JP2006008837A - Ethylenic polymer and molded product obtained from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel ethylenic polymer which is excellent in moldability and mechanical strength, a thermoplastic resin composition containing the same, and, more specifically, a molded product made of the thermoplastic resin composition, preferably a blow molded product. <P>SOLUTION: The ethylenic polymer [A] is a copolymer of ethylene and a 4-10C α-olefin and satisfies the following requirements: [F1] an MFR of 0.1-1.0 g/10 min, [F2] a density (d) of 890-960 kg/m<SP>3</SP>, [F3] a ratio [MT/η<SP>*</SP>(P)] of melt tension [MT (g)] to [η<SP>*</SP>(P)] of from 7.00×10<SP>-5</SP>to 9.00×10<SP>-4</SP>and [F4] a sum [(A+B) (/1,000C)] of the numbers of methyl branches [A(/1,000C)] and ethyl branches [B(/1,000C)] per 1,000C atoms of ≤1.4. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel ethylene polymer excellent in moldability, mechanical strength and thermal stability as compared with conventionally known ethylene polymers, and a thermoplastic resin composition containing the ethylene polymer More specifically, the present invention relates to a molded product, preferably a blow molded product, comprising the ethylene polymer and a thermoplastic resin composition containing the ethylene polymer.

  Ethylene copolymers are molded by various molding methods and are used for various purposes. Depending on these molding methods and applications, the properties required for the ethylene-based copolymer are different. For example, in order to prevent sagging or tearing in blow molding, an ethylene copolymer having a high melt tension relative to the molecular weight must be selected. Similar characteristics are necessary to minimize bubble swaying in inflation molding or width drop in T-die molding.

  High-pressure process low-density polyethylene is used for applications such as hollow containers because it has a high melt tension and good moldability compared to an ethylene polymer produced using a Ziegler catalyst. However, high-pressure low-density polyethylene is expected to be inferior in mechanical strength because it has a complicated long-chain branched structure.

  Further, among Ziegler catalyst systems, an ethylene polymer obtained using a metallocene catalyst system is excellent in mechanical strength, but is inferior in melt tension, so that deterioration of moldability is expected.

  Since the ethylene polymer obtained by polymerization using a chromium catalyst contains many long chain branches, the molecular spread is small, and therefore the mechanical strength is inferior. In addition, in the case of a copolymer of ethylene and α-olefin, a hard and brittle component is formed when almost no α-olefin is contained, whereas when α-olefin is excessively copolymerized, stickiness may be caused. Or a soft component having a weak crystal structure is formed. Furthermore, since an ethylene polymer obtained using a chromium catalyst has many terminal vinyl groups, it is expected to be inferior in thermal stability.

  JP-A-11-166083 discloses an ethylene resin composition comprising an ethylene polymer comprising a high molecular weight component and a low molecular weight component obtained using a Ziegler catalyst, and an ethylene polymer obtained using a chromium catalyst. Things are disclosed. Since this ethylene-based resin composition contains an ethylene-based polymer obtained using a chromium-based catalyst, it is expected to be inferior in mechanical strength and thermal stability. Furthermore, since a Ziegler catalyst that is a multi-site catalyst is used, the composition distribution is expected to be wide.

  In order to solve such a problem, various ethylene polymers into which long chain branches are introduced have been disclosed.

JP-A-2-276807 discloses an ethylene polymer obtained by solution polymerization in the presence of a catalyst comprising ethylenebis (indenyl) hafnium dichloride and methylalumoxane, and JP-A-4-213309 discloses a silica. An ethylene polymer obtained by gas phase polymerization in the presence of a catalyst composed of ethylenebis (indenyl) zirconium dichloride and methylalumoxane supported on a catalyst is disclosed in WO 93/08221 as a solution in the presence of a constrained geometric catalyst. An ethylene polymer obtained by polymerization is disclosed in JP-A-8-311260 as a catalyst comprising a racemic and meso isomer of Me ₂ Si (2-Me-Ind) ₂ supported on silica and methylalumoxane. An ethylene polymer obtained by gas phase polymerization in the presence of a chemically treated montmorillonite is disclosed in JP-A-8-34819. JP-A-8-319313 discloses an ethylene polymer obtained by slurry polymerization in the presence of a catalyst comprising bis (cyclopentadienyl) zirconium dichloride supported on Cp * Ti (OMe) ₃ and methylalumone. An ethylene-based polymer obtained by polymerization using a catalyst comprising xane is disclosed.

  These ethylene polymers are described as having improved melt tension and excellent moldability compared to linear ethylene polymers without long-chain branching, but their effects may be insufficient. is expected.

  As described above, it has been difficult to efficiently obtain a resin excellent in moldability and mechanical strength from the conventional known techniques. In other words, if an ethylene polymer having excellent moldability and mechanical strength appears, it can be said that its industrial value is extremely large.

As a result of intensive studies in view of such circumstances, the present inventors have found an ethylene polymer having excellent moldability and mechanical strength by imparting a specific molecular structure and melt properties. It came to be completed.
Japanese Patent Laid-Open No. 11-166083 JP-A-2-276807 JP-A-4-213309 WO93 / 008221 Publication JP-A-8-311260 JP-A-8-034819 JP-A-8-319313

  The present invention relates to a novel ethylene polymer excellent in moldability and mechanical strength as compared with conventionally known ethylene polymers, and a thermoplastic resin composition containing the ethylene polymer, more specifically An object of the present invention is to provide a molded article, preferably a blow molded article, comprising the ethylene polymer and a thermoplastic resin composition containing the ethylene polymer.

The ethylene polymer of the present invention is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, and is characterized by satisfying the following requirements [F1] to [F4] simultaneously.
[F1] The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.1 to 1.0 g / 10 min.
[F2] The density (d) is in the range of 890 to 960 kg / m ³ .
[F3] The ratio [MT / η ^* (g / P)] of the melt tension [MT (g)] at 190 ° C. and the shear viscosity [η ^* (P)] at an angular velocity of 1.0 rad / sec at 200 ° C. The range is from 7.00 × 10 ^{−5 to} 9.00 × 10 ⁻⁴ .
[F4] Sum of the number of methyl branches [A (/ 1000C)] and the number of ethyl branches [B (/ 1000C)] per 1000 carbon atoms measured by ¹³ C-NMR [(A + B) (/ 1000C )] Is 1.4 or less.

The ethylene-based polymer according to the present invention preferably satisfies any one or more of the following [f1] to [f3] in addition to the above requirements.
[f1] The ratio (Mz / Mw) of the Z average molecular weight (Mz) and the weight average molecular weight (Mw) measured by GPC is 10 or more.
[f2] Number of terminal vinyl groups per molecular chain (V) calculated from the number of terminal vinyl groups per 1000 carbon atoms measured by IR [v (/ 1000 C)] and the number average molecular weight (Mn) measured by GPC Is 0.47 / 1 molecular chain or less.
[f3] Maximum melting point peak [Tm (° C.)] and density (d) in DSC satisfy the following relational expression (Eq-1).

The ethylene polymer of the present invention is
A transition metal compound of Group 4 of the Periodic Table comprising at least one solid support and (A) (a) a ligand having a cyclopentadienyl skeleton, (b) an organoaluminum oxy compound, and (c) a general formula (I ) A polyfunctional organic halide represented by

[In the formula (I), R is an (o + p) -valent group containing one or more halogen atoms, o and p are positive integers satisfying (o + p) ≧ 2, and Q ¹ and Q ² are − OH, —NH ₂ or —NLH (in —NLH, L represents a halogen atom, a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, sulfur Any group selected from a containing group, a nitrogen-containing group or a phosphorus-containing group.), L and R, N and R, and N and N may be bonded to each other to form a ring. And a solid transition metal catalyst component obtained by contacting, if necessary,
(B) An ethylene polymer obtained by polymerization using a catalyst system formed from an organoaluminum compound.

  By blending the ethylene polymer according to the present invention with another resin, a thermoplastic resin composition having excellent moldability and excellent mechanical strength can be obtained. By processing the ethylene polymer according to the present invention and the resin composition containing the ethylene polymer, a molded body excellent in moldability and mechanical strength, preferably a blow molded body, is obtained.

  The ethylene-based polymer of the present invention and the thermoplastic resin composition containing the ethylene-based polymer can produce a molded product having good moldability and excellent mechanical strength, preferably a blow molded product.

Hereinafter, the ethylene polymer according to the present invention will be specifically described.
The ethylene-based polymer according to the present invention comprises ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 4 to 10 carbon atoms (however, when butene-1 is used as a comonomer, A copolymer of ethylene and an α-olefin having 6 to 10 carbon atoms is more preferable. Examples of the α-olefin having 4 to 10 carbon atoms used for copolymerization with ethylene include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene.
Such an ethylene polymer has the characteristics shown in the following [F1] to [F4].

  [F1] The melt flow rate (MFR) is in the range of 0.1 to 1.0 g / 10 min. When the melt flow rate (MFR) is 0.1 g / 10 min or more, the shear viscosity of the resulting ethylene polymer is not too high and the moldability is good. When the melt flow rate (MFR) is 1.0 g / 10 min or less, the resulting ethylene polymer has good impact strength.

  The melt flow rate (MFR) strongly depends on the molecular weight. The smaller the melt flow rate (MFR), the larger the molecular weight, and the larger the melt flow rate (MFR), the smaller the molecular weight. Further, it is known that the molecular weight of an ethylene polymer is determined by the composition ratio of hydrogen and ethylene (hydrogen / ethylene) in the polymerization system (for example, Kazuo Soga, KODANSHA “CATALYTIC OLEFIN POLYMERIZATION”, p376 (1990)). For this reason, by increasing / decreasing hydrogen / ethylene, it is possible to produce an ethylene polymer having a melt flow rate (MFR) at the upper limit / lower limit of the claims.

  Melt flow rate (MFR) is measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89.

[F2] The density (d) is in the range of 890 to 960 kg / m ³ , preferably 900 to 940 kg / m ³ , more preferably 905 to 935 kg / m ³ . When the density (d) is 890 kg / m ³ or more, the resulting ethylene polymer has good heat resistance, and when the density (d) is 960 kg / m ³ or less, the environmental stress of the ethylene polymer obtained is Good destructibility (ESCR).

  The density depends on the α-olefin content of the ethylene polymer. The smaller the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. It is also known that the α-olefin content in an ethylene polymer is determined by the composition ratio of α-olefin and ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Makromol). Chem. 193, p.606 (1992)). For this reason, it is possible to produce an ethylene polymer having the density of the lower limit / upper limit of the claims by increasing / decreasing α-olefin / ethylene.

  The density (d) was measured with a density gradient tube after heat-treating the measurement sample at 120 ° C. for 1 hour and linearly cooling to room temperature over 1 hour.

[F3] The ratio [MT / η ^* (g / P)] of the melt tension [MT (g)] to the shear viscosity [η ^* (P)] at 200 ° C. and an angular velocity of 1.0 rad / sec is 7.00. × 10 ^{−5 to} 9.00 × 10 ⁻⁴ , preferably 1.00 × 10 ^{−4 to} 9.00 × 10 ⁻⁴ . When MT / η * is 7.00 × 10 ⁻⁵ or more, the resulting ethylene polymer is excellent in moldability, specifically, it is difficult for the melt parison to sag and tear in blow molding.

MT / η ^* is the ratio of the molecular weight of the ethylene polymer polymerized in the <previous stage> to the molecular weight of the ethylene polymer polymerized in the <follower stage> in the production method shown in Example 1 ( <Previous stage> molecular weight / <follower stage> molecular weight), and MT / η ^* increases as the <previous stage> molecular weight / <lower stage> molecular weight increases, and MT / η ^* increases as the <previous stage> molecular weight / <follower stage> molecular weight decreases. ^* Becomes smaller. Further, it is known that the molecular weight of an ethylene polymer is determined by the composition ratio (hydrogen / ethylene) of hydrogen and ethylene in the polymerization system (for example, Kazuo Soga, KODANSHA “CATALYTIC OLEFIN POLYMERIZATION”, p376 ( 1990)). Therefore, by adjusting hydrogen / ethylene and increasing / decreasing the <previous stage> molecular weight / <follower stage> molecular weight, it is possible to produce an ethylene polymer having MT / η ^* of the upper and lower limits of the claims. .

  The melt tension (MT) is determined by measuring the stress when the molten polymer is stretched at a constant rate. For the measurement, an MT measuring machine manufactured by Toyo Seiki Seisakusho was used. The conditions were a resin temperature of 190 ° C., a melting time of 6 minutes, a barrel diameter of 9.55 mmφ, an extrusion speed of 15 mm / min, a winding speed of 10 to 20 m / min, a nozzle diameter of 2.095 mmφ, and a nozzle length of 8 mm.

Further, the shear viscosity (η ^* ) at 200 ° C. and the angular velocity of 1.0 rad / sec is the angular velocity [ω (rad / sec)] dispersion of the shear viscosity (η ^* ) at the measurement temperature of 200 ° C. of 0.02512 ≦ ω ≦ 400. It is determined by measuring in the range. A rheometer RDS-II manufactured by Rheometrics was used for the measurement. The sample holder was a 25 mmφ parallel plate, and the sample thickness was about 1.8 mm. The number of measurement points was 5 per ω digit. The amount of strain was appropriately selected within a range of 5 to 20% so that the torque in the measurement range could be detected and torque was not exceeded. The sample used for the shear viscosity measurement was a press-molding machine manufactured by Shinfuji Metal Industry Co., Ltd., preheating temperature 190 ° C., preheating time 5 minutes, heating temperature 190 ° C., heating time 2 minutes, heating pressure 100 kg / cm ² , cooling temperature 20 The measurement sample was prepared by press molding to a thickness of 2 mm under the conditions of a cooling pressure of 100 kg / cm ² at 5 ° C. and a cooling time of 5 minutes.

[F4] The sum of the number of methyl branches [A (/ 1000C)] and the number of ethyl branches [B (/ 1000C)] [(A + B) (/ 1000C)] measured by ¹³ C-NMR is 1.4. Hereinafter, it is preferably 1.0 or less, more preferably 0.6 or less. The number of methyl branches and the number of ethyl branches defined in the present invention are defined as a number per 1000 carbons as described later.

  If there are short chain branches such as methyl branch and ethyl branch in the ethylene-based polymer, the short chain branch is incorporated into the crystal and the interplanar spacing of the crystal widens, which may reduce the mechanical strength of the resin. It is known (for example, Zenjiro Osawa et al .: Life prediction and longevity technology of polymer, p.481, NTS (2002)). Therefore, when the sum of the number of methyl branches and the number of ethyl branches (A + B) is 1.4 or less, the resulting ethylene polymer has good mechanical strength.

  The number of methyl branches and the number of ethyl branches in the ethylene polymer strongly depend on the polymerization method of the ethylene polymer, and the ethylene polymer obtained by high pressure radical polymerization is obtained by coordination polymerization using a Ziegler type catalyst system. Compared to the obtained ethylene polymer, the number of methyl branches and the number of ethyl branches are large. In the case of coordination polymerization, the number of methyl branches and the number of ethyl branches in the ethylene polymer strongly depend on the composition ratio of propylene, 1-butene and ethylene (propylene / ethylene, 1-butene / ethylene) in the polymerization system. To do. Therefore, by increasing or decreasing 1-butene / ethylene, it is possible to produce an ethylene polymer having the sum of the number of methyl branches and the number of ethyl branches (A + B) in the claims.

^The number of methyl branches and the number of ethyl branches measured by ¹³ C-NMR are determined as follows. The measurement was carried out using an ECP500 type nuclear magnetic resonance apparatus (1H: 500 MHz) manufactured by JEOL Ltd. at a cumulative number of 10,000 to 30,000. The main chain methylene peak (29.97 ppm) was used as the chemical shift standard. In a commercial NMR measurement quartz glass tube with a diameter of 10 mm, PE sample 250 to 400 mg and Wako Pure Chemical Industries, Ltd. special grade o-dichlorobenzene: ISOTEC benzene-d6 = 5: 1 (volume ratio) 3 ml of the mixed solution was added, and the mixture was heated at 120 ° C. and uniformly dispersed. Assignment of each absorption in the NMR spectrum was carried out according to Chemical Domain No. 141 NMR-Review and Experiment Guide [I], pages 132-133. The number of methyl branches per 1,000 carbons was calculated from the integrated intensity ratio of the absorption of methyl groups derived from methyl branches (19.9 ppm) to the integrated sum of absorptions appearing in the range of 5 to 45 ppm. The number of ethyl branches was calculated from the integrated intensity ratio of the absorption (10.8 ppm) of ethyl groups derived from ethyl branches to the integrated sum of absorptions appearing in the range of 5 to 45 ppm.

  The ethylene-based polymer according to the present invention preferably satisfies any one or more of the following [f1] to [f3] in addition to the above requirements.

  [f1] The ratio (Mz / Mw) of Z average molecular weight (Mz) and weight average molecular weight (Mw) measured by GPC is 10 or more, preferably 15 or more. When Mz / Mw is 10 or more, the melt tension of the resulting ethylene-based polymer is increased and the moldability is excellent.

  Mz / Mw widens the difference between the molecular weight of the ethylene polymer polymerized in the <front stage> and the molecular weight of the ethylene polymer polymerized in the <back stage> in the production method shown in Example 1. It becomes large and becomes small when the difference is narrowed. Further, it is known that the molecular weight of an ethylene polymer is determined by the composition ratio of hydrogen and ethylene (hydrogen / ethylene) in the polymerization system (for example, Kazuo Soga, KODANSHA “CATALYTIC OLEFIN POLYMERIZATION”, p376 ( 1990)). For this reason, by adjusting hydrogen / ethylene, the molecular weight of the ethylene polymer polymerized in the <front stage> and the molecular weight of the ethylene polymer polymerized in the <back stage> are increased or decreased. It is possible to produce an ethylene-based polymer having Mz / Mw.

The Z average molecular weight (Mz) and the weight average molecular weight (Mw) were measured as follows using GPC-150C manufactured by Waters. The separation columns were TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size was 7.5 mm in inner diameter and 600 mm in length, the column temperature was 140 ° C., and o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase. Industry) and BHT (Takeda Pharmaceutical) 0.025 wt% as an antioxidant, moved at 1.0 ml / min, sample concentration 0.1 wt%, sample injection volume 500 microliters, detector A differential refractometer was used. Standard polystyrenes were manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and pressure chemicals were used for 1000 <Mw <4 × 10 ⁶ . The molecular weight calculation is a value obtained by universal calibration and conversion as PE.

  [f2] Number of terminal vinyl groups per molecular chain (V) calculated from the number of terminal vinyl groups per 1000 carbon atoms measured by IR [v (/ 1000 C)] and the number average molecular weight (Mn) measured by GPC Is 0.47 / 1 molecular chain or less, preferably 0.30 / 1 molecular chain or less. When the number of terminal vinyl groups per molecular chain (V) is 0.47 / 1 molecular chain or less, the resulting ethylene polymer is excellent in thermal stability during molding.

  The number of terminal vinyl groups per molecular chain (V) strongly depends on the composition ratio of hydrogen and ethylene in the polymerization system (hydrogen / ethylene). When hydrogen / ethylene is increased, the number of terminal vinyl groups per molecular chain ( V) decreases, and the number of terminal vinyl groups per molecular chain (V) increases when hydrogen / ethylene is decreased. For this reason, in the production method shown in Example 1, by increasing / decreasing hydrogen / ethylene in <previous stage>, an ethylene-based polymer having the number of terminal vinyl groups (V) per molecular chain as claimed is produced. It is possible.

  The number of terminal vinyl groups per molecular chain (V) is expressed by the following formula (Eq-3) using the number average molecular weight (Mn) measured by GPC and the number of terminal vinyl groups per 1000 carbon atoms (v) measured by IR. Determined by.

  The number average molecular weight (Mn) was measured by the same method as described above using GPC-150C manufactured by Waters.

The number of terminal vinyl groups per 1000 carbon atoms (v) was measured using an infrared spectrophotometer FT-IR 410 model manufactured by JASCO Corporation as follows. The sample to be measured is about 0.3 g of ethylene polymer sandwiched in the order of a Teflon (registered trademark) sheet (0.1 mm thick), an aluminum plate (0.1 mm thick), and an iron plate (2 to 3 mm thick), and this is heated with a hydraulic molding machine. temperature 180 ° C., the heating time of 3 minutes, pressed at a molding pressure 50 to 100 / cm ^2, then, was prepared by cooling for 1 minute, pressure 0~50kg / cm ² at room temperature. Measurements by transmission method, the measuring range 5000cm ^-1 ~400cm ^-1, resolution 2 cm ^-1, were carried out at accumulated number 4 times. From a calibration curve prepared using polyethylene derived from a terminal vinyl group detected at 910 cm −1 as a key band and containing no unsaturated bond, and polyethylene having all vinyl groups at one end, the number of carbon atoms was 1000 The number of terminal vinyl groups per unit (v (/ 1000 C)) was quantified.

  [f3] The maximum melting point peak [Tm (° C.)] and density (d) in DSC satisfy the following relational expression (Eq-1).

Preferably, the following relational expression (Eq-2) is satisfied.

When the maximum peak (Tm) of the melting point is 0.315 × d−170 or less, the composition distribution of the obtained ethylene polymer is narrow, and therefore there are few components that cause stickiness.

  As described above, the maximum peak (Tm) of the melting point depends on the distribution (composition distribution) of α-olefins between the molecular chains of the resulting ethylene polymer, in addition to the density (d). When the density is the same, the wider the composition distribution, the smaller the molecular chain of α-olefin, and the formation of thick crystals. Therefore, the maximum peak (Tm) of the melting point becomes higher, and the narrower the composition distribution, the more the α-olefin. Since each molecular chain exists uniformly and does not form a thick crystal, the maximum peak (Tm) of the melting point is low. In the case of Ziegler catalysts, it is known that the composition distribution of the resulting ethylene polymer is wide due to heterogeneous active sites (for example, Kazuo Matsuura et al .: Polyethylene Technology Reader, p.20, Industrial Research Committee (2001 )). Therefore, when the density of the ethylene polymer is the same, the maximum peak (Tm) of the melting point becomes high. In the case of a metallocene catalyst, since the active sites are homogeneous, the resulting ethylene polymer composition distribution becomes narrow. As a result, when the density is the same, the maximum peak (Tm) of the melting point becomes low. The maximum melting point peak (Tm) at the same density can be varied depending on the polymerization temperature. If the polymerization temperature is raised, the inside of the polymerization system becomes uniform and the composition distribution tends to be narrow. As a result, the maximum peak (Tm) of the melting point at the same density is lowered. If the polymerization temperature is lowered, the inside of the polymerization system becomes non-uniform and the composition distribution tends to be broadened. As a result, the maximum peak (Tm) of the melting point at the same density is increased. Therefore, an ethylene polymer satisfying the relationship between the maximum peak (Tm) and the density (d) of the melting point in the claims by increasing / decreasing the polymerization temperature in <previous stage> in the production method shown in Example 1 Can be manufactured.

The maximum peak (Tm) of the melting point was measured as follows using Pyris 1 manufactured by PERKIN ELMER. The sample used for the measurement was a pre-heating temperature of 190 ° C., a pre-heating time of 5 minutes, a heating temperature of 190 ° C., a heating time of 2 minutes, a heating pressure of 100 kg / cm ² , a cooling temperature of 20 ° C. The measurement sample was prepared by press molding to a thickness of 2 mm under the condition of a cooling time of 5 minutes and a cooling pressure of 100 kg / cm ² . About 5 mg of a measurement sample was packed in an aluminum pan, and measurement was performed with a temperature profile of [cond-1] to [cond-4] in a nitrogen atmosphere (nitrogen: 20 ml / min).
[cond-1] Temperature increased from 30 ° C to 200 ° C at 10 ° C / min
[cond-2] Hold at 200 ° C for 5 minutes, then cool down to 30 ° C at 20 ° C / min
[cond-3] Temperature rising from 30 ° C. to 200 ° C. at 10 ° C./min The temperature of the maximum peak in the endothermic curve obtained by the measurement of the above [cond-3] was defined as the maximum peak [Tm (° C.)] .

  The ethylene-based polymer according to the present invention having the above-described characteristics includes, for example, a periodic support including a solid support as described later and one or more ligands having (A) (a) a cyclopentadienyl skeleton. Table 4 Group 4 transition metal compounds, (b) organoaluminum oxy compounds, and (c) polyfunctional organic halides represented by general formula (I),

[In the formula (I), R is an (o + p) -valent group containing one or more halogen atoms, o and p are positive integers satisfying (o + p) ≧ 2, and Q ¹ and Q ² are − OH, —NH ₂ or —NLH (in —NLH, L represents a halogen atom, a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, sulfur Any group selected from a containing group, a nitrogen-containing group or a phosphorus-containing group.), L and R, N and R, and N and N may be bonded to each other to form a ring. In the presence of a catalyst system formed from a solid transition metal catalyst component obtained by contacting the catalyst and, if necessary, (B) an organoaluminum compound, ethylene and an α-olefin having 6 to 20 carbon atoms; Can be produced such that the density of the resulting copolymer is 890 to 950 kg / cm ³ , but is not necessarily limited to this production method. Hereinafter, (a) a transition metal compound, (b) an organoaluminum oxy compound, (c) a polyfunctional organic halide, and (B) an organoaluminum compound used as necessary will be described in detail.

(A) Transition metal compound The transition metal compound (a) used in the present invention includes, for example, a transition metal of Group 4 of the periodic table containing at least one ligand having a cyclopentadienyl skeleton represented by the general formula (II). A compound.

[In the general formula (II), R ^{1 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ alkyl group, a C _{3 to} C ₂₀ cycloalkyl group, or a C _{2 to} C ₂₀ group. It is selected from alkenyl groups, C ₆ -C ₂₀ aryl groups, and C ₇ -C ₂₀ arylalkyl groups, and may contain silicon, halogen or germanium atoms, R ³ and R ⁴ , R ⁴ and R ^5, and At least one of R ⁵ and R ⁶ may be bonded to each other to form a ring. R ⁷ is a divalent group that binds two ligands, and includes a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, germanium, or tin-containing Two substituents on the same carbon, silicon, germanium, and tin atoms may be bonded to each other to form a ring. t ¹ and t ² are each independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , A group selected from a nitrogen-containing group and a phosphorus-containing group. M is a transition metal selected from titanium, zirconium and hafnium. ]

In the general formula (II), examples of the halogen atom represented by R ^{1 to} R ⁶ include chlorine, bromine, fluorine, and iodine atoms. Examples of the C _{1 to} C ₂₀ alkyl group include a methyl group, an ethyl group, and n -Propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, octyl group, nonyl group, dodecyl group, icosyl group, Norbornyl group, adamantyl group, etc .; C ₃ -C ₂₀ cycloalkyl group as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc .; C ₂ -C ₂₀ alkenyl group as vinyl group, propenyl group, cyclohexenyl aryl alkyl C 7 _{-C 20,} benzyl, phenylethyl, etc. _{phenylpropyl;} group such as C The aryl group of ₆ -C _20, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, alpha-or β- naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, Examples include aseantrilenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like.

Examples of the halogen-containing group as R ^{1 to} R ⁶ include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and a group in which one or more hydrogen atoms of the aryl group are substituted with an appropriate halogen atom. Can be mentioned.

  Examples of the silicon or germanium-containing group include alkyl groups, cycloalkyl groups, alkenyl groups, arylalkyl groups, and groups in which one or more carbon atoms of the aryl group are substituted with silicon or germanium atoms.

R ^{1 to} R ⁶ may be the same as or different from each other, and at least one of adjacent groups, ie, R ³ and R ⁴ , R ⁴ and R ^5, and R ⁵ and R ^6. The sets may be bonded to each other to form a ring. Examples of the indenyl group forming such a ring include 4,5-benzoindenyl group, 5,6-benzoindenyl group, 6,7-benzoindenyl group, α-acenaphthoindenyl group and carbon thereof. Examples thereof include alkyl substituted products of 1 to 10.

R ⁷ is a divalent group that binds two ligands, of which C ₁ -C ₂₀ hydrocarbon groups include alkylene groups such as methylene, ethylene, propylene, diisopropylmethylene, methyl-t -Substituted alkylene groups such as butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, methylnaphthylmethylene, dinaphthylmethylene, isopropylidene, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, And cycloalkylene groups such as cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanilidene, and the like, and C ₁ -C ₂₀ halogen-containing carbon. Examples of the hydride group include groups in which one or more hydrogen atoms of the hydrocarbon group are substituted with an appropriate halogen atom.

Examples of the C ₁ -C ₂₀ silicon-containing group include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, methylnaphthylsilylene, dinaphthyl. (Substituted) silylene groups such as silylene, cyclodimethylene silylene, cyclotrimethylene silylene, cyclotetramethylene silylene, cyclopentamethylene silylene, cyclohexamethylene silylene, cycloheptamethylene silylene, and the like, germanium, tin-containing groups as In the silicon-containing group, a group obtained by converting silicon into germanium or tin can be used.

t ¹ and t ² are each independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , A group selected from a nitrogen-containing group and a phosphorus-containing group. Examples of the halogen atom include chlorine, bromine, fluorine, and iodine atoms. Examples of the C _{1 to} C ₂₀ hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Group, alkyl group such as t-butyl group, n-hexyl group and n-decyl group, aryl group such as phenyl group, 1-naphthyl group and 2-naphthyl group, aralkyl group such as benzyl group, etc. Examples of the C _{1 to} C ₂₀ halogen-containing hydrocarbon group include a group in which one or more of the hydrogen atoms in the hydrocarbon group are substituted with an appropriate halogen atom, such as a trifluoromethyl group. Examples of the silicon-containing group include a trimethylsilyl group and dimethyl (t-butyl) silyl group. Examples of the oxygen-containing group include a methoxy group and an ethoxy group. Examples of the sulfur-containing group include a thiol group and a sulfonic acid group. Examples of the nitrogen-containing group include a dimethylamino group, and examples of the phosphorus-containing group include a phenylphosphine group. t ¹ and t ² may be the same as or different from each other.

  Examples of the transition metal compound of the component (a) represented by the general formula (II) include, for example, JP-A-4-268308, JP-A-5-306304, JP-A-6-110509, JP-A-6-157661. Examples thereof include compounds described in JP-A-6-184179, JP-A-6-345809, JP-A-7-149815, JP-A-7-188318, and JP-A-7-258321.

  Specific examples include ethylene bis (indenyl) zirconium dichloride, ethylene bis (2-methylindenyl) zirconium dichloride, 1,3-propylene bis (indenyl) zirconium dichloride, 1,3-propylene bis (2-methylindenyl). Zirconium dichloride, 1,2-propylenebis (indenyl) zirconium dichloride, 1,2-propylenebis (2-methylindenyl) zirconium dichloride, 2,3-butylenebis (indenyl) zirconium dichloride, 2,3-butylenebis (2- Methylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl 4-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-ethylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-propylindenyl) zirconium dichloride, dimethylsilylenebis (2 -Methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-anthracenylindenyl) zirconium dichloride, dimethylsilylene Bis (2-methylbenz [e] indenyl) zirconium dichloride, dimethylsilylenebis (2-methylbenz [f] indenyl) zirconium dichloride, dimethylsilylenebis (2-ethylindenyl) ) Zirconium dichloride, dimethylsilylenebis (2-ethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-ethylbenz [e] indenyl) zirconium dichloride, dimethylsilylenebis (2,5-dimethyl-4-methylindene) Nyl) zirconium dichloride, dimethylsilylene bis (2,5-dimethyl-4-ethylindenyl) zirconium dichloride, dimethylsilylene bis (2,5-dimethyl-4-propylindenyl) zirconium dichloride, dimethylsilylene bis (2,5 -Dimethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2,5-dimethyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2,5-dimethyl-4) -Anthracenylindenyl) zirconium dichloride, dimethylsilylenebis (2,6-dimethyl-4-methylindenyl) zirconium dichloride, dimethylsilylenebis (2,6-dimethyl-4-ethylindenyl) zirconium dichloride, dimethylsilylene Bis (2,6-dimethyl-4-propylindenyl) zirconium dichloride, dimethylsilylenebis (2,6-dimethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2,6-dimethyl-4-naphthylindene) Nyl) zirconium dichloride, dimethylsilylene bis (2,6-dimethyl-4-anthracenylindenyl) zirconium dichloride, dimethylsilylene bis (2,7-dimethyl-4-methylindenyl) zirconium dichloride Dimethylsilylene bis (2,7-dimethyl-4-ethylindenyl) zirconium dichloride, dimethylsilylene bis (2,7-dimethyl-4-propylindenyl) zirconium dichloride, dimethylsilylene bis (2,7-dimethyl-4-l) Phenylindenyl) zirconium dichloride, dimethylsilylene bis (2,7-dimethyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylene bis (2,7-dimethyl-4-anthracenylindenyl) zirconium dichloride, phenylmethylsilylene Bis (indenyl) zirconium dichloride, phenylmethylsilylenebis (2-methylindenyl) zirconium dichloride, phenylmethylsilylenebis (2-methyl-4-methylindenyl) zirconium dichloride Phenylmethylsilylenebis (2-methyl-4-ethylindenyl) zirconium dichloride, phenylmethylsilylenebis (2-methyl-4-propylindenyl) zirconium dichloride, phenylmethylsilylenebis (2-methyl-4-phenylindene) Nyl) zirconium dichloride, phenylmethylsilylene bis (2-methyl-4-naphthylindenyl) zirconium dichloride, phenylmethylsilylene bis (2-methyl-4-anthracenylindenyl) zirconium dichloride, phenylmethylsilylene bis (2- Methylbenz [e] indenyl) zirconium dichloride, phenylmethylsilylenebis (2-methylbenz [f] indenyl) zirconium dichloride, phenylmethylsilylenebis (2-ethylindenyl) ) Zirconium dichloride, phenylmethylsilylenebis (2-ethyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylenebis (2-ethylbenz [e] indenyl) zirconium dichloride, phenylmethylsilylenebis (2,5-dimethyl-4) -Methylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,5-dimethyl-4-ethylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,5-dimethyl-4-propylindenyl) zirconium dichloride, phenylmethyl Silylene bis (2,5-dimethyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylene bis (2,5-dimethyl-4-naphthylindenyl) zirconium dichloride, Phenylmethylsilylenebis (2,5-dimethyl-4-anthracenylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-methylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,6 -Dimethyl-4-ethylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-propylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-phenylindenyl) zirconium Dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-naphthylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-anthracenylindenyl) zirconium dichloride, Phenylmethylsilylenebis (2,7-dimethyl-4-methylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,7-dimethyl-4-ethylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,7-dimethyl) -4-propylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,7-dimethyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,7-dimethyl-4-naphthylindenyl) zirconium dichloride, Phenylmethylsilylenebis (2,7-dimethyl-4-anthracenylindenyl) zirconium dichloride, and dibromide compounds, dialkyl compounds, diaralkyl compounds, disilyl compounds of the above metallocene compounds, Examples include dialkoxy compounds, dithiol compounds, disulfonic acid compounds, diamino compounds, diphosphine compounds, and metallocene compounds in which the central metal of the above compound is titanium or hafnium.

  The bridged metallocene compound of the present invention can be produced by a known method, and the production method is not particularly limited. As a known production method, for example, WO 01/27174 by the present applicant can be cited.

(B) Organoaluminum Oxy Compound The organoaluminum oxy compound (b) used in the present invention may be a conventionally known aluminoxane, or a benzene insoluble organic as exemplified in JP-A-2-78687. An aluminum oxy compound may be used.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

Specifically, as the organoaluminum compound used in preparing the aluminoxane, a general formula: R ^a _m Al (OR ^b ) _n H _p X _q (wherein R ^a and R ^b are the same or different from each other). A hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, and p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Specific examples of such compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride. Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those that are insoluble or hardly soluble in benzene are preferred. These organoaluminum oxy compounds (B-2) are used singly or in combination of two or more.

(C) Polyfunctional organic halide (c) The polyfunctional organic halide is a compound represented by the following general formula (I).

[In the formula (I), R is an (o + p) -valent group containing one or more halogen atoms, o and p are positive integers satisfying (o + p) ≧ 2, and Q ¹ and Q ² are —OH, —NH ₂ or —NLH (in —NLH, L represents a halogen atom, a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, An arbitrary group selected from a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group.), L and R, N and R, and N and N may be bonded to each other to form a ring. ]

In general formula (I), among L in the substituted amino group represented by —NLH in Q ¹ and Q ² , examples of the halogen atom include chlorine, bromine, fluorine, and iodine atoms, and C _{1 to} C ₂₀ Examples of the hydrocarbon group include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, n-decyl group, and phenyl group. Aryl groups such as 1-naphthyl group and 2-naphthyl group, and aralkyl groups such as benzyl group.

Examples of the C _{1 to} C ₂₀ halogen-containing hydrocarbon group include groups in which one or more hydrogen atoms in the hydrocarbon group are substituted with an appropriate halogen atom, such as a trifluoromethyl group. Examples of the silicon-containing group include a trimethylsilyl group and dimethyl (t-butyl) silyl group. Examples of the oxygen-containing group include a methoxy group and an ethoxy group. Examples of the sulfur-containing group include a thiol group and a sulfonic acid group. Examples of the nitrogen-containing group include a dimethylamino group, and examples of the phosphorus-containing group include a phenylphosphine group.

  Specific examples of such polyfunctional organic halides represented by the general formula (I) include OH-R-OH type compounds (the definition of R is the same as that of the general formula (I)), and 3- Fluorocatechol, 4-fluorocatechol, 3,4-difluorocatechol, 3,5-difluorocatechol, 3,6-difluorocatechol, 3,4,5-trifluorocatechol, 3,4,6-trifluorocatechol, tetra Fluorocatechol, 3- (trifluoromethyl) catechol, 4- (trifluoromethyl) catechol, 3,4-di (trifluoromethyl) catechol, 3,5-di (trifluoromethyl) catechol, 3,6-di (Trifluoromethyl) catechol, 3,4,5-tri (trifluoromethyl) catechol, 3,4,6-tri (trifluoro) Til) catechol, tetra (trifluoromethyl) catechol, 2-fluororesorcin, 4-fluororesorcin, 5-fluororesorcin, 2,4-difluororesorcin, 2,5-fluororesorcin, 4,5-difluororesorcin, 4, 6-difluororesorcin, 5,6-difluororesorcin, 2,4,5-trifluororesorcin, 4,5,6-trifluororesorcin, tetrafluororesorcin, 2- (trifluoromethyl) resorcin, 4- (trifluoro Methyl) resorcin, 5- (trifluoromethyl) resorcin, 2,4-di (trifluoromethyl) resorcin, 2,5- (trifluoromethyl) resorcin, 4,5-di (trifluoromethyl) resorcin, 4, 6-di (trifluoromethyl) resorcin, , 6-di (trifluoromethyl) resorcin, 2,4,5-tri (trifluoromethyl) resorcin, 4,5,6-tri (trifluoromethyl) resorcin, tetra (trifluoromethyl) resorcin, 2-fluoro Hydroquinone, 3-fluorohydroquinone, 2,3-difluorohydroquinone, 2,5-difluorohydroquinone, 2,6-difluorohydroquinone, 2,3,5-trifluorohydroquinone, 2,3,6-trifluorohydroquinone, tetrafluoro Hydroquinone, 2- (trifluoromethyl) hydroquinone, 3- (trifluoromethyl) hydroquinone, 2,3-di (trifluoromethyl) hydroquinone, 2,5-di (trifluoromethyl) hydroquinone, 2,6-di ( Trifluoromethyl) high Droquinone, 2,3,5-tri (trifluoromethyl) hydroquinone, 2,3,6-tri (trifluoromethyl) hydroquinone, tetra (trifluoromethyl) hydroquinone, 1,3-bis (2-hydroxyhexafluoroisopropyl) ) Benzene, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene, 2-fluoro-1,5-dihydroxynaphthalene, 3-fluoro-1,5-dihydroxynaphthalene, 4-fluoro-1,5-dihydroxynaphthalene, 2, 3-difluoro-1,5-dihydroxynaphthalene, 2,4-difluoro-1,5-dihydroxynaphthalene, 2,6-difluoro-1,5-dihydroxynaphthalene, 2,7-difluoro-1,5-dihydroxynaphthalene, 2,8- Difluoro-1, -Dihydroxynaphthalene, 3,4-difluoro-1,5-dihydroxynaphthalene, 3,8-difluoro-1,5-dihydroxynaphthalene, 4,8-difluoro-1,5-dihydroxynaphthalene, 2,3,4-trifluoro-1, 5-dihydroxynaphthalene, 2,3,6-trifluoro-1,5-dihydroxynaphthalene, 2,3,7-trifluoro-1,5-dihydroxynaphthalene, 2,3,8-trifluoro-1,5-dihydroxynaphthalene, 2,3,6,7-tetrafluoro-1,5-dihydroxynaphthalene, hexafluoro-1,5-dihydroxynaphthalene, 1-fluoro-2,6-dihydroxynaphthalene, 3-fluoro-2,6-dihydroxynaphthalene, 4- Fluoro-2,6-dihydroxynaphthalene, , 3-Difluoro-2,6-dihydroxynaphthalene, 1,4-difluoro-2,6-dihydroxynaphthalene, 1,5-difluoro-2,6-dihydroxynaphthalene, 3,4-difluoro-2,6-dihydroxynaphthalene, 3,5 -Difluoro-2,6-dihydroxynaphthalene, 4,5-difluoro-2,6-dihydroxynaphthalene, 1,3,4-trifluoro-2,6-dihydroxynaphthalene, 1,3,5-trifluoro-2,6-dihydroxynaphthalene 3,4,5-trifluoro-2,6-dihydroxynaphthalene, 1,3,4,5-tetrafluoro-2,6-dihydroxynaphthalene, hexafluoro-2,6-dihydroxynaphthalene, 2,3,4, 5-tetrafluorobiphenol, 2,2 ', 4,4'-tetra Fluoro-4,4′-biphenol, 2,2 ′, 3,3 ′, 4,4 ′, 5,5 ′, 6,6′-octafluoro-4,4′-biphenol, 4,4′-bis ( 2-hydroxyhexafluoroisopropyl) diphenyl, bis (2,3-difluoro-4-hydroxy) methane, bis (2,6-difluoro-4-hydroxy) methane, bis (3,5-difluoro-4-hydroxy) methane, bis ( Tetrafluoro-4-hydroxy) methane, 4,4′-bis (2-hydroxyhexafluoroisopropyl) diphenyl ether, 4,4′-isopropylidenebis (2,6-difluorophenol), tetrafluoroethylene fricoh, Hexafluoro-1,3-propaneglycol, 2,2 ', 3,3'-tetrafluoro-1,4-butanediol Octafluoro-1,4-butanediol, perfluoro-1,5-pentanediol, perfluoro-1,6-hexanediol, perfluoro-1,7-heptanediol, perfluoro-1,8-octanediol, and the above OH-R- The compound etc. which substituted the fluorine atom of OH compound by the bromine atom and the chlorine atom are mentioned.

As the H ₂ N—R—NH ₂ compound (the definition of R is the same as that of the general formula (I)), 2-amino-3-fluoroaniline, 2-amino-4-fluoroaniline, 2-amino-5-fluoro Aniline, 2-amino-3,4-difluoroaniline, 2-amino-3,5-difluoroaniline, 2-amino-3,6-difluoroaniline, 2-amino-3,4,5-trifluoroaniline, 2 -Amino-3,4,6-trifluoroaniline, 2-amino-tetrafluoroaniline, 2-amino-3- (trifluoromethyl) aniline, 2-amino-4- (trifluoromethyl) aniline, 2-amino -3,4-di (trifluoromethyl) aniline, 2-amino-3,5-di (trifluoromethyl) aniline, 2-amino-3,6-di (trifluoromethyl) Niline, 2-amino-3,4,5-tri (trifluoromethyl) aniline, 2-amino-3,4,6-tri (trifluoromethyl) aniline, 2-amino-tetra (trifluoromethyl) aniline, 3-amino-2-fluoroaniline, 3-amino-4-fluoroaniline, 3-amino-5-fluoroaniline, 3-amino-2,4-difluoroaniline, 3-amino-2,5-fluoroaniline, 3 -Amino-4,5-difluoroaniline, 3-amino-4,6-difluoroaniline, 3-amino-5,6-difluoroaniline, 3-amino-2,4,5-trifluoroaniline, 3-amino- 4,5,6-trifluoroaniline, 3-amino-tetrafluoroaniline, 3-amino-2- (trifluoromethyl) aniline, 3-amino 4- (trifluoromethyl) aniline, 3-amino-5- (trifluoromethyl) aniline, 3-amino-2,4-di (trifluoromethyl) aniline, 3-amino-2,5- (trifluoromethyl) ) Aniline, 3-amino-4,5-di (trifluoromethyl) aniline, 3-amino-4,6-di (trifluoromethyl) aniline, 3-amino-5,6-di (trifluoromethyl) aniline 3-amino-2,4,5-tri (trifluoromethyl) aniline, 3-amino-4,5,6-tri (trifluoromethyl) aniline, 3-amino-tetra (trifluoromethyl) aniline, 4 -Amino-2-fluoroaniline, 4-amino-3-fluoroaniline, 4-amino-2,3-difluoroaniline, 4-amino-2,5-difluoroaniline 4-amino-2,6-difluoroaniline, 4-amino-2,3,5-trifluoroaniline, 4-amino-2,3,6-trifluoroaniline, 4-amino-tetrafluoroaniline, 4 -Amino-2- (trifluoromethyl) aniline, 4-amino-3- (trifluoromethyl) aniline, 4-amino-2,3-di (trifluoromethyl) aniline, 4-amino-2,5-di (Trifluoromethyl) aniline, 4-amino-2,6-di (trifluoromethyl) aniline, 4-amino-2,3,5-tri (trifluoromethyl) aniline, 4-amino-2,3,6 -Tri (trifluoromethyl) aniline, 4-amino-tetra (trifluoromethyl) aniline, 2-amino-6-fluorobenzylamine, 1,5-diamino-2-fur Lonaphthalene, 1,5-diamino-3-fluoronaphthalene, 1,5-diamino-4-fluoronaphthalene, 1,5-diamino-2,3-difluoronaphthalene, 1,5-diamino-2,4-difluoronaphthalene 1,5-diamino-2,6-difluoronaphthalene, 1,5-diamino-2,7-difluoronaphthalene, 1,5-diamino-2,8-difluoronaphthalene, 1,5-diamino-3,4- Difluoronaphthalene, 1,5-diamino-3,8-difluoronaphthalene, 1,5-diamino-4,8-difluoronaphthalene, 1,5-diamino-2,3,4-trifluoronaphthalene, 1,5-diamino -2,3,6-trifluoronaphthalene, 1,5-diamino-2,3,7-trifluoronaphthalene, 1,5-diamino-2 3,8-trifluoronaphthalene, 1,5-diamino-2,3,6,7-tetrafluoronaphthalene, 1,5-diamino-hexafluoronaphthalene, 2,6-diamino-1-fluoronaphthalene, 2,6 -Diamino-3-fluoronaphthalene, 2,6-diamino-4-fluoronaphthalene, 2,6-diamino-1,3-difluoronaphthalene, 2,6-diamino-1,4-difluoronaphthalene, 2,6-diamino -1,5-difluoronaphthalene, 2,6-diamino-3,4-difluoronaphthalene, 2,6-diamino-3,5-difluoronaphthalene, 2,6-diamino-4,5-difluoronaphthalene, 2,6 -Diamino-1,3,4-trifluoronaphthalene, 2,6-diamino-1,3,5-trifluoronaphthalene, 2,6- Diamino-3,4,5-trifluoronaphthalene, 2,6-diamino-1,3,4,5-tetrafluoronaphthalene, 2,6-diamino-hexafluoronaphthalene, 4-amino-4 '-(N- Methylamino) -2,3,4,5-tetrafluorobiphenyl, 4-amino-4 '-(N-methylamino) -2,2', 4,4'-tetrafluorobiphenyl, 4-amino-4 ' -(N-methylamino) -2,2 ', 3,3', 4,4 ', 5,5', 6,6'-octafluorobiphenyl, 2,2'-bis (trifluoromethyl) -4 , 4′-diaminobiphenyl, 3,3′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 4,4′-diaminooctafluorobiphenyl, bis (4-amino-2,3-difluorophenyl) Methane, bis (4-amino-2, -Difluorophenyl) methane, bis (4-amino-3,5-difluorophenyl) methane, bis (4-amino-tetrafluorophenyl) methane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane 2,2-bis [4- (4-aminophenyl)]-hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-bis (2-amino-hexafluoroisopropyl) ) Diphenyl ether, 4,4′-isopropylidenebis (2,6-difluoroaniline), 2,4-diamino-6- (4-fluorophenyl) pyrimidine, 2,4-diamino-5-fluoroquinazoline, 4,4 '-Diaminooctafluorobiphenyl, tetrafluorosuccinamide, tetrafluoroethylene di Min, hexafluoro-1,3-propenediamine, 2,2 ′, 3,3′-tetrafluoro-1,4-butylenediamine, octafluoro-1,4-butylenediamine, decafluoro-1,5-pentene Fluorine atoms of diamine, perfluoro-1,6-hexenediamine, perfluoro-1,7-heptenediamine, perfluoro-1,8-octenediamine and the above H ₂ N—R—NH ₂ compound were substituted with bromine atoms and chlorine atoms. Compounds and the like.

  HLN-R-NLH type compounds (the definitions of R and L are the same as those in formula (I)) include 3-fluoro-1,2-di (N-methylamino) benzene, 4-fluoro-1,2- Di (N-methylamino) benzene, 3,4-difluoro-1,2-di (N-methylamino) benzene, 3,5-difluoro-1,2-di (N-methylamino) benzene, 3,6 -Difluoro-1,2-di (N-methylamino) benzene, 3,4,5-trifluoro-1,2-di (N-methylamino) benzene, 3,4,6-trifluoro-1,2 -Di (N-methylamino) benzene, tetrafluoro-1,2-di (N-methylamino) benzene, 2-fluoro-1,3-di (N-methylamino) benzene, 4-fluoro-1,3 -Di (N-methylamino) benzene, 5-phenyl Oro-1,3-di (N-methylamino) benzene, 2,4-difluoro-1,3-di (N-methylamino) benzene, 2,5-fluoro-1,3-di (N-methylamino) ) Benzene, 4,5-difluoro-1,3-di (N-methylamino) benzene, 4,6-difluoro-1,3-di (N-methylamino) benzene, 5,6-difluoro-1,3 -Di (N-methylamino) benzene, 2,4,5-trifluoro-1,3-di (N-methylamino) benzene, 4,5,6-trifluoro-1,3-di (N-methyl) Amino) benzene, tetrafluoro-1,3-di (N-methylamino) benzene, 2-fluoro-1,4-di (N-methylamino) benzene, 3-fluoro-1,4-di (N-methyl) Amino) benzene, 2,3-difluoro-1, -Di (N-methylamino) benzene, 2,5-difluoro-1,4-di (N-methylamino) benzene, 2,6-difluoro-1,4-di (N-methylamino) benzene, 2, 3,5-trifluoro-1,4-di (N-methylamino) benzene, 2,3,6-trifluoro-1,4-di (N-methylamino) benzene, tetrafluoro-1,4-di (N-methylamino) benzene, 2-fluoro-1,5-di (N-methylamino) naphthalene, 3-fluoro-1,5-di (N-methylamino) naphthalene, 4-fluoro-1,5-di (N -Methylamino) naphthalene, 2,3-difluoro-1,5-di (N-methylamino) naphthalene, 2,4-difluoro-1,5-di (N-methylamino) naphthalene, 2,6-difluoro-1,5 -Di ( N-methylamino) naphthalene, 2,7-difluoro-1,5-di (N-methylamino) naphthalene, 2,8-difluoro-1,5-di (N-methylamino) naphthalene, 3,4-difluoro-1, 5-di (N-methylamino) naphthalene, 3,8-difluoro-1,5-di (N-methylamino) naphthalene, 4,8-difluoro-1,5-di (N-methylamino) naphthalene, 2,3 , 4-Trifluoro-1,5-di (N-methylamino) naphthalene, 2,3,6-trifluoro-1,5-di (N-methylamino) naphthalene, 2,3,7-trifluoro-1,5 -Di (N-methylamino) naphthalene, 2,3,8-trifluoro-1,5-di (N-methylamino) naphthalene, 2,3,6,7-tetrafluoro-1,5-di (N- Methyl Mino) naphthalene, hexafluoro-1,5-di (N-methylamino) naphthalene, 4,4′-di (N-methylamino) -2,3,4,5-tetrafluorobiphenyl, 4,4′- Di (N-methylamino) -2,2 ′, 4,4′-tetrafluorobiphenyl, 4,4′-di (N-methylamino) -2,2 ′, 3,3 ′, 4,4 ′, 5,5 ′, 6,6′-octafluorobiphenyl, bis (4- (N-methylamino) -2,3-difluorophenyl) methane, bis ((N-methylamino) -2,6-difluorophenyl) Methane, bis (4- (N-methylamino) -3,5-difluorophenyl) methane, bis (4- (N-methylamino) -tetrafluorophenyl) methane, 4,4′-bis (2- (N -Methylamino) -hexafluoroisopropyl) Diphenyl ether, tetrafluoroethylenediamine, hexafluoro-1,3-propenediamine, 2,2 ′, 3,3′-hexafluoro-1,4-butylenediamine, octafluoro-1,4-butylenediamine, decafluoro-1 , 5-pentenediamine, perfluoro-1,6-hexenediamine, perfluoro-1,7-heptenediamine, perfluoro-1,8-octenediamine, 1,2-di (N-methylamino) tetrafluoroethane, 1,3-di ( N-methylamino) hexafluoropropane, 1,4-di (N-methylamino) -2,2 ′, 3,3′-hexafluorobutane, 1,4-di (N-methylamino) -octafluorobutane 1,5-di (N-methylamino) -decafluoropentane, 1,6-di (N-methylamino) -Perfluorohexane, 1,7-di (N-methylamino) -perfluoropentane, 1,8-di (N-methylamino) -perfluorooctane, 5-fluorouracil, 6-fluorouracil, 1-fluoroxanthine, 3-fluoroxanthine, 7-fluoroxanthine, 3-fluoroadenine, 5-fluoromethyluracil, 5-trifluoromethyluracil, 6-fluoromethyllauracil, 1-fluoromethylxanthine, 3-fluoromethylxanthine, 7-fluoro Examples include methylxanthine, 3-fluoromethyladenine, and compounds in which the fluorine atom of the HLN-R-NLH type compound is substituted with a bromine atom or a chlorine atom.

HO—R—NH type ₂ compounds (the definition of R is the same as in formula (I)) include 2-amino-3-fluorophenol, 2-amino-4-fluorophenol, 2-amino-3,4- Difluorophenol, 2-amino-3,5-difluorophenol, 2-amino-3,6-difluorophenol, 2-amino-3,4,5-trifluorophenol, 2-amino-3,4,6-tri Fluorophenol, 2-amino-tetrafluorophenol, 2-amino-3- (trifluoromethyl) phenol, 2-amino-4- (trifluoromethyl) phenol, 2-amino-3,4-di (trifluoromethyl) ) Phenol, 2-amino-3,5-di (trifluoromethyl) phenol, 2-amino-3,6-di (trifluoromethyl) phenol, 2-amino-3,4,5-tri (trifluoromethyl) phenol, 2-amino-3,4,6-tri (trifluoromethyl) phenol, 2-amino-tetra (trifluoromethyl) phenol, 3- Amino-2-fluorophenol, 3-amino-4-fluorophenol, 3-amino-5-fluorophenol, 3-amino-2,4-difluorophenol, 3-amino-2,5-fluorophenol, 3-amino -4,5-difluorophenol, 3-amino-4,6-difluorophenol, 3-amino-5,6-difluorophenol, 3-amino-2,4,5-trifluorophenol, 3-amino-4, 5,6-trifluorophenol, 3-amino-tetrafluorophenol, 3-amino-2- (trifluoromethyl) fluoro Nord, 3-amino-4- (trifluoromethyl) phenol, 3-amino-5- (trifluoromethyl) phenol, 3-amino-2,4-di (trifluoromethyl) phenol, 3-amino-2, 5- (trifluoromethyl) phenol, 3-amino-4,5-di (trifluoromethyl) phenol, 3-amino-4,6-di (trifluoromethyl) phenol, 3-amino-5,6-di (Trifluoromethyl) phenol, 3-amino-2,4,5-tri (trifluoromethyl) phenol, 3-amino-4,5,6-tri (trifluoromethyl) phenol, 3-amino-tetra (tri Fluoromethyl) phenol, 4-amino-2-fluorophenol, 4-amino-3-fluorophenol, 4-amino-2,3-difluoro Enol, 4-amino-2,5-difluorophenol, 4-amino-2,6-difluorophenol, 4-amino-2,3,5-trifluorophenol, 4-amino-2,3,6-trifluoro Phenol, 4-amino-tetrafluorophenol, 4-amino-2- (trifluoromethyl) phenol, 4-amino-3- (trifluoromethyl) phenol, 4-amino-2,3-di (trifluoromethyl) Phenol, 4-amino-2,5-di (trifluoromethyl) phenol, 4-amino-2,6-di (trifluoromethyl) phenol, 4-amino-2,3,5-tri (trifluoromethyl) Phenol, 4-amino-2,3,6-trifluoro (trifluoromethyl) phenol, 4-amino-tetra (trifluoromethyl) pheno 5-amino-2-fluoro-1-hydroxynaphthalene, 5-amino-3-fluoro-1-hydroxynaphthalene, 5-amino-4-fluoro-1-hydroxynaphthalene, 5-amino-2,3-difluoro-1- Hydroxynaphthalene, 5-amino-2,4-difluoro-1-hydroxynaphthalene, 5-amino-2,6-difluoro-1-hydroxynaphthalene, 5-amino-2,7-difluoro-1-hydroxynaphthalene, 5-amino-2 , 8-difluoro-1-hydroxynaphthalene, 5-amino-3,4-difluoro-1-hydroxynaphthalene, 5-amino-3,8-difluoro-1-hydroxynaphthalene, 5-amino-4,8-difluoro-1-hydroxynaphthalene 5-amino-2,3,4-trifluoro-1 Hydroxynaphthalene, 5-amino-2,3,6-trifluoro-1-hydroxynaphthalene, 5-amino-2,3,7-trifluoro-1-hydroxynaphthalene, 5-amino-2,3,8-trifluoro-1 -Hydroxynaphthalene, 5-amino-2,3,6,7-tetrafluoro-1-hydroxynaphthalene, 5-amino-hexafluoro-1-hydroxynaphthalene, 2-amino-1-fluoro-6-hydroxynaphthalene, 2-amino -3-fluoro-6-hydroxynaphthalene, 2-amino-4-fluoro-6-hydroxynaphthalene naphthalene, 2-amino-1,3-difluoro-6-hydroxynaphthalene, 2-amino-1,4-difluoro-6-hydroxynaphthalene, 2 -Amino-1,5-difluoro-6-hydroxy Naphthalene, 2-amino-3,4-difluoro-6-hydroxynaphthalene, 2-amino-3,5-difluoro-6-hydroxynaphthalene, 2-amino-4,5-difluoro-6-hydroxynaphthalene, 2-amino-1,3,4 Trifluoro-6-hydroxynaphthalene, 2-amino-1,3,5-trifluoro-6-hydroxynaphthalene, 2-amino-3,4,5-trifluoro-6-hydroxynaphthalene, 2-amino-1,3,4,5 -Tetrafluoro-6-hydroxynaphthalene, 2-amino-hexafluoro-6-hydroxynaphthalene, bis (4-amino-2,3-difluorophenyl) methane, bis (4-amino-2,6-difluorophenyl) methane, Bis (4-hydroxy3,5-difluorophenyl) methane Bis (4-hydroxytetrafluorophenyl) methane, 4,4′-bis (2-amino-hexafluoroisopropyl) diphenyl ether, 4,4′-isopropylidenebis (2,6-difluoroaniline), 3,5 -Bis (trifluoromethyl) benzamidooxime, 5- (trifluoromethyl) pyridine-2-arboxamidooxime, 2-amino-tetrafluoroethanol, 3-amino-hexafluoro-1-propanol, 4-amino-2 2 ′, 3,3′-tetrafluoro-1-butanol, 4-amino-octafluoro-1-butanol, 5-amino-perfluoro-1-pentanol, 6-amino-perfluoro-1-hexanol, 7 -Amino-perfluoro-1-heptanol, 8-amino-perfluoro-1-oct Cyclohexanol and the fluorine atoms of the HO-R-NH ₂ compound, a bromine atom, the compound was replaced by a chlorine atom.

  HO-R-NLH type compounds (the definitions of L and R are the same as those in formula (I)) include 2- (N-methylamino) -3-fluorophenol and 2- (N-methylamino) -4- Fluorophenol, 2- (N-methylamino) -3,4-difluorophenol, 2- (N-methylamino) -3,5-difluorophenol, 2- (N-methylamino) -3,6-difluorophenol 2- (N-methylamino) -3,4,5-trifluorophenol, 2- (N-methylamino) -3,4,6-trifluorophenol, 2- (N-methylamino) -tetrafluoro Phenol, 3- (N-methylamino) -2-fluorophenol, 3- (N-methylamino) -4-fluorophenol, 3- (N-methylamino) -5-fluorophenol 3- (N-methylamino) -2,4-difluorophenol, 3- (N-methylamino) -2,5-fluorophenol, 3- (N-methylamino) -4,5-difluorophenol, 3- (N-methylamino) -4,6-difluorophenol, 3- (N-methylamino) -5,6-difluorophenol, 3- (N-methylamino) -2,4,5-trifluorophenol, 3 -(N-methylamino) -4,5,6-trifluorophenol, 3- (N-methylamino) tetrafluorophenol, 4- (N-methylamino) -2-fluorophenol, 4- (N-methyl) Amino) -3-fluorophenol, 4- (N-methylamino) -2,3-difluorophenol, 4- (N-methylamino) -2,5-difluorophenol, -(N-methylamino) -2,6-difluorophenol, 4- (N-methylamino) -2,3,5-trifluorophenol, 4- (N-methylamino) -2,3,6-trifluoro Fluorophenol, 4- (N-methylamino) tetrafluorophenol, 5- (N-methylamino) -2-fluoro-1-hydroxynaphthalene, 5- (N-methylamino) -3-fluoro-1-hydroxynaphthalene 5- (N-methylamino) -4-fluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,3-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2, 4-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,6-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,7-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,8-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -3,4-difluoro-1-hydroxy Naphthalene, 5- (N-methylamino) -3,8-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -4,8-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,3,4-trifluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,3,6-trifluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,3 7-trifluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,3,8-trifluoro-1-hydroxynaphthalene, 5- (N-methylaphthalene) C) -2,3,6,7-tetrafluoro-1-hydroxynaphthalene, 5- (N-methylamino) hexafluoro-1-hydroxynaphthalene, 2- (N-methylamino) -1-fluoro-6- Hydroxynaphthalene, 2- (N-methylamino) -3-fluoro-6-hydroxynaphthalene, 2- (N-methylamino) -4-fluoro-6-hydroxynaphthalenenaphthalene, 2- (N-methylamino) -1 , 3-difluoro-6-hydroxynaphthalene, 2- (N-methylamino) -1,4-difluoro-6-hydroxynaphthalene, 2- (N-methylamino) -1,5-difluoro-6-hydroxynaphthalene, 2- (N-methylamino) -3,4-difluoro-6-hydroxynaphthalene, 2- (N-methylamino) -3,5-diph Oro-6-hydroxynaphthalene, 2- (N-methylamino) -4,5-difluoro-6-hydroxynaphthalene, 2- (N-methylamino) -1,3,4-trifluoro-6-hydroxynaphthalene, 2- (N-methylamino) -1,3,5-trifluoro-6-hydroxynaphthalene, 2- (N-methylamino) -3,4,5-trifluoro-6-hydroxynaphthalene, 2- (N -Methylamino) -1,3,4,5-tetrafluoro-6-hydroxynaphthalene, 2- (N-methylamino) hexafluoro-6-hydroxynaphthalene, bis (4- (N-methylamino) -2, 3-difluorophenyl) methane, bis (4- (N-methylamino) -2,6-difluorophenyl) methane, bis (4-hydroxy3,5-difluorophe Nyl) methane, bis (4-hydroxytetrafluorophenyl) methane, 4,4′-bis (2- (N-methylamino) hexafluoroisopropyl) diphenyl ether, 4,4′-isopropylidenebis (2,6-di) Fluoroaniline), 2- (N-methylamino) tetrafluoroethanol, 3- (N-methylamino) hexafluoro-1-propanol, 4- (N-methylamino) -2,2 ′, 3,3 ′ -Tetrafluoro-1-butanol, 4- (N-methylamino) octafluoro-1-butanol, 5- (N-methylamino) perfluoro-1-pentanol, 6- (N-methylamino) perfluoro-1- Hexanol, 7- (N-methylamino) perfluoro-1-heptanol, 8- (N-methylamino) perfluoro-1 Octanol, 2- (N-trifluoromethylamino) -3-fluorophenol, 2- (N-trifluoromethylamino) -4-fluorophenol, 2- (N-trifluoromethylamino) -3,4-difluoro Phenol, 2- (N-trifluoromethylamino) -3,5-difluorophenol, 2- (N-trifluoromethylamino) -3,6-difluorophenol, 2- (N-trifluoromethylamino) -3 , 4,5-trifluorophenol, 2- (N-trifluoromethylamino) -3,4,6-trifluorophenol, 2- (N-trifluoromethylamino) tetrafluorophenol, 3- (N-trifluorophenol) Fluoromethylamino) -2-fluorophenol, 3- (N-trifluoromethylamino) -4-fluoro Enol, 3- (N-trifluoromethylamino) -5-fluorophenol, 3- (N-trifluoromethylamino) -2,4-difluorophenol, 3- (N-trifluoromethylamino) -2,5 -Fluorophenol, 3- (N-trifluoromethylamino) -4,5-difluorophenol, 3- (N-trifluoromethylamino) -4,6-difluorophenol, 3- (N-trifluoromethylamino) -5,6-difluorophenol, 3- (N-trifluoromethylamino) -2,4,5-trifluorophenol, 3- (N-trifluoromethylamino) -4,5,6-trifluorophenol, 3- (N-trifluoromethylamino) tetrafluorophenol, 4- (N-trifluoromethylamino) -2-fur Orophenol, 4- (N-trifluoromethylamino) -3-fluorophenol, 4- (N-trifluoromethylamino) -2,3-difluorophenol, 4- (N-trifluoromethylamino) -2, 5-difluorophenol, 4- (N-trifluoromethylamino) -2,6-difluorophenol, 4- (N-trifluoromethylamino) -2,3,5-trifluorophenol, 4- (N-trifluorophenol) Fluoromethylamino) -2,3,6-trifluorophenol, 4- (N-trifluoromethylamino) tetrafluorophenol, 5- (N-trifluoromethylamino) -2-fluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -3-fluoro-1-hydroxynaphthalene, 5- (N-trifluoro) Romethylamino) -4-fluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,3-difluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,4-difluoro-1- Hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,6-difluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,7-difluoro-1-hydroxynaphthalene, 5- (N- Trifluoromethylamino) -2,8-difluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -3,4-difluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -3, 8-difluoro-1-hydroxynaphthalene, 5- (N-trifluoro) Romethylamino) -4,8-difluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,3,4-trifluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2, 3,6-trifluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,3,7-trifluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,3 8-trifluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,3,6,7-tetrafluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) hexafluoro-1 -Hydroxynaphthalene, 2- (N-trifluoromethylamino) -1-fluoro-6-hydroxyna Phthalene, 2- (N-trifluoromethylamino) -3-fluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -4-fluoro-6-hydroxynaphthalenenaphthalene, 2- (N-trifluoromethyl) Amino) -1,3-difluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -1,4-difluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -1,5- Difluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -3,4-difluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -3,5-difluoro-6-hydroxynaphthalene, 2, -(N-trifluoromethylamino) -4,5-difluoro-6-hydroxy Naphthalene, 2- (N-trifluoromethylamino) -1,3,4-trifluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -1,3,5-trifluoro-6-hydroxy Naphthalene, 2- (N-trifluoromethylamino) -3,4,5-trifluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -1,3,4,5-tetrafluoro-6 -Hydroxynaphthalene, 2- (N-trifluoromethylamino) hexafluoro-6-hydroxynaphthalene, bis (4- (N-trifluoromethylamino) -2,3-difluorophenyl) methane, bis (4- (N -Trifluoromethylamino) -2,6-difluorophenyl) methane, bis (4-hydroxy3,5-difluorophenyl) Tan, bis (4-hydroxytetrafluorophenyl) methane, 4,4′-bis (2- (N-trifluoromethylamino) hexafluoroisopropyl) diphenyl ether, 4,4′-isopropylidenebis (2,6-di) Fluoroaniline), 2- (N-trifluoromethylamino) tetrafluoroethanol, 3- (N-trifluoromethylamino) hexafluoro-1-propanol, 4- (N-trifluoromethylamino) -2,2 ', 3,3'-tetrafluoro-1-butanol, 4- (N-trifluoromethylamino) octafluoro-1-butanol, 5- (N-trifluoromethylamino) perfluoro-1-pentanol, 6 -(N-trifluoromethylamino) perfluoro-1-hexanol, 7- (N-trifluoro) Romethylamino) perfluoro-1-heptanol, 8- (N-trifluoromethylamino) perfluoro-1-octanol and compounds obtained by substituting the fluorine atom of the HO-R-NLH type compound with a bromine atom or a chlorine atom.

H ₂ N—R—NLH type compounds (the definitions of L and R are the same as those in formula (I)) include 2- (N-methylamino) -3-fluoroaniline, 2- (N-methylamino) — 4-fluoroaniline, 2- (N-methylamino) -3,4-difluoroaniline, 2- (N-methylamino) -3,5-difluoroaniline, 2- (N-methylamino) -3,6- Difluoroaniline, 2- (N-methylamino) -3,4,5-trifluoroaniline, 2- (N-methylamino) -3,4,6-trifluoroaniline, 2- (N-methylamino) tetra Fluoroaniline, 3- (N-methylamino) -2-fluoroaniline, 3- (N-methylamino) -4-fluoroaniline, 3- (N-methylamino) -5-fluoroaniline, 3- (N- Methyla C) -2,4-difluoroaniline, 3- (N-methylamino) -2,5-fluoroaniline, 3- (N-methylamino) -4,5-difluoroaniline, 3- (N-methylamino) -4,6-difluoroaniline, 3- (N-methylamino) -5,6-difluoroaniline, 3- (N-methylamino) -2,4,5-trifluoroaniline, 3- (N-methylamino) ) -4,5,6-trifluoroaniline, 3- (N-methylamino) tetrafluoroaniline, 4- (N-methylamino) -2-fluoroaniline, 4- (N-methylamino) -3-fluoro Aniline, 4- (N-methylamino) -2,3-difluoroaniline, 4- (N-methylamino) -2,5-difluoroaniline, 4- (N-methylamino) -2,6-difluoroa Niline, 4- (N-methylamino) -2,3,5-trifluoroaniline, 4- (N-methylamino) -2,3,6-trifluoroaniline, 4- (N-methylamino) tetrafluoro Aniline, 5-amino-2-fluoro-1- (N-methylamino) naphthalene, 5-amino-3-fluoro-1- (N-methylamino) naphthalene, 5-amino-4-fluoro-1- (N-methylamino) ) Naphthalene, 5-amino-2,3-difluoro-1- (N-methylamino) naphthalene, 5-amino-2,4-difluoro-1- (N-methylamino) naphthalene, 5-amino-2,6-difluoro- 1- (N-methylamino) naphthalene, 5-amino-2,7-difluoro-1- (N-methylamino) naphthalene, 5-amino-2,8-difluoro- -(N-methylamino) naphthalene, 5-amino-3,4-difluoro-1- (N-methylamino) naphthalene, 5-amino-3,8-difluoro-1- (N-methylamino) naphthalene, 5-amino -4,8-difluoro-1- (N-methylamino) naphthalene, 5-amino-2,3,4-trifluoro-1- (N-methylamino) naphthalene, 5-amino-2,3,6-trifluoro- 1- (N-methylamino) naphthalene, 5-amino-2,3,7-trifluoro-1- (N-methylamino) naphthalene, 5-amino-2,3,8-trifluoro-1- (N-methyl) Amino) naphthalene, 5-amino-2,3,6,7-tetrafluoro-1- (N-methylamino) naphthalene, 5-amino-hexafluoro-1- (N-methylamino) Naphthalene, 2-amino-1-fluoro-6- (N-methylamino) naphthalene, 2-amino-3-fluoro-6- (N-methylamino) naphthalene, 2-amino-4-fluoro-6- (N-methylamino) Naphthalenenaphthalene, 2-amino-1,3-difluoro-6- (N-methylamino) naphthalene, 2-amino-1,4-difluoro-6- (N-methylamino) naphthalene, 2-amino-1,5-difluoro-6- (N-methylamino) naphthalene, 2-amino-3,4-difluoro-6- (N-methylamino) naphthalene, 2-amino-3,5-difluoro-6- (N-methylamino) naphthalene, 2-amino-4,5 -Difluoro-6- (N-methylamino) naphthalene, 2-amino-1,3,4-trifluoro-6- (N- Tilamino) naphthalene, 2-amino-1,3,5-trifluoro-6- (N-methylamino) naphthalene, 2-amino-3,4,5-trifluoro-6- (N-methylamino) naphthalene, 2-amino-1 , 3,4,5-Tetrafluoro-6- (N-methylamino) naphthalene, 2-amino-hexafluoro-6- (N-methylamino) naphthalene, 4-amino-4 '-(N-methylamino) -2,3,4,5-tetrafluorobiphenyl, 4-amino-4 '-(N-methylamino) -2,2', 4,4'-tetrafluorobiphenyl, 4-amino-4 '-(N -Methylamino) -2,2 ', 3,3', 4,4 ', 5,5', 6,6'-octafluorobiphenyl, (4-amino-2,3-difluorophenyl) (4- ( N-methylamino) -2,3-diflu Rophenyl) methane, (4-amino-2,6-difluorophenyl) (4- (N-methylamino) -2,6-difluorophenyl) methane, (4-amino-3,5-difluorophenyl) (4- (N-methylamino) -3,5-difluorophenyl) methane, (4-amino-tetrafluorophenyl) (4- (N-methylamino) -tetrafluorophenyl) methane, (4- (2-amino-hexa Fluoroisopropyl)) (4- (4- (N-methylamino) -hexafluoroisopropyl)) diphenyl ether, 1-amino-2- (N-methylamino) tetrafluoroethane, 1-amino-3- (N-methyl Amino) -hexafluoropropane, 1-amino-4- (N-methylamino) -2,2 ′, 3,3′-hexafluorobutane, 1-amino- -(N-methylamino) -octafluorobutane, 1-amino-5- (N-methylamino) -decafluoropentane, 1-amino-6- (N-methylamino) -perfluorohexane, 1-amino- 7- (N-methylamino) -perfluoropentane, 1-amino-8- (N-methylamino) -perfluorooctane, (4-bromotetrafluorophenyl) hydrazine, 2-chloro-6-fluorofailhydrazine, 3-chloro-4-fluorophenylhydrazine, 2-chloro-4- (trifluoromethyl) phenylhydrazine, 2-chloro-5-trifluoromethylphenylhydrazine, 2,4-dictoto 6- (trifluoromethyl) phenylhydrazine, 2, 6-dictoto 6- (trifluoromethyl) phenylhydrazine, 2,4- Fluorophenylhydrazine, 2,5-fluorophenylhydrazine, 5-fluoro-2-methylphenylhydrazine, 4-fluorophenylhydrazine, pentafluorophenylhydrazine, 4- (trifluoromethoxy) phenylhydrazine, 2- (trifluoromethyl) Examples include phenylhydrazine, 2-amino-6-fluoro-purine, 2-amino-6-trifluoromethyl-purine, and compounds in which the fluorine atom of the H ₂ N—R—NLH type compound is substituted with a bromine atom or a chlorine atom. .

  Of these, tetrafluororesorcin, tetrafluorohydroquinone, tetrabromohydroquinone, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene, 4,4′-bis (2-hydroxyhexafluoroisopropyl) diphenyl are preferable. 4,4′-bis (2-hydroxyhexafluoroisopropyl) diphenyl ether, 2,2 ′, 3,3′-tetrafluoro-1,4-butanediol, 2-amino-5-fluoroaniline, 2-amino-6 -Fluorobenzylamine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'- Diaminooctafluorobiphenyl, 2,2-bis (3-amino- -Methylphenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenyl)]-hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,4-diamino-6- (4-fluorophenyl) pyrimidine, 2,4-diamino-5-fluoroquinazoline, 4,4′-diaminooctafluorobiphenyl, tetrafluorosuccinamide, 5-trifluoromethyluracil, 4-amino-3-fluorophenol, 3,5-bis (trifluoromethyl) benzamide oxime, 5- (trifluoromethyl) pyridine-2-arboxamidooxime, (4-bromotetrafluorophenyl) hydrazine, 2-chloro-6-fluorofailhydrazine, 3- Chloro-4-fluorofailhydride , 2-chloro-4- (trifluoromethyl) phenylhydrazine, 2-chloro-5-trifluoromethylphenylhydrazine, 2,4-dictoto 6- (trifluoromethyl) phenylhydrazine, 2,6-dictoto 6- (tri Fluoromethyl) phenylhydrazine, 2,4-fluorophenylhydrazine, 2,5-fluorophenylhydrazine, 5-fluoro-2-methylphenylhydrazine, 4-fluorophenylhydrazine, pentafluorophenylhydrazine, 4- (trifluoromethoxy) phenyl Hydrazine and 2- (trifluoromethyl) phenylhydrazine, particularly preferably tetrafluororesorcin, tetrafluorohydroquinone, tetrabromohydroquinone, 4,4′-diaminooctafluorobifu It is a nenyl.

(B) Organoaluminum compound The catalyst for olefin polymerization according to the present invention is obtained by contacting (A) (a) a transition metal compound, (b) an organoaluminum oxy compound, and (c) a polyfunctional organic halide. A solid transition metal catalyst component to be produced, and (B) an organoaluminum compound, if necessary.

  Examples of the (B) organoaluminum compound used in the present invention include an organoaluminum compound represented by the following general formula (III).

R ^a _n AlT _3-n (III)
(In the formula, ^Ra is a hydrocarbon group having 1 to 12 carbon atoms, T is a halogen atom or a hydrogen atom, and n is 1 to 3).

In the general formula (III), R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, a methyl group, an ethyl group, an n-propyl group, Examples thereof include isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, isohexyl group, heptyl group, nonyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

  Specific examples of the organoaluminum compound (d) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; isoprenylaluminum Alkenyl aluminum: Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethyl aluminum Alkylaluminum sesquihalides such as skibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide; dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum, diisopropylaluminum hydride, di- Alkyl aluminum hydrides such as n-butyl aluminum hydride, diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride, di-sec-nonyl aluminum hydride And the like.

  As the organoaluminum compound (B), a compound represented by the following general formula (IV) can also be used.

^{_{R a n AlU 3-n ...}} (IV)
(In the formula, R ^a is the same as above, and U represents —OR ^b group, —OSiR ^c ₃ group, —OAlR ^d ₂ group, —NR ^e ₂ group, —SiR ^f ₃ group, or —N (R ^g ). AlR ^h ₂ group, n is 1-2, R ^b , R ^c , R ^d , and R ^h are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc. ^e is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and ^Rf and ^Rg are a methyl group, an ethyl group, etc.)

As such an organoaluminum compound, specifically, the following compounds are used.
_{^{(1) R a n Al (}} OR b) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide; (2) R a n Al}} (OSiR c 3) 3 compounds represented by _-n, for example _{Et 2 Al (OSiMe 3),} (iso-Bu) 2 Al (OSiMe 3), such as _{(iso-Bu) 2 Al (} OSiEt 3); (3) R a n Al ( OAlR ^d ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc .; (4) R ^a _n Al (NR ^e ) _3-n compounds represented, for example, _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2 AlNHEt, Et 2 AlN (SiMe 3) 2, (iso-Bu) 2 AlN ( etc. _{^{iMe 3) 2; (5)}} R a n Al (SiR f 3) a compound represented by _3-n, for example (such as _{iso-Bu) 2 AlSiMe 3;} (6) R a n Al [N ^{(R g} ) AlR ^h ₂ ] _3-n compounds such as Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Among the organoaluminum compounds represented by the above general formulas (III) and (IV), a compound represented by the general formula R ^a ₃ Al is preferable, and R ^a is an alkyl group having 1 to 4 carbon atoms. Is preferred.

Solid Carrier The solid carrier used in the present invention is an inorganic or organic compound, and a granular or particulate solid having a particle size of 10 to 300 μm, preferably 20 to 200 μm is used. Of these, porous oxides are preferable as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc., or these For example, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. be able to. Among these, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable. The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such a solid carrier has different properties depending on the type and production method, but the solid carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g. The pore volume is desirably 0.3 to 2.5 cm ³ / g. The solid carrier is used after calcining at a temperature of 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

  Furthermore, examples of solid carriers that can be used in the present invention include granular or fine particle solids of organic compounds having a particle size of 10 to 300 μm. Examples of these organic compounds include (co) polymers, vinylcyclohexane and styrene, which are mainly composed of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Examples thereof include a polymer or copolymer produced as a main component.

  Next, the solid catalyst for olefin polymerization of the present invention will be described more specifically. The solid catalyst for olefin polymerization of the present invention includes a transition metal compound of Group 4 of the periodic table, comprising (A) (a) one or more ligands having a cyclopentadienyl skeleton, and (b) organoaluminum. An oxy compound, and (c) a solid transition metal catalyst component obtained by contacting the polyfunctional organic halide represented by the general formula (I), and (B) an organoaluminum compound, if necessary. It is characterized by that. When the (A) solid transition metal catalyst component is prepared from the components (a), (b) and (c), the component (d) an organoaluminum compound can be further coexisted. As the (d) organoaluminum compound, the aforementioned (B) organoaluminum compound can be used without limitation.

  Next, a method for preparing the (A) solid transition metal catalyst component will be described. In the case of preparing the solid transition metal catalyst component (A) from the component (a), component (b), component (c) and solid support, the component (a), component (b), component (c) and solid state It can be prepared by bringing the support into mixed contact in an inert hydrocarbon.

  The order of mixing the components at this time is arbitrary, but it is desirable to avoid mixing and contacting the component (a) and the component (c) directly. Such direct contact may cause decomposition and alteration of the component (a), and there is a high possibility that the catalytic activity of the finally obtained olefin polymerization catalyst will be significantly reduced.

As a preferable contact order, for example,
i) A method in which component (b) is mixed and contacted with a solid carrier, and then component (a) is contacted and then component (c) is contacted.
ii) A method in which component (b) is mixed and contacted with a solid carrier, and then component (c) is contacted, and then component (a) is contacted,
iii) A method in which component (a) and component (b) are first mixed and contacted, and then a solid carrier and subsequently component (c) are mixed and contacted,
iv) A method in which the solid carrier is brought into contact with the contact mixture of component (b) and component (c), and then component (a) is mixed and contacted.

  In the case of preparing the (A) solid transition metal catalyst component from the component (a), the component (b), the component (c), the component (d) and the solid carrier, the component (a), the component (b), the component ( c), component (d) and the solid support can be prepared by mixing contact in an inert hydrocarbon.

  The order of mixing the components at this time is arbitrary, but it is desirable to avoid mixing and contacting the component (a) and the component (c) for the same reason as described above.

As a preferable contact order, for example,
i) The component (b) is mixed and contacted with the solid carrier, and then the component (a) is contacted, and then the component (c), the component (d), or the contact between the component (c) and the component (d) A method of contacting the mixture,
ii) A method in which component (b) is mixed and contacted with a solid carrier, and then component (c) is contacted, and then component (a) or component (d) is contacted,
iii) First, the component (a) and the component (b) are mixed and contacted, and then the solid carrier, followed by the component (c), the component (d), or the contact mixture of the component (c) and the component (d), How to contact,
iv) A method in which a solid carrier is brought into contact with the contact mixture of component (b) and component (c) and then component (a) or component (d) is mixed and contacted.

In the present invention, when the above components are mixed, the component (a) is 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 5 × 10 ⁻⁶ to 2 × 10 ⁻⁴ mol, per 1 g of the solid carrier. The concentration of component (a) is in the range of 10 ^{−5 to} 5 × 10 ⁻³ mol / liter-solvent, preferably 5 × 10 ⁻⁵ to 2 × 10 ⁻² mol / liter-solvent. . Component (b) is an atomic ratio (Al / transition metal) between aluminum (Al) derived from component (b) and a transition metal derived from component (a), and is 10 to 1000, preferably 50 to 500. Used in the amount of. Component (c) is 0.01 to 5.0 mol, preferably 0.02 to 1.0 mol, more preferably 0.03 to 0.5 mol, relative to 1 mol of aluminum derived from component (b). Used in the amount of. When component (d) is used, a gram atomic ratio (Al-d / a) of aluminum atom (Al-d) in component (d) and aluminum atom (Al-b) in component (b) is used. Al-b) and is used in an amount of 0.01 to 2.0, preferably 0.02 to 1.0.
The mixing temperature at the time of mixing each of the above components is −50 to 150 ° C., preferably −20 to 120 ° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes. Further, the mixing temperature may be changed during the mixing contact.

  In the present invention, as one of the preferred contact forms, the component (b) and the component (c) are mixed and contacted in advance in an inert hydrocarbon, and include a mixed contact product of the component (b) and the component (c). After preparing the solution, there can be mentioned a method in which the solution and other components are mixed and contacted. In mixing and contacting the component (b) and the component (c), the concentration of the component (b) is in the range of 0.01 to 5 mol / liter-solvent, preferably 0.1 to 3 mol / liter-solvent. is there. Component (c) is 0.01 to 5.0 mol, preferably 0.02 to 1.0 mol, more preferably 0.03 to 0.5 mol, relative to 1 mol of aluminum derived from component (b). It is desirable that the amount of The mixing temperature at the time of mixing and contacting the component (b) and the component (c) is -20 to 150 ° C, preferably 0 to 120 ° C, and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes. .

  Specific examples of the inert hydrocarbon used in the preparation of the catalyst in the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclo Examples thereof include alicyclic hydrocarbons such as pentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

In the olefin polymerization catalyst according to the present invention, the transition metal atom derived from the component (a). Component (b) and optionally used component (d) supported in an amount of 5 × 10 ^{−5 to} 5 × 10 ⁻² gram atoms, preferably 10 ⁻⁵ to 10 ⁻² gram atoms per gram of solid support. Is supported in an amount of 10 ^{−3 to} 1.0 gram atom, preferably 5 × 10 ^{−3 to} 5 × 10 ⁻¹ gram atom, and component (c) is 5 × 10 ^{−5 to} 5 It is desirable that it is supported in an amount of × 10 ⁻² mol, preferably 10 ⁻⁵ to 10 ⁻² mol. The component (B) used as necessary is desirably used in an amount of 500 mol or less, preferably 1 to 200 mol per gram atom of the transition metal atom derived from the component (a).

In the olefin polymerization according to the present invention, the polymerization reaction may be performed in a single stage, or may be performed in two or more stages. However, as already described, the multistage polymerization system is such that the density (d), MFR, and the sum of the number of methyl branches and the number of ethyl branches (A + B) of the ethylene-based polymer of the present invention are maintained at substantially constant values. Since MT / η ^* can be arbitrarily varied within the scope of the claims of the present invention, a multistage, preferably a two-stage or three-stage polymerization reaction system is usually employed. The two-stage polymerization in the present invention is usually composed of a first-stage polymerization (sometimes referred to as “preliminary polymerization” in the following description) and a second-stage polymerization (main polymerization) step. The three-stage polymerization of the present invention usually comprises a preliminary polymerization and a two-stage main polymerization step.

  The prepolymerization catalyst can be prepared by prepolymerizing an olefin usually in an inert hydrocarbon solvent in the presence of the component (a), the component (b), the component (c) and the solid carrier. In addition, it is preferable that the olefin polymerization catalyst is formed from each said component (a), component (b), component (c), and a solid support. In addition to this olefin polymerization catalyst, component (d) may be further added.

In the preliminary polymerization, the component (a) is used in an amount of 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 5 × 10 ⁻⁶ to 2 × 10 ⁻⁴ mol as a transition metal per 1 g of the solid support. Component (b) is an atomic ratio (Al / transition metal) of aluminum (Al) of component (b) and transition metal of component (a), and is used in an amount of 10 to 1000, preferably 50 to 500. . Component (c) is used in an amount of 0.01 to 5.0 mol, preferably 0.02 to 1.0 mol, more preferably 0.03 to 0.5 mol, per 1 mol of component (b). It is done. When component (d) is used, the atomic ratio (Al-d / Al) of aluminum atoms (Al-d) in component (d) to aluminum atoms (Al-b) in component (b) -B) is used in an amount of 0.01 to 5.0, preferably 0.02 to 1.0.

The concentration of the transition metal compound (a) or the olefin polymerization catalyst formed from each component in the prepolymerization system is usually 10 ⁻⁶ to 2 × 10 ⁻² mol / liter, in a transition metal / polymerization volume ratio of 1 liter, 5 × 10 ⁻⁵ to 10 ⁻² mol / liter is desirable.

  The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours. In the prepolymerization, an olefin similar to the olefin used in the polymerization described later is used, but an olefin mainly composed of ethylene is preferable.

  The prepolymerization catalyst may introduce olefin into an olefin polymerization catalyst suspension prepared using an inert hydrocarbon solvent, and the olefin polymerization catalyst produced in the inert hydrocarbon solvent is separated from the suspension. After that, it may be suspended again in an inert hydrocarbon, and the olefin may be introduced into the resulting suspension.

  The prepolymerization desirably produces an olefin polymer (prepolymer) in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g, per 1 g of the solid carrier.

The prepolymerization can be carried out in any of batch, semi-continuous and continuous methods. In the prepolymerized catalyst thus obtained, the transition metal atom derived from the component (a) is 10 ⁻⁷ to 4 × 10 ⁻² gram atom, preferably 5 × 10 ⁻⁷ to 2 ×, per 1 g of the solid support. Supported in an amount of 10 ⁻² gram atoms, aluminum atoms derived from component (b) are 10 ^{−6 to} 9.0 × 10 ⁻¹ gram atoms, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻¹ gram atoms. It is desirable that the component (c) is supported in an amount of 5 × 10 ⁻⁸ to 4 × 10 ⁻² mol, preferably 10 ⁻⁸ to 2 × 10 ⁻² mol.

  Next, the olefin polymerization method according to the present invention will be described. In the present invention, olefin polymerization is carried out in the presence of the above solid catalyst for olefin polymerization. The polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method.

  In the liquid phase polymerization method, the same inert hydrocarbon used in the catalyst preparation described above can be used as the solvent, or the olefin itself can be used as the solvent.

When performing olefin polymerization using the olefin polymerization catalyst of the present invention, the catalyst as described above is 10 ⁻⁸ to 10 ⁻³ gram as the concentration of transition metal atoms derived from the component (a) in the polymerization system. It is desirable to use in an amount of atoms / liter (polymerization volume), preferably 10 ⁻⁷ to 10 ⁻⁴ grams atom / liter (polymerization volume). At this time, an organoaluminum oxy compound may be used if desired. The amount of the organoaluminum oxy compound used is desirably in the range of 0 to 500 mol per gram atom of the transition metal atom derived from the component (a).

  The polymerization temperature of the olefin is desirably in the range of −50 to 100 ° C., preferably 0 to 90 ° C. when the slurry polymerization method is performed, and 0 to 250 when the liquid phase polymerization method is performed. It is desirable that the temperature be in the range of 20 ° C., preferably 20 to 200 ° C. When carrying out the gas phase polymerization method, the polymerization temperature is 0 to 120 ° C, preferably 20 to 100 ° C. The polymerization pressure is under normal pressure to 10 MPa, preferably normal pressure to 5 MPa, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the resulting olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. Examples of the olefin that can be polymerized by the olefin polymerization catalyst of the present invention include ethylene and an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4- Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; cyclic olefins having 5 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene , 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, etc. Can do. Furthermore, styrene, vinylcyclohexane, diene, etc. can also be used.

  In order to suppress variation in physical property values, the ethylene polymer particles obtained by the polymerization reaction and other components added as desired are melted by an arbitrary method, kneaded, granulated, and the like.

  By blending the ethylene polymer according to the present invention with another thermoplastic resin, a thermoplastic resin composition having excellent moldability and excellent mechanical strength can be obtained. The blend ratio of the present ethylene polymer and other thermoplastic resin is 99.1 / 0.1 to 0.1 / 99.9.

  Other thermoplastic resins include crystalline thermoplastic resins such as polyolefins, polyamides, polyesters and polyacetals; amorphous heats such as polystyrene, acrylonitrile / butadiene / styrene copolymers (ABS), polycarbonates, polyphenylene oxides, polyacrylates, etc. A plastic resin is used. Polyvinyl chloride is also preferably used.

  Specific examples of the polyolefin include ethylene polymers, propylene polymers, butene polymers, 4-methyl-1-pentene polymers, 3-methyl-1-butene polymers, hexene polymers, and the like. Is mentioned. Of these, ethylene polymers, propylene polymers, and 4-methyl-1-pentene polymers are preferred. When ethylene polymers are used, even if the ethylene polymer according to the present invention is used, It may be a polymer or an ethylene / polar group-containing vinyl copolymer, but a conventional ethylene polymer is more preferred.

  Specific examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycaprolactone, polyhydroxybutyrate, and the like.

  Specific examples of the polyamide include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon-46, and aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines. Can be mentioned.

  Specific examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde and the like. Among these, polyformaldehyde is particularly preferable.

  The polystyrene may be a homopolymer of styrene, or a binary copolymer of styrene and acrylonitrile, methyl methacrylate, or α-methylstyrene.

  The ABS includes a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and a structural unit derived from styrene. Is preferably used in an amount of 40 to 60 mol%.

  Examples of the polycarbonate include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl). And polymers obtained from butane and the like. Of these, polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.

  As the polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene oxide) is preferably used.

  As the polyacrylate, polymethyl methacrylate or polybutyl acrylate is preferably used.

  The above thermoplastic resins may be used alone or in combination of two or more. A particularly preferable thermoplastic resin is polyolefin, and an ethylene polymer is more particularly preferable.

  The ethylene-based polymer according to the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, and an anti-blocking agent as long as the object of the present invention is not impaired in addition to the thermoplastic resin. Additives such as an antifogging agent, a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, and an antioxidant may be blended as necessary.

  By processing the ethylene polymer according to the present invention and the resin composition containing the ethylene polymer, a molded product, preferably a film, having excellent moldability and mechanical strength can be obtained.

  The ethylene copolymer of the present invention is processed by general blow molding, film molding, injection molding, and extrusion molding. Although the obtained film can be used as a single layer, various functions can be imparted by forming a multilayer. In that case, the coextrusion method in each said shaping | molding method is mentioned.

  As the molded product obtained by processing the ethylene polymer of the present invention and the thermoplastic resin composition containing the ethylene polymer, a bottle container by blow molding, an industrial chemical can, a gasoline tank, a film by film molding, Examples include tubes, pipes, tear caps by extrusion molding, injection molded products such as daily goods, fibers, and large molded products by rotational molding.

  EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

Preparation of Solid Component (S) 13 g (component E) of silica (SiO ₂ ) dried at 250 ° C. for 10 hours under nitrogen flow was suspended in 100 mL of toluene, and then cooled to 0 ° C. To this suspension, 52.6 mL of a toluene solution of methylalumoxane (component B: Albemarle product) (1.75 mmol / mL in terms of Al atom) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 2 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours, and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed four times with toluene, and then toluene was added to prepare a toluene slurry of the solid component (S). A part of the obtained solid component (S) was collected and examined for concentration. As a result, the slurry concentration was 0.1216 g / mL, and the Al concentration was 0.575 mmol / mL. Moreover, when a part of the supernatant was collected and the concentration was measured, the Al concentration was 0.001 mmol / mL or less.

Preparation of solid catalyst component (X) To a nitrogen-substituted 400 mL glass flask was charged 208 mL of toluene, and the toluene slurry of the solid component (S) prepared above (8.0 g in terms of solid part) was charged with stirring. . Next, 126 mL of a toluene solution (0.0015 mmol / mL in terms of Zr atom) of ethylenebis (indenyl) zirconium dichloride (component A) was added dropwise and reacted at room temperature for 2 hours. Thereafter, the supernatant was removed by decantation and washed once with toluene to obtain a 250 mL toluene slurry. Next, 150 mL of a toluene solution in which 1.377 g (component C) of tetrafluorohydroquinone was dissolved was charged at room temperature, and the temperature was raised to 40 ° C., followed by reaction for 30 minutes. Thereafter, the supernatant was removed by decantation and washed once with toluene to obtain a 250 mL toluene slurry. Furthermore, 150 mL of a toluene solution of methylalumoxane (Albemarle product; Component B) (0.253 mmol / mL in terms of Al atom) was added dropwise over 10 minutes, and the temperature was raised to 40 ° C., followed by reaction for 30 minutes. Thereafter, the supernatant was removed by decantation, washed 3 times with toluene and 3 times with decane, and 150 mL of decane was added to prepare a decane slurry of the solid catalyst component (X). A part of the resulting decane slurry of the solid catalyst component (X) was collected to examine the concentration. As a result, the Zr concentration was 0.0892 mg / mL and the Al concentration was 11.2 mg / mL.

Preparation of prepolymerization catalyst component (Q) 500 mL of purified heptane was placed in a 1-liter internal volume SUS autoclave sufficiently purged with nitrogen, and ethylene was circulated to saturate the liquid phase and gas phase with ethylene. In an ethylene atmosphere at 20 ° C., 0.375 mmol (component D) of triisobutylaluminum and component (X) of solid catalyst (0.0254 mmol in terms of zirconium atom) were charged in this order. The ethylene pressure was adjusted to 0.78 MPa · G, polymerization was carried out at 20 ° C. for 8 hours, and then the pressure was released, and the ethylene in the autoclave was replaced with nitrogen. The contents were transferred to a 1 L container sufficiently purged with nitrogen, washed with decane three times, and decane was added to prepare a decane slurry of the prepolymerized catalyst component (Q). A part of the resulting decane slurry of the prepolymerization catalyst component (Q) was sampled to examine the slurry concentration and the prepolymerization amount. The slurry concentration = 0.1693 g / mL, and the prepolymerization amount per 1 g of the solid catalyst component was 31 g / g-solid catalyst component. The front where polymer gel permeation chromatography measurement of the obtained polymer by the (GPC) was carried out, Mw before polymer 75.4 × ¹⁰ 4, Mz was 735.6 × 10 ^4.

Polymerization Purified heptane (500 mL) was placed in a 1-liter SUS autoclave sufficiently purged with nitrogen, ethylene was circulated, and the liquid phase and gas phase were saturated with ethylene. Next, after replacing the inside of the system with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.085 vol%), 1-hexene 60 mL, triisobutylaluminum 0.375 mmol (component D), prepolymerization catalyst component (Q ) 1.44 g was charged in this order. The temperature was raised to 65 ° C., and polymerization was carried out at 0.78 MPa · G for 30 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 98.9 g of an ethylene / 1-hexene copolymer.

To prepare the measurement sample, Irganox 1076 (Ciba Specialty Chemicals) 0.1% by weight and Irgafos168 (Ciba Specialty Chemicals) 0.1% by weight were added to the resulting ethylene polymer as a heat-resistant stabilizer. Using a plastmill, the mixture was melt-kneaded for 5 minutes at a resin temperature of 180 ° C. and a rotation speed of 50 rpm. Further, this molten polymer was cooled using a press molding machine manufactured by Shindo Metal Industry Co., Ltd. under the conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm ² . Table 1 shows the results of physical property measurement using the sample.

  Example 1 satisfies the requirements described in claims 1 and 2. For this reason, it is expected that the melted parison does not easily sag and tear in blow molding, is excellent in impact strength and environmental stress fracture resistance (ESCR), and is further excellent in thermal stability.

Claims (6)

An ethylene polymer, which is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms and satisfies the following requirements [F1] to [F4] simultaneously.
[F1] Melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 0.1
The range is 1.0 g / 10 min.
[F2] The density (d) is in the range of 890 to 960 kg / m ³ .
[F3] Ratio of melt tension [MT (g)] at 190 ° C to shear viscosity [η ^* (P)] at 200 ° C and angular velocity of 1.0 rad / sec [MT / η ^* (g / P) ] Is 7.00 × 10 ⁻⁵ ~
The range is 9.00 × 10 ⁻⁴ .
[F4] Number of methyl branches per 1000 carbon atoms measured by ¹³ C-NMR [A
(/ 1000C)] and the number of ethyl branches [B (/ 1000C)] [(A + B) (/ 1000C)] is 1.4 or less. The ethylene polymer according to claim 1, wherein any one or more of the following requirements [f1] to [f3] is satisfied.
[f1] Ratio of Z average molecular weight (Mz) and weight average molecular weight (Mw) measured by GPC (Mz /
Mw) is 10 or more.
[f2] Number of terminal vinyl groups per 1000 carbon atoms measured by IR [v (/ 1000 C)]
And the number average molecular weight (Mn) measured by GPC, the number of terminal vinyl groups per molecular chain (V) is 0.47 / 1 molecular chain or less.
[f3] Maximum peak [Tm (° C)] of melting point in DSC and density (d)
(Eq-1) is satisfied.

A transition metal compound of Group 4 of the Periodic Table comprising at least one solid support and (A) (a) a ligand having a cyclopentadienyl skeleton, (b) an organoaluminum oxy compound, and (c) a general formula (I ) A polyfunctional organic halide represented by

[In the formula (I), R is an (o + p) -valent group containing one or more halogen atoms, o and p are positive integers satisfying (o + p) ≧ 2, and Q ¹ and Q ² are − OH, —NH ₂ or —NLH (in —NLH, L represents a halogen atom, a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, sulfur Any group selected from a containing group, a nitrogen-containing group or a phosphorus-containing group.), L and R, N and R, and N and N may be bonded to each other to form a ring. And a solid transition metal catalyst component obtained by contacting, if necessary,
The ethylene-based polymer according to claim 1, which is obtained by polymerization using a catalyst system formed from (B) an organoaluminum compound.   The thermoplastic resin composition containing the ethylene polymer in any one of Claims 1-3.   The molded object obtained from the thermoplastic resin composition containing the ethylene-type polymer in any one of Claims 1-4, and an ethylene-type polymer.   A blow molded article obtained from the ethylene polymer according to claim 5 and a thermoplastic resin composition containing the ethylene polymer.