diameter of 10 mm, 250 to 400 mg of sample and 2 ml of special grade hexachlorobutadiene manufactured by Wako Pure Chemical Industries, Ltd. were placed, heated at 120 ° C., and uniformly dispersed. . Assignment of each absorption in the NMR spectrum was carried out according to Chemistry Special Issue 141 NMR-Review and Experiment Guide [I], pages 132-133. The measurement was performed under the 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 (CaF2 cell) manufactured by FOXBORO, and infrared light of 3.42 μm (2924 cm ⁻¹ ) was detected with an absorbance mode setting of 10 seconds response time. 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 using 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% by weight of BHT (Takeda Pharmaceutical) as an antioxidant, moved at 1.0 ml / min, and the sample concentration was 0.
The amount of sample injection was 500 μl, and a differential refractometer was used as a 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. An example of calculation is shown in FIG.

★ 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 ηsp 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 ηsp is measured in the same manner. This dilution operation is further repeated twice, and the value of ηsp / C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity (see the following formula).

★ Density (d)
Using a hydraulic heat press manufactured by Shinfuji Metal Industry Co., Ltd. set at 190 ° C, a 0.5 mm thick sheet was formed at a pressure of 100 kg / cm2 (spacer shape; 45 x 45 x 0.5 on a 240 x 240 x 0.5 mm thick plate) A sample for measurement was 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 at 20 ° C., 9 mm). 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.

★ Environmental stress crack resistance test of press sheet: 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 Specimen 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: Set to a specimen holder with an inner dimension of 11.75mm and a length of 165mm using a 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 test of press sheet
In accordance with the description of the flexural modulus section of JIS K6922-2 Table 3 General properties and test conditions, the evaluation was performed according to the test method for bending properties described in JIS K7171. That is, a test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was punched from a 4 mm-thick press sheet taken out at a molding temperature of 180 ° C., an average cooling rate of 15 ° C./min, and 40 ° C., and supported at 23 ° C. The flexural modulus was measured at a distance of 64 mm and a test speed of 2.0 mm / min.

★ 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 rheometer RDS-II manufactured by Rheometrics was used to measure the angular frequency (ω (rad / sec)) dispersion of the storage elastic modulus G ′ (Pa) and 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 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 / cm2 A cylindrical bottle with 1,000 cc and a weight of 50 g was obtained.

★ 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. 5).

★ Measurement of buckling strength of bottle When the bottle obtained by blow molding as described above is erected, when a load is applied from the top of the bottle to the bottom at 23 ° C and a test speed of 20 mm / min, it is compressed. The maximum load produced was recorded as the buckling strength.

  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).

[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 ( 20 ~ 25 ℃) di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride 31.06mmol / L solution was added 2L (61.12mmol) and stirred for 60 minutes did. 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.

[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, 0.07 mmol / hr, triethylaluminum is 20 mmol / hr, and ethylene is 7.0 kg / hr. Hydrogen is continuously supplied at 40 N-liter / hr, and the viscosity measured at 25 ° C. using a B-type viscometer is 500 mPa · s (polyethylene glycol) (polypropylene glycol) block copolymer (first Kogyo Seiyaku Co., Ltd., trade name EPAN720) is continuously supplied at 0.5 g / hr, and the polymerization tank contents are continuously withdrawn so that the liquid level in the polymerization tank is constant, and the polymerization temperature is 80. Polymerization was carried out under the conditions of ° C, reaction pressure of 7.6 kg / cm ² G, and 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 content was continuously fed to the second polymerization tank together with hexane 43 liter / hr, ethylene 3.0 kg / hr, hydrogen 5.5 N-liter / hr, 1-hexene 110 g / hr, polymerization temperature 75 ° C., Polymerization was continued under the conditions of a reaction pressure of 3.3 kg / cm 2 G and an average residence time of 1.4 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.

  0.20 parts by weight of tri (2,4-di-t-butylphenyl) phosphate as a secondary antioxidant and 100 parts by weight of n-octadecyl-3- (4 0.20 parts by weight of '-hydroxy-3', 5'-di-t-butylphenyl) propinate was mixed with 0.15 parts by weight of calcium stearate as a hydrochloric acid absorbent. 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. A granulated sample was obtained. A press sheet was prepared using the sample, and the physical properties were measured. The results are shown in Tables 1-4. Compared to the comparative example, the balance between rigidity and ESCR is excellent. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molding has better rigidity and ESCR than the comparative example.

[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, 0.2 mmol / hr, triethylaluminum is 20 mmol / hr, and ethylene is 11.0 kg / hr. Hydrogen is continuously supplied at 75 N-liter / hr, and the viscosity measured at 25 ° C. using a B-type viscometer is 370 mPa · s (polyethylene glycol) (polypropylene glycol) block copolymer (Asahi Denka) The product name, Adeka Pluronic L-71, manufactured by Co., Ltd. is continuously supplied at 0.8 g / hr, and the polymerization tank contents are continuously withdrawn so that the liquid level in the polymerization tank is constant, and polymerization is performed. Polymerization was carried out under the conditions of a temperature of 85 ° C., a reaction pressure of 7.5 kg / cm ² G, and an average residence time of 2.4 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 content was continuously fed to the second polymerization tank together with hexane 43 liter / hr, ethylene 5.5 kg / hr, hydrogen 4.0 N-liter / hr, 1-hexene 98 g / hr, polymerization temperature 75 ° C., Polymerization was continued under the conditions of a reaction pressure of 2.9 kg / cm ² G and an average residence time of 1.3 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. Thereafter, a single screw extruder manufactured by Plako Co., Ltd. was used and granulated at the same set temperature and resin extrusion amount as used in Example 1 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. Compared to the comparative example, the balance between rigidity and ESCR is excellent. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molding has better rigidity and ESCR than the comparative example.

[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, 0.2 mmol / hr, triethylaluminum is 20 mmol / hr, and ethylene is 11.0 kg / hr. Hydrogen is continuously supplied at 80 N-liter / hr, and the viscosity measured at 25 ° C. using a B-type viscometer is 370 mPa · s (polyethylene glycol) (polypropylene glycol) block copolymer (Asahi Denka) The product name, Adeka Pluronic L-71, manufactured by Co., Ltd. is continuously supplied at 0.8 g / hr, and the polymerization tank contents are continuously withdrawn so that the liquid level in the polymerization tank is constant, and polymerization is performed. Polymerization was carried out under the conditions of a temperature of 85 ° C., a reaction pressure of 7.6 kg / cm ² G, and an average residence time of 2.4 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 5.5 kg / hr, hydrogen 3.4 N-liter / hr, 1-hexene 66 g / hr, polymerization temperature 75 ° C., Polymerization was continued under the conditions of a reaction pressure of 3.0 kg / cm ² G and an average residence time of 1.3 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. Thereafter, a single screw extruder manufactured by Plako Co., Ltd. was used and granulated at the same set temperature and resin extrusion amount as used in Example 1 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. Compared to the comparative example, the balance between rigidity and ESCR is excellent. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molding has better rigidity and ESCR than the comparative example.

[polymerization]
In the first polymerization tank, hexane is 45 liters / hr, the solid catalyst component (δ) obtained in Synthesis Example 2 is 0.1 mmol / hr in terms of Zr atoms, triethylaluminum is 20 mmol / hr, and ethylene is 7.0 kg / hr. Hydrogen is continuously supplied at 75 N-liter / hr, and the viscosity measured at 25 ° C. using a B-type viscometer is 370 mPa · s (polyethylene glycol) (polypropylene glycol) block copolymer (Asahi Denka) The product name, Adeka Pluronic L-71, manufactured by Co., Ltd. is continuously supplied at 0.8 g / hr, and the polymerization tank contents are continuously withdrawn so that the liquid level in the polymerization tank is constant, and polymerization is performed. Polymerization was carried out under the conditions of a temperature of 85 ° C., a reaction pressure of 7.5 kg / cm 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 3.5 kg / hr, hydrogen 3.0 N-liter / hr, 1-hexene 52 g / hr, polymerization temperature 75 ° C., Polymerization was continued under the conditions of a reaction pressure of 3.2 kg / cm 2 G and an average residence time of 1.3 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. Thereafter, a single screw extruder manufactured by Plako Co., Ltd. was used and granulated at the same set temperature and resin extrusion amount as used in Example 1 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. Compared to the comparative example, the balance between rigidity and ESCR is excellent. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molding has better rigidity and ESCR than the comparative example.

[polymerization]
In the first polymerization tank, hexane was 45 liters / hr, the solid catalyst component (δ) obtained in Synthesis Example 2 was converted to Zr atoms, 0.08 mmol / hr, triethylaluminum 20 mmol / hr, and ethylene 7.0 kg / hr. Hydrogen was continuously supplied at 52 N-liter / hr, and the viscosity measured at 25 ° C. using a B-type viscometer was 370 mPa · s (polyethylene glycol) (polypropylene glycol) block copolymer (Asahi Denka) The product name, Adeka Pluronic L-71, manufactured by Co., Ltd. is continuously supplied at 0.8 g / hr, and the polymerization tank contents are continuously withdrawn so that the liquid level in the polymerization tank is constant, and polymerization is performed. Polymerization was carried out under the conditions of a temperature of 85 ° C., a reaction pressure of 7.3 kg / cm 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.

  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, a single screw extruder manufactured by Plako Co., Ltd. was used and granulated at the same set temperature and resin extrusion amount as used in Example 1 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. Compared to the comparative example, the balance between rigidity and ESCR is excellent. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molding has better rigidity and ESCR than the comparative example.

[polymerization]
In the first polymerization tank, hexane was 45 (liter / hr), the solid catalyst component (δ) obtained in Synthesis Example 2 was converted to Zr atom, 0.13 (mmol / hr), and triethylaluminum was 20 (mmol / hr) The ethylene was continuously supplied at 11.0 (kg / hr) and hydrogen at 50 (N-liter / hr), and the viscosity measured at 25 ° C. using a B-type viscometer was 370 (mPa · s). A (polyethylene glycol) (polypropylene glycol) block copolymer (trade name Adeka Pluronic L-71, manufactured by Asahi Denka Co., Ltd.) is continuously supplied at 0.8 (g / hr), and the liquid level in the polymerization tank is The polymerization was carried out under the conditions of a polymerization temperature of 75 ° C., a reaction pressure of 7.5 (kg / cm ² G), and an average residence time of 2.6 hours while continuously extracting the contents of the polymerization tank so as to be constant.

In the contents continuously extracted from the first polymerization tank, unreacted ethylene and hydrogen were substantially removed by a flash drum maintained at 60 ° C. with an internal pressure of 0.30 (kg / cm ² G).

Thereafter, the content was continuously added to the second polymerization tank together with hexane 43 (liter / hr), ethylene 4.7 (kg / hr), hydrogen 3.0 (N-liter / hr), 1-hexene 97 (g / hr). The polymerization was continued under the conditions of a polymerization temperature of 75 ° C., a reaction pressure of 3.2 (kg / cm ² G), and an average residence time of 1.3 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. It was. 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, an example using a single screw extruder manufactured by Plako
The sample was granulated at the same set temperature and resin extrusion rate as used in 1 to prepare 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. Compared to the comparative example, the balance between rigidity and ESCR is excellent. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molding has better rigidity and ESCR than the comparative example.

[polymerization]
In the first polymerization tank, hexane is 45 (liter / hr), the solid catalyst component (δ) obtained in Synthesis Example 2 is 0.1 (mmol / hr) converted to Zr atom, and triethylaluminum is 20 (mmol / hr) The ethylene was continuously supplied at 9.1 (kg / hr) and hydrogen at 50 (N-liter / hr), and the viscosity measured at 25 ° C. using a B-type viscometer was 370 (mPa · s). A (polyethylene glycol) (polypropylene glycol) block copolymer (trade name Adeka Pluronic L-71, manufactured by Asahi Denka Co., Ltd.) is continuously supplied at 0.8 (g / hr), and the liquid level in the polymerization tank is The polymerization was carried out under the conditions of a polymerization temperature of 75 ° C., a reaction pressure of 7.5 (kg / cm ² G), and an average residence time of 2.6 hours while continuously extracting the contents of the polymerization tank so as to be constant.

In the contents continuously extracted from the first polymerization tank, unreacted ethylene and hydrogen were substantially removed by a flash drum maintained at 60 ° C. with an internal pressure of 0.30 (kg / cm ² G).

Thereafter, the content was continuously added to the second polymerization tank together with hexane 43 (liter / hr), ethylene 3.9 (kg / hr), hydrogen 1.0 (N-liter / hr), 1-hexene 100 (g / hr). The polymerization was continued under the conditions of a polymerization temperature of 75 ° C., a reaction pressure of 3.2 (kg / cm ² G), and an average residence time of 1.3 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. It was. 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. Thereafter, a single screw extruder manufactured by Plako Co., Ltd. was used and granulated at the same set temperature and resin extrusion amount as used in Example 1 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. Compared to the comparative example, the balance between rigidity and ESCR is excellent. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molding has better rigidity and ESCR than the comparative example.

[polymerization]
In the first polymerization tank, hexane is 45 (liter / hr), the solid catalyst component (δ) obtained in Synthesis Example 2 is 0.1 (mmol / hr) converted to Zr atom, and triethylaluminum is 20 (mmol / hr) The ethylene was continuously supplied at 7.0 (kg / hr) and hydrogen at 75 (N-liter / hr), and the viscosity measured at 25 ° C. using a B-type viscometer was 370 (mPa · s). A (polyethylene glycol) (polypropylene glycol) block copolymer (trade name Adeka Pluronic L-71, manufactured by Asahi Denka Co., Ltd.) is continuously supplied at 0.8 (g / hr), and the liquid level in the polymerization tank is Polymerization was carried out under the conditions of a polymerization temperature of 85 ° C., a reaction pressure of 7.5 (kg / cm ² G), and an average residence time of 2.6 hours while continuously extracting the contents of the polymerization tank so as to be constant.

In the contents continuously extracted from the first polymerization tank, unreacted ethylene and hydrogen were substantially removed by a flash drum maintained at 60 ° C. with an internal pressure of 0.30 (kg / cm ² G).

Thereafter, the contents are continuously added to the second polymerization tank together with hexane 43 (liter / hr), ethylene 3.5 (kg / hr), hydrogen 3.0 (N-liter / hr), 1-hexene 150 (g / hr). The polymerization was continued under the conditions of a polymerization temperature of 75 ° C., a reaction pressure of 3.2 (kg / cm ² G), and an average residence time of 1.3 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. It was. 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. Thereafter, a single screw extruder manufactured by Plako Co., Ltd. was used and granulated at the same set temperature and resin extrusion amount as used in Example 1 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. Compared to the comparative example, the balance between rigidity and ESCR is excellent. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molding has better rigidity and ESCR than the comparative example.

[Comparative Example 1]
A sample for measurement was a pellet made by Hi-Zex 6008B manufactured by Mitsui Chemicals. 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 4. It was found that the balance between the rigidity and the ESCR property was inferior to that of the example. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molded body is inferior to the examples.

[Comparative Example 2]
A press sheet was prepared using Hi-Zex 6700B 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. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molded body is inferior to the examples.

[Comparative Example 3]
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, both rigidity and ESCR properties are inferior. In addition, Tables 4 and 5 show the results of measuring the physical properties of bottles formed using the samples. The bottle molded body is inferior to the examples.

  The ethylene-based polymer of the present invention is excellent in moldability, mechanical strength, and environmental stress fracture resistance, and further provides a molded body excellent in appearance. When used in an extrusion molded article such as an ethylene polymer blow molded article according to the present invention, excellent characteristics are given.

2 is a CFC contour diagram of the ethylene polymer obtained in Example 2. FIG. 3 is a three-dimensional GPC chart (bird's eye view) and Th viewed from the low temperature side of the ethylene polymer obtained in Example 2. 2 is a CFC contour diagram of the ethylene polymer obtained in Comparative Example 1. FIG. It is a GPC chart which showed an example of GPC separation analysis. It is a schematic diagram of a pinch-off part. It is the figure which showed the relationship between a bending elastic modulus (M) and environmental stress fracture resistance ESCR (T) about a comparative example and an Example.

Claims (6)

An ethylene-based polymer containing 0.02 to 0.50 mol% of a structural unit derived from an α-olefin having 6 to 10 carbon atoms, and in cross fractionation (CFC), either of the following (1) or (2) An ethylene polymer satisfying at least one.
(1) The elution component at 80 ° C. or less is 5% or less with respect to the total elution amount of CFC.
(2) The following relational expression (Eq-1) is satisfied.

(In Eq-1, Sx is the total area value of all peaks based on components eluting at 70 to 85 ° C., and Stotal is the total area value of all peaks based on components eluting at 0 to 145 ° C.) The ethylene polymer according to claim 1, which simultaneously satisfies the following requirements (1 ') to (5').
(1 ') The density (d) is in the range of 945 to 975 kg / m ³ .
(2 ′) The intrinsic viscosity ([η]) measured in decalin at 135 ° C. is in the range of 1.6 to 2.8 (dL / g).
(3 ′) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC is in the range of 5-30.
(4 ') When the GPC curve is separated into two lognormal distribution curves, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of each curve is 1.5 to 3.5, high molecular weight side The weight-average molecular weight (Mw2) of the curve separated into two is 200,000 to 800,000.
(5 ') When the elution temperature at the peak of the strongest peak with a molecular weight of 100,000 or more in cross fractionation (CFC) is Th (° C), the fraction eluted with [(Th-1) to Th] (° C) In the GPC curve, the molecular weight of the strongest peak at a molecular weight of 100,000 or more is in the range of 200,000 to 800,000. In accordance with ASTM-D-790, when the flexural modulus measured at 23 ° C is M, the environmental stress fracture resistance ESCR (hr) at 50 ° C measured according to ASTM-D-1693 is T When 1,500 ≦ M ≦ 1,800 (MPa), T ≧ 10 (hr), and 600 ≦ M <1500 (MPa), the relationship between M and T is expressed by the following equation (Eq-2 3. The ethylene polymer according to claim 2, which is suitably used for a blow molded article characterized by satisfying

  4. The blow according to claim 3, 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 0.6 to 0.9. An ethylene polymer suitably used for a molded article. 5. A blow molded article comprising the ethylene polymer according to claim 4.   The blow molded article according to claim 4, wherein the molded article is a gasoline tank, an industrial chemical can or a bottle container.

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